JP2016102206A - Epoxy resin composition - Google Patents
Epoxy resin composition Download PDFInfo
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- JP2016102206A JP2016102206A JP2015222480A JP2015222480A JP2016102206A JP 2016102206 A JP2016102206 A JP 2016102206A JP 2015222480 A JP2015222480 A JP 2015222480A JP 2015222480 A JP2015222480 A JP 2015222480A JP 2016102206 A JP2016102206 A JP 2016102206A
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- epoxy resin
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 229920006295 polythiol Polymers 0.000 claims abstract description 10
- 239000002683 reaction inhibitor Substances 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 6
- ZFMOJHVRFMOIGF-UHFFFAOYSA-N 2,4,6-trimethoxy-1,3,5,2,4,6-trioxatriborinane Chemical compound COB1OB(OC)OB(OC)O1 ZFMOJHVRFMOIGF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 3
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 claims description 3
- 238000003860 storage Methods 0.000 abstract description 24
- 230000008859 change Effects 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 238000007385 chemical modification Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 230000020169 heat generation Effects 0.000 abstract 1
- -1 cyclic siloxane Chemical class 0.000 description 16
- 229910002012 Aerosil® Inorganic materials 0.000 description 14
- 238000001723 curing Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 238000007792 addition Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- 238000012790 confirmation Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 125000003396 thiol group Chemical group [H]S* 0.000 description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- QSOFJLDXOMMNNK-UHFFFAOYSA-N 2-(hydroxymethyl)-2-methylpropane-1,3-diol 3-sulfanylbutanoic acid Chemical compound CC(S)CC(O)=O.CC(S)CC(O)=O.CC(S)CC(O)=O.OCC(C)(CO)CO QSOFJLDXOMMNNK-UHFFFAOYSA-N 0.000 description 2
- WBEKRAXYEBAHQF-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;3-sulfanylbutanoic acid Chemical compound CC(S)CC(O)=O.CC(S)CC(O)=O.CC(S)CC(O)=O.CCC(CO)(CO)CO WBEKRAXYEBAHQF-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- VTLHIRNKQSFSJS-UHFFFAOYSA-N [3-(3-sulfanylbutanoyloxy)-2,2-bis(3-sulfanylbutanoyloxymethyl)propyl] 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCC(COC(=O)CC(C)S)(COC(=O)CC(C)S)COC(=O)CC(C)S VTLHIRNKQSFSJS-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- NKMOLEYVYVWWJC-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis[2-(3-sulfanylbutanoyloxy)ethyl]-1,3,5-triazinan-1-yl]ethyl 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCCN1C(=O)N(CCOC(=O)CC(C)S)C(=O)N(CCOC(=O)CC(C)S)C1=O NKMOLEYVYVWWJC-UHFFFAOYSA-N 0.000 description 1
- LJBWJFWNFUKAGS-UHFFFAOYSA-N 2-[bis(2-hydroxyphenyl)methyl]phenol Chemical compound OC1=CC=CC=C1C(C=1C(=CC=CC=1)O)C1=CC=CC=C1O LJBWJFWNFUKAGS-UHFFFAOYSA-N 0.000 description 1
- LABQKWYHWCYABU-UHFFFAOYSA-N 4-(3-sulfanylbutanoyloxy)butyl 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCCCCOC(=O)CC(C)S LABQKWYHWCYABU-UHFFFAOYSA-N 0.000 description 1
- 102100027123 55 kDa erythrocyte membrane protein Human genes 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 101001057956 Homo sapiens 55 kDa erythrocyte membrane protein Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- KUGSJJNCCNSRMM-UHFFFAOYSA-N ethoxyboronic acid Chemical compound CCOB(O)O KUGSJJNCCNSRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FPLYNRPOIZEADP-UHFFFAOYSA-N octylsilane Chemical compound CCCCCCCC[SiH3] FPLYNRPOIZEADP-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、ポリチオール化合物を硬化剤とするエポキシ樹脂に関するものである。 The present invention relates to an epoxy resin using a polythiol compound as a curing agent.
従来、特許文献１などの文献に記載される様に、ＣＭＯＳセンサーなどのカメラモジュールの組み立てには加熱硬化型エポキシ樹脂組成物、または室温硬化型の二液型エポキシ樹脂組成物が汎用されている。しかしながら、組み立てに際しては、エポキシ樹脂組成物の塗布量等を高い精度で制御することが必要とされる。さらには、カメラモジュールなどの電子部品においては、加熱時の部品のズレや電子部品そのものに与える悪影響から、エポキシ樹脂組成物を低温（８０℃以下など）で、短時間（１０分以内など）により硬化させることが最適とされる。また、原料由来の低分子量環状シロキサン（（ＳｉＯ（ＣＨ３）２）ｎ、ｎ＝３〜２０）がエポキシ樹脂組成物に含まれていると硬化時に揮発して、センサー等に付着し不具合が発生する。 Conventionally, as described in documents such as Patent Document 1, a thermosetting epoxy resin composition or a room temperature curable two-component epoxy resin composition has been widely used for assembling a camera module such as a CMOS sensor. . However, when assembling, it is necessary to control the application amount of the epoxy resin composition with high accuracy. Furthermore, in electronic parts such as camera modules, the epoxy resin composition can be used at a low temperature (eg, 80 ° C. or less) and in a short time (eg, within 10 minutes) due to the adverse effects on the electronic parts themselves during component heating. It is best to cure. In addition, if the low molecular weight cyclic siloxane derived from the raw material ((SiO (CH 3 ) 2 ) n , n = 3 to 20) is contained in the epoxy resin composition, it volatilizes at the time of curing and adheres to the sensor or the like. Occur.
特許文献２の様なエポキシ基を有する樹脂とポリチオール化合物の組成物は知られていたが、当該硬化物は軟質であることから電気電子部品の精密な組み立てには不向きである。さらに、エポキシ樹脂（主剤）がフレキシブルな構造を有すると硬化速度が遅く、加熱中に組成物が流動しやすい。また、当該文献には塗布形状を制御する様な技術は開示されていない。 Although the composition of the resin and polythiol compound which has an epoxy group like patent document 2 was known, since the said hardened | cured material is soft, it is unsuitable for the precise assembly of an electrical / electronic component. Furthermore, when the epoxy resin (main agent) has a flexible structure, the curing rate is slow, and the composition tends to flow during heating. Moreover, the technique which controls an application | coating shape is not indicated by the said literature.
