JP5911700B2 - Flame retardant epoxy resin, composition containing epoxy resin as essential component, and cured product - Google Patents
Flame retardant epoxy resin, composition containing epoxy resin as essential component, and cured product Download PDFInfo
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- JP5911700B2 JP5911700B2 JP2011247987A JP2011247987A JP5911700B2 JP 5911700 B2 JP5911700 B2 JP 5911700B2 JP 2011247987 A JP2011247987 A JP 2011247987A JP 2011247987 A JP2011247987 A JP 2011247987A JP 5911700 B2 JP5911700 B2 JP 5911700B2
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- JP
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- Prior art keywords
- epoxy resin
- phosphorus
- type epoxy
- molecular weight
- containing 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.)
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- 229920000647 polyepoxide Polymers 0.000 title claims description 192
- 239000003822 epoxy resin Substances 0.000 title claims description 191
- 239000000203 mixture Substances 0.000 title claims description 24
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title description 4
- 239000003063 flame retardant Substances 0.000 title description 4
- 229920003986 novolac Polymers 0.000 claims description 86
- 229910052698 phosphorus Inorganic materials 0.000 claims description 84
- 239000011574 phosphorus Substances 0.000 claims description 81
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 60
- -1 phosphorus compound Chemical class 0.000 claims description 37
- 238000009826 distribution Methods 0.000 claims description 22
- 238000005227 gel permeation chromatography Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- 125000004437 phosphorous atom Chemical group 0.000 claims description 6
- 238000011088 calibration curve Methods 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 119
- 230000015572 biosynthetic process Effects 0.000 description 54
- 238000003786 synthesis reaction Methods 0.000 description 54
- 229910000831 Steel Inorganic materials 0.000 description 40
- 239000010959 steel Substances 0.000 description 40
- 239000004593 Epoxy Substances 0.000 description 31
- 229920005989 resin Polymers 0.000 description 25
- 239000011347 resin Substances 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 19
- 150000002989 phenols Chemical class 0.000 description 19
- 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 16
- 230000000052 comparative effect Effects 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 230000000704 physical effect Effects 0.000 description 13
- 150000001299 aldehydes Chemical class 0.000 description 12
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 12
- 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 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 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 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229930003836 cresol Natural products 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000004843 novolac epoxy resin Substances 0.000 description 8
- 239000005011 phenolic resin Substances 0.000 description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 150000004780 naphthols Chemical class 0.000 description 6
- 229960001755 resorcinol Drugs 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 125000003710 aryl alkyl group Chemical group 0.000 description 5
- JWAZRIHNYRIHIV-UHFFFAOYSA-N beta-hydroxynaphthyl Natural products C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000003607 modifier Substances 0.000 description 5
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 5
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 4
- 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 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 239000012778 molding material Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- 239000003566 sealing material Substances 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 description 2
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 2
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- 239000000539 dimer Substances 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
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- MODAACUAXYPNJH-UHFFFAOYSA-N 1-(methoxymethyl)-4-[4-(methoxymethyl)phenyl]benzene Chemical group C1=CC(COC)=CC=C1C1=CC=C(COC)C=C1 MODAACUAXYPNJH-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5397—Phosphine oxides
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/04—Epoxynovolacs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Description
本発明は、電子回路基板に用いられるプリプレグ、銅張り積層板や電子部品に用いられるフィルム材・封止材・成形材・注型材・接着剤・電気絶縁塗料、難燃性の必要な複合材、粉体塗料などに適したリン含有エポキシ樹脂及び組成物、硬化物に関する。 The present invention relates to a prepreg used for an electronic circuit board, a copper-clad laminate, and a film material / sealing material / molding material / casting material / adhesive / electric insulating paint used for electronic parts, a composite material that requires flame retardancy The present invention relates to a phosphorus-containing epoxy resin and composition suitable for powder coatings, and a cured product.
エポキシ樹脂は接着性、耐熱性、成形性に優れていることから電子部品、電気機器、自動車部品、ＦＲＰ、スポーツ用品など広範囲に使用されており、これらのうち電子部品、電気機器に使用される銅張り積層板や封止材には火災の防止・遅延など安全性の理由から臭素化エポキシ樹脂が使用されていた。 Epoxy resins are widely used in electronic parts, electrical equipment, automotive parts, FRP, sports equipment, etc. because of their excellent adhesiveness, heat resistance, and moldability. Among these, they are used in electronic parts and electrical equipment. Brominated epoxy resins were used for copper-clad laminates and encapsulants for safety reasons such as fire prevention and delay.
臭素に代表されるハロゲンをエポキシ樹脂に導入することにより難燃性が付与され、エポキシ基の高反応性により優れた硬化物が得られている。しかし、燃焼した際にハロゲン化合物などの有害な物質を生成する可能性がありハロゲンを使用しない難燃性付与エポキシ樹脂の要求が高まっている。 By introducing a halogen represented by bromine into an epoxy resin, flame retardancy is imparted, and an excellent cured product is obtained due to the high reactivity of the epoxy group. However, there is a possibility of producing a harmful substance such as a halogen compound when burned, and there is an increasing demand for a flame retardant epoxy resin that does not use halogen.
