WO2015041226A1 - Polymer dispersant for inorganic pigment - Google Patents
Polymer dispersant for inorganic pigment Download PDFInfo
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- WO2015041226A1 WO2015041226A1 PCT/JP2014/074492 JP2014074492W WO2015041226A1 WO 2015041226 A1 WO2015041226 A1 WO 2015041226A1 JP 2014074492 W JP2014074492 W JP 2014074492W WO 2015041226 A1 WO2015041226 A1 WO 2015041226A1
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- mass
- group
- polymer dispersant
- formula
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- 239000001023 inorganic pigment Substances 0.000 title claims abstract description 157
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 87
- 229920000642 polymer Polymers 0.000 title claims abstract description 67
- 229920001577 copolymer Polymers 0.000 claims abstract description 54
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims description 47
- 239000002002 slurry Substances 0.000 claims description 47
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 41
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 38
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 18
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 12
- 229910002113 barium titanate Inorganic materials 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000011354 acetal resin Substances 0.000 claims description 5
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 229920006324 polyoxymethylene Polymers 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 4
- DJOYTAUERRJRAT-UHFFFAOYSA-N 2-(n-methyl-4-nitroanilino)acetonitrile Chemical compound N#CCN(C)C1=CC=C([N+]([O-])=O)C=C1 DJOYTAUERRJRAT-UHFFFAOYSA-N 0.000 claims description 4
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021523 barium zirconate Inorganic materials 0.000 claims description 4
- DQBAOWPVHRWLJC-UHFFFAOYSA-N barium(2+);dioxido(oxo)zirconium Chemical compound [Ba+2].[O-][Zr]([O-])=O DQBAOWPVHRWLJC-UHFFFAOYSA-N 0.000 claims description 4
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 239000000919 ceramic Substances 0.000 abstract description 29
- 239000000470 constituent Substances 0.000 abstract 3
- 239000000178 monomer Substances 0.000 description 45
- 239000002245 particle Substances 0.000 description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- 239000006185 dispersion Substances 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 14
- -1 polyoxyethylene group Polymers 0.000 description 14
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 229920001223 polyethylene glycol Polymers 0.000 description 11
- 239000000523 sample Substances 0.000 description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000002216 antistatic agent Substances 0.000 description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002296 dynamic light scattering Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- XMGZWGBXVLJOKE-UHFFFAOYSA-N acetic acid;toluene Chemical compound CC(O)=O.CC1=CC=CC=C1 XMGZWGBXVLJOKE-UHFFFAOYSA-N 0.000 description 2
- 239000012445 acidic reagent Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- UMSCPKPEJAYDKK-UHFFFAOYSA-N butan-1-amine;toluene Chemical compound CCCCN.CC1=CC=CC=C1 UMSCPKPEJAYDKK-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000004815 dispersion polymer Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000007869 azo polymerization initiator Substances 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
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- 238000004581 coalescence Methods 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002484 inorganic compounds Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
- C09K23/44—Ether carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
- C09B67/0085—Non common dispersing agents
- C09B67/009—Non common dispersing agents polymeric dispersing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/006—Metal
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/007—Metal oxide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/002—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
Definitions
- the present invention relates to a polymer dispersant for inorganic pigment, a dispersion method using the same, and a slurry composition.
- Patent Document 1 discloses a binder resin used for an inorganic fine particle-dispersed paste composition containing inorganic fine particles.
- Patent Document 2 discloses a polymer dispersant for an inorganic pigment composed of three structural units including a structural unit having an acid group and a structural unit having a macromonomer.
- Ceramic sheets typified by green sheets used in multilayer ceramic capacitors also have handling properties such as peelability of the ceramic sheet after slurry coating (hereinafter also referred to as “sheet peelability”) as the sheet becomes thinner.
- sheet peelability peelability of the ceramic sheet after slurry coating
- Patent Document 1 mentions the use of a methacrylic acid ester copolymer containing a polyethylene glycol chain having an ethylene oxide repeat number of 90 as a binder resin.
- Patent Document 2 refers to a polymer dispersant containing polyethylene glycol having an average addition mole number of 23 as a dispersant for highly dispersing barium titanate particles.
- the present invention provides a polymer dispersant for an inorganic pigment capable of producing a ceramic sheet having excellent dispersibility and sheet peelability of the inorganic pigment.
- the structural unit (a) represented by the formula (1) is 1% by mass or more and 45% by mass or less and the structural unit (b) represented by the formula (2) in all the structural units.
- a non-aqueous solvent containing a copolymer hereinafter also referred to as “copolymer of the present invention”
- the dispersant of the invention containing 55% by mass to 99% by mass.
- R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group, and M represents a hydrogen atom or a cation.
- R 4 , R 5 , R 6 and R 8 are the same or different and each represents a hydrogen atom, a methyl group or an ethyl group, and R 7 is a straight or branched chain having 2 to 4 carbon atoms.
- X 1 represents an oxygen atom or NH
- n represents an average added mole number of the —R 7 —O— group, which is greater than 50 and equal to or less than 140.
- the present invention relates to a method for dispersing a basic inorganic pigment using the polymer dispersant for inorganic pigments of the present invention.
- the present invention further includes a slurry composition containing a non-aqueous solvent, a basic inorganic pigment, and the polymer dispersant for an inorganic pigment of the present invention (hereinafter also referred to as “slurry composition of the present invention”).
- slurry composition of the present invention a slurry composition containing a non-aqueous solvent, a basic inorganic pigment, and the polymer dispersant for an inorganic pigment of the present invention.
- the polymer dispersant for inorganic pigment of the present invention is a ceramic sheet formed from a slurry composition containing the dispersant while highly dispersing inorganic pigment particles in a non-aqueous solvent.
- the effect that the peeling force at the time of peeling from the release film can be reduced can be obtained.
- this invention can show
- the inventor of the present invention includes a copolymer containing the structural unit (a) having an acid group represented by the formula (1) and the structural unit (b) represented by the formula (2). It has been found that by making it exist in a proportion, it is possible to achieve good dispersibility of the inorganic pigment in the non-aqueous solvent and to improve the sheet peelability.
- “to achieve good dispersibility of the inorganic pigment” means that in one or a plurality of embodiments, the inorganic pigment can be dispersed in a state of a primary particle size or a state close thereto, and a binder resin is further added. Also means that good dispersibility can be maintained.
- “improvement of sheet peelability” means, in one or a plurality of embodiments, when a ceramic sheet formed from a slurry composition containing an inorganic pigment and a polymer dispersant is peeled from a release film. It means that peeling force is reduced.
- the constitutional unit (a) of the copolymer in the dispersant of the present invention is strongly adsorbed mainly on the surface of the inorganic pigment, so that the copolymer is prevented from being detached from the surface of the inorganic pigment. Can coat the surface of inorganic pigments.
- the structural unit (b) of the copolymer mainly brings about a strong steric repulsion between the inorganic pigment particles, the aggregation of the inorganic pigment particles and the subsequent interaction with the binder resin can be reduced. It is thought that the property improves.
- the dispersant of the present invention is composed of the copolymer of the present invention.
- the dispersant of the present invention includes the copolymer of the present invention, and may further include other components.
- Other components include, but are not limited to, a solvent, a plasticizer, an antistatic agent, a binder resin, and the like in one or more embodiments.
- the structural unit (a) in the copolymer of the present invention is a structural unit represented by the formula (1).
- the structural unit (a) has a neutralizable acidic group and is considered to have a function of suppressing the detachment of the copolymer from the surface of the inorganic pigment by strongly adsorbing to the surface of the inorganic pigment.
- R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group, and M represents a hydrogen atom or a cation.
- R 1 and R 2 are preferably a hydrogen atom or a methyl group from the viewpoints of improving the dispersibility of the inorganic pigment and improving the peelability of the sheet and ease of introduction of the structural unit (a) into the copolymer.
- it is a hydrogen atom
- R 3 is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
- M is preferably a hydrogen atom from the same viewpoint as described above.
- the structural unit (a) examples include a structural unit derived from a monomer having a carboxy group (hereinafter also referred to as “monomer (a)”), a structural unit obtained by introducing a carboxy group after polymerization, and the like. From the viewpoint of properties, it is preferably a structural unit derived from the monomer (a).
- the structural unit (a) is preferably a structural unit derived from a monomer having an ethylenically unsaturated double bond copolymerizable with the monomer forming the structural unit (b) from the viewpoint of ease of production.
- the monomer (a) is preferably a monomer represented by the formula (4) from the viewpoint of improving the dispersibility of the inorganic pigment and improving the sheet peelability.
- R 1 , R 2 , and R 3 are the same or different and represent a hydrogen atom, a methyl group, or an ethyl group, and M represents a hydrogen atom or a cation.
- R 1 , R 2 , R 3 , and M are the same as those in the structural unit (a) in one or more embodiments.
- Examples of the monomer (a) include (meth) acrylic acid, crotonic acid, and the like. From the viewpoint of improving dispersibility of the inorganic pigment and ease of introduction of the structural unit (a) into the copolymer, It is meth) acrylic acid, more preferably methacrylic acid.
- (meth) acrylic acid means at least one selected from acrylic acid and methacrylic acid.
- the proportion of the structural unit (a) in all the structural units constituting the copolymer of the present invention is 1% by mass or more from the viewpoint of increasing the adsorption rate to the inorganic pigment and improving the dispersibility of the inorganic pigment. , Preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, further preferably 12% by mass or more, and from the same viewpoint, it is 45% by mass or less, preferably 35%. It is not more than mass%, more preferably not more than 24 mass%, still more preferably not more than 18 mass%.
- the structural unit (b) in the copolymer of the present invention is a structural unit represented by the formula (2).
- the structural unit (b) is nonionic, brings about a strong steric repulsion between the inorganic pigment particles, suppresses the aggregation of the inorganic pigment particles, reduces the interaction between the ceramic sheet and the release film, and peels off. It is thought that the effect which improves property is expressed.
- R 4 , R 5 , R 6 and R 8 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group, and R 7 is a linear or branched alkylene having 2 to 4 carbon atoms.
- X 1 represents an oxygen atom or NH
- n represents the average added mole number of the —R 7 —O— group, which is greater than 50 and not greater than 140.
- R 4 and R 5 are preferably a hydrogen atom or a methyl group, more preferably from the viewpoint of improving the dispersibility of the inorganic pigment and the sheet, and the ease of introducing the structural unit (b) into the copolymer.
- n exceeds 50, preferably 51 or more, more preferably 58 or more, still more preferably 72 or more, even more preferably 88 or more, and even more preferably.
- N is 110 or more, and n is 140 or less, preferably 130 or less, from the viewpoint of manufacturability.
- the structural unit (b) examples include a structural unit derived from a monomer having a nonionic group (hereinafter also referred to as “monomer (b)”), a structural unit obtained by introducing a nonionic group after polymerization, and the like. From the viewpoint of ease of production, it is preferably a structural unit derived from the monomer (b).
- the nonionic group examples include polyoxyalkylene groups such as a polyoxyethylene group and a polyoxypropylene group.
- the structural unit (b) is preferably a structural unit derived from a monomer having an ethylenically unsaturated double bond copolymerizable with the monomer forming the structural unit (a) from the viewpoint of ease of production.
- the monomer (b) is preferably a monomer represented by the formula (5) from the viewpoint of improving the dispersibility of the inorganic pigment, the stability of the dispersion, and the improvement of the sheet peelability.
- R 4 , R 5 , R 6 , R 7 , R 8 , X 1 , and n are the same as those in the structural unit (b) in one or more embodiments.
- Monomers (b) include methoxypolyethylene glycol (meth) acrylate, methoxypoly (ethylene glycol / propylene glycol) mono (meth) acrylate, ethoxypoly (ethylene glycol / propylene glycol) mono (meth) acrylate, polyethylene glycol mono (meth) acrylate Polypropylene glycol mono (meth) acrylate, 2-methoxyethyl (meth) acrylamide, 2-ethoxyethyl (meth) acrylamide, 3-methoxypropyl (meth) acrylamide and the like.
- methoxypolyethylene glycol (meth) acrylate is preferable, and methoxypolyethyleneglycol methacrylate is more preferable from the viewpoint of dispersibility improvement of inorganic pigment, dispersion stability, and sheet peelability.
- (meth) acrylate means at least one selected from acrylate and methacrylate.
- (meth) acrylamide means at least one selected from acrylamide and methacrylamide.
- the proportion of the structural unit (b) in all the structural units constituting the copolymer of the present invention is 55% by mass or more, preferably 60% by mass, from the viewpoint of improving the dispersibility of the inorganic pigment and improving the sheet peelability. % Or more, more preferably 65% by mass or more, and from the same viewpoint, it is 99% by mass or less, preferably 95% by mass or less, more preferably 87% by mass or less, still more preferably 80% by mass or less, and even more. Preferably it is 75 mass% or less.
- the mass ratio of the structural unit (a) to the structural unit (b) in the copolymer of the present invention is preferably from the viewpoint of improving dispersibility and peelability of the inorganic pigment. Is 0.05 or more, more preferably 0.12 or more, still more preferably 0.16 or more, still more preferably 0.19 or more, and from the viewpoint of improving the dispersibility of the inorganic pigment, preferably 0.50 or less, More preferably, it is 0.35 or less, More preferably, it is 0.28 or less, From a viewpoint of a peelable improvement, More preferably, it is 0.24 or less.
- the copolymer of the present invention preferably further contains a structural unit (c).
- the structural unit (c) is a structural unit represented by the formula (3) in one or a plurality of embodiments.
- the structural unit (c) is hydrophobic and is considered to suppress re-elution of the copolymer into the non-aqueous solvent.
- R 9 , R 10 , and R 11 are the same or different and each represents a hydrogen atom, a methyl group, or an ethyl group, X 3 represents an oxygen atom or NH, and R 12 and R 13 have 1 carbon atom.
- the hydrocarbon group of 30 or less is shown.
- R 9 and R 10 are preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
- R 11 is preferably a hydrogen atom or a methyl group
- X 3 is preferably an oxygen atom
- R 12 is preferably an alkyl group or an alkenyl group
- R 12 has one or more carbon atoms, preferably Is 22 or less, more preferably 18 or less.
- R 12 include methyl group, ethyl group, butyl group, octyl group, 2-ethylhexyl group, decyl group, lauryl group, myristyl group, cetyl group, stearyl group, oleyl group, and behenyl group.
- R 13 is preferably a phenyl group or an alkyl group having 1 to 22 carbon atoms.
- the structural unit (c) examples include structural units derived from the monomer (c) described below. From the viewpoint of improving dispersibility and peelability, the structural unit is preferably derived from an alkyl (meth) acrylate, more preferably methyl methacrylate, A structural unit derived from one or more selected from the group consisting of stearyl methacrylate and stearyl acrylate, more preferably a structural unit derived from methyl methacrylate.
- the structural unit (c) is preferably a monomer represented by the formula (6) (hereinafter also referred to as “monomer (c)”) from the viewpoint of ease of introduction of the structural unit (c) into the copolymer. It is a derived structural unit.
- R 9 , R 10 , R 11 , R 12 , R 13 , and X 3 are the same as those in the structural unit (c) in one or more embodiments.
- Alkyl (meth) acrylates alkyl (meth) acrylamides such as butyl (meth) acrylamide, octyl (meth) acrylamide, lauryl (meth) acrylamide, stearyl (meth) acrylamide, and behenyl (meth) acrylamide; 1-decene, 1-octadecene ⁇ -olefins such as styrene; and styrene.
- alkyl (meth) acrylamides such as butyl (meth) acrylamide, octyl (meth) acrylamide, lauryl (meth) acrylamide, stearyl (meth) acrylamide, and behenyl (meth) acrylamide
- 1-decene, 1-octadecene ⁇ -olefins such as styrene; and styrene.
- alkyl (meth) acrylate and styrene preferably alkyl (meth) acrylate and styrene, more preferably methyl (meth) acrylate and stearyl (meth) acrylate, and further preferably from the viewpoint of improving dispersibility and peelability.
- the proportion of the structural unit (c) in all the structural units constituting the copolymer of the present invention is preferably 0% by mass or more, more preferably 3 from the viewpoint of improving the dispersibility of the inorganic pigment and improving the sheet peelability. From the same viewpoint, it is preferably 35% by mass or less, more preferably 25% by mass or less, and still more preferably 18% by mass or less. is there.
- the mass ratio of the structural unit (c) to the structural unit (b) in the copolymer of the present invention is preferably from the viewpoint of improving dispersibility of the inorganic pigment. 05 or more, more preferably 0.06 or more, still more preferably 0.10 or more, still more preferably 0.18 or more, and from the same viewpoint, preferably 0.70 or less, more preferably 0.60 or less, More preferably, it is 0.50 or less, More preferably, it is 0.25 or less.
- the copolymer of the present invention may contain other structural units other than the structural units (a), (b) and (c) as long as the effects of the present invention are not impaired.
- the proportion of the other structural units in all the structural units constituting the copolymer of the present invention is preferably 10% by mass or less, more preferably 3% by mass or less, and still more preferably, from the viewpoint of manifesting the effects of the present invention. Is 1% by mass or less.
- the copolymer of the present invention can be obtained by a known method such as, for example, polymerizing a monomer component containing the monomer (a), the monomer (b), and, if necessary, the monomer (c) by a solution polymerization method.
- the mass ratio of the structural unit (a) in all structural units is the sum of the monomer (a) with respect to all monomer components used in the polymerization and the monomer capable of adding an acid group that can be neutralized after polymerization. It can be regarded as a mass ratio.
- the mass ratio of the structural unit (b) in all the structural units can be regarded as a mass ratio with respect to the sum of the monomer (b) with respect to all monomer components used in the polymerization and the monomer capable of introducing a nonionic group after the polymerization.
- the mass ratio of the structural unit (c) to the structural unit (b) is determined by the polymerization of the monomer (b) and the hydrophobic monomer (c) in all monomer components used in the polymerization. It can be regarded as a mass ratio with respect to the sum total of monomers capable of introducing a nonionic group later.
- the present invention provides a method for producing the dispersant of the present invention, which is a monomer (a) or a monomer capable of adding a neutralizable acidic group after polymerization, monomer (b) or nonionic after polymerization.
- Examples of the solvent used in the solution polymerization include aromatic hydrocarbons such as toluene and xylene; lower alcohols such as ethanol and 2-propanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and diethylene glycol dimethyl ether.
- the amount of the solvent is preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 1 part by mass of all monomers.
- the polymerization initiator known radical polymerization initiators can be used, and examples thereof include azo polymerization initiators, hydroperoxides, dialkyl peroxides, diacyl peroxides, and ketone peroxides.
- the amount of the polymerization initiator is preferably 1 mol or more, more preferably 2 mol or more, still more preferably 3 mol or more, preferably 15 mol or less, more preferably 12 mol or less, based on 100 mol of all monomers. Preferably it is 9 mol or less.
- the polymerization reaction is preferably performed in a nitrogen stream, the reaction temperature is preferably 60 ° C. or higher and 180 ° C. or lower, and the reaction time is preferably 0.5 hour or longer and 20 hours or shorter.
- a polymerization chain transfer agent may be further added.
- the polymerization chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-tetradecyl mercaptan, mercaptoethanol, 3-mercapto-1,2-propanediol and mercaptosuccinic acid.
- the arrangement of the structural unit (a), the structural unit (b), and the structural unit (c) may be random, block, or graft.
- the weight average molecular weight of the copolymer of the present invention is preferably 1000 or more, more preferably 2000 or more, and further preferably 4000 or more, from the viewpoint of improving the dispersibility of the inorganic pigment and improving the sheet peelability. Therefore, it is preferably 100,000 or less, more preferably 50000 or less, still more preferably 30000 or less, and even more preferably 15000 or less.
- the weight average molecular weight is a value measured by GPC (gel permeation chromatography), and details of measurement conditions are as shown in Examples.
- the copolymer and / or the inorganic pigment polymer dispersant produced as described above is a dispersibility of an inorganic pigment in a non-aqueous solvent, preferably a dispersibility of a basic inorganic pigment, a dispersion stability and a sheet peelability. Excellent. Therefore, the dispersant of the present invention is used for dispersing an inorganic pigment in a non-aqueous solvent, and preferably used for dispersing a basic inorganic pigment in a non-aqueous solvent.
- the solubility parameter (unit: [(MPa) 1/2 ]) of the non-aqueous solvent that can be used in the present invention is preferably 20 or more from the viewpoint of improving the dispersibility of the inorganic pigment and compatibility with the polymer dispersant. More preferably, it is 21 or more, preferably 30 or less, more preferably 26 or less.
- the solubility parameter was measured by the method of Fedors [R. F. Fedors. Polym. Eng. Sci. , 14, 147 (1974)].
- the solubility parameter can be suitably adjusted by mixing two or more organic solvents.
- Non-aqueous solvents that can be used in the present invention include xylene (18.2), ethyl acetate (18.2), toluene (18.3), tetrahydrofuran (18.5), methyl ethyl ketone (19.3), acetone. (19.7), butyl cellosolve (20.2), dimethylformamide (24.7), n-propanol (24.9), ethanol (26.2), dimethyl sulfoxide (26.4), n-butanol (28 .1) or more selected from organic solvents such as methanol (29.7). Numbers in parentheses are solubility parameters.
- the surface of an inorganic pigment has both an acid point and a base point.
- the strength of the acid and base in the non-aqueous solvent can be determined by a back titration method, and it can be identified whether the inorganic pigment to be dispersed is acidic or basic.
- the reverse titration method is a method in which a basic reagent (or acidic reagent) whose concentration is known in advance is mixed with an inorganic pigment at a certain ratio, sufficiently neutralized, and then solid-liquid separated with a centrifuge, The supernatant is titrated, and the acid amount (or base amount) is determined from the reduced amount of basic reagent (or acid reagent).
- the amount of base and the amount of acid are determined as follows.
- the inorganic pigment is preferably a basic inorganic pigment from the viewpoint of improving the dispersibility of the inorganic pigment and improving the sheet peelability.
- a basic inorganic pigment is an inorganic compound in which the amount of base defined above is greater than the amount of acid defined above, specifically, metal oxides such as titanium oxide, magnesium oxide, barium oxide, and aluminum oxide.
- Metal carbonates such as magnesium carbonate and barium carbonate; complex oxides such as barium zirconate, calcium zirconate, calcium titanate, barium titanate, strontium titanate, etc., preferably magnesium oxide, barium carbonate, titanium oxide ,
- the basic inorganic pigment in the present invention is more preferably the composite oxide from the viewpoint of improving the characteristics of the ceramic sheet, and further preferably barium titanate.
- the average particle size (hereinafter also referred to as “D50”) by the dynamic light scattering method is preferably 500 nm or less, more preferably 200 nm or less, and further preferably 100 nm or less from the viewpoint of improving dispersibility, and maintains dispersibility. From the viewpoint, it is preferably 5 nm or more, more preferably 7 nm or more, and further preferably 8 nm or more.
- the D50 is a particle diameter at which the frequency distribution of the scattering intensity based on the principle of the dynamic light scattering method described later becomes 50%, and can be measured by the method described in the examples.
- the BET average particle diameter of the inorganic pigment preferably refers to the average particle diameter of the powdered inorganic pigment, and is calculated as follows.
- the BET average particle diameter of the inorganic pigment is determined by assuming that the inorganic pigment particle is a sphere having a particle diameter R (m), the BET specific surface area S (m 2 / g) measured by the nitrogen adsorption method, and the specific gravity ⁇ of the inorganic pigment particle. It can be determined using (g / cm 3 ).
- the BET specific surface area is a surface area per unit mass
- R (nm) 6000 / (S ⁇ ⁇ )
- the BET average particle diameter can be obtained. For example, if the BET specific surface area of barium titanate (specific gravity 6.0) is 5.0 (m 2 / g), the BET average particle diameter is 200 nm.
- Another aspect of the present invention is a dispersion method, which includes a step of dispersing an inorganic pigment in a non-aqueous solvent using the dispersant of the present invention.
- the dispersion step includes, for example, mixing a basic inorganic pigment, the dispersant of the present invention, and a non-aqueous solvent, preferably with zirconia beads.
- the amount of the inorganic pigment to be mixed and the dispersant of the present invention can be within the range of the content of each component in the slurry composition described later.
- the inorganic pigment can be finely dispersed in the non-aqueous solvent, and a slurry composition described later can be produced. Therefore, this invention is the manufacturing method of a slurry composition as the aspect, Comprising: The process of disperse
- the present invention in still another aspect, is a slurry composition, which contains a non-aqueous solvent, an inorganic pigment, and a polymer dispersant, and the polymer dispersant is the dispersant or co-polymer of the present invention.
- a slurry composition that is a coalescence can be provided. According to the slurry composition of the present invention, fine dispersion of the inorganic pigment can be suitably realized as described later.
- the content of the inorganic pigment in the slurry composition is preferably 5% by mass or more, more preferably 10% by mass or more from the viewpoint of improving dispersibility, and from the same viewpoint, preferably 60% by mass or less, more preferably It is 50 mass% or less.
- the content of the copolymer of the present invention with respect to 100 parts by mass of the inorganic pigment varies depending on the particle size of the inorganic pigment. For example, when using an inorganic pigment having a BET average particle size of 10 to 500 nm, preferably 0.1 mass. Part or more, more preferably 0.2 part by weight or more, and from the same viewpoint, it is preferably 10 parts by weight or less, more preferably 5 parts by weight or less.
- Evaluation of dispersibility in the dispersion and the slurry can be performed by, for example, measuring the viscosity of the slurry and measuring the sedimentation time of the dispersed inorganic pigment, but the particle size distribution of the inorganic pigment in the slurry is determined by the inorganic pigment powder.
- it can be evaluated by measuring the particle size distribution of the inorganic pigment in the slurry, based on the knowledge that the slurry viscosity is low and the sedimentation time is long if it is close to the primary particle size of the body. Specifically, it can be evaluated as described in the examples.
