JPH04366117A - New resin, production thereof, resin composition, and cured article - Google Patents
New resin, production thereof, resin composition, and cured articleInfo
- Publication number
- JPH04366117A JPH04366117A JP16744691A JP16744691A JPH04366117A JP H04366117 A JPH04366117 A JP H04366117A JP 16744691 A JP16744691 A JP 16744691A JP 16744691 A JP16744691 A JP 16744691A JP H04366117 A JPH04366117 A JP H04366117A
- Authority
- JP
- Japan
- Prior art keywords
- naphthol
- formula
- resin
- epoxy resin
- weight
- 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
- 229920005989 resin Polymers 0.000 title claims abstract description 53
- 239000011347 resin Substances 0.000 title claims abstract description 53
- -1 production thereof Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000011342 resin composition Substances 0.000 title description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims abstract description 60
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 33
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 16
- 229950011260 betanaphthol Drugs 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 239000003377 acid catalyst Substances 0.000 claims abstract description 6
- 239000003822 epoxy resin Substances 0.000 claims description 65
- 229920000647 polyepoxide Polymers 0.000 claims description 65
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 33
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 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 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 13
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 12
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 11
- 229920003986 novolac Polymers 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 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 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910015900 BF3 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000004780 naphthols Chemical class 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000001721 transfer moulding Methods 0.000 description 3
- 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 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 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
- 150000001875 compounds Chemical class 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 150000003944 halohydrins Chemical class 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 150000004782 1-naphthols Chemical class 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-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
- SRJCJJKWVSSELL-UHFFFAOYSA-N 2-methylnaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(C)=CC=C21 SRJCJJKWVSSELL-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 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
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 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
- 229910000147 aluminium phosphate Inorganic materials 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
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は高信頼性半導体封止用に
有用な、ナフト−ル樹脂、エポキシ樹脂、樹脂組成物及
びその硬化物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to naphthol resins, epoxy resins, resin compositions, and cured products thereof useful for highly reliable semiconductor encapsulation.
【0002】0002
【従来の技術】エポキシ樹脂はその硬化物の優れた電気
特性、耐熱性、接着性等により電気・電子部品等の分野
で幅広く用いられている。BACKGROUND OF THE INVENTION Epoxy resins are widely used in the fields of electrical and electronic parts due to their cured products having excellent electrical properties, heat resistance, adhesive properties, etc.
【0003】しかし、近年特に電気・電子分野の発展に
伴い、高純度化をはじめ硬化物の耐熱性、耐湿性、密着
性等の向上、又、成形材中への充填物(フィラー等)の
高密度充填や成形作業性の向上を図るための低粘度化等
、諸特性の一層の向上が求められており、エポキシ樹脂
及びその組成物について多くの提案がなされてはいるが
、未だ充分とはいえない。However, in recent years, especially with the development of the electrical and electronic fields, there has been an increase in purification, improvements in heat resistance, moisture resistance, adhesion, etc. of cured products, and the addition of fillers (fillers, etc.) into molded materials. There is a need for further improvements in various properties, such as lower viscosity for higher density filling and improved molding workability, and although many proposals have been made for epoxy resins and their compositions, they are still insufficient. No, no.
【0004】0004
【発明が解決しようとする課題】本発明は溶融時の流動
性に優れ、しかもその硬化物において優れた耐熱性、耐
湿性、密着性を示す高信頼性半導体封止用として有用な
樹脂、その製造法、樹脂組成物及びその硬化物を提供す
るものである。[Problems to be Solved by the Invention] The present invention provides a resin useful for highly reliable semiconductor encapsulation, which exhibits excellent fluidity when melted and exhibits excellent heat resistance, moisture resistance, and adhesion in its cured product. The present invention provides a manufacturing method, a resin composition, and a cured product thereof.
【0005】[0005]
【課題を解決するための手段】本発明者らは前記のよう
な特性を付与又は向上させる方法について鋭意研究の結
果、本発明を完成した。即ち、本発明は、(1)式(1
)[Means for Solving the Problems] The present inventors have completed the present invention as a result of extensive research into methods for imparting or improving the above characteristics. That is, the present invention solves the problem of formula (1) (1)
)
【0006】[0006]
【化6】[C6]
【0007】(式中、R1 、R2 はそれぞれ独立し
て水素原子、ハロゲン原子、炭素数1〜4のアルキル基
、又はアリ−ル基を、Xは水素原子又は−CH2 OH
を示す。)で表されるナフト−ル樹脂、(2)式(2)
(In the formula, R1 and R2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group, and X represents a hydrogen atom or -CH2 OH
shows. ) naphthol resin, (2) formula (2)
【0008】[0008]
【化7】[C7]
【0009】で表される2−ナフトールメチロール化物
と式(3)2-naphthol methylol compound represented by and formula (3)
【0010】0010
【化8】[Chemical formula 8]
【0011】(式中、R1 、R2 はそれぞれ独立し
て水素原子、ハロゲン原子、炭素数1〜4のアルキル基
、又はアリール基を示す。)で表される1−ナフトール
類とを酸触媒の存在下、脱水縮合反応させ、必要により
更にアルカリ金属水酸化物の存在下、ホルムアルデヒド
と反応させることを特徴とする、上記式(1)のナフト
ール樹脂の製造法、(3)式(4)(In the formula, R1 and R2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group.) A method for producing a naphthol resin of the above formula (1), (3) a method for producing a naphthol resin of the above formula (1), which is characterized by carrying out a dehydration condensation reaction in the presence of an alkali metal hydroxide, and further reacting with formaldehyde if necessary in the presence of an alkali metal hydroxide.
【0012】0012
【化9】[Chemical formula 9]
【0013】(式中、R1 、R2 はそれぞれ独立し
て水素原子、ハロゲン原子、炭素数1〜4のアルキル基
、又はアリ−ル基を、Yは水素原子又は式(5)(In the formula, R1 and R2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group, and Y represents a hydrogen atom or a formula (5)
【化1
0】[Chemical 1
0]
【0014】で示される基を示す。)で表されるエポキ
シ樹脂、(4)エポキシ樹脂、硬化剤及び必要により硬
化促進剤を含むエポキシ樹脂組成物において、(A)エ
ポキシ樹脂として、上記式(4)のエポキシ樹脂を含み
、及び/又は、(B)硬化剤として上記式(1)のナフ
トール樹脂を含む、エポキシ樹脂組成物、(5)上記(
4)のエポキシ樹脂組成物の硬化物、に関するものであ
る。The group shown below is shown below. ), (4) an epoxy resin composition containing an epoxy resin, a curing agent and, if necessary, a curing accelerator; Or (B) an epoxy resin composition containing the naphthol resin of the above formula (1) as a curing agent, (5) the above (
The present invention relates to the cured product of the epoxy resin composition of 4).
