JP2004010700A - Novel phenolic resin and epoxy resin composition using the same as curing agent - Google Patents
Novel phenolic resin and epoxy resin composition using the same as curing agent Download PDFInfo
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- JP2004010700A JP2004010700A JP2002164109A JP2002164109A JP2004010700A JP 2004010700 A JP2004010700 A JP 2004010700A JP 2002164109 A JP2002164109 A JP 2002164109A JP 2002164109 A JP2002164109 A JP 2002164109A JP 2004010700 A JP2004010700 A JP 2004010700A
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- epoxy resin
- resin composition
- curing agent
- phenolic resin
- resin
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 46
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 46
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 35
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 30
- 239000000203 mixture Substances 0.000 title claims abstract description 29
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000010586 diagram Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- 229920003987 resole Polymers 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000011256 inorganic filler Substances 0.000 description 7
- 229910003475 inorganic filler Inorganic materials 0.000 description 7
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 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
- 239000005350 fused silica 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
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture 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
- 238000001721 transfer moulding Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- CZAZXHQSSWRBHT-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3,4,5,6-tetramethylphenol Chemical compound OC1=C(C)C(C)=C(C)C(C)=C1C1=CC=CC=C1O CZAZXHQSSWRBHT-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RIAHASMJDOMQER-UHFFFAOYSA-N 5-ethyl-2-methyl-1h-imidazole Chemical compound CCC1=CN=C(C)N1 RIAHASMJDOMQER-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 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
- 239000003513 alkali Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-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
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- WLAHGGSLQFSJKG-UHFFFAOYSA-N phenyl 2,3-diaminobenzenesulfonate Chemical compound NC1=CC=CC(S(=O)(=O)OC=2C=CC=CC=2)=C1N WLAHGGSLQFSJKG-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