これに対して、特許文献１ではエポキシ樹脂骨格にリン原子を導入することにより難燃性を付与する方法が開示されている。しかし、この方法では硬化反応に寄与するエポキシ基をリン化合物と反応していることから、硬化した際の架橋密度が低下し、硬化物物性は満足できるものではなかった。このことから特許文献２ではリン化合物とキノン化合物を反応することによってフェノール基を２個持つリン含有化合物とし、エポキシ樹脂との反応によりエポキシ樹脂骨格に導入する方法を開示している。この方法では硬化物物性は飛躍的に向上し、高い品質の銅張り積層板が得られるが、リン化合物とキノン化合物の反応工程を必要とすることから反応時間が長くなり、生産性においては劣っていた。特許文献３には、核体数３〜８に関するノボラック型エポキシ樹脂については記載があるものの、耐熱性と含浸性に関するものであり、難燃性については何らの開示も示唆もなされていない。
On the other hand, Patent Document 1 discloses a method of imparting flame retardancy by introducing phosphorus atoms into the epoxy resin skeleton. However, in this method, since the epoxy group contributing to the curing reaction is reacted with the phosphorus compound, the crosslink density when cured is lowered, and the physical properties of the cured product are not satisfactory. For this reason,
本発明者は、リン含有エポキシ樹脂について鋭意研究を重ねた結果、本発明を完成したものであり、特定の分子量分布を持つノボラック型エポキシ樹脂と特定のリン化合物を反応したリン含有エポキシ樹脂により難燃性を飛躍的に向上することに成功し、且つ、高価なリン化合物の量を低減すると共に特許文献１の利点である生産性を維持しつつ特許文献２に迫る硬化物物性を実現したものである。ノボラック型エポキシ樹脂を構成する二核体成分である二官能エポキシ樹脂は、リン化合物と反応した際にエポキシ基を持たない反応成分を生成するが、本発明で用いるノボラック型エポキシ樹脂は、二核体成分の含有率を低減することでエポキシ基を持たない反応成分の低減が出来、難燃性と物性の向上が可能となったものと考えられる。また、本発明で用いるノボラック型エポキシ樹脂は４核体以上の高分子量成分についても含有率を低減する事ができ、得られるリン含有エポキシ樹脂の難燃性と物性が更に向上するものと考えられる。これは、ノボラック型エポキシ樹脂に含有される４核体以上の高分子量成分にリン化合物が部分的に反応した際には、構造的に嵩高い部分を含むリン含有エポキシ樹脂となり、エポキシ基と硬化剤との反応においては立体障害により著しく硬化反応性を悪化させることが原因となっているのではないかと推測される。本発明は電子回路基板に用いられるプリプレグ、銅張り積層板や電子部品に用いられるフィルム材・封止材・成形材・注型材・接着剤・電気絶縁塗料、難燃性の必要な複合材、粉体塗料などに適し、コストを低減しつつ高品質な難燃性リン含有エポキシ樹脂及び該エポキシ樹脂組成物を提供するものである。
As a result of intensive research on phosphorus-containing epoxy resins, the present inventor has completed the present invention and is difficult to achieve with a phosphorus-containing epoxy resin obtained by reacting a novolac epoxy resin having a specific molecular weight distribution with a specific phosphorus compound. Successful improvement in flammability and reduction of the amount of expensive phosphorus compounds, while maintaining the productivity that is an advantage of Patent Document 1 while achieving the cured product properties approaching
すなわち、本発明は、
（１）ゲルパーミエーションクロマトグラフィーにおける測定において二核体含有率が１５面積％以下、三核体含有率が１５面積％〜６０面積％であり、数平均分子量が３５０〜７００である分子量分布を持つノボラック型エポキシ樹脂（Ａ）と一般式（１）で示されるリン化合物を必須成分として反応せしめて成るリン含有エポキシ樹脂、
（ゲルパーミエーションクロマトグラフィー測定条件）
東ソー株式会社製 ＴＳＫｇｅｌＧ４０００ＨＸＬ、ＴＳＫｇｅｌＧ３０００ＨＸＬ、ＴＳＫｇｅｌＧ２０００ＨＸＬ）を直列に備えたものを使用し、カラム温度は４０℃にした。また、溶離液にはテトラヒドロフランを用い、１ｍｌ／ｍｉｎの流速とし、検出器はＲＩ（示差屈折計）検出器を用いた。標準ポリスチレンによる検量線により数平均分子量を測定する。
That is, the present invention
(1) A molecular weight distribution having a binuclear content of 15 area% or less, a trinuclear content of 15 area% to 60 area%, and a number average molecular weight of 350 to 700 in the measurement by gel permeation chromatography. A phosphorus-containing epoxy resin obtained by reacting a novolac-type epoxy resin (A) having a phosphorus compound represented by the general formula (1) as an essential component;
(Gel permeation chromatography measurement conditions)
Tosoh Corporation TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL) were used in series, and the column temperature was 40 ° C. Tetrahydrofuran was used as the eluent, the flow rate was 1 ml / min, and an RI (differential refractometer) detector was used as the detector. The number average molecular weight is measured with a standard polystyrene calibration curve.
（２）上記（１）記載のリン含有エポキシ樹脂と硬化剤をエポキシ基１個に対して活性基0.3〜1.5個の範囲となるように配合してなるリン含有エポキシ樹脂組成物、
（３）上記（２）記載のリン含有エポキシ樹脂組成物を基材に含浸してなるプリプレグ、（４）上記（２）記載のリン含有エポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物、
（５）上記（２）記載のリン含有エポキシ樹脂組成物を硬化してなる積層板、
である。
(2) A phosphorus-containing epoxy resin composition obtained by blending the phosphorus-containing epoxy resin and the curing agent according to (1) so as to be in the range of 0.3 to 1.5 active groups with respect to one epoxy group,
(3) A prepreg obtained by impregnating a substrate with the phosphorus-containing epoxy resin composition described in (2) above, (4) a cured epoxy resin product obtained by curing the phosphorus-containing epoxy resin composition described in (2) above,
(5) A laminate obtained by curing the phosphorus-containing epoxy resin composition described in (2) above,
It is.
本発明の、特定の分子量分布を持つノボラック型エポキシ樹脂と特定のリン化合物を反応したリン含有エポキシ樹脂は、従来型の分子量分布を持つノボラック型エポキシ樹脂を用いて得られたものと比較して難燃性が飛躍的に向上し、高価なリン含有化合物を低減することが出来、その結果、硬化物物性の向上が可能であり、用いるノボラック型エポキシ樹脂の分子量分布を制御することにより特定の分子量分布とするものであり、良好な難燃性と優れた硬化物物性の両立を図ることが出来たものである。 The phosphorus-containing epoxy resin obtained by reacting a novolak type epoxy resin having a specific molecular weight distribution and a specific phosphorus compound of the present invention is compared with that obtained using a novolak type epoxy resin having a conventional molecular weight distribution. Flame retardancy is dramatically improved and expensive phosphorus-containing compounds can be reduced. As a result, it is possible to improve the physical properties of cured products, and by controlling the molecular weight distribution of the novolak type epoxy resin used The molecular weight distribution is achieved, and both good flame retardancy and excellent cured product properties can be achieved.
本発明について詳細に述べる。
ノボラック型エポキシ樹脂とはフェノール類とアルデヒド類の反応生成物であるノボラック樹脂とエピハロヒドリンとを反応して得られる多官能のノボラック型エポキシ樹脂である。使用されるフェノール類としてはフェノール、クレゾール、エチルフェノール、ブチルフェノール、スチレン化フェノール、クミルフェノール、ナフトール、カテコール、レゾルシノール、ナフタレンジオール、ビスフェノールＡなどが挙げられ、アルデヒド類としてはホルマリン、ホルムアルデヒド、ヒドロキシベンズアルデヒド、サリチルアルデヒドなどが挙げられる。また、アルデヒド類の代わりにキシリレンジメタノール、キシリレンジクロライド、ビスクロロメチルナフタレン、ビスクロロメチルビフェニルなどを用いたアラルキルフェノール樹脂も本発明ではノボラック型フェノール樹脂に含む。これらのノボラック型フェノール樹脂にエピハロヒドリンを用いてエポキシ化することでノボラック型エポキシ樹脂が得られる。
The present invention will be described in detail.
The novolak-type epoxy resin is a polyfunctional novolak-type epoxy resin obtained by reacting a novolak resin, which is a reaction product of phenols and aldehydes, with epihalohydrin. Examples of phenols used include phenol, cresol, ethylphenol, butylphenol, styrenated phenol, cumylphenol, naphthol, catechol, resorcinol, naphthalenediol, and bisphenol A. Examples of aldehydes include formalin, formaldehyde, and hydroxybenzaldehyde. And salicylaldehyde. In the present invention, an aralkylphenol resin using xylylenediethanol, xylylenedichloride, bischloromethylnaphthalene, bischloromethylbiphenyl or the like instead of aldehydes is also included in the present invention. Epoxylation of these novolac type phenolic resins with epihalohydrin yields novolac type epoxy resins.
