JP6849899B2 - Epoxy resin composition - Google Patents
Epoxy resin composition Download PDFInfo
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- JP6849899B2 JP6849899B2 JP2015222480A JP2015222480A JP6849899B2 JP 6849899 B2 JP6849899 B2 JP 6849899B2 JP 2015222480 A JP2015222480 A JP 2015222480A JP 2015222480 A JP2015222480 A JP 2015222480A JP 6849899 B2 JP6849899 B2 JP 6849899B2
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- 239000003822 epoxy resin Substances 0.000 title claims description 49
- 229920000647 polyepoxide Polymers 0.000 title claims description 49
- 239000000203 mixture Substances 0.000 title claims description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 17
- 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
- 229920006295 polythiol Polymers 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000004615 ingredient 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
- 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
- 239000002245 particle Substances 0.000 claims description 3
- 239000002683 reaction inhibitor Substances 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000003860 storage Methods 0.000 description 23
- -1 cyclic siloxane Chemical class 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 238000001723 curing Methods 0.000 description 16
- 229910002012 Aerosil® Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012790 confirmation Methods 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 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
- 125000003396 thiol group Chemical group [H]S* 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 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
- 238000010438 heat treatment Methods 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
- 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
- RQPNXPWEGVCPCX-UHFFFAOYSA-N 3-sulfanylbutanoic acid Chemical compound CC(S)CC(O)=O RQPNXPWEGVCPCX-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
- 239000004327 boric acid Substances 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000004132 cross linking 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
- 239000011521 glass Substances 0.000 description 2
- 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 2
- 238000013007 heat curing Methods 0.000 description 2
- 230000020169 heat generation Effects 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
- 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
- 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
- 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
- 102100027123 55 kDa erythrocyte membrane protein Human genes 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 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
- 229910020175 SiOH Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 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
- 239000003963 antioxidant agent Substances 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003086 colorant Substances 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
- 238000011161 development Methods 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
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 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
- 239000012634 fragment Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001879 gelation Methods 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
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 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
- 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 group 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
- 238000002360 preparation method Methods 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
- 238000004451 qualitative analysis 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
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 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
- KCNSDMPZCKLTQP-UHFFFAOYSA-N tetraphenylen-1-ol Chemical compound C12=CC=CC=C2C2=CC=CC=C2C2=CC=CC=C2C2=C1C=CC=C2O KCNSDMPZCKLTQP-UHFFFAOYSA-N 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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Epoxy Resins (AREA)
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 containing 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 heat-curable epoxy resin composition or a room temperature-curable two-component epoxy resin composition is widely used for assembling a camera module such as a CMOS sensor. .. However, at the time of assembly, it is necessary to control the coating amount of the epoxy resin composition and the like with high accuracy. Furthermore, in electronic parts such as camera modules, the epoxy resin composition is heated at a low temperature (80 ° C or less, etc.) for a short time (10 minutes or less, etc.) due to the displacement of the parts during heating and the adverse effect on the electronic parts themselves. It is best to cure. Further, 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 during curing and adheres to the sensor or the like, causing a problem. 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。 A composition of a resin having an epoxy group and a polythiol compound as in Patent Document 2 has been known, but since the cured product is soft, it is not suitable for precise assembly of electrical and electronic parts. Further, when the epoxy resin (main agent) has a flexible structure, the curing rate is slow and the composition tends to flow during heating. Further, the document does not disclose a technique for controlling the coating shape.
