JPH04370113A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPH04370113A JPH04370113A JP17191191A JP17191191A JPH04370113A JP H04370113 A JPH04370113 A JP H04370113A JP 17191191 A JP17191191 A JP 17191191A JP 17191191 A JP17191191 A JP 17191191A JP H04370113 A JPH04370113 A JP H04370113A
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- epoxy resin
- resin composition
- formula
- represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 44
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 239000002530 phenolic antioxidant Substances 0.000 claims abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 9
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 9
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 8
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 3
- PHQBTXISHUNQQN-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCC)C(C(C(O)(C1=CC=CC=C1)CCCCCCCCC)(CO)CO)O Chemical compound OP(O)OP(O)O.C(CCCCCCCC)C(C(C(O)(C1=CC=CC=C1)CCCCCCCCC)(CO)CO)O PHQBTXISHUNQQN-UHFFFAOYSA-N 0.000 claims description 2
- VYGUBTIWNBFFMQ-UHFFFAOYSA-N [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O Chemical group [N+](#[C-])N1C(=O)NC=2NC(=O)NC2C1=O VYGUBTIWNBFFMQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 abstract description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 239000011342 resin composition Substances 0.000 abstract 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 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 8
- 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 5
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 3
- -1 organic acid salt Chemical class 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 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 compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 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
- ABFCPWCUXLLRSC-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C ABFCPWCUXLLRSC-UHFFFAOYSA-N 0.000 description 1
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- 229920003319 Araldite® Polymers 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- BFDWGBUTFFXFGL-UHFFFAOYSA-N Clc1cc(Cl)c2OP(=O)c3ccccc3-c2c1 Chemical compound Clc1cc(Cl)c2OP(=O)c3ccccc3-c2c1 BFDWGBUTFFXFGL-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-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
- XZYMCKIPUJEQSY-UHFFFAOYSA-N [Na+].[Na+].[Na+].CCCCCC([O-])([O-])[O-] Chemical compound [Na+].[Na+].[Na+].CCCCCC([O-])([O-])[O-] XZYMCKIPUJEQSY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 239000000945 filler Substances 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
- 239000003112 inhibitor Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- ZQJDKPPZEMPWFK-UHFFFAOYSA-N n,n-dipentylpentan-1-amine;phenol Chemical compound OC1=CC=CC=C1.CCCCCN(CCCCC)CCCCC ZQJDKPPZEMPWFK-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- LJAGLQVRUZWQGK-UHFFFAOYSA-N oxecane-2,10-dione Chemical compound O=C1CCCCCCCC(=O)O1 LJAGLQVRUZWQGK-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 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
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】[Detailed description of the invention]
【０００１】0001
【産業上の利用分野】本発明は耐熱性及び耐光性に優れ
た透明エポキシ樹脂硬化物を与えるエポキシ樹脂組成物
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition that provides a cured transparent epoxy resin having excellent heat resistance and light resistance.
【０００２】0002
【従来の技術】一般に、エポキシ樹脂は、耐熱性、耐薬
品性、機械的特性、電気特性、接着性に優れ、電気部品
用、接着剤、土木建築用、ＩＣ封止剤、ＬＥＤ封止剤な
どに広く用いられている。[Prior Art] Generally, epoxy resins have excellent heat resistance, chemical resistance, mechanical properties, electrical properties, and adhesive properties, and are used for electrical parts, adhesives, civil engineering and construction, IC encapsulants, and LED encapsulants. It is widely used.
【０００３】その中で透明性を要求される用途では、エ
ポキシ樹脂と有機酸無水物系硬化剤と第三級アミンまた
はその有機酸塩を硬化促進剤として用いる場合、比較的
着色の少ない硬化物が得られることが知られており、ま
た特公昭６１−３６８５１号公報では、一般式（１）で
表わされる有機リン化合物をエポキシ樹脂組成物に含有
させることにより、着色がなく透明性に優れたエポキシ
樹脂組成物が得られることが提案され、優れた結果を与
えている。In applications that require transparency, when an epoxy resin, an organic acid anhydride curing agent, and a tertiary amine or an organic acid salt thereof are used as a curing accelerator, a cured product with relatively little coloring can be obtained. It is known that epoxy resin compositions can be obtained, and in Japanese Patent Publication No. 61-36851, by incorporating an organic phosphorus compound represented by the general formula (1) into an epoxy resin composition, it is possible to obtain an epoxy resin composition which is free from coloration and has excellent transparency. It has been proposed to obtain epoxy resin compositions with excellent results.
