JP5279036B2 - Novel epoxy resin, production method thereof, epoxy resin composition and cured product - Google Patents
Novel epoxy resin, production method thereof, epoxy resin composition and cured product Download PDFInfo
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- JP5279036B2 JP5279036B2 JP2010083523A JP2010083523A JP5279036B2 JP 5279036 B2 JP5279036 B2 JP 5279036B2 JP 2010083523 A JP2010083523 A JP 2010083523A JP 2010083523 A JP2010083523 A JP 2010083523A JP 5279036 B2 JP5279036 B2 JP 5279036B2
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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 26
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 16
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- 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 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000011342 resin composition Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 7
- -1 laminates Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- 239000003566 sealing material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- 239000004101 4-Hexylresorcinol Substances 0.000 description 2
- WFJIVOKAWHGMBH-UHFFFAOYSA-N 4-hexylbenzene-1,3-diol Chemical compound CCCCCCC1=CC=C(O)C=C1O WFJIVOKAWHGMBH-UHFFFAOYSA-N 0.000 description 2
- 235000019360 4-hexylresorcinol Nutrition 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000004844 aliphatic epoxy resin Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 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
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 150000001896 cresols Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 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
- 229960003258 hexylresorcinol Drugs 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-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
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000539 dimer Substances 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Description
本発明は、新規なエポキシ樹脂、該エポキシ樹脂の製造方法、該エポキシ樹脂含有組成物、及びその硬化物に関し、さらに詳しくは低粘度、低弾性等の特性に優れた硬化物を与える新規なエポキシ樹脂及びその製造方法及びエポキシ樹脂組成物及びその硬化物に関する。本発明のエポキシ樹脂組成物は、半導体封止材、成型材料、積層板、接着剤、塗料などの広範囲の用途に有用である。 The present invention relates to a novel epoxy resin, a method for producing the epoxy resin, the epoxy resin-containing composition, and a cured product thereof. It is related with resin, its manufacturing method, an epoxy resin composition, and its hardened | cured material. The epoxy resin composition of the present invention is useful for a wide range of applications such as semiconductor sealing materials, molding materials, laminates, adhesives, and paints.
従来、エポキシ樹脂は工業的に幅広い用途で使用されており、その要求性能も近年ますます高度化している。例えばエポキシ樹脂を主剤とする硬化性樹脂組成物の代表的分野に半導体封止材料があるが、近年、半導体素子の集積度の向上に伴い、パッケージサイズが大面積化、薄型化に向かうとともに、実装方式も表面実装化への移行が進展している。 Conventionally, epoxy resins have been used in a wide range of industrial applications, and their required performance has become increasingly sophisticated in recent years. For example, there is a semiconductor sealing material in a typical field of a curable resin composition mainly composed of an epoxy resin, but in recent years, with the improvement of the integration degree of semiconductor elements, the package size has become larger and thinner, The mounting method is also shifting to surface mounting.
そこで、近年、薄膜パッケージや大面積を封止するウェハーレベルパッケージの封止に、液状エポキシ樹脂組成物を用いた成型工法が用いられるようになってきた。封止成型に液状エポキシ樹脂組成物を使用すると、固形エポキシ樹脂組成物と比較して、成型時の樹脂組成物の粘度が非常に低くなる為、回路の損傷を起こし難く、また大面積を一括封止することが可能となることが期待される。 Therefore, in recent years, a molding method using a liquid epoxy resin composition has been used for sealing a thin film package or a wafer level package for sealing a large area. When a liquid epoxy resin composition is used for sealing molding, the viscosity of the resin composition at the time of molding is very low compared to a solid epoxy resin composition, so that it is difficult to cause circuit damage, and a large area is batched. It is expected to be possible to seal.
従来の液状封止材樹脂組成物として最も汎用されているものに、液状もしくは低融点の結晶性のビスフェノールＡ及びビスフェノールＦ型エポキシ樹脂にエポキシ樹脂硬化剤、シリカ、アルミナ等のフィラー及び反応性希釈剤としてエポキシ基を有する低粘度樹脂を配合したものがある。 The most widely used conventional liquid encapsulant resin compositions include liquid or low melting crystalline bisphenol A and bisphenol F type epoxy resins, epoxy resin curing agents, fillers such as silica and alumina, and reactive dilution. There is a compound containing a low-viscosity resin having an epoxy group as an agent.