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。 The conventional epoxy resin composition has both storage stability and low-temperature short-time curing, and the shape after application changes due to heat during heating or heat generation 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 diligent studies to achieve the above object, the present inventors have found a method for maintaining the coated shape without changing the shape of the epoxy resin composition after coating or generating fluidity and flowing. 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 below. The first embodiment of the present invention contains the components (A) to (E), and the component (B) is 25 to 95 parts by mass and the component (C) is 1 to 20 parts by mass with respect to 100 parts by mass of the component (A). Concerning an epoxy resin composition containing 5 to 25 parts by mass of component (D) and 0.01 to 5 parts by mass of component (E);
Component (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 a group However, R independently refers to a hydrocarbon group, and the total number of carbon atoms of R in each of the general formulas 3 to 5 is 3 or more;
(E) Ingredient: 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。 The second embodiment of the present invention is the epoxy resin composition according to the first embodiment, which has a thixo ratio of 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 the fourth embodiment of the present invention, the component (E) is at least one selected from the group consisting of phosphoric acid, tributyl borate, trimethoxyboroxin and methyl p-toluenesulfonate, from the first. The epoxy resin composition according to any one of the third embodiments.
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 the fifth embodiment of the present invention, the component (D) is amorphous silica chemically modified with a group represented by the following formula 6 or 7 excluding polydiorganosiloxane. The epoxy resin composition according to any one of the fourth embodiments.
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。 A 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。 A seventh embodiment of the present invention relates to any one of the first to sixth embodiments, wherein the component (B) is a polythiol compound having two or more functional groups of the following formula 2 in the molecule. The epoxy resin composition described.
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。 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 a low temperature in a short time, and changes its shape after coating due to heat during heating or heat generation during reaction. It is possible to maintain the coating shape by suppressing the occurrence of fluidity and flow. The epoxy resin composition of the present invention is particularly preferably used for electronic components such as camera modules.
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 the present specification, "X to Y" indicating a range means "X or more and Y or less". Unless otherwise specified, the operation and physical properties are measured under the conditions of room temperature (20 to 25 ° C.) / relative humidity of 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. The component (A) as the main component of the composition that can be used in the present invention is an epoxy resin. From the viewpoint that the molecular weight tends to increase at the time of cross-linking, a compound having two or more epoxy groups in one molecule is preferable. As the component (A), only one type may be used, or two or more types may be mixed and used. If the entire component (A) is liquid at 25 ° C, a solid epoxy resin at 25 ° C is used at 25 ° C. You may use it by dissolving it 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, and more preferably 700 ppm or less, from the viewpoint of storage stability. When it is 1000 ppm or less, storage stability can be maintained.
（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 condensing epichlorohydrin with polyhydric phenols such as bisphenols and polyhydric alcohols, and examples thereof include bisphenol A type, brominated bisphenol A type, and hydrogenated bisphenol A. Type, bisphenol F type, bisphenol S type, bisphenol AF type, biphenyl type, naphthalene type, fluorene type, novolac type, phenol novolac type, orthocresol novolac type, tris (hydroxyphenyl) methane type, tetraphenylol ethane type, etc. A glycidyl ether type epoxy resin can be exemplified. In addition, a glycidyl ester type epoxy resin obtained by condensing epichlorohydrin with a carboxylic acid such as a phthalic acid derivative or a fatty acid, a glycidyl amine type epoxy resin obtained by reacting epichlorohydrin with amines, cyanulic acids, and hydranthins, and further. Examples include, but are 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 development of low-temperature 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。 Commercially available epoxy resins include jER827 and 828EL manufactured by Mitsubishi Chemical Corporation, EPICLON (registered trademark) 830 and EXA-835LV manufactured by Dainippon Ink Industry Co., Ltd., and Epototo (registered) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Trademarks) YD-128, YDF-170, etc., but are not limited thereto.
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 multivalent thiol. The component (B) preferably has a plurality of primary thiol groups or secondary thiol groups in the molecule as in formulas 1 and 2. When it has a plurality of thiol groups, the cross-linking proceeds due to its polyfunctionality, and the molecular weight increases when the composition is cured. In particular, when the following component (E) is not contained, the effect on the storage stability differs between the primary thiol group and the secondary thiol group, and the secondary thiol group may be used in consideration of the stabilization of the storage stability. 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-mercaptobutylyloxy) butane, 1, 3,5-Tris (3-mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), Examples thereof include, but are not limited to, trimethylolethanetris (3-mercaptobutyrate), trimethylolpropanetris (3-mercaptobutyrate), and trimethylolethanetris (3-mercaptobutyrate). Examples of products include, but are not limited to, PEMP manufactured by SC Organic Chemistry Co., Ltd., PE1, BD1, NR1 and the like of the Karenz MT (trademark registration) series manufactured by Showa Denko KK. The above component (B) can be used alone or in combination of two or more.