ノボラック型エポキシ樹脂の具体例としては、エポトートＹＤＰＮ−６３８（新日鐵化学株式会社製 フェノールノボラック型エポキシ樹脂）、エピコート１５２、エピコート１５４（三菱化学株式会社製 フェノールノボラック型エポキシ樹脂）、エピクロンＮ−７４０、エピクロンＮ−７７０、エピクロンＮ−７７５（ＤＩＣ株式会社製 フェノールノボラック型エポキシ樹脂）、エポトートＹＤＣＮ−７００シリーズ（新日鐵化学株式会社製 クレゾールノボラック型エポキシ樹脂）、エピクロンＮ−６６０、エピクロンＮ−６６５、エピクロンＮ−６７０、エピクロンＮ−６７３、エピクロンＮ−６９５（ＤＩＣ株式会社製 クレゾールノボラック型エポキシ樹脂）、ＥＯＣＮ−１０２０、ＥＯＣＮ−１０２Ｓ、ＥＯＣＮ−１０４Ｓ（日本化薬株式会社製 クレゾールノボラック型エポキシ樹脂）、エポトートＺＸ−１０７１Ｔ、ＺＸ−１２７０、ＺＸ−１３４２（新日鐵化学株式会社製 アルキルノボラック型エポキシ樹脂）、エポトートＺＸ−１２４７、ＧＫ−５８５５（新日鐵化学株式会社製 スチレン化フェノールノボラック型エポキシ樹脂）、エポトートＺＸ−１１４２Ｌ（新日鐵化学株式会社製 ナフトールノボラック型エポキシ樹脂）、ＥＳＮ−１５５、ＥＳＮ−１８５Ｖ、ＥＳＮ−１７５（新日鐵化学株式会社製 βナフトールアラルキル型エポキシ樹脂）、ＥＳＮ−３００シリーズのＥＳＮ−３５５、ＥＳＮ−３７５（新日鐵化学株式会社製 ジナフトールアラルキル型エポキシ樹脂）、ＥＳＮ−４００シリーズのＥＳＮ−４７５Ｖ、ＥＳＮ−４８５（新日鐵化学株式会社製 αナフトールアラルキル型エポキシ樹脂）ビスフェノールノボラック型エポキシ樹脂等が挙げられるが、これらのエポキシ樹脂は本発明における特定の分子量分布を持っていない。 Specific examples of the novolac type epoxy resin include Epototo YDPN-638 (Phenol novolac type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epicoat 152, Epicoat 154 (Phenol novolac type epoxy resin manufactured by Mitsubishi Chemical Corporation), Epicron N- 740, Epicron N-770, Epicron N-775 (phenol novolac type epoxy resin manufactured by DIC Corporation), Epotot YDCN-700 series (Cresol novolac type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epicron N-660, Epicron N -665, Epicron N-670, Epicron N-673, Epicron N-695 (a cresol novolac epoxy resin manufactured by DIC Corporation), EOCN-1020, EOCN-102S, EOCN-104S (Japan) Cresol novolac type epoxy resin manufactured by Honka Pharmaceutical Co., Ltd., Epototo ZX-1071T, ZX-1270, ZX-1342 (alkyl novolak type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo ZX-1247, GK-5855 (new) Styrene phenol novolak type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo ZX-1142L (Naphthol novolak type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), ESN-155, ESN-185V, ESN-175 (Nippon Steel Chemical Co., Ltd.) Β-naphthol aralkyl type epoxy resin manufactured by Co., Ltd.), ESN-355 series ESN-355, ESN-375 (manufactured by Nippon Steel Chemical Co., Ltd., dinaphthol aralkyl type epoxy resin), ESN-400 series ESN-475V, ESN- 485 (Sunshine Although α-naphthol aralkyl type epoxy resin) of bisphenol novolak epoxy resin Co., Ltd. and the like, these epoxy resins does not have a particular molecular weight distribution in the present invention.
本発明で用いる特定の分子量分布を持つノボラック型エポキシ樹脂を得るには、フェノール類とアルデヒド類のモル比を調整することにより得られた粗フェノールノボラック樹脂から低分子量成分を除去することによって得たフェノールノボラック樹脂、または特許文献４、特許文献５に示すような製造方法により得られたフェノールノボラック樹脂をエポキシ化しても良い。
In order to obtain a novolac type epoxy resin having a specific molecular weight distribution used in the present invention, it was obtained by removing low molecular weight components from a crude phenol novolac resin obtained by adjusting the molar ratio of phenols and aldehydes. You may epoxidize a phenol novolak resin or the phenol novolak resin obtained by the manufacturing method as shown to patent document 4, the
フェノール類とアルデヒド類のモル比はアルデヒド類１モルに対するフェノール類のモル比で示され１以上の比率で製造されるが、モル比が大きい場合は二核体、三核体が多く生成され、モル比が小さい場合は高分子量体が多く生成し、二核体、三核体は少なくなる。 The molar ratio of phenols and aldehydes is indicated by the molar ratio of phenols to 1 mole of aldehydes, and is produced at a ratio of 1 or more. When the molar ratio is large, a large amount of dinuclear and trinuclear bodies are produced, When the molar ratio is small, a large amount of high molecular weight is formed, and dinuclear and trinuclear bodies are decreased.
本発明で用いる特定の分子量分布を持つノボラック型エポキシ樹脂は、得られた粗フェノールノボラック樹脂類から二核体成分及び／又は四核体成分を各種溶媒の溶解性差を利用して除去する方法、アルカリ水溶液に二核体を溶解して除去する方法などによって得ることが出来きるが、その他の公知の分離方法によっても良い。 The novolak-type epoxy resin having a specific molecular weight distribution used in the present invention is a method for removing dinuclear components and / or tetranuclear components from the obtained crude phenol novolac resins by utilizing the solubility difference of various solvents, Although it can be obtained by a method of dissolving and removing the dinuclear body in an aqueous alkali solution, it may be obtained by other known separation methods.
分子量を制御したフェノール樹脂に公知のエポキシ化の手法を用いて特定の分子量分布を持つノボラック型エポキシ樹脂を得ることが出来る。あるいは市販のノボラック型エポキシ樹脂から二核体エポキシ樹脂成分を各種方法により除去することによっても特定の分子量分布を持つノボラック型エポキシ樹脂を得ることが出来る。その他公知の分離方法によっても良い。 A novolak type epoxy resin having a specific molecular weight distribution can be obtained by using a known epoxidation technique for a phenol resin having a controlled molecular weight. Alternatively, a novolac type epoxy resin having a specific molecular weight distribution can also be obtained by removing a dinuclear epoxy resin component from a commercially available novolak type epoxy resin by various methods. Other known separation methods may also be used.
本発明の特定の分子量分布を持つノボラック型エポキシ樹脂は、二核体含有率が１５面積％以下、好ましくは５面積％〜１２面積％が好ましい。少量の二核体が含有することで、接着力などの物性を向上することが出来る。三核体含有率は１５面積％〜６０面積％であり、好ましくは２０面積％〜５０面積％が好ましい。数平均分子量は３５０〜７００、好ましくは３８０〜６００が好ましい。分子量分散度（重量平均分子量／数平均分子量）は１．１〜２．８のものが使用することができ、好ましい範囲は１．２〜２．５、より好ましくは１．２〜２．３であり、１．１未満では接着性などの物性に劣り、２．８を超える場合は難燃性や耐熱性などが低下する恐れがある。 The novolak type epoxy resin having a specific molecular weight distribution of the present invention has a binuclear content of 15 area% or less, preferably 5 area% to 12 area%. By containing a small amount of the binuclear body, physical properties such as adhesive strength can be improved. The trinuclear content is 15 area% to 60 area%, preferably 20 area% to 50 area%. The number average molecular weight is 350 to 700, preferably 380 to 600. A molecular weight dispersity (weight average molecular weight / number average molecular weight) of 1.1 to 2.8 can be used, and a preferable range is 1.2 to 2.5, and more preferably 1.2 to 2.3. If it is less than 1.1, the physical properties such as adhesiveness are inferior, and if it exceeds 2.8, flame retardancy and heat resistance may decrease.
