JP5621211B2 - Silicone resin composition for optical semiconductor encapsulation - Google Patents
Silicone resin composition for optical semiconductor encapsulation Download PDFInfo
- Publication number
- JP5621211B2 JP5621211B2 JP2009102163A JP2009102163A JP5621211B2 JP 5621211 B2 JP5621211 B2 JP 5621211B2 JP 2009102163 A JP2009102163 A JP 2009102163A JP 2009102163 A JP2009102163 A JP 2009102163A JP 5621211 B2 JP5621211 B2 JP 5621211B2
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- JP
- Japan
- Prior art keywords
- bis
- group
- meth
- trimethoxysilyl
- alkoxysilyl
- 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.)
- Expired - Fee Related
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- 230000003287 optical effect Effects 0.000 title claims description 27
- 239000004065 semiconductor Substances 0.000 title claims description 26
- 239000011342 resin composition Substances 0.000 title claims description 20
- 229920002050 silicone resin Polymers 0.000 title claims description 19
- 238000005538 encapsulation Methods 0.000 title claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 67
- 125000005370 alkoxysilyl group Chemical group 0.000 claims description 43
- -1 acryl Chemical group 0.000 claims description 38
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 31
- 239000003999 initiator Substances 0.000 claims description 31
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 150000002430 hydrocarbons Chemical group 0.000 claims description 14
- 125000000524 functional group Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- GFKCWAROGHMSTC-UHFFFAOYSA-N trimethoxy(6-trimethoxysilylhexyl)silane Chemical compound CO[Si](OC)(OC)CCCCCC[Si](OC)(OC)OC GFKCWAROGHMSTC-UHFFFAOYSA-N 0.000 claims description 6
- IZRJPHXTEXTLHY-UHFFFAOYSA-N triethoxy(2-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CC[Si](OCC)(OCC)OCC IZRJPHXTEXTLHY-UHFFFAOYSA-N 0.000 claims description 4
- JFFBPULXPLWPAA-UHFFFAOYSA-N trimethoxy(10-trimethoxysilyldecyl)silane Chemical compound CO[Si](OC)(OC)CCCCCCCCCC[Si](OC)(OC)OC JFFBPULXPLWPAA-UHFFFAOYSA-N 0.000 claims description 4
- MBIWXZXQMMLFAB-UHFFFAOYSA-N trimethoxy(9-trimethoxysilylnonyl)silane Chemical compound CO[Si](OC)(OC)CCCCCCCCC[Si](OC)(OC)OC MBIWXZXQMMLFAB-UHFFFAOYSA-N 0.000 claims description 4
- BMQGQVPUOLXPKP-UHFFFAOYSA-N trimethoxy(7-trimethoxysilylheptyl)silane Chemical compound CO[Si](OC)(OC)CCCCCCC[Si](OC)(OC)OC BMQGQVPUOLXPKP-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 51
- 239000000047 product Substances 0.000 description 26
- 239000011521 glass Substances 0.000 description 20
- 238000004040 coloring Methods 0.000 description 15
- 238000002834 transmittance Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 239000004205 dimethyl polysiloxane Substances 0.000 description 10
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 10
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 10
- 125000003545 alkoxy group Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 125000006850 spacer group Chemical group 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical class C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 3
- IVOIHMSMNONJSR-UHFFFAOYSA-N 2-methyl-2-[2-(2-methylbutan-2-ylperoxy)butan-2-ylperoxy]butane Chemical compound CCC(C)(C)OOC(C)(CC)OOC(C)(C)CC IVOIHMSMNONJSR-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- DPGYCJUCJYUHTM-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yloxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)CC(C)(C)C DPGYCJUCJYUHTM-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
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 2
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- JXCAHDJDIAQCJO-UHFFFAOYSA-N (1-tert-butylperoxy-2-ethylhexyl) hydrogen carbonate Chemical compound CCCCC(CC)C(OC(O)=O)OOC(C)(C)C JXCAHDJDIAQCJO-UHFFFAOYSA-N 0.000 description 1
- SWFHGTMLYIBPPA-UHFFFAOYSA-N (4-methoxyphenyl)-phenylmethanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 SWFHGTMLYIBPPA-UHFFFAOYSA-N 0.000 description 1
- VBQCFYPTKHCPGI-UHFFFAOYSA-N 1,1-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CCCCC1 VBQCFYPTKHCPGI-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- ZKEUVTROUPQVTM-UHFFFAOYSA-N 1-pentylperoxypentane Chemical compound CCCCCOOCCCCC ZKEUVTROUPQVTM-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZMMYZOSYBMIWIR-UHFFFAOYSA-N 2,2,4-trimethyl-4-(2,4,4-trimethylpentan-2-ylperoxy)pentane Chemical compound CC(C)(C)CC(C)(C)OOC(C)(C)CC(C)(C)C ZMMYZOSYBMIWIR-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-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
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- HXYDAOXNYINGCS-UHFFFAOYSA-J 2-ethylhexanoate;tin(4+) Chemical compound [Sn+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O HXYDAOXNYINGCS-UHFFFAOYSA-J 0.000 description 1
- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 description 1
- BRQMAAFGEXNUOL-UHFFFAOYSA-N 2-ethylhexyl (2-methylpropan-2-yl)oxy carbonate Chemical compound CCCCC(CC)COC(=O)OOC(C)(C)C BRQMAAFGEXNUOL-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- YAQDPWONDFRAHF-UHFFFAOYSA-N 2-methyl-2-(2-methylpentan-2-ylperoxy)pentane Chemical compound CCCC(C)(C)OOC(C)(C)CCC YAQDPWONDFRAHF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- SWIWVYUDWDVRPX-UHFFFAOYSA-N 4-[dimethoxy(methyl)silyl]butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCC[Si](C)(OC)OC SWIWVYUDWDVRPX-UHFFFAOYSA-N 0.000 description 1
- BVEYJWQCMOVMAR-UHFFFAOYSA-N 5-Hydroxy-4-octanone Chemical compound CCCC(O)C(=O)CCC BVEYJWQCMOVMAR-UHFFFAOYSA-N 0.000 description 1
- UBBNKENBCRDMOY-UHFFFAOYSA-N 5-[dimethoxy(methyl)silyl]pentyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCC[Si](C)(OC)OC UBBNKENBCRDMOY-UHFFFAOYSA-N 0.000 description 1
- PFGDZDUDTMKJHK-UHFFFAOYSA-N 6-[dimethoxy(methyl)silyl]hexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCCC[Si](C)(OC)OC PFGDZDUDTMKJHK-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- 101000720524 Gordonia sp. (strain TY-5) Acetone monooxygenase (methyl acetate-forming) Proteins 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 238000010894 electron beam technology Methods 0.000 description 1
- QKLCQKPAECHXCQ-UHFFFAOYSA-N ethyl phenylglyoxylate Chemical compound CCOC(=O)C(=O)C1=CC=CC=C1 QKLCQKPAECHXCQ-UHFFFAOYSA-N 0.000 description 1
- 239000010408 film Substances 0.000 description 1
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- 238000001746 injection moulding Methods 0.000 description 1
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- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 239000006078 metal deactivator Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- OHNSEOQMURBWPO-UHFFFAOYSA-N octan-3-yl hydrogen carbonate Chemical compound CCCCCC(CC)OC(O)=O OHNSEOQMURBWPO-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- FPLYNRPOIZEADP-UHFFFAOYSA-N octylsilane Chemical compound CCCCCCCC[SiH3] FPLYNRPOIZEADP-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000004980 phosphorus peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- OTRIBZPALGOVNZ-UHFFFAOYSA-N trimethoxy(4-trimethoxysilylbutyl)silane Chemical compound CO[Si](OC)(OC)CCCC[Si](OC)(OC)OC OTRIBZPALGOVNZ-UHFFFAOYSA-N 0.000 description 1
- SIWWUMIYHBHZEU-UHFFFAOYSA-N trimethoxy(5-trimethoxysilylheptan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(CC)CCC(C)[Si](OC)(OC)OC SIWWUMIYHBHZEU-UHFFFAOYSA-N 0.000 description 1
- OXQUKGVMOJFCGS-UHFFFAOYSA-N trimethoxy(5-trimethoxysilylhexan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)CCC(C)[Si](OC)(OC)OC OXQUKGVMOJFCGS-UHFFFAOYSA-N 0.000 description 1
- SSGNPAVXPKHOKS-UHFFFAOYSA-N trimethoxy(5-trimethoxysilylpentan-2-yl)silane Chemical compound CO[Si](OC)(OC)CCCC(C)[Si](OC)(OC)OC SSGNPAVXPKHOKS-UHFFFAOYSA-N 0.000 description 1
- MAFPECYMNWKRHR-UHFFFAOYSA-N trimethoxy(5-trimethoxysilylpentyl)silane Chemical compound CO[Si](OC)(OC)CCCCC[Si](OC)(OC)OC MAFPECYMNWKRHR-UHFFFAOYSA-N 0.000 description 1
- PRAIIRKDOKYQQY-UHFFFAOYSA-N trimethoxy(6-trimethoxysilylheptan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)CCCC(C)[Si](OC)(OC)OC PRAIIRKDOKYQQY-UHFFFAOYSA-N 0.000 description 1
- ODWVKKAQQWZKHG-UHFFFAOYSA-N trimethoxy(6-trimethoxysilylhexan-2-yl)silane Chemical compound CO[Si](OC)(OC)CCCCC(C)[Si](OC)(OC)OC ODWVKKAQQWZKHG-UHFFFAOYSA-N 0.000 description 1
- BHXFSPFDYQBPQY-UHFFFAOYSA-N trimethoxy(6-trimethoxysilylhexan-3-yl)silane Chemical compound CO[Si](OC)(OC)C(CC)CCC[Si](OC)(OC)OC BHXFSPFDYQBPQY-UHFFFAOYSA-N 0.000 description 1
- XXZYMMVFLZFHBD-UHFFFAOYSA-N trimethoxy(7-trimethoxysilylnonan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(CC)CCCCC(C)[Si](OC)(OC)OC XXZYMMVFLZFHBD-UHFFFAOYSA-N 0.000 description 1
- UPQNGNQELOQBLG-UHFFFAOYSA-N trimethoxy(7-trimethoxysilyloctan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)CCCCC(C)[Si](OC)(OC)OC UPQNGNQELOQBLG-UHFFFAOYSA-N 0.000 description 1
- SHCGUUKICQTMGF-UHFFFAOYSA-N trimethoxy(8-trimethoxysilyloctyl)silane Chemical compound CO[Si](OC)(OC)CCCCCCCC[Si](OC)(OC)OC SHCGUUKICQTMGF-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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- Chemical & Material Sciences (AREA)
- Led Device Packages (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Health & Medical Sciences (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
Description
本発明は、光半導体封止用シリコーン樹脂組成物に関する。 The present invention relates to a silicone resin composition for sealing an optical semiconductor.