（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。 The component (B) is contained in an amount of 25 to 95 parts by mass with respect to 100 parts by mass of the component (A). When the component (B) is 25 parts by mass or more, the viscosity of the composition can be lowered to obtain a diluting effect, and quick curing 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 amount of the component (B) added is 30 to 80 parts by mass with respect to 100 parts by mass of the component (A).
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。 The component (C) that can be used in the present invention is a curing accelerator that promotes the reaction between the component (A) and the component (B). The curing accelerator is a solid at 25 ° C., and a compound having an imidazole skeleton or a fine powder obtained by crushing an epoxy adduct compound in which a tertiary amine is added to an epoxy resin to stop the reaction in the middle can be used. Most preferable in consideration of storage stability and curability. Particularly preferred are epoxy adduct compounds 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。 Commercially available epoxy adduct compounds include Ajinomoto Fine-Techno Co., Ltd.'s Amicure (registered trademark) series, T & K TOKA Co., Ltd.'s Fuji Cure (registered trademark) series, and Asahi Kasei Chemicals Co., Ltd.'s Novacure (registered trademark). ) Series, etc., but not limited to these. Further, a plurality of curing accelerators can be used in combination. The above component (C) can be used alone or in combination of two or more.
（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。 The amount of the component (C) added is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the component (A). 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 amount of the component (C) added is 2 to 10 parts by mass with respect to 100 parts by mass of the component (A).
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 has been chemically modified by any of the groups represented by the following general formulas 3 to 5 except for polydiorganosiloxane. In formulas 3 to 5, R independently refers to a hydrocarbon group, preferably an alkyl group. In each of the formulas 3 to 5, the total number of carbon atoms of R is 3 or more, more preferably 3 to 15. If the total number of carbon atoms in R is less than 3, the composition cannot exhibit sufficient shape retention. In a preferred embodiment of the invention, in formulas 3-5, R is an independently linear, branched or cyclic alkyl group having 3 to 15 carbon atoms. Examples of the alkyl group having 3 to 15 carbon atoms include a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group and a pentadecyl group. Examples thereof include a group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and the like. The amorphous silica after production is in a state where silanol (≡SiOH) is exposed, but the surface treatment is performed by reacting a compound that reacts with silanol on the surface of the amorphous silica (chemical modification). For example, the amorphous silica chemically modified with the group represented by the formula 6 may be surface-modified with octylsilane as a compound that reacts with silanol. By adding the component (D), the viscosity and the thixo property can be controlled. The powder characteristics such as the average particle size and the shape are not particularly limited, but the average particle size is preferably 0.001 to 50 μm in consideration of the ease of dispersion in the epoxy resin and the clogging of the nozzle. In particular, amorphous silica that has been chemically modified with a group represented by the following formula 6 or 7 is most preferable. Specific examples of the component (D) include AEROSIL® R805 and RX200 manufactured by Nippon Aerosil Co., Ltd. The above component (D) can be used alone or in combination of two or more.
（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。 The amount of the component (D) added is 5 to 25 parts by mass with respect to 100 parts by mass of the component (A). When the amount of the component (D) is more than 5 parts by mass, the fluidity can be stabilized and the workability can be improved, and when the amount is less than 25 parts by mass, the storage stability can be maintained. The amount of the component (D) added is preferably 6 to 22 parts by mass, more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the component (A).