一般式（１）で示されるリン化合物の具体例としてはジメチルホスフィン、ジエチルホスフィン、ジフェニルホスフィン、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド（ＨＣＡ 三光化学株式会社製）、ジメチルホスフィンオキサイド、ジエチルホスフィンオキサイド、ジブチルホスフィンオキサイド、ジフェニルホスフィンオキサイド、１，４−シクロオクチレンホスフィンオキサイド、１，５−シクロオクチレンホスフィンオキサイド（ＣＰＨＯ 日本化学工業株式会社製）が挙げられる。これらのリン化合物は単独でも２種類以上混合して使用しても良く、これらに限定されるものではない。 Specific examples of the phosphorus compound represented by the general formula (1) include dimethylphosphine, diethylphosphine, diphenylphosphine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA Sanko Chemical Co., Ltd.) ), Dimethylphosphine oxide, diethylphosphine oxide, dibutylphosphine oxide, diphenylphosphine oxide, 1,4-cyclooctylenephosphine oxide, 1,5-cyclooctylenephosphine oxide (CPHO manufactured by Nippon Chemical Industry Co., Ltd.). These phosphorus compounds may be used alone or in combination of two or more, and are not limited thereto.
一般式（１）で示されるリン化合物と特定の分子量分布を持つノボラック型エポキシ樹脂を反応させる方法としては公知の方法で行うことが可能である。反応温度として１００℃〜２００℃、より好ましくは１２０℃〜１８０℃で攪拌下、反応を行う。一般式（１）で示されるリン化合物のリン原子に直結した活性水素と、エポキシ樹脂のエポキシ基が反応する。反応終点はエポキシ当量の追跡により理論エポキシ当量の９９％以上の値になったことで確認する。又は、エポキシ樹脂の酸価として一般式（１）で示されるリン化合物の残存量を追跡し、反応終点を確認する方法や液体クロマトグラフィ−等で代表される機器分析により残存する一般式（１）で示されるリン化合物を追跡する方法などがある。いずれの方法をとっても良いが、エポキシ樹脂と一般式（１）で示されるリン化合物を十分に反応させることが必要である。反応速度を考慮して必要に応じて触媒を使用する。具体的にはベンジルジメチルアミン等の第３級アミン類、テトラメチルアンモニウムクロライド等の第４級アンモニウム塩類、トリフェニルホスフィン、トリス（２，６−ジメトキシフェニル）ホスフィン等のホスフィン類、エチルトリフェニルホスホニウムブロマイド等のホスホニウム塩類、２−メチルイミダゾール、２−エチル４メチルイミダゾール等のイミダゾール類等各種触媒が使用できる。 As a method of reacting the phosphorus compound represented by the general formula (1) with a novolac type epoxy resin having a specific molecular weight distribution, it can be performed by a known method. The reaction is performed at 100 to 200 ° C., more preferably 120 to 180 ° C. with stirring as the reaction temperature. The active hydrogen directly bonded to the phosphorus atom of the phosphorus compound represented by the general formula (1) reacts with the epoxy group of the epoxy resin. The end point of the reaction is confirmed by tracking the epoxy equivalent and reaching a value of 99% or more of the theoretical epoxy equivalent. Alternatively, the remaining general amount of the phosphorus compound represented by the general formula (1) as the acid value of the epoxy resin is traced, and the general formula (1) remaining by the method of confirming the reaction end point or the instrumental analysis represented by liquid chromatography or the like There is a method of tracking the phosphorus compound represented by Any method may be used, but it is necessary to sufficiently react the epoxy resin and the phosphorus compound represented by the general formula (1). A catalyst is used as necessary in consideration of the reaction rate. Specifically, tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, ethyltriphenylphosphonium Various catalysts such as phosphonium salts such as bromide and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole can be used.
一般式（１）で示されるリン化合物と特定の分子量分布を持つノボラック型エポキシ樹脂を反応する際に、必要に応じて本発明の特性を損なわない程度で各種エポキシ樹脂変性剤を併用しても良い。変性剤としてはビスフェノールＡ、ビスフェノールＦ、ビスフェノールＡＤ、テトラブチルビスフェノールＡ、ハイドロキノン、メチルハイドロキノン、ジメチルハイドロキノン、ジブチルハイドロキノン、レゾルシン、メチルレゾルシン、ビフェノール、テトラメチルビフェノール、ジヒドロキシナフタレン、ジヒドロキシジフェニルエーテル、ジヒドロキシスチルベン類、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールＡノボラック樹脂、ジシクロペンタジエンフェノール樹脂、フェノールアラルキル樹脂、ナフトールノボラック樹脂、テルペンフェノール樹脂、重質油変性フェノール樹脂、臭素化フェノールノボラック樹脂などの種々のフェノール類や、種々のフェノール類と、ヒドロキシベンズアルデヒド、クロトンアルデヒド、グリオキザールなどの種々のアルデヒド類との縮合反応で得られる多価フェノール樹脂や、アニリン、フェニレンジアミン、トルイジン、キシリジン、ジエチルトルエンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルエタン、ジアミノジフェニルプロパン、ジアミノジフェニルケトン、ジアミノジフェニルスルフィド、ジアミノジフェニルスルホン、ビス（アミノフェニル）フルオレン、ジアミノジエチルジメチルジフェニルメタン、ジアミノジフェニルエーテル、ジアミノベンズアニリド、ジアミノビフェニル、ジメチルジアミノビフェニル、ビフェニルテトラアミン、ビスアミノフェニルアントラセン、ビスアミノフェノキシベンゼン、ビスアミノフェノキシフェニルエーテル、ビスアミノフェノキシビフェニル、ビスアミノフェノキシフェニルスルホン、ビスアミノフェノキシフェニルプロパン、ジアミノナフタレン等のアミン化合物が挙げられるがこれらに限定されるものではなく２種類以上併用しても良い。 When reacting the phosphorus compound represented by the general formula (1) with the novolak-type epoxy resin having a specific molecular weight distribution, various epoxy resin modifiers may be used together as long as they do not impair the characteristics of the present invention. good. Examples of the modifier include bisphenol A, bisphenol F, bisphenol AD, tetrabutyl bisphenol A, hydroquinone, methyl hydroquinone, dimethyl hydroquinone, dibutyl hydroquinone, resorcin, methyl resorcin, biphenol, tetramethyl biphenol, dihydroxy naphthalene, dihydroxy diphenyl ether, dihydroxy stilbene, Various phenols such as phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, dicyclopentadiene phenol resin, phenol aralkyl resin, naphthol novolak resin, terpene phenol resin, heavy oil modified phenol resin, brominated phenol novolak resin, , Various phenols and hydroxybenzaldehyde Polyhydric phenol resin obtained by condensation reaction with various aldehydes such as crotonaldehyde, glyoxal, aniline, phenylenediamine, toluidine, xylidine, diethyltoluenediamine, diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenylpropane, diaminodiphenyl ketone , Diaminodiphenyl sulfide, diaminodiphenyl sulfone, bis (aminophenyl) fluorene, diaminodiethyldimethyldiphenylmethane, diaminodiphenyl ether, diaminobenzanilide, diaminobiphenyl, dimethyldiaminobiphenyl, biphenyltetraamine, bisaminophenylanthracene, bisaminophenoxybenzene, bis Aminophenoxyphenyl ether, bisaminophenoxy Biphenyl, bis aminophenoxy phenyl sulfone, bis aminophenoxy phenyl propane, an amine compound such as diamino naphthalene may be used in combination of two or more kinds is not limited thereto.