しかし、近年の電子素子の高密度化及び小型化に伴い、液状封止材樹脂組成物にはこれまで以上に優れた耐クラック性や、耐湿性が求められており。またパッケージの大型化に伴い、反りも大きな問題となっている。これらの特性を改善する方法として、トランスファー成型用エポキシ樹脂組成物の場合と同様にシリカ、アルミナ等のフィラーを大量に充填することで低線膨張化させる方法があるが、充填材を大量に充填した液状封止材組成物は、高粘度化して、成型不良や微細な回路の損傷が発生する問題があった。 However, with recent increase in density and miniaturization of electronic devices, liquid sealing material resin compositions are required to have better crack resistance and moisture resistance than ever before. In addition, with the increase in size of packages, warping has become a major problem. As a method for improving these properties, there is a method of reducing the linear expansion by filling a large amount of filler such as silica and alumina as in the case of the epoxy resin composition for transfer molding. The liquid sealing material composition has a problem in that the viscosity is increased and molding failure or fine circuit damage occurs.
この問題点を解決する手段としてこれまで低粘度な脂肪族のエポキシ樹脂、例えば１，６−ヘキサンジオールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル等を反応性希釈材として用い、液状封止材樹脂組成物の低粘度化によるフィラーの高充填化及び樹脂硬化物の低弾性率化をはかる、いわゆる硬化樹脂の低応力化により反りやパッケージクラックを防止する方法があるが、ビスフェノール型エポキシ樹脂に脂肪族系エポキシ樹脂を配合した液状樹脂組成物は長期に貯蔵すると反応性希釈材として用いた脂肪族系エポキシ樹脂がブリードアウトし不均一な組成物となり易く、またその硬化物物性は、耐熱性が低下するといった根本的な欠陥を有しており実用上問題である。また、レゾルシノールジグリシジルエーテルを反応性希釈材として用いた液状樹脂組成物は、耐熱性が低下する問題点の解決には有効であるが硬化樹脂の低弾性化には十分ではなく、また特許文献１にはオキシメチレン鎖を有するエポキシ樹脂が、特許文献２ではオキシエチレン鎖を有するエポキシ樹脂が提案されているが、粘度にはまだ改良の余地があった。 As a means for solving this problem, a low-viscosity aliphatic epoxy resin such as 1,6-hexanediol diglycidyl ether, polypropylene glycol diglycidyl ether or the like is used as a reactive diluent, and a liquid encapsulant resin composition There is a method to prevent warpage and package cracking by reducing the stress of the cured resin, which increases the filling of the filler by lowering the viscosity of the product and lowering the elastic modulus of the cured resin. When stored for a long period of time, a liquid resin composition containing an epoxy resin tends to bleed out the aliphatic epoxy resin used as a reactive diluent, resulting in a non-uniform composition. This is a practical problem because it has a fundamental defect. In addition, a liquid resin composition using resorcinol diglycidyl ether as a reactive diluent is effective in solving the problem of reduced heat resistance, but is not sufficient for reducing the elasticity of a cured resin. Although an epoxy resin having an oxymethylene chain is proposed in 1 and an epoxy resin having an oxyethylene chain is proposed in Patent Document 2, there is still room for improvement in viscosity.
本発明は、上記の様な実情に鑑みて、長期保存性を持ち、低粘度でありかつ樹脂硬化物特性を損なうことなく低弾性率を有するエポキシ樹脂を求めて鋭意検討した結果、下記一般式（Ｉ）で表されるエポキシ樹脂及びその製造方法を提供するものであり、また、エポキシ樹脂及び硬化剤、さらに必要により硬化促進剤から構成されるエポキシ樹脂組成物において、該エポキシ樹脂成分として一般式（Ｉ）で表されるエポキシ樹脂を含有することを特徴とする新規なエポキシ樹脂組成物並びに該エポキシ樹脂からなる半導体封止材組成物を提供するものである。 In view of the above circumstances, the present invention has been intensively studied for an epoxy resin having long-term storage stability, low viscosity and low elastic modulus without impairing the properties of the cured resin. An epoxy resin represented by (I) and a method for producing the epoxy resin, and an epoxy resin composition composed of an epoxy resin and a curing agent, and further, if necessary, a curing accelerator, are generally used as the epoxy resin component. It is intended to provide a novel epoxy resin composition characterized by containing an epoxy resin represented by the formula (I) and a semiconductor sealing material composition comprising the epoxy resin.