従来のエポキシ樹脂組成物では、保存安定性と低温短時間硬化とを両立し、加熱時の熱または反応時の発熱により塗布後の形状が変わることや流動性が発生して流れてしまうなどして塗布形状を維持することが困難であった。 With conventional epoxy resin compositions, both storage stability and low-temperature, short-time curing are achieved, and the shape after application changes due to heat during heating or heat generated during reaction, and fluidity occurs and flows. It was difficult to maintain the coating shape.
本発明者らは、上記目的を達成するべく鋭意検討した結果、エポキシ樹脂組成物において塗布後の形状が変わることや流動性が発生して流れることが無く、塗布形状を維持する手法を見いだし、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have found a technique for maintaining the application shape without changing the shape after application in the epoxy resin composition and without causing flow and flow. The present invention has been completed.
本発明の要旨を次に説明する。本発明の第一の実施態様は、（Ａ）〜（Ｅ）成分を含み、（Ａ）成分１００質量部に対して（Ｂ）成分を２５〜９５質量部、（Ｃ）成分を１〜２０質量部、（Ｄ）成分を５〜２５質量部、および（Ｅ）成分を０．０１〜５質量部、含むエポキシ樹脂組成物に関する；
（Ａ）成分：エポキシ樹脂
（Ｂ）成分：ポリチオール化合物
（Ｃ）成分：硬化促進剤
（Ｄ）成分：ポリジオルガノシロキサンを除いた、後記の一般式３〜５のいずれか一つで表される基で化学修飾がなされているアモルファスシリカ
ただし、Ｒはそれぞれ独立して炭化水素基を指し、一般式３〜５それぞれにおいてＲの炭素数の合計が３以上である；
（Ｅ）成分：反応抑制剤。
The gist of the present invention will be described next. 1st embodiment of this invention contains (A)-(E) component, (B) component is 25-95 mass parts, (C) component is 1-20 with respect to 100 mass parts of (A) component. The epoxy resin composition comprising 5 parts by weight, 5-25 parts by weight of component (D), and 0.01-5 parts by weight of component (E);
(A) component: epoxy resin (B) component: polythiol compound (C) component: curing accelerator (D) component: represented by any one of the following general formulas 3 to 5 excluding polydiorganosiloxane Amorphous silica that has been chemically modified with a group wherein each R independently represents a hydrocarbon group, and in each of the general formulas 3 to 5, the total number of carbon atoms of R is 3 or more;
(E) component: Reaction inhibitor.
本発明の第二の実施態様は、チクソ比が４．０以上である第一の実施態様に記載のエポキシ樹脂組成物である。 2nd embodiment of this invention is an epoxy resin composition as described in 1st embodiment whose thixo ratio is 4.0 or more.
本発明の第三の実施態様は、前記（Ｃ）成分がエポキシアダクト化合物である第一または第二の実施態様に記載のエポキシ樹脂組成物である。 A third embodiment of the present invention is the epoxy resin composition according to the first or second embodiment, wherein the component (C) is an epoxy adduct compound.
本発明の第四の実施態様は、前記（Ｅ）成分が、燐酸、ホウ酸トリブチル、トリメトキシボロキシンおよびｐ−トルエンスルホン酸メチルからなる群から選択される少なくとも一つである、第一から第三の実施態様のいずれか１つに記載されるエポキシ樹脂組成物である。 In a fourth embodiment of the present invention, the component (E) is at least one selected from the group consisting of phosphoric acid, tributyl borate, trimethoxyboroxine and methyl p-toluenesulfonate. It is an epoxy resin composition as described in any one of 3rd embodiment.
本発明の第五の実施態様は、前記（Ｄ）成分が、ポリジオルガノシロキサンを除いた、下記の式６または式７により表される基で化学修飾がされているアモルファスシリカである第一から第四の実施態様のいずれか１つに記載のエポキシ樹脂組成物である。 In a fifth embodiment of the present invention, the component (D) is amorphous silica that is chemically modified with a group represented by the following formula 6 or 7 except for the polydiorganosiloxane. It is an epoxy resin composition as described in any one of 4th embodiment.
本発明の第六の実施態様は、前記（Ａ）成分がビスフェノール骨格を有するエポキシ樹脂である第一から第五の実施態様のいずれか１つに記載のエポキシ樹脂組成物である。 The sixth embodiment of the present invention is the epoxy resin composition according to any one of the first to fifth embodiments, wherein the component (A) is an epoxy resin having a bisphenol skeleton.
本発明の第七の実施態様は、前記（Ｂ）成分が、分子中に下記の式２の官能基を２つ以上有するポリチオール化合物である第一から第六の実施態様のいずれか１つに記載のエポキシ樹脂組成物である。 According to a seventh embodiment of the present invention, in any one of the first to sixth embodiments, the component (B) is a polythiol compound having two or more functional groups of the following formula 2 in the molecule. It is an epoxy resin composition of description.
本発明の第八の実施態様は、カメラモジュールの組み立てに使用される第一から第七の実施態様のいずれか１つに記載のエポキシ樹脂組成物である。 An eighth embodiment of the present invention is the epoxy resin composition according to any one of the first to seventh embodiments used for assembling a camera module.
本発明のエポキシ樹脂組成物は、低分子量環状シロキサンの発生が抑えられ、保存安定性と低温短時間での硬化を両立し、加熱時の熱または反応時の発熱により塗布後の形状が変わることや流動性が発生して流れることが抑えられ、塗布形状を維持することが可能である。本発明のエポキシ樹脂組成物は、特に、カメラモジュールなどの電子部品に好適に使用される。 The epoxy resin composition of the present invention suppresses the generation of low molecular weight cyclic siloxane, achieves both storage stability and curing at low temperature in a short time, and the shape after coating changes due to heat during heating or heat generated during reaction. It is possible to suppress the flow due to the occurrence of fluidity and maintain the coating shape. Especially the epoxy resin composition of this invention is used suitably for electronic components, such as a camera module.
本明細書において、範囲を示す「Ｘ〜Ｙ」は「Ｘ以上Ｙ以下」を意味する。また、特記しない限り、操作および物性等の測定は室温（２０〜２５℃）／相対湿度４０〜５０％の条件で測定する。 In this specification, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.
