JPH10306269A - Adhesive composition - Google Patents
Adhesive compositionInfo
- Publication number
- JPH10306269A JPH10306269A JP11536897A JP11536897A JPH10306269A JP H10306269 A JPH10306269 A JP H10306269A JP 11536897 A JP11536897 A JP 11536897A JP 11536897 A JP11536897 A JP 11536897A JP H10306269 A JPH10306269 A JP H10306269A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive composition
- acid
- polyolefin
- anhydride
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 40
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 40
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 25
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 8
- 239000011976 maleic acid Substances 0.000 claims abstract description 8
- 238000010559 graft polymerization reaction Methods 0.000 claims abstract description 3
- 150000008064 anhydrides Chemical class 0.000 claims abstract 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 17
- 150000008065 acid anhydrides Chemical class 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000005022 packaging material Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 9
- 235000013305 food Nutrition 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- -1 moisture Substances 0.000 description 11
- 229920000098 polyolefin Polymers 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000008188 pellet Substances 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000005003 food packaging material Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 239000012264 purified product Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-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
- 238000001226 reprecipitation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- ZWKNLRXFUTWSOY-QPJJXVBHSA-N (e)-3-phenylprop-2-enenitrile Chemical compound N#C\C=C\C1=CC=CC=C1 ZWKNLRXFUTWSOY-QPJJXVBHSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- AXWJKQDGIVWVEW-UHFFFAOYSA-N 2-(dimethylamino)butanedioic acid Chemical compound CN(C)C(C(O)=O)CC(O)=O AXWJKQDGIVWVEW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical compound NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- QLBNZADBIKYTKU-UHFFFAOYSA-N carbonic acid;3-(2-ethylhexylperoxymethyl)heptane Chemical compound OC(O)=O.CCCCC(CC)COOCC(CC)CCCC QLBNZADBIKYTKU-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 235000006694 eating habits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010571 fourier transform-infrared absorption spectrum Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は接着性に優れた接着
剤に関する。更にはポリオレフィンフイルム、金属等に
短時間接着でき、しかもレトルト殺菌等の加圧加熱工程
によって接着力低下の少ない接着剤に関する。TECHNICAL FIELD The present invention relates to an adhesive having excellent adhesiveness. Further, the present invention relates to an adhesive which can be adhered to a polyolefin film, a metal or the like for a short time, and has a small decrease in adhesive strength due to a pressure heating step such as retort sterilization.
【0002】[0002]
【従来の技術】近年食生活の多様化、高級化ならぴにイ
ンスタント化に伴って食品包装材の需要が著しく拡大
し、種々の熱可塑性樹脂フィルムが使用されているが、
なかでもレトルト食品包装材に対する需要が増大して
る。レトルト食品包装材には一般の食品包装材に要求さ
れる性質以外に、更に厳しい条件に適合する性質を兼ね
備えたものが要求される。すなわち一般の食品包装材に
求められる基本的な性質には(1)食品に直接接する場
合が多く、原材料は毒性のあるものであってはならず、
衛生性のよい素材であること、(2)食品の風味を長期
間維持するためにバリヤー性の良いものであること、
(3)紫外線などによる食品内容物の劣化、変質を防ぐ
ために光遮断性のよいこと、(4)機械的強度が高く、
耐衝撃性にも充分耐え得るものであること、(5)水
分、酸、アルカリなどの耐薬品性が強いものであるこ
と、(6)ヒートシール性がよく、極めて短時間に熱圧
着などの処理が可能であることなどが考えられる。以上
の外にレトルト食品包装材には(1)耐熱性がよいこ
と、(2)種々の食品内容物を詰めて、レトルト殺菌処
理を行なっても包装材に接着強度、その他の性質に劣化
が見られないことが必要である。従って、これら種々の
要求を単一の樹脂フイルム又は他の素材で満たすことは
無理であり、複合フィルム又は複合素材を食品包装材と
して使用している。レトルト用包装材の代表的な例とし
て、ポリエステル又はポリアミド(外層)/アルミニウ
ム箔(中間層)/ポリオレフィン(内層)が考えられ
る。ポリオレフィンとしてはポリプロビレン樹脂が多く
使用される。又用途により長期保存の必要がない場合に
は、前記包装材中のアルミニウム箔を除いた2層包装材
も使用されている。レトルト用包装材として、上記のよ
うな構成からなる、軟質包装に関する包装材だけでなく
飲料缶、食用缶などの分野で使用される素材も合めた場
合も、食品に接する内層はポリオレフィンなどの衛生性
の良い樹脂が有利と考えられ、多用される傾向にある。
ポリオレフィンの中でもポリプロピレン、ポリプチレン
など耐熱性の良いポリオレフィンが必要である。しかし
ながら、これらのポリオレフィンには他の基材との接着
性がほとんどなく、使用し難いものであることは周知で
ある。この点を改良する為にポリオレフィンに化学的、
物理的な処理を施したり、紫外線、電子線などのエネル
ギー源を利用した工夫がなされている。しかしながら実
際には(イ)非常に低い接着力しか得られないか、又例
え得られたとしても、(ロ)食品内容物が油水物の場
合、高温、高圧殺菌後、これら変性ポリオレフィンと他
の基材間の接着力は著しく低いものになってしまい実用
に耐えられない。従って、実際には、ポリオレフィンフ
ィルムの接着にポリウレタン樹脂が接着剤として多用さ
れている。2. Description of the Related Art In recent years, the demand for food packaging materials has been remarkably expanded with the diversification and upgrading of eating habits and the instantization, and various thermoplastic resin films have been used.