上記化合物は下記一般式（２）で表される２価フェノールにエピクロルヒドリンを反応させることにより製造することが出来る。 The above compound can be produced by reacting a dihydric phenol represented by the following general formula (2) with epichlorohydrin.
本発明について更に詳細に述べる。
本発明に係る上記一般式（Ｉ）におけるｎは５以下が好ましい。ｎが５より大きいと粘度が上昇し好ましくない。一般式（Ｉ）におけるｎは、平均値０〜５を示し好ましくは平均値０〜１が良好な物性を示す。本発明における一般式（２）で表される２価フェノールにエピクロルヒドリンを反応させる方法は、従来公知の方法が利用でき、特に制限されるものではない。即ち、２価フェノールの水酸基１モルに対してエピクロルヒドリンを１〜２０モル添加し、アルカリ金属水酸化物の存在下１０〜１２０℃、好ましくは４０〜１００℃で反応を行うことができる。
The present invention will be described in more detail.
In the above general formula (I) according to the present invention, n is preferably 5 or less. When n is larger than 5, the viscosity increases, which is not preferable. N in the general formula (I) represents an average value of 0 to 5, and preferably an average value of 0 to 1 indicates good physical properties. As a method of reacting epichlorohydrin with the dihydric phenol represented by the general formula (2) in the present invention, a conventionally known method can be used and is not particularly limited. That is, 1-20 mol of epichlorohydrin is added to 1 mol of a hydroxyl group of a dihydric phenol, and the reaction can be carried out at 10 to 120 ° C., preferably 40 to 100 ° C. in the presence of an alkali metal hydroxide.
一般式（Ｉ）におけるＲは炭素数４〜６の炭化水素基が好ましい。ただしＲがt-ブチル基の場合、骨格に柔軟性がないため、低弾性の発現が他の炭化水素基に比べて劣る。このため好ましくはＲは炭素数４〜６の直鎖の炭化水素基であり、さらに好ましくは炭素数６で直鎖であるn-ヘキシル基である。 R in the general formula (I) is preferably a hydrocarbon group having 4 to 6 carbon atoms. However, when R is a t-butyl group, since the skeleton is not flexible, the expression of low elasticity is inferior to other hydrocarbon groups. Therefore, R is preferably a linear hydrocarbon group having 4 to 6 carbon atoms, and more preferably an n-hexyl group having 6 carbon atoms and a straight chain.
反応の際に存在させるアルカリ金属水酸化物としては、水酸化ナトリウム、水酸化カリウム、水酸化リチウムまたはこれらの混合物等が挙げられ、水溶液の形で用いるのが好ましく、通常市販されている水酸化ナトリウム水溶液がより好ましい。 Examples of the alkali metal hydroxide to be present in the reaction include sodium hydroxide, potassium hydroxide, lithium hydroxide or a mixture thereof, and are preferably used in the form of an aqueous solution. A sodium aqueous solution is more preferable.
エピクロルヒドリンと２官能フェノール類との反応は、エポキシ基とは反応しない溶媒中で行う事ができ、具体的にはトルエン、キシレン、ベンゼン等の芳香族炭化水素類、メチルイソブチルケトン、メチルエチルケトン、シクロヘキサノン、アセトン等のケトン類、プロパノール、ブタノール等のアルコール類、ジエチレングリコールメチルエーテル、プロピレングリコールメチルエーテル、ジプロピレングリコールメチルエーテル等のグリコールエーテル類、ジエチルエーテル、ジブチルエーテル、エチルプロピルエーテル等の脂肪族エーテル類、ジオキサン、テトラヒドロフラン等の脂環式エーテル類が挙げられるがこれらに限定されるものではない。また、それら２種以上混合して使用することもできる。 The reaction of epichlorohydrin and bifunctional phenols can be carried out in a solvent that does not react with the epoxy group, specifically, aromatic hydrocarbons such as toluene, xylene, benzene, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, Ketones such as acetone, alcohols such as propanol and butanol, glycol ethers such as diethylene glycol methyl ether, propylene glycol methyl ether and dipropylene glycol methyl ether, aliphatic ethers such as diethyl ether, dibutyl ether and ethylpropyl ether, Examples thereof include, but are not limited to, alicyclic ethers such as dioxane and tetrahydrofuran. Moreover, it can also be used in mixture of 2 or more types thereof.
