JPH04353517A - Epoxy resin, epoxy resin composition and cured product thereof - Google Patents
Epoxy resin, epoxy resin composition and cured product thereofInfo
- Publication number
- JPH04353517A JPH04353517A JP15604591A JP15604591A JPH04353517A JP H04353517 A JPH04353517 A JP H04353517A JP 15604591 A JP15604591 A JP 15604591A JP 15604591 A JP15604591 A JP 15604591A JP H04353517 A JPH04353517 A JP H04353517A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- formula
- hydroxyl group
- general formula
- epoxy
- 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.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 98
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 98
- 239000000203 mixture Substances 0.000 title claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 abstract description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 22
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000004593 Epoxy Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 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 12
- 239000000460 chlorine Substances 0.000 description 11
- 229910052801 chlorine Inorganic materials 0.000 description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 8
- 239000000155 melt Substances 0.000 description 7
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- -1 laminates Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- LJBWJFWNFUKAGS-UHFFFAOYSA-N 2-[bis(2-hydroxyphenyl)methyl]phenol Chemical compound OC1=CC=CC=C1C(C=1C(=CC=CC=1)O)C1=CC=CC=C1O LJBWJFWNFUKAGS-UHFFFAOYSA-N 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 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 4
- 230000000694 effects Effects 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- 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
- 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 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-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
- 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
- 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
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 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
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 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
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 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
- 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
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 description 1
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 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
- KNRCVAANTQNTPT-UHFFFAOYSA-N methyl-5-norbornene-2,3-dicarboxylic anhydride Chemical compound O=C1OC(=O)C2C1C1(C)C=CC2C1 KNRCVAANTQNTPT-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 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)
Abstract
Description
【発明の詳細な説明】
【０００１】
【産業上の利用分野】本発明は耐熱性に優れるエポキシ
樹脂及びエポキシ樹脂組成物およびその硬化物に関する
ものであり、本発明の組成物は成形材料，注型材料，積
層材料，複合材料，塗料，接着剤，レジストなどの広範
囲の用途に極めて有用である。
【０００２】
【従来の技術】エポキシ樹脂は種々の硬化剤で硬化させ
ることにより、一般的に機械的性質，耐水性，耐薬品性
，耐熱性，電気的性質などの優れた硬化物となり、接着
剤，塗料，積層板，成形材料，注型材料などの幅広い分
野に利用されている。
【０００３】従来、工業的に最も使用されているエポキ
シ樹脂としてビスフェノ−ルＡにエピクロルヒドリンを
反応させて得られる液状および固形のビスフェノ−ルＡ