本発明の詳細を次に説明する。本発明に使用することができる組成物の主成分としての（Ａ）成分は、エポキシ樹脂である。架橋時に分子量が大きくなりやすい観点から、好ましくは、１分子内に２個以上のエポキシ基を有する化合物である。（Ａ）成分は、１種類だけ使用しても２種類以上を混合して使用しても良く、（Ａ）成分全体が２５℃で液状であれば、２５℃で固形のエポキシ樹脂を２５℃で液状のエポキシ樹脂に溶解させて使用しても良い。（Ａ）成分に含まれ得る塩素イオン濃度は、保存安定性の観点から、全塩素量が１０００ｐｐｍ（体積ｐｐｍ）以下であることが好ましく、さらに好ましくは、７００ｐｐｍ以下である。１０００ｐｐｍ以下であると保存安定性を維持することができる。 Details of the present invention will be described below. (A) component as a main component of the composition which can be used for this invention is an epoxy resin. From the viewpoint of easily increasing the molecular weight during crosslinking, a compound having two or more epoxy groups in one molecule is preferable. The component (A) may be used alone or in combination of two or more. If the entire component (A) is liquid at 25 ° C., an epoxy resin solid at 25 ° C. may be used at 25 ° C. And may be used by dissolving in a liquid epoxy resin. The chlorine ion concentration that can be contained in the component (A) is preferably 1000 ppm (volume ppm) or less, more preferably 700 ppm or less, from the viewpoint of storage stability. Storage stability can be maintained as it is 1000 ppm or less.
（Ａ）成分の具体例としては、エピクロルヒドリンとビスフェノール類などの多価フェノール類や多価アルコールとの縮合によって得られるものが例示でき、例えばビスフェノールＡ型、臭素化ビスフェノールＡ型、水添ビスフェノールＡ型、ビスフェノールＦ型、ビスフェノールＳ型、ビスフェノールＡＦ型、ビフェニル型、ナフタレン型、フルオレン型、ノボラック型、フェノールノボラック型、オルソクレゾールノボラック型、トリス（ヒドロキシフェニル）メタン型、テトラフェニロールエタン型などのグリシジルエーテル型エポキシ樹脂を例示することができる。その他にも、エピクロルヒドリンとフタル酸誘導体や脂肪酸などのカルボン酸との縮合によって得られるグリシジルエステル型エポキシ樹脂、エピクロルヒドリンとアミン類、シアヌル酸類、ヒダントイン類との反応によって得られるグリシジルアミン型エポキシ樹脂、さらには高分子量化、官能基付与等の様々な方法で変性したエポキシ樹脂を挙げられるが、これらに限定されるものではない。特に好ましくは、低温短時間硬化性の発現と粘度を考慮すると、ビスフェノールＡ型エポキシ樹脂やビスフェノールＦ型エポキシ樹脂等の、ビスフェノール骨格を有するエポキシ樹脂が好ましい。 Specific examples of the component (A) include those obtained by condensation of epichlorohydrin with polyhydric phenols such as bisphenols and polyhydric alcohols, such as bisphenol A type, brominated bisphenol A type, hydrogenated bisphenol A. Type, bisphenol F type, bisphenol S type, bisphenol AF type, biphenyl type, naphthalene type, fluorene type, novolak type, phenol novolak type, orthocresol novolak type, tris (hydroxyphenyl) methane type, tetraphenylolethane type, etc. A glycidyl ether type epoxy resin can be exemplified. In addition, glycidyl ester type epoxy resins obtained by condensation of epichlorohydrin with carboxylic acids such as phthalic acid derivatives and fatty acids, glycidyl amine type epoxy resins obtained by reaction of epichlorohydrin with amines, cyanuric acids, hydantoins, May include, but is not limited to, epoxy resins modified by various methods such as increasing the molecular weight and imparting functional groups. Particularly preferably, an epoxy resin having a bisphenol skeleton, such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin, is preferable in consideration of the expression of low temperature and short time curability and viscosity.
市販されているエポキシ樹脂としては、三菱化学株式会社製のｊＥＲ８２７、８２８ＥＬ等、大日本インキ工業株式会社製のＥＰＩＣＬＯＮ（登録商標）８３０、ＥＸＡ−８３５ＬＶ等、新日鉄住金化学株式会社製のエポトート（登録商標）ＹＤ−１２８、ＹＤＦ−１７０等が挙げられるが、これらに限定されるものではない。 Examples of commercially available epoxy resins include jER827 and 828EL manufactured by Mitsubishi Chemical Corporation, EPICLON (registered trademark) 830 manufactured by Dainippon Ink Industries, Ltd., EXA-835LV, and the like. (Trademark) YD-128, YDF-170, etc. are mentioned, However, it is not limited to these.
本発明で硬化剤として使用することができる（Ｂ）成分は、ポリチオール化合物である。本願のポリチオールは、多価チオールを意味する。（Ｂ）成分は式１や式２の様な１級チオール基または２級チオール基を分子内に複数有するものが好ましい。チオール基を複数有する場合、多官能であることで架橋が進み、組成物を硬化する際に分子量が大きくなる。特に、下記の（Ｅ）成分を含まない場合、１級チオール基と２級チオール基とで保存安定性に与える影響が異なり、保存安定性の安定化を考慮すると２級チオール基であることが好ましい。 The component (B) that can be used as a curing agent in the present invention is a polythiol compound. The polythiol of the present application means a polyvalent thiol. The component (B) preferably has a plurality of primary thiol groups or secondary thiol groups in the molecule as in formula 1 or formula 2. In the case of having a plurality of thiol groups, crosslinking proceeds due to polyfunctionality, and the molecular weight increases when the composition is cured. In particular, when the following component (E) is not included, the primary thiol group and the secondary thiol group have different effects on storage stability, and considering the stabilization of storage stability, the secondary thiol group may be a secondary thiol group. preferable.
（Ｂ）成分の具体例としては、ペンタエリスリトールテトラキス（３−メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３−メルカプトブチレート）、１，４−ビス（３−メルカプトブチリルオキシ）ブタン、１，３，５−トリス（３−メルカプトブチリルオキシエチル）−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン、トリメチロールプロパントリス（３−メルカプトブチレート）、トリメチロールエタントリス（３−メルカプトブチレート）、トリメチロールプロパントリス（３−メルカプトブチレート）、トリメチロールエタントリス（３−メルカプトブチレート）などが挙げられるが、これらに限定されるものではない。商品としては、ＳＣ有機化学株式会社製のＰＥＭＰなどが、昭和電工株式会社製のカレンズＭＴ（商標登録）シリーズのＰＥ１、ＢＤ１、ＮＲ１などが挙げられるがこれらに限定されるものではない。上記の（Ｂ）成分を１種単独で、または２種以上を混合して用いることができる。 Specific examples of the component (B) include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1, 3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), Trimethylol ethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylol ethane tris (3-mercaptobutyrate), and the like are exemplified, but the invention is not limited thereto. Examples of the product include, but are not limited to, PEMP manufactured by SC Organic Chemical Co., Ltd. and PE1, BD1, NR1, etc. of Karenz MT (trademark registered) series manufactured by Showa Denko KK. Said (B) component can be used individually by 1 type or in mixture of 2 or more types.