Above all, the demand for retort food packaging is increasing. In addition to the properties required for general food packaging materials, retort food packaging materials are required to have properties that meet more stringent requirements. In other words, the basic properties required for general food packaging materials are (1) In many cases, they come into direct contact with food, and the raw materials must not be toxic,
It must be a hygienic material, (2) it must have good barrier properties to maintain the flavor of the food for a long time,
(3) Good light blocking properties to prevent deterioration and deterioration of food contents due to ultraviolet rays, etc. (4) High mechanical strength,
(5) Strong resistance to chemicals such as moisture, acid, alkali, etc. (6) Good heat sealing properties, such as thermocompression bonding in a very short time It is possible that processing can be performed. In addition to the above, the retort food packaging material has (1) good heat resistance, (2) even if various food contents are packed and subjected to retort sterilization treatment, the packaging material does not deteriorate in adhesive strength and other properties. It is necessary not to be seen. Therefore, it is impossible to satisfy these various requirements with a single resin film or another material, and the composite film or the composite material is used as a food packaging material. As a typical example of the packaging material for retort, polyester or polyamide (outer layer) / aluminum foil (intermediate layer) / polyolefin (inner layer) can be considered. Polypropylene resins are often used as polyolefins. When long-term storage is not required depending on the application, a two-layer packaging material excluding the aluminum foil in the packaging material is also used. As a retort wrapping material, consisting of the above configuration, not only packaging materials related to flexible packaging but also materials used in the field of beverage cans, edible cans, etc. Resins with good hygiene are considered to be advantageous and tend to be frequently used.
Among the polyolefins, polyolefins having good heat resistance such as polypropylene and polybutylene are required. However, it is well known that these polyolefins have little adhesion to other substrates and are difficult to use. In order to improve this point, chemical
Ingenuity has been devised by applying a physical treatment or using an energy source such as an ultraviolet ray or an electron beam. However, in practice, (a) only a very low adhesive strength is obtained, or even if it is obtained, (b) if the food content is oil-water, after high-temperature, high-pressure sterilization, these modified polyolefins and other The adhesive strength between the substrates becomes extremely low and cannot be put to practical use. Therefore, in practice, polyurethane resin is frequently used as an adhesive for bonding a polyolefin film.
【0003】しかしながら、レトルト用ポリウレタン樹
脂接着剤には次のような欠点があるとされている。 (1)原料物質であるジイソシアネート又はポリオール
の未反応物もしくは低分子量物が食品内容物に移行し、
衛生性の点で問題が残る。 (2)包装材作成の接着剤とした場合、基材間の接着強
度が充分となるのに常温で約1週間、50〜60℃の加
温処理をしても日単位の熱成期間が必要であること。 (3)ポリオレフィンと他の基材の接着の場合、接着剤
部分に発泡が見られ、接着強度のバラツキが生じたり、
商品価値を低下させる。 (4)高温、特に140℃でのレトルト試験を行った
時、著しく基材間の接着強度低下が見られる。 (5)高価格である。この様な欠点があるにもかかわら
ず、現在レトルト用接着剤としてはポリウレタン樹脂以
外に実用に耐え得るものが見あたらないのが現状であ
る。この意味で種々の点で優れた耐レトルト樹脂の出現
が望まれていた。However, polyurethane resin adhesives for retorts are said to have the following disadvantages. (1) The unreacted or low molecular weight of diisocyanate or polyol as a raw material is transferred to food contents,
Problems remain in terms of hygiene. (2) In the case of using an adhesive for preparing a packaging material, the heat generation period per day is about one week at room temperature and a heating period of 50 to 60 ° C. even when the heating treatment is performed at 50 to 60 ° C. so that the adhesive strength between the base materials is sufficient. What you need. (3) In the case of bonding between a polyolefin and another base material, foaming is observed in an adhesive portion, and a variation in bonding strength occurs,
Decrease product value. (4) When the retort test is performed at a high temperature, particularly at 140 ° C., the adhesive strength between the substrates is significantly reduced. (5) High price. Despite these drawbacks, at present, there is no practically usable retort adhesive other than polyurethane resin. In this sense, the appearance of a retort-resistant resin excellent in various points has been desired.