型エポキシ樹脂がある。一方、耐熱性の要求されるＩＣ
の封止材にはノボラック型エポキシ樹脂が主に使用され
ている。
【０００４】また、トリス（ヒドロキシフェニル）メタ
ンのポリグリシジルエ−テル等の３官能タイプのエポキ
シ樹脂が高耐熱エポキシ樹脂として知られており、ＵＳ
Ｐ４６７２１０３ではＩＣの封止材に適した固形のトリ
ス（ヒドロキシフェニル）メタン型ポリグリシジルエ−
テルが報告されている。
【０００５】
【発明が解決しようとする課題】しかしながら、この固
形のトリス（ヒドロキシフェニル）メタン型ポリグリシ
ジルエ−テルはエポキシ基を介して高分子化させている
為、耐熱性が充分ではない。一方、最近の電子産業など
の目ざましい発達に伴い、これらに使用される電気絶縁
材料などに要求される耐熱性は益々厳しくなっており、
耐熱性に優れたエポキシ樹脂の出現が待ち望まれている
。
【０００６】
【課題を解決するための手段】本発明者らはこうした実
状に鑑み、耐熱性に優れるエポキシ樹脂を求めて鋭意研
究した結果、一般式（２）
【０００７】
【化２】
【０００８】（式中Ｒ１ 、Ｒ２ 及びＺ１ 、Ｚ２
及びｎは後記する式（１）に於けるのと同じ意味を表す
）で表わされるエポキシ樹脂のアルコ−ル性水酸基をエ
ポキシ化したエポキシ樹脂が前述された如き特性を兼ね
備えたものであることを見い出して本発明を完成させる
に到った。すなわち本発明は
（１）一般式（１）
【０００９】
【化３】
【００１０】（式中Ｒ１ 及びＲ２ は同一若しくは異
なり、２個以上のフェノール性水酸基をもつ化合物の水
酸基が除かれた残基を示す。Ｚ１ 及びＺ２ は同一若
しくは異なり０又は１以上の整数を示し、Ｚ１ とＺ２
の合計は１以上である。またＭはグリシジル基または
水素原子であり、ｎは１以上の整数を示す。但し、ｎが
１の場合Ｍは必ずグリシジル基であり、ｎが２以上の場
合Ｍは少なくとも１個はグリシジル基である。）で表さ
れるエポキシ樹脂
（２）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（１）のエポキシ樹脂を
含有することを特徴とするエポキシ樹脂組成物（３）（
２）項記載のエポキシ樹脂組成物の硬化物を提供するも
のである。
【００１１】本発明のエポキシ樹脂は例えば一般式（２
）で表されるエポキシ樹脂のアルコ−ル性水酸基とエピ
クロルヒドリンとの反応を例えば４級アンモニウム塩あ
るいはジメチルスルホキシドの存在下行うことにより得
ることができる。一般式（２）で表されるエポキシ樹脂
のアルコ−ル性水酸基とエピクロルヒドリンとの反応を
、一般のアルコ−ル類とエピクロルヒドリンとの反応で
行われているようにルイス酸触媒の存在下行うと一般式
（２）で表されるエポキシ樹脂のエポキシ基とアルコ−
ル性水酸基との反応も同時におこる為本発明の一般式（
２）で示される化合物のアルコ−ル性水酸基のみがエポ
キシ化されたエポキシ樹脂を得ることは困難である。尚
、過剰のエピクロルヒドリンを使用して強アルカリの存
在下で一般式（２）の化合物に反応させてもアルコ−ル
性水酸基には反応しない。本発明者らは鋭意検討の結果
一般式（２）で表されるエポキシ樹脂のアルコ−ル性水
酸基は一般のアルコ−ル類より反応性に富んでおり、ア
ルカリ金属水酸化物と例えば４級アンモニウム塩あるい
はジメチルスルホキシドを併用すると驚くべきことにア
ルコ−ル性水酸基とエピクロルヒドリンとの反応を選択
的に行えることを見い出し本発明を完成させるに到った
。またアルカリ金属水酸化物の量を調節することにより
一般式（２）で表されるエポキシ樹脂のアルコ−ル性水
酸基を所望の割合にエポキシ化することができる。
【００１２】以下、本発明の詳細を説明する。本発明の
一般式（１）で表されるエポキシ樹脂としては、例えば
一般式（１）におけるＲ１ 及びＲ２ が３個以上のフ
ェノール性水酸基をもつ化合物の水酸基が除かれた残基
を示すものとしては、式
【００１３】
【化４】
【００１４】
【化５】
【００１５】
【化６】
【００１６】
【化７】
【００１７】
【化８】
【００１８】
【化９】
【００１９】
【化１０】
【００２０】
【化１１】
【００２１】
【化１２】
【００２２】
【化１３】
【００２３】
【化１４】
【００２４】（式中ｐは０又は１以上の整数を示す）【
００２５】
【化１５】
【００２６】（式中ｐは０又は１以上の整数を示す）Ｒ
１ 及びＲ２ が２個のフェノール性水性基をもつ化合
物の水酸基が除かれた残基を示すものとしては、式【０
０２７】
【化１６】
【００２８】
【化１７】
【００２９】
【化１８】
【００３０】
【化１９】
【００３１】
【化２０】
【００３２】
【化２１】
【００３３】
【化２２】
【００３４】
【化２３】
【００３５】
【化２４】
【００３６】
【化２５】
【００３７】
【化２６】
【００３８】
【化２７】
【００３９】
【化２８】
【００４０】
【化２９】
【００４１】
【化３０】
【００４２】
【化３１】
【００４３】
【化３２】
【００４４】
【化３３】
【００４５】
【化３４】
【００４６】
【化３５】
【００４７】
【化３６】
【００４８】
【化３７】
【００４９】
【化３８】
【００５０】
【化３９】
【００５１】
【化４０】
【００５２】
【化４１】
【００５３】
【化４２】
【００５４】
【化４３】
【００５５】
【化４４】
【００５６】
【化４５】
【００５７】
【化４６】
【００５８】
【化４７】
【００５９】
【化４８】
【００６０】
【化４９】
【００６１】
【化５０】
【００６２】
【化５１】
【００６３】
【化５２】
【００６４】
【化５３】
【００６５】
【化５４】
【００６６】
【化５５】
【００６７】であるものなどが挙げられるがこれらに限
定されるものではない。また一般式（１）におけるＲ１
及びＲ２ は別々のものを含んでも良い。
【００６８】一般式（２）で表されるエポキシ樹脂のア
ルコ−ル性水酸基とエピクロルヒドリンとの反応はアル
カリ金属水酸化物の存在下、例えばジメチルスルホキシ
ドあるいは４級アンモニウム塩を使用することにより行
うことができる。その際溶剤としてアルコ−ル類、芳香
族炭化水素類、ケトン類、環状及びエ−テル化合物等を
併用しても構わない。ジメチルスルホキシドあるいは４
級アンモニウム塩を使用しないと反応が充分に進行せず
、アルカリ金属水酸物が多量に残存する為高分子化を起
こし本発明のエポキシ樹脂を製造することは困難である
。
【００６９】ジメチルスルホキシドの使用量は一般式（
２）で表されるエポキシ樹脂に対して５重量％〜３００
重量％が好ましい。一般式（２）で表されるエポキシ樹
脂に対して５重量％以下であると一般式（２）で表され
るエポキシ樹脂のアルコ−ル性水酸基とエピクロルヒド
リンとの反応が遅くなる為長時間の反応が必要となり好
ましくない。一般式（２）で表されるエポキシ樹脂に対
して３００重量％を超えると増量した効果はほとんどな
くなる一方容積効率も悪くなり好ましくない。
【００７０】４級アンモニウム塩としてはテトラメチル
アンモニウムクロライド、テトラメチルアンモニウムブ
ロマイド、トリメチルベンジルアンモニウムクロライド
等が挙げられ、その使用量は一般式（２）で表されるエ
ポキシ樹脂のアルコ−ル性水酸基１当量に対して０．３
〜５０ｇが好ましい。水酸基１当量に対して０．３ｇ未