【０００４】0004
【発明が解決しようとする課題】然しながら、上記提案
は、初期の着色防止には相当の成果があるが、熱的経時
変化や紫外線による着色の防止についてはまだ不充分で
あり、満足すべき域には達していない。[Problems to be Solved by the Invention] However, although the above proposal has achieved considerable results in preventing initial discoloration, it is still insufficient in preventing discoloration due to thermal changes over time and ultraviolet rays, and is not yet satisfactory. has not been reached.
【０００５】[0005]
【課題を解決するための手段】そこで本発明者は、これ
らの点を改良すべく鋭意検討を行った結果本発明に到達
した。[Means for Solving the Problems] Therefore, the present inventor conducted extensive studies to improve these points, and as a result, arrived at the present invention.
【０００６】本発明は、エポキシ樹脂（ａ）、有機多塩
基酸無水物（ｂ）、硬化促進剤（ｃ）および一般式（１
）で表わされる有機リン化合物（ｄ）を含有してなるエ
ポキシ樹脂組成物において、当該組成物中に一般式（２
）で表わされるフェノール系酸化防止剤及び／または一
般式（３）または（４）で表わされる有機ホスファイト
を上記（ａ）〜（ｄ）成分の総量に対して０．１〜２０
重量％含有してなるエポキシ樹脂組成物に関する。[0006] The present invention provides an epoxy resin (a), an organic polybasic acid anhydride (b), a curing accelerator (c) and a general formula (1).
) In the epoxy resin composition containing the organic phosphorus compound (d) represented by the general formula (2),
) and/or an organic phosphite represented by general formula (3) or (4) in an amount of 0.1 to 20% relative to the total amount of components (a) to (d) above.
% by weight of the epoxy resin composition.
【０００７】一般式（１）General formula (1)
【０００８】[0008]
【化６】
［ただし式（１）中、Ｒ１ 〜Ｒ８ は水素原子、ハロ
ゲン原子または炭素数１〜１０の一価脂肪族基もしくは
芳香族基であり、同一でも異っていてもよい。］一般式
（２）embedded image [In formula (1), R1 to R8 are a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 10 carbon atoms, or an aromatic group, and may be the same or different. ] General formula (2)
【０００９】[0009]
【化７】
［ただし式（２）中、ｎは１〜１０、Ｘは酸素原子、硫
黄原子、芳香族基を含んでいてもよい炭素数１〜２０の
一価〜多価脂肪族基、又は一般式（Ａ）で示すアルキル
イソシアヌル基を表わす。］
一般式（Ａ）[Formula (2), where n is 1 to 10, X is a monovalent to polyvalent aliphatic group having 1 to 20 carbon atoms, which may contain an oxygen atom, a sulfur atom, or an aromatic group, Or it represents an alkyl isocyanuric group represented by the general formula (A). ] General formula (A)
【００１０】0010
【化８】
［ただし式（Ａ）中のｍは１〜６を表わす。］一般式（
３）embedded image [However, m in formula (A) represents 1 to 6. ] General formula (
3)
【００１１】[0011]
【化９】
［ただし式（３）中のＲ１ は、炭素数６〜２０の一価
脂肪族基又は芳香族基を表わす。］
一般式（４）embedded image [However, R1 in formula (3) represents a monovalent aliphatic group or an aromatic group having 6 to 20 carbon atoms. ] General formula (4)
【００１２】0012
【化１０】
［ただし式（４）中のＲ２ ，Ｒ３ は炭素数６〜２０
の一価脂肪族基又は芳香族基を表わす。］である。[Formula (4), R2 and R3 have 6 to 20 carbon atoms]
represents a monovalent aliphatic group or an aromatic group. ].
【００１３】本発明において、エポキシ樹脂（ａ）とし
ては、公知のエポキシ樹脂のうち、無色または淡色で透
明な液状または固体状エポキシ樹脂が使用される。In the present invention, the epoxy resin (a) used is a colorless or light-colored transparent liquid or solid epoxy resin among known epoxy resins.