（Ａ）成分１００質量部に対して、（Ｂ）成分は２５〜９５質量部含まれる。（Ｂ）成分が２５質量部以上である場合は、組成物の粘度を低くして希釈効果が出せると共に、速硬化性を維持することができる。一方、（Ｂ）成分が９５質量部以下である場合は保存安定性が維持される。より好ましくは、（Ｂ）成分の添加量は、（Ａ）成分１００質量部に対して３０〜８０質量部である。 (A) 25-95 mass parts of (B) component is contained with respect to 100 mass parts of components. When the component (B) is 25 parts by mass or more, the viscosity of the composition can be lowered to achieve a diluting effect, and fast curability can be maintained. On the other hand, when the component (B) is 95 parts by mass or less, the storage stability is maintained. More preferably, the addition amount of (B) component is 30-80 mass parts with respect to 100 mass parts of (A) component.
本発明で使用することができる（Ｃ）成分としては、（Ａ）成分と（Ｂ）成分の反応を促進させる硬化促進剤である。硬化促進剤は２５℃において固体のものであり、イミダゾール骨格を有する化合物やエポキシ樹脂に三級アミンを付加させて反応を途中で止めているエポキシアダクト化合物を粉砕した微粉末などを使用することが、保存安定性と硬化性を考慮すると最も好ましい。特に好ましくは、保存安定性と反応性を考慮すると、エポキシアダクト化合物である。 (C) component which can be used by this invention is a hardening accelerator which accelerates | stimulates reaction of (A) component and (B) component. The curing accelerator is solid at 25 ° C., and a fine powder obtained by pulverizing a compound having an imidazole skeleton or an epoxy adduct compound in which a tertiary amine is added to an epoxy resin to stop the reaction in the middle is used. In view of storage stability and curability, it is most preferable. Particularly preferred is an epoxy adduct compound in view of storage stability and reactivity.
市販されているエポキシアダクト系化合物としては、味の素ファインテクノ株式会社製のアミキュア（登録商標）シリーズや、株式会社Ｔ＆Ｋ ＴＯＫＡ製のフジキュア（登録商標）シリーズや、旭化成ケミカルズ株式会社製のノバキュア（登録商標）シリーズなどが挙げられるが、これらに限定されるものではない。また、硬化促進剤を複数組み合わせて使用することもできる。上記の（Ｃ）成分を１種単独で、または２種以上を混合して用いることができる。 Examples of commercially available epoxy adduct compounds include the Amicure (registered trademark) series manufactured by Ajinomoto Fine Techno Co., Ltd., the Fuji Cure (registered trademark) series manufactured by T & K TOKA Co., Ltd., and Novacure (registered trademark) manufactured by Asahi Kasei Chemicals Corporation. ) Series and the like, but are not limited to these. A plurality of curing accelerators can be used in combination. Said (C) component can be used individually by 1 type or in mixture of 2 or more types.
（Ａ）成分１００質量部に対して、（Ｃ）成分の添加量は１〜２０質量部が好ましい。（Ｃ）成分が１質量部以上の場合は硬化性を発現し、２０質量部以下の場合は保存安定性を維持することができる。より好ましくは、（Ｃ）成分の添加量は、（Ａ）成分１００質量部に対して２〜１０質量部である。 (A) As for the addition amount of (C) component with respect to 100 mass parts of component, 1-20 mass parts is preferable. When the component (C) is 1 part by mass or more, curability is exhibited, and when it is 20 parts by mass or less, storage stability can be maintained. More preferably, the addition amount of (C) component is 2-10 mass parts with respect to 100 mass parts of (A) component.
本発明で使用することができる（Ｄ）成分としては、ポリジオルガノシロキサンを除いた、下記の一般式３〜式５で表される基のいずれかにより化学修飾がされているアモルファスシリカである。式３〜式５において、Ｒはそれぞれ独立して炭化水素基、好ましくはアルキル基を指す。式３〜式５それぞれにおいて、Ｒの炭素数の合計が３以上であり、さらに好ましくは３〜１５である。Ｒの炭素数の合計が３より少ないと、組成物は十分な形状保持性を示すことができない。本発明の好ましい一実施形態では、式３〜式５において、Ｒは、それぞれ独立して炭素数３〜１５の直鎖、分岐鎖または環状のアルキル基である。炭素数３〜１５のアルキル基としては、例えば、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等が例示できる。製造後のアモルファスシリカはシラノール（≡ＳｉＯＨ）が剥き出しの状態であるが、シラノールと反応する化合物をアモルファスシリカ表面で反応させること（化学修飾）で表面処理を行う。例えば、式６で表される基で化学修飾されたアモルファスシリカはシラノールと反応する化合物として、オクチルシランを用いて表面修飾すればよい。（Ｄ）成分を添加することで、粘度やチクソ性を制御することができる。平均粒径や形状などの粉体特性については特に限定はないが、エポキシ樹脂への分散のし易さとノズル詰まりを考慮すると、平均粒径は０．００１〜５０μｍが好ましい。特に、下記の式６または式７で表される基で化学修飾がなされているアモルファスシリカが最も好ましい。（Ｄ）成分の具体的な例としては、日本アエロジル株式会社製のＡＥＲＯＳＩＬ（登録商標） Ｒ８０５、ＲＸ２００が挙げられる。上記の（Ｄ）成分を１種単独で、または２種以上を混合して用いることができる。 The component (D) that can be used in the present invention is amorphous silica that is chemically modified by any of the groups represented by the following general formulas 3 to 5, excluding the polydiorganosiloxane. In Formulas 3 to 5, each R independently represents a hydrocarbon group, preferably an alkyl group. In each of Formulas 3 to 5, the total carbon number of R is 3 or more, more preferably 3 to 15. When the total number of carbon atoms in R is less than 3, the composition cannot exhibit sufficient shape retention. In one preferable embodiment of the present invention, in Formulas 3 to 5, R is each independently a linear, branched or cyclic alkyl group having 3 to 15 carbon atoms. Examples of the alkyl group having 3 to 15 carbon atoms include propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group. Group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and the like. The amorphous silica after production is in a state where silanol (≡SiOH) is exposed, but surface treatment is performed by reacting a compound that reacts with silanol on the amorphous silica surface (chemical modification). For example, amorphous silica chemically modified with a group represented by Formula 6 may be surface-modified using octylsilane as a compound that reacts with silanol. By adding the component (D), viscosity and thixotropy can be controlled. Although there are no particular limitations on the powder characteristics such as the average particle diameter and shape, the average particle diameter is preferably 0.001 to 50 μm in consideration of ease of dispersion in the epoxy resin and nozzle clogging. In particular, amorphous silica that is chemically modified with a group represented by the following formula 6 or 7 is most preferable. Specific examples of the component (D) include AEROSIL (registered trademark) R805 and RX200 manufactured by Nippon Aerosil Co., Ltd. Said (D) component can be used individually by 1 type or in mixture of 2 or more types.