満であると一般式（２）で表されるエポキシ樹脂のアル
コ−ル性水酸基とエピクロルヒドリンとの反応が遅くな
り長時間の反応が必要となり好ましくない。水酸基１当
量に対して５０ｇを超えると増量した効果はほとんどな
くなる一方コストが高くなり好ましくない。
【００７１】エピクロルヒドリンの使用量は一般式（２
）で表されるエポキシ樹脂のエポキシ化させたいアルコ
−ル性水酸基１当量に対して当量以上使用すれば良い。
しかしながら水酸基１当量に対して３０倍当量を超える
と増量した効果はほとんどなくなる一方容積効率も悪く
なり好ましくない。
【００７２】アルカリ金属水酸化物としては、苛性ソ−
ダ，苛性カリ，水酸化リチウム，水酸化カルシウムなど
が使用できるが苛性ソ−ダが好ましい。アルカリ金属水
酸化物の使用量は一般式（２）で表されるエポキシ樹脂
のエポキシ化したいアルコ−ル性水酸基１当量に対して
ほぼ当量使用すれば良い。一般式（２）で表されるエポ
キシ樹脂のアルコ−ル性水酸基を全量エポキシ化する場
合は過剰に使用しても構わないが、アルコ−ル性水酸基
１当量に対して２倍当量を超えると若干高分子化が起こ
る傾向にある。アルカリ金属水酸化物は固形でも水溶液
でも構わない。また水溶液を使用する場合は反応中、反
応系内の水は常圧下、減圧下において反応系外に留去し
ながら反応を行うこともできる。
【００７３】反応温度は３０〜１００℃が好ましい。反
応温度が３０℃未満であると反応が遅くなり長時間の反
応が必要となる。反応温度が１００℃を超えると副反応
が多く起こり好ましくない。
【００７４】反応終了後、過剰のエピクロルヒドリン及
びジメチルスルホキシドを減圧下留去した後、有機溶剤
に樹脂を溶解させアルカリ金属水酸化物で脱ハロゲン化
水素反応を行うことができる。一方、反応終了後、水洗
分離を行い副生塩およびジメチルスルホキシドあるいは
４級アンモニウム塩を分離し、油層より過剰のエピクロ
ルヒドリンを減圧下留去した後、有機溶剤に樹脂を溶解
させアルカリ金属水酸化物で脱ハロゲン化水素反応を行
っても良い。有機溶剤としては、メチルイソブチルケト
ン，ベンゼン，トルエン，キシレン等が使用できるが、
メチルイソブチルケトンが好ましい。それらは単独もし
くは混合系でも使用できる。
【００７５】本発明のエポキシ樹脂は単独でまたは他の
エポキシ樹脂との併用で通常のエポキシ樹脂の場合と同
様硬化剤、さらに必要により硬化促進剤等を添加するこ
とにより硬化させることができる。
【００７６】本発明で用いられる硬化剤はアミン系化合
物，酸無水物系化合物，アミド系化合物，フェノ−ル系
化合物などである。具体例としては、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，ジアミノジフェニルスルホン，イソホロンジアミ
ン，ジシアンジアミド，リノレン酸の２量体とエチレン
ジアミンとより合成されるポリアミド樹脂，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，テトラヒドロ無水フタル酸，メチルテトラヒ
ドロ無水フタル酸，無水メチルナジック酸，ヘキサヒド
ロ無水フタル酸，メチルヘキサヒドロ無水フタル酸，フ
ェノ−ルノボラック，及びこれらの変性物などが挙げら
れる。これらの硬化剤はそれぞれ単独で用いてもよいし
、２種以上組み合わせて用いてもよい。
【００７７】これらの硬化剤の使用量は、エポキシ基に
対して０．７〜１．２当量が好ましい。エポキシ基に対
して０．７当量に満たない場合、あるいは１．２当量を
越える場合、いずれも硬化が不完全となり良好な硬化物
性は得られない恐れがある。
【００７８】また本発明のエポキシ樹脂組成物は硬化促
進剤を用いて硬化させても差し支えない。硬化促進剤と
しては例えばイミダゾ−ル類，第３級アミン類，フェノ
−ル類，３フッ化ホウ素−モノエチルアミンコンプレッ
クスなどのルイス酸塩等が挙げられる。また、必要に応
じて無機または有機の充填剤等の種々の配合剤を添加す
ることができる。
【００７９】これらの硬化促進剤の使用量はエポキシ樹
脂１００重量部に対して０．１〜５．０重量部が好まし
い。
【００８０】本発明のエポキシ樹脂組成物は従来知られ
ている方法と同様の方法で容易にエポキシ樹脂硬化物を
得ることができる。例えば本発明のエポキシ樹脂と硬化
剤，充填剤及びその他の添加剤とを必要に応じて押出機
，ニ−ダ，ロ−ル等を用いて均一になるまで充分に混合
し、混合物を溶融後注型あるいはトランスファ−成形機
などを用いて成形し、さらに８０〜２００℃に加熱する
ことにより硬化物を得ることができる。また本発明の樹
脂組成物を溶剤に溶解させ、ガラス繊維，カ−ボン繊維
，ポリエステル繊維，ポリアミド繊維，アルミナ繊維，
紙などの基材に含浸させ加熱乾燥して得たプリプレグを
熱プレス成形して硬化物を得ることなどもできる。
【００８１】
【実施例】次に本発明を実施例、応用実施例および応用
比較例により具体的に説明するが、以下において部は特
に断わりのない限りすべて重量部であるものとする。ま
た加水分解性塩素含有量とはエポキシ樹脂をジオキサン
に溶解し、１Ｎ−水酸化カリウムのエタノ−ル溶液を加
え、還流状態で３０分間加熱した時に脱離する塩素イオ
ンを硝酸銀溶液で滴定して定量し、該化合物中の塩素原
子の重量を重量百分率で表したものである。
【００８２】実施例１
一般式（２）におけるＲ１ 及びＲ２ が【００８３】
【化５６】
【００８４】であるトリス（ヒドロキシフェニル）メタ
ンのポリグリシジルエ−テルにおいて、一般式（２）に
おける平均のｎが０．７８，エポキシ当量２０５，加水
分解性塩素含有量０．０７１％，軟化点７１．０℃，溶
融粘度（１５０℃）３．６ポイズのエポキシ樹脂（エポ
キシ樹脂（ｅ））１９９部をエピクロルヒドリン３７０
部に溶解させた後、撹拌下７０℃でテトラメチルアンモ
ニウムクロライド６部を加え、次いで４８％ＮａＯＨ３
０部を１００分かけて滴下した。滴下後さらに７０℃で
３時間反応を行った。反応終了後水２００部を加えて水
洗した。油水分離後、油層よりエピクロルヒドリンの大
半を減圧下に留去し、その後メチルイソブチルケトン４
５０部に溶解させ、さらに３０％ＮａＯＨ５部を加え７
０℃で１時間反応させた。反応終了後、水２００部で２
回水洗を行った。油水分離後、油層よりメチルイソブチ
ルケトンを蒸留回収して、エポキシ当量１８９，加水分
解性塩素含有量０．０７１％，軟化点７１．０℃，溶融
粘度（１５０℃）３．６ポイズのエポキシ樹脂（ａ）１
９５部を得た。得られたエポキシ樹脂（ａ）はエポキシ
当量から計算すると一般式（２）におけるアルコ−ル性
水酸基０．７８個の内約０．４６個がエポキシ化されて
いる。
【００８５】実施例２
一般式（２）におけるＲ１ 及びＲ２ が実施例１と同
じものであるトリス（ヒドロキシフェニル）メタンのポ
リグリシジルエ−テルにおいて、
【００８６】一般式（２）における平均のｎが０．７８
、エポキシ当量２０５、加水分解性素含有量０．０７１
％，軟化点７１．０℃，溶融粘度（１５０℃）３．６ポ
イズのエポキシ樹脂（エポキシ樹脂（ｅ））１９９部を
エピクロルヒドリン３７０部とジメチルスルホキシド１
８５部に溶解させた後、撹拌下７０℃で９８．５％Ｎａ
ＯＨ１０．６部を１００分かけて添加した。添加後さら
に７０℃で３時間反応を行った。次いで過剰の未反応エ
ピクロルヒドリンおよびジメチルスルホキシドの大半を