従来、（メタ）アクリル変性オルガノポリシロキサン、およびシリコーンオイルまたはＮ，Ｎ−ジアルキル置換アクリルアミドもしくはアクリロイルモルホリンのようなラジカル重合性モノマーなどを含有する硬化性シリコーン樹脂組成物が提案されている（特許文献１、２）。 Conventionally, a curable silicone resin composition containing (meth) acryl-modified organopolysiloxane and silicone oil or a radical polymerizable monomer such as N, N-dialkyl-substituted acrylamide or acryloylmorpholine has been proposed (Patent Literature). 1, 2).
しかしながら、本発明者は、シラノール基とアルコキシ基との縮合による硬化では密閉系の場合縮合反応の副生成物であるアルコールが系内から抜けず未硬化になること、ならびに（メタ）アクリル変性オルガノポリシロキサンがアルコキシシリル基を有さない場合および（メタ）アクリル変性オルガノポリシロキサンの重量平均分子量が１万より小さい場合ガラスとの接着性が低く、クラックが生じやすいことを見出した。
さらに、本発明者は、（メタ）アクリル変性オルガノポリシロキサンが耐湿熱接着性に劣ること、（メタ）アクリル変性オルガノポリシロキサンおよびＮ，Ｎ−ジアルキル置換アクリルアミドまたはアクリロイルモルホリンのようなラジカル重合性モノマーを含有する組成物が耐熱着色安定性に劣ることを見出した。
そこで、本発明は、密閉系内における硬化性、接着性、耐湿熱接着性、耐熱着色安定性に優れる光半導体封止用シリコーン樹脂組成物を提供することを目的とする。
However, in the case of curing by condensation of silanol groups and alkoxy groups, the present inventor found that in the case of a closed system, alcohol as a by-product of the condensation reaction does not escape from the system and becomes uncured, and (meth) acryl-modified organo It has been found that when the polysiloxane does not have an alkoxysilyl group and when the weight average molecular weight of the (meth) acryl-modified organopolysiloxane is less than 10,000, the adhesion to glass is low and cracks are likely to occur.
Furthermore, the present inventors have found that (meth) acryl-modified organopolysiloxane has poor wet heat resistance, (meth) acryl-modified organopolysiloxane and radical polymerizable monomers such as N, N-dialkyl-substituted acrylamide or acryloylmorpholine. It has been found that a composition containing the colorant is inferior in heat-resistant coloring stability.
Then, an object of this invention is to provide the silicone resin composition for optical semiconductor sealing excellent in sclerosis | hardenability in a closed system, adhesiveness, heat-and-moisture-resistant adhesiveness, and heat-resistant coloring stability.
本発明者は、上記課題を解決すべく鋭意研究した結果、（Ａ）１分子中に、下記式（Ｉ）で示される官能基を２個以上およびアルコキシシリル基を１個以上有し、重量平均分子量が１０，０００〜１５０，０００である（メタ)アクリル変性オルガノポリシロキサンと、
（Ｂ）ラジカル開始剤と、を含有する組成物に
（Ｃ）ビス（アルコキシシリル）アルカンを加えることによって、密閉系内における硬化性、接着性、耐湿熱接着性、耐熱着色安定性に優れる光半導体封止用シリコーン樹脂組成物が得られることを見出し、本発明を完成させた。
（式中、Ｒ1は水素原子またはメチル基であり、Ｒ4は炭素原子数１〜８の２価の炭化水素基である。）
As a result of diligent research to solve the above-mentioned problems, the present inventor has (A) two or more functional groups represented by the following formula (I) and one or more alkoxysilyl groups in one molecule. (Meth) acryl-modified organopolysiloxane having an average molecular weight of 10,000 to 150,000,
(B) Light excellent in curability, adhesiveness, moist heat and heat resistance, and heat resistant coloring stability in a closed system by adding (C) bis (alkoxysilyl) alkane to a composition containing a radical initiator It discovered that the silicone resin composition for semiconductor sealing was obtained, and completed this invention.
(In the formula, R 1 is a hydrogen atom or a methyl group, and R 4 is a divalent hydrocarbon group having 1 to 8 carbon atoms.)
すなわち、本発明は、下記１〜４を提供する。
１． （Ａ）１分子中に、下記式（Ｉ）で示される官能基を２個以上およびアルコキシシリル基を１個以上有し、重量平均分子量が１０，０００〜１５０，０００である（メタ)アクリル変性オルガノポリシロキサンと、
（Ｂ）ラジカル開始剤と、
（Ｃ）ビス（アルコキシシリル）アルカンとを含有する光半導体封止用シリコーン樹脂組成物。
（式中、Ｒ1は水素原子またはメチル基であり、Ｒ4は炭素原子数１〜８の２価の炭化水素基である。）
２． 前記（メタ）アクリル変性オルガノポリシロキサンが、下記式（２）で表される上記１に記載の光半導体封止用シリコーン樹脂組成物。
（式中、Ｒ1はそれぞれ水素原子またはメチル基であり、Ｒ2、Ｒ3はそれぞれアルキル基であり、Ｒ4はそれぞれ炭素原子数１〜８の２価の炭化水素基であり、ｎはそれぞれ１または２であり、ｍは100〜2000である。）
３． 前記ビス（アルコキシシリル）アルカンが、１，２−ビス（トリエトキシシリル）エタン、１，６−ビス（トリメトキシシリル）ヘキサン、１，７−ビス（トリメトキシシリル）ヘプタン、１，８−ビス（トリメトキシシリル）オクタン、１，９−ビス（トリメトキシシリル）ノナンおよび１，１０−ビス（トリメトキシシリル）デカンからなる群から選ばれる少なくとも１種である上記１または２に記載の光半導体封止用シリコーン樹脂組成物。
４． 前記ビス（アルコキシシリル）アルカンの量が、前記（メタ）アクリル変性オルガノポリシロキサン１００質量部に対して、0.01〜10質量部である上記１〜３のいずれかに記載の光半導体封止用シリコーン樹脂組成物。
That is, this invention provides the following 1-4.
1. (A) (meth) acryl having 2 or more functional groups represented by the following formula (I) and 1 or more alkoxysilyl groups in one molecule and having a weight average molecular weight of 10,000 to 150,000 Modified organopolysiloxane,
(B) a radical initiator;
(C) A silicone resin composition for encapsulating an optical semiconductor containing bis (alkoxysilyl) alkane.
(In the formula, R 1 is a hydrogen atom or a methyl group, and R 4 is a divalent hydrocarbon group having 1 to 8 carbon atoms.)
2. 2. The silicone resin composition for sealing an optical semiconductor according to 1 above, wherein the (meth) acryl-modified organopolysiloxane is represented by the following formula (2).
(Wherein R 1 is a hydrogen atom or a methyl group, R 2 and R 3 are each an alkyl group, R 4 is a divalent hydrocarbon group having 1 to 8 carbon atoms, and n is Each is 1 or 2, and m is 100-2000.)
3. The bis (alkoxysilyl) alkane, 1, 2-bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,7-bis (trimethoxysilyl) heptane, 1,8-bis 3. The optical semiconductor according to 1 or 2 above, which is at least one selected from the group consisting of (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane, and 1,10-bis (trimethoxysilyl) decane. Silicone resin composition for sealing.
4). The silicone for optical semiconductor encapsulation according to any one of 1 to 3 above, wherein the amount of the bis (alkoxysilyl) alkane is 0.01 to 10 parts by mass with respect to 100 parts by mass of the (meth) acryl-modified organopolysiloxane. Resin composition.
本発明の光半導体封止用シリコーン樹脂組成物は、密閉系内における硬化性、接着性、耐湿熱接着性、耐熱着色安定性に優れる。 The silicone resin composition for optical semiconductor encapsulation of the present invention is excellent in curability, adhesion, wet heat resistance, and heat resistant coloration stability in a closed system.
本発明について以下詳細に説明する。
本発明の光半導体封止用シリコーン樹脂組成物は、
（Ａ）１分子中に、下記式（Ｉ）で示される官能基を２個以上およびアルコキシシリル基を１個以上有し、重量平均分子量が１０，０００〜１５０，０００である（メタ)アクリル変性オルガノポリシロキサンと、
（Ｂ）ラジカル開始剤と、
（Ｃ）ビス（アルコキシシリル）アルカンとを含有する組成物である。
（式中、Ｒ1は水素原子またはメチル基であり、Ｒ4は炭素原子数１〜８の２価の炭化水素基である。）
本発明の光半導体封止用シリコーン樹脂組成物を以下「本発明の組成物」ということがある。
The present invention will be described in detail below.
The silicone resin composition for optical semiconductor encapsulation of the present invention is
(A) (meth) acryl having 2 or more functional groups represented by the following formula (I) and 1 or more alkoxysilyl groups in one molecule and having a weight average molecular weight of 10,000 to 150,000 Modified organopolysiloxane,
(B) a radical initiator;
(C) A composition containing bis (alkoxysilyl) alkane.
(In the formula, R 1 is a hydrogen atom or a methyl group, and R 4 is a divalent hydrocarbon group having 1 to 8 carbon atoms.)
The silicone resin composition for encapsulating an optical semiconductor of the present invention may be hereinafter referred to as “the composition of the present invention”.