一般式（１）で示されるリン化合物と特定の分子量分布を持つノボラック型エポキシ樹脂を反応する際に、必要に応じて各種エポキシ樹脂を本発明の特性を損なわない程度に使用することもできる。具体的にはエポトート ＹＤＣ−１３１２、ＺＸ−１０２７（新日鐵化学株式会社製 ハイドロキノン型エポキシ樹脂）、ＹＸ−４０００（三菱化学株式会社製）ＺＸ−１２５１（新日鐵化学株式会社製 ビフェノール型エポキシ樹脂）、エポトート ＹＤ−１２７、エポトート ＹＤ−１２８、エポトート ＹＤ−８１２５、エポトート ＹＤ−８２５ＧＳ、エポトート ＹＤ−０１１、エポトート ＹＤ−９００、エポトート ＹＤ−９０１（新日鐵化学株式会社製 ＢＰＡ型エポキシ樹脂）、エポトート ＹＤＦ−１７０、エポトート ＹＤＦ−８１７０、エポトート ＹＤＦ−８７０ＧＳ、エポトート ＹＤＦ−２００１（新日鐵化学株式会社製 ＢＰＦ型エポキシ樹脂）、エポトート ＹＤＰＮ−６３８（新日鐵化学株式会社製 フェノールノボラック型エポキシ樹脂）、エポトート ＹＤＣＮ−７０１（新日鐵化学株式会社製 クレゾールノボラック型エポキシ樹脂）、ＺＸ−１２０１（新日鐵化学株式会社製 ビスフェノールフルオレン型エポキシ樹脂）、ＮＣ−３０００（日本化薬株式会社製 ビフェニルアラルキルフェノール型エポキシ樹脂）、ＥＰＰＮ−５０１Ｈ、ＥＰＰＮ−５０２Ｈ（日本化薬株式会社製 多官能エポキシ樹脂）ＺＸ−１３５５（新日鐵化学株式会社製 ナフタレンジオール型エポキシ樹脂）、ＥＳＮ−１５５、ＥＳＮ−１８５Ｖ、ＥＳＮ−１７５（新日鐵化学株式会社製 βナフトールアラルキル型エポキシ樹脂）、ＥＳＮ−３５５、ＥＳＮ−３７５（新日鐵化学株式会社製 ジナフトールアラルキル型エポキシ樹脂）、ＥＳＮ−４７５Ｖ、ＥＳＮ−４８５（新日鐵化学株式会社製 αナフトールアラルキル型エポキシ樹脂）等の多価フェノール樹脂等のフェノール化合物と、エピハロヒドリンとから製造されるエポキシ樹脂、エポトート ＹＨ−４３４、エポトート ＹＨ−４３４ＧＳ（新日鐵化学株式会社製 ジアミノジフェニルメタンテトラグリシジルエーテル）等のアミン化合物と、エピハロヒドリンとから製造されるエポキシ樹脂、ＹＤ−１７１（新日鐵化学株式会社製 ダイマー酸型エポキシ樹脂）等のカルボン酸類と、エピハロヒドリンとから製造される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く２種類以上併用しても良い。 When reacting the phosphorus compound represented by the general formula (1) with a novolac type epoxy resin having a specific molecular weight distribution, various epoxy resins can be used as long as they do not impair the characteristics of the present invention. Specifically, Epototo YDC-1312, ZX-1027 (hydroquinone type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), YX-4000 (manufactured by Mitsubishi Chemical Corporation) ZX-1251 (biphenol type epoxy manufactured by Nippon Steel Chemical Co., Ltd.) Resin), Epototo YD-127, Epototo YD-128, Epototo YD-8125, Epototo YD-825GS, Epototo YD-011, Epototo YD-900, Epototo YD-901 (BPA type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) , Epototo YDF-170, Epototo YDF-8170, Epototo YDF-870GS, Epototo YDF-2001 (BPF type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo YDPN-638 (Phenolno manufactured by Nippon Steel Chemical Co., Ltd.) Rack type epoxy resin), Epototo YDCN-701 (Cresol novolac type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), ZX-1201 (Bisphenol fluorene type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), NC-3000 (Nippon Kayaku) Biphenylaralkylphenol type epoxy resin manufactured by Co., Ltd.), EPPN-501H, EPPN-502H (polyfunctional epoxy resin manufactured by Nippon Kayaku Co., Ltd.) ZX-1355 (Naphthalenediol type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), ESN- 155, ESN-185V, ESN-175 (β-naphthol aralkyl type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), ESN-355, ESN-375 (manufactured by Nippon Steel Chemical Co., Ltd., dinaphthol aralkyl type epoxy resin), ESN- 475V, ESN-485 Epoxy resins produced from phenolic compounds such as polyphenolic resins such as α-naphthol aralkyl epoxy resin manufactured by Nippon Steel Chemical Co., Ltd. and epihalohydrin, Epototo YH-434, Epototo YH-434GS (Nippon Steel Chemical Co., Ltd.) Manufactured from an epoxy compound produced from an amine compound such as diaminodiphenylmethane tetraglycidyl ether) and epihalohydrin, a carboxylic acid such as YD-171 (a dimer acid type epoxy resin produced by Nippon Steel Chemical Co., Ltd.), and an epihalohydrin However, it is not limited to these, and two or more types may be used in combination.
本発明のリン含有エポキシ樹脂組成物は特定の分子量分布を持つノボラック型エポキシ樹脂を用いたリン含有エポキシ樹脂を必須成分とし、硬化剤としては、各種フェノール樹脂類や酸無水物類、アミン類、ヒドラジッド類、酸性ポリエステル類等の通常使用されるエポキシ樹脂用硬化剤を使用することができ、これらの硬化剤は１種類だけ使用しても２種類以上使用しても良い。 The phosphorus-containing epoxy resin composition of the present invention has a phosphorus-containing epoxy resin using a novolac-type epoxy resin having a specific molecular weight distribution as an essential component, and as a curing agent, various phenol resins, acid anhydrides, amines, Commonly used curing agents for epoxy resins such as hydrazides and acidic polyesters can be used, and these curing agents may be used alone or in combination of two or more.
前述の硬化剤としてのフェノール樹脂類の具体例としては、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＣ、ビスフェノールＫ、ビスフェノールＺ、ビスフェノールＳ、テトラメチルビスフェノールＡ、テトラメチルビスフェノールＦ、テトラメチルビスフェノールＳ、テトラメチルビスフェノールＺ、ジヒドロキシジフェニルスルフィド、４，４’−チオビス（３−メチル−６−ｔｅｒｔ−ブチルフェノール）等のビスフェノール類、また、カテコール、レゾルシン、メチルレゾルシン、ハイドロキノン、モノメチルハイドロキノン、ジメチルハイドロキノン、トリメチルハイドロキノン、モノ−ｔｅｒｔ−ブチルハイドロキノン、ジ−ｔｅｒｔ−ブチルハイドロキノン等ジヒドロキシベンゼン類、ジヒドロキシナフタレン、ジヒドロキシメチルナフタレン、ジヒドロキシメチルナフタレン、トリヒドロキシナフタレン等ヒドロキシナフタレン類、フェノールノボラック樹脂、ＤＣ−５（新日鐵化学株式会社製 クレゾールノボラック樹脂）、ナフトールノボラック樹脂などのフェノール類及び／又はナフトール類とアルデヒド類との縮合物、ＳＮ−１６０、ＳＮ−３９５、ＳＮ−４８５（新日鐵化学株式会社製）等のフェノール類及び／又はナフトール類とキシリレングリコールとの縮合物、フェノール類及び／又はナフトール類とイソプロペニルアセトフェノンとの縮合物、フェノール類及び／又はナフトール類とジシクロペンタジエンとの反応物、フェノール類及び／又はナフトール類とビフェニル系縮合剤との縮合物等のフェノール化合物等が例示される。 Specific examples of the above-mentioned phenol resins as the curing agent include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethyl. Bisphenols such as bisphenol Z, dihydroxydiphenyl sulfide, 4,4′-thiobis (3-methyl-6-tert-butylphenol), catechol, resorcin, methylresorcin, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono -Dihydroxybenzenes such as tert-butylhydroquinone and di-tert-butylhydroquinone, dihydroxynaphthalene, di Hydroxylnaphthalenes such as droxymethylnaphthalene, dihydroxymethylnaphthalene, trihydroxynaphthalene, phenol novolac resin, DC-5 (Cresol novolak resin manufactured by Nippon Steel Chemical Co., Ltd.), phenols such as naphthol novolak resin, and / or naphthols Condensates with aldehydes, phenols such as SN-160, SN-395, SN-485 (manufactured by Nippon Steel Chemical Co., Ltd.) and / or condensates of naphthols and xylylene glycol, phenols and / or Examples include phenol compounds such as condensates of naphthols with isopropenyl acetophenone, phenols and / or reaction products of naphthols with dicyclopentadiene, phenols and / or condensates of naphthols with biphenyl condensing agents, etc. Is done.