減圧下に留去し、副生塩とジメチルスルホキシドを含む
反応生成物をメチルイソブチルケトン４５０部に溶解さ
せ、さらに３０％ＮａＯＨ５部を加え７０℃で１時間反
応させた。反応終了後、水２００部で２回水洗を行った
。油水分離後、油層よりメチルイソブチルケトンを蒸留
回収して、エポキシ当量１８７，加水分解性塩素含有量
０．０７％，軟化点７１．０℃，溶融粘度（１５０℃）
３．５ポイズのエポキシ樹脂（ｂ）１９７部を得た。
【００８７】得られたエポキシ樹脂（ｂ）はエポキシ当
量から計算すると一般式（２）におけるアルコ−ル性水
酸基０．７８個の内約０．５２個がエポキシ化されてい
る。
【００８８】実施例３
一般式（２）におけるＲ１ 及びＲ２ が【００８９】
【化５７】
【００９０】であるエポキシ樹脂において、一般式（２
）における平均のｎが１．４６，エポキシ当量３０８，
加水分解性塩素含有量０．１０７％，軟化点８８．０℃
，溶融粘度（１５０℃）１６ポイズのエポキシ樹脂（エ
ポキシ樹脂（ｆ））１８８部を使用した以外は実施例１
と同様にして、エポキシ当量２４１，加水分解性塩素含
有量０．０７４％，軟化点８２．０℃，溶融粘度（１５
０℃）１１．０ポイズのエポキシ樹脂（ｃ）１８７部を
得た。得られたエポキシ樹脂（ｃ）はエポキシ当量から
計算すると一般式（２）におけるアルコ−ル性水酸基１
．４６個のほとんどがエポキシ化されている。
【００９１】実施例４
一般式（２）におけるＲ１ 及びＲ２ が【００９２】
【化５８】
【００９３】（式中ｐは０又は１以上の整数を示す）で
あるクレゾ−ルノボラックエポキシ樹脂において、一般
式（２）における平均のｎが０．３８，上式における平
均のｐが２．２，エポキシ当量１９９，加水分解性塩素
含有量０．０３５％，軟化点４５．０℃，溶融粘度（１
５０℃）０．５ポイズのエポキシ樹脂（ｇ）２４０部を
使用した以外は実施例２と同様にしてエポキシ当量１９
０，加水分解性塩素含有量０．０３４％，軟化点４３．
５℃，溶融粘度（１５０℃）０．５ポイズのエポキシ樹
脂（ｄ）２４１部を得た。得られたエポキシ樹脂（ｄ）
はエポキシ当量から計算すると一般式（２）におけるア
ルコ−ル性水酸基０．３８個の内約０．３３個がエポキ
シ化されている。
【００９４】実施例１〜４で得られたエポキシ樹脂（ａ
）〜（ｄ）、比較としてエポキシ樹脂（ｅ）〜（ｇ）の
樹脂物性を表−１に示す。
【００９５】応用実施例１〜４および応用比較例１〜３
エポキシ樹脂として実施例１〜４で得られたエポキシ樹
脂（ａ）〜（ｄ）、比較としてエポキシ樹脂（ｅ）〜（
ｇ）、硬化剤としてカヤハ−ドＭＣＤ（日本化薬製、メ
チルエンドメチレンテトラヒドロフタル酸無水物）、硬
化促進剤として２Ｅ４ＭＺ（２−エチル−４−メチルイ
ミダゾ−ル）を用い、エポキシ樹脂のエポキシ基１個に
対して酸無水物基が０．９個になる様に表１に示す組成
（数値は重量部を示し）で配合して、これらを１００℃
で２時間、次いで１２０℃で２時間、更に２００℃で５
時間の条件で硬化せしめて試験片とし、ＪＩＳ Ｋ−
６９１１に準拠して熱変形温度、曲げ強度、吸水率を測
定した。結果を表１に示す。
【００９６】
表 １
項 目
応 用 実 施
例
１ ２
３ ４ エポキシ
樹脂（ａ） １００
エポキシ樹脂（ｂ）
１００ エポキシ樹脂（ｃ）
１００
エポキシ樹脂（ｄ）
１
００ エポキシ樹脂（ｅ）
エポキシ樹脂（ｆ）
エポキシ樹脂（ｇ）
樹 エポキシ当量（ｇ／ｅｑ）
１８９ １８７ ２４１
１９０ 脂 加水分解性塩素含有量（％）
０．０７１ ０．０７０ ０．０７４
０．０３４ 物 軟 化 点（℃）
７１．０ ７１．０ ８
２．０ ４３．５ 性 溶融粘度（１５０
℃，ｐｓ） ３．６ ３．５
１１．０ ０．５ 配 カヤハー
ドＭＣＤ ８４．８
８５．７ ６６．５ ８４．３ 合
２Ｅ４ＭＺ
１ １ １
１ 硬物 熱変形温度（℃）
２４５ ２４６ ２３７
２１７ 化性 曲げ強度（ｋｇ／ｍｍ２）
１１．９ １１．９
７．８ １１．８ 吸水率（１
００℃／２０ｈｒ，％） １．９１
１．９０ １．６４ １．３０【
００９７】
表１（続き）
項 目
応 用 比 較
例
１
２ ３ エポキシ樹脂（
ａ）
エポキシ樹脂（ｂ）
エポキシ樹脂（ｃ）
エポキシ樹脂（ｄ）
エポキシ樹脂（ｅ）
１００ エポキシ樹脂（ｆ）
１００
エポキシ樹脂（ｇ）
１００
樹 エポキシ当量（ｇ／ｅｑ）
２０５ ３０８ １９９
脂 加水分解性塩素含有量（％） ０．
０７１ ０．１０７ ０．０３５ 物
軟 化 点（℃）
７１．０ ８８．０ ４５．０
性 溶融粘度（１５０℃，ｐｓ）
３．６ １６．０ ０．
５ 配 カヤハードＭＣＤ
７８．１ ５２．０
８０．５ 合 ２Ｅ４ＭＺ
１ １
１ 硬物 熱変形温度（℃）
２３５ ２
１０ ２１０ 化性 曲げ強度（ｋ
ｇ／ｍｍ２） １１．８
７．９ ９．２
吸水率（１００℃／２０ｈｒ，％）
２．０ １．７５ １．３６
【００９８】表１から明らかように本発明のエポキ
シ樹脂はアルコール性酸基にエピクロルヒドリンを反応
させて多官能化していることにより、従来のエポキシ樹
脂と比較してエポキシ含有率が高くなり、それらを使用
して得られた硬化物は耐熱性、耐水性に優れていること
がわかる。
【００９９】
【発明の効果】本発明のエポキシ樹脂およびエポキシ樹
脂組成物は耐熱性の優れた硬化物を与えることができ、
成形材料，注型材料，積層材料，複合材料，塗料，接着
剤，レジストなどの広範囲の用途に極めて有用である。Detailed Description of the Invention [0001] [Field of Industrial Application] The present invention relates to an epoxy resin having excellent heat resistance, an epoxy resin composition, and a cured product thereof. It is extremely useful in a wide range of applications such as mold materials, laminated materials, composite materials, paints, adhesives, and resists. [Prior Art] By curing epoxy resin with various curing agents, it generally becomes a cured product with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., and has excellent adhesive properties. It is used in a wide range of fields, including agents, paints, laminates, molding materials, and casting materials. Conventionally, liquid and solid bisphenol A obtained by reacting bisphenol A with epichlorohydrin are the epoxy resins most used industrially.