【００１４】代表的に使用されるエポキシ樹脂としては
、ビスフェノールＡ、ビスフェノールＦなど二価フェノ
ールとエピクロルヒドリンより得られるビスフェノール
タイプのエポキシ樹脂、環状脂肪族タイプのエポキシ樹
脂、ヘキサヒドロフタル酸、テトラヒドロフタル酸など
の多塩基酸のグリシジルエステルタイプのエポキシ樹脂
、ノボラック型エポキシ樹脂、長鎖ポリオールのポリグ
リシジルエーテルタイプのエポキシ樹脂などであり、市
販品の例としては、シェルケミカル社の商品名エピコー
ト８２８，８２７，８１５，８３４，１００１，１００
４、チバガイギー社の商品名アラルダイトＣＹ−１８３
，ＣＹ−１８２，ＣＹ−１７５、ダウケミカル社の商品
名ＤＥＮ−４３１，ＤＥＮ−４３８，ＤＥＲ−７３２、
チッソ社の商品名チッソノックス２２１，２８９、ダイ
セル化学工業社の商品名セロキサイド２０２１などがあ
る。Typically used epoxy resins include bisphenol type epoxy resins obtained from dihydric phenols such as bisphenol A and bisphenol F and epichlorohydrin, cycloaliphatic type epoxy resins, hexahydrophthalic acid, and tetrahydrophthalic acid. Examples of commercially available products include glycidyl ester type epoxy resins of polybasic acids such as, novolac type epoxy resins, and polyglycidyl ether type epoxy resins of long chain polyols. ,815,834,1001,100
4. Ciba Geigy's product name: Araldite CY-183
, CY-182, CY-175, DOW Chemical Company product name DEN-431, DEN-438, DER-732,
Examples include Chisso Nox 221, 289 (trade name) manufactured by Chisso Corporation, Celoxide 2021 (trade name) manufactured by Daicel Chemical Industries, Ltd.
【００１５】有機多塩基酸無水物（ｂ）としては、無水
フタル酸、無水テトラヒドロフタル酸、無水ヘキサヒド
ロフタル酸、無水メチルテトラヒドロフタル酸、無水メ
チルヘキサヒドロフタル酸、無水３，６エンドメチレン
テトラヒドロフタル酸、無水アジピン酸、無水マレイン
酸、無水アゼライン酸、無水トリメリット酸、無水ピロ
メリット酸などがある。Examples of the organic polybasic acid anhydride (b) include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and 3,6 endomethylenetetrahydro anhydride. Examples include phthalic acid, adipic anhydride, maleic anhydride, azelaic anhydride, trimellitic anhydride, and pyromellitic anhydride.
【００１６】エポキシ樹脂に配合する有機多塩基酸無水
物の量は、好ましくはカルボキシル基換算で０．５〜１
．５当量の範囲である。[0016] The amount of organic polybasic acid anhydride blended into the epoxy resin is preferably 0.5 to 1 in terms of carboxyl group.
．． It is in the range of 5 equivalents.
【００１７】硬化促進剤（ｃ）としては、例えば、第三
級アミンおよびその塩、第四級アンモニウム化合物、ア
ルカリ金属アルコラート、ジアザビシクロアルケンなど
があり、代表例としては、ベンジルジメチルアミン、２
，４，６−トリス（ジメチルアミノメチル）フェノール
、２−エチル−４−メチルイミダゾール、これらの三フ
ッ化ホウ素との塩、トリス（ジメチルアミノメチル）フ
ェノール−トリス（２−エチルヘキソエート）、トリア
ミルアンモニウムフェノレート、ナトリウムヘキサント
リオレート、１，８−ジアザビシクロ（５，４，０）ウ
ンデセン−７などをあげることが出来る。Examples of the curing accelerator (c) include tertiary amines and their salts, quaternary ammonium compounds, alkali metal alcoholates, diazabicycloalkenes, and representative examples include benzyldimethylamine, diazabicycloalkenes, etc.
, 4,6-tris(dimethylaminomethyl)phenol, 2-ethyl-4-methylimidazole, their salts with boron trifluoride, tris(dimethylaminomethyl)phenol-tris(2-ethylhexoate), Examples include triamylammonium phenolate, sodium hexanetriolate, and 1,8-diazabicyclo(5,4,0)undecene-7.
【００１８】これらの硬化促進剤の添加量はエポキシ樹
脂と有機多塩基酸無水物硬化剤の合計量に対して好まし
くは、０．１〜５重量％である。The amount of these curing accelerators added is preferably 0.1 to 5% by weight based on the total amount of the epoxy resin and the organic polybasic acid anhydride curing agent.