【0004】[0004]
【発明が解決しようとする課題】耐レトルト接着剤とし
て使用可能な重合性不飽和結合を有するカルボン酸およ
びもしくはその酸無水物(以下重合性不飽和カルボン酸
として表す)で変性されたポリオレフィン樹脂として、
特公昭60−225号公報に開示されている。しかし、
重合性不飽和カルボン酸のグラフト効率が低く、未反応
モノマー、オリゴマーが残留するために反応後、有機溶
剤で洗浄することが必要となっている。このために使用
する有機溶剤は多量であり、この手法で得られた変性ポ
リオレフィン樹脂は、性能的には優れているものの工業
的なメリットを有する接着剤とは言い難い。A polyolefin resin modified with a carboxylic acid having a polymerizable unsaturated bond and / or an acid anhydride thereof (hereinafter referred to as a polymerizable unsaturated carboxylic acid) which can be used as a retort-resistant adhesive. ,
It is disclosed in Japanese Patent Publication No. 60-225. But,
Since the grafting efficiency of the polymerizable unsaturated carboxylic acid is low and unreacted monomers and oligomers remain, it is necessary to wash with an organic solvent after the reaction. The amount of the organic solvent used for this purpose is large, and the modified polyolefin resin obtained by this method is excellent in performance but hardly an adhesive having industrial merit.
【0005】[0005]
【課題を解決するための手段】本発明者は、上記の問題
点を解決するために鋭意研究した結果、ポリオレフィン
系樹脂を重合性不飽和カルボン酸でグラフト変性させる
場合に、スチレン系モノマーを共存させると、極めて少
量の重合性不飽和カルボン酸の添加で高いグラフト効率
が達成され、未反応物の除去のために別工程での精製処
理が必要なくなることを見出し本発明に到達した。第一
の発明は、ポリオレフィン樹脂を基材の1つとして含む
包装材用の接着剤としてポリオレフィン系樹脂(A)に
重合性不飽和結合を有するカルボン酸およびもしくはそ
の酸無水物(B)を溶融状態でグラフトさせた接着剤組
成物において,該グラフト重合を,スチレン系モノマー
(C)の存在下に行うことを特徴とする接着剤組成物で
ある。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that when a polyolefin resin is graft-modified with a polymerizable unsaturated carboxylic acid, a styrene monomer coexists. Then, it was found that a high grafting efficiency was achieved with the addition of a very small amount of a polymerizable unsaturated carboxylic acid, and it was not necessary to carry out a purification treatment in a separate step for removing unreacted substances. A first invention is to melt a carboxylic acid having a polymerizable unsaturated bond and / or an acid anhydride (B) thereof in a polyolefin resin (A) as an adhesive for a packaging material containing a polyolefin resin as one of the base materials. An adhesive composition characterized in that the graft polymerization is performed in the presence of a styrene monomer (C) in the adhesive composition grafted in a state.
【0006】第二の発明は、酸無水物(B)がマレイン
酸または無水マレイン酸であることを特徴とする第一発
明の接着剤組成物である。第三の発明は、スチレン系モ
ノマー(C)に対する酸無水物(B)の配合量が0.0
5〜1(モル比)であることを特徴とする第一発明ない
し第二発明いずれか記載の接着剤組成物である。第四の
発明は、ポリオレフィン系樹脂(A)100重量部に対
して酸無水物(B)とスチレン系モノマー(C)の合計
が1〜30重量部であることを特徴とする第一発明ない
し第三発明いずれか記載の接着剤組成物である。A second invention is the adhesive composition according to the first invention, wherein the acid anhydride (B) is maleic acid or maleic anhydride. In the third invention, the compounding amount of the acid anhydride (B) with respect to the styrene monomer (C) is 0.0
The adhesive composition according to any one of the first invention and the second invention, wherein the adhesive composition has a molar ratio of 5-1 (molar ratio). A fourth invention is characterized in that the total of the acid anhydride (B) and the styrene monomer (C) is 1 to 30 parts by weight based on 100 parts by weight of the polyolefin resin (A). An adhesive composition according to any one of the third inventions.
【0007】第五の発明は、被接着材の少なくとも1つ
がアルミニウムであることを特徴とする第一発明ないし
第四発明いずれか記載の接着剤組成物である。A fifth invention is the adhesive composition according to any one of the first to fourth inventions, wherein at least one of the materials to be bonded is aluminum.