- the slurry composition of the present invention contains additives such as low molecular weight compounds such as binder resins such as polyvinyl acetal resins, antistatic agents, plasticizers, lubricants, and dispersion aids, as long as the effects of the present invention are not impaired. May be.
- the binder resin is preferably a polyvinyl acetal resin, more preferably a polyvinyl butyral resin, from the viewpoint of improving sheet peelability and improving the performance of the ceramic sheet.
- the degree of acetalization of the polyvinyl acetal resin is preferably 55 mol% or more, more preferably 65 mol% or more, from the viewpoint of improving the solubility in a non-aqueous solvent and the flexibility of the ceramic sheet, and the strength of the ceramic sheet. From the viewpoint of improvement, it is preferably 80 mol% or less, more preferably 75 mol% or less.
- the content of the binder resin in the slurry composition of the present invention relative to 100 parts by mass of the inorganic pigment is preferably 2 parts by mass or more, more preferably 4 parts by mass or more, from the viewpoint of improving the sheet peelability and the strength of the ceramic sheet. More preferably, it is 6 parts by mass or more, and preferably 20 parts by mass or less, more preferably 18 parts by mass or less, still more preferably 16 parts by mass or less, and even more, from the viewpoint of sheet peelability and ease of forming the ceramic sheet. Preferably it is 11 mass parts or less, More preferably, it is 9 mass parts or less.
- plasticizer examples include phthalic acid diesters such as di (2-ethylhexyl) phthalate and dibutylphthalate, adipic acid diesters such as di (2-ethylhexyl) adipate, and alkylene glycol diesters such as triethylene glycol di (2-ethylhexyl) ester Of these, di (2-ethylhexyl) phthalate is preferred from the viewpoint of low volatility and improved flexibility of the ceramic sheet.
- the content of the plasticizer in the slurry composition of the present invention with respect to 100 parts by mass of the inorganic pigment is preferably 0.05 parts by mass or more, more preferably 0.1 parts, from the viewpoint of sheet peelability and ceramic sheet performance improvement. From the viewpoint of maintaining the strength of the ceramic sheet, it is preferably 15.0 parts by mass or less, more preferably 10.0 parts by mass or less.
- the antistatic agent is preferably a cationic antistatic agent from the viewpoint of improving peelability.
- the cationic antistatic agent include compounds having a nitrogen-containing heterocycle such as alkylimidazolines and alkylimidazoles.
- the content of the antistatic agent in the slurry composition of the present invention with respect to 100 parts by mass of the inorganic pigment is preferably 0.05 parts by mass or more, more preferably 0. From the viewpoint of maintaining the strength of the ceramic sheet, it is preferably 2.0 parts by mass or less, more preferably 1.5 parts by mass or less.
- the present invention further discloses the following composition, production method, or use.
- the structural unit (a) represented by the formula (1) is 1% by mass or more and 45% by mass or less, and the structural unit (b) represented by the formula (2) is 55% by mass.
- a polymer dispersant for an inorganic pigment comprising a copolymer containing 99% by mass or less and used in a non-aqueous solvent.
- R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group, and M represents a hydrogen atom or a cation.
- R 4 , R 5 , R 6 and R 8 are the same or different and each represents a hydrogen atom, a methyl group or an ethyl group, and R 7 is a straight or branched chain having 2 to 4 carbon atoms.
- R 7 is a straight or branched chain having 2 to 4 carbon atoms.
- X 1 represents an oxygen atom or NH
- n represents an average added mole number of the —R 7 —O— group, which is greater than 50 and equal to or less than 140.
- R 1 and R 2 in formula (1) are preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
- R 3 in formula (1) is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
- M in formula (1) is preferably an ammonium, organic ammonium, or hydrogen atom, more preferably a hydrogen atom.
- the proportion of the structural unit (a) in all the structural units constituting the copolymer is 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 8% by mass or more. More preferably, the polymer dispersant for inorganic pigments according to any one of ⁇ 1> to ⁇ 4>, which is 12% by mass or more.
- the proportion of the structural unit (a) in all the structural units constituting the copolymer is 45% by mass or less, preferably 35% by mass or less, more preferably 24% by mass or less, and still more preferably 18% by mass or less.
- the polymer dispersant for inorganic pigments according to any one of ⁇ 1> to ⁇ 5>, wherein ⁇ 7> The inorganic pigment according to any one of ⁇ 1> to ⁇ 6>, wherein the structural unit (a) is preferably a structural unit derived from one or more selected from the group consisting of acrylic acid and methacrylic acid.
- ⁇ 8> The polymer dispersion for an inorganic pigment according to any one of ⁇ 1> to ⁇ 7>, wherein R 4 and R 5 in formula (2) are preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. Agent.
- n in the formula (2) exceeds 50, preferably 51 or more, more preferably 58 or more, still more preferably 72 or more, still more preferably 88 or more, and even more preferably 110 or more, ⁇ 1 >
- n in formula (2) is 140 or less, preferably 130 or less.
- the proportion of the structural unit (b) in all the structural units constituting the copolymer is 55% by mass or more, preferably 60% by mass or more, more preferably 65% by mass or more, from ⁇ 1> to ⁇ 14>
- the proportion of the structural unit (b) in all the structural units constituting the copolymer is 99% by mass or less, preferably 95% by mass or less, more preferably 87% by mass or less, and still more preferably 80% by mass or less.
- the mass ratio of the structural unit (a) constituting the copolymer to the structural unit (b) (structural unit (a) / structural unit (b)) is preferably 0.05 or more, more preferably 0.8. 12 or more, more preferably 0.16 or more, still more preferably 0.19 or more, preferably 0.50 or less, more preferably 0.35 or less, still more preferably 0.28 or less, and even more preferably 0.
- the polymer dispersant for inorganic pigments according to any one of ⁇ 1> to ⁇ 17> preferably containing the structural unit (c) represented by the formula (3).
- R 9 , R 10 and R 11 are the same or different and each represents a hydrogen atom, a methyl group or an ethyl group, X 3 represents an oxygen atom or NH, and R 12 and R 13 represent the number of carbon atoms. 1 or more and 30 or less hydrocarbon group is shown.
- ⁇ 20> The polymer dispersant for inorganic pigments according to ⁇ 18> or ⁇ 19>, wherein R 9 and R 10 in formula (3) are preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
- R 9 and R 10 in formula (3) are preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
- R 11 in formula (3) is preferably a hydrogen atom or a methyl group.
- X 3 in formula (3) is preferably an oxygen atom.
- R 12 in formula (3) is preferably an alkyl group or an alkenyl group.
- the number of carbon atoms of R 12 in the formula (3) is 1 or more, preferably 22 or less, more preferably 18 or less, the high for inorganic pigments according to any one of ⁇ 18> to ⁇ 23> Molecular dispersant.
- R 12 in the formula (3) is preferably a methyl group, an ethyl group, a butyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a lauryl group, a myristyl group, a cetyl group, a stearyl group, an oleyl group, or The polymer dispersant for inorganic pigments according to any one of ⁇ 18> to ⁇ 24>, which is a behenyl group.
- R 13 of ⁇ 26> formula (3) is preferably an alkyl group having a phenyl group or having 1 to 22 carbon atoms, an inorganic pigment for polymeric dispersing agent according to any one of ⁇ 25> to ⁇ 18>.
- the proportion of the structural unit (c) in all the structural units constituting the copolymer is preferably 0% by mass or more, more preferably 3% by mass or more, more preferably 8% by mass or more, and still more preferably 12%.
- the proportion of the structural unit (c) in all the structural units constituting the copolymer is preferably 35% by mass or less, more preferably 25% by mass or less, and still more preferably 18% by mass or less.
- the mass ratio of the structural unit (c) to the structural unit (b) in the copolymer (structural unit (c) / structural unit (b)) is preferably 0.05 or more, more preferably 0.06 or more.
- the mass ratio of the structural unit (c) to the structural unit (b) in the copolymer (structural unit (c) / structural unit (b)) is preferably 0.70 or less, more preferably 0.60 or less.
- the polymer dispersant for inorganic pigments according to any one of ⁇ 18> to ⁇ 29>, more preferably 0.50 or less, and still more preferably 0.25 or less.
- the structural unit (c) is preferably a structural unit derived from alkyl (meth) acrylate, more preferably a structural unit derived from one or more selected from the group consisting of methyl methacrylate, stearyl methacrylate and stearyl acrylate, and more preferably.
- ⁇ 32> The polymer dispersion for an inorganic pigment according to any one of ⁇ 1> to ⁇ 31>, wherein the weight average molecular weight of the copolymer is preferably 1000 or more, more preferably 2000 or more, and still more preferably 4000 or more.
- Agent ⁇ 33>
- Polymer dispersant for inorganic pigments ⁇ 34> A method of dispersing a basic inorganic pigment using the polymer dispersant for inorganic pigments according to any one of ⁇ 1> to ⁇ 33>.
- the basic inorganic pigment is preferably one or more pigments selected from the group consisting of magnesium oxide, barium carbonate, titanium oxide, calcium titanate, barium titanate, barium zirconate and calcium zirconate, more preferably
- the content of the inorganic pigment in the slurry composition is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 60% by mass or less, more preferably 50% by mass or less, ⁇ 35 > Or ⁇ 36>.
- the content of the copolymer according to any one of ⁇ 1> to ⁇ 33> with respect to 100 parts by mass of the inorganic pigment preferably 0.8.
- the slurry composition according to any one of ⁇ 35> to ⁇ 37> which is 1 part by mass or more, more preferably 0.2 part by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less. . ⁇ 39>
- the slurry composition according to any one of ⁇ 35> to ⁇ 38> further comprising a polyvinyl acetal resin, more preferably a polyvinyl butyral resin.
- ⁇ 40> The slurry composition according to any one of ⁇ 35> to ⁇ 39>, for dispersing the inorganic pigment in a non-aqueous solvent.
- ⁇ 41> Use of the polymer dispersant for inorganic pigments according to any one of ⁇ 1> to ⁇ 33> in the production of a ceramic sheet.
- ⁇ 42> Use of the slurry composition according to any one of ⁇ 35> to ⁇ 39> in the production of a ceramic sheet.
- X in the notation “polyalkylene glycol (X mol)” represents the average number of moles of alkylene oxide added to the alkylene glycol. Measurement of the weight average molecular weight, solid content and particle size of the slurry composition, and evaluation of sheet peelability were performed by the following methods.
- Detector differential refractometer (attached to the apparatus), column: “TSK-GEL ⁇ -M” x 2 manufactured by Tosoh Corporation, column temperature: 40 ° C., eluent flow rate: 1 mL / min].
- polystyrene manufactured by Tosoh Corporation: molecular weights 5.26 ⁇ 10 2 , 1.02 ⁇ 10 5 , 8.42 ⁇ 10 6 ; Nishio Kogyo Co., Ltd .: molecular weight 4.0 ⁇ 10 3 , 3. 0 ⁇ 10 4 , 9.0 ⁇ 10 5 ) were used.
- a particle size distribution measuring device (“Zetasizer Nano ZS” manufactured by Sysmex Corporation) based on the principle of the photon correlation method (dynamic light scattering method) was used.
- a liquid obtained by mixing 0.025 g of the non-aqueous slurry composition and 2 mL of a toluene / ethanol mixed solvent (volume ratio: 48/52) as a dispersion medium was used as a sample.
- 1.2 mL of the sample was collected in a glass cell having an optical path length of 10 mm, placed in a measuring section, and measured by inputting the refractive index of the particles, the refractive index of the dispersion medium, and the sample viscosity as measurement parameters.
- the refractive index of the particles is 2.40.
- the refractive index of the dispersion medium was 1.423, and the sample viscosity was 0.752.
- the particle diameter at which the frequency distribution of the scattering intensity is 50% is D50, and the particle diameter at which the frequency distribution is 90% is D90.
- the test piece was fixed to a pedestal of a desktop precision tester (“Autograph AGS-X” manufactured by Shimadzu Corporation) equipped with a 90 ° peel test jig using double-sided tape.
- a desktop precision tester Autograph AGS-X” manufactured by Shimadzu Corporation
- the load cell was raised at a speed of 1 cm / sec to perform 90-degree peeling, and the average value of the load applied to the load cell during the period from 3 cm to 3 cm rising was defined as peeling force.
- peeling force The lower the peel strength, the better the peelability.
- Example 1 In a 1 L separable flask equipped with a reflux tube, a stirrer, a thermometer and a nitrogen introduction tube, 6.75 g of MAA, 31.5 g of PEG (60) MA, 6.75 g of MMA, 6.75 g of MPD 8 g and 27.0 g of ethanol (manufactured by Kishida Chemical Co., Ltd., reagent) were charged, the inside of the flask was purged with nitrogen while stirring, and the temperature was raised to 80 ° C.
- Examples 2 to 14, Comparative Examples 1 to 3 A polymer dispersant solution was prepared in the same manner as in Example 1 except that the compositions of the “initial charge monomer”, “initiator solution” and “dropping monomer solution” were changed according to the description in Table 1, respectively. Got. The solid content and the weight average molecular weight are as shown in Table 1.
- Method for preparing slurry composition 36 g of barium titanate powder (BET specific surface area 15 m 2 / g), 0.6 g of polymer dispersant (solid content), 50 g of zirconia beads having a diameter of 1 mm, and inclusion of barium titanate in the components excluding zirconia beads
- a toluene / ethanol mixed solvent (volume ratio: 48/52) in an amount of 50% by mass is placed in a 100 mL polyethylene container, and a desktop ball mill (“Big Rotor BR-2” manufactured by ASONE) is placed.
- the dispersion treatment was performed for 96 hours at room temperature and 120 r / min.
- the slurry compositions of Examples 1 to 14 have the same or better dispersibility as Comparative Examples 1 and 2, and the ceramic sheets obtained from the slurry compositions of Examples 1 to 14 are The peelability was superior to that of Comparative Examples 1 to 3.
- the present invention is useful for, for example, a manufacturing process of a slurry composition containing a basic inorganic pigment in a non-aqueous solvent and a manufacturing process of a ceramic sheet.
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Abstract
Provided is a polymer dispersant for an inorganic pigment, with which it is possible to produce a ceramic sheet having excellent sheet detachability and inorganic pigment dispersability. One embodiment of the present invention relates to a polymer dispersant for an inorganic pigment used in a non-aqueous solvent, said polymer dispersant including a copolymer that contains, in total constituent units, 1 mass% to 45 mass% inclusive of a constituent unit (a) represented by formula (1), and 55 mass% to 99 mass% inclusive of a constituent unit (b) represented by formula (2).
Description
本発明は、無機顔料用高分子分散剤、それを用いた分散方法及びスラリー組成物に関する。
The present invention relates to a polymer dispersant for inorganic pigment, a dispersion method using the same, and a slurry composition.
無機顔料を使うファインセラミック分野等においては、ナノスケールの微細構造を制御することで、小型化、高速化、低消費電力、高効率化、高容量化を実現する試みがなされている。
In the field of fine ceramics using inorganic pigments, attempts have been made to achieve miniaturization, high speed, low power consumption, high efficiency, and high capacity by controlling the nanoscale microstructure.
特許文献１は、無機微粒子を含有する無機微粒子分散ペースト組成物に用いられるバインダー樹脂を開示する。
特許文献２は、酸基を有する構成単位及びマクロモノマーを有する構成単位等を含む３つの構成単位からなる無機顔料用高分子分散剤を開示する。 Patent Document 1 discloses a binder resin used for an inorganic fine particle-dispersed paste composition containing inorganic fine particles.
Patent Document 2 discloses a polymer dispersant for an inorganic pigment composed of three structural units including a structural unit having an acid group and a structural unit having a macromonomer.
特許文献２は、酸基を有する構成単位及びマクロモノマーを有する構成単位等を含む３つの構成単位からなる無機顔料用高分子分散剤を開示する。 Patent Document 1 discloses a binder resin used for an inorganic fine particle-dispersed paste composition containing inorganic fine particles.
Patent Document 2 discloses a polymer dispersant for an inorganic pigment composed of three structural units including a structural unit having an acid group and a structural unit having a macromonomer.
非水系における塩基性無機顔料のナノ分散技術への要求は高く、分散剤の性能のさらなる改善が求められている。積層セラミックコンデンサに用いられるグリーンシートに代表されるセラミックシートにおいても、シートの薄膜化に伴い、スラリー塗工後のセラミックシートの剥離性（以下、「シート剥離性」ともいう）等のハンドリング性の改善が求められている。特許文献１は、エチレンオキサイド繰り返し数が９０であるポリエチレングリコール鎖を含有するメタクリル酸エステル共重合物をバインダー樹脂として使用することに言及している。しかしながら、同文献は、無機顔料用高分子分散剤ではなく、無機顔料用バインダー樹脂に関し、無機顔料の分散には不十分であると考えられる。他方、特許文献２は、チタン酸バリウム粒子を高分散する分散剤として、平均付加モル数が２３であるポリエチレングリコールを含有する高分子分散剤に言及している。しかしながら、シート剥離性にはさらなる向上の余地がある。
Demand for nano-dispersion technology for basic inorganic pigments in non-aqueous systems is high, and further improvement in the performance of dispersants is required. Ceramic sheets typified by green sheets used in multilayer ceramic capacitors also have handling properties such as peelability of the ceramic sheet after slurry coating (hereinafter also referred to as “sheet peelability”) as the sheet becomes thinner. There is a need for improvement. Patent Document 1 mentions the use of a methacrylic acid ester copolymer containing a polyethylene glycol chain having an ethylene oxide repeat number of 90 as a binder resin. However, this document relates to a binder resin for an inorganic pigment, not a polymer dispersant for an inorganic pigment, and is considered insufficient for dispersing the inorganic pigment. On the other hand, Patent Document 2 refers to a polymer dispersant containing polyethylene glycol having an average addition mole number of 23 as a dispersant for highly dispersing barium titanate particles. However, there is room for further improvement in sheet peelability.
よって、本発明は、一態様において、無機顔料の分散性とシート剥離性に優れるセラミックシートを製造可能な無機顔料用高分子分散剤を提供する。
Therefore, in one aspect, the present invention provides a polymer dispersant for an inorganic pigment capable of producing a ceramic sheet having excellent dispersibility and sheet peelability of the inorganic pigment.
本発明は、一態様において、全構成単位中、式（１）で表される構成単位（ａ）を１質量％以上４５質量％以下、及び、式（２）で表される構成単位（ｂ）を５５質量％以上９９質量％以下含有する共重合体（以下、「本発明の共重合体」ともいう）を含み、非水系溶媒中で用いる無機顔料用高分子分散剤（以下、「本発明の分散剤」ともいう）に関する。
In one embodiment of the present invention, the structural unit (a) represented by the formula (1) is 1% by mass or more and 45% by mass or less and the structural unit (b) represented by the formula (2) in all the structural units. ) In a non-aqueous solvent containing a copolymer (hereinafter also referred to as “copolymer of the present invention”) containing 55% by mass to 99% by mass. Also referred to as “the dispersant of the invention”.
本発明は、その他の態様において、本発明の無機顔料用高分子分散剤を用いて塩基性無機顔料を分散する方法に関する。
In another aspect, the present invention relates to a method for dispersing a basic inorganic pigment using the polymer dispersant for inorganic pigments of the present invention.
本発明はさらに、その他の態様において、非水系溶媒、塩基性無機顔料、及び本発明の無機顔料用高分子分散剤を含有するスラリー組成物（以下、「本発明のスラリー組成物」ともいう）に関する。
In another aspect, the present invention further includes a slurry composition containing a non-aqueous solvent, a basic inorganic pigment, and the polymer dispersant for an inorganic pigment of the present invention (hereinafter also referred to as “slurry composition of the present invention”). About.
本発明の無機顔料用高分子分散剤は、一又は複数の実施形態において、無機顔料粒子を非水系溶媒中で高分散しつつ、かつ該分散剤を含有するスラリー組成物から形成されたセラミックシートを離型フィルムから剥離する際の剥離力が低減できるという効果を奏しうる。これにより、一又は複数の実施形態において、本発明は、セラミックシートのハンドリングを容易にする効果を奏しうる。
In one or a plurality of embodiments, the polymer dispersant for inorganic pigment of the present invention is a ceramic sheet formed from a slurry composition containing the dispersant while highly dispersing inorganic pigment particles in a non-aqueous solvent. The effect that the peeling force at the time of peeling from the release film can be reduced can be obtained. Thereby, in one or some embodiment, this invention can show | play the effect which makes handling of a ceramic sheet easy.
本発明者は、式（１）で表される酸基を有する構成単位（ａ）及び式（２）で表される構成単位（ｂ）を含有する共重合体において、各構成単位を所定の割合で存在させることにより、非水系溶媒中において無機顔料の良好な分散性を実現できること、及び、シート剥離性を向上できることを見出した。本開示において、「無機顔料の良好な分散性を実現する」とは、一又は複数の実施形態において、無機顔料を一次粒子径の状態又はそれに近い状態に分散でき、さらにバインダー樹脂を添加しても、良好な分散性が維持できることをいう。本開示において、「シート剥離性の向上」とは、一又は複数の実施形態において、無機顔料と高分子分散剤とを含むスラリー組成物から形成されたセラミックシートを離型フィルムから剥離する際の剥離力が低減されることをいう。
The inventor of the present invention includes a copolymer containing the structural unit (a) having an acid group represented by the formula (1) and the structural unit (b) represented by the formula (2). It has been found that by making it exist in a proportion, it is possible to achieve good dispersibility of the inorganic pigment in the non-aqueous solvent and to improve the sheet peelability. In the present disclosure, “to achieve good dispersibility of the inorganic pigment” means that in one or a plurality of embodiments, the inorganic pigment can be dispersed in a state of a primary particle size or a state close thereto, and a binder resin is further added. Also means that good dispersibility can be maintained. In the present disclosure, “improvement of sheet peelability” means, in one or a plurality of embodiments, when a ceramic sheet formed from a slurry composition containing an inorganic pigment and a polymer dispersant is peeled from a release film. It means that peeling force is reduced.
非水系溶媒中の無機顔料の良好な分散性を実現できるメカニズムの詳細は不明であるが以下のことが推定される。まず、本発明の分散剤中の共重合体の構成単位（ａ）が主として無機顔料表面へ強く吸着することで、該共重合体が無機顔料表面から脱離することが抑制され、共重合体が無機顔料表面を被覆することができる。そして、該共重合体の構成単位（ｂ）が、主として無機顔料粒子間に強い立体的斥力をもたらすため、無機顔料粒子同士の凝集やその後のバインダー樹脂との相互作用を軽減できるために、分散性が向上すると考えられる。
シート剥離性を向上できるメカニズムの詳細は不明であるが以下のことが推定される。すなわち、該共重合体の構成単位（ｂ）が有する長鎖アルキレンオキシド基が、疎水性の高い離型フィルムとの界面に作用することによって、セラミックシートと離型フィルムとの相互作用が弱められる。これにより、シート剥離性が改善し、セラミックシートのハンドリング性も向上すると考えられる。
但し、これらは推定であって、本発明は、これらメカニズムに限定されない。 The details of the mechanism that can realize good dispersibility of the inorganic pigment in the non-aqueous solvent are unknown, but the following is presumed. First, the constitutional unit (a) of the copolymer in the dispersant of the present invention is strongly adsorbed mainly on the surface of the inorganic pigment, so that the copolymer is prevented from being detached from the surface of the inorganic pigment. Can coat the surface of inorganic pigments. And since the structural unit (b) of the copolymer mainly brings about a strong steric repulsion between the inorganic pigment particles, the aggregation of the inorganic pigment particles and the subsequent interaction with the binder resin can be reduced. It is thought that the property improves.
The details of the mechanism that can improve sheet peelability are unknown, but the following is presumed. That is, the long-chain alkylene oxide group of the structural unit (b) of the copolymer acts on the interface with the release film having high hydrophobicity, thereby weakening the interaction between the ceramic sheet and the release film. . Thereby, it is thought that sheet peelability improves and the handling property of a ceramic sheet also improves.
However, these are estimations, and the present invention is not limited to these mechanisms.
シート剥離性を向上できるメカニズムの詳細は不明であるが以下のことが推定される。すなわち、該共重合体の構成単位（ｂ）が有する長鎖アルキレンオキシド基が、疎水性の高い離型フィルムとの界面に作用することによって、セラミックシートと離型フィルムとの相互作用が弱められる。これにより、シート剥離性が改善し、セラミックシートのハンドリング性も向上すると考えられる。
但し、これらは推定であって、本発明は、これらメカニズムに限定されない。 The details of the mechanism that can realize good dispersibility of the inorganic pigment in the non-aqueous solvent are unknown, but the following is presumed. First, the constitutional unit (a) of the copolymer in the dispersant of the present invention is strongly adsorbed mainly on the surface of the inorganic pigment, so that the copolymer is prevented from being detached from the surface of the inorganic pigment. Can coat the surface of inorganic pigments. And since the structural unit (b) of the copolymer mainly brings about a strong steric repulsion between the inorganic pigment particles, the aggregation of the inorganic pigment particles and the subsequent interaction with the binder resin can be reduced. It is thought that the property improves.
The details of the mechanism that can improve sheet peelability are unknown, but the following is presumed. That is, the long-chain alkylene oxide group of the structural unit (b) of the copolymer acts on the interface with the release film having high hydrophobicity, thereby weakening the interaction between the ceramic sheet and the release film. . Thereby, it is thought that sheet peelability improves and the handling property of a ceramic sheet also improves.
However, these are estimations, and the present invention is not limited to these mechanisms.
本発明の分散剤は、一又は複数の実施形態において、本発明の共重合体からなる。本発明の分散剤は、一又は複数の実施形態において、本発明の共重合体を含み、さらにその他の成分を含みうる。その他の成分は、限定されない一又は複数の実施形態において、溶媒、可塑剤、帯電防止剤、バインダー樹脂等が挙げられる。
In one or a plurality of embodiments, the dispersant of the present invention is composed of the copolymer of the present invention. In one or a plurality of embodiments, the dispersant of the present invention includes the copolymer of the present invention, and may further include other components. Other components include, but are not limited to, a solvent, a plasticizer, an antistatic agent, a binder resin, and the like in one or more embodiments.