（Ａ）成分１００質量部に対して、（Ｄ）成分の添加量は５〜２５質量部含まれる。（Ｄ）成分が５質量部より多い場合は流動性を安定化すると共に作業性を向上することができ、２５質量部より少ない場合は保存安定性を維持することができる。（Ｄ）成分の添加量は、（Ａ）成分１００質量部に対して６〜２２質量部であることが好ましく、１０〜２０質量部であることがより好ましい。 (A) The addition amount of (D) component is 5-25 mass parts with respect to 100 mass parts of component. When the component (D) is more than 5 parts by mass, the fluidity can be stabilized and the workability can be improved, and when it is less than 25 parts by mass, the storage stability can be maintained. (D) It is preferable that it is 6-22 mass parts with respect to 100 mass parts of (A) component, and, as for the addition amount of (D) component, it is more preferable that it is 10-20 mass parts.
本発明で使用することができる（Ｅ）成分は、（Ｃ）成分の反応性を抑制する抑制剤である。（Ｅ）成分としては、ホウ酸エステル、リン酸、アルキルリン酸エステル、ｐ−トルエンスルホン酸を使用することができる。ホウ酸エステルとしては、トリブチルボレ−ト、トリメトキシボロキシン、ホウ酸エチル、エポキシ−フェノール−ホウ酸エステル配合物（四国化成工業株式会社製 キュアダクト Ｌ−０７Ｎ）などが挙げられるがこれらに限定されるものではない。アルキルリン酸エステルとしては、リン酸トリメチル、リン酸トリブチルなどを使用することができるが、これらに限定されるものではない。（Ｅ）成分は単独でも複数を混合して使用しても良い。保存安定性を考慮すると、リン酸、ホウ酸トリブチル、トリメトキシボロキシン、およびｐ−トルエンスルホン酸メチルからなる群から選択される１つ以上であることが好ましい。 The component (E) that can be used in the present invention is an inhibitor that suppresses the reactivity of the component (C). (E) As a component, boric acid ester, phosphoric acid, alkyl phosphoric acid ester, and p-toluenesulfonic acid can be used. Examples of the borate ester include tributyl borate, trimethoxyboroxine, ethyl borate, epoxy-phenol-borate ester compound (Cure Duct L-07N manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like. Is not to be done. Examples of the alkyl phosphate ester include trimethyl phosphate and tributyl phosphate, but are not limited thereto. Component (E) may be used alone or in combination. In view of storage stability, it is preferably at least one selected from the group consisting of phosphoric acid, tributyl borate, trimethoxyboroxine, and methyl p-toluenesulfonate.
（Ａ）成分１００質量部に対して、（Ｅ）成分の添加量は０．０１〜５．０質量部が好ましい。（Ｅ）成分が０．０１質量部より多い場合は保存安定性を発現し、５．０質量部より少ない場合は硬化性を維持することができる。より好ましくは、（Ｅ）成分の添加量は、（Ａ）成分１００質量部に対して２〜１０質量部である。 (A) As for the addition amount of (E) component with respect to 100 mass parts of component, 0.01-5.0 mass parts is preferable. When the component (E) is more than 0.01 parts by mass, storage stability is exhibited, and when it is less than 5.0 parts by mass, curability can be maintained. More preferably, the addition amount of (E) component is 2-10 mass parts with respect to 100 mass parts of (A) component.
本発明のエポキシ樹脂組成物には、本発明の所期の効果を損なわない範囲において、顔料、染料などの着色剤、難燃剤、可塑剤、酸化防止剤、消泡剤、シラン系カップリング剤、レベリング剤、レオロジーコントロール剤等の添加剤を適量配合しても良い。これらの添加により、樹脂強度・接着強さ・作業性・保存性等に優れた組成物およびその硬化物が得られる。 The epoxy resin composition of the present invention includes colorants such as pigments and dyes, flame retardants, plasticizers, antioxidants, antifoaming agents, and silane coupling agents as long as the desired effects of the present invention are not impaired. An appropriate amount of additives such as a leveling agent and a rheology control agent may be blended. By these additions, a composition excellent in resin strength, adhesive strength, workability, storage stability and the like and a cured product thereof can be obtained.
塗布後の形状を維持するためには、エポキシ樹脂組成物のチクソ比（低回転数のときの粘度／高回転数のときの粘度）が４〜２０であることが好ましく、さらに好ましくは４〜１５である。これにより、本発明を塗布後の形状と広がりを抑制し、硬化後も塗布時の端部が広がらず、塗布形状も変化しない。本発明のエポキシ樹脂組成物は塗布形状を加熱硬化時に維持できるため、精密な塗布特性が要求される電子部品の組み立て用途、特にカメラモジュールの組み立てに適している。一般的に、充填剤としてのＤ成分の添加量を増やすことにより、粘度が上がり、チクソ比も上がる傾向がある。なお、本明細書において「チクソ比」は、実施例に記載の方法で測定された値である。 In order to maintain the shape after coating, the thixo ratio (viscosity at low rotational speed / viscosity at high rotational speed) of the epoxy resin composition is preferably 4 to 20, and more preferably 4 to 15. As a result, the shape and spread after application of the present invention are suppressed, the end portion during application does not expand even after curing, and the application shape does not change. Since the epoxy resin composition of the present invention can maintain the coating shape at the time of heat curing, it is suitable for use in assembling electronic parts that require precise coating characteristics, particularly for assembling a camera module. Generally, increasing the amount of D component added as a filler tends to increase the viscosity and the thixo ratio. In the present specification, the “thixo ratio” is a value measured by the method described in Examples.