【0008】[0008]
【発明の実施の形態】本発明は、ポリオレフィン系樹脂
を、ラジカル発生剤の存在下に、重合性不飽和カルボン
酸とスチレン系モノマーとを用いて溶融混練してグラフ
ト変性させた接着剤組成物に関する。本発明におけるポ
リオレフィン系樹脂とは、エチレンもしくはプロピレン
の単独重合体、エチレンプロピレン共重合体またはエチ
レンもしくはプロピレンと他のオレフィン、例えば、1
−ブテン、1−ペンテン、1−ヘキセン、1−ヘプテ
ン、1−オクテン、4−メチル−1−ペンテン、1−デ
センの共重合体を含む。また、ボリオレフィン系樹脂と
してエチレン−酢酸ビニル共重合体のようなオレフィン
と異種モノマーとの共重合体を使用することができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to an adhesive composition obtained by melt-kneading a polyolefin-based resin with a polymerizable unsaturated carboxylic acid and a styrene-based monomer in the presence of a radical generator and graft-modified. About. The polyolefin-based resin in the present invention is a homopolymer of ethylene or propylene, an ethylene-propylene copolymer, or ethylene or propylene and another olefin such as 1
-Copolymers of butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene and 1-decene. Further, as the polyolefin resin, a copolymer of an olefin and a different monomer such as an ethylene-vinyl acetate copolymer can be used.
【0009】本発明におけるポリオレフィン系樹脂にグ
ラフト変性させるモノマーとしては重合性不飽和カルボ
ン酸とスチレン系モノマーが必須である。本発明に使用
する重合性不飽和カルボン酸としては、アクリル酸、メ
タクリル酸などのモノカルボン酸、イタコン酸、マレイ
ン酸、フマル酸などのジカルボン酸、無水イタコン酸、
無水マレイン酸などの酸無水物が例示されるが、なかで
も無水マレイン酸が最も好ましい。スチレン系モノマー
としては、スチレン、α−メチルスチレン、クロルスチ
レン、シアノスチレン、アミノスチレン、ヒドロキシス
チレン、ビニルトルエン、ジビニルベンゼンなどがあ
る。重合性不飽和カルボン酸の使用量は,スチレン系モ
ノマーに対して、モル比で0.01〜1、好ましくは、
0.2〜0.4である。1以上では、重合性不飽和カル
ボン酸の残留量が増加し、本発明の効果を得ることがで
きない。同時にポリオレフィン系樹脂の分子量低下も顕
著になる。0.01以下では、グラフト変性に寄与する
重合性不飽和カルボン酸の量が少なくなるので、所定の
接着強度を得ることができなくなる。使用するモノマー
の総量は用いたポリオレフィン系樹脂100部に対し、
1〜30部、好ましくは2〜15部が使用される。モノ
マーを使用量を30部より多くすると、グラフト変性に
寄与しないモノマーの重合物が多く生成し接着力が低下
する傾向がある。In the present invention, as the monomer to be graft-modified to the polyolefin resin, a polymerizable unsaturated carboxylic acid and a styrene monomer are essential. As the polymerizable unsaturated carboxylic acid used in the present invention, acrylic acid, monocarboxylic acid such as methacrylic acid, itaconic acid, maleic acid, dicarboxylic acid such as fumaric acid, itaconic anhydride,
Acid anhydrides such as maleic anhydride are exemplified, and among them, maleic anhydride is most preferred. Examples of the styrene monomer include styrene, α-methylstyrene, chlorostyrene, cyanostyrene, aminostyrene, hydroxystyrene, vinyltoluene, divinylbenzene, and the like. The amount of the polymerizable unsaturated carboxylic acid to be used is a molar ratio of 0.01 to 1 with respect to the styrene monomer, preferably,
0.2 to 0.4. If it is 1 or more, the residual amount of the polymerizable unsaturated carboxylic acid increases, and the effect of the present invention cannot be obtained. At the same time, the molecular weight of the polyolefin resin significantly decreases. If it is less than 0.01, the amount of the polymerizable unsaturated carboxylic acid contributing to the graft modification becomes small, so that a predetermined adhesive strength cannot be obtained. The total amount of the monomers used is based on 100 parts of the polyolefin resin used.
1 to 30 parts, preferably 2 to 15 parts, are used. If the amount of the monomer is more than 30 parts, a large amount of a polymer of the monomer which does not contribute to the graft modification tends to be formed, and the adhesive strength tends to decrease.