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- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
【課題】溶融粘度が低く、耐湿性，及び耐衝撃性等の機械特性を向上せしめるエポキシ樹脂組成物およびその硬化物の提供
【解決手段】成分（Ａ）として次の一般式（１）
（式中、Ｒはメチル基またはエチル基を表し、Ｘは水素原子またはメチル基を表す。また、ｎは０〜３の整数を表し、ｍは１〜５の整数を表す。）に示すように、フェノール樹脂骨格内にアルコキシフェノールを有し、かつ、分子量分布が狭い新規フェノール系樹脂を硬化剤として用いることを特徴とするエポキシ樹脂組成物。
【選択図】 なしAn epoxy resin composition having a low melt viscosity and improving mechanical properties such as moisture resistance and impact resistance, and a cured product thereof are provided. The following general formula (1) is used as component (A):
(Wherein, R represents a methyl group or an ethyl group, X represents a hydrogen atom or a methyl group, n represents an integer of 0 to 3, and m represents an integer of 1 to 5). An epoxy resin composition comprising a novel phenolic resin having an alkoxyphenol in the phenol resin skeleton and having a narrow molecular weight distribution as a curing agent.
[Selection diagram] None
Description
【０００１】
【発明が属する技術分野】
本発明は新規フェノール系樹脂及びこれを硬化剤として用いるエポキシ樹脂組成物、及びその硬化物に関する。詳しくは、本発明は、半導体封止用に有用であり、エポキシ硬化物の耐湿性、耐衝撃性等の機械特性を向上せしめる新規フェノール系樹脂、およびこれを硬化剤として用いるエポキシ樹脂組成物、及びその硬化物に関する。
【０００２】
【従来の技術】
ＩＣの封止においては、従来からエポキシ樹脂組成物を用いて素子を封止する方法が広く用いられ、そのエポキシ樹脂原料、また、硬化剤としてフェノール樹脂が利用されている。フェノール樹脂をエポキシ樹脂またはその硬化剤として、耐熱性複合材や耐熱性接着剤などに利用することは、近年ますます多種多様になり、工業的にも重要である。しかしながら、近年、ＩＣの高集積化に伴う素子の大型化および発生熱量の増大など、封止材に対する負荷が増大している一方で、技術的にはより実装密度を上げるために、パッケージに対する要求は、より小型、薄型であることが求められており，従来のフェノール樹脂ではその要求性能に対応することが難しくなっているのが現状である。
【０００３】
また、最近は実装方法にも変化が生じ、従来の配線盤裏からの半田付けを行う方法から、溶融半田浴中への浸漬やＩＲリフローによる方法へと変化してきており、それに伴いパッケージそのものが高温に曝されることとなる。したがって封止材に用いられる樹脂組成物に対しては高い水準の性能が求められる。例えば、耐湿性の向上、熱応力に対する可とう性の付与、対衝撃性等の機械的特性の向上等が求められる。
【０００４】
【発明が解決しようとする課題】
本発明の目的は、前述のように近年の電気・電子分野における技術の発達に伴う要求を満足させるエポキシ樹脂組成物、且つ、優れた性能を示す硬化物を提供することにある。具体的には、溶融粘度が低く、耐湿性，及び耐衝撃性を向上せしめるエポキシ樹脂組成物およびその硬化物を提供することにある。
【０００５】
【課題を解決するための手段】
本発明者は、上記課題を解決するために鋭意検討した結果、成分（Ａ）として下記一般式に示すように、フェノール樹脂骨格内にアルコキシフェノールを有し、かつ、分子量分布の狭い新規フェノール系樹脂である硬化剤、成分（Ｂ）として一分子中に少なくとも２つ以上のグリシジル基を有するエポキシ樹脂一種、或いは２種以上を必須成分とするエポキシ樹脂組成物の発明に至った。即ち、本発明は、エポキシ樹脂硬化物の架橋密度適度に低下させるために、硬化剤として用いられるフェノール樹脂において、フェノール性水酸基を部分的にアルコキシ化し、かつ反応の制御により得られた分子量分布の狭い新規フェノール系樹脂を用いることを特徴としている。これらの手段を用いることにより、溶融粘度が低いエポキシ樹脂組成物が得られ、更にそれらを硬化することにより耐湿性、及び耐衝撃性が向上した硬化物が得られる。
【０００６】
【化２】
（式中、Ｒはメチル基またはエチル基を表し、Ｘは水素原子またはメチル基を表す。また、ｎは０〜３の整数を表し、ｍは１〜５の整数を表す。但し、ｎ＝０の化合物の含有率は１０％以下である。）