（Ａ） （メタ）アクリル変性オルガノポリシロキサンについて以下に説明する。
本発明の組成物に含有される（メタ）アクリル変性オルガノポリシロキサンは、主鎖がオルガノポリシロキサンであり、１分子中に、式（Ｉ）で示される官能基を２個以上およびアルコキシシリル基を１個以上有する化合物であり、（メタ）アクリル変性オルガノポリシロキサンの重量平均分子量は１０，０００〜１５０，０００である。
（式中、Ｒ1は水素原子またはメチル基であり、Ｒ4は炭素原子数１〜８の２価の炭化水素基である。）
なお、本発明において（メタ）アクリルは、アクリルおよびメタクリルのうちの一方または両方を意味する。
(A) The (meth) acryl-modified organopolysiloxane will be described below.
The (meth) acryl-modified organopolysiloxane contained in the composition of the present invention has a main chain of organopolysiloxane, two or more functional groups represented by formula (I) and an alkoxysilyl group in one molecule. The (meth) acryl-modified organopolysiloxane has a weight average molecular weight of 10,000 to 150,000.
(In the formula, R 1 is a hydrogen atom or a methyl group, and R 4 is a divalent hydrocarbon group having 1 to 8 carbon atoms.)
In the present invention, (meth) acryl means one or both of acrylic and methacrylic.
主鎖としてのオルガノポリシロキサンは、特に制限されない。例えば、ジメチルポリシロキサン、ジエチルポリシロキサンが挙げられる。主鎖としてのオルガノポリシロキサンは、直鎖状および分岐状のうちのいずれであってもよい。 The organopolysiloxane as the main chain is not particularly limited. Examples thereof include dimethylpolysiloxane and diethylpolysiloxane. The organopolysiloxane as the main chain may be either linear or branched.
式（Ｉ）で示される官能基において、Ｒ4としての炭素原子数１〜８の２価の炭化水素基は特に制限されない。例えば、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンチレン基のようなアルキレン基；シクロヘキシレン基のようなシクロアルキレン基が挙げられる。
(メタ)アクリル変性オルガノポリシロキサンが有するアルコキシシリル基は特に制限されない。例えば、トリアルコキシシリル基、ジアルコキシ基を有する２価のシリル基、モノアルコキシ基およびモノアルキル基を有する２価のシリル基が挙げられる。アルコキシシリル基中のアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロピル基が挙げられる。アルコキシシリル基が有することができるアルキル基としては、例えば、メチル基、エチル基、プロピル基が挙げられる。
In the functional group represented by the formula (I), the divalent hydrocarbon group having 1 to 8 carbon atoms as R 4 is not particularly limited. For example, an alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a pentylene group; and a cycloalkylene group such as a cyclohexylene group.
The alkoxysilyl group of the (meth) acryl-modified organopolysiloxane is not particularly limited. Examples thereof include a trialkoxysilyl group, a divalent silyl group having a dialkoxy group, a divalent silyl group having a monoalkoxy group and a monoalkyl group. Examples of the alkoxy group in the alkoxysilyl group include a methoxy group, an ethoxy group, and a propyl group. Examples of the alkyl group that the alkoxysilyl group can have include a methyl group, an ethyl group, and a propyl group.
式（Ｉ）で示される官能基は主鎖としてのオルガノポリシロキサンの側鎖および／または末端に結合することができる。式（Ｉ）で示される官能基は主鎖としてのオルガノポリシロキサンの両末端に結合することができる。
アルコキシシリル基は主鎖としてのオルガノポリシロキサンの側鎖および／または末端に結合することができる。アルコキシシリル基は主鎖としてのオルガノポリシロキサンの両末端に結合することができる。
The functional group represented by the formula (I) can be bonded to the side chain and / or terminal of the organopolysiloxane as the main chain. The functional group represented by the formula (I) can be bonded to both ends of the organopolysiloxane as the main chain.
The alkoxysilyl group can be bonded to the side chain and / or terminal of the organopolysiloxane as the main chain. The alkoxysilyl group can be bonded to both ends of the organopolysiloxane as the main chain.
本発明において、式（Ｉ）中のケイ素原子を、(メタ)アクリル変性オルガノポリシロキサンが有するアルコキシシリル基とすることができる。
式（Ｉ）中のケイ素原子がアルコキシシリル基である場合、式（Ｉ）で示される官能基として、例えば、下記式（１）で表されるものが挙げられる。
（式中、Ｒ1は水素原子またはメチル基であり、Ｒ2、Ｒ3はそれぞれアルキル基であり、Ｒ4は炭素原子数１〜８の２価の炭化水素基であり、ｎは１または２である。）
式（Ｉ）で示される官能基は、密閉系内における硬化性、接着性、耐湿熱接着性、耐熱着色安定性により優れるという観点から、式（１）で表されるものが好ましい。
In the present invention, the silicon atom in the formula (I) can be an alkoxysilyl group of the (meth) acryl-modified organopolysiloxane.
When the silicon atom in the formula (I) is an alkoxysilyl group, examples of the functional group represented by the formula (I) include those represented by the following formula (1).
Wherein R 1 is a hydrogen atom or a methyl group, R 2 and R 3 are each an alkyl group, R 4 is a divalent hydrocarbon group having 1 to 8 carbon atoms, and n is 1 or 2)
The functional group represented by the formula (I) is preferably the one represented by the formula (1) from the viewpoint that it is more excellent in curability, adhesion, wet heat and heat resistance, and heat resistant coloring stability in a closed system.
式（１）で示される基は主鎖としてのオルガノポリシロキサンの側鎖および／または末端に結合することができる。式（１）で示される基は主鎖としてのオルガノポリシロキサンの両末端に結合することができる。 The group represented by the formula (1) can be bonded to the side chain and / or the terminal of the organopolysiloxane as the main chain. The group represented by the formula (1) can be bonded to both ends of the organopolysiloxane as the main chain.
式（１）で示される基において、Ｒ2、Ｒ3としてのアルキル基は特に制限されない。例えば、メチル基、エチル基が挙げられる。
また、式（１）中、Ｒ4としての炭素原子数１〜８の２価の炭化水素基は特に制限されない。例えば、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンチレン基が挙げられる。
ｎは、密閉系内における硬化性、接着性、耐湿熱接着性、耐熱着色安定性により優れるという観点から、２であるのが好ましい。
In the group represented by the formula (1), alkyl groups as R 2 and R 3 are not particularly limited. Examples thereof include a methyl group and an ethyl group.
In formula (1), the divalent hydrocarbon group having 1 to 8 carbon atoms as R 4 is not particularly limited. Examples include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a pentylene group.
n is preferably 2 from the viewpoint that it is more excellent in curability, adhesion, wet heat and heat resistance and heat resistant coloration stability in a closed system.
(メタ)アクリル変性オルガノポリシロキサンとしては、例えば、下記式（２）で表されるものが挙げられる。
（式中、Ｒ1はそれぞれ水素原子またはメチル基であり、Ｒ2、Ｒ3はそれぞれアルキル基であり、Ｒ4はそれぞれ炭素原子数１〜８の２価の炭化水素基であり、ｎは１または２であり、ｍは１００〜２，０００である。）
Ｒ1〜Ｒ4、ｎは式（１）と同義である。
ｍは、密閉系内における硬化性、接着性、耐湿熱接着性、耐熱着色安定性により優れ、作業性に優れるという観点から、１００〜１，３５０であるのが好ましい。
Examples of the (meth) acryl-modified organopolysiloxane include those represented by the following formula (2).
(Wherein R 1 is a hydrogen atom or a methyl group, R 2 and R 3 are each an alkyl group, R 4 is a divalent hydrocarbon group having 1 to 8 carbon atoms, and n is 1 or 2 and m is 100 to 2,000.)
R < 1 > -R < 4 >, n is synonymous with Formula (1).
m is preferably 100 to 1,350 from the viewpoints of excellent curability, adhesiveness, moist heat and heat resistance and heat-resistant coloring stability in a closed system, and excellent workability.
(メタ)アクリル変性オルガノポリシロキサンは、密閉系内における硬化性、接着性、耐湿熱接着性、耐熱着色安定性により優れるという観点から、式（２）で表されるものが好ましい。 The (meth) acryl-modified organopolysiloxane is preferably represented by the formula (2) from the viewpoint that it is more excellent in curability, adhesion, wet heat resistance, and heat resistant coloration stability in a closed system.
本発明において、（メタ）アクリル変性オルガノポリシロキサンの重量平均分子量は１０，０００〜１５０，０００である。
(メタ)アクリル変性オルガノポリシロキサンの重量平均分子量は、密閉系内における硬化性、接着性、耐湿熱接着性、耐熱着色安定性により優れ、作業性に優れるという観点から、１０，０００〜１００，０００が好ましい。
式（２）中のｎが２の場合、(メタ)アクリル変性オルガノポリシロキサンの重量平均分子量は耐熱着色安定性により優れ、透明性に優れるという観点から、1０，０００〜１００，０００であるのが好ましい。
なお本発明において（メタ）アクリル変性オルガノポリシロキサンの重量平均分子量は、クロロホルムを溶媒とするゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）によるポリスチレン換算で表わされるものとする。
(メタ)アクリル変性オルガノポリシロキサンはそれぞれ単独でまたは２種以上を組み合わせて使用することができる。
In the present invention, the (meth) acryl-modified organopolysiloxane has a weight average molecular weight of 10,000 to 150,000.
The weight average molecular weight of the (meth) acryl-modified organopolysiloxane is 10,000 to 100,000 from the viewpoint that it is excellent in curability, adhesion, wet heat and heat resistance, heat resistant color stability in a closed system, and excellent workability. 000 is preferred.
When n in the formula (2) is 2, the weight average molecular weight of the (meth) acryl-modified organopolysiloxane is 10,000 to 100,000 from the viewpoint of excellent heat-resistant coloring stability and excellent transparency. Is preferred.
In the present invention, the weight average molecular weight of the (meth) acryl-modified organopolysiloxane is expressed in terms of polystyrene by gel permeation chromatography (GPC) using chloroform as a solvent.
The (meth) acryl-modified organopolysiloxane can be used alone or in combination of two or more.