【0015】式(1)のナフトール樹脂は、上記(2)
の製造法により、即ち、式(2)で表される2−ナフト
ールメチロール化物と式(3)で表される1−ナフトー
ル類とを、酸触媒の存在下、脱水縮合反応させ、必要に
より更に、アルカリ金属水酸化物の存在下ホルムアルデ
ヒドと反応させることにより得ることが出来る。[0015] The naphthol resin of formula (1) has the above-mentioned (2)
According to the production method, the 2-naphthol methylol compound represented by formula (2) and the 1-naphthol compound represented by formula (3) are subjected to a dehydration condensation reaction in the presence of an acid catalyst, and if necessary, further can be obtained by reacting with formaldehyde in the presence of an alkali metal hydroxide.
【0016】式(2)の2−ナフトールメチロール化物
は公知の化合物であり、例えば、2−ナフトールをアル
カリ金属水酸化物の存在下ホルムアルデヒドと反応させ
ることにより合成することが出来る。The 2-naphthol methylol compound of formula (2) is a known compound, and can be synthesized, for example, by reacting 2-naphthol with formaldehyde in the presence of an alkali metal hydroxide.
【0017】式(3)で表される1−ナフトール類とし
ては1−ナフトール、2−メチル−1−ナフトール、4
−メチル−1−ナフトール、等が挙げられ、1−ナフト
ール類の使用量は2−ナフトールメチロール化物1モル
に対して好ましくは0.9〜20モル倍、特に好ましく
は1〜2モル倍である。The 1-naphthols represented by formula (3) include 1-naphthol, 2-methyl-1-naphthol, and 4-naphthol.
-Methyl-1-naphthol, etc., and the amount of 1-naphthol used is preferably 0.9 to 20 times, particularly preferably 1 to 2 times by mole, per mole of the 2-naphthol methylol compound. .
【0018】脱水縮合反応に用いられる酸触媒としては
塩酸、硫酸、燐酸、パラトルエンスルホン酸などのプロ
トン酸、三弗化ホウ素、三弗化ホウ素エーテル錯体、塩
化亜鉛、塩化アルミニウムなどのルイス酸の他、酢酸、
シュウ酸等を用いることが出来る。これらのうち塩酸、
シュウ酸、パラトルエンスルホン酸などが好ましく用い
られ、これら酸触媒の使用量は2−ナフトールメチロー
ル化物に対し好ましくは0.01〜0.2モル倍である
。Acid catalysts used in the dehydration condensation reaction include protonic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and para-toluenesulfonic acid; Lewis acids such as boron trifluoride, boron trifluoride ether complex, zinc chloride, and aluminum chloride; Others, acetic acid,
Oxalic acid etc. can be used. Among these, hydrochloric acid,
Oxalic acid, para-toluenesulfonic acid, etc. are preferably used, and the amount of these acid catalysts used is preferably 0.01 to 0.2 times the mole of the 2-naphthol methylol compound.
【0019】この2−ナフトールメチロール化物と1−
ナフトール類との酸触媒存在下に於ける脱水縮合反応は
通常10〜100℃で行われ、好ましくは20〜60℃
で行われる。更に、反応時間は通常1〜10時間の範囲
で選定できる。又、この反応は水を始めメタノール、メ
チルイソブチルケトン、トルエン等の適当な溶媒の存在
下に行うことが好ましい。溶媒の使用量は特に限定され
るものではないが、通常2−ナフトールメチロール化物
に対して1〜30重量倍用いられる。This 2-naphthol methylol compound and 1-
The dehydration condensation reaction with naphthols in the presence of an acid catalyst is usually carried out at 10 to 100°C, preferably 20 to 60°C.
It will be held in Furthermore, the reaction time can usually be selected within the range of 1 to 10 hours. Further, this reaction is preferably carried out in the presence of a suitable solvent such as water, methanol, methyl isobutyl ketone, toluene, and the like. The amount of the solvent used is not particularly limited, but it is usually used in an amount of 1 to 30 times the weight of the 2-naphthol methylol compound.
【0020】更に、脱水縮合反応液は過剰のトルエン、
メチルイソブチルケトン等の溶媒の存在下、その系内が
中性になるまで水洗を繰り返し、水を分離排水後、加熱
減圧下、溶媒及び未反応物を除去すると式(1)のナフ
トール樹脂(但しX=H)が得られる。Furthermore, the dehydration condensation reaction solution contains excess toluene,
In the presence of a solvent such as methyl isobutyl ketone, the system is repeatedly washed with water until the system becomes neutral, and after separating and draining the water, the solvent and unreacted substances are removed under heating and reduced pressure. X=H) is obtained.
【0021】式(1)においてXが−CH2 OHであ
るナフト−ル樹脂は、式(1)においてX=Hのナフト
−ル樹脂をアルカリ金属水酸化物の存在下ホルムアルデ
ヒドと反応させることにより得られる。A naphthol resin in which X is -CH2OH in formula (1) can be obtained by reacting a naphthol resin in which X=H in formula (1) with formaldehyde in the presence of an alkali metal hydroxide. It will be done.
【0022】この反応において、アルカリ金属水酸化物
(例えば、水酸化ナトリウム、水酸化カリウム)の使用
量は式(1)においてX=Hのナフト−ル樹脂の水酸基
1当量に対して好ましくは0.2〜3モル、特に好まし
くは0.4〜1.2モルであり、ホルムアルデヒドと反
応を行う前に該アルカリ金属水酸化物の水溶液(通常5
〜50重量%の水溶液)を加え、式(1)においてX=
Hのナフト−ル樹脂の水酸基の一部または全部をアルカ
リ金属塩とし系内を均一相としておくことが好ましい。
このアルカリ金属塩とする反応は通常20〜80℃、好
ましくは40〜60℃の温度で行われる。In this reaction, the amount of alkali metal hydroxide (eg, sodium hydroxide, potassium hydroxide) used is preferably 0 per equivalent of hydroxyl group of the naphthol resin where X=H in formula (1). .2 to 3 mol, particularly preferably 0.4 to 1.2 mol, and an aqueous solution (usually 5 mol) of the alkali metal hydroxide is added before the reaction with formaldehyde.
~50% by weight aqueous solution), and in formula (1), X=
It is preferable that part or all of the hydroxyl groups of the naphthol resin (H) be made into an alkali metal salt to form a homogeneous phase in the system. This reaction to form the alkali metal salt is usually carried out at a temperature of 20 to 80°C, preferably 40 to 60°C.
【0023】次いで、この一部または全部をアルカリ金
属塩としたナフト−ル樹脂1モルに対してホルムアルデ
ヒドを好ましくは0.8〜2.0モル、特に好ましくは
1〜1.2モル添加しメチロ−ル化反応を行う。Next, formaldehyde is preferably added in an amount of 0.8 to 2.0 mol, particularly preferably 1 to 1.2 mol, per 1 mol of naphthol resin in which part or all of the alkali metal salt is used. - carry out the conversion reaction.