実施例
次に実施例を挙げて本発明を更に詳細に説明するが、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。（以下、エポキシ樹脂組成物を単に組成物とも呼ぶ。）
［実施例１〜１０、比較例１〜１０］
組成物を調製するために下記の成分を準備した。
（Ａ）成分：エポキシ樹脂
・ビスフェノールＦ型エポキシ樹脂（ＥＰＩＣＬＯＮ（登録商標） ＥＸＡ−８３５ＬＶ ＤＩＣ株式会社製、含有塩素イオン濃度３００ｐｐｍ以下）
（Ｂ）成分：ポリチオール化合物
・ペンタエリスリトールテトラキス（３−メルカプトプロピオネート）（ＰＥＭＰ−２０Ｐ ＳＣ有機化学株式会社製）
・ペンタエリスリトールテトラキス（３−メルカプトブチレート）（カレンズＭＴ（登録商標）ＰＥ１ 昭和電工株式会社製）
（Ｃ）成分：硬化促進剤
・エポキシアダクト型硬化促進剤（フジキュア（登録商標）ＦＸＲ−１０８１ 株式会社Ｔ＆Ｋ ＴＯＫＡ製）
（Ｄ）成分：ポリジオルガノシロキサンを除いた、特定の化学修飾がされているアモルファスシリカ
・粉体表面が式６の基で修飾されたアモルファスシリカ（ＡＥＲＯＳＩＬ（登録商標） Ｒ８０５ 日本アエロジル株式会社製、平均一次粒径２００ｎｍ）
・粉体表面が式７の基で修飾されたアモルファスシリカ（ＡＥＲＯＳＩＬ（登録商標） ＲＸ２００ 日本アエロジル株式会社製、平均一次粒径２００ｎｍ）
（Ｄ’）成分：（Ｄ）成分以外のアモルファスシリカ
・粉体表面が化学修飾されていないアモルファスシリカ（ＡＥＲＯＳＩＬ（登録商標） ＃２００ 日本アエロジル株式会社製）
・粉体表面が式４のＲが共にメチル基のアモルファスシリカ（ＡＥＲＯＳＩＬ（登録商標） Ｒ９７２ 日本アエロジル株式会社製）
・粉体表面がポリジメチルシロキサンで化学修飾されているアモルファスシリカ（ＡＥＲＯＳＩＬ（登録商標） ＲＹ２００ 日本アエロジル株式会社製）
・粉体表面が式３のＲがメタクリロキシ基のアモルファスシリカ（ＡＥＲＯＳＩＬ（登録商標） Ｒ７２００ 日本アエロジル株式会社製）
（Ｅ）：反応抑制剤
・リン酸（試薬）
・ホウ酸トリブチル（試薬）
・トリメトキシボロキシン（試薬）
・ｐ−トルエンスルホン酸メチル（試薬）。
EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. (Hereinafter, the epoxy resin composition is also simply referred to as a composition.)
[Examples 1 to 10, Comparative Examples 1 to 10]
The following ingredients were prepared to prepare the composition.
(A) component: Epoxy resin / bisphenol F type epoxy resin (EPICLON (registered trademark) EXA-835LV manufactured by DIC Corporation, containing chloride ion concentration of 300 ppm or less)
Component (B): polythiol compound / pentaerythritol tetrakis (3-mercaptopropionate) (PEM-20P SC Organic Chemical Co., Ltd.)
Pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz MT (registered trademark) PE1 manufactured by Showa Denko KK)
Component (C): curing accelerator / epoxy adduct type curing accelerator (Fujicure (registered trademark) FXR-1081, manufactured by T & K TOKA Corporation)
Component (D): Amorphous silica with specific chemical modification excluding polydiorganosiloxane. Amorphous silica whose powder surface is modified with the group of formula 6 (AEROSIL (registered trademark) R805 manufactured by Nippon Aerosil Co., Ltd., (Average primary particle size 200nm)
Amorphous silica whose powder surface is modified with a group of formula 7 (AEROSIL (registered trademark) RX200, manufactured by Nippon Aerosil Co., Ltd., average primary particle size 200 nm)
Component (D ′): Amorphous silica other than component (D) Amorphous silica whose powder surface is not chemically modified (AEROSIL (registered trademark) # 200 manufactured by Nippon Aerosil Co., Ltd.)
-Amorphous silica whose powder surface is R in formula 4 where both R are methyl groups (AEROSIL (registered trademark) R972, manufactured by Nippon Aerosil Co., Ltd.)
Amorphous silica whose powder surface is chemically modified with polydimethylsiloxane (AEROSIL (registered trademark) RY200 manufactured by Nippon Aerosil Co., Ltd.)
-Powder surface is amorphous silica in which R in formula 3 is methacryloxy group (AEROSIL (registered trademark) R7200 manufactured by Nippon Aerosil Co., Ltd.)
(E): Reaction inhibitor / phosphoric acid (reagent)
・ Tributyl borate (reagent)
・ Trimethoxyboroxine (reagent)
-Methyl p-toluenesulfonate (reagent).
実施例１〜１０および比較例１〜１０を調製する。（Ａ）成分、（Ｂ）成分、（Ｄ）成分を攪拌釜に秤量し、攪拌器で３０分間攪拌を行う。その後、（Ｃ）成分を秤量して、さらに３０分間攪拌を行った。最後に（Ｅ）成分を秤量して１５分間真空脱泡を行いながら攪拌した。詳細な調製量は表１と表３に従い、数値は全て質量部で表記する。 Examples 1-10 and Comparative Examples 1-10 are prepared. The components (A), (B), and (D) are weighed in a stirring vessel and stirred with a stirrer for 30 minutes. Thereafter, the component (C) was weighed and further stirred for 30 minutes. Finally, component (E) was weighed and stirred for 15 minutes while performing vacuum degassing. Detailed preparation amounts are shown in Tables 1 and 3, and all numerical values are expressed in parts by mass.
実施例１〜６、比較例１〜８について、粘度測定（初期）、形状保持性確認、保存安定性確認、硬化性確認、シロキサン含有確認を行い、その結果を表２にまとめた。 For Examples 1 to 6 and Comparative Examples 1 to 8, viscosity measurement (initial), shape retention confirmation, storage stability confirmation, curability confirmation, and siloxane content confirmation were performed, and the results are summarized in Table 2.