(メタ)アクリル変性オルガノポリシロキサンはその製造について特に制限されない。例えば、両末端にヒドロキシ基を有するオルガノポリシロキサン（例えば、式（３）で表されるオルガノポリシロキサン）と、式（４）で表される化合物とを反応させることによって製造することができる。
（式中、Ｒ1はそれぞれ水素原子またはメチル基であり、Ｒ2、Ｒ3はそれぞれアルキル基であり、Ｒ4はそれぞれ炭素原子数１〜８の２価の炭化水素基であり、ｎは２または３であり、ｍは100〜2000である。）
Ｒ1〜Ｒ4は式（１）と同義である。ｍは式（２）と同義である。
密閉系内における硬化性、接着性、耐湿熱接着性、耐熱着色安定性により優れ、加熱減量の抑制、硬化性に優れるという観点から、両末端にヒドロキシ基を有するオルガノポリシロキサン１モルに対して、式（４）で表される化合物を２モルを超える量で反応させるのが好ましい。
The (meth) acryl-modified organopolysiloxane is not particularly limited for its production. For example, it can be produced by reacting an organopolysiloxane having hydroxy groups at both ends (for example, an organopolysiloxane represented by the formula (3)) with a compound represented by the formula (4).
(Wherein R 1 is a hydrogen atom or a methyl group, R 2 and R 3 are each an alkyl group, R 4 is a divalent hydrocarbon group having 1 to 8 carbon atoms, and n is 2 or 3 and m is 100 to 2000.)
R < 1 > -R < 4 > is synonymous with Formula (1). m is synonymous with Formula (2).
From the viewpoints of excellent curability, adhesiveness, moist heat resistance and heat-resistant coloring stability in a closed system, suppression of heat loss, and excellent curability, with respect to 1 mol of an organopolysiloxane having hydroxy groups at both ends. It is preferable to react the compound represented by the formula (4) in an amount exceeding 2 mol.
（Ｂ） ラジカル開始剤について以下に説明する。
本発明の組成物に含有されるラジカル開始剤は、熱および／または光によって（メタ）アクリロイル基をラジカル重合させるものであれば特に制限されない。
ラジカル開始剤は、密閉系内における硬化性、耐熱着色安定性により優れ、耐光性に優れるという観点から、窒素原子もしくは硫黄原子またはベンゼン環を含まないものが好ましく、炭素原子、水素原子および酸素原子からなるものがより好ましい。
(B) The radical initiator will be described below.
The radical initiator contained in the composition of the present invention is not particularly limited as long as it allows radical polymerization of a (meth) acryloyl group by heat and / or light.
The radical initiator is preferably one that does not contain a nitrogen atom, a sulfur atom, or a benzene ring from the viewpoint of excellent curability in a closed system, heat-resistant coloring stability, and excellent light resistance, and includes a carbon atom, a hydrogen atom, and an oxygen atom. More preferably, it consists of
熱によるラジカル開始剤（熱ラジカル開始剤）としては、有機化酸化物系とアゾ化合物などが挙げられる。有機化酸化物としてはケトンパーオキサイド系、パーオキシケタール系、ハイドロパーオキサイド系、ジアルキルパーオキサイド系、ジアシルパーオキサイド系、、パーオキシエステル系、パーオキシジカーボネート系化合物が挙げられる。例えばメチルエチルケトンパーオキサイド、１，１−ジ（ｔ−ヘキシルパーオキシ）シクロヘキサン、２，２−（ｔ−ブチルパーオキシ）ブタン、２，２−ジ−（ｔ−アミルパーオキシ）ブタン、ｐ−メンタンパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ジアミルパーオキサイド、ジラウリルパーオキサイド、１，１，３，３−テトラメチルブチルパーオキシ−２−エチルヘキサノエート、ｔ−ブチルパーオキシ−２−エチルヘキシルモノカーボネート、ジ−（２エチルヘキシル）パーオキシジカーボネートのような脂肪族炭化水素のパーオキサイドやクメンハイドロパーオキサイド、ジクミルパーオキサイド、ジベンゾイルパーオキサイド、クミルパーオキシネオデカネート、ｔ−ブチルパーオキシベンゾエートなどの芳香族系か酸化物が挙げられる。
アゾ化合物としては例えば２，２’−アゾビス（２-メチルブチロニトリル）やジメチル２，２’−アゾビス（２メチルピオネート）や２，２’−アゾビス(２，４，４−トリメチルペンテイト)などが挙げられる。
Examples of the thermal radical initiator (thermal radical initiator) include organic oxides and azo compounds. Examples of the organic oxide include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates. For example, methyl ethyl ketone peroxide, 1,1-di (t-hexylperoxy) cyclohexane, 2,2- (t-butylperoxy) butane, 2,2-di- (t-amylperoxy) butane, p-men Tamperoxide, di-t-butyl peroxide, diamyl peroxide, dilauryl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxy-2- Aliphatic hydrocarbon peroxides such as ethylhexyl monocarbonate and di- (2 ethylhexyl) peroxydicarbonate, cumene hydroperoxide, dicumyl peroxide, dibenzoyl peroxide, cumylperoxyneodecanate, t-butyl Aromatic or acid such as peroxybenzoate Thing, and the like.
Examples of the azo compound include 2,2′-azobis (2-methylbutyronitrile), dimethyl 2,2′-azobis (2methylpionate), and 2,2′-azobis (2,4,4-trimethylpentate). ) And the like.
光によるラジカル開始剤（光ラジカル開始剤）としては、例えば、アセトフェノン系化合物、ベンゾインエーテル系化合物、ベンゾフェノン系化合物のようなカルボニル化合物、硫黄化合物、アゾ化合物、パーオキサイド化合物、ホスフィンオキサイド系化合物などが挙げられる。 Examples of light radical initiators (photo radical initiators) include carbonyl compounds such as acetophenone compounds, benzoin ether compounds, and benzophenone compounds, sulfur compounds, azo compounds, peroxide compounds, and phosphine oxide compounds. Can be mentioned.
具体的には例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、アセトイン、ブチロイン、トルオイン、ベンジル、ベンゾフェノン、ｐ−メトキシベンゾフェノン、ジエトキシアセトフェノン、α，α−ジメトキシ−α−フェニルアセトフェノン、メチルフェニルグリオキシレート、エチルフェニルグリオキシレート、４，４′−ビス（ジメチルアミノベンゾフェノン）、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−ヒドロキシ−シクロヘキシル−フェニルケトン等のカルボニル化合物；テトラメチルチウラムモノスルフィド、テトラメチルチウラムジスルフィド等の硫黄化合物；アゾビスイソブチロニトリル、アゾビス−２，４−ジメチルバレロ等のアゾ化合物；ベンゾイルパーオキサイド、ジターシャリーブチルパーオキサイド等のパーオキサイド化合物が挙げられる。 Specifically, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, Methylphenylglyoxylate, ethylphenylglyoxylate, 4,4'-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl-phenylketone, etc. Carbonyl compounds; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; azobisisobutyronitrile and azobis-2,4-dimethylvalero Compounds; benzoyl peroxide, include peroxide compounds such as di-tertiary butyl peroxide.
なかでも、密閉系内における硬化性、耐熱着色安定性により優れるという観点から、熱ラジカル開始剤が好ましく、脂肪族炭化水素のパーオキサイドがより好ましく、１，１，３，３−テトラメチルブチルパーオキシ−２−エチルヘキサノエート、２，２−ジ−（ｔ−アミルパーオキシ）ブタン、ｔ−ブチルパーオキシ−２−エチルヘキシルモノカーボネートがさらに好ましい。
ラジカル開始剤はそれぞれ単独でまたは２種以上を組み合わせて使用することができる。
Among them, from the viewpoint of excellent curability in a closed system and heat-resistant coloring stability, a thermal radical initiator is preferable, an aliphatic hydrocarbon peroxide is more preferable, and 1,1,3,3-tetramethylbutyl peroxide is preferable. Oxy-2-ethylhexanoate, 2,2-di- (t-amylperoxy) butane, and t-butylperoxy-2-ethylhexyl monocarbonate are more preferable.
The radical initiators can be used alone or in combination of two or more.
ラジカル開始剤の量は、（メタ）アクリル変性オルガノポリシロキサン１００質量部に対して、密閉系内における硬化性、耐熱着色安定性により優れるという観点から、0.01〜1質量部が好ましい。 The amount of the radical initiator is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the (meth) acryl-modified organopolysiloxane, from the viewpoint of excellent curability in the closed system and heat-resistant coloring stability.
（Ｃ）ビス（アルコキシシリル）アルカンについて以下に説明する。
本発明の組成物に含有されるビス（アルコキシシリル）アルカンは、１分子中にアルコキシシリル基を２個有する２価のアルカンである。
アルコキシシリル基におけるアルコキシ基は特に制限されない。例えば、メトキシ基、エトキシ基、イソプロポキシ基が挙げられる。
アルコキシシリル基は、アルコキシ基を１〜３個有することができる。アルコキシシリル基に結合することができる、アルコキシ基以外の基としては、例えば、メチル基、エチル基のようなアルキル基が挙げられる。
２価のアルカン（アルキレン基）は特に制限されない。２価のアルカンの炭素原子数は特に制限されない。２価のアルカンの炭素原子数は密閉系内における硬化性、接着性、耐湿熱接着性、耐熱着色安定性に優れるという観点から２〜３個が好ましい。
(C) The bis (alkoxysilyl) alkane will be described below.
The bis (alkoxysilyl) alkane contained in the composition of the present invention is a divalent alkane having two alkoxysilyl groups in one molecule.
The alkoxy group in the alkoxysilyl group is not particularly limited. Examples thereof include a methoxy group, an ethoxy group, and an isopropoxy group.
The alkoxysilyl group can have 1 to 3 alkoxy groups. Examples of the group other than the alkoxy group that can be bonded to the alkoxysilyl group include alkyl groups such as a methyl group and an ethyl group.
The divalent alkane (alkylene group) is not particularly limited . The number of carbon atoms of the divalent alkane is not particularly limited. The number of carbon atoms of the divalent alkane is preferably 2 to 3 from the viewpoint of excellent curability, adhesiveness, wet heat resistance, and heat resistant coloration stability in a closed system.
ビス(アルコキシシリル)アルカンとしては、例えば、下記式（ＩＩ）で表されるものが挙げられる。
式中、Ｒ7〜Ｒ8はそれぞれアルキル基であり、Ｒ9は２価の炭化水素基であり、ａはそれぞれ１〜３の整数である。アルキル基としては、例えば、メチル基、エチル基が挙げられる。Ｒ9としての２価の炭化水素基は上記の２価のアルカンと同義である。
Examples of the bis (alkoxysilyl) alkane include those represented by the following formula (II).