反応形態は、２官能フェノール類、エピクロルヒドリン及び溶媒を反応容器に仕込み、溶解した後、アルカリ金属水酸化物の水溶液を滴下しながら、常圧で７０〜１００℃、３０分〜４時間で行うことができる。その際、アルカリ金属水酸化物の水溶液は連続的に滴下しても良く、又分割して滴下しても良い。また２官能フェノール類をアルカリ金属水酸化物の水溶液及び溶媒に溶解した後、エピクロルヒドリンを滴下する方法でも良く、同様に常圧で７０〜１００℃、３０分〜４時間で行うことができる。反応温度が７０℃未満では反応が進みにくくなり、１００℃以上ではエピクロルヒドリンが反応系外に留出する危険があり好ましくない。このようにして反応を終了するが、加水分解性塩素量が多すぎる場合は、アルカリ金属水酸化物を前記全量範囲内で加えて、６０〜９０℃の温度で１０分〜２時間再閉環反応を行なった後、中和、水洗等の方法で過剰のアルカリ金属水酸化物や副生塩を除去し、さらに溶媒を減圧留去すると、精製された本発明のエポキシ樹脂が得られる。
また、反応で生成した生成水を減圧下又は常圧下反応系外に除去しながら反応を行うこともできる。
The reaction mode is that bifunctional phenols, epichlorohydrin and a solvent are charged into a reaction vessel and dissolved, and then an aqueous solution of an alkali metal hydroxide is added dropwise at 70 to 100 ° C. for 30 minutes to 4 hours at atmospheric pressure. Can do. At that time, the alkali metal hydroxide aqueous solution may be dropped continuously, or may be dropped dropwise. Moreover, after dissolving bifunctional phenols in the aqueous solution and solvent of an alkali metal hydroxide, the method of dripping epichlorohydrin may be sufficient, and it can carry out similarly at 70-100 degreeC and 30 minutes-4 hours at a normal pressure. If the reaction temperature is less than 70 ° C., the reaction is difficult to proceed, and if it is 100 ° C. or more, epichlorohydrin may be distilled out of the reaction system. In this way, the reaction is completed, but if the amount of hydrolyzable chlorine is too large, alkali metal hydroxide is added within the above-mentioned total amount range, and re-ringing reaction at a temperature of 60 to 90 ° C. for 10 minutes to 2 hours. Then, excess alkali metal hydroxide and by-product salt are removed by a method such as neutralization and washing, and the solvent is distilled off under reduced pressure to obtain a purified epoxy resin of the present invention.
The reaction can also be carried out while removing the water produced by the reaction from the reaction system under reduced pressure or normal pressure.