【００１９】一般式（１）で表わされる有機リン化合物
の例としては、９，１０−ジヒドロ−９−オキサ−１０
−フォスファフェナンスレン−１０−オキサイド、６，
８−ジクロル−９，１０−ジヒドロ−９−オキサ−１０
−フォスファフェナンスレン−１０−オキサイド、６，
８−ジ（ターシャリ−ブチル）−９，１０−ジヒドロ−
９−オキサ−１０−フォスファフェナンスレン−１０−
オキサイドなどがある。Examples of the organic phosphorus compound represented by the general formula (1) include 9,10-dihydro-9-oxa-10
-phosphaphenanthrene-10-oxide, 6,
8-dichloro-9,10-dihydro-9-oxa-10
-phosphaphenanthrene-10-oxide, 6,
8-di(tert-butyl)-9,10-dihydro-
9-Oxa-10-phosphaphenanthrene-10-
There are oxides, etc.
【００２０】これらの有機リン化合物の添加量はエポキ
シ樹脂、有機多塩基酸無水物、および硬化促進剤の合計
量に対して０．１〜２０重量％である。本発明の一般式
（２）で表わされるフェノール系酸化防止剤の例として
は、テトラキス−［メチレン−３−（３’，５’−ジ−
ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネー
ト］メタン、ｎ−オクタデシル−３−（３’，５’−ジ
−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネ
ート、トリス［β−（３，５−ジ−ｔ−ブチル−４−ヒ
ドロキシフェニル）プロピオニル−オキシエチル］イソ
シアヌレートなどがあげられる。The amount of these organic phosphorus compounds added is 0.1 to 20% by weight based on the total amount of the epoxy resin, organic polybasic acid anhydride, and hardening accelerator. Examples of the phenolic antioxidant represented by the general formula (2) of the present invention include tetrakis-[methylene-3-(3',5'-di-
t-butyl-4'-hydroxyphenyl)propionate] methane, n-octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, tris[β-(3,5- Examples include di-t-butyl-4-hydroxyphenyl)propionyl-oxyethyl]isocyanurate.
【００２１】これらフェノール系酸化防止剤の添加量は
、上記（ａ）〜（ｄ）の合計量に対して、０．１〜２０
重量％である。[0021] The amount of these phenolic antioxidants added is 0.1 to 20% of the total amount of (a) to (d) above.
Weight%.
【００２２】本発明の一般式（３）および（４）で表わ
される有機ホスファイトの例としては、トリフェニルホ
スファイト、トリス（ノニルフェニル）ホスファイト、
トリス（２，４−ジ−ｔ−ブチル−フェニル）ホスファ
イト、ジノニルフェニルペンタエリスリトールジホスフ
ァイト、ジオクタデシルペンタエリスリトールジホスフ
ァイト、ジ（２，４−ジ−ｔ−ブチル−フェニル）ペン
タエリスリトールジホスファイトなどがあげられる。Examples of the organic phosphites represented by the general formulas (3) and (4) of the present invention include triphenyl phosphite, tris(nonylphenyl) phosphite,
Tris(2,4-di-t-butyl-phenyl)phosphite, dinonylphenylpentaerythritol diphosphite, dioctadecylpentaerythritol diphosphite, di(2,4-di-t-butyl-phenyl)pentaerythritol Examples include diphosphite.
【００２３】これら有機ホスファイトの添加量は上記（
ａ）〜（ｄ）の合計量に対して０．１〜２０重量％であ
る。The amount of these organic phosphites added is as described above (
It is 0.1 to 20% by weight based on the total amount of a) to (d).
【００２４】フェノール系酸化防止剤および有機ホスフ
ァイトの添加量は、０．１重量％未満では効果が不充分
であり、２０重量％を越えるとエポキシ樹脂硬化物の物
性低下をもたらす恐れがある。If the amount of the phenolic antioxidant and organic phosphite added is less than 0.1% by weight, the effect will be insufficient, and if it exceeds 20% by weight, the physical properties of the cured epoxy resin product may deteriorate.
【００２５】本発明に係るエポキシ樹脂組成物は、通常
用いられる硬化条件で良好なエポキシ樹脂硬化物を得る
ことが出来る。好ましくは、８０〜１８０℃の温度で数
分〜２０時間の硬化条件が用いられる。[0025] The epoxy resin composition according to the present invention allows a good cured epoxy resin product to be obtained under commonly used curing conditions. Preferably, curing conditions of several minutes to 20 hours at temperatures of 80 to 180°C are used.