In the formula, R 7 to R 8 are each an alkyl group, R 9 is a divalent hydrocarbon group, and a is an integer of 1 to 3, respectively. Examples of the alkyl group include a methyl group and an ethyl group. The divalent hydrocarbon group as R 9 has the same meaning as the above divalent alkane.
ビス(アルコキシシリル)アルカンとしては、例えば、１，２ビス（トリエトキシリル）エタン、１，４−ビス（トリメトキシシリル）ブタン、１−メチルジメトキシシリル−４−トリメトキシシリルブタン、１，４−ビス（メチルジメトキシシリル）ブタン、１，５−ビス（トリメトキシシリル）ペンタン、１，４−ビス（トリメトキシシリル）ペンタン、１−メチルジメトキシシリル−５−トリメトキシシリルペンタン、１，５−ビス（メチルジメトキシシリル）ペンタン、１，６−ビス（トリメトキシシリル）ヘキサン、１，４−ビス（トリメトキシシリル）ヘキサン、１，５−ビス（トリメトキシシリル）ヘキサン、２，５−ビス（トリメトキシシリル）ヘキサン、１，６−ビス（メチルジメトキシシリル）ヘキサン、１，７−ビス（トリメトキシシリル）ヘプタン、２，５−ビス（トリメトキシシリル）ヘプタン、２，６−ビス（トリメトキシシリル）ヘプタン、１，８−ビス（トリメトキシシリル）オクタン、２，５−ビス（トリメトキシシリル）オクタン、２，７−ビス（トリメトキシシリル）オクタン、１，９−ビス（トリメトキシシリル）ノナン、２，７−ビス（トリメトキシシリル）ノナン、１，１０−ビス（トリメトキシシリル）デカン、３，８−ビス（トリメトキシシリル）デカンが挙げられる。 Examples of the bis (alkoxysilyl) alkane include 1,2bis (triethoxylyl) ethane, 1,4-bis (trimethoxysilyl) butane, 1-methyldimethoxysilyl-4-trimethoxysilylbutane, 1,4 -Bis (methyldimethoxysilyl) butane, 1,5-bis (trimethoxysilyl) pentane, 1,4-bis (trimethoxysilyl) pentane, 1-methyldimethoxysilyl-5-trimethoxysilylpentane, 1,5- Bis (methyldimethoxysilyl) pentane, 1,6-bis (trimethoxysilyl) hexane, 1,4-bis (trimethoxysilyl) hexane, 1,5-bis (trimethoxysilyl) hexane, 2,5-bis ( Trimethoxysilyl) hexane, 1,6-bis (methyldimethoxysilyl) hexane, 1,7-bis ( Limethoxysilyl) heptane, 2,5-bis (trimethoxysilyl) heptane, 2,6-bis (trimethoxysilyl) heptane, 1,8-bis (trimethoxysilyl) octane, 2,5-bis (trimethoxy Silyl) octane, 2,7-bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane, 2,7-bis (trimethoxysilyl) nonane, 1,10-bis (trimethoxysilyl) decane, 3,8-bis (trimethoxysilyl) deca emissions and the like.
ビス（アルコキシシリル）アルカンは、密閉系内における硬化性、接着性、耐湿熱接着性、耐熱着色安定性に優れるという観点から、式（ＩＩ）で表されるものが好ましく、ビス（トリアルコキシシリル）アルカンがより好ましく、１，２−ビス（トリエトキシシリル）エタン、１，６−ビス（トリメトキシシリル）ヘキサン、１，７−ビス（トリメトキシシリル）ヘプタン、１，８−ビス（トリメトキシシリル）オクタン、１，９−ビス（トリメトキシシリル）ノナンおよび１，１０−ビス（トリメトキシシリル）デカンからなる群から選ばれる少なくとも１種がより好ましく、１，６−ビス（トリメトキシシリル）ヘキサン、１，２ビス（トリエトキシリル）エタンがさらに好ましい。
ビス（アルコキシシリル）アルカンはそれぞれ単独でまたは２種以上を組み合わせて使用することができる。
The bis (alkoxysilyl) alkane is preferably represented by the formula (II) from the viewpoint of excellent curability, adhesion, heat-and-moisture resistance and heat-resistant coloring stability in a closed system, and bis (trialkoxysilyl). ) Alkanes are more preferred , 1,2-bis (triethoxysilyl) ethane, 1,6-bis (trimethoxysilyl) hexane, 1,7-bis (trimethoxysilyl) heptane, 1,8-bis (trimethoxy) More preferred is at least one selected from the group consisting of (silyl) octane, 1,9-bis (trimethoxysilyl) nonane and 1,10-bis (trimethoxysilyl) decane, and 1,6-bis (trimethoxysilyl) Hexane and 1,2 bis (triethoxylyl) ethane are more preferred.
Bis (alkoxysilyl) alkanes can be used alone or in combination of two or more.
ビス（アルコキシシリル）アルカンの量は、密閉系内における硬化性、接着性、耐湿熱接着性、耐熱着色安定性に優れるという観点から、（メタ）アクリル変性オルガノポリシロキサン１００質量部に対して、0.01〜10質量部であるのが好ましく、0.1〜３質量部であるのがより好ましい。 The amount of bis (alkoxysilyl) alkane is based on 100 parts by weight of (meth) acryl-modified organopolysiloxane from the viewpoint of excellent curability, adhesion, wet heat resistance, and heat resistant color stability in a closed system. It is preferable that it is 0.01-10 mass parts, and it is more preferable that it is 0.1-3 mass parts.
本発明の組成物は、密閉系内における硬化性、接着性、耐湿熱接着性、耐熱着色安定性により優れるという観点から、（メタ）アクリル変性オルガノポリシロキサンと、ラジカル開始剤と、ビス（アルコキシシリル）アルカンとからなる組成物（以上の３つの成分のみを含有する組成物）とすることができる。 The composition of the present invention has a (meth) acryl-modified organopolysiloxane, a radical initiator, a bis (alkoxy) from the viewpoint of being excellent in curability, adhesion, wet heat resistance, and heat resistant color stability in a closed system. A composition composed of (silyl) alkane (a composition containing only the above three components) can be used.
本発明の組成物は、(メタ)アクリル変性オルガノポリシロキサン、ラジカル開始剤、ビス(アルコキシシリル)アルカン以外に、本発明の目的や効果を損なわない範囲で必要に応じてさらに添加剤を含有することができる。
添加剤としては、例えば、無機フィラー、酸化防止剤、滑剤、紫外線吸収剤、熱光安定剤、分散剤、帯電防止剤、重合禁止剤、消泡剤、硬化促進剤、溶剤、無機蛍光体、老化防止剤、ラジカル禁止剤、接着性改良剤、難燃剤、界面活性剤、保存安定性改良剤、オゾン老化防止剤、増粘剤、可塑剤、放射線遮断剤、核剤、カップリング剤、導電性付与剤、リン系過酸化物分解剤、顔料、金属不活性化剤、物性調整剤が挙げられる。各種添加剤は特に制限されない。例えば、従来公知のものが挙げられる。
The composition of the present invention further contains additives as necessary within a range not impairing the object and effect of the present invention, in addition to (meth) acryl-modified organopolysiloxane, radical initiator, and bis (alkoxysilyl) alkane. be able to.
Examples of additives include inorganic fillers, antioxidants, lubricants, ultraviolet absorbers, thermal light stabilizers, dispersants, antistatic agents, polymerization inhibitors, antifoaming agents, curing accelerators, solvents, inorganic phosphors, Anti-aging agent, radical inhibitor, adhesion improver, flame retardant, surfactant, storage stability improver, ozone anti-aging agent, thickener, plasticizer, radiation blocker, nucleating agent, coupling agent, conductive Examples include property-imparting agents, phosphorus peroxide decomposers, pigments, metal deactivators, and physical property modifiers. Various additives are not particularly limited. For example, a conventionally well-known thing is mentioned.
本発明の組成物は、貯蔵安定性に優れるという観点から、実質的に水を含まないのが好ましい態様の１つとして挙げられる。本発明において実質的に水を含まないとは、本発明の組成物中における水の量が０．１質量％以下であることをいう。
また、本発明の組成物は、作業環境性に優れるという観点から、実質的に溶媒を含まないのが好ましい態様の１つとして挙げられる。本発明において実質的に溶媒を含まないとは、本発明の組成物中における溶媒の量が１質量％以下であることをいう。
From the viewpoint that the composition of the present invention is excellent in storage stability, it is mentioned as one of preferred embodiments that substantially does not contain water. In the present invention, “substantially free of water” means that the amount of water in the composition of the present invention is 0.1% by mass or less.
In addition, the composition of the present invention can be mentioned as one of preferred embodiments that substantially does not contain a solvent from the viewpoint of excellent work environment properties. The phrase “substantially free of solvent” in the present invention means that the amount of the solvent in the composition of the present invention is 1% by mass or less.
本発明の組成物は、その製造について特に制限されない。例えば、（メタ）アクリル変性オルガノポリシロキサンと、ラジカル開始剤と、ビス(アルコキシシリル)アルカンと、必要に応じて使用することができる添加剤とを混合することによって製造することができる。
本発明の組成物は、１液型または２液型として製造することが可能である。
The composition of the present invention is not particularly limited for its production. For example, it can be produced by mixing (meth) acryl-modified organopolysiloxane, a radical initiator, bis (alkoxysilyl) alkane, and an additive that can be used as necessary.
The composition of the present invention can be produced as a one-pack type or a two-pack type.
本発明の組成物は、光半導体封止用組成物として使用することができる。
本発明の組成物を適用することができる光半導体は特に制限されない。例えば、発光ダイオード（ＬＥＤ、例えば、白色ＬＥＤ）、有機電界発光素子（有機ＥＬ）、レーザーダイオード、ＬＥＤアレイが挙げられる。
The composition of this invention can be used as a composition for optical semiconductor sealing.
The optical semiconductor to which the composition of the present invention can be applied is not particularly limited. For example, a light emitting diode (LED, for example, white LED), an organic electroluminescent element (organic EL), a laser diode, and an LED array can be mentioned.