上記の、フェノール類としては、フェノール、クレゾール、キシレノール、ブチルフェノール、アミルフェノール、ノニルフェノール、ブチルメチルフェノール、トリメチルフェノール、フェニルフェノール等が挙げられ、ナフトール類としては、１−ナフトール、２−ナフトール等が挙げられる。 Examples of the phenols include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol, and phenylphenol. Examples of naphthols include 1-naphthol and 2-naphthol. It is done.
アルデヒド類としては、ホルムアルデヒド、アセトアルデヒド、プロピルアルデヒド、ブチルアルデヒド、バレルアルデヒド、カプロンアルデヒド、ベンズアルデヒド、クロルアルデヒド、ブロムアルデヒド、グリオキザール、マロンアルデヒド、スクシンアルデヒド、グルタルアルデヒド、アジピンアルデヒド、ピメリンアルデヒド、セバシンアルデヒド、アクロレイン、クロトンアルデヒド、サリチルアルデヒド、フタルアルデヒド、ヒドロキシベンズアルデヒド等が例示される。ビフェニル系縮合剤としてビス（メチロール）ビフェニル、ビス（メトキシメチル）ビフェニル、ビス（エトキシメチル）ビフェニル、ビス（クロロメチル）ビフェニル等が例示される。 Aldehydes include formaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chloraldehyde, bromaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipine aldehyde, pimelin aldehyde, sebacin aldehyde And acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde and the like. Examples of the biphenyl condensing agent include bis (methylol) biphenyl, bis (methoxymethyl) biphenyl, bis (ethoxymethyl) biphenyl, and bis (chloromethyl) biphenyl.
硬化剤としての酸無水物類の具体例としては、メチルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、無水ピロメリット酸、無水フタル酸、無水トリメリット酸、メチルナジック酸等の酸無水物類等が例示される。 Specific examples of acid anhydrides as curing agents include acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, phthalic anhydride, trimellitic anhydride, and methylnadic acid. Illustrated.
硬化剤としてのアミン類の具体例としては、ジエチレントリアミン、トリエチレンテトラミン、メタキシレンジアミン、イソホロンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルフォン、ジアミノジフェニルエーテル、ジシアンジアミド、ダイマー酸等の酸類とポリアミン類との縮合物であるポリアミドアミン等のアミン系化合物等が挙げられる。 Specific examples of amines as curing agents include condensates of acids such as diethylenetriamine, triethylenetetramine, metaxylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, dicyandiamide, and dimer acid with polyamines. Examples thereof include amine compounds such as certain polyamide amines.
また、本発明の特性を損なわない範囲で本発明のリン含有エポキシ樹脂以外のエポキシ樹脂を配合しても良く、具体的にはエポトート ＹＤ−１２８、エポトート ＹＤ−８１２５（新日鐵化学株式会社製 ＢＰＡ型エポキシ樹脂）、エポトート ＹＤＦ−１７０、エポトート ＹＤＦ−８１７０（新日鐵化学株式会社製 ＢＰＦ型エポキシ樹脂）、ＹＳＬＶ−８０ＸＹ（新日鐵化学株式会社製 テトラメチルビスフェノールＦ型エポキシ樹脂）、エポトート ＹＤＣ−１３１２（ヒドロキノン型エポキシ樹脂）、ｊＥＲ ＹＸ４０００Ｈ（三菱化学株式会社製 ビフェニル型エポキシ樹脂）、エポトート ＹＤＰＮ―６３８（新日鐵株式会社製 フェノールノボラック型エポキシ樹脂）、エポトート ＹＤＣＮ−７０１（新日鐵化学株式会社製 クレゾールノボラック型エポキシ樹脂）、エポトート ＺＸ−１２０１（新日鐵化学株式会社製 ビスフェノールフルオレン型エポキシ樹脂）、ＴＸ−０７１０（新日鐵化学株式会社製 ビスフェノールＳ型エポキシ樹脂）、エピクロン ＥＸＡ−１５１５（大日本化学工業株式会社製 ビスフェノールＳ型エポキシ樹脂）、ＮＣ−３０００（日本化薬株式会社製 ビフェニルアラルキルフェノール型エポキシ樹脂）、エポトート ＺＸ−１３５５、エポトート ＺＸ−１７１１（新日鐵化学株式会社製 ナフタレンジオール型エポキシ樹脂）、エポトート ＥＳＮ−１５５（新日鐵化学株式会社製 β−ナフトールアラルキル型エポキシ樹脂）、エポトート ＥＳＮ−３５５、エポトート ＥＳＮ−３７５（新日鐵化学株式会社製 ジナフトールアラルキル型エポキシ樹脂）、エポトート ＥＳＮ４７５Ｖ，エポトート ＥＳＮ−４８５（新日鐵化学株式会社製 α−ナルトールアラルキル型エポキシ樹脂）、ＥＰＰＮ−５０１Ｈ（日本化薬株式会社製 トリスフェニルメタン型エポキシ樹脂）、スミエポキシ ＴＭＨ−５７４（住友化学株式会社製 トリスフェニルメタン型エポキシ樹脂）等の多価フェノール樹脂のフェノール化合物とエピハロヒドリンとから製造されるエポキシ樹脂、エポトート ＹＨ−４３４、（新日鐵化学株式会社製 ジアミノジフェニルメタンテトラグリシジルアミン）等のアミン化合物とエピハロヒドリンとから製造されるエポキシ樹脂、ｊＥＲ ６３０（三菱化学株式会社製 アミノフェノール型エポキシ樹脂）、エポトート ＦＸ−２８９Ｂ、エポトート ＦＸ−３０５、ＴＸ−０９３２Ａ（新日鐵化学株式会社製 リン含有エポキシ樹脂）等のエポキシ樹脂をリン含有フェノール化合物等の変性剤と反応して得られるリン含有エポキシ樹脂、ＹＳＬＶ−１２０ＴＥ（新日鐵化学株式会社製 ビスチオエーテル型エポキシ樹脂）、エポトート ＺＸ−１６８４（新日鐵化学株式会社製 レゾルシノール型エポキシ樹脂）、デナコール ＥＸ−２０１（ナガセケムテックス株式会社製 レゾルシノール型エポキシ樹脂）、エピクロン ＨＰ−７２００Ｈ（ＤＩＣ株式会社製 ジシクロペンタジエン型エポキシ樹脂）、ウレタン変性エポキシ樹脂、オキサゾリドン環含有エポキシ樹脂、ＴＸ−０９２９、ＴＸ−０９３４（新日鐵化学株式会社製 アルキレングリコール型エポキシ樹脂）等が挙げられる。 In addition, an epoxy resin other than the phosphorus-containing epoxy resin of the present invention may be blended within a range not impairing the characteristics of the present invention. Specifically, Epototo YD-128, Epototo YD-8125 (manufactured by Nippon Steel Chemical Co., Ltd.) BPA type epoxy resin), Epototo YDF-170, Epototo YDF-8170 (BPF type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), YSLV-80XY (Tetramethylbisphenol F type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo YDC-1312 (hydroquinone type epoxy resin), jER YX4000H (biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation), Epototo YDPN-638 (Phenol novolac type epoxy resin manufactured by Nippon Steel Corporation), Epototo YDCN-701 (New Nippon Steel) Kure Co., Ltd. Zole novolac type epoxy resin), Epototo ZX-1201 (Bisphenol fluorene type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), TX-0710 (Bisphenol S type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epicron EXA-1515 (Large) Nippon Chemical Industry Co., Ltd. bisphenol S type epoxy resin), NC-3000 (Nippon Kayaku Co., Ltd. biphenyl aralkyl phenol type epoxy resin), Epototo ZX-1355, Epototo ZX-1711 (Nippon Chemical Co., Ltd. Naphthalenediol) Type epoxy resin), Epototo ESN-155 (β-naphthol aralkyl type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Epototo ESN-355, Epototo ESN-375 (manufactured by Nippon Steel