【００２６】このようにして得られたエポキシ樹脂硬化
物は、無色〜淡色で透明であり、加熱経時変化および紫
外線照射経時変化の両方に優れた安定性を有しており、
耐熱、耐光両性能を要求される用途に利用することが出
来る。これは本発明に係る、一般式（１）で表わされる
有機リン化合物と、一般式（２）で表わされるフェノー
ル系酸化防止剤および／または、一般式（３）または（
４）で表わされる有機ホスファイトを組合せて添加する
ことにより達成されるものである。The cured epoxy resin thus obtained is colorless to light-colored and transparent, and has excellent stability against changes over time under heating and under ultraviolet irradiation.
It can be used in applications that require both heat resistance and light resistance. This includes the organic phosphorus compound represented by the general formula (1) and the phenolic antioxidant represented by the general formula (2) and/or the general formula (3) or (
This is achieved by adding a combination of organic phosphites represented by 4).
【００２７】また本発明のエポキシ樹脂組成物には、公
知の酸化防止剤、光安定剤、紫外線吸収剤、希釈剤、充
填剤、増量剤、染料、可塑剤、チキソ剤、消泡剤などを
必要に応じて添加することが出来る。The epoxy resin composition of the present invention may also contain known antioxidants, light stabilizers, ultraviolet absorbers, diluents, fillers, extenders, dyes, plasticizers, thixotropic agents, antifoaming agents, etc. It can be added as necessary.
【００２８】[0028]
【実施例】次に実施例に基づいて本発明をさらに具体的
に説明する。EXAMPLES Next, the present invention will be explained in more detail based on examples.
【００２９】試験方法；エポキシ樹脂（エピコート８２
８）１００ｇと９，１０−ジヒドロ−９−オキサ−１０
−ホスファフェナンスレン−１０−オキサイド（ＨＣＡ
）１．８６ｇを混合し１００℃で溶解させたのち５０℃
以下に冷却し、無水メチルヘキサヒドロフタル酸８６ｇ
を添加して均一な樹脂液とする。Test method: Epoxy resin (Epicote 82
8) 100g and 9,10-dihydro-9-oxa-10
-phosphaphenanthrene-10-oxide (HCA
) 1.86g was mixed and dissolved at 100℃, then 50℃
Cooled to 86 g of methylhexahydrophthalic anhydride.
to make a uniform resin liquid.
【００３０】この樹脂液に、フェノール系酸化防止剤、
および／または有機ホスファイトを種類、数量を変えて
添加し、均一な樹脂液にする。次いで硬化促進剤として
１，８−ジアザ−ビシクロ（５，４，０）ウンデセン７
・２−エチルヘキサン酸塩（ＤＢＵ）を１ｇ添加し、均
一な樹脂液としてから、厚さ４ｍ／ｍ、巾１５ｍ／ｍ、
長さ１５０ｍ／ｍの硬化物が得られる金型に注入し、８
０℃で２時間予備硬化させ、さらに１５０℃で３時間本
硬化させた。[0030] A phenolic antioxidant,
and/or organic phosphites are added in different types and amounts to make the resin liquid uniform. Then, 1,8-diaza-bicyclo(5,4,0)undecene7 was used as a curing accelerator.
・After adding 1 g of 2-ethylhexanoate (DBU) to make a uniform resin liquid, the thickness was 4 m/m, the width was 15 m/m,
Pour into a mold that will yield a cured product with a length of 150 m/m, and
Preliminary curing was carried out at 0°C for 2 hours, and further main curing was carried out at 150°C for 3 hours.
【００３１】なお比較例としては、ＨＣＡのみ、フェノ
ール系酸化防止剤のみ、有機ホスファイトのみのものを
調製した。As comparative examples, samples containing only HCA, only phenolic antioxidant, and only organic phosphite were prepared.
【００３２】次いで、金型から硬化物を取り出しテスト
ピースとした。Next, the cured product was taken out from the mold and used as a test piece.
【００３３】このテストピースを色差計（スガ試験機社
製、カラーコンピューター、ＳＭ−３）により色度を測
定し、Ｌ値を透明性の指標、ｂ値を着色の指標とした。
試験結果を表１に示す。The chromaticity of this test piece was measured using a color difference meter (Color Computer, SM-3, manufactured by Suga Test Instruments Co., Ltd.), and the L value was used as an index of transparency, and the b value was used as an index of coloration. The test results are shown in Table 1.
【００３４】続いて、これらのテストピースを２組に分
け、１組はサンシャインウエザオメーター（スガ試験機
社製、ＷＥＬ−ＳＵＮ−ＤＣ）に入れ紫外線照射による
経時変化を調べた。その試験結果を表２に示す。Subsequently, these test pieces were divided into two sets, and one set was placed in a Sunshine Weatherometer (WEL-SUN-DC, manufactured by Suga Test Instruments Co., Ltd.) to examine changes over time due to ultraviolet irradiation. The test results are shown in Table 2.