本発明の組成物の使用方法としては、例えば、被着体（例えば、光半導体、ガラス）に本発明の組成物を付与し、本発明の組成物が付与された被着体を加熱および／または光照射して本発明の組成物を硬化させることが挙げられる。
例えば、複数のガラスの間に本発明の組成物を付与して硬化させて本発明の組成物を介して複数のガラスを接着させることによって、ガラスの積層体を得ることができる。
また、複数のガラスの間に光半導体を配置し、ガラスの間に本発明の組成物を付与し硬化させて本発明の組成物を介して複数のガラスを接着させ光半導体を封止することができる。
As a method of using the composition of the present invention, for example, the composition of the present invention is applied to an adherend (for example, an optical semiconductor, glass), and the adherend to which the composition of the present invention is applied is heated and / or Alternatively, light irradiation may be performed to cure the composition of the present invention.
For example, a glass laminate can be obtained by applying and curing the composition of the present invention between a plurality of glasses and bonding the plurality of glasses through the composition of the present invention.
Also, an optical semiconductor is disposed between a plurality of glasses, the composition of the present invention is applied between the glasses and cured, and the plurality of glasses are bonded via the composition of the present invention to seal the optical semiconductor. Can do.
本発明の組成物を被着体に付与する方法は特に制限されない。例えば、ディスペンサーを使用する方法、ポッティング法、スクリーン印刷、トランスファー成形、インジェクション成形が挙げられる。 The method for applying the composition of the present invention to the adherend is not particularly limited. Examples thereof include a method using a dispenser, a potting method, screen printing, transfer molding, and injection molding.
本発明の組成物を加熱する際の温度は、密閉系内における硬化性、接着性、耐湿接着熱性、耐熱着色安定性により優れ、薄膜硬化性に優れ、硬化時間、可使時間を適切な長さとすることができ、硬化物のクラックを抑制でき、硬化物の平滑性、成形性、物性に優れるという観点から、８０℃〜１５０℃付近で硬化させるのが好ましく、１５０℃付近がより好ましい。 The temperature at which the composition of the present invention is heated is excellent in curability, adhesion, moisture-resistant adhesive heat resistance and heat-resistant coloration stability in a closed system, excellent in thin film curability, and has an appropriate length of curing time and pot life. From the viewpoint of being able to suppress cracks in the cured product and being excellent in the smoothness, moldability, and physical properties of the cured product, it is preferably cured at around 80 ° C. to 150 ° C., more preferably around 150 ° C.
本発明の組成物を光照射で硬化させる場合、例えば、紫外線、電子線を用いることができる。
硬化は、硬化性、透明性に優れるという観点から、実質的に無水の条件下で行うことができる。本発明において、硬化が実質的に無水の条件下でなされるとは、加熱および／または光照射における環境の大気中の湿度が１０％ＲＨ以下であることをいう。
When the composition of the present invention is cured by light irradiation, for example, ultraviolet rays and electron beams can be used.
Curing can be performed under substantially anhydrous conditions from the viewpoint of excellent curability and transparency. In the present invention, the phrase “curing is performed under substantially anhydrous conditions” means that the atmospheric humidity of the environment in heating and / or light irradiation is 10% RH or less.
本発明の組成物を用いて得られる硬化物（硬化物の厚さが２ｍｍである場合）は、ＪＩＳ Ｋ０１１５：２００４に準じ紫外・可視吸収スペクトル測定装置（島津製作所社製、以下同様。）を用いて波長４００ｎｍにおいて測定された透過率が、８０％以上であるのが好ましく、８５％以上であるのがより好ましい。 A cured product obtained by using the composition of the present invention (when the thickness of the cured product is 2 mm) is an ultraviolet / visible absorption spectrum measuring apparatus (manufactured by Shimadzu Corporation, the same applies hereinafter) according to JIS K0115: 2004. The transmittance measured at a wavelength of 400 nm is preferably 80% or more, more preferably 85% or more.
また、本発明の組成物を用いて得られる硬化物は、初期硬化の後耐熱試験（初期硬化後の硬化物を１５０℃の条件下に１，０００時間置く試験）を行いその後の硬化物（厚さ：２ｍｍ）について、ＪＩＳ Ｋ０１１５：２００４に準じ紫外・可視スペクトル測定装置を用いて波長４００ｎｍにおいて測定された透過率が、８０％以上であるのが好ましく、８５％以上であるのがより好ましい。 In addition, the cured product obtained using the composition of the present invention is subjected to a heat resistance test after initial curing (a test in which the cured product after initial curing is placed at a temperature of 150 ° C. for 1,000 hours), and then the cured product ( (Thickness: 2 mm), the transmittance measured at a wavelength of 400 nm using an ultraviolet / visible spectrum measuring apparatus according to JIS K0115: 2004 is preferably 80% or more, more preferably 85% or more. .
本発明の組成物を用いて得られる硬化物は、その透過性保持率（耐熱試験後の透過率／初期硬化の際の透過率×１００）が、７０〜１００％であるのが好ましく、８０〜１００％であるのがより好ましい。 The cured product obtained using the composition of the present invention preferably has a permeability retention ratio (transmittance after heat test / transmittance at initial curing × 100) of 70 to 100%, 80 More preferably, it is -100%.
本発明の組成物は、光半導体以外にも、例えば、ディスプレイ材料、光記録媒体材料、光学機器材料、光部品材料、光ファイバー材料、光・電子機能有機材料、半導体集積回路周辺材料等の用途に用いることができる。 In addition to optical semiconductors, the composition of the present invention is used for applications such as display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fiber materials, optical / electronic functional organic materials, and semiconductor integrated circuit peripheral materials. Can be used.
以下に、実施例を示して本発明を具体的に説明する。ただし、本発明はこれらに限定されない。
１．変性オルガノポリシロキサンの製造
（１）変性オルガノポリシロキサン１
両端にヒドロキシ基を有するポリジメチルシロキサン（重量平均分子量２８，０００、商品名ｓｓ７０、信越化学工業社製）１００質量部、メタクリルオキシプロピルトリメトキシシラン（商品名ＫＢＭ５０３、信越化学工業社製。以下同様。）４質量部、および触媒として２エチルヘキサノエートスズ（関東化学社製）0.01質量部を反応容器に入れ、圧力を10ｍｍＨｇ、温度を60℃に保ちながら6時間反応させた。
得られた反応物について1Ｈ−ＮＭＲ分析を行い、ポリジメチルシロキサンの両末端のシラノール基が消失しメタクリルオキシプロピルジメトキシシリル基であることを確認した。
得られたポリジメチルシロキサンを変性オルガノポリシロキサン１とする。
変性オルガノポリシロキサン１の重量平均分子量は、クロロホルムを溶媒とするゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）によるポリスチレン換算（以下同様）で、重量平均分子量３５，０００であった。
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
1. Production of modified organopolysiloxane (1) Modified organopolysiloxane 1
100 parts by mass of polydimethylsiloxane having hydroxy groups at both ends (weight average molecular weight 28,000, trade name ss70, manufactured by Shin-Etsu Chemical Co., Ltd.), methacryloxypropyltrimethoxysilane (trade name KBM503, manufactured by Shin-Etsu Chemical Co., Ltd., and so on) .) 4 parts by mass and 0.01 part by mass of 2-ethylhexanoate tin (manufactured by Kanto Chemical Co., Ltd.) as a catalyst were placed in a reaction vessel and reacted for 6 hours while maintaining the pressure at 10 mmHg and the temperature at 60 ° C.
The obtained reaction product was subjected to 1 H-NMR analysis, and it was confirmed that the silanol groups at both ends of the polydimethylsiloxane disappeared to be methacryloxypropyldimethoxysilyl groups.
The obtained polydimethylsiloxane is referred to as modified organopolysiloxane 1.
The weight average molecular weight of the modified organopolysiloxane 1 was 35,000 in terms of polystyrene by gel permeation chromatography (GPC) using chloroform as a solvent (hereinafter the same).
（２）変性オルガノポリシロキサン２
原料としてのポリジメチルシロキサンを、両端にヒドロキシ基を有するポリジメチルシロキサン（重量平均分子量６0，０００、商品名ｘ−２１−５８４８、信越化学工業社製）100質量部に代えたほかは、変性オルガノポリシロキサン１と同様にして両端にメタクリルオキシプロピルジメトキシシリル基を有するポリジメチルシロキサンを製造した。
得られたポリジメチルシロキサンを変性オルガノポリシロキサン２とする。
変性オルガノポリシロキサン２の重量平均分子量は６３，０００であった。
(2) Modified organopolysiloxane 2
Except that the polydimethylsiloxane as a raw material was replaced with 100 parts by mass of polydimethylsiloxane having hydroxy groups at both ends (weight average molecular weight 60,000, trade name x-21-5848, manufactured by Shin-Etsu Chemical Co., Ltd.), modified organo In the same manner as polysiloxane 1, polydimethylsiloxane having methacryloxypropyldimethoxysilyl groups on both ends was produced.
The obtained polydimethylsiloxane is referred to as modified organopolysiloxane 2.
The modified organopolysiloxane 2 had a weight average molecular weight of 63,000.
２．光半導体封止用シリコーン樹脂組成物の製造
下記第１表に示す成分を同表に示す量（質量部）で用いてそれらを真空機付攪拌機で均一に混合し、光半導体封止用シリコーン樹脂組成物を製造した。
2. Production of Silicone Resin Composition for Optical Semiconductor Encapsulation Using the components shown in Table 1 below in the amounts (parts by mass), uniformly mixing them with a stirrer equipped with a vacuum machine, A composition was prepared.