Chemical Co., Ltd., dinaphthol aralkyl) Type epoxy resin), Epototo ESN475V, Epototo ESN-485 (alpha-nartol aralkyl type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), EPPN-501H (Nippon Kayaku Co., Ltd. trisphenylmethane type epoxy resin), Sumiepoxy TMH Epoxy resin produced from a phenolic compound of a polyhydric phenol resin such as -574 (Sumitomo Chemical Co., Ltd. trisphenyl methane type epoxy resin) and epihalohydrin, Epototo YH-434 (Diaminodiphenylmethane tetra produced by Nippon Steel Chemical Co., Ltd.) An epoxy resin produced from an amine compound such as glycidylamine) and an epihalohydrin, jER 630 (an aminophenol-type epoxy resin manufactured by Mitsubishi Chemical Corporation), epototo FX-289B, epototo FX-305 , A phosphorous-containing epoxy resin obtained by reacting an epoxy resin such as TX-0932A (phosphorus-containing epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.) with a modifier such as a phosphorus-containing phenol compound, YSLV-120TE (Nippon Steel Chemical Co., Ltd.) Company bisthioether epoxy resin), Epototo ZX-1684 (Resorcinol epoxy resin manufactured by Nippon Steel Chemical Co., Ltd.), Denacol EX-201 (Resorcinol epoxy resin manufactured by Nagase ChemteX Corporation), Epiklon HP-7200H (DIC) Dicyclopentadiene type epoxy resin manufactured by Co., Ltd.), urethane-modified epoxy resin, oxazolidone ring-containing epoxy resin, TX-0929, TX-0934 (Nippon Steel Chemical Co., Ltd. alkylene glycol type epoxy resin) and the like.
本発明のエポキシ樹脂組成物のリン含有率は０．８％〜７％、好ましくは１％〜６％、より好ましくは１．５％〜４％の範囲であることが望ましい。０．８％よりも少ないと難燃性が得られず、７％よりも多いと耐熱性が低くなり、吸湿性が高くなるなど物性が悪くなる。 The phosphorus content of the epoxy resin composition of the present invention is desirably 0.8% to 7%, preferably 1% to 6%, more preferably 1.5% to 4%. If it is less than 0.8%, flame retardancy cannot be obtained, and if it is more than 7%, the heat resistance is lowered and the hygroscopic property is increased, resulting in poor physical properties.
本発明組成物には必要に応じて第３級アミン、第４級アンモニウム塩、ホスフィン類、イミダゾール類等の公知公用のエポキシ樹脂硬化促進剤を配合することができる。具体的にはトリフェニルホスフィンなどのホスフィン化合物、テトラフェニルホスフォニウムブロマイド等のホスホニウム塩、２−メチルイミダゾール、２−フェニルイミダゾール、２−エチル−４−メチルイミダゾール、２−ウンデシルイミダゾール、１−シアノエチル−２−メチルイミダゾール等のイミダゾール類及びそれらとトリメリット酸、イソシアヌル酸、硼素等との塩であるイミダゾール塩類、ベンジルジメチルアミン、２，４，６−トリス（ジメチルアミノメチル）フェノール等のアミン類、トリメチルアンモニウムクロライド等の４級アンモニウム塩類、ジアザビシクロ化合物及びそれらとフェノール類、フェノールノボラック樹脂類等との塩類、３フッ化硼素とアミン類、エーテル化合物等との錯化合物、芳香族ホスホニウム又はヨードニウム塩などが例示できる。これら硬化剤は、単独でも良いし、２種類以上を併用しても良い。 The composition of the present invention can be blended with known and publicly known epoxy resin curing accelerators such as tertiary amines, quaternary ammonium salts, phosphines, and imidazoles, if necessary. Specifically, phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1- Imidazoles such as cyanoethyl-2-methylimidazole and imidazole salts which are salts thereof with trimellitic acid, isocyanuric acid, boron, etc., amines such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol , Quaternary ammonium salts such as trimethylammonium chloride, diazabicyclo compounds and salts thereof with phenols, phenol novolac resins, etc., complex compounds of boron trifluoride with amines, ether compounds, etc., aromatic phosphonic compounds Such as arm or iodonium salts can be exemplified. These curing agents may be used alone or in combination of two or more.
本発明のリン含有エポキシ樹脂組成物には、粘度調整用として有機溶剤も用いることができる。用いることが出来る有機溶剤としては、Ｎ，Ｎ−ジメチルホルムアミド等のアミド類、エチレングリコールモノメチルエーテル等のエーテル類、アセトン、メチルエチルケトン等のケトン類、メタノール、エタノール等のアルコール類、ベンゼン、トルエン等の芳香族炭化水素類等が挙げられ、これらの溶剤のうちの一又は複数種を混合したものを、エポキシ樹脂濃度として３０〜８０重量％の範囲で配合することができる。 In the phosphorus-containing epoxy resin composition of the present invention, an organic solvent can also be used for viscosity adjustment. Examples of organic solvents that can be used include amides such as N, N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol and ethanol, benzene and toluene. Aromatic hydrocarbons etc. are mentioned, What mixed one or more types of these solvents can be mix | blended in 30-80 weight% as an epoxy resin density | concentration.
また、必要に応じて水酸化アルミニウム、水酸化マグネシウム、タルク、焼成タルク、クレー、カオリン、ベーマイト、酸化チタン、ガラス粉末、シリカバルーン等の無機充填剤や微粒子ゴム、熱可塑性エラストマーなどの有機充填材、ガラス繊維、パルプ繊維、合成繊維、セラミック繊維等の繊維質充填材、ガラスクロス・アラミドクロス、カーボンファイバーなどの補強材、顔料等を用いることが出来る。 If necessary, inorganic fillers such as aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, boehmite, titanium oxide, glass powder, silica balloon, and organic fillers such as fine particle rubber and thermoplastic elastomer Further, fiber fillers such as glass fiber, pulp fiber, synthetic fiber and ceramic fiber, glass cloth / aramid cloth, reinforcing material such as carbon fiber, pigment, and the like can be used.