上記一般式（１）で表されるエポキシ樹脂を含有するエポキシ樹脂組成物は低粘度、弾性率等の優れた特性を有する樹脂組成物を提供する。本発明に係るエポキシ樹脂組成物に用いられる硬化剤としては、通常エポキシ樹脂を硬化させるのに使用するものであれば使用することが出来る。具体的にはジアミノジフェニルメタン、ジエチレントリアミン、トリエチレンテトラミン、イソホロンジアミン、ダイマー酸等の酸類とポリアミン類との縮合物であるポリアミドアミン等のアミン系化合物、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、ヘキサヒドロ無水フタル酸等酸無40水物系化合物、フェノール、クレゾール、ビスフェノールＡ、ナフトール、ナフタレンジオール等のフェノール類とホルムアルデヒド等のアルデヒド類やケトン類との縮合反応により得られるノボラック型フェノール樹脂、また、フェノール、クレゾール、ビスフェノールＡ、ナフトール、ナフタレンジオール等のフェノール類とキシリレングリコールとの縮合反応等により得られるアラルキル型フェノール樹脂等のフェノール系化合物類、ジシアンジアミド及びその誘導体、２−メチルイミダゾ−ル、２−エチル−４−メチルイミダゾール等のイミダゾール類及びその誘導体、アジピン酸ジヒドラジド、イソフタル酸ジヒドラジド等のヒドラジド類、ＢＦ３ 錯体等が挙げられるが特にこれらに限定されるわけではない。これら硬化剤は、単独でも良いし、２種類以上を併用しても良い。本発明の樹脂組成物には、必要に応じて硬化促進剤を使用することができる。例えば、ホスフィン類、イミダゾール類、第３級アミン、ＢＦ３錯体等公知の種々の硬化促進剤が使用でき特に限定されるわけではない。硬化促進剤を用いる場合、エポキシ樹脂に対して０．０１〜１０重量％の範囲が好ましい The epoxy resin composition containing the epoxy resin represented by the general formula (1) provides a resin composition having excellent characteristics such as low viscosity and elastic modulus. As a hardening | curing agent used for the epoxy resin composition which concerns on this invention, if normally used for hardening an epoxy resin, it can be used. Specifically, amine compounds such as polyamines that are condensates of acids such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, isophoronediamine, and dimer acid and polyamines, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride Obtained by condensation reaction of acid, maleic anhydride, hexahydrophthalic anhydride and other acid-free 40 water-based compounds, phenols, cresols, bisphenol A, naphthol, naphthalenediol and other aldehydes and ketones Novolak-type phenolic resins, and aralkyl-type phenolic resins such as phenols, cresols, bisphenol A, naphthol, naphthalenediol, and other phenols obtained by the condensation reaction of xylylene glycol, etc. Diol compounds, dicyandiamide and derivatives thereof, imidazoles and derivatives thereof such as 2-methylimidazole and 2-ethyl-4-methylimidazole, hydrazides such as adipic acid dihydrazide and isophthalic acid dihydrazide, and BF3 complexes. Although it is mentioned, it is not necessarily limited to these. These curing agents may be used alone or in combination of two or more. A curing accelerator can be used in the resin composition of the present invention as necessary. For example, various known curing accelerators such as phosphines, imidazoles, tertiary amines, and BF3 complexes can be used and are not particularly limited. When using a hardening accelerator, the range of 0.01 to 10 weight% with respect to an epoxy resin is preferable.
以下、実施例により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に限定されるものではない。また以下の例に記載に「部」とは、特に記載しない限り「重量部」を意味する。また、分析方法は次の通りである。
エポキシ当量の測定法はＪＩＳ Ｋ−７２３６に従い測定した。
粘度の測定法はＪＩＳ Ｋ−７２３３に従い測定した。即ち５００ｍＬの円筒缶に樹脂４００ｇをはかりとって、２５±０．２℃の恒温水槽で５時間放置して恒温にし、回転粘度計のローターを樹脂に浸漬して測定した。
加水分解性塩素量の測定方法はＪＩＳ−７２４３−２に従い測定した。即ちサンプル約２ｇを三角フラスコに秤取り、ジオキサンで溶解後、０．１Ｎ−ＫＯＨメタノール溶液２５ｍｌを加え、７０℃の温水中で３０分反応させた。次いで２００ｍｌビーカー移し取り、アセトン、イオン交換水、及び酢酸３ｍｌを加えた後に０．０１Ｎ−ＡｇＮＯ３水溶液による電位差滴定で求めた。表１には上記の測定結果を併記した。
合成例１
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In the following examples, “parts” means “parts by weight” unless otherwise specified. The analysis method is as follows.
The measuring method of epoxy equivalent was measured according to JIS K-7236.
The viscosity was measured according to JIS K-7233. That is, 400 g of the resin was weighed in a 500 mL cylindrical can and allowed to stand for 5 hours in a constant temperature water bath of 25 ± 0.2 ° C., and the rotor of the rotational viscometer was immersed in the resin for measurement.
The measuring method of the amount of hydrolyzable chlorine was measured according to JIS-7243-2. That is, about 2 g of a sample was weighed in an Erlenmeyer flask, dissolved in dioxane, added with 25 ml of a 0.1 N KOH methanol solution, and reacted in warm water at 70 ° C. for 30 minutes. Next, the sample was transferred to a 200 ml beaker, and acetone, ion-exchanged water, and 3 ml of acetic acid were added thereto, and then determined by potentiometric titration with a 0.01N-AgNO3 aqueous solution. Table 1 shows the above measurement results.