［粘度測定（初期）］
以下の測定条件に従い、循環恒温槽を用いてカップを２５℃に調整したコーンプレート型回転粘度計（Ｅ型粘度計）を用いる。コーンは３°×Ｒ１２タイプを使用する。組成物を０．５ｃｃ採取して、サンプルカップの中心部に吐出する。サンプルカップを本体に取り付け、３分間測定を行う。２．５ｒｐｍの回転速度と２５．０ｒｐｍの回転速度を測定し、それぞれ「初期粘度１（ｍＰａ・ｓ）」、「初期粘度２（ｍＰａ・ｓ）」とする。また、粘度１／粘度２の計算値を「チクソ比」とする。粘度型の測定範囲を超えて粘度が高い場合は「−」と記載し、チクソ比が計算できない場合も「−」と記載する。吐出時に糸引きなど不具合が発生を考慮すると、粘度１は１０〜２００ｍＰａ・ｓで、粘度２は１〜３０ｍＰａ・ｓであることが好ましい。また、流れ性を考慮すると、チクソ比が４〜２０であることが好ましい。
[Viscosity measurement (initial)]
In accordance with the following measurement conditions, a cone plate type rotational viscometer (E type viscometer) whose cup is adjusted to 25 ° C. using a circulating thermostat is used. The cone uses a 3 ° × R12 type. 0.5 cc of the composition is collected and discharged to the center of the sample cup. Attach the sample cup to the main body and measure for 3 minutes. The rotational speed of 2.5 rpm and the rotational speed of 25.0 rpm are measured and set to “initial viscosity 1 (mPa · s)” and “initial viscosity 2 (mPa · s)”, respectively. The calculated value of viscosity 1 / viscosity 2 is defined as “thixo ratio”. When the viscosity is high beyond the measurement range of the viscosity type, “−” is described, and when the thixo ratio cannot be calculated, “−” is also described. Considering the occurrence of problems such as stringing during discharge, the viscosity 1 is preferably 10 to 200 mPa · s, and the viscosity 2 is preferably 1 to 30 mPa · s. In consideration of fluidity, the thixo ratio is preferably 4-20.
［形状保持性確認］
組成物を０．１ｇをガラス板に吐出して、吐出時の形状を写真に撮ると共に組成物を塗布した側とは反対側から塗布時の端部に目印を付ける。その後、ガラス板を４５°に傾けた状態で、８０℃雰囲気下で１０分放置する。放置後の形状を写真と比較すると共に放置後の端部の位置を確認して、下記の評価基準から「形状保持性」を確認する。精密塗布ができるためには「○」であることが好ましい。
評価基準
○：塗布時の端部の広がりはなく、形状も変化しない
△：塗布時の端部の広がりはないが、形状が変化している
×：塗布時の端部が広がっている。
[Confirm shape retention]
0.1 g of the composition is discharged onto a glass plate, and the shape at the time of discharge is photographed, and a mark is given to the end portion at the time of application from the side opposite to the side where the composition is applied. Thereafter, the glass plate is left to stand in an atmosphere of 80 ° C. for 10 minutes while being inclined at 45 °. The shape after being left is compared with a photograph, and the position of the end after being left is confirmed, and “shape retention” is confirmed from the following evaluation criteria. In order to enable precise coating, “◯” is preferable.
Evaluation criteria ○: The end portion does not spread during application and the shape does not change. Δ: The end portion does not expand during application, but the shape changes. ×: The end portion during application widens.
［保存安定性確認］
組成物調製後に容器に保管し、２５℃雰囲気下で７日間放置する。その後、容器を開封し、下記の評価基準に従って「保存安定性」を評価する。本発明の保存安定性としては、「○」であることが好ましい。
評価基準
○：ゲル化せず流動性がある
×：ゲル化して流動性がない。
[Confirm storage stability]
After preparation of the composition, it is stored in a container and allowed to stand at 25 ° C. for 7 days. Thereafter, the container is opened, and “storage stability” is evaluated according to the following evaluation criteria. The storage stability of the present invention is preferably “◯”.
Evaluation criteria ○: No gelation and fluidity ×: Gelation and no fluidity
［硬化性確認］
８０℃に設定したホットプレート上に組成物を０．１ｇ滴下して、先端が尖った棒を組成物に接触させてタックが無くなる状態、つまり硬化するまでの時間をタイマーで測定する。下記の評価基準に従い「硬化性」を評価する。本発明の硬化性は６分以内であることが好ましい。
評価基準
○：６分以内
×：６分より長い。
[Curability check]
0.1 g of the composition is dropped on a hot plate set at 80 ° C., and a stick with a sharp tip is brought into contact with the composition to measure the state until tack is eliminated, that is, the time until curing. “Curability” is evaluated according to the following evaluation criteria. The curability of the present invention is preferably within 6 minutes.
Evaluation criteria ○: within 6 minutes ×: longer than 6 minutes.
［シロキサン確認］
ガスクロマトグラフ質量分析計（一般的にＧＣ−ＭＳと呼ばれる。）を用いて低分子量環状シロキサン（（ＳｉＯ（ＣＨ３）２）ｎ、ｎ＝３〜２０）の定性分析を行った。（Ｄ）成分または（Ｄ’）成分をアルミカップ入れて、ＧＣ−ＭＳのヘッドスペース内にて設置して、８５℃にて３時間加熱してアウトガスを抽出して、ガスクロマトグラフにより各種アウトガス成分を分離する。低分子量環状シロキサンのフラグメントが確認されたか否かを下記の評価基準により評価して、「シロキサン」として表記する。本発明においては低分子量環状シロキサンが発生しないこと好ましい。
評価基準
○：低分子量環状シロキサンが発生しない
×：低分子量環状シロキサンが発生する。
[Siloxane confirmation]
A low molecular weight cyclic siloxane ((SiO (CH 3 ) 2 ) n , n = 3 to 20) was qualitatively analyzed using a gas chromatograph mass spectrometer (generally called GC-MS). (D) Component or (D ′) component is put in an aluminum cup, installed in the head space of GC-MS, heated at 85 ° C. for 3 hours to extract outgas, and various outgas components by gas chromatograph Isolate. Whether or not a low molecular weight cyclic siloxane fragment has been confirmed is evaluated according to the following evaluation criteria and expressed as “siloxane”. In the present invention, it is preferable that low molecular weight cyclic siloxane is not generated.