［構成単位（ａ）］
本発明の共重合体における構成単位（ａ）は、式（１）で表される構成単位である。構成単位（ａ）は中和可能な酸性基を有するものであり、無機顔料表面へ強く吸着することで、共重合体が無機顔料表面から脱離することを抑制する働きを有すると考えられる。
式（１）中、Ｒ1、Ｒ2、及びＲ3は同一又は異なり、水素原子、メチル基又はエチル基を示し、Ｍは水素原子又は陽イオンを示す。
[Structural unit (a)]
The structural unit (a) in the copolymer of the present invention is a structural unit represented by the formula (1). The structural unit (a) has a neutralizable acidic group and is considered to have a function of suppressing the detachment of the copolymer from the surface of the inorganic pigment by strongly adsorbing to the surface of the inorganic pigment.
In formula (1), R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group, and M represents a hydrogen atom or a cation.
本発明の共重合体における構成単位（ａ）は、式（１）で表される構成単位である。構成単位（ａ）は中和可能な酸性基を有するものであり、無機顔料表面へ強く吸着することで、共重合体が無機顔料表面から脱離することを抑制する働きを有すると考えられる。
The structural unit (a) in the copolymer of the present invention is a structural unit represented by the formula (1). The structural unit (a) has a neutralizable acidic group and is considered to have a function of suppressing the detachment of the copolymer from the surface of the inorganic pigment by strongly adsorbing to the surface of the inorganic pigment.
無機顔料の分散性向上及びシート剥離性の向上の観点並びに共重合体への構成単位（ａ）の導入の容易性の観点から、Ｒ1及びＲ2は、好ましくは水素原子又はメチル基、より好ましくは水素原子であり、Ｒ3は、好ましくは水素原子又はメチル基、より好ましくはメチル基である。Ｍの陽イオンとしては、一又は複数の実施形態において、アンモニウム、有機アンモニウム等が挙げられる。Ｍは、上述と同様の観点から、好ましくは水素原子である。
R 1 and R 2 are preferably a hydrogen atom or a methyl group from the viewpoints of improving the dispersibility of the inorganic pigment and improving the peelability of the sheet and ease of introduction of the structural unit (a) into the copolymer. Preferably, it is a hydrogen atom, and R 3 is preferably a hydrogen atom or a methyl group, more preferably a methyl group. Examples of the cation of M include ammonium and organic ammonium in one or more embodiments. M is preferably a hydrogen atom from the same viewpoint as described above.
構成単位（ａ）としては、カルボキシ基を有するモノマー（以下、「モノマー（ａ）」ともいう）由来の構成単位や、重合後にカルボキシ基を導入して得られる構成単位等が挙げられ、製造容易性の観点から、好ましくはモノマー（ａ）由来の構成単位である。構成単位（ａ）は、製造容易性の観点から、好ましくは、構成単位（ｂ）を形成するモノマーと共重合可能なエチレン性不飽和二重結合を有するモノマーに由来する、構成単位である。
Examples of the structural unit (a) include a structural unit derived from a monomer having a carboxy group (hereinafter also referred to as “monomer (a)”), a structural unit obtained by introducing a carboxy group after polymerization, and the like. From the viewpoint of properties, it is preferably a structural unit derived from the monomer (a). The structural unit (a) is preferably a structural unit derived from a monomer having an ethylenically unsaturated double bond copolymerizable with the monomer forming the structural unit (b) from the viewpoint of ease of production.
モノマー（ａ）としては、無機顔料の分散性向上及びシート剥離性の向上の観点から、好ましくは式（４）で表されるモノマーである。
式（４）中、Ｒ1、Ｒ2、及びＲ3は同一又は異なり、水素原子、メチル基又はエチル基を示し、Ｍは水素原子又は陽イオンを示す。
The monomer (a) is preferably a monomer represented by the formula (4) from the viewpoint of improving the dispersibility of the inorganic pigment and improving the sheet peelability.
In formula (4), R 1 , R 2 , and R 3 are the same or different and represent a hydrogen atom, a methyl group, or an ethyl group, and M represents a hydrogen atom or a cation.
式（４）において、Ｒ1、Ｒ2、Ｒ3、及びＭは、一又は複数の実施形態において、上述の構成単位（ａ）と同様である。
In Formula (4), R 1 , R 2 , R 3 , and M are the same as those in the structural unit (a) in one or more embodiments.
モノマー（ａ）としては、（メタ）アクリル酸、クロトン酸等が挙げられ、無機顔料の分散性向上、及び共重合体への構成単位（ａ）の導入の容易性の観点から、好ましくは（メタ）アクリル酸、より好ましくはメタクリル酸である。本明細書において、「（メタ）アクリル酸」とは、アクリル酸及びメタクリル酸から選ばれる少なくとも１種を意味する。
Examples of the monomer (a) include (meth) acrylic acid, crotonic acid, and the like. From the viewpoint of improving dispersibility of the inorganic pigment and ease of introduction of the structural unit (a) into the copolymer, It is meth) acrylic acid, more preferably methacrylic acid. In this specification, “(meth) acrylic acid” means at least one selected from acrylic acid and methacrylic acid.
本発明の共重合体を構成する全構成単位中の構成単位（ａ）の割合は、無機顔料への吸着率を高くし、無機顔料の分散性を向上する点から、１質量％以上であり、好ましくは３質量％以上、より好ましくは５質量％以上、更に好ましくは８質量％以上、更に好ましくは１２質量％以上であり、同様の観点から、４５質量％以下であって、好ましくは３５質量％以下、より好ましくは２４質量%以下、更に好ましくは１８質量％以下である。
The proportion of the structural unit (a) in all the structural units constituting the copolymer of the present invention is 1% by mass or more from the viewpoint of increasing the adsorption rate to the inorganic pigment and improving the dispersibility of the inorganic pigment. , Preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, further preferably 12% by mass or more, and from the same viewpoint, it is 45% by mass or less, preferably 35%. It is not more than mass%, more preferably not more than 24 mass%, still more preferably not more than 18 mass%.
［構成単位（ｂ）］
本発明の共重合体における構成単位（ｂ）は、式（２）で表される構成単位である。構成単位（ｂ）は非イオン性であり、無機顔料粒子間に強い立体的斥力をもたらし、無機顔料粒子同士の凝集を抑制するとともに、セラミックシートと離型フィルムとの相互作用を低減し、剥離性を向上させる効果を発現すると考えられる。
[Structural unit (b)]
The structural unit (b) in the copolymer of the present invention is a structural unit represented by the formula (2). The structural unit (b) is nonionic, brings about a strong steric repulsion between the inorganic pigment particles, suppresses the aggregation of the inorganic pigment particles, reduces the interaction between the ceramic sheet and the release film, and peels off. It is thought that the effect which improves property is expressed.
本発明の共重合体における構成単位（ｂ）は、式（２）で表される構成単位である。構成単位（ｂ）は非イオン性であり、無機顔料粒子間に強い立体的斥力をもたらし、無機顔料粒子同士の凝集を抑制するとともに、セラミックシートと離型フィルムとの相互作用を低減し、剥離性を向上させる効果を発現すると考えられる。
The structural unit (b) in the copolymer of the present invention is a structural unit represented by the formula (2). The structural unit (b) is nonionic, brings about a strong steric repulsion between the inorganic pigment particles, suppresses the aggregation of the inorganic pigment particles, reduces the interaction between the ceramic sheet and the release film, and peels off. It is thought that the effect which improves property is expressed.
式（２）中、Ｒ4、Ｒ5、Ｒ6及びＲ8は同一又は異なり、水素原子、メチル基又はエチル基を示し、Ｒ7は炭素数２以上４以下の直鎖又は分岐鎖のアルキレン基を示し、Ｘ1は酸素原子又はＮＨを示し、ｎは－Ｒ7－Ｏ－基の平均付加モル数であって５０を超え１４０以下の数を示す。無機顔料の分散性向上及びシート剥離性の向上の観点並びに共重合体への構成単位（ｂ）の導入の容易性の観点から、Ｒ4及びＲ5は好ましくは水素原子又はメチル基、より好ましくは水素原子であり、Ｒ6は、好ましくは水素原子又はメチル基、より好ましくはメチル基であり、Ｒ7は好ましくはエチレン基又はプロピレン基、より好ましくはエチレン基であり、Ｒ8は、好ましくはメチル基又はエチル基、より好ましくはメチル基であり、Ｘ1は好ましくは酸素原子である。無機顔料の分散性向上及びシート剥離性の向上の観点から、ｎは５０を超え、好ましくは５１以上、より好ましくは５８以上、更に好ましくは７２以上、更により好ましくは８８以上、更により好ましくは１１０以上であり、製造容易性の観点から、ｎは１４０以下であり、好ましくは１３０以下である。
In the formula (2), R 4 , R 5 , R 6 and R 8 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group, and R 7 is a linear or branched alkylene having 2 to 4 carbon atoms. X 1 represents an oxygen atom or NH, and n represents the average added mole number of the —R 7 —O— group, which is greater than 50 and not greater than 140. R 4 and R 5 are preferably a hydrogen atom or a methyl group, more preferably from the viewpoint of improving the dispersibility of the inorganic pigment and the sheet, and the ease of introducing the structural unit (b) into the copolymer. Is a hydrogen atom, R 6 is preferably a hydrogen atom or a methyl group, more preferably a methyl group, R 7 is preferably an ethylene group or a propylene group, more preferably an ethylene group, and R 8 is preferably Is a methyl group or an ethyl group, more preferably a methyl group, and X 1 is preferably an oxygen atom. From the viewpoint of improving the dispersibility of the inorganic pigment and improving the sheet peelability, n exceeds 50, preferably 51 or more, more preferably 58 or more, still more preferably 72 or more, even more preferably 88 or more, and even more preferably. N is 110 or more, and n is 140 or less, preferably 130 or less, from the viewpoint of manufacturability.
構成単位（ｂ）としては、非イオン性基を有するモノマー（以下、「モノマー（ｂ）」ともいう）由来の構成単位や、重合後に非イオン性基を導入して得られる構成単位等が挙げられ、製造容易性の観点から、好ましくはモノマー（ｂ）由来の構成単位である。非イオン性基としては、例えば、ポリオキシエチレン基、ポリオキシプロピレン基等のポリオキシアルキレン基が挙げられる。構成単位（ｂ）は、製造容易性の観点から、好ましくは、構成単位（ａ）を形成するモノマーと共重合可能なエチレン性不飽和二重結合を有するモノマーに由来する、構成単位である。
Examples of the structural unit (b) include a structural unit derived from a monomer having a nonionic group (hereinafter also referred to as “monomer (b)”), a structural unit obtained by introducing a nonionic group after polymerization, and the like. From the viewpoint of ease of production, it is preferably a structural unit derived from the monomer (b). Examples of the nonionic group include polyoxyalkylene groups such as a polyoxyethylene group and a polyoxypropylene group. The structural unit (b) is preferably a structural unit derived from a monomer having an ethylenically unsaturated double bond copolymerizable with the monomer forming the structural unit (a) from the viewpoint of ease of production.
モノマー（ｂ）としては、無機顔料の分散性向上、分散の安定性及びシート剥離性の向上の観点から、好ましくは式（５）で表されるモノマーである。
The monomer (b) is preferably a monomer represented by the formula (5) from the viewpoint of improving the dispersibility of the inorganic pigment, the stability of the dispersion, and the improvement of the sheet peelability.
式（５）中、Ｒ4、Ｒ5、Ｒ6、Ｒ7、Ｒ8、Ｘ1、及びｎは、一又は複数の実施形態において、上述の構成単位（ｂ）と同様である。
In Formula (5), R 4 , R 5 , R 6 , R 7 , R 8 , X 1 , and n are the same as those in the structural unit (b) in one or more embodiments.
モノマー（ｂ）としては、メトキシポリエチレングリコール（メタ）アクリレート、メトキシポリ（エチレングリコール／プロピレングリコール）モノ（メタ）アクリレート、エトキシポリ（エチレングリコール／プロピレングリコール）モノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、２－メトキシエチル（メタ）アクリルアミド、２－エトキシエチル（メタ）アクリルアミド、３－メトキシプロピル（メタ）アクリルアミド等が挙げられる。これらの中でも、無機顔料の分散性向上、分散の安定性及びシート剥離性の観点から、好ましくはメトキシポリエチレングリコール（メタ）アクリレート、より好ましくはメトキシポリエチレングリコールメタクリレートである。本明細書において、「（メタ）アクリレート」とは、アクリレート及びメタクリレートから選ばれる少なくとも１種を意味する。同様に、「（メタ）アクリルアミド」とは、アクリルアミド及びメタクリルアミドから選ばれる少なくとも１種を意味する。
Monomers (b) include methoxypolyethylene glycol (meth) acrylate, methoxypoly (ethylene glycol / propylene glycol) mono (meth) acrylate, ethoxypoly (ethylene glycol / propylene glycol) mono (meth) acrylate, polyethylene glycol mono (meth) acrylate Polypropylene glycol mono (meth) acrylate, 2-methoxyethyl (meth) acrylamide, 2-ethoxyethyl (meth) acrylamide, 3-methoxypropyl (meth) acrylamide and the like. Among these, methoxypolyethylene glycol (meth) acrylate is preferable, and methoxypolyethyleneglycol methacrylate is more preferable from the viewpoint of dispersibility improvement of inorganic pigment, dispersion stability, and sheet peelability. In this specification, “(meth) acrylate” means at least one selected from acrylate and methacrylate. Similarly, “(meth) acrylamide” means at least one selected from acrylamide and methacrylamide.
本発明の共重合体を構成する全構成単位中の構成単位（ｂ）の割合は、無機顔料の分散性向上及びシート剥離性の向上の観点から、５５質量％以上であり、好ましくは６０質量％以上、より好ましくは６５質量％以上であり、同様の観点から、９９質量％以下であり、好ましくは９５質量％以下、より好ましくは８７質量％以下、更に好ましくは８０質量％以下、更により好ましくは７５質量％以下である。
The proportion of the structural unit (b) in all the structural units constituting the copolymer of the present invention is 55% by mass or more, preferably 60% by mass, from the viewpoint of improving the dispersibility of the inorganic pigment and improving the sheet peelability. % Or more, more preferably 65% by mass or more, and from the same viewpoint, it is 99% by mass or less, preferably 95% by mass or less, more preferably 87% by mass or less, still more preferably 80% by mass or less, and even more. Preferably it is 75 mass% or less.
本発明の共重合体における構成単位（ａ）の構成単位（ｂ）に対する質量比（構成単位（ａ）／構成単位（ｂ））は、無機顔料の分散性及び剥離性向上の観点から、好ましくは０．０５以上、より好ましくは０．１２以上、更に好ましくは０．１６以上、更により好ましくは０．１９以上であり、無機顔料の分散性向上の観点から、好ましくは０．５０以下、より好ましくは０．３５以下、更に好ましくは０．２８以下であり、剥離性向上の観点から、更により好ましくは０．２４以下である。
The mass ratio of the structural unit (a) to the structural unit (b) in the copolymer of the present invention (structural unit (a) / structural unit (b)) is preferably from the viewpoint of improving dispersibility and peelability of the inorganic pigment. Is 0.05 or more, more preferably 0.12 or more, still more preferably 0.16 or more, still more preferably 0.19 or more, and from the viewpoint of improving the dispersibility of the inorganic pigment, preferably 0.50 or less, More preferably, it is 0.35 or less, More preferably, it is 0.28 or less, From a viewpoint of a peelable improvement, More preferably, it is 0.24 or less.
［構成単位（ｃ）］
本発明の共重合体は、分散性向上の観点から、好ましくはさらに、構成単位（ｃ）を含有する。構成単位（ｃ）は、一又は複数の実施形態において、式（３）で表される構成単位である。構成単位（ｃ）は疎水性であり、共重合体が非水系溶媒中へ再溶出することを抑制すると考えられる。
[Structural unit (c)]
From the viewpoint of improving dispersibility, the copolymer of the present invention preferably further contains a structural unit (c). The structural unit (c) is a structural unit represented by the formula (3) in one or a plurality of embodiments. The structural unit (c) is hydrophobic and is considered to suppress re-elution of the copolymer into the non-aqueous solvent.
本発明の共重合体は、分散性向上の観点から、好ましくはさらに、構成単位（ｃ）を含有する。構成単位（ｃ）は、一又は複数の実施形態において、式（３）で表される構成単位である。構成単位（ｃ）は疎水性であり、共重合体が非水系溶媒中へ再溶出することを抑制すると考えられる。
From the viewpoint of improving dispersibility, the copolymer of the present invention preferably further contains a structural unit (c). The structural unit (c) is a structural unit represented by the formula (3) in one or a plurality of embodiments. The structural unit (c) is hydrophobic and is considered to suppress re-elution of the copolymer into the non-aqueous solvent.
式（３）において、Ｒ9、Ｒ10、及びＲ11は同一又は異なり、水素原子、メチル基又はエチル基を示し、Ｘ3は酸素原子又はＮＨを示し、Ｒ12及びＲ13は炭素数１以上３０以下の炭化水素基を示す。無機顔料の分散性向上及び共重合体への構成単位（ｃ）の導入の容易性の観点から、Ｒ9及びＲ10は、好ましくは水素原子又はメチル基、より好ましくは水素原子であり、Ｒ11は、好ましくは水素原子又はメチル基であり、Ｘ3は、好ましくは酸素原子であり、Ｒ12は好ましくはアルキル基又はアルケニル基であり、Ｒ12の炭素数は、１以上であり、好ましくは２２以下、より好ましくは１８以下である。Ｒ12としては、メチル基、エチル基、ブチル基、オクチル基、２－エチルヘキシル基、デシル基、ラウリル基、ミリスチル基、セチル基、ステアリル基、オレイル基、ベヘニル基等が挙げられる。同様の観点から、Ｒ13は、好ましくはフェニル基又は炭素数１以上２２以下のアルキル基である。
構成単位（ｃ）としては、後述のモノマー（ｃ）由来の構成単位が挙げられ、分散性及び剥離性向上の観点から、好ましくはアルキル（メタ）アクリレート由来の構成単位、より好ましくはメチルメタクリレート、ステアリルメタクリレート及びステアリルアクリレートからなる群より選ばれる１種以上に由来する構成単位、更に好ましくはメチルメタクリレートに由来する構成単位である。 In Formula (3), R 9 , R 10 , and R 11 are the same or different and each represents a hydrogen atom, a methyl group, or an ethyl group, X 3 represents an oxygen atom or NH, and R 12 and R 13 have 1 carbon atom. The hydrocarbon group of 30 or less is shown. From the viewpoint of improving the dispersibility of the inorganic pigment and the ease of introducing the structural unit (c) into the copolymer, R 9 and R 10 are preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. 11 is preferably a hydrogen atom or a methyl group, X 3 is preferably an oxygen atom, R 12 is preferably an alkyl group or an alkenyl group, and R 12 has one or more carbon atoms, preferably Is 22 or less, more preferably 18 or less. Examples of R 12 include methyl group, ethyl group, butyl group, octyl group, 2-ethylhexyl group, decyl group, lauryl group, myristyl group, cetyl group, stearyl group, oleyl group, and behenyl group. From the same viewpoint, R 13 is preferably a phenyl group or an alkyl group having 1 to 22 carbon atoms.
Examples of the structural unit (c) include structural units derived from the monomer (c) described below. From the viewpoint of improving dispersibility and peelability, the structural unit is preferably derived from an alkyl (meth) acrylate, more preferably methyl methacrylate, A structural unit derived from one or more selected from the group consisting of stearyl methacrylate and stearyl acrylate, more preferably a structural unit derived from methyl methacrylate.
構成単位（ｃ）としては、後述のモノマー（ｃ）由来の構成単位が挙げられ、分散性及び剥離性向上の観点から、好ましくはアルキル（メタ）アクリレート由来の構成単位、より好ましくはメチルメタクリレート、ステアリルメタクリレート及びステアリルアクリレートからなる群より選ばれる１種以上に由来する構成単位、更に好ましくはメチルメタクリレートに由来する構成単位である。 In Formula (3), R 9 , R 10 , and R 11 are the same or different and each represents a hydrogen atom, a methyl group, or an ethyl group, X 3 represents an oxygen atom or NH, and R 12 and R 13 have 1 carbon atom. The hydrocarbon group of 30 or less is shown. From the viewpoint of improving the dispersibility of the inorganic pigment and the ease of introducing the structural unit (c) into the copolymer, R 9 and R 10 are preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. 11 is preferably a hydrogen atom or a methyl group, X 3 is preferably an oxygen atom, R 12 is preferably an alkyl group or an alkenyl group, and R 12 has one or more carbon atoms, preferably Is 22 or less, more preferably 18 or less. Examples of R 12 include methyl group, ethyl group, butyl group, octyl group, 2-ethylhexyl group, decyl group, lauryl group, myristyl group, cetyl group, stearyl group, oleyl group, and behenyl group. From the same viewpoint, R 13 is preferably a phenyl group or an alkyl group having 1 to 22 carbon atoms.
Examples of the structural unit (c) include structural units derived from the monomer (c) described below. From the viewpoint of improving dispersibility and peelability, the structural unit is preferably derived from an alkyl (meth) acrylate, more preferably methyl methacrylate, A structural unit derived from one or more selected from the group consisting of stearyl methacrylate and stearyl acrylate, more preferably a structural unit derived from methyl methacrylate.
構成単位（ｃ）としては、共重合体への構成単位（ｃ）の導入の容易性の観点から、好ましくは式（６）で表されるモノマー（以下「モノマー（ｃ）」ともいう）に由来する構成単位である。
The structural unit (c) is preferably a monomer represented by the formula (6) (hereinafter also referred to as “monomer (c)”) from the viewpoint of ease of introduction of the structural unit (c) into the copolymer. It is a derived structural unit.
式（６）中、Ｒ9、Ｒ10、Ｒ11、Ｒ12、Ｒ13、及びＸ3は、一又は複数の実施形態において、上述の構成単位（ｃ）と同様である。
In formula (6), R 9 , R 10 , R 11 , R 12 , R 13 , and X 3 are the same as those in the structural unit (c) in one or more embodiments.
モノマー（ｃ）としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、オクチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、ベヘニル（メタ）アクリレート等のアルキル（メタ）アクリレート；ブチル（メタ）アクリルアミド、オクチル（メタ）アクリルアミド、ラウリル（メタ）アクリルアミド、ステアリル（メタ）アクリルアミド、ベヘニル（メタ）アクリルアミド等のアルキル（メタ）アクリルアミド；１－デセン、１－オクタデセン等のα－オレフィン；及びスチレン等が挙げられる。
これらの中でも、分散安定性の観点から、好ましくはアルキル（メタ）アクリレート及びスチレン、より好ましくはメチル（メタ）アクリレート及びステアリル（メタ）アクリレートであり、分散性及び剥離性向上の観点から、更に好ましくはメチル（メタ）アクリレート、更により好ましくはメチルメタクリレートである。 As the monomer (c), methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, etc. Alkyl (meth) acrylates; alkyl (meth) acrylamides such as butyl (meth) acrylamide, octyl (meth) acrylamide, lauryl (meth) acrylamide, stearyl (meth) acrylamide, and behenyl (meth) acrylamide; 1-decene, 1-octadecene Α-olefins such as styrene; and styrene.
Among these, from the viewpoint of dispersion stability, preferably alkyl (meth) acrylate and styrene, more preferably methyl (meth) acrylate and stearyl (meth) acrylate, and further preferably from the viewpoint of improving dispersibility and peelability. Is methyl (meth) acrylate, even more preferably methyl methacrylate.
これらの中でも、分散安定性の観点から、好ましくはアルキル（メタ）アクリレート及びスチレン、より好ましくはメチル（メタ）アクリレート及びステアリル（メタ）アクリレートであり、分散性及び剥離性向上の観点から、更に好ましくはメチル（メタ）アクリレート、更により好ましくはメチルメタクリレートである。 As the monomer (c), methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, etc. Alkyl (meth) acrylates; alkyl (meth) acrylamides such as butyl (meth) acrylamide, octyl (meth) acrylamide, lauryl (meth) acrylamide, stearyl (meth) acrylamide, and behenyl (meth) acrylamide; 1-decene, 1-octadecene Α-olefins such as styrene; and styrene.
Among these, from the viewpoint of dispersion stability, preferably alkyl (meth) acrylate and styrene, more preferably methyl (meth) acrylate and stearyl (meth) acrylate, and further preferably from the viewpoint of improving dispersibility and peelability. Is methyl (meth) acrylate, even more preferably methyl methacrylate.
本発明の共重合体を構成する全構成単位中の構成単位（ｃ）の割合は、無機顔料の分散性向上及びシート剥離性の向上の観点から、好ましくは０質量％以上、より好ましくは３質量％以上、より好ましくは８質量％以上、更に好ましくは１２質量％以上であり、同様の観点から、好ましくは３５質量％以下、より好ましくは２５質量％以下、更に好ましくは１８質量％以下である。
The proportion of the structural unit (c) in all the structural units constituting the copolymer of the present invention is preferably 0% by mass or more, more preferably 3 from the viewpoint of improving the dispersibility of the inorganic pigment and improving the sheet peelability. From the same viewpoint, it is preferably 35% by mass or less, more preferably 25% by mass or less, and still more preferably 18% by mass or less. is there.
本発明の共重合体における構成単位（ｃ）の構成単位（ｂ）に対する質量比（構成単位（ｃ）／構成単位（ｂ））は、無機顔料の分散性向上の観点から、好ましくは０．０５以上、より好ましくは０．０６以上、更に好ましくは０．１０以上、更により好ましくは０．１８以上であり、同様の観点から、好ましくは０．７０以下、より好ましくは０．６０以下、更に好ましくは０．５０以下、更により好ましくは０．２５以下である。
The mass ratio of the structural unit (c) to the structural unit (b) in the copolymer of the present invention (structural unit (c) / structural unit (b)) is preferably from the viewpoint of improving dispersibility of the inorganic pigment. 05 or more, more preferably 0.06 or more, still more preferably 0.10 or more, still more preferably 0.18 or more, and from the same viewpoint, preferably 0.70 or less, more preferably 0.60 or less, More preferably, it is 0.50 or less, More preferably, it is 0.25 or less.