第１表に示されている各成分は、以下のとおりである。
・（Ａ）変性ポリシロキサン１：上記のようにして製造した変性ポリシロキサン１
・（Ａ）変性ポリシロキサン２：上記のようにして製造した変性ポリシロキサン２
・ポリシロキサン１：商品名ｘ−２２−１６４ＡＳ、信越化学工業社製。下記式（５）で表され、式中のＲ6がメチル基であり、分子中にアルコキシシリル基がない、メタクリル変性ジメチルポリシロキサン。Ｍｗ＝９００
・ポリシロキサン２：下記式（５）で表され、式中のＲ6がメチル基であり、重量平均分子量が１，７２０であり、メタクリロイル基の官能基当量が８６０ｇ／モルである化合物（信越化学工業社製）
・ポリシロキサン３：Ｍｗ＝3０００での両末端シラノール（KF−9701，信越化学社製）１００ｇとＫＢＭ５０３を２５ｇ投入した。あとの製造法は変性ポリシロキサン１，２に同じであり、製造後の重量平均分子量は８，０００であった。
・（Ｂ）ラジカル開始剤１：熱ラジカル開始剤、化合物名１，１，３，３−テトラメチルブチルパーオキシ−２−エチルヘキサノエート、商品名パーオクタO（日本油脂社製）
・（Ｂ）ラジカル開始剤２：光ラジカル開始剤、商品名イルガキュア５００（１−ヒドロキシ−シクロヘキシル−フェニルケトンとベンゾフェノンとの１：１混合物）（チバスペシャル社製）
・（Ｂ）ラジカル開始剤３：熱ラジカル開始剤、商品名パーヘキシルD（日本油脂社製）（ジ−ｔ−ヘキシルパーオキサイド）
・（Ｂ）ラジカル開始剤４：熱ラジカル開始剤、商品名カヤケタールAM−c55（化薬アクゾ社製）（２，２−ジ（ｔ−アミルパーオキシ）ブタン
・（Ｂ）ラジカル開始剤５：熱ラジカル開始剤、商品名トリゴノックス１１７（化薬アクゾ社製）（ｔ−ブチルパーオキシ２−エチルヘキシルカーボネート）
・（Ｃ）ビス（アルコキシシリル）アルカン１：下記式で表される１，６ビス（トリメトキシシリル）へキサン（商品名Ｚ−６８３０、東レダウコーニング社製）
・（Ｃ）ビス（アルコキシシリル）アルカン２：下記式で表される１，２ビス(トリエトキシシリル)エタン（ＫＢＥ３０２６，信越化学工業社製）
・（Ｅ）ジメチルポリシロキサン１：下記式で表される化合物（商品名ｓｓ−１０、信越化学工業社製、Ｍｗ＝４２，０００）
・（Ｆ）アルコキシオリゴマー：商品名ｘ−４０−９２４６、信越化学工業社製、（Ｍｗ＝６０００）
・（Ｇ）ナフテン酸ジルコニル：日本化学産業社製
・（Ｈ）エポキシシリコーン：エポキシ変性ポリシロキサン（商品名：ＫＦ１０１、信越化学工業社製）
・（Ｉ）カチオン重合触媒：ＢＦ3・Ｅｔ2Ｏ（ＢＦ3エチルエテラート錯体、東京化成工業社製）
・（Ｊ）シリコーンオイル：末端トリメチルシリル基末端シリコーンオイル、商品名KF96-5000cs(信越化学工業社製）
・（Ｋ）アクリロイルモルホリン：ACMO、興人社製
・（Ｌ）Ｎ，Ｎ−ジメチルアクリルアミド：関東化学社製
Each component shown in Table 1 is as follows.
(A) Modified polysiloxane 1: Modified polysiloxane 1 produced as described above
(A) Modified polysiloxane 2: Modified polysiloxane 2 produced as described above
Polysiloxane 1: Trade name x-22-164AS, manufactured by Shin-Etsu Chemical Co., Ltd. A methacryl-modified dimethylpolysiloxane represented by the following formula (5), wherein R 6 is a methyl group, and there is no alkoxysilyl group in the molecule. Mw = 900
Polysiloxane 2: a compound represented by the following formula (5), wherein R 6 is a methyl group, the weight average molecular weight is 1,720, and the functional group equivalent of the methacryloyl group is 860 g / mol (Shin-Etsu (Made by Chemical Industries)
Polysiloxane 3: 100 g of both-end silanol (KF-9701, manufactured by Shin-Etsu Chemical Co., Ltd.) and MBM = 503 at 25 Mw were added. The subsequent production method was the same as that for the modified polysiloxanes 1 and 2, and the weight average molecular weight after production was 8,000.
(B) radical initiator 1: thermal radical initiator, compound name 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, trade name perocta O (manufactured by NOF Corporation)
(B) Radical initiator 2: Photoradical initiator, trade name Irgacure 500 (1: 1 mixture of 1-hydroxy-cyclohexyl-phenyl ketone and benzophenone) (manufactured by Ciba Special)
(B) Radical initiator 3: Thermal radical initiator, trade name Perhexyl D (manufactured by NOF Corporation) (di-t-hexyl peroxide)
(B) radical initiator 4: thermal radical initiator, trade name Kayaketal AM-c55 (manufactured by Kayaku Akzo) (2,2-di (t-amylperoxy) butane) (B) radical initiator 5: Thermal radical initiator, trade name Trigonox 117 (manufactured by Kayaku Akzo) (t-butylperoxy 2-ethylhexyl carbonate)
(C) bis (alkoxysilyl) alkane 1: 1,6 bis (trimethoxysilyl) hexane represented by the following formula (trade name Z-6830, manufactured by Toray Dow Corning)
(C) Bis (alkoxysilyl) alkane 2: 1,2-bis (triethoxysilyl) ethane represented by the following formula (KBE3026, manufactured by Shin-Etsu Chemical Co., Ltd.)
(E) Dimethylpolysiloxane 1: Compound represented by the following formula (trade name ss-10, manufactured by Shin-Etsu Chemical Co., Ltd., Mw = 42,000)
(F) Alkoxy oligomer: trade name x-40-9246, manufactured by Shin-Etsu Chemical Co., Ltd. (Mw = 6000)
・ (G) Zirconyl naphthenate: manufactured by Nippon Chemical Industry Co., Ltd. (H) Epoxy silicone: Epoxy-modified polysiloxane (trade name: KF101, manufactured by Shin-Etsu Chemical Co., Ltd.)
(I) Cationic polymerization catalyst: BF 3 · Et 2 O (BF 3 ethyl etherate complex, manufactured by Tokyo Chemical Industry Co., Ltd.)
・ (J) Silicone oil: Terminal trimethylsilyl group-terminated silicone oil, trade name KF96-5000cs (manufactured by Shin-Etsu Chemical Co., Ltd.)
(K) acryloylmorpholine: ACMO, manufactured by Kojin Co., Ltd. (L) N, N-dimethylacrylamide: manufactured by Kanto Chemical Co., Inc.
３．評価
上記のようにして得た光半導体封止用シリコーン樹脂組成物について、以下の方法で、密閉系初期硬化状態、透過率、透過率保持率、耐熱着色安定性、硬化時ガラス接着性、湿熱接着性、耐熱クラック性を評価した。結果を第１表に示す。
＜サンプルの作製＞
サンプルの作製について添付の図面を用いて以下に説明する。
図１は、実施例において本発明の光半導体封止用シリコーン樹脂組成物を硬化させるために使用した型を模式的に表す断面図である。
図１において、型８は、ガラス２（縦５ｃｍ、横５ｃｍ、厚さ４ｍｍ）と、アルミ板４との間にシリコンモールドのスペーサー１（縦５ｃｍ、横５ｃｍ、高さ２ｍｍ）を有し、アルミ板４とスペーサー１との間にＰＥＴ３（離型紙としてポリエチレンテレフタレートのフィルムを使用。）を有する。型８はジグ（図示せず。）で固定されている。
以下のようにして得られた組成物を直接ガラス２に塗布し、ガラス２とＰＥＴ３との間に、ガラス２の上の組成物をはさみ、内部６に組成物を充填する。充填後、内部６を密閉し（図示せず。）、以下の硬化条件で組成物６を硬化させ硬化物６とした。
3. Evaluation About the silicone resin composition for optical semiconductor encapsulation obtained as described above, in the following manner, a sealed initial curing state, transmittance, transmittance retention, heat-resistant coloring stability, glass adhesiveness during curing, wet heat Adhesion and heat crack resistance were evaluated. The results are shown in Table 1.
<Preparation of sample>
Production of a sample will be described below with reference to the accompanying drawings.
FIG. 1 is a cross-sectional view schematically showing a mold used for curing the silicone resin composition for sealing an optical semiconductor of the present invention in Examples.
In FIG. 1, a mold 8 has a silicon mold spacer 1 (vertical 5 cm, lateral 5 cm, height 2 mm) between a glass 2 (vertical 5 cm, lateral 5 cm, thickness 4 mm) and an aluminum plate 4. Between the aluminum plate 4 and the spacer 1, there is PET3 (polyethylene terephthalate film is used as a release paper). The mold 8 is fixed with a jig (not shown).
The composition obtained as follows is applied directly to the glass 2, the composition on the glass 2 is sandwiched between the glass 2 and the PET 3, and the interior 6 is filled with the composition. After filling, the inside 6 was sealed (not shown), and the composition 6 was cured under the following curing conditions to obtain a cured product 6.
＜硬化条件＞
（１）組成物が光ラジカル開始剤を含有する場合
型８に光照射装置（商品名：ＧＳ ＵＶＳＹＳＴＥＭ ＴＹＰＥ Ｓ２５０―０１、ジーエス・ユアサ ライティング社製。光源としてメタルハイドロランプを使用し、積算光量１，８００ｍＪ／ｃｍ2で照射した。）で波長２５０〜３８０ｎｍの紫外線を光量１２０ｍＷ／ｃｍで４０秒間照射し、積算光量１８００ｍＪ／ｃｍ2として、硬化物を得た。
<Curing conditions>
(1) When the composition contains a photo-radical initiator A light irradiation device (trade name: GS UVSYSTEM TYPE S250-01, manufactured by GS Yuasa Lighting Co., Ltd., using a metal hydrolamp as a light source, integrated light quantity 1 , 800 mJ / cm 2 ) was irradiated for 40 seconds at a light amount of 120 mW / cm with a wavelength of 250 to 380 nm to obtain a cured product with an integrated light amount of 1800 mJ / cm 2 .
（２）組成物が熱ラジカル開始剤を含有する場合
型８を電気オーブンに入れて、１５０℃で３時間加熱して硬化物を得た。
(2) When the composition contains a thermal radical initiator The mold 8 was put in an electric oven and heated at 150 ° C. for 3 hours to obtain a cured product.