There is a mold epoxy resin. On the other hand, ICs that require heat resistance
Novolac type epoxy resin is mainly used as the sealing material. [0004] In addition, trifunctional epoxy resins such as polyglycidyl ether of tris(hydroxyphenyl)methane are known as highly heat-resistant epoxy resins, and are
P4672103 is a solid tris(hydroxyphenyl)methane type polyglycidyl ether suitable for IC sealing material.
tell has been reported. [0005] However, since this solid tris(hydroxyphenyl)methane type polyglycidyl ether is polymerized through epoxy groups, it does not have sufficient heat resistance. On the other hand, with the recent remarkable development of the electronics industry, the heat resistance required of the electrical insulating materials used in these products is becoming increasingly strict.
The emergence of epoxy resins with excellent heat resistance is eagerly awaited. [Means for Solving the Problems] In view of the above-mentioned circumstances, the present inventors conducted extensive research in search of an epoxy resin with excellent heat resistance, and as a result, the general formula (2) [Chemical formula 2] ] (In the formula, R1, R2 and Z1, Z2
and n represent the same meanings as in formula (1) below), in which the alcoholic hydroxyl group of the epoxy resin is epoxidized, and the epoxy resin has the above-mentioned characteristics. This discovery led to the completion of the present invention. That is, the present invention relates to (1) general formula (1) [0009] [0010] (wherein R1 and R2 are the same or different, the residue of a compound having two or more phenolic hydroxyl groups from which the hydroxyl group has been removed) represents a group.Z1 and Z2 are the same or different and represent an integer of 0 or 1 or more, and Z1 and Z2
The sum of is 1 or more. Moreover, M is a glycidyl group or a hydrogen atom, and n represents an integer of 1 or more. However, when n is 1, M is always a glycidyl group, and when n is 2 or more, at least one M is a glycidyl group. ) Epoxy resin represented by (2) An epoxy resin composition composed of an epoxy resin, a curing agent, and, if necessary, a curing accelerator, containing an epoxy resin of general formula (1) as the epoxy resin component. Characteristic epoxy resin composition (3) (
The present invention provides a cured product of the epoxy resin composition described in item 2). The epoxy resin of the present invention has, for example, the general formula (2
) can be obtained by reacting the alcoholic hydroxyl group of the epoxy resin with epichlorohydrin in the presence of, for example, a quaternary ammonium salt or dimethyl sulfoxide. When the reaction between the alcoholic hydroxyl group of the epoxy resin represented by the general formula (2) and epichlorohydrin is carried out in the presence of a Lewis acid catalyst, as is done in the reaction between general alcohols and epichlorohydrin, Epoxy group of epoxy resin represented by general formula (2) and alcohol
Since the reaction with the basic hydroxyl group also occurs at the same time, the general formula of the present invention (
It is difficult to obtain an epoxy resin in which only the alcoholic hydroxyl group of the compound shown in 2) is epoxidized. Note that even if excess epichlorohydrin is used to react with the compound of general formula (2) in the presence of a strong alkali, it will not react with the alcoholic hydroxyl group. As a result of intensive studies by the present inventors, the alcoholic hydroxyl group of the epoxy resin represented by the general formula (2) is more reactive than general alcohols, and it has been found that the alcoholic hydroxyl group of the epoxy resin represented by the general formula (2) is more reactive than general alcohols. It was surprisingly discovered that the reaction between alcoholic hydroxyl groups and epichlorohydrin can be carried out selectively when ammonium salt or dimethyl sulfoxide is used in combination, and the present invention has been completed. Furthermore, by adjusting the amount of alkali metal hydroxide, the alcoholic hydroxyl groups of the epoxy resin represented by the general formula (2) can be epoxidized to a desired ratio. The details of the present invention will be explained below. The epoxy resin represented by the general formula (1) of the present invention includes, for example, those in which R1 and R2 in the general formula (1) represent residues from which the hydroxyl group of a compound having three or more phenolic hydroxyl groups has been removed. is represented by the formula: [Image Omitted] [Image Omitted] [Image Omitted] 10] [Formula 11] [0021] [Formula 12] [Formula 13] [Formula 14] [Formula p represents an integer of 0 or 1 or more] [
[0025] R (in the formula, p represents an integer of 0 or 1 or more)
1 and R2 represent residues from which the hydroxyl group of a compound having two phenolic aqueous groups has been removed, the formula
[Formula 16] [Formula 17] [Formula 17] [Formula 18] [Formula 19] [Formula 19] [Formula 20] [Formula 20] [Formula 20] [Formula 20] embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image 44] [Formula 45] [Formula 45] [Formula 46] [Formula 47] [Formula 47] [Formula 48] [Formula 49] [Formula 49] [Formula 49] [Formula 51] ] [Chemical 52] [Chemical 52] [Chemical 53] [Chemical 53] [Chemical 54] [Chemical 54] [Chemical 55] [0067] Examples include, but are not limited to, the following. Also, R1 in general formula (1)
and R2 may include different ones. The reaction between the alcoholic hydroxyl group of the epoxy resin represented by the general formula (2) and epichlorohydrin can be carried out in the presence of an alkali metal hydroxide, for example, by using dimethyl sulfoxide or a quaternary ammonium salt. Can be done. At that time, alcohols, aromatic hydrocarbons, ketones, cyclic and ether compounds, etc. may be used in combination as a solvent. Dimethyl sulfoxide or 4
If a class ammonium salt is not used, the reaction will not proceed sufficiently and a large amount of alkali metal hydroxide will remain, causing polymerization and making it difficult to produce the epoxy resin of the present invention. The amount of dimethyl sulfoxide used is determined by the general formula (
5% to 300% by weight based on the epoxy resin represented by 2)
Weight percent is preferred. If the amount is 5% by weight or less based on the epoxy resin represented by the general formula (2), the reaction between the alcoholic hydroxyl group of the epoxy resin represented by the general formula (2) and epichlorohydrin will be slow, resulting in a long-term reaction. This is not preferable as it requires a reaction. If the amount exceeds 300% by weight based on the epoxy resin represented by the general formula (2), the effect of increasing the amount will hardly be achieved, and the volumetric efficiency will also deteriorate, which is not preferable. Examples of quaternary ammonium salts include tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride, etc., and the amount used is 1 to 1 of the alcoholic hydroxyl group of the epoxy resin represented by the general formula (2). 0.3 for equivalent weight