また、成分（Ａ）は、二核体含有率が１０％以下である分子量分布の狭いノボラック型フェノール系樹脂であり、その樹脂中のフェノール性水酸基のアルコキシ化率が３０〜６０％であることを特徴とするフェノール系樹脂である。また、前記エポキシ樹脂組成物と無機充填材を含むエポキシ樹脂組成物において、無機充填材を５０〜９２重量％含む半導体封止用エポキシ樹脂組成物である。また、成分（Ｂ）のエポキシ樹脂がｏ−クレゾールノボラック型エポキシ樹脂及び／またはビフェニル型エポキシ樹脂である前期エポキシ樹脂組成物、及びその硬化物に関するものである。
【０００８】
本発明のエポキシ樹脂組成物は、特定の温度における溶融粘性を著しく低減させたフェノール系樹脂を硬化剤として使用しており、充填材の充填率を高めることができ、成形性に優れるという特徴を有しており、ＩＣ封止として使用するのに好適である。更に硬化剤として用いた新規フェノール系樹脂のフェノール性水酸基のうち、３０〜６０％がアルコキシ化されていることにより、当該エポキシ樹脂組成物の硬化物は適度な可とう性を有していることから、耐衝撃性、耐湿性に優れた硬化物を得ることができる。次に本発明の樹脂を得る方法について、具体的に説明する。
【０００９】
本発明にかかる新規フェノール系樹脂を製造する具体的な方法は、一般的製法により得られるレゾール樹脂に対し、アルカリ条件下にてアルコキシ化剤として例えば硫酸ジメチルを用いることにより一般式（２）のアルコキシ化レゾールを得ることができる。
【００１０】
【化３】
（式中、Ｒはメチル基またはエチル基を表し、Ｘは水素原子またはメチル基を表す。また、ｋは０〜２の整数を表す。）次いで酸性条件下にて過剰のフェノール類との脱水縮合により，目的物である新規フェノール系樹脂を得ることができる。
【００１２】
上記反応において、レゾール樹脂は、フェノール、或いはクレゾール等のアルキルフェノールなどを原料としたレゾール樹脂を用いることができ、アルコキシ化剤としては、硫酸ジメチル、硫酸ジエチル、あるいはハロゲン化アルキル等を用いることができる。例えば、硫酸ジメチルの場合、レゾール樹脂１００重量部に対して８０〜１４０重量部をアルカリ性下、４０〜６０℃において４〜６時間で反応させることができる。上記アルカリ条件は、水酸化カリウム、水酸化ナトリウム、水酸化カルシウム、水酸化マグネシウムなどの水溶液を用いることができ、例えば、３０％水酸化ナトリウムをレゾール樹脂１００重量部に対し、１００〜１６０重量部用いることにより反応を進行させることができる。次いで、アルコキシ化レゾール樹脂との反応に用いられるフェノール類は、レゾール樹脂に対して、２倍モル以上、通常２〜１０倍モルの範囲で用いられるが、好ましくは、３〜６倍モル量の範囲で用いられる。
【００１３】
上記酸触媒としては、塩酸、硫酸、ｐ−トルエンスルホン酸、シュウ酸、蟻酸等が挙げられる。このような酸触媒は、例えば、３５％塩酸の場合は、レゾール樹脂１００重量部に対して、１〜２０重量部、好ましくは５〜１０重量部の範囲で用いられる。
【００１４】
反応は、通常、４０℃から１２０℃、好ましくは、６０℃から１００℃にて撹拌しながら、２〜８時間程度、通常、４〜６時間程度行えば良い。反応終了後、得られた反応液にアンモニア水、水酸化ナトリウム水溶液等のアルカリを加えて、酸触媒を中和し、次いで中和塩を除去する目的で水洗を行い、得られた油層から未反応のフェノール類を留去することによって目的とする新規フェノール系樹脂を得ることができる。
【００１５】
次に、エポキシ樹脂組成物について述べる。本発明のエポキシ樹脂組成物は、硬化剤として成分（Ａ）、すなわち、前記の本発明による新規フェノール系樹脂を使用することを特徴としている。本発明において用いられるエポキシ樹脂としては、エポキシ樹脂として一般に使用されているものであればよく、このようなエポキシ樹脂としては、例えば、フェノールノボラック型エポキシ樹脂、ｏ−クレゾールノボラック型エポキシ樹脂、フェノール、ナフトール類のキシリレン結合によるアラルキル樹脂のエポキシ化物、フェノール−ジシクロペンタジエン樹脂のエポキシ化物、ビスフェノールＡ、ビスフェノールＳ、ビスフェノールＦ、ビフェノール等のエポキシ化物、ジアミノジフェニルメタン、ジアミノジフェニルスルホン酸などのポリアミンとエピクロルヒドリンの反応により得られるグリシジルアミン型エポキシ樹脂などがあり、これらを適宜何種類でも併用することができる。エポキシ樹脂と硬化剤との当量比は、特に限定されないが、０．５〜１．５が好ましい。
【００１６】
半導体封止用エポキシ樹脂組成物においては、無機充填材を必須成分として使用する。この無機充填材の使用量は、全エポキシ樹脂組成物の５０〜９２重量％であることが好ましく、更に好ましくは、７０〜９２重量％であることが耐湿性、機械強度向上の面から好ましい。無機充填材としては、シリカ、アルミナ、窒化ケイ素、炭化ケイ素、タルク、ケイ酸カルシウム、炭酸カルシウム、マイカ、クレー、チタンホワイト等の粉体、ガラス繊維、カーボン繊維等の繊維体が例示される。これらの中で熱膨張率と熱伝導率の点から、結晶性シリカおよび／または溶融シリカが好ましい。
【００１７】
本発明において、エポキシ樹脂組成物を硬化させるにあたって、硬化促進剤を使用することが望ましい。かかる硬化促進剤としては、２−メチルイミダゾール、２−メチル−４−エチルイミダゾール等のイミダゾール類、トリエタノールアミン、トリエチレンジアミン等のアミン類、トリブチルホスフィン、トリフェニルホスフィン等の有機ホスフィン類、１，８−ジアザ−ビシクロ（５，４，０）ウンデセン−７−及びその誘導体がある。これらの硬化促進剤は、単独、或いは、２種類以上併用してもよく、また、これらの硬化促進剤の配合は、エポキシ化物、またはエポキシ化合物および硬化剤の合計１００重量部に対して０．０１〜１０重量部の範囲で用いられる。
【００１８】