【0024】この反応で使用するホルムアルデヒドとし
ては水溶液であるホルマリン、粉末や粒状のパラホルム
アルデヒド等が使用できる。又、この反応は水を始め、
メタノ−ル、エタノ−ル等のアルコ−ル類の他、トルエ
ン等の溶媒を単独で、または併用で使用できるが、好ま
しくは水を使用し、好ましくは0〜60℃、特に好まし
くは0〜30℃の温度で反応を行う。水等の溶媒の使用
量は特に限定されるものではないが、好ましくは式(1
)においてX=Hのナフト−ル樹脂及びそのアルカリ金
属塩の合計重量に対して50〜500重量%を用いる。As the formaldehyde used in this reaction, formalin in the form of an aqueous solution, paraformaldehyde in the form of powder or granules, etc. can be used. Also, this reaction starts with water,
In addition to alcohols such as methanol and ethanol, solvents such as toluene can be used alone or in combination, but water is preferably used, and the temperature is preferably 0 to 60°C, particularly preferably 0 to 60°C. The reaction is carried out at a temperature of 30°C. Although the amount of solvent such as water to be used is not particularly limited, it is preferable that the formula (1
), 50 to 500% by weight is used based on the total weight of the naphthol resin with X=H and its alkali metal salt.
【0025】又、反応時間は反応温度にもよるが、0.
5〜5時間が適当である。かくして反応した後、酸によ
って中和を行う。この酸による中和は発熱に注意しメチ
ロ−ル化反応と同様に0〜30℃で実施することが好ま
しい。[0025]Also, the reaction time depends on the reaction temperature, but the reaction time is 0.
5 to 5 hours is appropriate. After this reaction, neutralization is carried out with an acid. This neutralization with an acid is preferably carried out at 0 to 30 DEG C. in the same manner as the methylolation reaction, taking care to avoid heat generation.
【0026】このようにして、式(1)においてXが−
CH2 OHであるナフト−ル樹脂を含む溶液が得られ
る。In this way, in equation (1), X is -
A solution is obtained containing naphthol resin which is CH2OH.
【0027】式(4)のエポキシ樹脂は、式(1)のナ
フト−ル樹脂にエピハロヒドリンを反応させることによ
って得られる。この反応に使用されるエピハロヒドリン
としては、エピクロルヒドリン、エピブロムヒドリンな
どがあるが、工業的に入手しやすく安価なエピクロルヒ
ドリンが好ましい。この反応は従来公知のノボラック型
フェノール樹脂とエピハロヒドリンからポリグリシジル
エーテルを得る方法に準じて行うことができる。The epoxy resin of formula (4) can be obtained by reacting the naphthol resin of formula (1) with epihalohydrin. Epihalohydrin used in this reaction includes epichlorohydrin, epibromohydrin, etc., and epichlorohydrin is preferred because it is industrially easily available and inexpensive. This reaction can be carried out in accordance with a conventionally known method for obtaining polyglycidyl ether from a novolac type phenol resin and epihalohydrin.
【0028】例えば式(1)のナフトール樹脂と過剰の
エピクロルヒドリンの混合物に水酸化ナトリウム、水酸
化カリウム等のアルカリ金属水酸化物の固体を添加し、
または、添加しながら20℃〜120℃の間の温度で反
応させる。この際アルカリ金属水酸化物は水溶液を使用
してもよく、その場合は該アルカリ金属水酸化物を連続
的に添加すると共に反応系内から減圧下、または常圧下
、連続的に水及びエピクロルヒドリンを留出せしめ更に
分液し水は除去しエピクロルヒドリンは反応系内に連続
的に戻す方法でもよい。For example, by adding a solid alkali metal hydroxide such as sodium hydroxide or potassium hydroxide to a mixture of the naphthol resin of formula (1) and excess epichlorohydrin,
Alternatively, the reaction is carried out at a temperature between 20<0>C and 120<0>C while being added. At this time, an aqueous solution of the alkali metal hydroxide may be used. In that case, the alkali metal hydroxide is continuously added and water and epichlorohydrin are continuously added from the reaction system under reduced pressure or normal pressure. A method may also be used in which the water is removed by distillation, followed by liquid separation, and the epichlorohydrin is continuously returned to the reaction system.
【0029】上記の方法においてエピクロルヒドリンの
使用量はナフトール樹脂中の水酸基(フェノ−ル性水酸
基及びアルコ−ル性水酸基)1当量に対して通常1〜2
0モル、好ましくは2〜10モルである。アルカリ金属
水酸化物の使用量はナフトール樹脂中の水酸基(フェノ
−ル性水酸基及びアルコ−ル性水酸基)1当量に対し通
常0.8〜1.5モル、好ましくは0.9〜1.1モル
の範囲である。更に、反応を円滑に進行させるためにメ
タノール、エタノールなどのアルコール類又はジメチル
スルホン、ジメチルスルホオキシド(以下DMSO)な
どの非プロトン性極性溶媒を添加することは好ましい、
この反応は通常1〜20時間の範囲で行われる。In the above method, the amount of epichlorohydrin used is usually 1 to 2 per equivalent of hydroxyl group (phenolic hydroxyl group and alcoholic hydroxyl group) in the naphthol resin.
0 mol, preferably 2 to 10 mol. The amount of alkali metal hydroxide used is usually 0.8 to 1.5 mol, preferably 0.9 to 1.1 mol per equivalent of hydroxyl group (phenolic hydroxyl group and alcoholic hydroxyl group) in the naphthol resin. It is in the molar range. Furthermore, in order to make the reaction proceed smoothly, it is preferable to add an alcohol such as methanol or ethanol or an aprotic polar solvent such as dimethyl sulfone or dimethyl sulfoxide (hereinafter referred to as DMSO).
This reaction is usually carried out for 1 to 20 hours.
【0030】また、ナフトール樹脂と過剰のエピハロヒ
ドリンの混合物に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などの第四級アンモニウ
ム塩を触媒として使用し50℃〜150℃で反応させ、
得られるハロヒドリンエーテルに水酸化ナトリウム、水
酸化カリウム等のアルカリ金属水酸化物の固体または水
溶液を加え再び20〜120℃の間の温度で反応させて
ハロヒドリンエーテルを閉環させてグリシジルエーテル
を得ることもできる。この場合第四級アンモニウム塩の
使用量はナフトール樹脂の水酸基(フェノ−ル性水酸基
及びアルコ−ル性水酸基)1当量に対して0.001〜
0.2モル、好ましくは0.005〜0.1モルの範囲
である。[0030]Also, a mixture of naphthol resin and excess epihalohydrin is reacted at 50°C to 150°C using a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, or trimethylbenzylammonium chloride as a catalyst,
A solid or aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to the obtained halohydrin ether and reacted again at a temperature between 20 and 120°C to ring-close the halohydrin ether to form glycidyl ether. You can also get In this case, the amount of quaternary ammonium salt used is 0.001 to 1 equivalent of hydroxyl group (phenolic hydroxyl group and alcoholic hydroxyl group) of the naphthol resin.