［その他の構成単位］
本発明の共重合体は、本発明の効果を損なわない範囲で、構成単位（ａ）、（ｂ）及び（ｃ）以外のその他の構成単位を含んでもよい。本発明の共重合体を構成する全構成単位中の、前記その他の構成単位の割合は、本発明の効果発現させる観点から、好ましくは１０質量％以下、より好ましくは３質量％以下、更に好ましくは１質量％以下である。 [Other structural units]
The copolymer of the present invention may contain other structural units other than the structural units (a), (b) and (c) as long as the effects of the present invention are not impaired. The proportion of the other structural units in all the structural units constituting the copolymer of the present invention is preferably 10% by mass or less, more preferably 3% by mass or less, and still more preferably, from the viewpoint of manifesting the effects of the present invention. Is 1% by mass or less.
本発明の共重合体は、本発明の効果を損なわない範囲で、構成単位（ａ）、（ｂ）及び（ｃ）以外のその他の構成単位を含んでもよい。本発明の共重合体を構成する全構成単位中の、前記その他の構成単位の割合は、本発明の効果発現させる観点から、好ましくは１０質量％以下、より好ましくは３質量％以下、更に好ましくは１質量％以下である。 [Other structural units]
The copolymer of the present invention may contain other structural units other than the structural units (a), (b) and (c) as long as the effects of the present invention are not impaired. The proportion of the other structural units in all the structural units constituting the copolymer of the present invention is preferably 10% by mass or less, more preferably 3% by mass or less, and still more preferably, from the viewpoint of manifesting the effects of the present invention. Is 1% by mass or less.
［無機顔料用高分子分散剤中の共重合体の調製］
本発明の共重合体は、例えば、モノマー（ａ）、モノマー（ｂ）、必要に応じてモノマー（ｃ）を含むモノマー成分を溶液重合法で重合させる等、公知の方法で得ることができる。本発明の一実施形態において、構成単位（ａ）の全構成単位中の質量比は、重合に用いる全モノマー成分に対するモノマー（ａ）と重合後に中和可能な酸性基を付加できるモノマーとの合計の質量比と見なすことができる。構成単位（ｂ）の全構成単位中の質量比は、重合に用いる全モノマー成分に対するモノマー（ｂ）と、重合後に非イオン性基を導入できるモノマーとの合計に対する質量比と見なすことができる。構成単位（ｃ）の構成単位（ｂ）に対する質量比（構成単位（ｃ）／構成単位（ｂ））は、重合に用いる全モノマー成分における疎水性モノマー（ｃ）の、モノマー（ｂ）と重合後に非イオン性基を導入できるモノマーとの合計に対する質量比と見なすことができる。したがって、本発明は、その他の態様において、本発明の分散剤の製造方法であって、モノマー（ａ）又は重合後に中和可能な酸性基を付加できるモノマー、モノマー（ｂ）又は重合後に非イオン性基を導入できるモノマー、並びに、必要に応じて疎水性モノマー（ｃ）を、それぞれ、上述した構成単位（ａ）、（ｂ）、必要に応じて（ｃ）の含有量で含むモノマー成分を重合させることを含む製造方法である。 [Preparation of copolymer in polymer dispersant for inorganic pigment]
The copolymer of the present invention can be obtained by a known method such as, for example, polymerizing a monomer component containing the monomer (a), the monomer (b), and, if necessary, the monomer (c) by a solution polymerization method. In one embodiment of the present invention, the mass ratio of the structural unit (a) in all structural units is the sum of the monomer (a) with respect to all monomer components used in the polymerization and the monomer capable of adding an acid group that can be neutralized after polymerization. It can be regarded as a mass ratio. The mass ratio of the structural unit (b) in all the structural units can be regarded as a mass ratio with respect to the sum of the monomer (b) with respect to all monomer components used in the polymerization and the monomer capable of introducing a nonionic group after the polymerization. The mass ratio of the structural unit (c) to the structural unit (b) (structural unit (c) / structural unit (b)) is determined by the polymerization of the monomer (b) and the hydrophobic monomer (c) in all monomer components used in the polymerization. It can be regarded as a mass ratio with respect to the sum total of monomers capable of introducing a nonionic group later. Therefore, in another aspect, the present invention provides a method for producing the dispersant of the present invention, which is a monomer (a) or a monomer capable of adding a neutralizable acidic group after polymerization, monomer (b) or nonionic after polymerization. A monomer component containing a monomer capable of introducing a functional group and, if necessary, a hydrophobic monomer (c) with the contents of the structural units (a), (b), and (c) as necessary, respectively. It is a manufacturing method including polymerizing.
本発明の共重合体は、例えば、モノマー（ａ）、モノマー（ｂ）、必要に応じてモノマー（ｃ）を含むモノマー成分を溶液重合法で重合させる等、公知の方法で得ることができる。本発明の一実施形態において、構成単位（ａ）の全構成単位中の質量比は、重合に用いる全モノマー成分に対するモノマー（ａ）と重合後に中和可能な酸性基を付加できるモノマーとの合計の質量比と見なすことができる。構成単位（ｂ）の全構成単位中の質量比は、重合に用いる全モノマー成分に対するモノマー（ｂ）と、重合後に非イオン性基を導入できるモノマーとの合計に対する質量比と見なすことができる。構成単位（ｃ）の構成単位（ｂ）に対する質量比（構成単位（ｃ）／構成単位（ｂ））は、重合に用いる全モノマー成分における疎水性モノマー（ｃ）の、モノマー（ｂ）と重合後に非イオン性基を導入できるモノマーとの合計に対する質量比と見なすことができる。したがって、本発明は、その他の態様において、本発明の分散剤の製造方法であって、モノマー（ａ）又は重合後に中和可能な酸性基を付加できるモノマー、モノマー（ｂ）又は重合後に非イオン性基を導入できるモノマー、並びに、必要に応じて疎水性モノマー（ｃ）を、それぞれ、上述した構成単位（ａ）、（ｂ）、必要に応じて（ｃ）の含有量で含むモノマー成分を重合させることを含む製造方法である。 [Preparation of copolymer in polymer dispersant for inorganic pigment]
The copolymer of the present invention can be obtained by a known method such as, for example, polymerizing a monomer component containing the monomer (a), the monomer (b), and, if necessary, the monomer (c) by a solution polymerization method. In one embodiment of the present invention, the mass ratio of the structural unit (a) in all structural units is the sum of the monomer (a) with respect to all monomer components used in the polymerization and the monomer capable of adding an acid group that can be neutralized after polymerization. It can be regarded as a mass ratio. The mass ratio of the structural unit (b) in all the structural units can be regarded as a mass ratio with respect to the sum of the monomer (b) with respect to all monomer components used in the polymerization and the monomer capable of introducing a nonionic group after the polymerization. The mass ratio of the structural unit (c) to the structural unit (b) (structural unit (c) / structural unit (b)) is determined by the polymerization of the monomer (b) and the hydrophobic monomer (c) in all monomer components used in the polymerization. It can be regarded as a mass ratio with respect to the sum total of monomers capable of introducing a nonionic group later. Therefore, in another aspect, the present invention provides a method for producing the dispersant of the present invention, which is a monomer (a) or a monomer capable of adding a neutralizable acidic group after polymerization, monomer (b) or nonionic after polymerization. A monomer component containing a monomer capable of introducing a functional group and, if necessary, a hydrophobic monomer (c) with the contents of the structural units (a), (b), and (c) as necessary, respectively. It is a manufacturing method including polymerizing.
溶液重合に用いられる溶媒としては、例えばトルエン、キシレン等の芳香族系炭化水素；エタノール、２－プロパノール等の低級アルコール；アセトン、メチルエチルケトン等のケトン；テトラヒドロフラン、ジエチレングリコールジメチルエーテル等のエーテルが挙げられる。溶媒の量は、全モノマー１質量部に対し、好ましくは０．５質量部以上１０質量部以下である。
Examples of the solvent used in the solution polymerization include aromatic hydrocarbons such as toluene and xylene; lower alcohols such as ethanol and 2-propanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and diethylene glycol dimethyl ether. The amount of the solvent is preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 1 part by mass of all monomers.
重合開始剤としては、公知のラジカル重合開始剤を用いることができ、例えばアゾ系重合開始剤、ヒドロ過酸化物類、過酸化ジアルキル類、過酸化ジアシル類、ケトンペルオキシド類等が挙げられる。重合開始剤の量は、全モノマー１００モルに対し、好ましくは１モル以上、より好ましくは２モル以上、更に好ましくは３モル以上であり、好ましくは１５モル以下、より好ましくは１２モル以下、更に好ましくは９モル以下である。重合反応は、好ましくは窒素気流下で行い、反応温度は、好ましくは６０℃以上１８０℃以下、反応時間は、好ましくは０．５時間以上２０時間以下である。
As the polymerization initiator, known radical polymerization initiators can be used, and examples thereof include azo polymerization initiators, hydroperoxides, dialkyl peroxides, diacyl peroxides, and ketone peroxides. The amount of the polymerization initiator is preferably 1 mol or more, more preferably 2 mol or more, still more preferably 3 mol or more, preferably 15 mol or less, more preferably 12 mol or less, based on 100 mol of all monomers. Preferably it is 9 mol or less. The polymerization reaction is preferably performed in a nitrogen stream, the reaction temperature is preferably 60 ° C. or higher and 180 ° C. or lower, and the reaction time is preferably 0.5 hour or longer and 20 hours or shorter.
重合の際には、さらに重合連鎖移動剤を添加してもよい。重合連鎖移動剤の具体例としては、オクチルメルカプタン、ｎ－ドデシルメルカプタン、ｔ－ドデシルメルカプタン、ｎ－テトラデシルメルカプタン、メルカプトエタノール、３－メルカプト－１，２－プロパンジオール、メルカプトコハク酸等のメルカプタン類；チウラムジスルフィド類；炭化水素類；不飽和環状炭化水素化合物；不飽和ヘテロ環状化合物等が挙げられ、これらは、それぞれ単独で又は２種以上を混合して用いることができる。
In the polymerization, a polymerization chain transfer agent may be further added. Specific examples of the polymerization chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-tetradecyl mercaptan, mercaptoethanol, 3-mercapto-1,2-propanediol and mercaptosuccinic acid. Thiuram disulfides; hydrocarbons; unsaturated cyclic hydrocarbon compounds; unsaturated heterocyclic compounds, and the like. These may be used alone or in admixture of two or more.
本発明の共重合体において、構成単位（ａ）、構成単位（ｂ）、構成単位（ｃ）の配列は、ランダム、ブロック、又はグラフトのいずれでも良い。
In the copolymer of the present invention, the arrangement of the structural unit (a), the structural unit (b), and the structural unit (c) may be random, block, or graft.
本発明の共重合体の重量平均分子量は、無機顔料の分散性向上及びシート剥離性の向上の観点から、好ましくは１０００以上、より好ましくは２０００以上、更に好ましくは４０００以上であり、同様の観点から、好ましくは１０００００以下、より好ましくは５００００以下、更に好ましくは３００００以下、更により好ましくは１５０００以下である。重量平均分子量はＧＰＣ（ゲルパーミエーションクロマトグラフィー）により測定した値であり、測定条件の詳細は実施例に示す通りである。
The weight average molecular weight of the copolymer of the present invention is preferably 1000 or more, more preferably 2000 or more, and further preferably 4000 or more, from the viewpoint of improving the dispersibility of the inorganic pigment and improving the sheet peelability. Therefore, it is preferably 100,000 or less, more preferably 50000 or less, still more preferably 30000 or less, and even more preferably 15000 or less. The weight average molecular weight is a value measured by GPC (gel permeation chromatography), and details of measurement conditions are as shown in Examples.
以上のようにして製造される共重合体及び／又は無機顔料用高分子分散剤は、非水系溶媒における無機顔料の分散性、好ましくは塩基性無機顔料の分散性、分散安定性及びシート剥離性に優れる。したがって、本発明の分散剤は、非水系溶媒における無機顔料の分散に用い、好ましくは非水系溶媒における塩基性無機顔料の分散に用いる。
The copolymer and / or the inorganic pigment polymer dispersant produced as described above is a dispersibility of an inorganic pigment in a non-aqueous solvent, preferably a dispersibility of a basic inorganic pigment, a dispersion stability and a sheet peelability. Excellent. Therefore, the dispersant of the present invention is used for dispersing an inorganic pigment in a non-aqueous solvent, and preferably used for dispersing a basic inorganic pigment in a non-aqueous solvent.
［非水系溶媒］
本発明で使用できる非水系溶媒の溶解度パラメータ（単位：［（ＭＰａ）1/2］）は、無機顔料の分散性向上、及び上記高分子分散剤との相溶性の観点から、好ましくは２０以上、より好ましくは２１以上であり、好ましくは３０以下、より好ましくは２６以下である。前記溶解度パラメータは、Ｆｅｄｏｒｓの方法［Ｒ．Ｆ．Ｆｅｄｏｒｓ． Ｐｏｌｙｍ． Ｅｎｇ． Ｓｃｉ．，１４，１４７（１９７４）］により計算された値をいう。 [Non-aqueous solvent]
The solubility parameter (unit: [(MPa) 1/2 ]) of the non-aqueous solvent that can be used in the present invention is preferably 20 or more from the viewpoint of improving the dispersibility of the inorganic pigment and compatibility with the polymer dispersant. More preferably, it is 21 or more, preferably 30 or less, more preferably 26 or less. The solubility parameter was measured by the method of Fedors [R. F. Fedors. Polym. Eng. Sci. , 14, 147 (1974)].
本発明で使用できる非水系溶媒の溶解度パラメータ（単位：［（ＭＰａ）1/2］）は、無機顔料の分散性向上、及び上記高分子分散剤との相溶性の観点から、好ましくは２０以上、より好ましくは２１以上であり、好ましくは３０以下、より好ましくは２６以下である。前記溶解度パラメータは、Ｆｅｄｏｒｓの方法［Ｒ．Ｆ．Ｆｅｄｏｒｓ． Ｐｏｌｙｍ． Ｅｎｇ． Ｓｃｉ．，１４，１４７（１９７４）］により計算された値をいう。 [Non-aqueous solvent]
The solubility parameter (unit: [(MPa) 1/2 ]) of the non-aqueous solvent that can be used in the present invention is preferably 20 or more from the viewpoint of improving the dispersibility of the inorganic pigment and compatibility with the polymer dispersant. More preferably, it is 21 or more, preferably 30 or less, more preferably 26 or less. The solubility parameter was measured by the method of Fedors [R. F. Fedors. Polym. Eng. Sci. , 14, 147 (1974)].
前記溶解度パラメータは、２種以上の有機溶媒を混合することにより好適に調整することができる。このような混合溶媒の溶解度パラメータは、前記方法により求めることもできるが、簡便な方法として、混合溶媒の各成分の溶解度パラメータと体積分率とから計算して求めることもできる。例えば、トルエンとエタノールとを体積分率５０：５０で混合した場合、その溶解度パラメータは、（１８．３）×０．５＋（２６．２）×０．５＝２２．３となる。
The solubility parameter can be suitably adjusted by mixing two or more organic solvents. Such a solubility parameter of the mixed solvent can be obtained by the above-described method, but as a simple method, it can also be obtained by calculation from the solubility parameter and volume fraction of each component of the mixed solvent. For example, when toluene and ethanol are mixed at a volume fraction of 50:50, the solubility parameter is (18.3) × 0.5 + (26.2) × 0.5 = 22.3.
本発明で使用できる非水系溶媒としては、キシレン（１８．２）、酢酸エチル（１８．２）、トルエン（１８．３）、テトラハイドロフラン（１８．５）、メチルエチルケトン（１９．３）、アセトン（１９．７）、ブチルセロソルブ（２０．２）、ジメチルホルムアミド（２４．７）、ｎ－プロパノール（２４．９）、エタノール（２６．２）、ジメチルスルホキシド（２６．４）、ｎ－ブタノール（２８．７）、メタノール（２９．７）等の有機溶媒から選ばれる１種以上が挙げられる。（ ）内の数値は、溶解度パラメータである。
Non-aqueous solvents that can be used in the present invention include xylene (18.2), ethyl acetate (18.2), toluene (18.3), tetrahydrofuran (18.5), methyl ethyl ketone (19.3), acetone. (19.7), butyl cellosolve (20.2), dimethylformamide (24.7), n-propanol (24.9), ethanol (26.2), dimethyl sulfoxide (26.4), n-butanol (28 .1) or more selected from organic solvents such as methanol (29.7). Numbers in parentheses are solubility parameters.
［無機顔料］
一般に、無機顔料の表面は酸点、塩基点の両方をもっている。非水系溶媒中における酸及び塩基の強度は逆滴定法で求めることが可能であり、分散させたい無機顔料が酸性であるか塩基性であるか同定することができる。逆滴定法とは、あらかじめ濃度が既知である塩基性試薬（又は酸性試薬）を一定の割合で無機顔料と混合し、十分に中和させた後、遠心分離機等で、固液分離させ、その上澄み液を滴定し、減少した塩基性試薬の量（又は酸性試薬の量）から酸量（又は塩基量）を求める方法である。本発明において塩基量及び酸量は下記により求められる。 [Inorganic pigment]
In general, the surface of an inorganic pigment has both an acid point and a base point. The strength of the acid and base in the non-aqueous solvent can be determined by a back titration method, and it can be identified whether the inorganic pigment to be dispersed is acidic or basic. The reverse titration method is a method in which a basic reagent (or acidic reagent) whose concentration is known in advance is mixed with an inorganic pigment at a certain ratio, sufficiently neutralized, and then solid-liquid separated with a centrifuge, The supernatant is titrated, and the acid amount (or base amount) is determined from the reduced amount of basic reagent (or acid reagent). In the present invention, the amount of base and the amount of acid are determined as follows.
一般に、無機顔料の表面は酸点、塩基点の両方をもっている。非水系溶媒中における酸及び塩基の強度は逆滴定法で求めることが可能であり、分散させたい無機顔料が酸性であるか塩基性であるか同定することができる。逆滴定法とは、あらかじめ濃度が既知である塩基性試薬（又は酸性試薬）を一定の割合で無機顔料と混合し、十分に中和させた後、遠心分離機等で、固液分離させ、その上澄み液を滴定し、減少した塩基性試薬の量（又は酸性試薬の量）から酸量（又は塩基量）を求める方法である。本発明において塩基量及び酸量は下記により求められる。 [Inorganic pigment]
In general, the surface of an inorganic pigment has both an acid point and a base point. The strength of the acid and base in the non-aqueous solvent can be determined by a back titration method, and it can be identified whether the inorganic pigment to be dispersed is acidic or basic. The reverse titration method is a method in which a basic reagent (or acidic reagent) whose concentration is known in advance is mixed with an inorganic pigment at a certain ratio, sufficiently neutralized, and then solid-liquid separated with a centrifuge, The supernatant is titrated, and the acid amount (or base amount) is determined from the reduced amount of basic reagent (or acid reagent). In the present invention, the amount of base and the amount of acid are determined as follows.
１）塩基量の求め方
試料としての無機顔料２ｇを精秤し、１／１００Ｎ 酢酸－トルエン／エタノール（容量比４８：５２）溶液３０ｍＬに入れ、超音波洗浄器（Ｂｒａｎｓｏｎ社製「１５１０Ｊ－ＭＴ」）で１時間分散処理し、分散液を得る。２４時間静置後、分散液の一部を遠心分離機（日立社製「ＣＰ－５６Ｇ」）を用いて、２５，０００ｒｐｍ、６０分の条件で固液分離する。分離した液体部１０ｍＬをフェノールフタレイン指示薬が添加されているトルエン／エタノール溶剤（容量比２：１）２０ｍＬに加えた後、１／１００Ｎ 水酸化カリウム－エタノール溶液にて中和滴定する。この時の滴定量をＸｍＬ、１／１００Ｎ 酢酸－トルエン／エタノール（容量比４８：５２）溶液１０ｍＬを中和するのに必要な滴定量をＢｍＬ、試料の量をＳｇとすると、以下の式で、塩基量が求められる。
塩基量（μｍｏｌ／ｇ）＝３０×（Ｂ－Ｘ）／Ｓ 1) Determination of the amount of base 2 g of inorganic pigment as a sample was precisely weighed and placed in 30 mL of a 1 / 100N acetic acid-toluene / ethanol (volume ratio 48:52) solution, and an ultrasonic cleaner (Branson “1510J-MT” )) For 1 hour to obtain a dispersion. After allowing to stand for 24 hours, a part of the dispersion is subjected to solid-liquid separation using a centrifuge (“CP-56G” manufactured by Hitachi, Ltd.) at 25,000 rpm for 60 minutes. 10 mL of the separated liquid portion is added to 20 mL of a toluene / ethanol solvent (volume ratio 2: 1) to which a phenolphthalein indicator is added, and then neutralized with a 1/100 N potassium hydroxide-ethanol solution. When the titration amount at this time is XmL, the titration amount required to neutralize 10 mL of 1 / 100N acetic acid-toluene / ethanol (volume ratio 48:52) solution is BmL, and the amount of the sample is Sg, The amount of base is determined.
Base amount (μmol / g) = 30 × (BX) / S
試料としての無機顔料２ｇを精秤し、１／１００Ｎ 酢酸－トルエン／エタノール（容量比４８：５２）溶液３０ｍＬに入れ、超音波洗浄器（Ｂｒａｎｓｏｎ社製「１５１０Ｊ－ＭＴ」）で１時間分散処理し、分散液を得る。２４時間静置後、分散液の一部を遠心分離機（日立社製「ＣＰ－５６Ｇ」）を用いて、２５，０００ｒｐｍ、６０分の条件で固液分離する。分離した液体部１０ｍＬをフェノールフタレイン指示薬が添加されているトルエン／エタノール溶剤（容量比２：１）２０ｍＬに加えた後、１／１００Ｎ 水酸化カリウム－エタノール溶液にて中和滴定する。この時の滴定量をＸｍＬ、１／１００Ｎ 酢酸－トルエン／エタノール（容量比４８：５２）溶液１０ｍＬを中和するのに必要な滴定量をＢｍＬ、試料の量をＳｇとすると、以下の式で、塩基量が求められる。
塩基量（μｍｏｌ／ｇ）＝３０×（Ｂ－Ｘ）／Ｓ 1) Determination of the amount of base 2 g of inorganic pigment as a sample was precisely weighed and placed in 30 mL of a 1 / 100N acetic acid-toluene / ethanol (volume ratio 48:52) solution, and an ultrasonic cleaner (Branson “1510J-MT” )) For 1 hour to obtain a dispersion. After allowing to stand for 24 hours, a part of the dispersion is subjected to solid-liquid separation using a centrifuge (“CP-56G” manufactured by Hitachi, Ltd.) at 25,000 rpm for 60 minutes. 10 mL of the separated liquid portion is added to 20 mL of a toluene / ethanol solvent (volume ratio 2: 1) to which a phenolphthalein indicator is added, and then neutralized with a 1/100 N potassium hydroxide-ethanol solution. When the titration amount at this time is XmL, the titration amount required to neutralize 10 mL of 1 / 100N acetic acid-toluene / ethanol (volume ratio 48:52) solution is BmL, and the amount of the sample is Sg, The amount of base is determined.
Base amount (μmol / g) = 30 × (BX) / S
２）酸量の求め方
試料としての無機顔料２ｇを精秤し、１／１００Ｎ ｎ－ブチルアミン－トルエン／エタノール（容量比４８：５２）溶液３０ｍＬに入れ、超音波洗浄器（Ｂｒａｎｓｏｎ社製「１５１０Ｊ－ＭＴ」）で１時間分散処理し、分散液を得る。２４時間静置後、分散液の一部を遠心分離機（日立社製「ＣＰ－５６Ｇ」）を用いて、２５，０００ｒｐｍ、６０分の条件で固液分離する。分離した液体部１０ｍＬをブロムクレゾールグリーン指示薬が添加されているトルエン／エタノール溶剤（容量比２：１）２０ｍＬに加えた後、１／１００Ｎ 塩酸－エタノール溶液にて中和滴定する。この時の滴定量をＸｍＬ、１／１００Ｎ ｎ－ブチルアミン－トルエン／エタノール（容量比４８：５２）溶液１０ｍＬを中和するのに必要な滴定量をＢｍＬ、試料の量をＳｇとすると、以下の式で、酸量が求められる。
酸量（μｍｏｌ／ｇ）＝３０×（Ｂ－Ｘ）／Ｓ 2) Determination of acid amount 2 g of inorganic pigment as a sample was precisely weighed and placed in 30 mL of a 1 / 100N n-butylamine-toluene / ethanol (volume ratio 48:52) solution, and an ultrasonic cleaner (Branson “1510J”). -MT ") for 1 hour to obtain a dispersion. After allowing to stand for 24 hours, a part of the dispersion is subjected to solid-liquid separation using a centrifuge (“CP-56G” manufactured by Hitachi, Ltd.) at 25,000 rpm for 60 minutes. 10 mL of the separated liquid is added to 20 mL of a toluene / ethanol solvent (volume ratio 2: 1) to which bromocresol green indicator is added, and then neutralized with a 1/100 N hydrochloric acid-ethanol solution. Assuming that the titer at this time is XmL, the titer required for neutralizing 10 mL of 1 / 100N n-butylamine-toluene / ethanol (volume ratio 48:52) is BmL, and the amount of sample is Sg, The acid amount is determined by the formula.