本発明のエポキシ樹脂組成物においては、機械強度、耐熱性等の改質剤として各種の添加剤を用いてもよい。例えば、シラン系、チタネート系、アルミネート系及びジルコアルミネート系等のカップリング剤を用いることにより樹脂と無機充填材との接着性を向上させることができる。特に、エポキシ樹脂と反応する官能基を有するシラン系カップリング剤が好ましく、かかるシラン系カップリング剤の例としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、Ｎ−（２−アミノメチル）−３−アミノプロピルメトキシシラン、３−アミノプロピルトリエトキシシラン、３−グリシドキシプロピルトリエトキシシラン、３−メルカプトプロピルトリメトキシシラン等を挙げることができる。これらを単独或いは併用して使用することができる。
【００１９】
また、本発明の半導体封止用エポキシ樹脂組成物には、必要に応じて脂肪酸、ワックスなどの離型剤、ブロム化物、アンチモン、リン等の難燃剤、カーボンブラック等の着色剤等を配合し、混合、混練してＩＣ封止用の成形材料とすることができる。
【００２０】
以下実施例を挙げて本発明を説明するが、本発明はこれにより何ら制限されるものではない。
【００２１】
新規フェノール系樹脂の製造
実施例１
オルソクレゾール１０８．０ｇ（１．０ｍｏｌ）と５０％ホルマリン水溶液１３２．０ｇ（２．２ｍｏｌ）を反応容器に仕込み、冷却下３０％水酸化ナトリウム水溶液１３３．３ｇ（１．０ｍｏｌ）を、３０℃以下を保ちながら１時間かけて滴下を行った。滴下終了後、４０℃まで昇温し、２時間反応させた。次いで硫酸ジメチル１２６．０ｇ（１．０ｍｏｌ）を４０℃にて１時間かけて滴下後、６０℃まで昇温し、２時間反応させフェノール性水酸基がメトキシ化されたレゾール樹脂を合成した。反応終了後、水層を分離し、引き続きフェノール２８２．０ｇ（３．０ｍｏｌ）、及び３５％塩酸９．１ｇを加え、９０℃にて４時間反応させた。反応終了後、２５％アンモニア水溶液６．０ｇにより中和し、水洗により中和塩を除去後、６０ｍｍＨｇで２００℃まで加熱し未反応のフェノールを除去した。目的のフェノール系樹脂の軟化温度は７７℃、１５０℃におけるＩＣＩ溶融粘度は０．８ポイズであった。
【００２２】
実施例２
オルソクレゾール１０８．０ｇ（１．０ｍｏｌ）と５０％ホルマリン水溶液１３２．０ｇ（２．２ｍｏｌ）を反応容器に仕込み、冷却下３０％水酸化ナトリウム水溶液１３３．３ｇ（１．０ｍｏｌ）を、３０℃以下を保ちながら１時間かけて滴下を行った。滴下終了後、６０℃まで昇温し、４時間反応させた。次いで硫酸ジメチル１２６．０ｇ（１．０ｍｏｌ）を４０℃にて１時間かけて滴下後、６０℃まで昇温し、２時間反応させレゾール樹脂を合成した。反応終了後、水層を分離し、引き続きフェノール２８２．０ｇ（３．０ｍｏｌ）、及び３５％塩酸９．１ｇを加え、９０℃にて４時間反応させた。反応終了後、２５％アンモニア水溶液６．０ｇにより中和し、水洗により中和塩を除去後、６０ｍｍＨｇで２００℃まで加熱し未反応のフェノールを除去した。目的のフェノール系樹脂の軟化温度は９２℃、１５０℃におけるＩＣＩ溶融粘度は２．５ポイズであった。
【００２３】
実施例３、及び４
硬化剤として、実施例１、２において得られた本発明にかかる新規フェノール系樹脂を用い、エポキシ樹脂としてテトラメチルビフェノール型エポキシ樹脂（商品名：ＹＸ−４０００、エポキシ当量１８４ｇ／ｅｑ、油化シェルエポキシ（株）製）、硬化促進剤としてトリフェニルホスフィン、無機充填材として不定型溶融シリカ（ヒューズレックスＲＤ−８、（株）龍森製）を用い、表２に示す割合で９０℃にて３分間ロール混練してエポキシ樹脂組成物を得た。
【００２４】
比較例
硬化剤としてフェノールノボラック樹脂（商品名：ＰＳＭ−４３２７、水酸基当量１０４ｇ／ｅｑ、軟化点９２℃、１５０℃におけるＩＣＩ溶融粘度２．７ポイズ、群栄化学工業（株）製）を用い、実施例と同様の条件にてエポキシ樹脂組成物を得た。
【００２５】
実施例１、及び２で得られた新規フェノール系樹脂及び比較例で硬化剤として用いたフェノール樹脂の特性値を表１に示す。各々のＧＰＣチャート、及び赤外吸収スペクトルを図１〜６に示す。
【００２６】
【表１】
実施例３，４および比較例で得られたエポキシ樹脂組成物の物性は、トランスファー成形により得られたテストピースを用い測定した。硬化条件は、トランスファー成形（１７５℃、３０ｋｇ／ｃｍ２、３ｍｉｎ）後、１８０℃／６Ｈｒのキュアを行った。各測定結果を表２に示す。
・ガラス転移温度：ＴＭＡ法（セイコーインスツルメンツ（株）製、ＴＭＡ／ＳＳ１２０で測定）
・吸湿率：恒温恒湿槽（８５℃／８５％／１６８Ｈｒ）にて放置後の重量増加を測定。
・スパイラルフロー：ＥＭＭＩ１−６６に準じて測定。
・破壊靱性：Ａ．Ｆ．Ｙｅｅ，Ｒ．Ａ．Ｐｅａｒｓｏｎ，Ｊｏｕｒｎａｌ ｏｆＭａｔｅｒｉａｌｓ Ｓｃｉｅｎｃｅ，２１，２４６２（１９８６）記載の方法に準じて測定。
【００２８】
【表２】
【発明の効果】
本発明による新規フェノール系樹脂は、分子量分布が狭く、フェノール樹脂骨格内にアルコキシフェノールを有しており、当該フェノール系樹脂を硬化剤として用い、エポキシ樹脂を反応硬化させると架橋密度を適度に低減した硬化物を得ることができ、接着性を損なうことなく耐湿性、及び耐衝撃性に優れたエポキシ樹脂硬化物を得ることができる。
【図面の簡単な説明】
【図１】実施例１により得られた新規フェノール系樹脂のＧＰＣによる測定結果を示すものである。
【図２】実施例１により得られた新規フェノール系樹脂の赤外吸収スペクトルを示すものである。
【図３】実施例２により得られた新規フェノール系樹脂のＧＰＣによる測定結果を示すものである。