（３）組成物がカチオン重合触媒を含有する場合
型８を電気オーブンに入れて、８０℃で１時間、さらにその後１５０℃で１時間加熱して硬化物を得た。
(3) When the composition contains a cationic polymerization catalyst The mold 8 was placed in an electric oven and heated at 80 ° C. for 1 hour and then at 150 ° C. for 1 hour to obtain a cured product.
＜評価条件＞
（１）密閉系初期硬化状態
型８を用いて組成物を上記の条件で硬化させ、初期の硬化状態を評価した。
評価基準は、硬化後表面タックがあるかどうかを確認しタックがない場合を「○」、タックありもしくは未硬化の場合を「×」とした。組成物が白濁した場合を「白濁」とした。
<Evaluation conditions>
(1) Sealed initial curing state The composition was cured using the mold 8 under the above conditions, and the initial curing state was evaluated.
As the evaluation criteria, it was confirmed whether or not there was a surface tack after curing, and “O” was given when there was no tack, and “X” was given when tack was present or not cured. The case where the composition became cloudy was designated as “cloudy”.
（２）透過率、透過率保持率
透過率評価試験において、型８を用いて組成物を上記の条件で硬化させて得られた初期硬化物、および耐熱試験（初期硬化物をさらに１５０℃の条件下で１，０００時間加熱する試験）後の硬化物（いずれも厚さが２ｍｍ）についてそれぞれ、ＪＩＳ Ｋ０１１５：２００４に準じ紫外・可視吸収スペクトル測定装置（島津製作所社製）を用いて波長４００ｎｍにおける透過率を測定した。また、耐熱試験後の透過率の初期の透過率に対する保持率を下記計算式によって求めた。
透過率保持率（％）＝（耐熱試験後の透過率）／（初期の透過率）×１００
(2) Transmittance, Transmittance Retention Rate In the transmittance evaluation test, an initial cured product obtained by curing the composition using the mold 8 under the above conditions, and a heat resistance test (the initial cured product is further heated at 150 ° C. 400 nm wavelength using a UV / visible absorption spectrum measuring apparatus (manufactured by Shimadzu Corp.) according to JIS K0115: 2004 for each cured product (each having a thickness of 2 mm) after 1,000 hours of heating under conditions) The transmittance was measured. Moreover, the retention with respect to the initial transmittance of the transmittance after the heat test was obtained by the following calculation formula.
Transmittance retention rate (%) = (Transmittance after heat resistance test) / (Initial transmittance) × 100
（３）耐熱着色安定性
型８を用いて組成物を上記の条件で硬化させて得られた初期硬化物、および耐熱試験（初期硬化物を１５０℃の条件下で１，０００時間加熱する試験）後の硬化物について、耐熱試験後の硬化物が、初期硬化物と比較して黄変したかどうかを目視で観察した。
(3) Heat-resistant coloring stability Initial cured product obtained by curing the composition under the above conditions using the mold 8, and a heat resistance test (a test in which the initial cured product is heated at a temperature of 150 ° C. for 1,000 hours) ) Regarding the cured product after, it was visually observed whether the cured product after the heat resistance test was yellow compared with the initial cured product.
（４）硬化時ガラス接着性
型８を用いて組成物を上記の条件で硬化させて得られた初期硬化物（手はがし試験の前に予め、スペーサー１、ＰＥＴ３およびアルミ板４を型８から外す。）を用いて手はがし試験（条件：室温２３℃、５５％ＲＨ。）を行い、試験後の硬化物の破壊形態によって硬化時（初期硬化段階）における接着性を評価した。
硬化時ガラス接着性の評価基準は、破壊形態が凝集破壊である場合を「○」、破壊形態が界面破壊である場合を「×」とした。
(4) Glass adhesiveness during curing An initial cured product obtained by curing the composition using the mold 8 under the above conditions (spacer 1, PET3 and aluminum plate 4 are removed from the mold 8 in advance of the hand peeling test. A hand peeling test (conditions: room temperature 23 ° C., 55% RH) was performed, and the adhesiveness at the time of curing (initial curing stage) was evaluated according to the fracture form of the cured product after the test.
The evaluation criteria for glass adhesiveness during curing were “◯” when the fracture mode was cohesive failure and “x” when the fracture mode was interfacial fracture.
（５）耐湿熱接着性
型８（硬化時ガラス接着性と同様の方法。）を用いて150℃３ｈにて硬化させ、型8からスペーサー１、ＰＥＴ３およびアルミ板４を外し１２１℃、１００％ＲＨの条件下に２４時間放置した。その後、手はがし試験により凝集破壊（ＣＦ）となった場合○、界面剥離（ＡＦ）した場合×とした。
(5) Moisture and heat-resistant adhesion Cured at 150 ° C. for 3 hours using a mold 8 (the same method as glass adhesion during curing), and the spacer 1, PET3 and aluminum plate 4 are removed from the mold 8 at 121 ° C. and 100%. It was left for 24 hours under the condition of RH. Thereafter, it was rated as ○ when cohesive failure (CF) was obtained by the hand peeling test, and x when interfacial peeling (AF) occurred.
（６）耐熱クラック性
型８を用いて組成物を上記の条件で硬化させて得られた初期硬化物を１５０℃の条件下に５００時間置いた。加熱後に得られた硬化物が、クラック無しの場合を「○」、クラックありの場合を「×」とした。
(6) Heat-resistant cracking property An initial cured product obtained by curing the composition under the above conditions using the mold 8 was placed under a condition of 150 ° C. for 500 hours. When the cured product obtained after heating had no cracks, “◯” was given, and when there were cracks, “x” was given.
第１表に示す結果から明らかなように、ビス（アルコキシシリル）アルカンを含まない比較例１、２は耐湿熱接着性に劣った。（メタ）アクリル変性オルガノポリシロキサン、ラジカル開始剤、ビス(アルコキシシリル)アルカンを含有しない比較例３（シラノール基とアルコキシ基との縮合のみによる硬化）は密閉系内で硬化させると縮合反応の副生成物であるアルコールが系内から抜けないため未硬化となった。比較例４、５［（メタ）アクリル変性オルガノポリシロキサンがアルコキシシリル基を有さない場合］、比較例６［（メタ）アクリル変性オルガノポリシロキサンの重量平均分子量が１万より小さい場合］は、ガラスとの接着性が低く耐熱クラックに劣った。エポキシシリコーンを含有する比較例７は耐熱着色安定性に劣った。ビス（アルコキシシリル）アルカンを含有せず代わりにシリコーンオイルを含有する比較例８は接着性に劣った。ビス（アルコキシシリル）アルカンを含有せずラジカル重合性モノマーを含有する比較例９、１０は相溶性せず白濁し透明性、硬化性に劣った。
これに対して、実施例１〜６は、密閉系内における硬化性、接着性（ガラスとの接着性、ガラス／ガラス間の接着性）、耐湿熱接着性、耐熱着色安定性に優れる。
As is apparent from the results shown in Table 1, Comparative Examples 1 and 2 containing no bis (alkoxysilyl) alkane were inferior in wet heat resistance. Comparative Example 3 containing no (meth) acryl-modified organopolysiloxane, radical initiator, or bis (alkoxysilyl) alkane (curing only by condensation of silanol groups and alkoxy groups) is a side effect of the condensation reaction when cured in a closed system. Since the product alcohol did not escape from the system, it was uncured. Comparative Examples 4 and 5 [when the (meth) acryl-modified organopolysiloxane has no alkoxysilyl group], Comparative Example 6 [when the weight average molecular weight of the (meth) acryl-modified organopolysiloxane is less than 10,000] Low adhesion to glass and inferior heat-resistant cracks. Comparative Example 7 containing epoxy silicone was inferior in heat-resistant coloring stability. Comparative Example 8, which did not contain bis (alkoxysilyl) alkane and contained silicone oil instead, was inferior in adhesion. Comparative Examples 9 and 10 containing a radical polymerizable monomer without containing bis (alkoxysilyl) alkane were not compatible and became cloudy and inferior in transparency and curability.
On the other hand, Examples 1-6 are excellent in sclerosis | hardenability in a closed system, adhesiveness (adhesion with glass, adhesiveness between glass / glass), heat-and-moisture resistance, and heat-resistant coloring stability.
１ スペーサー
２ ガラス
３ ＰＥＴ
４ アルミ板
６ 本発明の組成物（内部６、硬化後硬化物６となる）
８ 型
1 Spacer 2 Glass 3 PET
4 Aluminum plate 6 Composition of the present invention (internal 6 and cured product 6 after curing)
Type 8
Claims (4)
（Ｂ）ラジカル開始剤と、
（Ｃ）ビス（アルコキシシリル）アルカンとを含有し、
前記ビス（アルコキシシリル）アルカンの量が、前記（メタ）アクリル変性オルガノポリシロキサン１００質量部に対して、０．０１〜３質量部である、光半導体封止用シリコーン樹脂組成物。
（式中、Ｒ1は水素原子またはメチル基であり、Ｒ4は炭素原子数１〜８の２価の炭化水素基である。） (A) (Meth) acrylic modification having one or more alkoxysilyl groups and two functional groups represented by the following formula (I) and a weight average molecular weight of 10,000 to 150,000 in one molecule Organopolysiloxane,
(B) a radical initiator;
(C) bis (alkoxysilyl) alkane ,
The silicone resin composition for optical semiconductor sealing whose quantity of the said bis (alkoxy silyl) alkane is 0.01-3 mass parts with respect to 100 mass parts of the said (meth) acryl modified organopolysiloxane .
(In the formula, R 1 is a hydrogen atom or a methyl group, and R 4 is a divalent hydrocarbon group having 1 to 8 carbon atoms.)
（式中、Ｒ1はそれぞれ水素原子またはメチル基であり、Ｒ2、Ｒ3はそれぞれアルキル基であり、Ｒ4はそれぞれ炭素原子数１〜８の２価の炭化水素基であり、ｎはそれぞれ１または２であり、ｍは１００〜２０００である。） The silicone resin composition for optical semiconductor encapsulation according to claim 1, wherein the (meth) acryl-modified organopolysiloxane is represented by the following formula (2).
(Wherein R 1 is a hydrogen atom or a methyl group, R 2 and R 3 are each an alkyl group, R 4 is a divalent hydrocarbon group having 1 to 8 carbon atoms, and n is Each is 1 or 2, and m is 100-2000.)
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