Acid amount (μmol / g) = 30 × (BX) / S
試料としての無機顔料２ｇを精秤し、１／１００Ｎ ｎ－ブチルアミン－トルエン／エタノール（容量比４８：５２）溶液３０ｍＬに入れ、超音波洗浄器（Ｂｒａｎｓｏｎ社製「１５１０Ｊ－ＭＴ」）で１時間分散処理し、分散液を得る。２４時間静置後、分散液の一部を遠心分離機（日立社製「ＣＰ－５６Ｇ」）を用いて、２５，０００ｒｐｍ、６０分の条件で固液分離する。分離した液体部１０ｍＬをブロムクレゾールグリーン指示薬が添加されているトルエン／エタノール溶剤（容量比２：１）２０ｍＬに加えた後、１／１００Ｎ 塩酸－エタノール溶液にて中和滴定する。この時の滴定量をＸｍＬ、１／１００Ｎ ｎ－ブチルアミン－トルエン／エタノール（容量比４８：５２）溶液１０ｍＬを中和するのに必要な滴定量をＢｍＬ、試料の量をＳｇとすると、以下の式で、酸量が求められる。
酸量（μｍｏｌ／ｇ）＝３０×（Ｂ－Ｘ）／Ｓ 2) Determination of acid amount 2 g of inorganic pigment as a sample was precisely weighed and placed in 30 mL of a 1 / 100N n-butylamine-toluene / ethanol (volume ratio 48:52) solution, and an ultrasonic cleaner (Branson “1510J”). -MT ") for 1 hour to obtain a dispersion. After allowing to stand for 24 hours, a part of the dispersion is subjected to solid-liquid separation using a centrifuge (“CP-56G” manufactured by Hitachi, Ltd.) at 25,000 rpm for 60 minutes. 10 mL of the separated liquid is added to 20 mL of a toluene / ethanol solvent (volume ratio 2: 1) to which bromocresol green indicator is added, and then neutralized with a 1/100 N hydrochloric acid-ethanol solution. Assuming that the titer at this time is XmL, the titer required for neutralizing 10 mL of 1 / 100N n-butylamine-toluene / ethanol (volume ratio 48:52) is BmL, and the amount of sample is Sg, The acid amount is determined by the formula.
Acid amount (μmol / g) = 30 × (BX) / S
本発明において、無機顔料は、無機顔料の分散性向上及びシート剥離性の向上の観点から、好ましくは塩基性無機顔料である。塩基性無機顔料とは、上記定義の塩基量が上記定義の酸量よりも大きな値をもつ無機化合物であり、具体的には、酸化チタン、酸化マグネシウム、酸化バリウム、酸化アルミニウム等の金属酸化物；炭酸マグネシウム、炭酸バリウム等の金属炭酸塩；ジルコン酸バリウム、ジルコン酸カルシウム、チタン酸カルシウム、チタン酸バリウム、チタン酸ストロンチウム等の複合酸化物が挙げられ、好ましくは酸化マグネシウム、炭酸バリウム、酸化チタン、チタン酸カルシウム、チタン酸バリウム、ジルコン酸バリウム及びジルコン酸カルシウムからなる群から選択される１種以上の顔料である。本発明における塩基性無機顔料としては、セラミックシートの特性を向上させる観点から、より好ましくは前記複合酸化物であり、更に好ましくはチタン酸バリウムである。
In the present invention, the inorganic pigment is preferably a basic inorganic pigment from the viewpoint of improving the dispersibility of the inorganic pigment and improving the sheet peelability. A basic inorganic pigment is an inorganic compound in which the amount of base defined above is greater than the amount of acid defined above, specifically, metal oxides such as titanium oxide, magnesium oxide, barium oxide, and aluminum oxide. Metal carbonates such as magnesium carbonate and barium carbonate; complex oxides such as barium zirconate, calcium zirconate, calcium titanate, barium titanate, strontium titanate, etc., preferably magnesium oxide, barium carbonate, titanium oxide , One or more pigments selected from the group consisting of calcium titanate, barium titanate, barium zirconate and calcium zirconate. The basic inorganic pigment in the present invention is more preferably the composite oxide from the viewpoint of improving the characteristics of the ceramic sheet, and further preferably barium titanate.
本発明の分散剤を好適に用いることができる無機顔料のＢＥＴ比表面積に基づく平均粒径（以下、「ＢＥＴ平均粒径」ともいう）、及び本発明のスラリー組成物に含まれる無機顔料の動的光散乱法による平均粒径（以下、「Ｄ５０」ともいう）は、分散性向上の観点から、好ましくは５００ｎｍ以下、より好ましくは２００ｎｍ以下、更に好ましくは１００ｎｍ以下であり、分散性を維持する観点から、好ましくは５ｎｍ以上、より好ましくは７ｎｍ以上、更に好ましくは８ｎｍ以上である。前記Ｄ５０は、後述の動的光散乱法の原理に基づく散乱強度の頻度分布が５０％となる粒径であり、実施例記載の方法で測定できる。無機顔料のＢＥＴ平均粒径は、好ましくは粉末状の無機顔料の平均粒径をいい、以下のようにして算出される。
The average particle diameter based on the BET specific surface area (hereinafter also referred to as “BET average particle diameter”) of the inorganic pigment to which the dispersant of the present invention can be suitably used, and the movement of the inorganic pigment contained in the slurry composition of the present invention. The average particle size (hereinafter also referred to as “D50”) by the dynamic light scattering method is preferably 500 nm or less, more preferably 200 nm or less, and further preferably 100 nm or less from the viewpoint of improving dispersibility, and maintains dispersibility. From the viewpoint, it is preferably 5 nm or more, more preferably 7 nm or more, and further preferably 8 nm or more. The D50 is a particle diameter at which the frequency distribution of the scattering intensity based on the principle of the dynamic light scattering method described later becomes 50%, and can be measured by the method described in the examples. The BET average particle diameter of the inorganic pigment preferably refers to the average particle diameter of the powdered inorganic pigment, and is calculated as follows.
（無機顔料のＢＥＴ平均粒径の算出方法）
無機顔料のＢＥＴ平均粒径は、無機顔料粒子を粒子径Ｒ（ｍ）の球と仮定して、窒素吸着法により測定されたＢＥＴ比表面積Ｓ（ｍ2／ｇ）、無機顔料粒子の比重ρ（ｇ／ｃｍ3）を用いて、求めることができる。すなわち、ＢＥＴ比表面積は単位質量当たりの表面積であるので、表面積をＡ（ｍ2）、粒子の質量をＷ（ｇ）とすると、
Ｓ（ｍ2／ｇ）＝Ａ（ｍ2）／Ｗ（ｇ）
＝［４×π×（Ｒ／２）2］／［４／３×π×（Ｒ／２）3×ρ×１０6］
＝６／（Ｒ×ρ×１０6）
の関係式が求められる。粒子径の単位を変換すると、
Ｒ（ｎｍ）＝６０００／（Ｓ×ρ）
の式となり、ＢＥＴ平均粒径求めることができる。例えば、チタン酸バリウム（比重６．０）のＢＥＴ比表面積が５．０（ｍ2／ｇ）であれば、そのＢＥＴ平均粒径は、２００ｎｍとなる。 (Calculation method of BET average particle diameter of inorganic pigment)
The BET average particle diameter of the inorganic pigment is determined by assuming that the inorganic pigment particle is a sphere having a particle diameter R (m), the BET specific surface area S (m 2 / g) measured by the nitrogen adsorption method, and the specific gravity ρ of the inorganic pigment particle. It can be determined using (g / cm 3 ). That is, since the BET specific surface area is a surface area per unit mass, if the surface area is A (m 2 ) and the mass of the particles is W (g),
S (m 2 / g) = A (m 2 ) / W (g)
= [4 × π × (R / 2) 2 ] / [4/3 × π × (R / 2) 3 × ρ × 10 6 ]
= 6 / (R × ρ × 10 6 )
Is obtained. When the unit of particle size is converted,
R (nm) = 6000 / (S × ρ)
The BET average particle diameter can be obtained. For example, if the BET specific surface area of barium titanate (specific gravity 6.0) is 5.0 (m 2 / g), the BET average particle diameter is 200 nm.
無機顔料のＢＥＴ平均粒径は、無機顔料粒子を粒子径Ｒ（ｍ）の球と仮定して、窒素吸着法により測定されたＢＥＴ比表面積Ｓ（ｍ2／ｇ）、無機顔料粒子の比重ρ（ｇ／ｃｍ3）を用いて、求めることができる。すなわち、ＢＥＴ比表面積は単位質量当たりの表面積であるので、表面積をＡ（ｍ2）、粒子の質量をＷ（ｇ）とすると、
Ｓ（ｍ2／ｇ）＝Ａ（ｍ2）／Ｗ（ｇ）
＝［４×π×（Ｒ／２）2］／［４／３×π×（Ｒ／２）3×ρ×１０6］
＝６／（Ｒ×ρ×１０6）
の関係式が求められる。粒子径の単位を変換すると、
Ｒ（ｎｍ）＝６０００／（Ｓ×ρ）
の式となり、ＢＥＴ平均粒径求めることができる。例えば、チタン酸バリウム（比重６．０）のＢＥＴ比表面積が５．０（ｍ2／ｇ）であれば、そのＢＥＴ平均粒径は、２００ｎｍとなる。 (Calculation method of BET average particle diameter of inorganic pigment)
The BET average particle diameter of the inorganic pigment is determined by assuming that the inorganic pigment particle is a sphere having a particle diameter R (m), the BET specific surface area S (m 2 / g) measured by the nitrogen adsorption method, and the specific gravity ρ of the inorganic pigment particle. It can be determined using (g / cm 3 ). That is, since the BET specific surface area is a surface area per unit mass, if the surface area is A (m 2 ) and the mass of the particles is W (g),
S (m 2 / g) = A (m 2 ) / W (g)
= [4 × π × (R / 2) 2 ] / [4/3 × π × (R / 2) 3 × ρ × 10 6 ]
= 6 / (R × ρ × 10 6 )
Is obtained. When the unit of particle size is converted,
R (nm) = 6000 / (S × ρ)
The BET average particle diameter can be obtained. For example, if the BET specific surface area of barium titanate (specific gravity 6.0) is 5.0 (m 2 / g), the BET average particle diameter is 200 nm.
［分散方法］
本発明は、その他の態様として、分散方法であって、本発明の分散剤を用いて無機顔料を非水系溶媒中で分散させる工程を含む。上記分散工程は、例えば、塩基性無機顔料、本発明の分散剤、及び非水系溶媒を、好ましくはジルコニアビーズと共に混合することを含む。混合する無機顔料及び本発明の分散剤の量は、後述するスラリー組成物における各成分の含有量の範囲内とすることができる。本発明の分散方法によれば、無機顔料を非水系溶媒に微細に分散させることができ、後述するスラリー組成物を製造することができる。したがって、本発明は、その態様として、スラリー組成物の製造方法であって、本発明の分散剤を用いて無機顔料を非水系溶媒中で分散させる工程を含む。 [Distribution method]
Another aspect of the present invention is a dispersion method, which includes a step of dispersing an inorganic pigment in a non-aqueous solvent using the dispersant of the present invention. The dispersion step includes, for example, mixing a basic inorganic pigment, the dispersant of the present invention, and a non-aqueous solvent, preferably with zirconia beads. The amount of the inorganic pigment to be mixed and the dispersant of the present invention can be within the range of the content of each component in the slurry composition described later. According to the dispersion method of the present invention, the inorganic pigment can be finely dispersed in the non-aqueous solvent, and a slurry composition described later can be produced. Therefore, this invention is the manufacturing method of a slurry composition as the aspect, Comprising: The process of disperse | distributing an inorganic pigment in a non-aqueous solvent using the dispersing agent of this invention is included.
本発明は、その他の態様として、分散方法であって、本発明の分散剤を用いて無機顔料を非水系溶媒中で分散させる工程を含む。上記分散工程は、例えば、塩基性無機顔料、本発明の分散剤、及び非水系溶媒を、好ましくはジルコニアビーズと共に混合することを含む。混合する無機顔料及び本発明の分散剤の量は、後述するスラリー組成物における各成分の含有量の範囲内とすることができる。本発明の分散方法によれば、無機顔料を非水系溶媒に微細に分散させることができ、後述するスラリー組成物を製造することができる。したがって、本発明は、その態様として、スラリー組成物の製造方法であって、本発明の分散剤を用いて無機顔料を非水系溶媒中で分散させる工程を含む。 [Distribution method]
Another aspect of the present invention is a dispersion method, which includes a step of dispersing an inorganic pigment in a non-aqueous solvent using the dispersant of the present invention. The dispersion step includes, for example, mixing a basic inorganic pigment, the dispersant of the present invention, and a non-aqueous solvent, preferably with zirconia beads. The amount of the inorganic pigment to be mixed and the dispersant of the present invention can be within the range of the content of each component in the slurry composition described later. According to the dispersion method of the present invention, the inorganic pigment can be finely dispersed in the non-aqueous solvent, and a slurry composition described later can be produced. Therefore, this invention is the manufacturing method of a slurry composition as the aspect, Comprising: The process of disperse | distributing an inorganic pigment in a non-aqueous solvent using the dispersing agent of this invention is included.
［スラリー組成物］
本発明の分散剤を用いれば、非水系溶媒に無機顔料が分散したスラリー組成物を得ることができる。したがって、本発明は、さらにその他の態様において、スラリー組成物であって、非水系溶媒、無機顔料、及び高分子分散剤を含有し、上記高分子分散剤が、本発明の分散剤又は共重合体であるスラリー組成物を提供できる。本発明のスラリー組成物によれば、後述するとおり、無機顔料の微細な分散を好適に実現できる。 [Slurry composition]
By using the dispersant of the present invention, a slurry composition in which an inorganic pigment is dispersed in a non-aqueous solvent can be obtained. Therefore, the present invention, in still another aspect, is a slurry composition, which contains a non-aqueous solvent, an inorganic pigment, and a polymer dispersant, and the polymer dispersant is the dispersant or co-polymer of the present invention. A slurry composition that is a coalescence can be provided. According to the slurry composition of the present invention, fine dispersion of the inorganic pigment can be suitably realized as described later.
本発明の分散剤を用いれば、非水系溶媒に無機顔料が分散したスラリー組成物を得ることができる。したがって、本発明は、さらにその他の態様において、スラリー組成物であって、非水系溶媒、無機顔料、及び高分子分散剤を含有し、上記高分子分散剤が、本発明の分散剤又は共重合体であるスラリー組成物を提供できる。本発明のスラリー組成物によれば、後述するとおり、無機顔料の微細な分散を好適に実現できる。 [Slurry composition]
By using the dispersant of the present invention, a slurry composition in which an inorganic pigment is dispersed in a non-aqueous solvent can be obtained. Therefore, the present invention, in still another aspect, is a slurry composition, which contains a non-aqueous solvent, an inorganic pigment, and a polymer dispersant, and the polymer dispersant is the dispersant or co-polymer of the present invention. A slurry composition that is a coalescence can be provided. According to the slurry composition of the present invention, fine dispersion of the inorganic pigment can be suitably realized as described later.
スラリー組成物における無機顔料の含有量は、分散性向上の観点から、好ましくは５質量％以上、より好ましくは１０質量％以上であり、同様の観点から、好ましくは６０質量％以下、より好ましくは５０質量％以下である。無機顔料１００質量部に対する本発明の共重合体の含有量は、無機顔料の粒径により異なるが、例えば、ＢＥＴ平均粒径が１０～５００ｎｍの無機顔料を使用する場合、好ましくは０．１質量部以上、より好ましくは０．２質量部以上であり、同様の観点から、好ましくは１０質量部以下、より好ましくは５質量部以下である。
The content of the inorganic pigment in the slurry composition is preferably 5% by mass or more, more preferably 10% by mass or more from the viewpoint of improving dispersibility, and from the same viewpoint, preferably 60% by mass or less, more preferably It is 50 mass% or less. The content of the copolymer of the present invention with respect to 100 parts by mass of the inorganic pigment varies depending on the particle size of the inorganic pigment. For example, when using an inorganic pigment having a BET average particle size of 10 to 500 nm, preferably 0.1 mass. Part or more, more preferably 0.2 part by weight or more, and from the same viewpoint, it is preferably 10 parts by weight or less, more preferably 5 parts by weight or less.
分散液及びスラリーにおける分散性の評価は、例えば、スラリー粘度の測定、分散された無機顔料の沈降時間等を測定することでも評価できるが、スラリー中の無機顔料の粒度分布が、その無機顔料粉体の一次粒子径に近いものであればスラリー粘度は低く沈降時間も長くなるという知見から、本発明においては、スラリー中の無機顔料の粒度分布を測定することで評価できる。具体的には、実施例に記載のとおり評価できる。
Evaluation of dispersibility in the dispersion and the slurry can be performed by, for example, measuring the viscosity of the slurry and measuring the sedimentation time of the dispersed inorganic pigment, but the particle size distribution of the inorganic pigment in the slurry is determined by the inorganic pigment powder. In the present invention, it can be evaluated by measuring the particle size distribution of the inorganic pigment in the slurry, based on the knowledge that the slurry viscosity is low and the sedimentation time is long if it is close to the primary particle size of the body. Specifically, it can be evaluated as described in the examples.
［スラリー組成物におけるその他の成分］
本発明のスラリー組成物は、本発明の効果を損なわない範囲で、ポリビニルアセタール樹脂等のバインダー樹脂、帯電防止剤、可塑剤、潤滑剤、分散助剤等の低分子化合物等の添加剤を含有してもよい。 [Other components in slurry composition]
The slurry composition of the present invention contains additives such as low molecular weight compounds such as binder resins such as polyvinyl acetal resins, antistatic agents, plasticizers, lubricants, and dispersion aids, as long as the effects of the present invention are not impaired. May be.
本発明のスラリー組成物は、本発明の効果を損なわない範囲で、ポリビニルアセタール樹脂等のバインダー樹脂、帯電防止剤、可塑剤、潤滑剤、分散助剤等の低分子化合物等の添加剤を含有してもよい。 [Other components in slurry composition]
The slurry composition of the present invention contains additives such as low molecular weight compounds such as binder resins such as polyvinyl acetal resins, antistatic agents, plasticizers, lubricants, and dispersion aids, as long as the effects of the present invention are not impaired. May be.
上記バインダー樹脂としては、シート剥離性の向上及びセラミックシートの性能向上の観点から、好ましくはポリビニルアセタール樹脂であり、より好ましくはポリビニルブチラール樹脂である。前記ポリビニルアセタール樹脂のアセタール化度は、非水系溶媒への溶解性及びセラミックシートの可撓性向上の観点から、好ましくは５５モル％以上、より好ましくは６５モル％以上であり、セラミックシートの強度向上の観点から、好ましくは８０モル％以下、より好ましくは７５モル％以下である。
The binder resin is preferably a polyvinyl acetal resin, more preferably a polyvinyl butyral resin, from the viewpoint of improving sheet peelability and improving the performance of the ceramic sheet. The degree of acetalization of the polyvinyl acetal resin is preferably 55 mol% or more, more preferably 65 mol% or more, from the viewpoint of improving the solubility in a non-aqueous solvent and the flexibility of the ceramic sheet, and the strength of the ceramic sheet. From the viewpoint of improvement, it is preferably 80 mol% or less, more preferably 75 mol% or less.
本発明のスラリー組成物中におけるバインダー樹脂の、無機顔料１００質量部に対する含有量は、シート剥離性及びセラミックシートの強度向上の観点から、好ましくは２質量部以上、より好ましくは４質量部以上、更に好ましくは６質量部以上であり、シート剥離性及びセラミックシートの形成の容易性の観点から、好ましくは２０質量部以下、より好ましくは１８質量部以下、更に好ましくは１６質量部以下、更により好ましくは１１質量部以下、更により好ましくは９質量部以下である。
The content of the binder resin in the slurry composition of the present invention relative to 100 parts by mass of the inorganic pigment is preferably 2 parts by mass or more, more preferably 4 parts by mass or more, from the viewpoint of improving the sheet peelability and the strength of the ceramic sheet. More preferably, it is 6 parts by mass or more, and preferably 20 parts by mass or less, more preferably 18 parts by mass or less, still more preferably 16 parts by mass or less, and even more, from the viewpoint of sheet peelability and ease of forming the ceramic sheet. Preferably it is 11 mass parts or less, More preferably, it is 9 mass parts or less.
上記可塑剤としては、ジ（２－エチルヘキシル）フタレート、ジブチルフタレート等のフタル酸ジエステル、ジ（２－エチルヘキシル）アジペート等のアジピン酸ジエステル、トリエチレングリコールジ（２－エチルヘキシル）エステル等のアルキレングリコールジエステル等が挙げられ、低揮発性及びセラミックシートの柔軟性向上の観点から、好ましくはジ（２－エチルヘキシル）フタレートである。本発明のスラリー組成物における可塑剤の、無機顔料１００質量部に対する含有量は、シート剥離性及びセラミックシートの性能向上の観点から、好ましくは０．０５質量部以上が、より好ましくは０．１質量部以上であり、セラミックシートの強度を維持する観点から、好ましくは１５．０質量部以下、より好ましくは１０．０質量部以下である。
Examples of the plasticizer include phthalic acid diesters such as di (2-ethylhexyl) phthalate and dibutylphthalate, adipic acid diesters such as di (2-ethylhexyl) adipate, and alkylene glycol diesters such as triethylene glycol di (2-ethylhexyl) ester Of these, di (2-ethylhexyl) phthalate is preferred from the viewpoint of low volatility and improved flexibility of the ceramic sheet. The content of the plasticizer in the slurry composition of the present invention with respect to 100 parts by mass of the inorganic pigment is preferably 0.05 parts by mass or more, more preferably 0.1 parts, from the viewpoint of sheet peelability and ceramic sheet performance improvement. From the viewpoint of maintaining the strength of the ceramic sheet, it is preferably 15.0 parts by mass or less, more preferably 10.0 parts by mass or less.
上記帯電防止剤としては、剥離性向上の観点から、好ましくはカチオン性の帯電防止剤である。前記カチオン性の帯電防止剤としては、例えば、アルキルイミダゾリン、アルキルイミダゾール等の含窒素複素環を有する化合物が挙げられる。本発明のスラリー組成物における帯電防止剤の、無機顔料１００質量部に対する含有量は、シート剥離性及びセラミックシートの性能向上の観点から、好ましくは０．０５質量部以上が、より好ましくは０．１質量部以上であり、セラミックシートの強度を維持する観点から、好ましくは２．０質量部以下、より好ましくは１．５質量部以下である。
The antistatic agent is preferably a cationic antistatic agent from the viewpoint of improving peelability. Examples of the cationic antistatic agent include compounds having a nitrogen-containing heterocycle such as alkylimidazolines and alkylimidazoles. The content of the antistatic agent in the slurry composition of the present invention with respect to 100 parts by mass of the inorganic pigment is preferably 0.05 parts by mass or more, more preferably 0. From the viewpoint of maintaining the strength of the ceramic sheet, it is preferably 2.0 parts by mass or less, more preferably 1.5 parts by mass or less.
上述した実施形態に関し、本発明はさらに以下の組成物、製造方法、或いは用途を開示する。
Regarding the embodiment described above, the present invention further discloses the following composition, production method, or use.
＜１＞ 全構成単位中、式（１）で表される構成単位（ａ）を１質量％以上４５質量％以下、及び、式（２）で表される構成単位（ｂ）を５５質量％以上９９質量％以下含有する共重合体を含み、非水系溶媒中で用いる、無機顔料用高分子分散剤。
［式（１）中、Ｒ1、Ｒ2、及びＲ3は同一又は異なり、水素原子、メチル基又はエチル基を示し、Ｍは水素原子又は陽イオンを示す。］
［式（２）中、Ｒ4、Ｒ5、Ｒ6及びＲ8は同一又は異なり、水素原子、メチル基又はエチル基を示し、Ｒ7は炭素数２以上４以下の直鎖又は分岐鎖のアルキレン基を示し、Ｘ1は酸素原子又はＮＨを示し、ｎは－Ｒ7－Ｏ－基の平均付加モル数であって５０を超え１４０以下の数を示す。］
<1> In all the structural units, the structural unit (a) represented by the formula (1) is 1% by mass or more and 45% by mass or less, and the structural unit (b) represented by the formula (2) is 55% by mass. A polymer dispersant for an inorganic pigment, comprising a copolymer containing 99% by mass or less and used in a non-aqueous solvent.