【図４】実施例２により得られた新規フェノール系樹脂の赤外吸収スペクトルを示すものである。
【図５】比較例に用いたフェノール樹脂のＧＰＣによる測定結果を示すものである。
【図６】比較例に用いたフェノール樹脂の赤外吸収スペクトルを示すものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel phenolic resin, an epoxy resin composition using the same as a curing agent, and a cured product thereof. Specifically, the present invention is useful for semiconductor encapsulation, a novel phenolic resin that improves mechanical properties such as moisture resistance and impact resistance of an epoxy cured product, and an epoxy resin composition using the same as a curing agent, And a cured product thereof.
[0002]
[Prior art]
Conventionally, in sealing an IC, a method of sealing an element using an epoxy resin composition has been widely used, and an epoxy resin raw material and a phenol resin as a curing agent have been used. The use of phenolic resins as epoxy resins or hardeners thereof in heat-resistant composites and heat-resistant adhesives has become increasingly diverse in recent years and is industrially important. However, in recent years, while the load on the encapsulant has been increasing due to the increase in the size of elements and the amount of heat generated due to the high integration of ICs, technically, the demand for packages has been increasing in order to further increase the packaging density. Are required to be smaller and thinner, and it is currently difficult for conventional phenolic resins to meet the required performance.
[0003]
In recent years, the mounting method has also changed, and the conventional method of soldering from the back of the wiring board has been changed to a method of immersion in a molten solder bath or IR reflow. It will be exposed to high temperatures. Therefore, a high level of performance is required for the resin composition used for the sealing material. For example, it is required to improve moisture resistance, impart flexibility to thermal stress, and improve mechanical properties such as impact resistance.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide an epoxy resin composition that satisfies the demands associated with the recent technological developments in the electric and electronic fields and a cured product that exhibits excellent performance as described above. Specifically, it is an object of the present invention to provide an epoxy resin composition having a low melt viscosity and improving moisture resistance and impact resistance, and a cured product thereof.