Synthesis example 1
攪拌装置、温度計、連続滴下装置、減圧下にエピクロルヒドリンと水の共沸蒸気を冷却凝縮し、エピクロルヒドリンだけを反応系に戻す装置の付いたセパラブルフラスコに４−ヘキシルレゾルシノール５０部、エピクロルヒドリン１９１部、ジエチレングリコールジメチルエーテル２９部を加えて６５℃に昇温した後４９％濃度の水酸化ナトリウム２０部を３時間かけて滴下反応させた。その間、生成した水はエピクロルヒドリンとの共沸により順次除去した。反応終了後系内を１０ｍｍＨｇの減圧にし、１５０℃まで昇温して過剰のエピクロルヒドリンを回収した。生成物をトルエン２００部に溶解、水洗によって複製した食塩を除去、ロータリーエバポレーターでトルエンを留去することにより、薄褐色液状のエポキシ化合物７２部（以下「エポキシ樹脂Ａ」、収率９１％）を得た。得られたエポキシ化合物のエポキシ当量は１６４．８ｇ／ｅｑ、２５℃における粘度は２００ｍＰａ・ｓ、加水分解性塩素は７０ｐｐｍであった。
合成例２
Stirring device, thermometer, continuous dripping device, epichlorohydrin and water azeotropic vapor under reduced pressure are cooled and condensed, and separable flask equipped with a device for returning only epichlorohydrin to the reaction system 50 parts 4-hexylresorcinol, 191 parts epichlorohydrin Then, 29 parts of diethylene glycol dimethyl ether was added and the temperature was raised to 65 ° C., and then 20 parts of sodium hydroxide with a concentration of 49% was dropped over 3 hours. Meanwhile, the produced water was sequentially removed by azeotropy with epichlorohydrin. After completion of the reaction, the pressure inside the system was reduced to 10 mmHg, and the temperature was raised to 150 ° C. to recover excess epichlorohydrin. Dissolving the product in 200 parts of toluene, removing the duplicated salt by washing with water, and distilling off the toluene with a rotary evaporator, 72 parts of a light brown liquid epoxy compound (hereinafter referred to as “epoxy resin A”, yield 91%) Obtained. The epoxy equivalent of the obtained epoxy compound was 164.8 g / eq, the viscosity at 25 ° C. was 200 mPa · s, and hydrolyzable chlorine was 70 ppm.
Synthesis example 2
４−ヘキシルレゾルシノールの代わりにレゾルシノール５０部を用いた以外は実施例１と同様に反応を行い、常温で液状のエポキシ樹脂（以下「エポキシ樹脂Ｂ」）を得た。得られたエポキシ化合物のエポキシ当量は１２７．６ｇ／ｅｑ、２５℃における粘度は８００ｍＰａ／ｓ、加水分解性塩素は９０ｐｐｍであった。
これらの測定値を市販のビスフェノールＡ型エポキシ樹脂（ＹＤ−８１２５）と共に表１に示した。
A reaction was carried out in the same manner as in Example 1 except that 50 parts of resorcinol was used instead of 4-hexyl resorcinol to obtain a liquid epoxy resin (hereinafter referred to as “epoxy resin B”) at room temperature. The epoxy equivalent of the obtained epoxy compound was 127.6 g / eq, the viscosity at 25 ° C. was 800 mPa / s, and hydrolyzable chlorine was 90 ppm.
These measured values are shown in Table 1 together with a commercially available bisphenol A type epoxy resin (YD-8125).
合成例１で得たエポキシ樹脂Ａ第２表で表される配合に従って配合しエポキシ樹脂組成物を得た。硬化剤としてＫＡＹＡＨＡＲＤ Ａ−Ａ（活性水素当量６３．５、日本化薬社製）、硬化促進材として２Ｅ４ＭＺ（四国化成社製）を使用した。
このエポキシ樹脂組成物を幅10mm、厚さ4mm、長さ160mmの金属型に注型し、目的の試験片を得た。
比較例１及び比較例２
Epoxy resin A obtained in Synthesis Example 1 was blended according to the blend represented by Table 2 to obtain an epoxy resin composition. KAYAHARD AA (active hydrogen equivalent 63.5, manufactured by Nippon Kayaku Co., Ltd.) was used as a curing agent, and 2E4MZ (produced by Shikoku Kasei Co., Ltd.) was used as a curing accelerator.