【００３５】他の１組は１５０℃に保持したギヤーオー
ブン（東洋精機社製、ギヤーオーブンＳＢ−Ｐ）に入れ
加熱経時変化を調べた。その試験結果を表３に示す。The other set was placed in a gear oven (Toyo Seiki Co., Ltd., Gear Oven SB-P) maintained at 150°C, and changes over time during heating were examined. The test results are shown in Table 3.
【００３６】[0036]
【表１】[Table 1]
【００３７】[0037]
【表２】[Table 2]
【００３８】[0038]
【表３】
表１〜３における注［（ａ）〜（ｇ）］（ａ）エピコー
ト８２８；油化シエルエポキシ社製、ビスフェノールＡ
グリシジ （エポキシ樹脂） ルエーテル
、エポキシ価１９０（ｂ）ＭＨ−７００ ；新日
本理化社製、無水メチルヘキサヒドロフタル酸
（有機多塩基酸無水物）
（ｃ）ＤＢＵ ；サンアボット社製
、ＤＢＵ、ＳＡ−１０２ （硬化促進剤）
１，８−ジアザビシクロ（５，４，０）ウンデセ
ン−
７・２−エチルヘキサン酸塩（ｄ）ＨＣＡ
；三光化学社製、９，１０−ジヒドロ−９−
オキサ−１ （有機リン化合物）０−フォスファ
フェナンスレン−１０−オキサイド（ｃ）１０１０
；チバガイギー社製、テトラキス［メチレ
ン−３−（３ （フェノール系 ’，
５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニ
酸化防止剤） ル）プロピオネート］
メタン（ｆ）セカノック ；大阪精化工業社
製、セカノック２０１、トリス［β− （フェノ
ール系酸 （３，５−ジ−ｔ−ブチル−４−ヒド
ロキシフェニル 化防止剤）
）プロピオニル−オキシエチル］イソシアヌレート（
ｇ）ＰＥＰ−４Ｃ ；旭電化社製、ＰＥＰ−４Ｃ
、ジノニルフェニルペンタ （有機ホスファ
エリスリトールジホスファイト イ
ト）
表１は硬化直後の結果である
。[Table 3] Notes in Tables 1 to 3 [(a) to (g)] (a) Epicote 828; manufactured by Yuka Ciel Epoxy Co., Ltd., bisphenol A
Glyshidi (epoxy resin) ether, epoxy value 190 (b) MH-700; manufactured by Shinnihon Chemical Co., Ltd., methylhexahydrophthalic anhydride
(Organic polybasic acid anhydride) (c) DBU; manufactured by Sun Abbott, DBU, SA-102 (curing accelerator)
1,8-diazabicyclo(5,4,0)undecene-
7,2-ethylhexanoate (d) HCA
; Manufactured by Sanko Kagaku Co., Ltd., 9,10-dihydro-9-
Oxa-1 (Organic phosphorus compound) 0-phosphaphenanthrene-10-oxide (c) 1010
; Manufactured by Ciba Geigy, Tetrakis[methylene-3-(3 (phenolic)',
5'-di-t-butyl-4'-hydroxyphenylene
Antioxidant) Propionate]
Methane (f) Sekanok; manufactured by Osaka Seika Kogyo Co., Ltd., Sekanok 201, Tris [β- (phenolic acid (3,5-di-t-butyl-4-hydroxyphenylation inhibitor))
) propionyl-oxyethyl] isocyanurate (
g) PEP-4C; manufactured by Asahi Denka Co., Ltd., PEP-4C
, dinonylphenylpenta (organic phosphatide)
erythritol diphosphite)
Table 1 shows the results immediately after curing.
【００３９】表２は紫外線照射による経時変化の結果で
ある。比較例は大きく劣化するが、実施例では劣化が少
なく抑えられている。Table 2 shows the results of changes over time due to ultraviolet irradiation. Although the comparative example shows significant deterioration, the deterioration is suppressed to a small extent in the example.
【００４０】表３は加熱経時変化の結果である。比較例
は大きく変化するが、実施例では劣化が少なく抑えられ
ている。Table 3 shows the results of changes over time during heating. Although the comparative example shows a large change, the deterioration is suppressed to a small extent in the example.