[0005]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, as shown in the following general formula, as a component (A), a novel phenolic compound having an alkoxyphenol in a phenol resin skeleton and having a narrow molecular weight distribution. The present invention has led to the invention of a curing agent which is a resin, one kind of epoxy resin having at least two or more glycidyl groups in one molecule as component (B), or an epoxy resin composition containing two or more kinds as essential components. That is, the present invention, in order to appropriately reduce the crosslinking density of the epoxy resin cured product, in the phenol resin used as a curing agent, partially alkoxylated phenolic hydroxyl groups, and the molecular weight distribution obtained by controlling the reaction. It is characterized by using a new narrow phenolic resin. By using these means, an epoxy resin composition having a low melt viscosity can be obtained, and by further curing them, a cured product having improved moisture resistance and impact resistance can be obtained.
[0006]
Embedded image
(In the formula, R represents a methyl group or an ethyl group, X represents a hydrogen atom or a methyl group, n represents an integer of 0 to 3, and m represents an integer of 1 to 5, where n = The content of compound 0 is 10% or less.)
The component (A) is a novolak-type phenolic resin having a narrow molecular weight distribution and a binuclear body content of 10% or less, and the phenolic hydroxyl group alkoxylation rate in the resin is 30 to 60%. It is a phenolic resin characterized by the following. The epoxy resin composition containing the epoxy resin composition and the inorganic filler is an epoxy resin composition for semiconductor encapsulation containing 50 to 92% by weight of the inorganic filler. The present invention also relates to an epoxy resin composition wherein the epoxy resin of the component (B) is an o-cresol novolak type epoxy resin and / or a biphenyl type epoxy resin, and a cured product thereof.
[0008]
The epoxy resin composition of the present invention uses a phenolic resin having a significantly reduced melt viscosity at a specific temperature as a curing agent, and can increase the filling rate of a filler, and is excellent in moldability. And is suitable for use as an IC seal. Furthermore, since the phenolic hydroxyl groups of the novel phenolic resin used as a curing agent are 30 to 60% alkoxylated, the cured product of the epoxy resin composition has appropriate flexibility. Thus, a cured product excellent in impact resistance and moisture resistance can be obtained. Next, a method for obtaining the resin of the present invention will be specifically described.
[0009]
A specific method for producing the novel phenolic resin according to the present invention is to use a dimethyl sulfate of the general formula (2) by using, for example, dimethyl sulfate as an alkoxylating agent under alkaline conditions with respect to a resol resin obtained by a general production method. An alkoxylated resole can be obtained.
[0010]
Embedded image
(In the formula, R represents a methyl group or an ethyl group, X represents a hydrogen atom or a methyl group, and k represents an integer of 0 to 2.) Then, dehydration with an excess phenol under acidic conditions By the condensation, a novel phenolic resin as an object can be obtained.
[0012]
In the above reaction, a resole resin can be a phenol or a resole resin obtained from an alkylphenol such as cresol as a raw material, and dimethyl sulfate, diethyl sulfate, or an alkyl halide can be used as an alkoxylating agent. . For example, in the case of dimethyl sulfate, 80 to 140 parts by weight based on 100 parts by weight of the resole resin can be reacted under alkaline conditions at 40 to 60 ° C. for 4 to 6 hours. As the alkaline condition, an aqueous solution of potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, or the like can be used. For example, 100% to 160 parts by weight of 30% sodium hydroxide is added to 100 parts by weight of the resole resin. The reaction can be advanced by using the compound. Next, the phenol used in the reaction with the alkoxylated resole resin is used in an amount of at least 2 times, usually 2 to 10 times the mole of the resole resin, and preferably 3 to 6 times the amount of the resol resin. Used in range.
[0013]
Examples of the acid catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, formic acid and the like. For example, in the case of 35% hydrochloric acid, such an acid catalyst is used in an amount of 1 to 20 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the resole resin.
[0014]
The reaction may be carried out usually at 40 ° C. to 120 ° C., preferably at 60 ° C. to 100 ° C., for about 2 to 8 hours, usually about 4 to 6 hours. After completion of the reaction, an alkali such as aqueous ammonia or an aqueous sodium hydroxide solution is added to the obtained reaction solution to neutralize the acid catalyst, and then washed with water for the purpose of removing neutralized salts. The desired novel phenolic resin can be obtained by distilling off the phenols in the reaction.