0.2 mol, preferably in the range of 0.005 to 0.1 mol.
【0031】通常、これらの反応物は水洗後、または、
水洗無しに加熱減圧下過剰のエピハロヒドリンを除去し
た後、再びトルエン、メチルイソブチルケトン等の溶媒
に溶解し、水酸化ナトリウム、水酸化カリウム等のアル
カリ金属水酸化物の水溶液を加えて再び反応を行う。こ
の場合アルカリ金属水酸化物の使用量は使用したナフト
ール樹脂の水酸基(フェノ−ル性水酸基及びアルコ−ル
性水酸基)1当量に対して0.01〜0.2モル、好ま
しくは0.05〜0.1モルである。反応温度は通常5
0〜120℃の間で行われ、反応時間は通常0.5〜2
時間である。[0031] Usually, these reactants are washed with water or
After removing excess epihalohydrin under heating and reduced pressure without washing with water, it is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to carry out the reaction again. . In this case, the amount of alkali metal hydroxide used is 0.01 to 0.2 mol, preferably 0.05 to 0.2 mol, per equivalent of hydroxyl group (phenolic hydroxyl group and alcoholic hydroxyl group) of the naphthol resin used. It is 0.1 mole. The reaction temperature is usually 5
It is carried out between 0 and 120°C, and the reaction time is usually 0.5 to 2
It's time.
【0032】反応終了後副生した塩を濾過、水洗等によ
り除去し、更に加熱減圧下トルエン、メチルイソブチル
ケトン等の溶媒を留去することにより加水分解性ハロゲ
ンの少ない本発明のエポキシ樹脂を得ることができる。After the completion of the reaction, by-produced salts are removed by filtration, washing with water, etc., and solvents such as toluene and methyl isobutyl ketone are distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention with less hydrolyzable halogen. be able to.
【0033】なお、原料として、上記の式(1)におい
てXが−CH2OHであるナフト−ル樹脂を含む溶液を
用いる場合、該ナフト−ル樹脂を含む溶液にエピクロル
ヒドリン等のエピハロヒドリンを添加し水洗を行った後
、減圧下で共沸により脱水を行い、更に、上記と同様に
エポキシ化反応を行うことによりエポキシ樹脂が得られ
る。In addition, when a solution containing a naphthol resin in which X in the above formula (1) is -CH2OH is used as a raw material, an epihalohydrin such as epichlorohydrin is added to the solution containing the naphthol resin, and the solution is washed with water. After this, an epoxy resin is obtained by dehydrating by azeotropy under reduced pressure and further performing an epoxidation reaction in the same manner as above.
【0034】以下、本発明のエポキシ樹脂組成物につい
て説明する。本発明のエポキシ樹脂組成物において、式
(4)のエポキシ樹脂を用いる場合、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併用して使用す
ることが出来る。併用する場合、本発明のエポキシ樹脂
の全エポキシ樹脂中に占める割合は30重量%以上が好
ましく、特に40重量%以上が好ましい。The epoxy resin composition of the present invention will be explained below. When using the epoxy resin of formula (4) in the epoxy resin composition of the present invention, the epoxy resin of the present invention can be used alone or in combination with other epoxy resins. When used together, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more.
【0035】本発明のエポキシ樹脂と併用されうる他の
エポキシ樹脂としては、ノボラック型エポキシ樹脂、ビ
スフェノールA型エポキシ樹脂、ビスフェノールF型エ
ポキシ樹脂、ビスフェノールS型エポキシ樹脂、脂環式
エポキシ樹脂、ビフェニル型エポキシ樹脂等が挙げられ
るが、ノボラック型エポキシ樹脂の使用が耐熱性の点で
特に有利である。その具体例としては、クレゾールノボ
ラック型エポキシ樹脂、フェノールノボラック型エポキ
シ樹脂、臭素化フェノールノボラック型エポキシ樹脂な
どが挙げられるがこれらに限定されるものではない。こ
れらは単独で用いてもよく、2種以上併用してもよい。Other epoxy resins that can be used in combination with the epoxy resin of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, alicyclic epoxy resins, and biphenyl type epoxy resins. Examples include epoxy resins, but the use of novolac type epoxy resins is particularly advantageous in terms of heat resistance. Specific examples thereof include, but are not limited to, cresol novolac type epoxy resins, phenol novolac type epoxy resins, brominated phenol novolac type epoxy resins, and the like. These may be used alone or in combination of two or more.
【0036】本発明のエポキシ樹脂組成物において、式
(1)のナフトール樹脂を用いる場合、本発明のナフト
ール樹脂は単独でまたは、他のエポキシ樹脂硬化剤と併
用して使用することが出来る。併用する場合、本発明の
ナフトール樹脂の全硬化剤中に占める割合は、30重量
%以上が好ましく、特に40重量%以上が好ましい。When the naphthol resin of formula (1) is used in the epoxy resin composition of the present invention, the naphthol resin of the present invention can be used alone or in combination with other epoxy resin curing agents. When used together, the proportion of the naphthol resin of the present invention in the total curing agent is preferably 30% by weight or more, particularly preferably 40% by weight or more.
【0037】本発明のナフトール樹脂と併用されうる他
のエポキシ樹脂硬化剤としては、例えば、脂肪族ポリア
ミン、芳香族ポリアミン、ポリアミドポリアミン等のポ
リアミン系硬化剤、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等の酸無水物系硬化剤、フェ
ノールノボラック、クレゾールノボラック等のフェノー
ル系硬化剤、三弗化ホウ素等のルイス酸またはそれらの
塩類、ジシアンジアミド類などの硬化剤が挙げられるが
、これらに限定されるものではない。これらは単独で用
いてもよく、2種以上併用してもよい。Other epoxy resin curing agents that can be used in combination with the naphthol resin of the present invention include, for example, polyamine curing agents such as aliphatic polyamines, aromatic polyamines, and polyamide polyamines, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, etc. Examples include, but are not limited to, curing agents such as acid anhydride curing agents such as acids, phenol curing agents such as phenol novolak and cresol novolak, Lewis acids such as boron trifluoride or their salts, and dicyandiamides. It's not something you can do. These may be used alone or in combination of two or more.