Evaluation criteria ○: Low molecular weight cyclic siloxane does not occur ×: Low molecular weight cyclic siloxane occurs.
実施例１〜６と比較例１、２および４を比較すると、（Ｄ）成分が特定のものしか形状保持性を発現することができない。また、実施例１〜６と比較例５〜７を比較すると、（Ａ）成分１００質量部に対して（Ｂ）成分が２５〜９５質量部の範囲で形状保持性および硬化性を両立させることができる。比較例５においては、（Ｂ）成分の添加量が少なすぎて、組成物の希釈効果が低く粘度が非常に高くなり加工する際に吐出することが困難である。また、比較例６と７では（Ｂ）成分が多すぎて、逆に硬化が進まず形状保持性または硬化性が低下している。実施例１〜６と比較例８との比較で、（Ａ）成分１００質量部に対して（Ｄ）成分が５〜２５質量部で形状保持性が維持されることが分かる。比較例３では、チクソ比が高いが、（Ｄ’）成分から低分子量環状シロキサンが発生するため電子部品には適していない。 When Examples 1-6 are compared with Comparative Examples 1, 2, and 4, only the specific component (D) can exhibit shape retention. Moreover, when Examples 1-6 are compared with Comparative Examples 5-7, both (B) component is 25-95 mass parts with respect to 100 mass parts of (A) component, and shape retentivity and sclerosis | hardenability are made compatible. Can do. In Comparative Example 5, the addition amount of the component (B) is too small, the effect of diluting the composition is low, the viscosity is very high, and it is difficult to discharge when processing. Further, in Comparative Examples 6 and 7, the component (B) is too much, and conversely, curing does not proceed and shape retention or curability is lowered. Comparison between Examples 1 to 6 and Comparative Example 8 shows that the shape retention is maintained at 5 to 25 parts by mass of component (D) with respect to 100 parts by mass of component (A). In Comparative Example 3, the thixo ratio is high, but low molecular weight cyclic siloxane is generated from the component (D ′), so that it is not suitable for electronic parts.
実施例７〜１０、比較例９、１０について粘度測定（保管後）、形状保持性確認、硬化性確認、シロキサン確認を行い、その結果を表４にまとめた。 For Examples 7 to 10 and Comparative Examples 9 and 10, viscosity measurement (after storage), shape retention confirmation, curability confirmation, and siloxane confirmation were performed, and the results are summarized in Table 4.
［粘度測定（保管後）］
組成物調製後に前記の粘度測定を行い、その後、２５℃雰囲気下で７日間放置して、初期粘度の測定と同じ方法で再度粘度測定を行った。その際の結果を「保管後粘度１（ｍＰａ・ｓ）」、「保管後粘度２（ｍＰａ・ｓ）」、「保管後チクソ比」とする。変化率が（保管後−初期）／初期×１００で計算値を「変化率（％）」とする。変化率は−５０％〜＋５０％である事が好ましく、さらに好ましくは−１０％〜＋１０％である。変化率が±５０％の範囲内であると、例えばシリンジで一定の圧力で加圧した時に、粘度が変化しにくく塗布量が安定する。また、塗布時に糸曳しにくくなる等の利点が挙げられる。粘度の測定範囲が超えるものは「−」と記載する。また、その際の変化率も「−」と記載する。
[Viscosity measurement (after storage)]
After preparing the composition, the above-mentioned viscosity measurement was performed, and then the mixture was allowed to stand in an atmosphere at 25 ° C. for 7 days, and the viscosity measurement was performed again by the same method as the measurement of the initial viscosity. The results at that time are defined as “viscosity after storage 1 (mPa · s)”, “viscosity after storage 2 (mPa · s)”, and “thixo ratio after storage”. The rate of change is (after storage-initial) / initial × 100, and the calculated value is “change rate (%)”. The rate of change is preferably -50% to + 50%, more preferably -10% to + 10%. When the rate of change is within a range of ± 50%, for example, when the pressure is increased with a syringe at a constant pressure, the viscosity hardly changes and the coating amount is stabilized. In addition, there is an advantage that it is difficult to take the string during application. Those exceeding the measurement range of viscosity are described as “−”. Further, the rate of change at that time is also described as “−”.
実施例１、７〜１０と比較例９、１０を比較すると、（Ｅ）成分を使用することで変化率を低くすることができる。また、実施例７〜１０でも形状保持性、硬化性を維持し、低分子量環状シロキサンの発生も無い。 When Examples 1 and 7 to 10 and Comparative Examples 9 and 10 are compared, the rate of change can be lowered by using the component (E). In Examples 7 to 10, shape retention and curability are maintained and no low molecular weight cyclic siloxane is generated.
産業上の利用可能性
本発明のエポキシ樹脂組成物は塗布時の形状を加熱硬化時に維持できるため、精密な塗布特性が可能であり、低温硬化できるので電子部品への悪影響も少なく、電子部品の組み立て用途全般に使用することが可能である。
INDUSTRIAL APPLICABILITY The epoxy resin composition of the present invention can maintain the shape at the time of application at the time of heat-curing, so it can provide precise application characteristics and can be cured at low temperature, so there is little adverse effect on electronic parts, It can be used for general assembly applications.
Claims (8)
（Ａ）成分：エポキシ樹脂
（Ｂ）成分：ポリチオール化合物
（Ｃ）成分：硬化促進剤
（Ｄ）成分：ポリジオルガノシロキサンを除いた、下記の一般式３〜５のいずれか一つで表される基で化学修飾がなされているアモルファスシリカ
（Ｅ）成分：反応抑制剤。 (A)-(E) component is included, (A) component is 100-mass part, (B) component is 25-95 mass part, (C) component is 1-20 mass part, (D) component is 5- 25 parts by mass and an epoxy resin composition containing 0.01 to 5 parts by mass of component (E);
(A) component: epoxy resin (B) component: polythiol compound (C) component: curing accelerator (D) component: represented by any one of the following general formulas 3 to 5 excluding polydiorganosiloxane Amorphous silica chemically modified with groups
(E) component: Reaction inhibitor.
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| JP6849899B2 (en) | 2021-03-31 |
| CN105585937B (en) | 2020-01-03 |
| KR102359684B1 (en) | 2022-02-07 |
| KR20160056784A (en) | 2016-05-20 |
| CN105585937A (en) | 2016-05-18 |
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