[0015]
Next, the epoxy resin composition will be described. The epoxy resin composition of the present invention is characterized by using the component (A) as a curing agent, that is, the above-mentioned novel phenolic resin according to the present invention. The epoxy resin used in the present invention may be any one generally used as an epoxy resin.Examples of such an epoxy resin include a phenol novolak type epoxy resin, an o-cresol novolak type epoxy resin, and phenol. Epoxidized aralkyl resin by xylylene bond of naphthols, epoxidized phenol-dicyclopentadiene resin, epoxidized bisphenol A, bisphenol S, bisphenol F, biphenol, etc., polyamino such as diaminodiphenylmethane, diaminodiphenylsulfonic acid and epichlorohydrin There are glycidylamine-type epoxy resins obtained by the reaction, and any number of these can be used in combination. The equivalent ratio between the epoxy resin and the curing agent is not particularly limited, but is preferably 0.5 to 1.5.
[0016]
In the epoxy resin composition for semiconductor encapsulation, an inorganic filler is used as an essential component. The amount of the inorganic filler to be used is preferably 50 to 92% by weight, more preferably 70 to 92% by weight, based on the total epoxy resin composition, from the viewpoint of improving moisture resistance and mechanical strength. Examples of the inorganic filler include powders such as silica, alumina, silicon nitride, silicon carbide, talc, calcium silicate, calcium carbonate, mica, clay, and titanium white, and fibrous bodies such as glass fiber and carbon fiber. Among these, crystalline silica and / or fused silica are preferred from the viewpoints of thermal expansion coefficient and thermal conductivity.
[0017]
In the present invention, it is desirable to use a curing accelerator when curing the epoxy resin composition. Examples of the curing accelerator include imidazoles such as 2-methylimidazole and 2-methyl-4-ethylimidazole; amines such as triethanolamine and triethylenediamine; organic phosphines such as tributylphosphine and triphenylphosphine; There is 8-diaza-bicyclo (5,4,0) undecene-7- and its derivatives. These curing accelerators may be used alone or in combination of two or more. In addition, these curing accelerators may be added in an amount of 0.1 to 100 parts by weight of the epoxidized product or the total amount of the epoxy compound and the curing agent. It is used in the range of 01 to 10 parts by weight.
[0018]
In the epoxy resin composition of the present invention, various additives may be used as a modifier for mechanical strength, heat resistance and the like. For example, by using a silane-based, titanate-based, aluminate-based, or zircoaluminate-based coupling agent, the adhesiveness between the resin and the inorganic filler can be improved. In particular, a silane coupling agent having a functional group that reacts with an epoxy resin is preferable. Examples of such a silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, and N- (2-aminomethyl) -3. -Aminopropylmethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like. These can be used alone or in combination.
[0019]
In addition, the epoxy resin composition for semiconductor encapsulation of the present invention may optionally contain a release agent such as a fatty acid and a wax, a bromide, a flame retardant such as antimony and phosphorus, and a coloring agent such as carbon black. , Mixed and kneaded to obtain a molding material for IC sealing.
[0020]
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
[0021]
Production Example 1 of New Phenolic Resin
108.0 g (1.0 mol) of orthocresol and 132.0 g (2.2 mol) of a 50% aqueous solution of formalin were charged into a reaction vessel, and 133.3 g (1.0 mol) of a 30% aqueous sodium hydroxide solution was cooled to 30 ° C. or lower. The solution was dropped over 1 hour while maintaining the temperature. After completion of the dropwise addition, the temperature was raised to 40 ° C., and the reaction was performed for 2 hours. Next, 126.0 g (1.0 mol) of dimethyl sulfate was added dropwise at 40 ° C. over 1 hour, then the temperature was raised to 60 ° C., and the mixture was reacted for 2 hours to synthesize a resole resin having methoxylated phenolic hydroxyl groups. After the completion of the reaction, the aqueous layer was separated, and subsequently 282.0 g (3.0 mol) of phenol and 9.1 g of 35% hydrochloric acid were added and reacted at 90 ° C. for 4 hours. After completion of the reaction, the reaction mixture was neutralized with 6.0 g of a 25% aqueous ammonia solution, and the neutralized salt was removed by washing with water. The softening temperature of the target phenolic resin was 77 ° C., and the ICI melt viscosity at 150 ° C. was 0.8 poise.