【0010】本発明におけるラジカル発生剤とは、通常
のラジカル重合の開始剤であり熱、光などによって容易
に分解して重合開始できる活性なラジカルを発生する物
質をいう。過酸化物系として過硫酸アンモニウムのよう
な過硫酸塩類、過酸化水素、t −ブチルハイドロパーオ
キシド、クメンハイドロパーオキシドのようなヒドロパ
ーオキシド類、2,2−ビス(t −ブチルパーオキシ
ド)オクタンのようなパーオキシケタール類、ジクミル
パーオキシド、t −ブチルクミルパーオキシド、ジーク
ミルパーオキシドのようなジアルキルパーオキシド類、
オクタノイルパーオキシド、デカノイルパーオキシド、
ラウロイルパー才キシド、ベンゾイルパーオキシド等の
ジアシルパー才キシド類、ジーイソプロピルパーオキシ
カーボネート、ジ(2−エチルヘキシル)パーオキシド
カーボネート等のパーオキシドカーボネート類、t −ブ
チルパーオキシイソブチレート、t −ブチルパーオキシ
ベンゾエト等のパーオキシエステル類、2, 2’−アゾ
ビスイソブチロニトリル等のアゾ化合物、銅、鉄粉塩化
ベンジルなどの混合物、酸化剤と還元剤の組合せによる
レドックス開始剤、さらに金属アルキル、金属アルキル
と酸素ドナーまたは金属ハライドの組合せ、またはアル
キルパーオキシ金属等の有機金属化合物を用いることが
できる。これらのラジカル発生剤はグラフト反応におい
て使用する有機溶剤や反応温度等の条件により選定され
るが、本発明においてはボリオレフィン系樹脂を加熱溶
解させグラフト反応を行う温度、例えば150〜220
℃において半減期が1分程度のものが適当である。それ
らのうちでも特に代表的なものを例示すると、ジ−t e
rt−ブチルパーオキサイド、tert−ブチルクミルパーオ
キサイド、ジメチルージ(t e r t −ブチルパーオキ
シ)へキサン、ビス(t e rt −ブチルパーオキシイソ
プロピル)ベンゼン、ジメチルージ(tert−ブチルパー
オキシ)へキシン、p −メンタンーハイドロパーオキサ
イド、ジイソプロピルベンゼンハイドロパーオキサイド
またはキユメンハイドロパーオキサイドなどである。ラ
ジカル重合開始剤の使用量は特に制限はされないが、通
常ポリオレフィン樹脂100部に対して0.01〜5重
量部、好ましくは0.1〜1部である。[0010] The radical generator in the present invention refers to a substance which is an ordinary initiator for radical polymerization and generates an active radical which can be easily decomposed by heat or light to initiate polymerization. As the peroxide system, persulfates such as ammonium persulfate, hydrogen peroxide, hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide, 2,2-bis (t-butyl peroxide) octane Peroxyketals such as dicumyl peroxide, t-butylcumyl peroxide, dialkyl peroxides such as sicumyl peroxide;
Octanoyl peroxide, decanoyl peroxide,
Diacyl peroxides such as lauroyl peroxide and benzoyl peroxide; peroxide carbonates such as diisopropyl peroxycarbonate and di (2-ethylhexyl) peroxide carbonate; t-butylperoxyisobutyrate; t-butyl peroxide Peroxyesters such as oxybenzoate, azo compounds such as 2,2'-azobisisobutyronitrile, mixtures of copper and iron powder benzyl chloride, redox initiators by combining oxidizing agents and reducing agents, and metals Alkyl, combinations of metal alkyls with oxygen donors or metal halides, or organometallic compounds such as alkyl peroxy metals can be used. These radical generators are selected depending on conditions such as the organic solvent used in the graft reaction and the reaction temperature. In the present invention, the temperature at which the polyolefin resin is heated and dissolved to perform the graft reaction, for example, 150 to 220
Those having a half-life of about 1 minute at ℃ are suitable. Among them, particularly representative ones are exemplified by di-te
rt-butyl peroxide, tert-butylcumyl peroxide, dimethyldi (tert-butylperoxyisopropyl) benzene, bis (tert-butylperoxyisopropyl) benzene, dimethyldi (tert-butylperoxy) hexine, p-mentha Hydroperoxide, diisopropylbenzene hydroperoxide, and cumene hydroperoxide. The amount of the radical polymerization initiator is not particularly limited, but is usually 0.01 to 5 parts by weight, preferably 0.1 to 1 part by weight, per 100 parts of the polyolefin resin.