This epoxy resin composition was cast into a metal mold having a width of 10 mm, a thickness of 4 mm, and a length of 160 mm to obtain a target test piece.
Comparative Example 1 and Comparative Example 2
合成例２として得たエポキシ樹脂Ｂ及び比較例２としてビスフェノールＡ型エポキシ樹脂ＹＤ−８１２５（エポキシ当量１７１．８ｇ／ｅｑ、粘度４,４００ｍＰａ／ｓ、東都化成社製）をそれぞれ実施例１と同様に表２に従って配合しエポキシ樹脂組成物を得た。このエポキシ樹脂組成物を実施例１と同様に幅10mm、厚さ4mm、長さ160mmの金属型に注型し、目的の試験片を得た。
これらの試験片について下記の試験法によってそれぞれの物性知を測定した。その結果を表２に示した。
硬化物特性の測定方法
１．吸水度 温度４０℃、湿度８５％ＲＨなる条件下で２００時間処理した時の重量変化を求めた。
２．ガラス転移点 ガラス転移温度及び動的粘弾性率はセイコーインスツルメンス社製ＤＭＡ１２０によって測定し、ガラス転移温度はＴａｎδピーク値で示した。
３．貯蔵弾性率
４．曲げ強度 曲げ強度率はＪＩＳ Ｋ６９１１で測定
５．曲げ弾性率 曲げ弾性率はＪＩＳ Ｋ６９１１における熱硬化性プラスチック一般試験方法に基づき、精密万能試験機によるクロスヘッドスピード毎分２ｍｍ／分の速度で測定を実施した。装置は島津製作所（株）製のオートグラフＡＧＳ−Ｈを使用した。
Epoxy resin B obtained as Synthesis Example 2 and bisphenol A type epoxy resin YD-8125 (epoxy equivalent 171.8 g / eq, viscosity 4,400 mPa / s, manufactured by Tohto Kasei Co., Ltd.) as Comparative Example 2 are the same as in Example 1. Were mixed according to Table 2 to obtain an epoxy resin composition. The epoxy resin composition was cast into a metal mold having a width of 10 mm, a thickness of 4 mm, and a length of 160 mm in the same manner as in Example 1 to obtain a target test piece.
The physical properties of these test pieces were measured by the following test methods. The results are shown in Table 2.
Method for measuring properties of cured product Water absorption The change in weight when treated for 200 hours under conditions of a temperature of 40 ° C. and a humidity of 85% RH was determined.
2. Glass transition temperature The glass transition temperature and the dynamic viscoelastic modulus were measured by DMA 120 manufactured by Seiko Instruments Inc., and the glass transition temperature was indicated by a Tan δ peak value.
3. 3. Storage elastic modulus Bending strength Bending strength rate is measured according to JIS K6911. Flexural modulus The flexural modulus was measured at a crosshead speed of 2 mm / min with a precision universal testing machine based on the general thermosetting plastic test method in JIS K6911. The apparatus used was Autograph AGS-H manufactured by Shimadzu Corporation.
本発明のエポキシ樹脂は、表１に示すとおり、低粘度であり、かつ、本発明の新規なエポキシ樹脂を使用した硬化物は、表２からも明らかなように、遜色無い吸水率を示し、かつ低弾性であることから低応力化に優れる。従って、本発明のエポキシ樹脂を使用したエポキシ樹脂組成物は、半導体封止材、成型材料、積層板、接着剤、塗料などの広範囲の用途に有用である。 As shown in Table 1, the epoxy resin of the present invention has a low viscosity, and the cured product using the novel epoxy resin of the present invention exhibits a water absorption rate comparable to that shown in Table 2, In addition, it is excellent in reducing stress because of its low elasticity. Therefore, the epoxy resin composition using the epoxy resin of the present invention is useful for a wide range of applications such as semiconductor sealing materials, molding materials, laminates, adhesives, paints and the like.
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