【0038】本発明のエポキシ樹脂組成物において、硬
化剤の使用量は、エポキシ樹脂のエポキシ基1当量に対
して0.5〜1.5当量が好ましく特に0.6〜1.2
当量が好ましい。In the epoxy resin composition of the present invention, the amount of curing agent used is preferably 0.5 to 1.5 equivalents, particularly 0.6 to 1.2 equivalents per equivalent of epoxy groups in the epoxy resin.
Equivalent amounts are preferred.
【0039】硬化促進剤は必要に応じて使用され、2−
メチルイミダゾール、2−エチルイミダゾール等のイミ
ダゾール系化合物、2−(ジメチルアミノメチル)フェ
ノール等の第3アミン系化合物、トリフェニルホスフィ
ン化合物等、公知の種々の硬化促進剤が使用でき、特に
限定されるものではない。硬化促進剤を用いる場合、そ
の使用量はエポキシ樹脂100重量部に対して0.01
〜15重量部の範囲が好ましく、特に0.1〜10重量
部の範囲が好ましい。A curing accelerator is used as necessary, and 2-
Various known curing accelerators can be used, including imidazole compounds such as methylimidazole and 2-ethylimidazole, tertiary amine compounds such as 2-(dimethylaminomethyl)phenol, and triphenylphosphine compounds, and are not particularly limited. It's not a thing. When using a curing accelerator, the amount used is 0.01 parts by weight per 100 parts by weight of the epoxy resin.
A range of 15 parts by weight is preferred, and a range of 0.1 to 10 parts by weight is particularly preferred.
【0040】本発明のエポキシ樹脂組成物には、更に必
要に応じて公知の添加剤を配合することが出来る。添加
剤としては、例えば、シリカ、アルミナ、タルク、ガラ
ス繊維等の無機充填剤、シランカップリング剤のような
充填剤の表面処理剤、離型剤、顔料等が挙げられる。The epoxy resin composition of the present invention may further contain known additives, if necessary. Examples of additives include inorganic fillers such as silica, alumina, talc, and glass fibers, surface treatment agents for fillers such as silane coupling agents, mold release agents, and pigments.
【0041】本発明のエポキシ樹脂組成物は、各成分を
均一に混合することにより得られ、通常130〜170
℃の温度で30〜300秒の範囲で予備硬化し、更に、
150〜200℃の温度で2〜8時間、後硬化すること
により充分な硬化反応が進行し、本発明の硬化物が得ら
れる。又、エポキシ樹脂組成物の成分を溶剤等に均一に
分散または溶解させ、溶媒を除去し硬化させることもで
きる。The epoxy resin composition of the present invention is obtained by uniformly mixing each component, and usually has a molecular weight of 130 to 170
Precure at a temperature of 30 to 300 seconds, and further,
By post-curing at a temperature of 150 to 200°C for 2 to 8 hours, a sufficient curing reaction proceeds, and the cured product of the present invention can be obtained. Alternatively, the components of the epoxy resin composition can be uniformly dispersed or dissolved in a solvent, and the composition can be cured after removing the solvent.
【0042】こうして得られる硬化物は、耐熱性を保持
しながら、耐湿性をも具備するという優れた性能を有す
る。又、エポキシ樹脂成分、硬化剤成分の両方に本発明
の樹脂を用いることによりその効果は増加する。従って
、本発明のナフト−ル樹脂及びエポキシ樹脂は、耐熱性
、耐湿性の要求される広範な分野でエポキシ樹脂として
、あるいは硬化剤として用いることが出来る。具体的に
は、絶縁材料、積層板、封止材料等あらゆる電気・電子
材料の配合成分として有用である。又、成形材料、複合
材料の他、塗料材料等の分野にも用いることが出来る。[0042] The cured product thus obtained has excellent performance in that it maintains heat resistance and also has moisture resistance. Moreover, the effect is increased by using the resin of the present invention for both the epoxy resin component and the curing agent component. Therefore, the naphthol resin and epoxy resin of the present invention can be used as an epoxy resin or as a curing agent in a wide range of fields where heat resistance and moisture resistance are required. Specifically, it is useful as a compounding component of all electrical and electronic materials such as insulating materials, laminates, and sealing materials. In addition to molding materials and composite materials, it can also be used in fields such as paint materials.
【0043】更に、本発明のナフト−ル樹脂及びエポキ
シ樹脂は、溶融粘度が低く抑えられているため、フィラ
ー等の充填物の高密度充填を可能にし、更に、従来通り
のトランスファー成形等の手法を用いることもでき作業
性も良好である。Furthermore, since the naphthol resin and epoxy resin of the present invention have a low melt viscosity, they enable high-density filling with fillers and the like, and furthermore, they can be used in conventional methods such as transfer molding. can also be used and has good workability.
【0044】[0044]
【実施例】以下本発明を実施例により具体的に説明する
。尚、実施例中の軟化点とはJIS K2425(環
球法)による値であり、水酸基当量、エポキシ当量はg
/eqを示す。又、加水分解性塩素量とはジオキサン中
、1N−KOH−エタノールで30分間、還流下分解し
た時に生じる(滴定される)塩素量(ppm)である。
尚、本発明はこれら実施例に限定されるものではない。[Examples] The present invention will be specifically explained below using examples. In addition, the softening point in the examples is a value according to JIS K2425 (ring and ball method), and the hydroxyl equivalent and epoxy equivalent are g
/eq is shown. The amount of hydrolyzable chlorine is the amount (ppm) of chlorine produced (titrated) when decomposed with 1N-KOH-ethanol in dioxane under reflux for 30 minutes. Note that the present invention is not limited to these examples.
【0045】実施例1
(1)2−ナフトールメチロール化物の合成温度計、冷
却管、滴下ロート、撹拌器を取り付けたフラスコに2−
ナフトール288重量部(2モル)、20wt%−水酸
化ナトリウム水溶液400重量部(2モル)を仕込み系
内を40℃に加熱し1時間反応させた。次いで系内を5
℃に冷却し粒状パラホルムアルデヒド(純分92%)6
8重量部(2.1モル)を添加し5℃で4時間反応させ
た。反応終了後、酢酸(純分99%)126重量部を発
熱に注意しながら滴下し中和した。次いで、メチルイソ
ブチルケトン1000重量部を添加した後水洗を繰り返
し過剰のホルムアルデヒドを除去し式(2)で表される
2−ナフト−ルメチロ−ル化物を含む溶液(反応混合物
)を得た。Example 1 (1) Synthesis of 2-naphthol methylol compound In a flask equipped with a thermometer, condenser, dropping funnel, and stirrer, 2-naphthol methylol compound was added.