~50g is preferred. If the amount is less than 0.3 g per equivalent of hydroxyl group, the reaction between the alcoholic hydroxyl group of the epoxy resin represented by the general formula (2) and epichlorohydrin becomes slow and a long reaction time is required, which is not preferable. If the amount exceeds 50 g per equivalent of hydroxyl group, the effect of increasing the amount will be almost negated, but the cost will increase, which is not preferable. The amount of epichlorohydrin used is determined by the general formula (2
) may be used in an amount equal to or more than one equivalent of the alcoholic hydroxyl group to be epoxidized in the epoxy resin represented by (). However, if the amount exceeds 30 times the equivalent of 1 equivalent of hydroxyl group, the effect of increasing the amount will be almost negated, and the volumetric efficiency will also deteriorate, which is not preferable. As the alkali metal hydroxide, caustic soda
Caustic soda, caustic potash, lithium hydroxide, calcium hydroxide, etc. can be used, but caustic soda is preferred. The amount of alkali metal hydroxide used may be approximately equivalent to 1 equivalent of alcoholic hydroxyl group to be epoxidized in the epoxy resin represented by general formula (2). When epoxidizing the entire alcoholic hydroxyl group of the epoxy resin represented by the general formula (2), it may be used in excess, but if it exceeds 2 equivalents per equivalent of alcoholic hydroxyl group, There is a tendency for some polymerization to occur. The alkali metal hydroxide may be either solid or an aqueous solution. Further, when an aqueous solution is used, the reaction can be carried out while water in the reaction system is distilled out of the reaction system under normal pressure or reduced pressure. [0073] The reaction temperature is preferably 30 to 100°C. If the reaction temperature is less than 30°C, the reaction will be slow and a long reaction time will be required. If the reaction temperature exceeds 100°C, many side reactions occur, which is not preferable. After the reaction is completed, excess epichlorohydrin and dimethyl sulfoxide are distilled off under reduced pressure, and then the resin is dissolved in an organic solvent and a dehydrohalogenation reaction can be carried out with an alkali metal hydroxide. On the other hand, after the completion of the reaction, water washing is performed to separate by-product salts and dimethyl sulfoxide or quaternary ammonium salts, excess epichlorohydrin is distilled off from the oil layer under reduced pressure, and the resin is dissolved in an organic solvent to form an alkali metal hydroxide. The dehydrohalogenation reaction may also be carried out. As the organic solvent, methyl isobutyl ketone, benzene, toluene, xylene, etc. can be used.
Methyl isobutyl ketone is preferred. They can be used alone or in combination. The epoxy resin of the present invention can be cured alone or in combination with other epoxy resins by adding a curing agent and, if necessary, a curing accelerator, etc., as in the case of ordinary epoxy resins. The curing agents used in the present invention include amine compounds, acid anhydride compounds, amide compounds, and phenol compounds. Specific examples include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride, and pyroanhydride. Examples include mellitic acid, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolak, and modified products thereof. These curing agents may be used alone or in combination of two or more. The amount of these curing agents used is preferably 0.7 to 1.2 equivalents based on the epoxy group. If the amount is less than 0.7 equivalents or more than 1.2 equivalents relative to the epoxy group, curing may be incomplete and good cured physical properties may not be obtained. Furthermore, the epoxy resin composition of the present invention may be cured using a curing accelerator. Examples of the curing accelerator include imidazoles, tertiary amines, phenols, and Lewis acid salts such as boron trifluoride-monoethylamine complex. Moreover, various compounding agents such as inorganic or organic fillers can be added as necessary. The amount of these curing accelerators used is preferably 0.1 to 5.0 parts by weight per 100 parts by weight of the epoxy resin. From the epoxy resin composition of the present invention, a cured epoxy resin product can be easily obtained by a method similar to a conventionally known method. For example, the epoxy resin of the present invention, a curing agent, a filler, and other additives are thoroughly mixed using an extruder, kneader, roll, etc. as necessary until the mixture becomes uniform, and then the mixture is melted. A cured product can be obtained by molding using a casting or transfer molding machine and further heating to 80 to 200°C. Alternatively, the resin composition of the present invention can be dissolved in a solvent to produce glass fibers, carbon fibers, polyester fibers, polyamide fibers, alumina fibers, etc.
A cured product can also be obtained by hot press molding a prepreg obtained by impregnating a base material such as paper and drying by heating. [Example] Next, the present invention will be specifically explained with reference to Examples, Applied Examples, and Applied Comparative Examples. In the following, all parts are by weight unless otherwise specified. Hydrolyzable chlorine content is determined by dissolving the epoxy resin in dioxane, adding a 1N ethanol solution of potassium hydroxide, and heating under reflux for 30 minutes. The chlorine ions released are titrated with a silver nitrate solution. The weight of chlorine atoms in the compound is expressed as a weight percentage. Example 1 In the polyglycidyl ether of tris(hydroxyphenyl)methane in which R1 and R2 in the general formula (2) are 199 parts of epoxy resin (epoxy resin (e)) with n of 0.78, epoxy equivalent of 205, hydrolyzable chlorine content of 0.071%, softening point of 71.0°C, and melt viscosity (150°C) of 3.6 poise. Epichlorohydrin 370
After dissolving 6 parts of tetramethylammonium chloride at 70°C with stirring, then 48% NaOH3
0 part was added dropwise over 100 minutes. After the dropwise addition, the reaction was further carried out at 70°C for 3 hours. After the reaction was completed, 200 parts of water was added for washing. After oil and water separation, most of the epichlorohydrin was distilled off from the oil layer under reduced pressure, and then methyl isobutyl ketone 4
Dissolve in 50 parts and add 5 parts of 30% NaOH to 7
The reaction was carried out at 0°C for 1 hour. After the reaction is complete, add 200 parts of water to
Washed twice with water. After oil and water separation, methyl isobutyl ketone is distilled and recovered from the oil layer to obtain an epoxy resin with an epoxy equivalent of 189, a hydrolyzable chlorine content of 0.071%, a softening point of 71.0°C, and a melt viscosity (150°C) of 3.6 poise. (a)1
Got 95 copies. In the obtained epoxy resin (a), about 0.46 out of 0.78 alcoholic hydroxyl groups in general formula (2) are epoxidized, as calculated from the epoxy equivalent. Example 2 In the polyglycidyl ether of tris(hydroxyphenyl)methane in which R1 and R2 in the general formula (2) are the same as in Example 1, the average n in the general formula (2) is is 0.78
, epoxy equivalent 205, hydrolyzable element content 0.071
%, 199 parts of epoxy resin (epoxy resin (e)) with a softening point of 71.0°C and a melt viscosity (150°C) of 3.6 poise were mixed with 370 parts of epichlorohydrin and 1 part of dimethyl sulfoxide.