【００４１】[0041]
【発明の効果】本発明のエポキシ樹脂組成物によれば、
硬化初期の透明性が良好で着色が少なく、紫外線照射お
よび加熱による経時変化の少ないエポキシ樹脂硬化物を
得ることが出来る。したがって本発明はたとえば光学的
用途に重要なエポキシ樹脂組成物を提供することが出来
る。[Effect of the invention] According to the epoxy resin composition of the present invention,
It is possible to obtain a cured epoxy resin product that has good transparency in the initial stage of curing, has little coloring, and has little change over time due to ultraviolet irradiation and heating. Therefore, the present invention can provide epoxy resin compositions that are important for optical applications, for example.
Claims (5)
水物（ｂ）、硬化促進剤（ｃ）および、一般式（１）で
表わされる有機リン化合物（ｄ）、を含有するエポキシ
樹脂組成物において、当該組成物中に一般式（２）で表
わされるフェノール系酸化防止剤及び／または一般式（
３）又は（４）で表わされる有機ホスファイトを上記（
ａ）〜（ｄ）成分の総量に対して０．１〜２０重量％含
有してなるエポキシ樹脂組成物、 一般式（１） 【化１】 ［ただし式（１）中、Ｒ１ 〜Ｒ８ は水素原子、ハロ
ゲン原子または炭素数１〜１０の一価脂肪族基もしくは
芳香族基であり、同一でも異っていてもよい。］一般式
（２） 【化２】 ［ただし式（２）中、ｎは１〜１０、Ｘは酸素原子、硫
黄原子、芳香族基を含んでいてもよい炭素数１〜２０の
一価〜多価脂肪族基、又は一般式（Ａ）で示すアルキル
イソシアヌル基を表わす。］ 一般式（Ａ） 【化３】 ［ただし式（Ａ）中のｍは１〜６を表わす。］一般式（
３） 【化４】 ［ただし式（３）中のＲ１ は、炭素数６〜２０の一価
脂肪族基又は芳香族基を表わす。］ 一般式（４） 【化５】 ［ただし式（４）中のＲ２ ，Ｒ３ は炭素数６〜２０
の一価脂肪族基又は芳香族基を表わす。］。Claim 1: An epoxy resin composition containing an epoxy resin (a), an organic polybasic acid anhydride (b), a curing accelerator (c), and an organic phosphorus compound (d) represented by the general formula (1). In the composition, the phenolic antioxidant represented by the general formula (2) and/or the general formula (
The organic phosphite represented by 3) or (4) above (
An epoxy resin composition containing 0.1 to 20% by weight based on the total amount of components a) to (d), general formula (1) [Formula (1), R1 to R8 are hydrogen] atoms, halogen atoms, or monovalent aliphatic groups or aromatic groups having 1 to 10 carbon atoms, which may be the same or different. ] General formula (2) [Chemical formula 2] [In formula (2), n is 1 to 10, and It represents a polyvalent aliphatic group or an alkyl isocyanuric group represented by the general formula (A). ] General formula (A) [Chemical formula 3] [However, m in formula (A) represents 1 to 6. ] General formula (
3) embedded image [However, R1 in formula (3) represents a monovalent aliphatic group or aromatic group having 6 to 20 carbon atoms. ] General formula (4) [Chemical formula 5] [However, R2 and R3 in formula (4) have a carbon number of 6 to 20
represents a monovalent aliphatic group or an aromatic group. ].
系酸化防止剤がテトラキス−［メチレン−３−（３’，
５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プ
ロピオネート］メタンである請求項１のエポキシ樹脂組
成物。Claim 2: The phenolic antioxidant represented by the general formula (2) is tetrakis-[methylene-3-(3',
The epoxy resin composition according to claim 1, which is 5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane.
系酸化防止剤がｎ−オクタデシル−３−（３’，５’−
ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオ
ネートである請求項１のエポキシ樹脂組成物。Claim 3: The phenolic antioxidant represented by the general formula (2) is n-octadecyl-3-(3',5'-
The epoxy resin composition of claim 1, which is di-t-butyl-4'-hydroxyphenyl) propionate.
系酸化防止剤がトリス［β−（３，５−ジ−ｔ−ブチル
−４−ヒドロキシフェニル）プロピオニル−オキシエチ
ル］イソシアヌレートである請求項１のエポキシ樹脂組
成物。Claim 4: Claim 1 wherein the phenolic antioxidant represented by the general formula (2) is tris[β-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-oxyethyl]isocyanurate. epoxy resin composition.