288 parts by weight (2 mol) of naphthol and 400 parts by weight (2 mol) of a 20 wt % aqueous sodium hydroxide solution were charged, and the inside of the system was heated to 40°C and reacted for 1 hour. Then 5 inside the system
Cool to ℃ and add granular paraformaldehyde (92% purity)6
8 parts by weight (2.1 mol) was added and reacted at 5° C. for 4 hours. After the reaction was completed, 126 parts by weight of acetic acid (purity 99%) was added dropwise to neutralize the mixture while being careful not to generate heat. Next, 1000 parts by weight of methyl isobutyl ketone was added and water washing was repeated to remove excess formaldehyde to obtain a solution (reaction mixture) containing the 2-naphthol methylol compound represented by formula (2).
【0046】(2) ナフトール樹脂の合成この反応
混合物に1−ナフトール576重量部(4モル)を仕込
み系内を均一相とした。更にパラトルエンスルホン酸5
重量部を添加した後、30℃で2時間反応させ、次いで
、50℃で1時間反応させた。反応終了後、反応混合物
を分液ロートに移し、水洗を繰り返し中性に戻した。そ
の後油層からロータリーエバポレーターを使用し加熱減
圧下、メチルイソブチルケトン及び1−ナフトールを除
去しナフトール樹脂(A)570重量部を得た。得られ
たナフトール樹脂(A)の150℃におけるICI粘度
は1.7ps、軟化点は82℃、水酸基当量は151で
あった。(2) Synthesis of naphthol resin 576 parts by weight (4 moles) of 1-naphthol was added to the reaction mixture to form a homogeneous phase in the system. Furthermore, para-toluenesulfonic acid 5
After adding parts by weight, the mixture was reacted at 30°C for 2 hours, and then at 50°C for 1 hour. After the reaction was completed, the reaction mixture was transferred to a separatory funnel and washed with water repeatedly to return it to neutrality. Thereafter, methyl isobutyl ketone and 1-naphthol were removed from the oil layer using a rotary evaporator under heating and reduced pressure to obtain 570 parts by weight of naphthol resin (A). The resulting naphthol resin (A) had an ICI viscosity of 1.7 ps at 150°C, a softening point of 82°C, and a hydroxyl equivalent of 151.
【0047】又、このナフトール樹脂(A)を溶媒にテ
トラヒドロフラン(以下THF)を用いて次のGPC分
析装置により分析したところ図1に示される分子量分布
曲線を得た。When this naphthol resin (A) was analyzed using the following GPC analyzer using tetrahydrofuran (hereinafter referred to as THF) as a solvent, the molecular weight distribution curve shown in FIG. 1 was obtained.
【0048】
送液ポンプ:L−6000 (日立製作所製
)カラム :GPC KF−803(1本)+
GPC KF−802.5(2本)
+GPC KF−802(1本) (
昭和電工製)カラム温度:40℃
溶媒 :THF 1ml/min検出
器 :RI
(エルマ光学製)データ処
理:CR−4A (島津製作所製)Liquid pump: L-6000 (manufactured by Hitachi) Column: GPC KF-803 (1 piece) +
GPC KF-802.5 (2 pieces)
+GPC KF-802 (1 piece) (
(manufactured by Showa Denko) Column temperature: 40°C Solvent: THF 1ml/min Detector: RI
(Manufactured by Elma Optical) Data processing: CR-4A (Manufactured by Shimadzu Corporation)
【0
049】この分析条件で分析を行った上記ナフトール樹
脂(A)のメインピークのリテイションタイムは、標準
ポリスチレンを使用した検量線より、ナフトール環2個
を有する2核体の分子量に相当し、この2核体と思われ
るメインピーク成分を分取し、マススペクトル(FAB
−MS)によって分析したところM+ 300が得られ
たことにより次式(6)で表される2核体であることを
確認した。0
[049] The retention time of the main peak of the above naphthol resin (A) analyzed under these analysis conditions corresponds to the molecular weight of a dinuclear substance having two naphthol rings, as determined from the calibration curve using standard polystyrene. The main peak component, which is thought to be a dinuclear body, was separated and subjected to mass spectrum (FAB).
-MS), M+ 300 was obtained, confirming that it was a dinuclear body represented by the following formula (6).
【0050】[0050]
【化11】[Chemical formula 11]
【0051】実施例2
エポキシ樹脂の合成
実施例1の(2)で得られたナフトール樹脂(A)15
1重量部にエピクロルヒドリン555重量部(6モル)
、DMSO140重量部を加え溶解後、40℃に加熱し
、フレーク状水酸化ナトリウム(純分99%)42重量
部(1.04モル)を100分間かけて添加し、その後
、更に50℃で2時間、70℃で1時間反応させた。
次いで、水洗を繰り返し中性に戻した後、油層からロ
ータリーエバポレーターを使用し加熱減圧下、過剰のエ
ピクロルヒドリンを留去し、残留物に500重量部のメ
チルイソブチルケトンを添加し溶解した。Example 2 Synthesis of epoxy resin Naphthol resin (A) 15 obtained in Example 1 (2)
555 parts by weight (6 moles) of epichlorohydrin per part by weight
, 140 parts by weight of DMSO was added and dissolved, heated to 40°C, 42 parts by weight (1.04 mol) of flaky sodium hydroxide (99% pure) was added over 100 minutes, and then further heated at 50°C for 2 hours. The reaction was carried out at 70° C. for 1 hour.
Next, after returning to neutrality by repeated washing with water, excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure using a rotary evaporator, and 500 parts by weight of methyl isobutyl ketone was added and dissolved in the residue.
【0052】更に、このメチルイソブチルケトンの溶液
を70℃に加熱し30重量%の水酸化ナトリウム水溶液
10重量部を添加し、1時間反応させた後、水洗を繰り
返し行い中性とした。次いで、油層から加熱減圧下メチ
ルイソブチルケトンを留去し、エポキシ樹脂(B)19
0重量部を得た。得られたエポキシ樹脂(B)の150
℃におけるICI粘度は0.9ps、軟化点は70.5
℃、エポキシ当量は212、加水分解性塩素量は250
ppmであった。Further, this methyl isobutyl ketone solution was heated to 70° C., 10 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added, and after reacting for 1 hour, the solution was made neutral by repeated washing with water. Next, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain epoxy resin (B) 19
0 parts by weight were obtained. 150 of the obtained epoxy resin (B)
ICI viscosity at °C is 0.9 ps, softening point is 70.5
°C, epoxy equivalent is 212, hydrolyzable chlorine amount is 250
It was ppm.
【0053】このエポキシ樹脂(B)を液体クロマトグ
ラフィー(GPC、分析条件は上記ナフトール樹脂の分
析と同じ)で分析し、図2に示される分子量分布曲線を
得た。又、2核体と思われるメインピーク成分を分取し
マススペクトル(FAB−MS)により分析したところ
M+ 412が得られたことにより、メインピ−ク成分
は次式(7)で表される2核体であることを確認した。This epoxy resin (B) was analyzed by liquid chromatography (GPC, the analysis conditions were the same as those for the naphthol resin) to obtain the molecular weight distribution curve shown in FIG. 2. In addition, when the main peak component that is thought to be a dinuclear substance was fractionated and analyzed by mass spectrometry (FAB-MS), M+ 412 was obtained, so the main peak component was 2 expressed by the following formula (7). It was confirmed that it was a nuclear body.