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). As the component (E), borate ester, phosphoric acid, alkyl phosphoric acid ester, and p-toluenesulfonic acid can be used. Examples of the boric acid ester include, but are limited to, tributylborate, trimethoxyboroxin, ethyl borate, epoxy-phenol-boric acid ester compound (Cure Duct L-07N manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like. It is not something that is done. As the alkyl phosphate ester, trimethyl phosphate, tributyl phosphate and the like can be used, but the present invention is not limited thereto. The component (E) may be used alone or in combination of two or more. Considering storage stability, it is preferably one or more selected from the group consisting of phosphoric acid, tributyl borate, trimethoxyboroxin, 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。 The amount of the component (E) added is preferably 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the component (A). When the amount of the component (E) is more than 0.01 parts by mass, storage stability can be exhibited, and when it is less than 5.0 parts by mass, curability can be maintained. More preferably, the amount of the component (E) added is 2 to 10 parts by mass with respect to 100 parts by mass of the component (A).
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 contains colorants such as pigments and dyes, flame retardants, plasticizers, antioxidants, defoamers, and silane coupling agents as long as the intended effects of the present invention are not impaired. , Leveling agents, rheology control agents and other additives may be added in appropriate amounts. By adding these, a composition having excellent resin strength, adhesive strength, workability, storage stability, etc. 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 epoxy resin composition preferably has a thixo ratio (viscosity at low rotation speed / viscosity at high rotation speed) of 4 to 20, and more preferably 4 to 20. It is 15. As a result, the present invention suppresses the shape and spread after coating, the edge portion at the time of coating does not widen even after curing, and the coating shape does not change. Since the epoxy resin composition of the present invention can maintain the coating shape during heat curing, it is suitable for assembling electronic components that require precise coating characteristics, particularly for assembling camera modules. Generally, by increasing the amount of the D component added as a filler, the viscosity tends to increase and the thixo ratio also tends to increase. In addition, in this specification, "tixo ratio" is a value measured by the method described in Example.
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) Ingredients: Epoxy resin, bisphenol F type epoxy resin (EPICLON (registered trademark) EXA-835LV DIC Corporation, chlorine ion concentration of 300 ppm or less)
(B) Ingredient: Polythiol compound, pentaerythritol tetrakis (3-mercaptopropionate) (PEMP-20P SC Organic Chemistry Co., Ltd.)
・ Pentaerythritol tetrakis (3-mercaptobutyrate) (Carens MT (registered trademark) PE1 manufactured by Showa Denko KK)
(C) Ingredients: Curing Accelerator / Epoxy Adduct Type Curing Accelerator (Fuji Cure (registered trademark) FXR-1081, manufactured by T & K TOKA Co., Ltd.)
Component (D): Amorphous silica with specific chemical modification excluding polydiorganosiloxane ・ Amorphous silica with powder surface modified by the group of formula 6 (AEROSIL® R805 manufactured by Aerosil Japan Co., Ltd., Average primary particle size 200 nm)
Amorphous silica whose powder surface is modified with the group of formula 7 (AEROSIL® 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® # 200 manufactured by Aerosil Japan Co., Ltd.)
Amorphous silica with a powder surface of formula 4 in which both R are methyl groups (AEROSIL® R972 manufactured by Nippon Aerosil Co., Ltd.)
Amorphous silica whose powder surface is chemically modified with polydimethylsiloxane (AEROSIL® RY200 manufactured by Aerosil Japan Co., Ltd.)
Amorphous silica with a powder surface of formula 3 and R of a methacryloxy group (AEROSIL® R7200 manufactured by Aerosil Japan Co., Ltd.)
(E): Reaction inhibitor / phosphoric acid (reagent)
・ Tributyl borate (reagent)
・ Trimethoxyboroxin (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 pot and stirred with a stirrer for 30 minutes. Then, the component (C) was weighed and stirred for another 30 minutes. Finally, the component (E) was weighed and stirred for 15 minutes while performing vacuum defoaming. 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)]
A cone plate type rotational viscometer (E type viscometer) in which the cup is adjusted to 25 ° C. using a circulating constant temperature bath is used according to the following measurement conditions. The cone uses a 3 ° x 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 rotation speed of 2.5 rpm and the rotation speed of 25.0 rpm are measured and set to "initial viscosity 1 (mPa · s)" and "initial viscosity 2 (mPa · s)", respectively. Further, the calculated value of viscosity 1 / viscosity 2 is defined as the "thixo ratio". If the viscosity exceeds the measurement range of the viscosity type, it is described as "-", and if the thixo ratio cannot be calculated, it is described as "-". 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. Further, considering the flowability, the thixo ratio is preferably 4 to 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。
[Confirmation of shape retention]
0.1 g of the composition is discharged onto a glass plate, the shape at the time of discharge is photographed, and the end portion at the time of application is marked from the side opposite to the side where the composition is applied. Then, the glass plate is tilted at 45 ° and left for 10 minutes in an atmosphere of 80 ° C. Compare the shape after leaving with the photograph and confirm the position of the end after leaving, and confirm the "shape retention" from the following evaluation criteria. It is preferably "○" in order to enable precision coating.