【0011】また、ポリオレフィン系樹脂の酸化防止に
使用される酸化防止剤はリン系酸化防止剤、ホスファイ
ト系酸化防止剤、フェノール系酸化防止剤のほか金属石
鹸類などを単独であるいは混合して使用することができ
る。本発明のようなポリオレフィン樹脂のグラフト反応
は、溶媒で溶解させた状態で行う溶媒法によって実施す
ることもできるが、この場合にはグラフト効率が著しく
低く、本発明の目的には適さない。溶融法によるグラフ
ト反応は、押し出し機等の連続混練機を用いることがで
きる。連続混練機としては、1軸押出機、2軸押出機を
用いることができるが、原料の供給性、滞留時間の制御
の点からは、2軸押出機のほうが望ましい。ポリオレフ
ィン系樹脂を押出機に供給し溶融させ、重合性不飽和カ
ルボン酸とスチレン系モノマーと反応させる。重合性不
飽和カルボン酸とスチレン系モノマーは、あらかじめポ
リオレフィン系樹脂と混合した後、押し出し機に供給し
てもよいし、液体モノマーの量が多い場合には液注ポン
プを用いてポリオレフィン系樹脂とは別に供給しても良
い。押出機のベント口がある場合には、ベントアップし
ない程度に減圧度を調整すれば、未反応物がより除去さ
れるので好ましい。The antioxidants used to prevent the oxidation of polyolefin resins include phosphorus antioxidants, phosphite antioxidants, phenolic antioxidants and metal soaps alone or in combination. Can be used. The grafting reaction of the polyolefin resin as in the present invention can be carried out by a solvent method in which the polyolefin resin is dissolved in a solvent. However, in this case, the grafting efficiency is extremely low and is not suitable for the purpose of the present invention. For the graft reaction by the melting method, a continuous kneader such as an extruder can be used. As a continuous kneader, a single-screw extruder or a twin-screw extruder can be used, but a twin-screw extruder is more preferable from the viewpoint of controlling the supply of raw materials and the residence time. The polyolefin resin is supplied to an extruder and melted, and is reacted with the polymerizable unsaturated carboxylic acid and the styrene monomer. The polymerizable unsaturated carboxylic acid and the styrene-based monomer may be mixed with the polyolefin-based resin in advance and then supplied to the extruder, or when the amount of the liquid monomer is large, the polyolefin-based resin is mixed with the polyolefin-based resin using a liquid injection pump. May be supplied separately. If the extruder has a vent, it is preferable to adjust the degree of pressure reduction so as not to vent up, because unreacted substances are removed more.
【0012】[0012]
【実施例】次に、本発明を実施例および比較例により具
体的に説明するが、本発明はこれらの実施例のみに限定
されるものではない。グラフト効率は次のように定義し
た。 <グラフト効率>反応物約1gを精秤し、加熱キシレン
で溶解しメチルアルコールで再沈させ、その沈殿物をガ
ラスフィルターで濾過し、精製物を回収した。再沈法に
よる精製した樹脂を熱プレスにより厚さ約0.1mmの
フィルムに成形し、フーリエ変換赤外線吸収スペクトル
を測定した。本スペクトルから、1780cm-1のカル
ボニル基及び840cm-1の吸収ピーク面積比より、予
め滴定法により作成した検量線より精製物の酸価を求め
た。滴定法により無水マレイン酸の酸価を測定すると約
570になることから、グラフト率を次式により求め
た。Next, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. Graft efficiency was defined as follows. <Graft efficiency> About 1 g of the reaction product was precisely weighed, dissolved in heated xylene, reprecipitated with methyl alcohol, and the precipitate was filtered through a glass filter to collect a purified product. The resin purified by the reprecipitation method was formed into a film having a thickness of about 0.1 mm by a hot press, and the Fourier transform infrared absorption spectrum was measured. From this spectrum, the absorption peak area ratio of the carbonyl groups and 840 cm -1 in 1780 cm -1, was determined acid value of the purified product from a calibration curve prepared in advance by titration. When the acid value of maleic anhydride was measured by a titration method to be about 570, the graft ratio was determined by the following equation.
【0013】マレイン酸グラフト率(重量%)=(酸
価/570)×100 グラフト効率は下式により定義した。マレイン酸グラフ
ト率は再沈法による精製物基準のためグラフト効率は1
00%以上になる場合もある。 グラフト効率(%)=(マレイン酸グラフト率/仕込み
配合中のマレイン酸含有率)×100 実施例1 MFI=5.0g/10分のポリプロピレン樹脂100重
量部、無水マレイン酸5重量部、ジ−t e rt−ブチルパ
ーオキサイド0.5重量部をヘンシェルミキサーで10
分間混合した。この混合物を30mmφ2軸押出機(L
/D=51.5)に供給した。さらに液注ポンプを用い
てスチレンモノマーを10重量部の比率になるように供
給した。原料の供給量、押出機のスクリュー回転数は、
押出機での滞留時間が2分以上になるように調整し、バ
レル温度は200℃(ただし、フィーダー部は160
℃)で、かつ、ダイス温度が210℃となるように設定
した。ベント部では、ベントアップしない程度に減圧度
を調整した。ここで得られたペレットを、そのまま用い
て、15μmアルミニウム箔(アルミニウム箔/ポリエ
ステル貼り合せ物)に5μmの塗膜厚でエクストルーダ
ー塗布する(グイス部温度235℃)。塗布直後、得ら
れた積層体の裏面(ポリエステル)を1秒間熱ロール
(180℃)に接触させて加熱処理し、表面に塗布され
た接着剤を充分アルミニウムに接着させる。更に該接着
剤上に70μmポリプロピレンフィルムを重ね合せた後
180℃の熱ロール上を60m/分の速度で通過させ
た。該積層体のポリプロピレンフイルム/アルミニウム
箔の接着強度は1020g/15mmとなり層間の剥離
が起らずに、高い接着強度を示すことが確認された。該
積層体で袋を作製し、内容物として水、サラダ油/水
(1:1)、3%酢酸水溶液などを封入して120℃、
30分問のレトルト試験を行なった。レトルト試験後、
該積層体の接着強度を測定したところ、表1のとおりで
あった。Maleic acid graft ratio (% by weight) = (acid
(Value / 570) × 100 The grafting efficiency was defined by the following equation. The grafting efficiency is 1 because the graft ratio of maleic acid is based on the purified product by the reprecipitation method.