[In the formula (1), R 1 , R 2 and R 3 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group, and M represents a hydrogen atom or a cation. ]
[In the formula (2), R 4 , R 5 , R 6 and R 8 are the same or different and each represents a hydrogen atom, a methyl group or an ethyl group, and R 7 is a straight or branched chain having 2 to 4 carbon atoms. Represents an alkylene group, X 1 represents an oxygen atom or NH, and n represents an average added mole number of the —R 7 —O— group, which is greater than 50 and equal to or less than 140. ]
＜２＞ 式（１）のＲ1及びＲ2が、好ましくは水素原子又はメチル基、より好ましくは水素原子である、＜１＞に記載の無機顔料用高分子分散剤。
＜３＞ 式（１）のＲ3が、好ましくは水素原子又はメチル基、より好ましくはメチル基である、＜１＞又は＜２＞に記載の無機顔料用高分子分散剤。
＜４＞ 式（１）のＭが、好ましくはアンモニウム、有機アンモニウム、又は水素原子、より好ましくは水素原子である、＜１＞から＜３＞のいずれかに記載の無機顔料用高分子分散剤。
＜５＞ 共重合体を構成する全構成単位中の構成単位（ａ）の割合が、１質量％以上、好ましくは３質量％以上、より好ましくは５質量％以上、更に好ましくは８質量％以上、更に好ましくは１２質量％以上である、＜１＞から＜４＞のいずれかに記載の無機顔料用高分子分散剤。
＜６＞ 共重合体を構成する全構成単位中の構成単位（ａ）の割合が、４５質量％以下、好ましくは３５質量％以下、より好ましくは２４質量%以下、更に好ましくは１８質量％以下である、＜１＞から＜５＞のいずれかに記載の無機顔料用高分子分散剤。
＜７＞ 構成単位（ａ）が、好ましくはアクリル酸及びメタクリル酸からなる群より選ばれる１種以上に由来する構成単位である、＜１＞から＜６＞のいずれかに記載の無機顔料用高分子分散剤。
＜８＞ 式（２）のＲ4及びＲ5が、好ましくは水素原子又はメチル基、より好ましくは水素原子である、＜１＞から＜７＞のいずれかに記載の無機顔料用高分子分散剤。
＜９＞ 式（２）のＲ6が、好ましくは水素原子又はメチル基、より好ましくはメチル基である、＜１＞から＜８＞のいずれかに記載の無機顔料用高分子分散剤。
＜１０＞ 式（２）のＲ7が、好ましくはエチレン基又はプロピレン基、より好ましくはエチレン基である、＜１＞から＜９＞のいずれかに記載の無機顔料用高分子分散剤。
＜１１＞ 式（２）のＲ8が、好ましくはメチル基又はエチル基、より好ましくはメチル基である、＜１＞から＜１０＞のいずれかに記載の無機顔料用高分子分散剤。
＜１２＞ 式（２）のＸ1が、好ましくは酸素原子である、＜１＞から＜１１＞のいずれかに記載の無機顔料用高分子分散剤。
＜１３＞ 式（２）のｎが、５０を超え、好ましくは５１以上、より好ましくは５８以上、更に好ましくは７２以上、更により好ましくは８８以上、更により好ましくは１１０以上である、＜１＞から＜１２＞のいずれかに記載の無機顔料用高分子分散剤。
＜１４＞ 式（２）のｎが、１４０以下、好ましくは１３０以下である、＜１＞から＜１３＞のいずれかに記載の無機顔料用高分子分散剤。
＜１５＞ 共重合体を構成する全構成単位中の構成単位（ｂ）の割合が、５５質量％以上、好ましくは６０質量％以上、より好ましくは６５質量％以上である、＜１＞から＜１４＞のいずれかに記載の無機顔料用高分子分散剤。
＜１６＞ 共重合体を構成する全構成単位中の構成単位（ｂ）の割合が、９９質量％以下、好ましくは９５質量％以下、より好ましくは８７質量％以下、更に好ましくは８０質量％以下、更により好ましくは７５質量％以下である、＜１＞から＜１５＞のいずれかに記載の無機顔料用高分子分散剤。
＜１７＞ 共重合体を構成する構成単位（ａ）の構成単位（ｂ）に対する質量比（構成単位（ａ）／構成単位（ｂ））が、好ましくは０．０５以上、より好ましくは０．１２以上、更に好ましくは０．１６以上、更により好ましくは０．１９以上であり、好ましくは０．５０以下、より好ましくは０．３５以下、更に好ましくは０．２８以下、更により好ましくは０．２４以下である、＜１＞から＜１６＞のいずれかに記載の無機顔料用高分子分散剤。
＜１８＞ さらに、好ましくは式（３）で表される構成単位（ｃ）を含有する、＜１＞から＜１７＞のいずれかに記載の無機顔料用高分子分散剤。
［式（３）中、Ｒ9、Ｒ10、及びＲ11は同一又は異なり、水素原子、メチル基又はエチル基を示し、Ｘ3は酸素原子又はＮＨを示し、Ｒ12及びＲ13は炭素数１以上３０以下の炭化水素基を示す。］
＜１９＞ 構成単位（ｂ）に対する構成単位（ｃ）の質量比（（ｃ）／（ｂ））が、好ましくは０．０５以上０．７０以下である、＜１８＞に記載の無機顔料用高分子分散剤。
＜２０＞ 式（３）のＲ9及びＲ10が、好ましくは水素原子又はメチル基、より好ましくは水素原子である、＜１８＞又は＜１９＞に記載の無機顔料用高分子分散剤。
＜２１＞ 式（３）のＲ11が、好ましくは水素原子又はメチル基である、＜１８＞から＜２０＞のいずれかに記載の無機顔料用高分子分散剤。
＜２２＞ 式（３）のＸ3が、好ましくは酸素原子である、＜１８＞から＜２１＞のいずれかに記載の無機顔料用高分子分散剤。
＜２３＞ 式（３）のＲ12が、好ましくはアルキル基又はアルケニル基である、＜１８＞から＜２２＞のいずれかに記載の無機顔料用高分子分散剤。
＜２４＞ 式（３）のＲ12の炭素数が、１以上であり、好ましくは２２以下、より好ましくは１８以下である、＜１８＞から＜２３＞のいずれかに記載の無機顔料用高分子分散剤。
＜２５＞ 式（３）のＲ12が、好ましくはメチル基、エチル基、ブチル基、オクチル基、２－エチルヘキシル基、デシル基、ラウリル基、ミリスチル基、セチル基、ステアリル基、オレイル基、又はベヘニル基である、＜１８＞から＜２４＞のいずれかに記載の無機顔料用高分子分散剤。
＜２６＞ 式（３）のＲ13が、好ましくはフェニル基又は炭素数１以上２２以下のアルキル基である、＜１８＞から＜２５＞のいずれかに記載の無機顔料用高分子分散剤。
＜２７＞ 共重合体を構成する全構成単位中の構成単位（ｃ）の割合が、好ましくは０質量％以上、より好ましくは３質量％以上、より好ましくは８質量％以上、更に好ましくは１２質量％以上である、＜１８＞から＜２６＞のいずれかに記載の無機顔料用高分子分散剤。
＜２８＞ 共重合体を構成する全構成単位中の構成単位（ｃ）の割合が、好ましくは３５質量％以下、より好ましくは２５質量％以下、更に好ましくは１８質量％以下である、＜１８＞から＜２７＞のいずれかに記載の無機顔料用高分子分散剤。
＜２９＞ 共重合体における構成単位（ｃ）の構成単位（ｂ）に対する質量比（構成単位（ｃ）／構成単位（ｂ））が、好ましくは０．０５以上、より好ましくは０．０６以上、更に好ましくは０．１０以上、更により好ましくは０．１８以上である、＜１８＞から＜２８＞のいずれかに記載の無機顔料用高分子分散剤。
＜３０＞ 共重合体における構成単位（ｃ）の構成単位（ｂ）に対する質量比（構成単位（ｃ）／構成単位（ｂ））が、好ましくは０．７０以下、より好ましくは０．６０以下、更に好ましくは０．５０以下、更により好ましくは０．２５以下である、＜１８＞から＜２９＞のいずれかに記載の無機顔料用高分子分散剤。
＜３１＞ 構成単位（ｃ）が、好ましくはアルキル（メタ）アクリレート由来の構成単位、より好ましくはメチルメタクリレート、ステアリルメタクリレート及びステアリルアクリレートからなる群より選ばれる１種以上に由来する構成単位、更に好ましくはメチルメタクリレートに由来する構成単位である、＜１８＞から＜３０＞のいずれかに記載の無機顔料用高分子分散剤。
＜３２＞ 共重合体の重量平均分子量が、好ましくは１０００以上、より好ましくは２０００以上、更に好ましくは４０００以上である、＜１＞から＜３１＞のいずれかに記載の無機顔料用高分子分散剤。
＜３３＞ 共重合体の重量平均分子量が、好ましくは１０００００以下、より好ましくは５００００以下、更に好ましくは３００００以下、更により好ましくは１５０００以下である、＜１＞から＜３２＞のいずれかに記載の無機顔料用高分子分散剤。
＜３４＞ ＜１＞から＜３３＞のいずれかに記載の無機顔料用高分子分散剤を用いて、塩基性無機顔料を分散する方法。
＜３５＞ 非水系溶媒、塩基性無機顔料、及び＜１＞から＜３３＞のいずれかに記載の無機顔料用高分子分散剤を含有する、スラリー組成物。
＜３６＞ 塩基性無機顔料が、好ましくは酸化マグネシウム、炭酸バリウム、酸化チタン、チタン酸カルシウム、チタン酸バリウム、ジルコン酸バリウム及びジルコン酸カルシウムからなる群から選択される１種以上の顔料、より好ましくはチタン酸バリウムである、＜３５＞に記載のスラリー組成物。
＜３７＞ スラリー組成物における無機顔料の含有量が、好ましくは５質量％以上、より好ましくは１０質量％以上であり、好ましくは６０質量％以下、より好ましくは５０質量％以下である、＜３５＞又は＜３６＞に記載のスラリー組成物。
＜３８＞ 無機顔料１００質量部に対する＜１＞から＜３３＞のいずれかに記載の共重合体の含有量が、ＢＥＴ平均粒径が１０～５００ｎｍの無機顔料を使用する場合、好ましくは０．１質量部以上、より好ましくは０．２質量部以上であり、好ましくは１０質量部以下、より好ましくは５質量部以下である、＜３５＞から＜３７＞のいずれかに記載のスラリー組成物。
＜３９＞ 好ましくは、さらに、ポリビニルアセタール樹脂、より好ましくは、ポリビニルブチラール樹脂を含有する、＜３５＞から＜３８＞のいずれかに記載のスラリー組成物。
＜４０＞ 無機顔料を非水系溶媒に分散するための、＜３５＞から＜３９＞のいずれかに記載のスラリー組成物。
＜４１＞ セラミックシートの製造における、＜１＞から＜３３＞のいずれかに記載の無機顔料用高分子分散剤の使用。
＜４２＞ セラミックシートの製造における、＜３５＞から＜３９＞のいずれかに記載のスラリー組成物の使用。 <2> The polymer dispersant for inorganic pigments according to <1>, wherein R 1 and R 2 in formula (1) are preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
<3> The polymer dispersant for inorganic pigments according to <1> or <2>, wherein R 3 in formula (1) is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
<4> The polymer dispersant for inorganic pigments according to any one of <1> to <3>, wherein M in formula (1) is preferably an ammonium, organic ammonium, or hydrogen atom, more preferably a hydrogen atom. .
<5> The proportion of the structural unit (a) in all the structural units constituting the copolymer is 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 8% by mass or more. More preferably, the polymer dispersant for inorganic pigments according to any one of <1> to <4>, which is 12% by mass or more.
<6> The proportion of the structural unit (a) in all the structural units constituting the copolymer is 45% by mass or less, preferably 35% by mass or less, more preferably 24% by mass or less, and still more preferably 18% by mass or less. The polymer dispersant for inorganic pigments according to any one of <1> to <5>, wherein
<7> The inorganic pigment according to any one of <1> to <6>, wherein the structural unit (a) is preferably a structural unit derived from one or more selected from the group consisting of acrylic acid and methacrylic acid. Polymer dispersant.
<8> The polymer dispersion for an inorganic pigment according to any one of <1> to <7>, wherein R 4 and R 5 in formula (2) are preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. Agent.
<9> The polymer dispersant for inorganic pigments according to any one of <1> to <8>, wherein R 6 in formula (2) is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
<10> The polymer dispersant for inorganic pigments according to any one of <1> to <9>, wherein R 7 in formula (2) is preferably an ethylene group or a propylene group, more preferably an ethylene group.
<11> The polymer dispersant for inorganic pigments according to any one of <1> to <10>, wherein R 8 in formula (2) is preferably a methyl group or an ethyl group, more preferably a methyl group.
<12> The polymer dispersant for inorganic pigments according to any one of <1> to <11>, wherein X 1 in formula (2) is preferably an oxygen atom.
<13> n in the formula (2) exceeds 50, preferably 51 or more, more preferably 58 or more, still more preferably 72 or more, still more preferably 88 or more, and even more preferably 110 or more, <1 > To <12> The polymer dispersant for inorganic pigments according to any one of the above.
<14> The polymer dispersant for inorganic pigments according to any one of <1> to <13>, wherein n in formula (2) is 140 or less, preferably 130 or less.
<15> The proportion of the structural unit (b) in all the structural units constituting the copolymer is 55% by mass or more, preferably 60% by mass or more, more preferably 65% by mass or more, from <1> to <14> The polymer dispersant for inorganic pigments according to any one of 14>.
<16> The proportion of the structural unit (b) in all the structural units constituting the copolymer is 99% by mass or less, preferably 95% by mass or less, more preferably 87% by mass or less, and still more preferably 80% by mass or less. The polymer dispersant for inorganic pigments according to any one of <1> to <15>, further preferably 75% by mass or less.
<17> The mass ratio of the structural unit (a) constituting the copolymer to the structural unit (b) (structural unit (a) / structural unit (b)) is preferably 0.05 or more, more preferably 0.8. 12 or more, more preferably 0.16 or more, still more preferably 0.19 or more, preferably 0.50 or less, more preferably 0.35 or less, still more preferably 0.28 or less, and even more preferably 0. The polymer dispersant for inorganic pigments according to any one of <1> to <16>, which is 24 or less.
<18> Furthermore, the polymer dispersant for inorganic pigments according to any one of <1> to <17>, preferably containing the structural unit (c) represented by the formula (3).
[In the formula (3), R 9 , R 10 and R 11 are the same or different and each represents a hydrogen atom, a methyl group or an ethyl group, X 3 represents an oxygen atom or NH, and R 12 and R 13 represent the number of carbon atoms. 1 or more and 30 or less hydrocarbon group is shown. ]
<19> The inorganic pigment according to <18>, wherein the mass ratio ((c) / (b)) of the structural unit (c) to the structural unit (b) is preferably 0.05 or more and 0.70 or less. Polymer dispersant.
<20> The polymer dispersant for inorganic pigments according to <18> or <19>, wherein R 9 and R 10 in formula (3) are preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
<21> The polymer dispersant for inorganic pigments according to any one of <18> to <20>, wherein R 11 in formula (3) is preferably a hydrogen atom or a methyl group.
<22> The polymer dispersant for inorganic pigments according to any one of <18> to <21>, wherein X 3 in formula (3) is preferably an oxygen atom.
<23> The polymer dispersant for inorganic pigments according to any one of <18> to <22>, wherein R 12 in formula (3) is preferably an alkyl group or an alkenyl group.
<24> The number of carbon atoms of R 12 in the formula (3) is 1 or more, preferably 22 or less, more preferably 18 or less, the high for inorganic pigments according to any one of <18> to <23> Molecular dispersant.
<25> R 12 in the formula (3) is preferably a methyl group, an ethyl group, a butyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a lauryl group, a myristyl group, a cetyl group, a stearyl group, an oleyl group, or The polymer dispersant for inorganic pigments according to any one of <18> to <24>, which is a behenyl group.
R 13 of <26> formula (3) is preferably an alkyl group having a phenyl group or having 1 to 22 carbon atoms, an inorganic pigment for polymeric dispersing agent according to any one of <25> to <18>.
<27> The proportion of the structural unit (c) in all the structural units constituting the copolymer is preferably 0% by mass or more, more preferably 3% by mass or more, more preferably 8% by mass or more, and still more preferably 12%. The polymer dispersant for inorganic pigments according to any one of <18> to <26>, which is at least% by mass.
<28> The proportion of the structural unit (c) in all the structural units constituting the copolymer is preferably 35% by mass or less, more preferably 25% by mass or less, and still more preferably 18% by mass or less. > To <27> The polymer dispersant for inorganic pigments according to any one of the above.
<29> The mass ratio of the structural unit (c) to the structural unit (b) in the copolymer (structural unit (c) / structural unit (b)) is preferably 0.05 or more, more preferably 0.06 or more. The polymer dispersant for inorganic pigments according to any one of <18> to <28>, more preferably 0.10 or more, and still more preferably 0.18 or more.
<30> The mass ratio of the structural unit (c) to the structural unit (b) in the copolymer (structural unit (c) / structural unit (b)) is preferably 0.70 or less, more preferably 0.60 or less. The polymer dispersant for inorganic pigments according to any one of <18> to <29>, more preferably 0.50 or less, and still more preferably 0.25 or less.
<31> The structural unit (c) is preferably a structural unit derived from alkyl (meth) acrylate, more preferably a structural unit derived from one or more selected from the group consisting of methyl methacrylate, stearyl methacrylate and stearyl acrylate, and more preferably. Is a structural unit derived from methyl methacrylate, The polymer dispersant for inorganic pigments according to any one of <18> to <30>.
<32> The polymer dispersion for an inorganic pigment according to any one of <1> to <31>, wherein the weight average molecular weight of the copolymer is preferably 1000 or more, more preferably 2000 or more, and still more preferably 4000 or more. Agent.
<33> The copolymer according to any one of <1> to <32>, wherein the copolymer has a weight average molecular weight of preferably 100,000 or less, more preferably 50000 or less, still more preferably 30000 or less, and even more preferably 15000 or less. Polymer dispersant for inorganic pigments.
<34> A method of dispersing a basic inorganic pigment using the polymer dispersant for inorganic pigments according to any one of <1> to <33>.
<35> A slurry composition containing a non-aqueous solvent, a basic inorganic pigment, and the polymer dispersant for inorganic pigments according to any one of <1> to <33>.
<36> The basic inorganic pigment is preferably one or more pigments selected from the group consisting of magnesium oxide, barium carbonate, titanium oxide, calcium titanate, barium titanate, barium zirconate and calcium zirconate, more preferably The slurry composition according to <35>, wherein is a barium titanate.
<37> The content of the inorganic pigment in the slurry composition is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 60% by mass or less, more preferably 50% by mass or less, <35 > Or <36>.
<38> When an inorganic pigment having a BET average particle size of 10 to 500 nm is used as the content of the copolymer according to any one of <1> to <33> with respect to 100 parts by mass of the inorganic pigment, preferably 0.8. The slurry composition according to any one of <35> to <37>, which is 1 part by mass or more, more preferably 0.2 part by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less. .
<39> Preferably, the slurry composition according to any one of <35> to <38>, further comprising a polyvinyl acetal resin, more preferably a polyvinyl butyral resin.
<40> The slurry composition according to any one of <35> to <39>, for dispersing the inorganic pigment in a non-aqueous solvent.
<41> Use of the polymer dispersant for inorganic pigments according to any one of <1> to <33> in the production of a ceramic sheet.
<42> Use of the slurry composition according to any one of <35> to <39> in the production of a ceramic sheet.
＜３＞ 式（１）のＲ3が、好ましくは水素原子又はメチル基、より好ましくはメチル基である、＜１＞又は＜２＞に記載の無機顔料用高分子分散剤。
＜４＞ 式（１）のＭが、好ましくはアンモニウム、有機アンモニウム、又は水素原子、より好ましくは水素原子である、＜１＞から＜３＞のいずれかに記載の無機顔料用高分子分散剤。
＜５＞ 共重合体を構成する全構成単位中の構成単位（ａ）の割合が、１質量％以上、好ましくは３質量％以上、より好ましくは５質量％以上、更に好ましくは８質量％以上、更に好ましくは１２質量％以上である、＜１＞から＜４＞のいずれかに記載の無機顔料用高分子分散剤。
＜６＞ 共重合体を構成する全構成単位中の構成単位（ａ）の割合が、４５質量％以下、好ましくは３５質量％以下、より好ましくは２４質量%以下、更に好ましくは１８質量％以下である、＜１＞から＜５＞のいずれかに記載の無機顔料用高分子分散剤。
＜７＞ 構成単位（ａ）が、好ましくはアクリル酸及びメタクリル酸からなる群より選ばれる１種以上に由来する構成単位である、＜１＞から＜６＞のいずれかに記載の無機顔料用高分子分散剤。
＜８＞ 式（２）のＲ4及びＲ5が、好ましくは水素原子又はメチル基、より好ましくは水素原子である、＜１＞から＜７＞のいずれかに記載の無機顔料用高分子分散剤。
＜９＞ 式（２）のＲ6が、好ましくは水素原子又はメチル基、より好ましくはメチル基である、＜１＞から＜８＞のいずれかに記載の無機顔料用高分子分散剤。
＜１０＞ 式（２）のＲ7が、好ましくはエチレン基又はプロピレン基、より好ましくはエチレン基である、＜１＞から＜９＞のいずれかに記載の無機顔料用高分子分散剤。
＜１１＞ 式（２）のＲ8が、好ましくはメチル基又はエチル基、より好ましくはメチル基である、＜１＞から＜１０＞のいずれかに記載の無機顔料用高分子分散剤。
＜１２＞ 式（２）のＸ1が、好ましくは酸素原子である、＜１＞から＜１１＞のいずれかに記載の無機顔料用高分子分散剤。
＜１３＞ 式（２）のｎが、５０を超え、好ましくは５１以上、より好ましくは５８以上、更に好ましくは７２以上、更により好ましくは８８以上、更により好ましくは１１０以上である、＜１＞から＜１２＞のいずれかに記載の無機顔料用高分子分散剤。
＜１４＞ 式（２）のｎが、１４０以下、好ましくは１３０以下である、＜１＞から＜１３＞のいずれかに記載の無機顔料用高分子分散剤。
＜１５＞ 共重合体を構成する全構成単位中の構成単位（ｂ）の割合が、５５質量％以上、好ましくは６０質量％以上、より好ましくは６５質量％以上である、＜１＞から＜１４＞のいずれかに記載の無機顔料用高分子分散剤。
＜１６＞ 共重合体を構成する全構成単位中の構成単位（ｂ）の割合が、９９質量％以下、好ましくは９５質量％以下、より好ましくは８７質量％以下、更に好ましくは８０質量％以下、更により好ましくは７５質量％以下である、＜１＞から＜１５＞のいずれかに記載の無機顔料用高分子分散剤。
＜１７＞ 共重合体を構成する構成単位（ａ）の構成単位（ｂ）に対する質量比（構成単位（ａ）／構成単位（ｂ））が、好ましくは０．０５以上、より好ましくは０．１２以上、更に好ましくは０．１６以上、更により好ましくは０．１９以上であり、好ましくは０．５０以下、より好ましくは０．３５以下、更に好ましくは０．２８以下、更により好ましくは０．２４以下である、＜１＞から＜１６＞のいずれかに記載の無機顔料用高分子分散剤。
＜１８＞ さらに、好ましくは式（３）で表される構成単位（ｃ）を含有する、＜１＞から＜１７＞のいずれかに記載の無機顔料用高分子分散剤。
＜１９＞ 構成単位（ｂ）に対する構成単位（ｃ）の質量比（（ｃ）／（ｂ））が、好ましくは０．０５以上０．７０以下である、＜１８＞に記載の無機顔料用高分子分散剤。
＜２０＞ 式（３）のＲ9及びＲ10が、好ましくは水素原子又はメチル基、より好ましくは水素原子である、＜１８＞又は＜１９＞に記載の無機顔料用高分子分散剤。
＜２１＞ 式（３）のＲ11が、好ましくは水素原子又はメチル基である、＜１８＞から＜２０＞のいずれかに記載の無機顔料用高分子分散剤。
＜２２＞ 式（３）のＸ3が、好ましくは酸素原子である、＜１８＞から＜２１＞のいずれかに記載の無機顔料用高分子分散剤。
＜２３＞ 式（３）のＲ12が、好ましくはアルキル基又はアルケニル基である、＜１８＞から＜２２＞のいずれかに記載の無機顔料用高分子分散剤。
＜２４＞ 式（３）のＲ12の炭素数が、１以上であり、好ましくは２２以下、より好ましくは１８以下である、＜１８＞から＜２３＞のいずれかに記載の無機顔料用高分子分散剤。
＜２５＞ 式（３）のＲ12が、好ましくはメチル基、エチル基、ブチル基、オクチル基、２－エチルヘキシル基、デシル基、ラウリル基、ミリスチル基、セチル基、ステアリル基、オレイル基、又はベヘニル基である、＜１８＞から＜２４＞のいずれかに記載の無機顔料用高分子分散剤。
＜２６＞ 式（３）のＲ13が、好ましくはフェニル基又は炭素数１以上２２以下のアルキル基である、＜１８＞から＜２５＞のいずれかに記載の無機顔料用高分子分散剤。
＜２７＞ 共重合体を構成する全構成単位中の構成単位（ｃ）の割合が、好ましくは０質量％以上、より好ましくは３質量％以上、より好ましくは８質量％以上、更に好ましくは１２質量％以上である、＜１８＞から＜２６＞のいずれかに記載の無機顔料用高分子分散剤。
＜２８＞ 共重合体を構成する全構成単位中の構成単位（ｃ）の割合が、好ましくは３５質量％以下、より好ましくは２５質量％以下、更に好ましくは１８質量％以下である、＜１８＞から＜２７＞のいずれかに記載の無機顔料用高分子分散剤。
＜２９＞ 共重合体における構成単位（ｃ）の構成単位（ｂ）に対する質量比（構成単位（ｃ）／構成単位（ｂ））が、好ましくは０．０５以上、より好ましくは０．０６以上、更に好ましくは０．１０以上、更により好ましくは０．１８以上である、＜１８＞から＜２８＞のいずれかに記載の無機顔料用高分子分散剤。
＜３０＞ 共重合体における構成単位（ｃ）の構成単位（ｂ）に対する質量比（構成単位（ｃ）／構成単位（ｂ））が、好ましくは０．７０以下、より好ましくは０．６０以下、更に好ましくは０．５０以下、更により好ましくは０．２５以下である、＜１８＞から＜２９＞のいずれかに記載の無機顔料用高分子分散剤。
＜３１＞ 構成単位（ｃ）が、好ましくはアルキル（メタ）アクリレート由来の構成単位、より好ましくはメチルメタクリレート、ステアリルメタクリレート及びステアリルアクリレートからなる群より選ばれる１種以上に由来する構成単位、更に好ましくはメチルメタクリレートに由来する構成単位である、＜１８＞から＜３０＞のいずれかに記載の無機顔料用高分子分散剤。
＜３２＞ 共重合体の重量平均分子量が、好ましくは１０００以上、より好ましくは２０００以上、更に好ましくは４０００以上である、＜１＞から＜３１＞のいずれかに記載の無機顔料用高分子分散剤。
＜３３＞ 共重合体の重量平均分子量が、好ましくは１０００００以下、より好ましくは５００００以下、更に好ましくは３００００以下、更により好ましくは１５０００以下である、＜１＞から＜３２＞のいずれかに記載の無機顔料用高分子分散剤。
＜３４＞ ＜１＞から＜３３＞のいずれかに記載の無機顔料用高分子分散剤を用いて、塩基性無機顔料を分散する方法。
＜３５＞ 非水系溶媒、塩基性無機顔料、及び＜１＞から＜３３＞のいずれかに記載の無機顔料用高分子分散剤を含有する、スラリー組成物。
＜３６＞ 塩基性無機顔料が、好ましくは酸化マグネシウム、炭酸バリウム、酸化チタン、チタン酸カルシウム、チタン酸バリウム、ジルコン酸バリウム及びジルコン酸カルシウムからなる群から選択される１種以上の顔料、より好ましくはチタン酸バリウムである、＜３５＞に記載のスラリー組成物。
＜３７＞ スラリー組成物における無機顔料の含有量が、好ましくは５質量％以上、より好ましくは１０質量％以上であり、好ましくは６０質量％以下、より好ましくは５０質量％以下である、＜３５＞又は＜３６＞に記載のスラリー組成物。
＜３８＞ 無機顔料１００質量部に対する＜１＞から＜３３＞のいずれかに記載の共重合体の含有量が、ＢＥＴ平均粒径が１０～５００ｎｍの無機顔料を使用する場合、好ましくは０．１質量部以上、より好ましくは０．２質量部以上であり、好ましくは１０質量部以下、より好ましくは５質量部以下である、＜３５＞から＜３７＞のいずれかに記載のスラリー組成物。
＜３９＞ 好ましくは、さらに、ポリビニルアセタール樹脂、より好ましくは、ポリビニルブチラール樹脂を含有する、＜３５＞から＜３８＞のいずれかに記載のスラリー組成物。
＜４０＞ 無機顔料を非水系溶媒に分散するための、＜３５＞から＜３９＞のいずれかに記載のスラリー組成物。
＜４１＞ セラミックシートの製造における、＜１＞から＜３３＞のいずれかに記載の無機顔料用高分子分散剤の使用。
＜４２＞ セラミックシートの製造における、＜３５＞から＜３９＞のいずれかに記載のスラリー組成物の使用。 <2> The polymer dispersant for inorganic pigments according to <1>, wherein R 1 and R 2 in formula (1) are preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
<3> The polymer dispersant for inorganic pigments according to <1> or <2>, wherein R 3 in formula (1) is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
<4> The polymer dispersant for inorganic pigments according to any one of <1> to <3>, wherein M in formula (1) is preferably an ammonium, organic ammonium, or hydrogen atom, more preferably a hydrogen atom. .