Evaluation Criteria ◯: The edge part at the time of application does not spread and the shape does not change Δ: The edge part at the time of application does not spread but the shape changes ×: The edge part at the time of application is widened.
［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。
[Confirmation of storage stability]
After preparing the composition, it is stored in a container and left in an atmosphere of 25 ° C. for 7 days. After that, 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 ×: Gelling 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。
[Confirmation of curability]
0.1 g of the composition is dropped onto a hot plate set at 80 ° C., and a state in which a stick with a sharp tip is brought into contact with the composition to eliminate tack, that is, the time until curing is measured with a timer. Evaluate "curability" 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。
[Confirmation of siloxane]
A gas chromatograph mass spectrometer (generally called GC-MS) was used to perform qualitative analysis of low molecular weight cyclic siloxane ((SiO (CH 3 ) 2 ) n , n = 3 to 20). The component (D) or component (D') is placed in an aluminum cup, placed in the headspace of GC-MS, heated at 85 ° C. for 3 hours to extract outgas, and various outgas components are extracted by gas chromatography. To separate. Whether or not a fragment of a low molecular weight cyclic siloxane was confirmed is evaluated according to the following evaluation criteria, and is 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 is not generated ×: Low molecular weight cyclic siloxane is generated.
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。 Comparing Examples 1 to 6 with Comparative Examples 1, 2 and 4, only a specific component (D) can exhibit shape retention. Further, when Examples 1 to 6 and Comparative Examples 5 to 7 are compared, the shape retention and the curability are compatible with each other in the range of 25 to 95 parts by mass of the component (B) with respect to 100 parts by mass of the component (A). Can be done. In Comparative Example 5, the amount of the component (B) added is too small, the dilution effect of the composition is low, the viscosity is very high, and it is difficult to discharge the composition during processing. Further, in Comparative Examples 6 and 7, the amount of the component (B) is too large, and on the contrary, the curing does not proceed and the shape retention or the curability is lowered. By comparing Examples 1 to 6 with Comparative Example 8, it can be seen that the shape retention is maintained when the component (D) is 5 to 25 parts by mass with respect to 100 parts by mass of the component (A). In Comparative Example 3, although the thixo ratio is high, it is not suitable for electronic components because low molecular weight cyclic siloxane is generated from the component (D').
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。 Viscosity measurement (after storage), shape retention confirmation, curability confirmation, and siloxane confirmation were performed for Examples 7 to 10 and Comparative Examples 9 and 10, 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 viscosity was measured again in the same method as the initial viscosity measurement after being left to stand in an atmosphere of 25 ° C. for 7 days. The results at that time are "viscosity after storage 1 (mPa · s)", "viscosity after storage 2 (mPa · s)", and "chixo ratio after storage". The rate of change is (after storage-initial) / initial x 100, and the calculated value is "rate of change (%)". The rate of change is preferably −50% to + 50%, more preferably −10% to + 10%. When the rate of change is within the range of ± 50%, the viscosity is unlikely to change and the coating amount is stable, for example, when pressurized with a syringe at a constant pressure. In addition, there are advantages such as difficulty in pulling a thread at the time of application. If the viscosity exceeds the measurement range, it is described as "-". In addition, 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。 Comparing Examples 1 and 7 to 10 with Comparative Examples 9 and 10, the rate of change can be lowered by using the component (E). Further, even in Examples 7 to 10, shape retention and curability are maintained, and low molecular weight cyclic siloxane is not 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 Since the epoxy resin composition of the present invention can maintain its shape at the time of coating during heat curing, it is possible to have precise coating characteristics, and since it can be cured at low temperature, it has little adverse effect on electronic components, and it is possible to use It can be used for all assembly purposes.