It may be more than 00%. Grafting efficiency (%) = (maleic acid graft ratio / maleic acid content in charge blending) × 100 Example 1 MFI = 5.0 g / 10 min 100 parts by weight of polypropylene resin, 5 parts by weight of maleic anhydride, 0.5 parts by weight of tert-butyl peroxide was added to 10 parts by a Henschel mixer.
Mix for minutes. This mixture is mixed with a 30 mmφ twin screw extruder (L
/D=51.5). Further, a styrene monomer was supplied so as to have a ratio of 10 parts by weight using a liquid injection pump. The feed rate of the raw materials and the screw rotation speed of the extruder
The residence time in the extruder was adjusted to be 2 minutes or more, and the barrel temperature was 200 ° C (however, the feeder section was 160 ° C).
° C) and the die temperature is set to 210 ° C. At the vent portion, the degree of pressure reduction was adjusted so as not to vent up. The pellets obtained here are directly used and extruded onto a 15 μm aluminum foil (aluminum foil / polyester laminate) with a coating thickness of 5 μm (grease temperature: 235 ° C.). Immediately after the application, the back surface (polyester) of the obtained laminate is heated for 1 second by contacting it with a hot roll (180 ° C.), and the adhesive applied on the surface is sufficiently adhered to aluminum. Further, a 70 μm polypropylene film was overlaid on the adhesive, and then passed on a hot roll at 180 ° C. at a speed of 60 m / min. The adhesive strength between the polypropylene film and the aluminum foil of the laminate was 1020 g / 15 mm, and it was confirmed that the laminate did not peel off and showed high adhesive strength. A bag is prepared from the laminate, and water, salad oil / water (1: 1), a 3% acetic acid aqueous solution and the like are enclosed as contents, and the mixture is heated at 120 ° C.
A 30-minute retort test was performed. After the retort test,
When the adhesive strength of the laminate was measured, it was as shown in Table 1.
【0014】実施例2 MFI=11g/10分のポリプロピレン樹脂100重量
部、無水マレイン酸2重量部、ジ−t e rt−ブチルパー
オキサイド0.5重量部をヘンシェルミキサーで10分
間混合した。この混合物を30mmφ2軸押出機に供給
した。さらに液注ポンプを用いてスチレンモノマーを1
0重量部の比率になるように供給した。原料の供給量、
押出機のスクリュー回転数は、押出機での滞留時間が2
分以上になるように調整し、バレル温度が200℃(た
だし、フィーダー部は160℃)で、かつ、ダイス温度
が210℃となるように設定した。ここで得られたペレ
ットを実施例1と同様のレトルト試験を行ったところ、
表1のとおりであった。Example 2 100 parts by weight of a polypropylene resin having an MFI of 11 g / 10 min, 2 parts by weight of maleic anhydride, and 0.5 part by weight of di-tert-butyl peroxide were mixed for 10 minutes using a Henschel mixer. This mixture was supplied to a 30 mmφ twin screw extruder. Furthermore, 1 styrene monomer was added using a liquid injection pump.
It was supplied so as to have a ratio of 0 parts by weight. Raw material supply,
The screw rotation speed of the extruder is such that the residence time in the extruder is 2
The barrel temperature was set to 200 ° C. (however, the feeder section was 160 ° C.) and the die temperature was set to 210 ° C. When the pellets obtained here were subjected to the same retort test as in Example 1,
As shown in Table 1.