<5> The proportion of the structural unit (a) in all the structural units constituting the copolymer is 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 8% by mass or more. More preferably, the polymer dispersant for inorganic pigments according to any one of <1> to <4>, which is 12% by mass or more.
<6> The proportion of the structural unit (a) in all the structural units constituting the copolymer is 45% by mass or less, preferably 35% by mass or less, more preferably 24% by mass or less, and still more preferably 18% by mass or less. The polymer dispersant for inorganic pigments according to any one of <1> to <5>, wherein
<7> The inorganic pigment according to any one of <1> to <6>, wherein the structural unit (a) is preferably a structural unit derived from one or more selected from the group consisting of acrylic acid and methacrylic acid. Polymer dispersant.
<8> The polymer dispersion for an inorganic pigment according to any one of <1> to <7>, wherein R 4 and R 5 in formula (2) are preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. Agent.
<9> The polymer dispersant for inorganic pigments according to any one of <1> to <8>, wherein R 6 in formula (2) is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
<10> The polymer dispersant for inorganic pigments according to any one of <1> to <9>, wherein R 7 in formula (2) is preferably an ethylene group or a propylene group, more preferably an ethylene group.
<11> The polymer dispersant for inorganic pigments according to any one of <1> to <10>, wherein R 8 in formula (2) is preferably a methyl group or an ethyl group, more preferably a methyl group.
<12> The polymer dispersant for inorganic pigments according to any one of <1> to <11>, wherein X 1 in formula (2) is preferably an oxygen atom.
<13> n in the formula (2) exceeds 50, preferably 51 or more, more preferably 58 or more, still more preferably 72 or more, still more preferably 88 or more, and even more preferably 110 or more, <1 > To <12> The polymer dispersant for inorganic pigments according to any one of the above.
<14> The polymer dispersant for inorganic pigments according to any one of <1> to <13>, wherein n in formula (2) is 140 or less, preferably 130 or less.
<15> The proportion of the structural unit (b) in all the structural units constituting the copolymer is 55% by mass or more, preferably 60% by mass or more, more preferably 65% by mass or more, from <1> to <14> The polymer dispersant for inorganic pigments according to any one of 14>.
<16> The proportion of the structural unit (b) in all the structural units constituting the copolymer is 99% by mass or less, preferably 95% by mass or less, more preferably 87% by mass or less, and still more preferably 80% by mass or less. The polymer dispersant for inorganic pigments according to any one of <1> to <15>, further preferably 75% by mass or less.
<17> The mass ratio of the structural unit (a) constituting the copolymer to the structural unit (b) (structural unit (a) / structural unit (b)) is preferably 0.05 or more, more preferably 0.8. 12 or more, more preferably 0.16 or more, still more preferably 0.19 or more, preferably 0.50 or less, more preferably 0.35 or less, still more preferably 0.28 or less, and even more preferably 0. The polymer dispersant for inorganic pigments according to any one of <1> to <16>, which is 24 or less.
<18> Furthermore, the polymer dispersant for inorganic pigments according to any one of <1> to <17>, preferably containing the structural unit (c) represented by the formula (3).
<19> The inorganic pigment according to <18>, wherein the mass ratio ((c) / (b)) of the structural unit (c) to the structural unit (b) is preferably 0.05 or more and 0.70 or less. Polymer dispersant.
<20> The polymer dispersant for inorganic pigments according to <18> or <19>, wherein R 9 and R 10 in formula (3) are preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
<21> The polymer dispersant for inorganic pigments according to any one of <18> to <20>, wherein R 11 in formula (3) is preferably a hydrogen atom or a methyl group.
<22> The polymer dispersant for inorganic pigments according to any one of <18> to <21>, wherein X 3 in formula (3) is preferably an oxygen atom.
<23> The polymer dispersant for inorganic pigments according to any one of <18> to <22>, wherein R 12 in formula (3) is preferably an alkyl group or an alkenyl group.
<24> The number of carbon atoms of R 12 in the formula (3) is 1 or more, preferably 22 or less, more preferably 18 or less, the high for inorganic pigments according to any one of <18> to <23> Molecular dispersant.
<25> R 12 in the formula (3) is preferably a methyl group, an ethyl group, a butyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a lauryl group, a myristyl group, a cetyl group, a stearyl group, an oleyl group, or The polymer dispersant for inorganic pigments according to any one of <18> to <24>, which is a behenyl group.
R 13 of <26> formula (3) is preferably an alkyl group having a phenyl group or having 1 to 22 carbon atoms, an inorganic pigment for polymeric dispersing agent according to any one of <25> to <18>.
<27> The proportion of the structural unit (c) in all the structural units constituting the copolymer is preferably 0% by mass or more, more preferably 3% by mass or more, more preferably 8% by mass or more, and still more preferably 12%. The polymer dispersant for inorganic pigments according to any one of <18> to <26>, which is at least% by mass.
<28> The proportion of the structural unit (c) in all the structural units constituting the copolymer is preferably 35% by mass or less, more preferably 25% by mass or less, and still more preferably 18% by mass or less. > To <27> The polymer dispersant for inorganic pigments according to any one of the above.
<29> The mass ratio of the structural unit (c) to the structural unit (b) in the copolymer (structural unit (c) / structural unit (b)) is preferably 0.05 or more, more preferably 0.06 or more. The polymer dispersant for inorganic pigments according to any one of <18> to <28>, more preferably 0.10 or more, and still more preferably 0.18 or more.
<30> The mass ratio of the structural unit (c) to the structural unit (b) in the copolymer (structural unit (c) / structural unit (b)) is preferably 0.70 or less, more preferably 0.60 or less. The polymer dispersant for inorganic pigments according to any one of <18> to <29>, more preferably 0.50 or less, and still more preferably 0.25 or less.
<31> The structural unit (c) is preferably a structural unit derived from alkyl (meth) acrylate, more preferably a structural unit derived from one or more selected from the group consisting of methyl methacrylate, stearyl methacrylate and stearyl acrylate, and more preferably. Is a structural unit derived from methyl methacrylate, The polymer dispersant for inorganic pigments according to any one of <18> to <30>.
<32> The polymer dispersion for an inorganic pigment according to any one of <1> to <31>, wherein the weight average molecular weight of the copolymer is preferably 1000 or more, more preferably 2000 or more, and still more preferably 4000 or more. Agent.
<33> The copolymer according to any one of <1> to <32>, wherein the copolymer has a weight average molecular weight of preferably 100,000 or less, more preferably 50000 or less, still more preferably 30000 or less, and even more preferably 15000 or less. Polymer dispersant for inorganic pigments.
<34> A method of dispersing a basic inorganic pigment using the polymer dispersant for inorganic pigments according to any one of <1> to <33>.
<35> A slurry composition containing a non-aqueous solvent, a basic inorganic pigment, and the polymer dispersant for inorganic pigments according to any one of <1> to <33>.
<36> The basic inorganic pigment is preferably one or more pigments selected from the group consisting of magnesium oxide, barium carbonate, titanium oxide, calcium titanate, barium titanate, barium zirconate and calcium zirconate, more preferably The slurry composition according to <35>, wherein is a barium titanate.
<37> The content of the inorganic pigment in the slurry composition is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 60% by mass or less, more preferably 50% by mass or less, <35 > Or <36>.
<38> When an inorganic pigment having a BET average particle size of 10 to 500 nm is used as the content of the copolymer according to any one of <1> to <33> with respect to 100 parts by mass of the inorganic pigment, preferably 0.8. The slurry composition according to any one of <35> to <37>, which is 1 part by mass or more, more preferably 0.2 part by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less. .
<39> Preferably, the slurry composition according to any one of <35> to <38>, further comprising a polyvinyl acetal resin, more preferably a polyvinyl butyral resin.
<40> The slurry composition according to any one of <35> to <39>, for dispersing the inorganic pigment in a non-aqueous solvent.
<41> Use of the polymer dispersant for inorganic pigments according to any one of <1> to <33> in the production of a ceramic sheet.
<42> Use of the slurry composition according to any one of <35> to <39> in the production of a ceramic sheet.
以下、実施例により本発明を説明する。以下の実施例において、「ポリアルキレングリコール（Ｘモル）」とする表記におけるＸは、当該アルキレングリコールのアルキレンオキシド平均付加モル数を示す。重量平均分子量、固形分及びスラリー組成物の粒径の測定、並びにシート剥離性の評価は、以下の方法により行った。
Hereinafter, the present invention will be described with reference to examples. In the following examples, X in the notation “polyalkylene glycol (X mol)” represents the average number of moles of alkylene oxide added to the alkylene glycol. Measurement of the weight average molecular weight, solid content and particle size of the slurry composition, and evaluation of sheet peelability were performed by the following methods.
（１）重量平均分子量の測定
ゲル浸透クロマトグラフィー（以下「ＧＰＣ」ともいう）法を用いた。試料をＮ，Ｎ－ジメチルホルムアミドで希釈し、試料の固形分濃度０．３質量％の溶液を調製して試料溶液とし、その１００μＬを測定に供した。Ｎ，Ｎ－ジメチルホルムアミドに、リン酸とリチウムブロマイドをそれぞれ６０ｍｍｏｌ／Ｌと５０ｍｍｏｌ／Ｌの濃度となるように溶解した液を溶離液として、ＧＰＣ〔装置：東ソー株式会社製「ＨＬＣ－８１２０ＧＰＣ」、検出器：示差屈折計（装置付属）、カラム：東ソー株式会社製「ＴＳＫ－ＧＥＬ α－Ｍ」×２本、カラム温度：４０℃、溶離液流速：１ｍＬ／ｍｉｎ〕により、測定した。標準物質としては、ポリスチレン（東ソー株式会社製：分子量 ５．２６×１０2、１．０２×１０5、８．４２×１０6；西尾工業株式会社製：分子量 ４．０×１０3、３．０×１０4、９．０×１０5）を用いた。 (1) Measurement of weight average molecular weight Gel permeation chromatography (hereinafter also referred to as “GPC”) was used. The sample was diluted with N, N-dimethylformamide to prepare a solution having a solid content concentration of 0.3% by mass as a sample solution, and 100 μL thereof was used for measurement. As an eluent, a solution obtained by dissolving phosphoric acid and lithium bromide in N, N-dimethylformamide so as to have a concentration of 60 mmol / L and 50 mmol / L respectively was used as an eluent. Detector: differential refractometer (attached to the apparatus), column: “TSK-GEL α-M” x 2 manufactured by Tosoh Corporation, column temperature: 40 ° C., eluent flow rate: 1 mL / min]. As a standard substance, polystyrene (manufactured by Tosoh Corporation: molecular weights 5.26 × 10 2 , 1.02 × 10 5 , 8.42 × 10 6 ; Nishio Kogyo Co., Ltd .: molecular weight 4.0 × 10 3 , 3. 0 × 10 4 , 9.0 × 10 5 ) were used.
ゲル浸透クロマトグラフィー（以下「ＧＰＣ」ともいう）法を用いた。試料をＮ，Ｎ－ジメチルホルムアミドで希釈し、試料の固形分濃度０．３質量％の溶液を調製して試料溶液とし、その１００μＬを測定に供した。Ｎ，Ｎ－ジメチルホルムアミドに、リン酸とリチウムブロマイドをそれぞれ６０ｍｍｏｌ／Ｌと５０ｍｍｏｌ／Ｌの濃度となるように溶解した液を溶離液として、ＧＰＣ〔装置：東ソー株式会社製「ＨＬＣ－８１２０ＧＰＣ」、検出器：示差屈折計（装置付属）、カラム：東ソー株式会社製「ＴＳＫ－ＧＥＬ α－Ｍ」×２本、カラム温度：４０℃、溶離液流速：１ｍＬ／ｍｉｎ〕により、測定した。標準物質としては、ポリスチレン（東ソー株式会社製：分子量 ５．２６×１０2、１．０２×１０5、８．４２×１０6；西尾工業株式会社製：分子量 ４．０×１０3、３．０×１０4、９．０×１０5）を用いた。 (1) Measurement of weight average molecular weight Gel permeation chromatography (hereinafter also referred to as “GPC”) was used. The sample was diluted with N, N-dimethylformamide to prepare a solution having a solid content concentration of 0.3% by mass as a sample solution, and 100 μL thereof was used for measurement. As an eluent, a solution obtained by dissolving phosphoric acid and lithium bromide in N, N-dimethylformamide so as to have a concentration of 60 mmol / L and 50 mmol / L respectively was used as an eluent. Detector: differential refractometer (attached to the apparatus), column: “TSK-GEL α-M” x 2 manufactured by Tosoh Corporation, column temperature: 40 ° C., eluent flow rate: 1 mL / min]. As a standard substance, polystyrene (manufactured by Tosoh Corporation: molecular weights 5.26 × 10 2 , 1.02 × 10 5 , 8.42 × 10 6 ; Nishio Kogyo Co., Ltd .: molecular weight 4.0 × 10 3 , 3. 0 × 10 4 , 9.0 × 10 5 ) were used.
（２）固形分の測定
シャーレにガラス棒と乾燥無水硫酸ナトリウム１０ｇを入れ、そこに試料１ｇを量り採り、ガラス棒で混合し、１０５℃の減圧乾燥機（圧力８ｋＰａ）で２時間乾燥した。乾燥後の質量を秤り、次式より得られた値を固形分とした。
固形分（質量％）＝｛［（乾燥後の質量－（シャーレの重さ＋ガラス棒の重さ＋無水硫酸ナトリウムの質量））］／試料の質量｝×１００ (2) Measurement of solid content A glass rod and 10 g of dry anhydrous sodium sulfate were placed in a petri dish, and 1 g of a sample was weighed and mixed with the glass rod, and dried for 2 hours with a 105 ° C. vacuum dryer (pressure 8 kPa). The mass after drying was weighed, and the value obtained from the following formula was used as the solid content.
Solid content (mass%) = {[(mass after drying− (weight of petri dish + weight of glass rod + mass of anhydrous sodium sulfate)]] / mass of sample} × 100
シャーレにガラス棒と乾燥無水硫酸ナトリウム１０ｇを入れ、そこに試料１ｇを量り採り、ガラス棒で混合し、１０５℃の減圧乾燥機（圧力８ｋＰａ）で２時間乾燥した。乾燥後の質量を秤り、次式より得られた値を固形分とした。
固形分（質量％）＝｛［（乾燥後の質量－（シャーレの重さ＋ガラス棒の重さ＋無水硫酸ナトリウムの質量））］／試料の質量｝×１００ (2) Measurement of solid content A glass rod and 10 g of dry anhydrous sodium sulfate were placed in a petri dish, and 1 g of a sample was weighed and mixed with the glass rod, and dried for 2 hours with a 105 ° C. vacuum dryer (pressure 8 kPa). The mass after drying was weighed, and the value obtained from the following formula was used as the solid content.
Solid content (mass%) = {[(mass after drying− (weight of petri dish + weight of glass rod + mass of anhydrous sodium sulfate)]] / mass of sample} × 100
（３）スラリー組成物の粒径の測定
粒径測定装置として、光子相関法（動的光散乱法）の原理に基づく粒度分布測定機（シスメックス社製「ゼータサイザーナノＺＳ」）を使用した。非水系スラリー組成物 ０．０２５ｇと、分散媒としてトルエン／エタノール混合溶媒（容積比：４８／５２） ２ｍＬとを混合して得られた液を試料とした。光路長１０ｍｍの硝子セルに、前記試料を１．２ｍＬ採取し、測定部に入れ、測定パラメータとして、粒子の屈折率、分散媒の屈折率及びサンプル粘度を入力して測定した。例えば、無機顔料がチタン酸バリウムの場合、粒子の屈折率を２．４０とした。分散媒の屈折率は１．４２３、サンプル粘度は０．７５２とした。散乱強度の頻度分布が５０％となる粒径をＤ５０、９０％となる粒径をＤ９０とした。 (3) Measurement of Particle Size of Slurry Composition As a particle size measuring device, a particle size distribution measuring device (“Zetasizer Nano ZS” manufactured by Sysmex Corporation) based on the principle of the photon correlation method (dynamic light scattering method) was used. A liquid obtained by mixing 0.025 g of the non-aqueous slurry composition and 2 mL of a toluene / ethanol mixed solvent (volume ratio: 48/52) as a dispersion medium was used as a sample. 1.2 mL of the sample was collected in a glass cell having an optical path length of 10 mm, placed in a measuring section, and measured by inputting the refractive index of the particles, the refractive index of the dispersion medium, and the sample viscosity as measurement parameters. For example, when the inorganic pigment is barium titanate, the refractive index of the particles is 2.40. The refractive index of the dispersion medium was 1.423, and the sample viscosity was 0.752. The particle diameter at which the frequency distribution of the scattering intensity is 50% is D50, and the particle diameter at which the frequency distribution is 90% is D90.
粒径測定装置として、光子相関法（動的光散乱法）の原理に基づく粒度分布測定機（シスメックス社製「ゼータサイザーナノＺＳ」）を使用した。非水系スラリー組成物 ０．０２５ｇと、分散媒としてトルエン／エタノール混合溶媒（容積比：４８／５２） ２ｍＬとを混合して得られた液を試料とした。光路長１０ｍｍの硝子セルに、前記試料を１．２ｍＬ採取し、測定部に入れ、測定パラメータとして、粒子の屈折率、分散媒の屈折率及びサンプル粘度を入力して測定した。例えば、無機顔料がチタン酸バリウムの場合、粒子の屈折率を２．４０とした。分散媒の屈折率は１．４２３、サンプル粘度は０．７５２とした。散乱強度の頻度分布が５０％となる粒径をＤ５０、９０％となる粒径をＤ９０とした。 (3) Measurement of Particle Size of Slurry Composition As a particle size measuring device, a particle size distribution measuring device (“Zetasizer Nano ZS” manufactured by Sysmex Corporation) based on the principle of the photon correlation method (dynamic light scattering method) was used. A liquid obtained by mixing 0.025 g of the non-aqueous slurry composition and 2 mL of a toluene / ethanol mixed solvent (volume ratio: 48/52) as a dispersion medium was used as a sample. 1.2 mL of the sample was collected in a glass cell having an optical path length of 10 mm, placed in a measuring section, and measured by inputting the refractive index of the particles, the refractive index of the dispersion medium, and the sample viscosity as measurement parameters. For example, when the inorganic pigment is barium titanate, the refractive index of the particles is 2.40. The refractive index of the dispersion medium was 1.423, and the sample viscosity was 0.752. The particle diameter at which the frequency distribution of the scattering intensity is 50% is D50, and the particle diameter at which the frequency distribution is 90% is D90.
（４）シート剥離性の評価
フィルムアプリケーター（ギャップ５０μｍ）を用い、シリコーン処理された離型フィルム（帝人デュポンフィルム社製「ピューレックス Ａ３１」）にスラリー組成物を塗工し、６０℃にて１６時間乾燥し、セラミックスシートを成形した。乾燥後のセラミックシートの厚みは５～８μｍであった。得られたセラミックシートを、前記離型フィルムとともに短辺４ｃｍ、長辺１０ｃｍの寸法に裁断して試験片とし、スラリー組成物を塗工した面と反対側（離形フィルム側）を下にして、９０度剥離試験用治具を装着した卓上型精密試験機（島津製作所社製「オートグラフ ＡＧＳ－Ｘ」）の台座に、両面テープを用いて試験片を固定した。次に、試験片の短辺側のセラミックシートの片端を離型フィルムから１ｃｍ剥離した後、クリップで挟み、クリップをロードセルに固定した。その後、ロードセルを１ｃｍ／秒の速度で上昇させて９０度剥離を行い、ロードセルが３ｃｍ上昇してから６ｃｍ上昇するまでの間にロードセルにかかる荷重の平均値を、剥離力とした。剥離力が低いほど、剥離性は良好である。 (4) Evaluation of sheet releasability Using a film applicator (gap 50 μm), the slurry composition was applied to a silicone-treated release film (“Purex A31” manufactured by Teijin DuPont Films Ltd.). The ceramic sheet was formed by drying for a period of time. The thickness of the ceramic sheet after drying was 5 to 8 μm. The obtained ceramic sheet together with the release film was cut into dimensions of a short side of 4 cm and a long side of 10 cm to obtain a test piece, with the side opposite to the surface coated with the slurry composition (release film side) facing down. The test piece was fixed to a pedestal of a desktop precision tester (“Autograph AGS-X” manufactured by Shimadzu Corporation) equipped with a 90 ° peel test jig using double-sided tape. Next, one end of the ceramic sheet on the short side of the test piece was peeled 1 cm from the release film, and then sandwiched between clips to fix the clip to the load cell. Thereafter, the load cell was raised at a speed of 1 cm / sec to perform 90-degree peeling, and the average value of the load applied to the load cell during the period from 3 cm to 3 cm rising was defined as peeling force. The lower the peel strength, the better the peelability.
フィルムアプリケーター（ギャップ５０μｍ）を用い、シリコーン処理された離型フィルム（帝人デュポンフィルム社製「ピューレックス Ａ３１」）にスラリー組成物を塗工し、６０℃にて１６時間乾燥し、セラミックスシートを成形した。乾燥後のセラミックシートの厚みは５～８μｍであった。得られたセラミックシートを、前記離型フィルムとともに短辺４ｃｍ、長辺１０ｃｍの寸法に裁断して試験片とし、スラリー組成物を塗工した面と反対側（離形フィルム側）を下にして、９０度剥離試験用治具を装着した卓上型精密試験機（島津製作所社製「オートグラフ ＡＧＳ－Ｘ」）の台座に、両面テープを用いて試験片を固定した。次に、試験片の短辺側のセラミックシートの片端を離型フィルムから１ｃｍ剥離した後、クリップで挟み、クリップをロードセルに固定した。その後、ロードセルを１ｃｍ／秒の速度で上昇させて９０度剥離を行い、ロードセルが３ｃｍ上昇してから６ｃｍ上昇するまでの間にロードセルにかかる荷重の平均値を、剥離力とした。剥離力が低いほど、剥離性は良好である。 (4) Evaluation of sheet releasability Using a film applicator (gap 50 μm), the slurry composition was applied to a silicone-treated release film (“Purex A31” manufactured by Teijin DuPont Films Ltd.). The ceramic sheet was formed by drying for a period of time. The thickness of the ceramic sheet after drying was 5 to 8 μm. The obtained ceramic sheet together with the release film was cut into dimensions of a short side of 4 cm and a long side of 10 cm to obtain a test piece, with the side opposite to the surface coated with the slurry composition (release film side) facing down. The test piece was fixed to a pedestal of a desktop precision tester (“Autograph AGS-X” manufactured by Shimadzu Corporation) equipped with a 90 ° peel test jig using double-sided tape. Next, one end of the ceramic sheet on the short side of the test piece was peeled 1 cm from the release film, and then sandwiched between clips to fix the clip to the load cell. Thereafter, the load cell was raised at a speed of 1 cm / sec to perform 90-degree peeling, and the average value of the load applied to the load cell during the period from 3 cm to 3 cm rising was defined as peeling force. The lower the peel strength, the better the peelability.