Claims (7)
（Ａ）成分：ビスフェノール骨格を有するエポキシ樹脂
（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平均粒径が０．００１〜０．２μｍであ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。 Contains components (A) to (E), 25 to 95 parts by mass of component (B), 1 to 20 parts by mass of component (C), and 5 to 5 parts by mass of component (D) with respect to 100 parts by mass of component (A). Epoxy resin composition containing 25 parts by mass and 0.01 to 5 parts by mass of component (E);
(A) Component: Epoxy resin having a bisphenol skeleton (B) Component: Polythiol compound (C) Component: Curing accelerator (D) Component: Any one of the following general formulas 3 to 5 excluding polydiorganosiloxane. Amorphous silica having an average particle size of 0.001 to 0.2 μm chemically modified with the group represented by
However, R independently refers to a hydrocarbon group, and the total number of carbon atoms of R in each of the general formulas 3 to 5 is 3 or more;
(E) Ingredient: Reaction inhibitor.
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| JP2501258B2 (en) * | 1991-08-30 | 1996-05-29 | 住友ベークライト株式会社 | Insulating resin paste |
| EP0872504A1 (en) * | 1995-08-04 | 1998-10-21 | Asahi Denka Kogyo Kabushiki Kaisha | Curable epoxy resin composition which gives flexible cured article |
| JPH0987363A (en) * | 1995-09-25 | 1997-03-31 | Nippon Zeon Co Ltd | Photocurable composition, sealing material, method for sealing, and sealed liquid crystal |
| JPH11106483A (en) * | 1997-09-30 | 1999-04-20 | Hitachi Chem Co Ltd | Epoxy resin composition |
| JPH11256013A (en) * | 1998-03-12 | 1999-09-21 | Ajinomoto Co Inc | Epoxy resin composition |
| DE102006033136A1 (en) * | 2006-07-18 | 2008-01-31 | Evonik Degussa Gmbh | Surface modified silicic acid, modified using a surface modifying agent such as cyclic polysiloxane, useful e.g. as self-sealing materials |
| KR101394808B1 (en) * | 2006-12-22 | 2014-05-13 | 덴끼 가가꾸 고교 가부시키가이샤 | Amorphous silica powder, method for production thereof, and semiconductor sealing material |
| JP4452755B2 (en) * | 2007-06-15 | 2010-04-21 | 積水化学工業株式会社 | Sealant for optical semiconductor element and optical semiconductor element |
| CN101386700A (en) * | 2007-09-12 | 2009-03-18 | 德古萨有限责任公司 | Curing composition containing fumed silica |
| JP5441447B2 (en) * | 2009-03-06 | 2014-03-12 | ソマール株式会社 | Insulating paint for electronic parts and electronic parts using the same |
| JP4839392B2 (en) | 2009-05-07 | 2011-12-21 | ルネサスエレクトロニクス株式会社 | Solid-state imaging device |
| JP2014500895A (en) * | 2010-11-05 | 2014-01-16 | ヘンケル アイルランド リミテッド | Epoxy-thiol composition with improved stability |
| WO2012093510A1 (en) * | 2011-01-05 | 2012-07-12 | ナミックス株式会社 | Resin composition |
| JP5598343B2 (en) * | 2011-01-17 | 2014-10-01 | 信越化学工業株式会社 | Liquid epoxy resin composition for semiconductor encapsulation and semiconductor device |
| JP5855420B2 (en) * | 2011-10-27 | 2016-02-09 | 株式会社タムラ製作所 | Conductive resin composition and printed wiring board using conductive resin composition |
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