【0054】[0054]
【化12】[Chemical formula 12]
【0055】実施例3
(1)ナフトール樹脂メチロール化物の合成温度計、冷
却管、滴下ロート、撹拌器を取り付けたフラスコに実施
例1の(2)で得られたナフトール樹脂(A)151重
量部(1水酸基当量)、20wt%−水酸化ナトリウム
水溶液200重量部(1モル)を仕込み系内を50℃に
加熱し1時間反応させた。次いで系内を5℃に冷却し粒
状パラホルムアルデヒド(純分92%)18重量部(0
.55モル)を添加し5℃で4時間反応させた。反応終
了後、酢酸(純分99%)63重量部を発熱に注意しな
がら滴下し中和した。次いで、エピクロルヒドリン60
0重量部を添加した後、水洗を繰り返し過剰のホルムア
ルデヒドを除去し、その後、油層からロータリーエバポ
レーターを使用し、減圧下、共沸脱水により水分を留去
し除去した。Example 3 (1) Synthesis of methylolated naphthol resin 151 parts by weight of the naphthol resin (A) obtained in (2) of Example 1 was placed in a flask equipped with a thermometer, cooling tube, dropping funnel, and stirrer. (1 hydroxyl group equivalent), 200 parts by weight (1 mol) of a 20 wt % aqueous sodium hydroxide solution was added, the inside of the system was heated to 50° C., and the reaction was carried out for 1 hour. Next, the inside of the system was cooled to 5°C, and 18 parts by weight (0
.. 55 mol) was added and reacted at 5°C for 4 hours. After the reaction was completed, 63 parts by weight of acetic acid (99% pure) was added dropwise to neutralize the mixture while being careful not to generate heat. Then, epichlorohydrin 60
After adding 0 parts by weight, excess formaldehyde was removed by repeated washing with water, and then water was distilled off from the oil layer by azeotropic dehydration under reduced pressure using a rotary evaporator.
【0056】(2)エポキシ樹脂の合成次に、このよう
にして得られたナフトール樹脂メチロール化物[式(1
)においてR1 =H、R2 =H、X=−CH2 O
H]を含むエピクロルヒドリン溶液中にエピクロルヒド
リン350重量部、DMSO210重量部を加えた後、
40℃に加熱し、フレーク状水酸化ナトリウム(純分9
9%)63重量部(1.56モル)を100分間かけて
添加し、その後、更に50℃で2時間、60℃で1時間
反応させた。次いで、水洗を繰り返し中性に戻した後、
油層からロータリーエバポレーターを使用し加熱減圧下
、過剰のエピクロルヒドリンを留去し、残留物に500
重量部のメチルイソブチルケトンを添加し溶解した。(2) Synthesis of epoxy resin Next, the methylolated naphthol resin [formula (1)
), R1=H, R2=H, X=-CH2O
After adding 350 parts by weight of epichlorohydrin and 210 parts by weight of DMSO to an epichlorohydrin solution containing H],
Heat to 40℃ and add flaky sodium hydroxide (purity 9
9%) was added over 100 minutes, and then the reaction was further carried out at 50°C for 2 hours and at 60°C for 1 hour. Next, after repeatedly washing with water to return it to neutrality,
Excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure using a rotary evaporator, and the residue was
Parts by weight of methyl isobutyl ketone were added and dissolved.
【0057】更に、このメチルイソブチルケトンの溶液
を70℃に加熱し30重量%の水酸化ナトリウム水溶液
10重量部を添加し、1時間反応させた後、水洗を繰り
返し行い中性とした。次いで、油層から加熱減圧下メチ
ルイソブチルケトンを留去し、エポキシ樹脂(C)19
0重量部を得た。得られたエポキシ樹脂(C)の150
℃におけるICI粘度は1.2ps、軟化点は64.0
℃、エポキシ当量は188、加水分解性塩素量は420
ppmであった。Further, this methyl isobutyl ketone solution was heated to 70° C., 10 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added, and after reacting for 1 hour, the solution was made neutral by repeated washing with water. Next, methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain epoxy resin (C) 19
0 parts by weight were obtained. 150 of the obtained epoxy resin (C)
ICI viscosity at °C is 1.2 ps, softening point is 64.0
°C, epoxy equivalent is 188, hydrolyzable chlorine amount is 420
It was ppm.
【0058】このエポキシ樹脂(C)を液体クロマトグ
ラフィー(GPC、分析条件は上記ナフトール樹脂の分
析と同じ)で分析し、図3に示される分子量分布曲線を
得た。又、2核体と思われるメインピーク成分を分取し
マススペクトル(FAB−MS)により分析したところ
M+ 498が得られたことによりメインピ−ク成分は
次式(8)で表される2核体であることを確認した。This epoxy resin (C) was analyzed by liquid chromatography (GPC, the analysis conditions were the same as those for the above-mentioned naphthol resin), and the molecular weight distribution curve shown in FIG. 3 was obtained. In addition, when the main peak component that is thought to be a dinuclear substance was fractionated and analyzed by mass spectrometry (FAB-MS), M+ 498 was obtained, so the main peak component was a dinuclear compound expressed by the following formula (8) I confirmed that it was the body.
【0059】[0059]
【化13】[Chemical formula 13]
【0060】応用実施例1〜3、比較例1〜2実施例1
で得られたナフトール樹脂(A)を使用し、又、比較例
1としてビスフェノールA型樹脂(水酸基当量116、
150℃におけるICI粘度0.1ps)を使用し、こ
れら硬化剤100重量部に対してエポキシ樹脂(o−ク
レゾールノボラック形エポキシ樹脂、EOCN−102
0(日本化薬(株)製、エポキシ当量200、150℃
におけるICI粘度3.2ps)及び硬化促進剤(トリ
フェニルホスフィン)を表1に示す使用量で配合し、ト
ランスファー成形により樹脂成形体を調製し表1に示す
硬化条件により硬化させた。Application Examples 1-3, Comparative Examples 1-2 Example 1
In addition, as Comparative Example 1, a bisphenol A type resin (hydroxyl equivalent: 116,
An epoxy resin (o-cresol novolak type epoxy resin, EOCN-102) was used for 100 parts by weight of these curing agents.
0 (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 200, 150°C
(ICI viscosity 3.2 ps) and a curing accelerator (triphenylphosphine) were blended in the amounts shown in Table 1, a resin molded body was prepared by transfer molding, and cured under the curing conditions shown in Table 1.