After dissolving in 85 parts of 98.5% Na at 70°C with stirring
10.6 parts of OH was added over 100 minutes. After the addition, the reaction was further carried out at 70°C for 3 hours. Next, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide were distilled off under reduced pressure, and the reaction product containing the by-product salt and dimethyl sulfoxide was dissolved in 450 parts of methyl isobutyl ketone, and 5 parts of 30% NaOH was added thereto at 70°C. The reaction was allowed to proceed for 1 hour. After the reaction was completed, washing was performed twice with 200 parts of water. After oil and water separation, methyl isobutyl ketone is distilled and recovered from the oil layer to obtain an epoxy equivalent of 187, a hydrolyzable chlorine content of 0.07%, a softening point of 71.0°C, and a melt viscosity (150°C).
197 parts of 3.5 poise epoxy resin (b) was obtained. In the obtained epoxy resin (b), about 0.52 out of 0.78 alcoholic hydroxyl groups in general formula (2) are epoxidized, as calculated from the epoxy equivalent. Example 3 In the epoxy resin in which R1 and R2 in the general formula (2) are
), the average n is 1.46, the epoxy equivalent is 308,
Hydrolyzable chlorine content 0.107%, softening point 88.0℃
, Example 1 except that 188 parts of an epoxy resin (epoxy resin (f)) with a melt viscosity (150° C.) of 16 poise was used.
Similarly, the epoxy equivalent was 241, the hydrolyzable chlorine content was 0.074%, the softening point was 82.0°C, and the melt viscosity was
0° C.) 187 parts of epoxy resin (c) of 11.0 poise was obtained. The obtained epoxy resin (c) has alcoholic hydroxyl group 1 in general formula (2) when calculated from the epoxy equivalent.
．． Most of the 46 pieces are epoxidized. Example 4 In a cresol novolac epoxy resin in which R1 and R2 in the general formula (2) are: The average n in the general formula (2) is 0.38, the average p in the above formula is 2.2, the epoxy equivalent is 199, the hydrolyzable chlorine content is 0.035%, the softening point is 45.0°C, the melt viscosity ( 1
The epoxy equivalent was 19 in the same manner as in Example 2 except that 240 parts of 0.5 poise epoxy resin (g) was used.
0, Hydrolyzable chlorine content 0.034%, Softening point 43.
241 parts of epoxy resin (d) having a melt viscosity (150°C) of 0.5 poise at 5°C was obtained. Obtained epoxy resin (d)
When calculated from the epoxy equivalent, about 0.33 out of 0.38 alcoholic hydroxyl groups in general formula (2) are epoxidized. Epoxy resins (a) obtained in Examples 1 to 4
) to (d), and the resin physical properties of epoxy resins (e) to (g) are shown in Table 1 for comparison. Application Examples 1 to 4 and Application Comparative Examples 1 to 3
Epoxy resins (a) to (d) obtained in Examples 1 to 4 as epoxy resins, and epoxy resins (e) to (d) obtained in Examples 1 to 4 for comparison.
g), using Kayahard MCD (manufactured by Nippon Kayaku Co., Ltd., methylendomethylenetetrahydrophthalic anhydride) as a curing agent and 2E4MZ (2-ethyl-4-methylimidazole) as a curing accelerator; The compositions shown in Table 1 (numbers indicate parts by weight) were blended so that the number of acid anhydride groups was 0.9 per group, and these were heated at 100°C.
for 2 hours, then at 120°C for 2 hours, and then at 200°C for 5 hours.
A test piece is prepared by hardening it under the conditions of JIS K-
Heat distortion temperature, bending strength, and water absorption were measured in accordance with 6911. The results are shown in Table 1. Table 1 Item
Application implementation
example
1 2
3 4 Epoxy resin (a) 100
Epoxy resin (b)
100 Epoxy resin (c)
100
Epoxy resin (d)
1
00 Epoxy resin (e) Epoxy resin (f) Epoxy resin (g) Tree Epoxy equivalent (g/eq)
189 187 241
190 Fat Hydrolyzable chlorine content (%)
0.071 0.070 0.074
0.034 Softening point (℃)
71.0 71.0 8
2.0 43.5 Properties Melt viscosity (150
°C, ps) 3.6 3.5
11.0 0.5 Kaya Hard MCD 84.8
85.7 66.5 84.3
2E4MZ
1 1 1
1 Hard material heat distortion temperature (℃)
245 246 237
217 Bending strength (kg/mm2)
11.9 11.9
7.8 11.8 Water absorption rate (1
00℃/20hr,%) 1.91
1.90 1.64 1.30 [
Table 1 (continued) Item
Application comparison
example
1
2 3 Epoxy resin (
a) Epoxy resin (b) Epoxy resin (c) Epoxy resin (d) Epoxy resin (e)
100 Epoxy resin (f)
100
Epoxy resin (g)
100
Tree Epoxy equivalent (g/eq)
205 308 199
Fat Hydrolyzable chlorine content (%) 0.
071 0.107 0.035 Softening point (℃)
71.0 88.0 45.0
Melt viscosity (150℃, ps)
3.6 16.0 0.