される有機ホスファイトがジノニルフェニルペンタエリ
スリトールジホスファイトである請求項１のエポキシ樹
脂組成物。5. The epoxy resin composition according to claim 1, wherein the organic phosphite represented by the general formula (3) or the general formula (4) is dinonylphenylpentaerythritol diphosphite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17191191A JPH04370113A (en) | 1991-06-18 | 1991-06-18 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17191191A JPH04370113A (en) | 1991-06-18 | 1991-06-18 | Epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04370113A true JPH04370113A (en) | 1992-12-22 |
Family
ID=15932119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17191191A Pending JPH04370113A (en) | 1991-06-18 | 1991-06-18 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04370113A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5804621A (en) * | 1995-11-27 | 1998-09-08 | Sumitomo Chemical Company, Limited | Polymeric composition |
| JP2000080251A (en) * | 1998-09-03 | 2000-03-21 | Matsushita Electric Works Ltd | Phosphorus-modified flame-retardant epoxy resin composition and its production and molded product and laminate using the phosphorus-modified flame-retardant epoxy resin composition |
| EP1000624A1 (en) * | 1998-10-13 | 2000-05-17 | Schill & Seilacher GmbH & Co. | Use of DOP as antioxidant, anti-ageing additive and medicament |
| US6403690B1 (en) * | 1999-06-09 | 2002-06-11 | Matsushita Electric Works, Ltd. | Flame retardant resin composition |
| JP2003012896A (en) * | 2001-06-29 | 2003-01-15 | Stanley Electric Co Ltd | Uv-resistant epoxy resin, and light emitting diode or wavelength conversion element sealed by using the epoxy resin |
| WO2008099635A1 (en) * | 2007-02-09 | 2008-08-21 | Konica Minolta Opto, Inc. | Optical element, electronic module, and method for production of electronic module |
| CN104559060A (en) * | 2014-12-31 | 2015-04-29 | 东莞市赛恩思实业有限公司 | Halogen-free flame-retardant epoxy resin composition for LED encapsulation and preparation method for halogen-free flame-retardant epoxy resin composition |
| JP2017031270A (en) * | 2015-07-30 | 2017-02-09 | 新日本理化株式会社 | Epoxy resin composition and epoxy cured product |
| JP2018076538A (en) * | 2018-01-29 | 2018-05-17 | 京セラ株式会社 | Epoxy resin compositions for optical semiconductor, and resin-sealed electronic component device |
| JP2018095765A (en) * | 2016-12-15 | 2018-06-21 | 新日本理化株式会社 | Epoxy resin composition and cured epoxy thin film |
-
1991
- 1991-06-18 JP JP17191191A patent/JPH04370113A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5804621A (en) * | 1995-11-27 | 1998-09-08 | Sumitomo Chemical Company, Limited | Polymeric composition |
| JP2000080251A (en) * | 1998-09-03 | 2000-03-21 | Matsushita Electric Works Ltd | Phosphorus-modified flame-retardant epoxy resin composition and its production and molded product and laminate using the phosphorus-modified flame-retardant epoxy resin composition |
| EP1000624A1 (en) * | 1998-10-13 | 2000-05-17 | Schill & Seilacher GmbH & Co. | Use of DOP as antioxidant, anti-ageing additive and medicament |
| US6403690B1 (en) * | 1999-06-09 | 2002-06-11 | Matsushita Electric Works, Ltd. | Flame retardant resin composition |
| JP2003012896A (en) * | 2001-06-29 | 2003-01-15 | Stanley Electric Co Ltd | Uv-resistant epoxy resin, and light emitting diode or wavelength conversion element sealed by using the epoxy resin |
| WO2008099635A1 (en) * | 2007-02-09 | 2008-08-21 | Konica Minolta Opto, Inc. | Optical element, electronic module, and method for production of electronic module |
| CN104559060A (en) * | 2014-12-31 | 2015-04-29 | 东莞市赛恩思实业有限公司 | Halogen-free flame-retardant epoxy resin composition for LED encapsulation and preparation method for halogen-free flame-retardant epoxy resin composition |
| JP2017031270A (en) * | 2015-07-30 | 2017-02-09 | 新日本理化株式会社 | Epoxy resin composition and epoxy cured product |
| JP2018095765A (en) * | 2016-12-15 | 2018-06-21 | 新日本理化株式会社 | Epoxy resin composition and cured epoxy thin film |
| JP2018076538A (en) * | 2018-01-29 | 2018-05-17 | 京セラ株式会社 | Epoxy resin compositions for optical semiconductor, and resin-sealed electronic component device |
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