【0061】更に、実施例2〜3で得られたエポキシ樹
脂(B)、(C)を使用し、又、比較例2としてビスフ
ェノールA型エポキシ樹脂(エポキシ当量189、15
0℃におけるICI粘度0.1ps以下)を使用し、こ
れらエポキシ樹脂150重量部に対して硬化剤(フェノ
ールノボラック樹脂(日本化薬(株)製)PN−80、
150℃におけるICI粘度1.5ps、軟化点86℃
、OH当量106)及び硬化促進剤(トリフェニルフォ
スフィン)を表1に示す使用量で配合し、トランスファ
ー成形により樹脂成形体を調製し表1に示す硬化条件で
硬化させた。Furthermore, the epoxy resins (B) and (C) obtained in Examples 2 to 3 were used, and as Comparative Example 2, bisphenol A type epoxy resins (epoxy equivalents 189, 15
A curing agent (phenol novolac resin (manufactured by Nippon Kayaku Co., Ltd.) PN-80,
ICI viscosity at 150°C 1.5 ps, softening point 86°C
, OH equivalent 106) and a curing accelerator (triphenylphosphine) in the amounts shown in Table 1, a resin molded body was prepared by transfer molding, and cured under the curing conditions shown in Table 1.
【0062】この様にして得られた硬化物の熱変形温度
及び吸水率を測定した結果を表1に示す。尚、熱変形温
度及び吸水率の測定条件は次のとおり。Table 1 shows the results of measuring the heat distortion temperature and water absorption of the cured product thus obtained. The measurement conditions for heat distortion temperature and water absorption rate are as follows.
【0063】
熱変形温度: JIS K7207に規定された条
件吸水率 :試験片(硬化物) 直径
50mm厚さ 3mm
円盤100℃の水中で24時間煮沸した後の重量増加量
(重量%)Heat distortion temperature: Conditions specified in JIS K7207 Water absorption: Test piece (cured product) Diameter
50mm thickness 3mm
Weight increase after boiling the disk in water at 100℃ for 24 hours (weight%)
【0064】[0064]
【0065】[0065]
【発明の効果】本発明のナフトール樹脂、エポキシ樹脂
は、その硬化物において優れた耐熱性及び耐湿性を得る
ことが出来るほか、溶融時の流動性に優れているため、
半導体封止剤として使用する場合に充填物(フィラー)
等の高密度充填が可能となる。又、本発明の製造法によ
れば、ナフトール類の多官能性2核体を高収率でしかも
容易に得ることが出来る。[Effects of the Invention] The naphthol resin and epoxy resin of the present invention not only provide excellent heat resistance and moisture resistance in their cured products, but also have excellent fluidity when melted.
Filler when used as a semiconductor encapsulant
This enables high-density packing such as Furthermore, according to the production method of the present invention, polyfunctional dinuclear bodies of naphthols can be easily obtained in high yield.
【図1】実施例1で得られたナフトール樹脂(A)の分
子量分布曲線[Figure 1] Molecular weight distribution curve of naphthol resin (A) obtained in Example 1
【図2】実施例2で得られたエポキシ樹脂(B)の分子
量分布曲線[Figure 2] Molecular weight distribution curve of epoxy resin (B) obtained in Example 2
【図3】実施例3で得られたエポキシ樹脂(C)の分子
量分布曲線[Figure 3] Molecular weight distribution curve of epoxy resin (C) obtained in Example 3
Claims (5)
ハロゲン原子、炭素数1〜4のアルキル基、又はアリー
ル基を、Xは水素原子又は−CH2 OHを示す。)で
表されるナフト−ル樹脂。Claim 1: Formula (1) [Formula 1] (wherein R1 and R2 are each independently a hydrogen atom,
A halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group, and X represents a hydrogen atom or -CH2OH. ) naphthol resin.
化3】 (式中、R1 、R2 はそれぞれ独立して水素原子、
ハロゲン原子、炭素数1〜4のアルキル基、又はアリー
ル基を示す。)で表される1−ナフト−ル類とを酸触媒
の存在下、脱水縮合反応させ、必要により更にアルカリ
金属水酸化物の存在下、ホルムアルデヒドと反応させる
ことを特徴とする、請求項1記載のナフトール樹脂の製
造法。[Claim 2] A 2-naphthol methylol compound represented by formula (2) [Chemical formula 2] and a 2-naphthol methylol compound represented by formula (3) [
embedded image (wherein R1 and R2 are each independently a hydrogen atom,
It represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group. ) in the presence of an acid catalyst, and if necessary further reacted with formaldehyde in the presence of an alkali metal hydroxide. method for producing naphthol resin.
ハロゲン原子、炭素数1〜4のアルキル基、又はアリー
ル基を、Yは水素原子又は式(5) 【化5】 で示される基を示す。)で表されるエポキシ樹脂。Claim 3: Formula (4) [Image Omitted] (wherein R1 and R2 are each independently a hydrogen atom,
Y represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group, and Y represents a hydrogen atom or a group represented by formula (5). ) Epoxy resin.
促進剤を含むエポキシ樹脂組成物において、(A)エポ
キシ樹脂として、請求項3記載のエポキシ樹脂を含み、
及び/又は、(B)硬化剤として請求項1記載のナフト
ール樹脂を含む、エポキシ樹脂組成物。4. An epoxy resin composition containing an epoxy resin, a curing agent, and optionally a curing accelerator, which contains the epoxy resin according to claim 3 as (A) the epoxy resin;
and/or (B) an epoxy resin composition comprising the naphthol resin according to claim 1 as a curing agent.
物。5. A cured product of the epoxy resin composition according to claim 4.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16744691A JPH04366117A (en) | 1991-06-13 | 1991-06-13 | New resin, production thereof, resin composition, and cured article |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16744691A JPH04366117A (en) | 1991-06-13 | 1991-06-13 | New resin, production thereof, resin composition, and cured article |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04366117A true JPH04366117A (en) | 1992-12-18 |
Family
ID=15849858
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP16744691A Pending JPH04366117A (en) | 1991-06-13 | 1991-06-13 | New resin, production thereof, resin composition, and cured article |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04366117A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006219378A (en) * | 2005-02-08 | 2006-08-24 | Sumitomo Chemical Co Ltd | Epoxy compound and epoxy resin cured product |
JP2012041396A (en) * | 2010-08-16 | 2012-03-01 | Dic Corp | Epoxy resin composition, curable resin composition, its cured product, and printed wiring board |
-
1991
- 1991-06-13 JP JP16744691A patent/JPH04366117A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006219378A (en) * | 2005-02-08 | 2006-08-24 | Sumitomo Chemical Co Ltd | Epoxy compound and epoxy resin cured product |
JP2012041396A (en) * | 2010-08-16 | 2012-03-01 | Dic Corp | Epoxy resin composition, curable resin composition, its cured product, and printed wiring board |
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