[0022]
Example 2
108.0 g (1.0 mol) of orthocresol and 132.0 g (2.2 mol) of a 50% aqueous solution of formalin were charged into a reaction vessel, and 133.3 g (1.0 mol) of a 30% aqueous sodium hydroxide solution was cooled to 30 ° C. or lower. The solution was dropped over 1 hour while maintaining the temperature. After completion of the dropping, the temperature was raised to 60 ° C., and the reaction was performed for 4 hours. Next, 126.0 g (1.0 mol) of dimethyl sulfate was added dropwise at 40 ° C. over 1 hour, then the temperature was raised to 60 ° C., and the mixture was reacted for 2 hours to synthesize a resol resin. After the completion of the reaction, the aqueous layer was separated, and subsequently 282.0 g (3.0 mol) of phenol and 9.1 g of 35% hydrochloric acid were added and reacted at 90 ° C. for 4 hours. After completion of the reaction, the reaction mixture was neutralized with 6.0 g of a 25% aqueous ammonia solution, and the neutralized salt was removed by washing with water. The softening temperature of the target phenolic resin was 92 ° C., and the ICI melt viscosity at 150 ° C. was 2.5 poise.
[0023]
Examples 3 and 4
As the curing agent, the novel phenolic resin according to the present invention obtained in Examples 1 and 2 was used, and as the epoxy resin, a tetramethylbiphenol type epoxy resin (trade name: YX-4000, epoxy equivalent: 184 g / eq, oiled shell) Epoxy Co., Ltd.), triphenylphosphine as a curing accelerator, and amorphous fused silica (Fuselex RD-8, manufactured by Tatsumori Co., Ltd.) as an inorganic filler at a rate shown in Table 2 at 90 ° C. Roll kneading was performed for 3 minutes to obtain an epoxy resin composition.
[0024]
A phenol novolak resin (trade name: PSM-4327, hydroxyl equivalent 104 g / eq, softening point 92 ° C., ICI melt viscosity at 150 ° C. 2.7 poise at 150 ° C., manufactured by Gun Ei Chemical Co., Ltd.) was used as a comparative curing agent. An epoxy resin composition was obtained under the same conditions as in the example.
[0025]
Table 1 shows the characteristic values of the novel phenolic resins obtained in Examples 1 and 2 and the phenolic resin used as a curing agent in Comparative Examples. Each GPC chart and infrared absorption spectrum are shown in FIGS.
[0026]
[Table 1]
The physical properties of the epoxy resin compositions obtained in Examples 3 and 4 and Comparative Example were measured using test pieces obtained by transfer molding. Curing conditions were as follows: transfer molding (175 ° C., 30 kg / cm 2 , 3 min), followed by curing at 180 ° C./6 Hr. Table 2 shows the measurement results.
Glass transition temperature: TMA method (measured by TMA / SS120, manufactured by Seiko Instruments Inc.)
-Moisture absorption: The weight increase after standing in a thermo-hygrostat (85 ° C / 85% / 168Hr) was measured.
-Spiral flow: Measured according to EMMI1-66.
-Fracture toughness: A. F. Yee, R .; A. Measured according to the method described in Pearson, Journal of Materials Science, 21, 462 (1986).
[0028]
[Table 2]
【The invention's effect】
The novel phenolic resin according to the present invention has a narrow molecular weight distribution and has an alkoxyphenol in the phenolic resin skeleton. When the phenolic resin is used as a curing agent and the epoxy resin is cured by reaction, the crosslinking density is appropriately reduced. A cured epoxy resin having excellent moisture resistance and impact resistance can be obtained without deteriorating the adhesiveness.
[Brief description of the drawings]
FIG. 1 shows the results of GPC measurement of the novel phenolic resin obtained in Example 1.
FIG. 2 shows an infrared absorption spectrum of the novel phenolic resin obtained in Example 1.
FIG. 3 shows the results of GPC measurement of the novel phenolic resin obtained in Example 2.
FIG. 4 shows an infrared absorption spectrum of the novel phenolic resin obtained in Example 2.
FIG. 5 shows the results of measurement of the phenolic resin used in the comparative example by GPC.
FIG. 6 shows an infrared absorption spectrum of a phenol resin used in a comparative example.
Claims (2)
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| JP2002164109A JP2004010700A (en) | 2002-06-05 | 2002-06-05 | Novel phenolic resin and epoxy resin composition using the same as curing agent |
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| JP2002164109A JP2004010700A (en) | 2002-06-05 | 2002-06-05 | Novel phenolic resin and epoxy resin composition using the same as curing agent |
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