実施例及び比較例に用いた高分子分散剤の詳細を表１に示す。ここで、表１及び以下の実施例に用いた原料の略号は次の通りである。
・ＭＭＡ：メチルメタクリレート（三菱瓦斯化学社製）
・ＳＭＡ：ステアリルメタクリレート（新中村化学工業社製「ＮＫエステル Ｓ」）
・ＳＡ：ステアリルアクリレート（大阪有機化学工業社製「ＳＴＡ」）
・ＰＥＧ（４５）ＭＡ：メトキシポリエチレングリコール（４５モル）メタクリレート（新中村化学工業社製「ＮＫ－エステル Ｍ－４５０Ｇ」）
・ＰＥＧ（６０）ＭＡ：メトキシポリエチレングリコール（６０モル）メタクリレート（東邦化学工業社製「ＭＥ－２６０」）
・ＰＥＧ（７４）ＭＡ：メトキシポリエチレングリコール（７４モル）メタクリレート（東邦化学工業社製「ＭＥ－３２０」）
・ＰＥＧ（９０）ＭＡ：メトキシポリエチレングリコール（９０モル）メタクリレート（日油社製「ブレンマー ＰＭＥ－４０００」）
・ＰＥＧ（１２０）ＭＡ：メトキシポリエチレングリコール（１２０モル）メタクリレート（花王社製、品番：化学工業製品中間体）
・ＭＡＡ：メタクリル酸（三菱瓦斯化学社製「ＧＥ－１１０」）
・ＡＡ：アクリル酸（和光純薬工業社製）
・ＭＰＤ：３－メルカプト－１，２－プロパンジオール（旭化学工業社製「１－チオグリセロール」）
・Ｖ－６５Ｂ：２，２'－アゾビス（２，４－ジメチルバレロニトリル）（和光純薬工業社製） The details of the polymer dispersant used in Examples and Comparative Examples are shown in Table 1. Here, the abbreviations of the raw materials used in Table 1 and the following examples are as follows.
・ MMA: Methyl methacrylate (Mitsubishi Gas Chemical Co., Ltd.)
SMA: Stearyl methacrylate (“NK Ester S” manufactured by Shin-Nakamura Chemical Co., Ltd.)
SA: Stearyl acrylate (“STA” manufactured by Osaka Organic Chemical Industry Co., Ltd.)
PEG (45) MA: methoxy polyethylene glycol (45 mol) methacrylate (“NK-ester M-450G” manufactured by Shin-Nakamura Chemical Co., Ltd.)
PEG (60) MA: methoxypolyethylene glycol (60 mol) methacrylate (“ME-260” manufactured by Toho Chemical Industry Co., Ltd.)
PEG (74) MA: methoxypolyethylene glycol (74 mol) methacrylate (“ME-320” manufactured by Toho Chemical Industry Co., Ltd.)
PEG (90) MA: methoxypolyethylene glycol (90 mol) methacrylate (“Blenmer PME-4000” manufactured by NOF Corporation)
PEG (120) MA: methoxypolyethylene glycol (120 mol) methacrylate (manufactured by Kao Corporation, product number: chemical industrial product intermediate)
MAA: methacrylic acid (“GE-110” manufactured by Mitsubishi Gas Chemical Company)
-AA: Acrylic acid (Wako Pure Chemical Industries, Ltd.)
MPD: 3-mercapto-1,2-propanediol (“1-thioglycerol” manufactured by Asahi Chemical Industry Co., Ltd.)
V-65B: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
・ＭＭＡ：メチルメタクリレート（三菱瓦斯化学社製）
・ＳＭＡ：ステアリルメタクリレート（新中村化学工業社製「ＮＫエステル Ｓ」）
・ＳＡ：ステアリルアクリレート（大阪有機化学工業社製「ＳＴＡ」）
・ＰＥＧ（４５）ＭＡ：メトキシポリエチレングリコール（４５モル）メタクリレート（新中村化学工業社製「ＮＫ－エステル Ｍ－４５０Ｇ」）
・ＰＥＧ（６０）ＭＡ：メトキシポリエチレングリコール（６０モル）メタクリレート（東邦化学工業社製「ＭＥ－２６０」）
・ＰＥＧ（７４）ＭＡ：メトキシポリエチレングリコール（７４モル）メタクリレート（東邦化学工業社製「ＭＥ－３２０」）
・ＰＥＧ（９０）ＭＡ：メトキシポリエチレングリコール（９０モル）メタクリレート（日油社製「ブレンマー ＰＭＥ－４０００」）
・ＰＥＧ（１２０）ＭＡ：メトキシポリエチレングリコール（１２０モル）メタクリレート（花王社製、品番：化学工業製品中間体）
・ＭＡＡ：メタクリル酸（三菱瓦斯化学社製「ＧＥ－１１０」）
・ＡＡ：アクリル酸（和光純薬工業社製）
・ＭＰＤ：３－メルカプト－１，２－プロパンジオール（旭化学工業社製「１－チオグリセロール」）
・Ｖ－６５Ｂ：２，２'－アゾビス（２，４－ジメチルバレロニトリル）（和光純薬工業社製） The details of the polymer dispersant used in Examples and Comparative Examples are shown in Table 1. Here, the abbreviations of the raw materials used in Table 1 and the following examples are as follows.
・ MMA: Methyl methacrylate (Mitsubishi Gas Chemical Co., Ltd.)
SMA: Stearyl methacrylate (“NK Ester S” manufactured by Shin-Nakamura Chemical Co., Ltd.)
SA: Stearyl acrylate (“STA” manufactured by Osaka Organic Chemical Industry Co., Ltd.)
PEG (45) MA: methoxy polyethylene glycol (45 mol) methacrylate (“NK-ester M-450G” manufactured by Shin-Nakamura Chemical Co., Ltd.)
PEG (60) MA: methoxypolyethylene glycol (60 mol) methacrylate (“ME-260” manufactured by Toho Chemical Industry Co., Ltd.)
PEG (74) MA: methoxypolyethylene glycol (74 mol) methacrylate (“ME-320” manufactured by Toho Chemical Industry Co., Ltd.)
PEG (90) MA: methoxypolyethylene glycol (90 mol) methacrylate (“Blenmer PME-4000” manufactured by NOF Corporation)
PEG (120) MA: methoxypolyethylene glycol (120 mol) methacrylate (manufactured by Kao Corporation, product number: chemical industrial product intermediate)
MAA: methacrylic acid (“GE-110” manufactured by Mitsubishi Gas Chemical Company)
-AA: Acrylic acid (Wako Pure Chemical Industries, Ltd.)
MPD: 3-mercapto-1,2-propanediol (“1-thioglycerol” manufactured by Asahi Chemical Industry Co., Ltd.)
V-65B: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
［実施例１］
還流管、攪拌装置、温度計及び窒素導入管を取り付けた１Ｌセパラブルフラスコに、「初期仕込み用モノマー」としてＭＡＡ ６．７５ｇ、ＰＥＧ（６０）ＭＡ ３１．５ｇ、ＭＭＡ ６．７５ｇ、ＭＰＤ １．８ｇ及びエタノール（キシダ化学社製、試薬） ２７．０ｇを仕込み、フラスコ内を撹拌しながら窒素置換し、８０℃まで昇温した。フラスコ内を８０℃で撹拌しながら、「開始剤液」としてＶ－６５Ｂ １．３５ｇ及びエタノール １２．１５ｇの混合液をフラスコ内に添加し、次いで、「滴下用モノマー液」としてＭＭＡ ６０．７５ｇ、ＰＥＧ（６０）ＭＡ ２８３．５ｇ、ＭＡＡ ６０．７５ｇ、ＭＰＤ １６．２ｇ、Ｖ－６５Ｂ １２．１５ｇ及びエタノール ２４３．０ｇの混合液を、３時間かけてフラスコ内に滴下した。更に８０℃で３時間攪拌し、冷却した。濃度調整のためにエタノールをフラスコ内に添加し、高分子分散剤溶液を得た。固形分は５５．８質量％、重量平均分子量は８７１８であった。 [Example 1]
In a 1 L separable flask equipped with a reflux tube, a stirrer, a thermometer and a nitrogen introduction tube, 6.75 g of MAA, 31.5 g of PEG (60) MA, 6.75 g of MMA, 6.75 g of MPD 8 g and 27.0 g of ethanol (manufactured by Kishida Chemical Co., Ltd., reagent) were charged, the inside of the flask was purged with nitrogen while stirring, and the temperature was raised to 80 ° C. While stirring the inside of the flask at 80 ° C., a liquid mixture of 1.35 g of V-65B and 12.15 g of ethanol as “initiator liquid” was added to the flask, and then 60.75 g of MMA as “monomer liquid for dropping”. , PEG (60) MA 283.5 g, MAA 60.75 g, MPD 16.2 g, V-65B 12.15 g and ethanol 243.0 g were dropped into the flask over 3 hours. The mixture was further stirred at 80 ° C. for 3 hours and cooled. To adjust the concentration, ethanol was added to the flask to obtain a polymer dispersant solution. The solid content was 55.8% by mass and the weight average molecular weight was 8718.
還流管、攪拌装置、温度計及び窒素導入管を取り付けた１Ｌセパラブルフラスコに、「初期仕込み用モノマー」としてＭＡＡ ６．７５ｇ、ＰＥＧ（６０）ＭＡ ３１．５ｇ、ＭＭＡ ６．７５ｇ、ＭＰＤ １．８ｇ及びエタノール（キシダ化学社製、試薬） ２７．０ｇを仕込み、フラスコ内を撹拌しながら窒素置換し、８０℃まで昇温した。フラスコ内を８０℃で撹拌しながら、「開始剤液」としてＶ－６５Ｂ １．３５ｇ及びエタノール １２．１５ｇの混合液をフラスコ内に添加し、次いで、「滴下用モノマー液」としてＭＭＡ ６０．７５ｇ、ＰＥＧ（６０）ＭＡ ２８３．５ｇ、ＭＡＡ ６０．７５ｇ、ＭＰＤ １６．２ｇ、Ｖ－６５Ｂ １２．１５ｇ及びエタノール ２４３．０ｇの混合液を、３時間かけてフラスコ内に滴下した。更に８０℃で３時間攪拌し、冷却した。濃度調整のためにエタノールをフラスコ内に添加し、高分子分散剤溶液を得た。固形分は５５．８質量％、重量平均分子量は８７１８であった。 [Example 1]
In a 1 L separable flask equipped with a reflux tube, a stirrer, a thermometer and a nitrogen introduction tube, 6.75 g of MAA, 31.5 g of PEG (60) MA, 6.75 g of MMA, 6.75 g of MPD 8 g and 27.0 g of ethanol (manufactured by Kishida Chemical Co., Ltd., reagent) were charged, the inside of the flask was purged with nitrogen while stirring, and the temperature was raised to 80 ° C. While stirring the inside of the flask at 80 ° C., a liquid mixture of 1.35 g of V-65B and 12.15 g of ethanol as “initiator liquid” was added to the flask, and then 60.75 g of MMA as “monomer liquid for dropping”. , PEG (60) MA 283.5 g, MAA 60.75 g, MPD 16.2 g, V-65B 12.15 g and ethanol 243.0 g were dropped into the flask over 3 hours. The mixture was further stirred at 80 ° C. for 3 hours and cooled. To adjust the concentration, ethanol was added to the flask to obtain a polymer dispersant solution. The solid content was 55.8% by mass and the weight average molecular weight was 8718.
［実施例２～１４、比較例１～３］
「初期仕込み用モノマー」、「開始剤液」及び「滴下用モノマー液」の組成をそれぞれ表１の記載に従って変更したことを除いては、実施例１と同様の方法により、高分子分散剤溶液を得た。固形分及び重量平均分子量は、表１に示した通りである。 [Examples 2 to 14, Comparative Examples 1 to 3]
A polymer dispersant solution was prepared in the same manner as in Example 1 except that the compositions of the “initial charge monomer”, “initiator solution” and “dropping monomer solution” were changed according to the description in Table 1, respectively. Got. The solid content and the weight average molecular weight are as shown in Table 1.
「初期仕込み用モノマー」、「開始剤液」及び「滴下用モノマー液」の組成をそれぞれ表１の記載に従って変更したことを除いては、実施例１と同様の方法により、高分子分散剤溶液を得た。固形分及び重量平均分子量は、表１に示した通りである。 [Examples 2 to 14, Comparative Examples 1 to 3]
A polymer dispersant solution was prepared in the same manner as in Example 1 except that the compositions of the “initial charge monomer”, “initiator solution” and “dropping monomer solution” were changed according to the description in Table 1, respectively. Got. The solid content and the weight average molecular weight are as shown in Table 1.
（スラリー組成物の調製方法）
チタン酸バリウム粉末（ＢＥＴ比表面積１５ｍ2／ｇ） ３６ｇと、高分子分散剤 ０．６ｇ（固形分）と、直径１ｍｍのジルコニアビーズ ５０ｇと、ジルコニアビーズを除いた成分中のチタン酸バリウムの含有量が５０質量％になる量のトルエン／エタノール混合溶媒（容積比：４８／５２）とを、容量１００ｍＬのポリエチレン製容器に入れ、卓上型ボールミル（アズワン社製「ビッグローター ＢＲ－２」）を用い、室温、１２０ｒ／ｍｉｎの条件で９６時間分散処理を行った。次いで、ポリビニルブチラール樹脂（積水化学工業社製「エスレック ＢＭ－１」；ブチラール化度６５モル％、水酸基量３４モル％、分子量約４万） ２．８ｇと、ジ（２－エチルヘキシル）フタレート ０．５６ｇと、アルキルイミダゾリン（花王社製「ホモゲノール Ｌ－９５」） ０．２ｇと、チタン酸バリウムの含有量がスラリー組成物に対して３０質量％になる量のトルエン／エタノール混合溶媒（容積比：４８／５２）とを、前記容器に加え、前記卓上型ボールミルを用い、室温、１２０ｒ／ｍｉｎの条件で２時間分散処理を行った。ジルコニアビーズを２００メッシュナイロン濾過で取り除き、スラリー組成物を得た。 (Method for preparing slurry composition)
36 g of barium titanate powder (BET specific surface area 15 m 2 / g), 0.6 g of polymer dispersant (solid content), 50 g of zirconia beads having a diameter of 1 mm, and inclusion of barium titanate in the components excluding zirconia beads A toluene / ethanol mixed solvent (volume ratio: 48/52) in an amount of 50% by mass is placed in a 100 mL polyethylene container, and a desktop ball mill (“Big Rotor BR-2” manufactured by ASONE) is placed. The dispersion treatment was performed for 96 hours at room temperature and 120 r / min. Next, 2.8 g of polyvinyl butyral resin (“S-REC BM-1” manufactured by Sekisui Chemical Co., Ltd .; butyralization degree 65 mol%, hydroxyl group amount 34 mol%, molecular weight about 40,000) and di (2-ethylhexyl) phthalate 0. 56 g, 0.2 g of alkylimidazoline (“Homogenol L-95” manufactured by Kao Corporation), and a toluene / ethanol mixed solvent (volume ratio: volume ratio) in which the barium titanate content is 30% by mass with respect to the slurry composition 48/52) was added to the container, and dispersion treatment was performed for 2 hours under the conditions of room temperature and 120 r / min using the desktop ball mill. The zirconia beads were removed by 200 mesh nylon filtration to obtain a slurry composition.
チタン酸バリウム粉末（ＢＥＴ比表面積１５ｍ2／ｇ） ３６ｇと、高分子分散剤 ０．６ｇ（固形分）と、直径１ｍｍのジルコニアビーズ ５０ｇと、ジルコニアビーズを除いた成分中のチタン酸バリウムの含有量が５０質量％になる量のトルエン／エタノール混合溶媒（容積比：４８／５２）とを、容量１００ｍＬのポリエチレン製容器に入れ、卓上型ボールミル（アズワン社製「ビッグローター ＢＲ－２」）を用い、室温、１２０ｒ／ｍｉｎの条件で９６時間分散処理を行った。次いで、ポリビニルブチラール樹脂（積水化学工業社製「エスレック ＢＭ－１」；ブチラール化度６５モル％、水酸基量３４モル％、分子量約４万） ２．８ｇと、ジ（２－エチルヘキシル）フタレート ０．５６ｇと、アルキルイミダゾリン（花王社製「ホモゲノール Ｌ－９５」） ０．２ｇと、チタン酸バリウムの含有量がスラリー組成物に対して３０質量％になる量のトルエン／エタノール混合溶媒（容積比：４８／５２）とを、前記容器に加え、前記卓上型ボールミルを用い、室温、１２０ｒ／ｍｉｎの条件で２時間分散処理を行った。ジルコニアビーズを２００メッシュナイロン濾過で取り除き、スラリー組成物を得た。 (Method for preparing slurry composition)
36 g of barium titanate powder (BET specific surface area 15 m 2 / g), 0.6 g of polymer dispersant (solid content), 50 g of zirconia beads having a diameter of 1 mm, and inclusion of barium titanate in the components excluding zirconia beads A toluene / ethanol mixed solvent (volume ratio: 48/52) in an amount of 50% by mass is placed in a 100 mL polyethylene container, and a desktop ball mill (“Big Rotor BR-2” manufactured by ASONE) is placed. The dispersion treatment was performed for 96 hours at room temperature and 120 r / min. Next, 2.8 g of polyvinyl butyral resin (“S-REC BM-1” manufactured by Sekisui Chemical Co., Ltd .; butyralization degree 65 mol%, hydroxyl group amount 34 mol%, molecular weight about 40,000) and di (2-ethylhexyl) phthalate 0. 56 g, 0.2 g of alkylimidazoline (“Homogenol L-95” manufactured by Kao Corporation), and a toluene / ethanol mixed solvent (volume ratio: volume ratio) in which the barium titanate content is 30% by mass with respect to the slurry composition 48/52) was added to the container, and dispersion treatment was performed for 2 hours under the conditions of room temperature and 120 r / min using the desktop ball mill. The zirconia beads were removed by 200 mesh nylon filtration to obtain a slurry composition.
（分散性及びシート剥離性の評価）
得られたスラリー組成物を用い、粒径（Ｄ５０及びＤ９０）の測定、及びシート剥離性の評価を行った。結果を表２に示す。 (Evaluation of dispersibility and sheet peelability)
Using the obtained slurry composition, the particle size (D50 and D90) was measured and the sheet peelability was evaluated. The results are shown in Table 2.
得られたスラリー組成物を用い、粒径（Ｄ５０及びＤ９０）の測定、及びシート剥離性の評価を行った。結果を表２に示す。 (Evaluation of dispersibility and sheet peelability)
Using the obtained slurry composition, the particle size (D50 and D90) was measured and the sheet peelability was evaluated. The results are shown in Table 2.
表２に示すとおり、実施例１～１４のスラリー組成物は、分散性が比較例１又は２と同程度又はそれ以上に優れ、実施例１～１４のスラリー組成物から得られたセラミックシートは、比較例１～３のそれよりも優れた剥離性を示した。
As shown in Table 2, the slurry compositions of Examples 1 to 14 have the same or better dispersibility as Comparative Examples 1 and 2, and the ceramic sheets obtained from the slurry compositions of Examples 1 to 14 are The peelability was superior to that of Comparative Examples 1 to 3.
以上説明したとおり、本発明は、例えば、非水系溶媒における塩基性無機顔料を含有するスラリー組成物の製造工程及びセラミックシートの製造工程に有用である。
As described above, the present invention is useful for, for example, a manufacturing process of a slurry composition containing a basic inorganic pigment in a non-aqueous solvent and a manufacturing process of a ceramic sheet.
Claims (17)
- 全構成単位中、式（１）で表される構成単位（ａ）を１質量％以上４５質量％以下、及び、式（２）で表される構成単位（ｂ）を５５質量％以上９９質量％以下含有する共重合体を含み、非水系溶媒中で用いる、無機顔料用高分子分散剤。
- 前記共重合体が、全構成単位中、構成単位（ｂ）を５５質量％以上９５質量％以下含有する共重合体である、請求項１に記載の無機顔料用高分子分散剤。 The polymer dispersant for inorganic pigments according to claim 1, wherein the copolymer is a copolymer containing 55% by mass or more and 95% by mass or less of the structural unit (b) in all the structural units.
- さらに、式（３）で表される構成単位（ｃ）を含有する、請求項１又は２に記載の無機顔料用高分子分散剤。
- さらに、式（３）で表される構成単位（ｃ）を含有し、構成単位（ｂ）に対する構成単位（ｃ）の質量比（（ｃ）／（ｂ））が０．０５以上０．７０以下である、請求項１又は２に記載の無機顔料用高分子分散剤。
- 式（２）のＲ7がエチレン基である、請求項１から４のいずれかに記載の無機顔料用高分子分散剤。 The polymer dispersant for inorganic pigments according to any one of claims 1 to 4, wherein R 7 in the formula (2) is an ethylene group.
- 構成単位（ａ）が、アクリル酸及びメタクリル酸からなる群より選ばれる１種以上に由来する構成単位である、請求項１から５のいずれかに記載の無機顔料用高分子分散剤。 The polymer dispersant for inorganic pigments according to any one of claims 1 to 5, wherein the structural unit (a) is a structural unit derived from one or more selected from the group consisting of acrylic acid and methacrylic acid.
- 前記共重合体の重量平均分子量が、１０００以上１０００００以下である、請求項１から６のいずれかに記載の無機顔料用高分子分散剤。 The polymer dispersant for inorganic pigments according to any one of claims 1 to 6, wherein the copolymer has a weight average molecular weight of 1,000 to 100,000.
- 前記共重合体を構成する構成単位（ａ）の構成単位（ｂ）に対する質量比（構成単位（ａ）／構成単位（ｂ））が、０．０５以上０．５０以下である、請求項１から７のいずれかに記載の無機顔料用高分子分散剤。 The mass ratio (structural unit (a) / structural unit (b)) of the structural unit (a) constituting the copolymer to the structural unit (b) is 0.05 or more and 0.50 or less. To 7. The polymer dispersant for inorganic pigments according to any one of 1 to 7.
- 式（３）におけるＲ9及びＲ10が水素原子である、請求項３から８のいずれかに記載の無機顔料用高分子分散剤。 The polymer dispersant for inorganic pigments according to any one of claims 3 to 8, wherein R 9 and R 10 in formula (3) are hydrogen atoms.
- 構成単位（ｃ）が、アルキル（メタ）アクリレート由来の構成単位である、請求項３から９のいずれかに記載の無機顔料用高分子分散剤。 The polymer dispersant for inorganic pigments according to any one of claims 3 to 9, wherein the structural unit (c) is a structural unit derived from an alkyl (meth) acrylate.
- 構成単位（ｃ）が、メチルメタクリレート、ステアリルメタクリレート及びステアリルアクリレートからなる群より選ばれる１種以上に由来する構成単位である、請求項３から１０のいずれかに記載の無機顔料用高分子分散剤。 The polymeric dispersant for inorganic pigments according to any one of claims 3 to 10, wherein the structural unit (c) is a structural unit derived from one or more selected from the group consisting of methyl methacrylate, stearyl methacrylate and stearyl acrylate. .
- 式（２）におけるＲ4及びＲ5が水素原子である、請求項１から１１のいずれかに記載の無機顔料用高分子分散剤。 The polymer dispersant for inorganic pigments according to any one of claims 1 to 11, wherein R 4 and R 5 in formula (2) are hydrogen atoms.
- 請求項１から１２のいずれかに記載の無機顔料用高分子分散剤を用いて、塩基性無機顔料を分散する方法。 A method of dispersing a basic inorganic pigment using the polymer dispersant for inorganic pigments according to any one of claims 1 to 12.
- 非水系溶媒、塩基性無機顔料、及び請求項１から１２のいずれかに記載の無機顔料用高分子分散剤を含有する、スラリー組成物。 A slurry composition containing a non-aqueous solvent, a basic inorganic pigment, and the polymer dispersant for an inorganic pigment according to any one of claims 1 to 12.
- さらに、ポリビニルアセタール樹脂を含有する、請求項１４に記載のスラリー組成物。 The slurry composition according to claim 14, further comprising a polyvinyl acetal resin.
- 塩基性無機顔料が、酸化マグネシウム、炭酸バリウム、酸化チタン、チタン酸カルシウム、チタン酸バリウム、ジルコン酸バリウム及びジルコン酸カルシウムからなる群から選択される顔料である、請求項１４又は１５に記載のスラリー組成物。 The slurry according to claim 14 or 15, wherein the basic inorganic pigment is a pigment selected from the group consisting of magnesium oxide, barium carbonate, titanium oxide, calcium titanate, barium titanate, barium zirconate and calcium zirconate. Composition.
- 無機顔料を非水系溶媒に分散するための、請求項１から１２のいずれかに記載の分散剤の使用。 Use of the dispersant according to any one of claims 1 to 12 for dispersing an inorganic pigment in a non-aqueous solvent.
Priority Applications (3)
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| KR1020167009250A KR20160054563A (en) | 2013-09-18 | 2014-09-17 | Polymer dispersant for inorganic pigment |
| JP2015501978A JPWO2015041226A1 (en) | 2013-09-18 | 2014-09-17 | Polymer dispersant for inorganic pigments |
| CN201480049250.2A CN105517698A (en) | 2013-09-18 | 2014-09-17 | Polymer dispersant for inorganic pigment |
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| JP2013-192586 | 2013-09-18 | ||
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| JP (1) | JPWO2015041226A1 (en) |
| KR (1) | KR20160054563A (en) |
| CN (1) | CN105517698A (en) |
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Cited By (4)
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|---|---|---|---|---|
| JP2012166154A (en) * | 2011-02-15 | 2012-09-06 | Nof Corp | Dispersant for carbon material, carbon material dispersion, and carbon material composition |
| WO2016143563A1 (en) * | 2015-03-10 | 2016-09-15 | 花王株式会社 | High-molecular dispersant for inorganic pigments |
| CN115785324A (en) * | 2023-02-09 | 2023-03-14 | 广东壮丽彩印股份有限公司 | Preparation method of dispersing agent for nano calcium carbonate |
| JP7510169B2 (en) | 2020-12-25 | 2024-07-03 | サンノプコ株式会社 | Dispersants for non-aqueous coating agents and non-aqueous coating agents |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR102307035B1 (en) * | 2019-06-26 | 2021-09-29 | 양유경 | Sidewalk block combined with ceramic art tile and method for manufacturing thereof |
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Also Published As
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| CN105517698A (en) | 2016-04-20 |
| TW201513930A (en) | 2015-04-16 |
| JPWO2015041226A1 (en) | 2017-03-02 |
| KR20160054563A (en) | 2016-05-16 |
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