5 Kaya Hard MCD
78.1 52.0
80.5 2E4MZ
1 1
1 Hard material heat distortion temperature (℃)
235 2
10 210 Flexibility Bending strength (k
g/mm2) 11.8
7.9 9.2
Water absorption rate (100℃/20hr,%)
2.0 1.75 1.36
As is clear from Table 1, the epoxy resin of the present invention has a higher epoxy content than conventional epoxy resins because the alcoholic acid groups are made polyfunctional by reacting epichlorohydrin. It can be seen that the cured product obtained using this method has excellent heat resistance and water resistance. Effects of the Invention: The epoxy resin and epoxy resin composition of the present invention can provide a cured product with excellent heat resistance.
It is extremely useful in a wide range of applications such as molding materials, casting materials, laminated materials, composite materials, paints, adhesives, and resists.
Claims (3)
上のフェノール性水酸基をもつ化合物の水酸基が除かれ
た残基を示す。Ｚ１ 及びＺ２ は同一若しくは異なり
０又は１以上の整数を示し、Ｚ１とＺ２ の合計は１以
上である。 またＭはグリシジル基又は水素原子であり、ｎは１以上
の整数を示す。但し、ｎが１の場合Ｍは必ずグリシジル
基であり、ｎが２以上の場合Ｍは少なくとも１個がグリ
シジル基である。）で表されるエポキシ樹脂。Claim 1: General formula (1) [Formula 1] (wherein R1 and R2 are the same or different and represent a residue from which a hydroxyl group is removed from a compound having two or more phenolic hydroxyl groups. Z1 and Z2 are They are the same or different and represent an integer of 0 or 1 or more, and the sum of Z1 and Z2 is 1 or more.M is a glycidyl group or a hydrogen atom, and n is an integer of 1 or more.However, when n is 1 M is always a glycidyl group, and when n is 2 or more, at least one M is a glycidyl group.
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請求項１項記載のエポキ
シ樹脂を含有することを特徴とするエポキシ樹脂組成物
。2. An epoxy resin composition comprising an epoxy resin, a curing agent, and, if necessary, a curing accelerator, which contains the epoxy resin according to claim 1 as the epoxy resin component. Composition.
化物。3. A cured product of the epoxy resin composition according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15604591A JP2879860B2 (en) | 1991-05-31 | 1991-05-31 | Epoxy resin, epoxy resin composition and cured product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15604591A JP2879860B2 (en) | 1991-05-31 | 1991-05-31 | Epoxy resin, epoxy resin composition and cured product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04353517A true JPH04353517A (en) | 1992-12-08 |
| JP2879860B2 JP2879860B2 (en) | 1999-04-05 |
Family
ID=15619117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15604591A Expired - Fee Related JP2879860B2 (en) | 1991-05-31 | 1991-05-31 | Epoxy resin, epoxy resin composition and cured product thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2879860B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001053375A1 (en) * | 2000-01-18 | 2001-07-26 | Taiyo Ink Manufacturing Co., Ltd. | Polynuclear epoxy compound, resin obtained therefrom curable with actinic energy ray, and photocurable/thermosetting resin composition containing the same |
| US10961208B1 (en) | 2019-12-24 | 2021-03-30 | Chang Chun Plastics Co., Ltd. | Product of glycidyl ether of a mono or polyhydric phenol |
-
1991
- 1991-05-31 JP JP15604591A patent/JP2879860B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001053375A1 (en) * | 2000-01-18 | 2001-07-26 | Taiyo Ink Manufacturing Co., Ltd. | Polynuclear epoxy compound, resin obtained therefrom curable with actinic energy ray, and photocurable/thermosetting resin composition containing the same |
| US10961208B1 (en) | 2019-12-24 | 2021-03-30 | Chang Chun Plastics Co., Ltd. | Product of glycidyl ether of a mono or polyhydric phenol |
| EP3842466A1 (en) | 2019-12-24 | 2021-06-30 | Chang Chun Plastics Co., Ltd. | Product of glycidyl ether of a mono or polyhydric phenol, epoxy resin composition, and process for producing product of glycidyl ether of a mono or polyhydric phenol |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2879860B2 (en) | 1999-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3659532B2 (en) | Epoxy resin, epoxy resin composition and cured product thereof | |
| JPH04220422A (en) | Epoxy resin, resin composition containing same, and cured article prepared from the composition | |
| KR0180927B1 (en) | Epoxy resin, epoxy resin composition and cured product thereof | |
| JP3659533B2 (en) | Epoxy resin, epoxy resin composition and cured product thereof | |
| JPH0317117A (en) | Heat-resistant epoxy resin composition | |
| JP2587739B2 (en) | Epoxy resin, epoxy resin composition and cured product thereof | |
| JPH04353517A (en) | Epoxy resin, epoxy resin composition and cured product thereof | |
| JP3441020B2 (en) | Epoxy resin, epoxy resin composition and cured product thereof | |
| JP5579300B2 (en) | Epoxy resin, epoxy resin composition and cured product thereof | |
| JP3939000B2 (en) | Novolac resin, epoxy resin, epoxy resin composition and cured product thereof | |
| JP3729472B2 (en) | Production method of epoxy resin | |
| JP4605420B2 (en) | Epoxy resin composition and cured product thereof | |
| JP2898383B2 (en) | Manufacturing method of epoxy resin | |
| JP3970036B2 (en) | Method for producing liquid epoxy resin | |
| JP4463453B2 (en) | Epoxy resin composition and cured product thereof | |
| JP3068285B2 (en) | Epoxy resin, epoxy resin composition and cured product thereof | |
| JPH06298904A (en) | Epoxy resin composition, epoxy resin mixture and its cured material | |
| JP3627878B2 (en) | Epoxy resin, epoxy resin composition and cured product thereof | |
| JP4036289B2 (en) | Liquid epoxy resin, epoxy resin composition and cured product thereof | |
| JPH04142326A (en) | Epoxy resin and its production | |
| JPH1077330A (en) | Epoxy resin, epoxy resin composition and its cured material | |
| JP3938592B2 (en) | Phenolic compounds | |
| JPH10195174A (en) | Epoxy resin, epoxy resin composition and cured material made therefrom | |
| JP4082668B2 (en) | Phenolic resin, epoxy resin composition and cured product thereof | |
| JP3736700B2 (en) | Polyphenols, epoxy resins, epoxy resin compositions and cured products thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080129 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110129 Year of fee payment: 12 |
|
| LAPS | Cancellation because of no payment of annual fees |