【0015】比較例1 スチレンモノマー10重量部(液注ポンプで供給),無
水マレイン酸12重量部とした以外は実施例1と同条件
で溶融混練を行い、ペレットを得た。ここで得られたペ
レットを実施例1と同様のレトルト試験を行ったとこ
ろ、表1のとおりであった。 比較例2 液注ポンプでスチレンモノマーを供給しない以外は実施
例1と同条件で溶融混練を行い、ペレットを得た。ペレ
ットは未反応の無水マレイン酸が多量に残留しているた
めに赤茶色に着色していた。本ペレットを用いてエクス
トルーダー塗布しようとしたが、樹脂の溶融粘度が低す
ぎるため、実施例1、2と同条件では安定押出できなか
った。ダイス部温度を170℃まで下げたが押出不良が
生じた。Comparative Example 1 Melt kneading was carried out under the same conditions as in Example 1 except that 10 parts by weight of styrene monomer (supplied by a liquid injection pump) and 12 parts by weight of maleic anhydride were used to obtain pellets. The pellets obtained here were subjected to the same retort test as in Example 1 and the results were as shown in Table 1. Comparative Example 2 Melt kneading was performed under the same conditions as in Example 1 except that the styrene monomer was not supplied by the liquid injection pump, to obtain pellets. The pellets were colored red-brown because a large amount of unreacted maleic anhydride remained. Extruder coating was attempted using the pellets, but stable extrusion could not be performed under the same conditions as in Examples 1 and 2 because the melt viscosity of the resin was too low. Although the die temperature was lowered to 170 ° C., extrusion failure occurred.
【0016】[0016]
【表1】 [Table 1]
【0017】[0017]
【発明の効果】本発明により、ポリオレフィン系樹脂を
重合性不飽和カルボン酸でグラフト変性させる場合に、
スチレン系モノマーを共存させると、極めて少量の重合
性不飽和カルボン酸の添加で高いグラフト効率が達成さ
れ、未反応物の除去のために別工程での精製処理が必要
なくなった。According to the present invention, when a polyolefin resin is graft-modified with a polymerizable unsaturated carboxylic acid,
When a styrenic monomer coexists, a high grafting efficiency was achieved by adding a very small amount of a polymerizable unsaturated carboxylic acid, and a separate purification treatment for removing unreacted substances became unnecessary.
Claims (5)
む包装材用の接着剤としてポリオレフィン系樹脂(A)
に重合性不飽和結合を有するカルボン酸およびもしくは
その酸無水物(B)を溶融状態でグラフトさせた接着剤
組成物において,該グラフト重合を,スチレン系モノマ
ー(C)の存在下に行うことを特徴とする接着剤組成
物。1. A polyolefin resin (A) as an adhesive for a packaging material containing a polyolefin resin as one of the substrates.
In an adhesive composition obtained by grafting a carboxylic acid having a polymerizable unsaturated bond and / or its anhydride (B) in a molten state, the graft polymerization is carried out in the presence of a styrene monomer (C). An adhesive composition characterized by the following:
レイン酸であることを特徴とする請求項1記載の接着剤
組成物。2. The adhesive composition according to claim 1, wherein the acid anhydride (B) is maleic acid or maleic anhydride.
物(B)の配合量が0.05〜1(モル比)であること
を特徴とする請求項1ないし2いずれか記載の接着剤組
成物。3. The adhesive composition according to claim 1, wherein the amount of the acid anhydride (B) to the styrene monomer (C) is 0.05 to 1 (molar ratio). Stuff.
に対して酸無水物(B)とスチレン系モノマー(C)の
合計が1〜30重量部であることを特徴とする請求項1
ないし3いずれか記載の接着剤組成物。4. The total amount of the acid anhydride (B) and the styrene monomer (C) is 1 to 30 parts by weight based on 100 parts by weight of the polyolefin resin (A).
4. The adhesive composition according to any one of items 3 to 3.
であることを特徴とする請求項の1〜4項いずれか記載
の接着剤組成物。5. The adhesive composition according to claim 1, wherein at least one of the adherends is aluminum.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11536897A JPH10306269A (en) | 1997-05-06 | 1997-05-06 | Adhesive composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11536897A JPH10306269A (en) | 1997-05-06 | 1997-05-06 | Adhesive composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH10306269A true JPH10306269A (en) | 1998-11-17 |
Family
ID=14660802
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11536897A Pending JPH10306269A (en) | 1997-05-06 | 1997-05-06 | Adhesive composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH10306269A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6426388B1 (en) | 1999-11-18 | 2002-07-30 | Nippon Paper Industries Co., Ltd. | Modified polyolefin composition and uses thereof |
JP2010260998A (en) * | 2009-05-11 | 2010-11-18 | Kaneka Corp | Adhesive resin composition and molding |
-
1997
- 1997-05-06 JP JP11536897A patent/JPH10306269A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6426388B1 (en) | 1999-11-18 | 2002-07-30 | Nippon Paper Industries Co., Ltd. | Modified polyolefin composition and uses thereof |
JP2010260998A (en) * | 2009-05-11 | 2010-11-18 | Kaneka Corp | Adhesive resin composition and molding |
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