エポキシ樹脂組成物の積層板評価を行った結果、エポキシ樹脂として特定の分子量分布を持つノボラック型エポキシ樹脂と一般式（１）で示されるリン化合物を反応して得られるリン含有エポキシ樹脂は生産性を維持したままリン含有率を低減しても難燃性が得られ、硬化物物性を向上することが出来、電子回路基板に用いられる銅張積層板のみならず電子部品に用いられる封止材・成形材・注型材・接着剤・電気絶縁塗料、難燃性の必要な複合材などに好適に用いることができるものである。 As a result of evaluation of the laminate of the epoxy resin composition, the phosphorus-containing epoxy resin obtained by reacting the novolac epoxy resin having a specific molecular weight distribution with the phosphorus compound represented by the general formula (1) as an epoxy resin is productive. Even if the phosphorus content is reduced while maintaining the above, flame retardancy can be obtained and the physical properties of the cured product can be improved, and a sealing material used not only for copper-clad laminates used for electronic circuit boards but also for electronic components -It can be suitably used for molding materials, casting materials, adhesives, electrical insulating paints, composite materials that require flame retardancy, and the like.
次に実施例及び比較例をあげて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。特に断りがない限り「部」は重量部を表し、「％」は重量％を表す。測定方法はそれぞれ以下の方法により測定した。
エポキシ当量：ＪＩＳ Ｋ７２３６に準じた。
二核体含有率、三核体含有率、数平均分子量、重量平均分子量：ゲルパーミエーションクロマトグラフィーを用いて分子量分布を測定し、二核体含有率、三核体含有率はピークの面積％から、数平均分子量および重量平均分子量は標準の単分散ポリスチレン（東ソー株式会社製 Ａ−５００，Ａ−１０００，Ａ−２５００，Ａ−５０００，Ｆ−１，Ｆ−２，Ｆ−４，Ｆ−１０，Ｆ−２０，Ｆ−４０）より求めた検量線より換算した。具体的には、本体（東ソー株式会社製 ＨＬＣ−８２２０ＧＰＣ）にカラム（東ソー株式会社製 ＴＳＫｇｅｌＧ４０００ＨＸＬ、ＴＳＫｇｅｌＧ３０００ＨＸＬ、ＴＳＫｇｅｌＧ２０００ＨＸＬ）を直列に備えたものを使用し、カラム温度は４０℃にした。また、溶離液にはテトラヒドロフランを用い、１ｍｌ／ｍｉｎの流速とし、検出器はＲＩ（示差屈折計）検出器を用いた。
リン含有量：試料に硫酸、塩酸、過塩素酸を加え、加熱して湿式灰化し、全てのリン原子をオルトリン酸とした。硫酸酸性溶液中でメタバナジン酸塩及びモリブデン酸塩を反応させ、生じたリンバードモリブデン酸錯体の４２０ｎｍにおける吸光度を測定し、予めリン酸二水素カリウムを用いて作成した検量線により、求めたリン原子含有量を重量％で表した。積層板のリン含有量は、積層板の樹脂成分に対する含有量として表した。
銅箔剥離強さ及び層間接着力：ＪＩＳ Ｃ６４８１に準じて測定し、層間接着力は７層目と８層目の間で引き剥がし測定した。
燃焼性：ＵＬ９４（Ｕｎｄｅｒｗｒｉｔｅｒｓ Ｌａｂｏｒａｔｏｒｉｅｓ Ｉｎｃ．の安全認証規格）に準じた。５本の試験片について試験を行い、１回目と２回目の接炎（５本それぞれ２回ずつで計１０回の接炎）後の有炎燃焼持続時間の合計時間を秒で表した。
ガラス転移温度ＤＳＣ：示差走査熱量測定装置（エスアイアイ・ナノテクノロジー株式会社製 ＥＸＳＴＡＲ６０００ ＤＳＣ６２００）にて１０℃／分の昇温条件で測定を行った時のＤＳＣ外挿値の温度で表した。
ガラス転移温度ＴＭＡ：熱機械分析装置（エスアイアイ・ナノテクノロジー株式会社製 ＥＸＳＴＡＲ６０００ ＴＭＡ／ＳＳ１２０Ｕ）にて５℃／分の昇温条件で測定を行った時のＴＭＡ外挿値の温度で表した。
使用したエポキシ樹脂として：――
ＹＤＦ−１７０Ｃ（新日鐵化学株式会社製 ビスフェノールＦ型エポキシ樹脂、ゲルパーミエーションクロマトグラフィーによる測定で二核体含有率８１．９面積％、三核体含有率５．３面積％、数平均分子量２５４、重量平均分子量２８５、分散度１．１２、エポキシ当量１６９ｇ／ｅｑ）
ＹＤＰＮ−６３８（新日鐵化学株式会社製 フェノールノボラック型エポキシ樹脂、ゲルパーミエーションクロマトグラフィーによる測定で二核体含有率２２．１面積％、三核体含有率１０．７面積％、数平均分子量４６３、重量平均分子量１００３、分散度２．１７、エポキシ当量１７６ｇ／ｅｑ）
ＹＤＣＮ−７００−２（新日鐵化学株式会社製 クレゾールノボラック型エポキシ樹脂、ゲルパーミエーションクロマトグラフィーによる測定で二核体含有率１０．５面積％、三核体含有率１０．９面積％、数平均分子量６３３、重量平均分子量１１８７、分散度１．８８、エポキシ当量２００ｇ／ｅｑ）
EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these. Unless otherwise specified, “parts” represents parts by weight, and “%” represents% by weight. The measurement method was measured by the following methods.
Epoxy equivalent: Conforms to JIS K7236.
Dinuclear content, trinuclear content, number average molecular weight, weight average molecular weight: Measure molecular weight distribution using gel permeation chromatography. Dinuclear content, trinuclear content is peak area% The number average molecular weight and the weight average molecular weight are standard monodisperse polystyrene (A-500, A-1000, A-2500, A-5000, F-1, F-2, F-4, F- manufactured by Tosoh Corporation). 10, F-20, F-40) was converted from the calibration curve obtained. Specifically, a main body (HLC-8220GPC manufactured by Tosoh Corporation) and a column (TSKgel G4000HXL, TSKgel G3000HXL, TSKgelG2000HXL manufactured by Tosoh Corporation) were used in series, and the column temperature was set to 40 ° C. Tetrahydrofuran was used as the eluent, the flow rate was 1 ml / min, and an RI (differential refractometer) detector was used as the detector.
Phosphorus content: Sulfuric acid, hydrochloric acid and perchloric acid were added to the sample and heated to wet ash to convert all phosphorus atoms to orthophosphoric acid. Phosphorus atoms obtained by reacting metavanadate and molybdate in a sulfuric acid acidic solution, measuring the absorbance at 420 nm of the resulting phosphobird molybdate complex, and using a calibration curve prepared in advance using potassium dihydrogen phosphate. The content was expressed in wt%. The phosphorus content of the laminate was expressed as the content relative to the resin component of the laminate.
Copper foil peel strength and interlayer adhesion: measured according to JIS C6481, and interlayer adhesion was measured by peeling between the seventh and eighth layers.
Flammability: Conforms to UL94 (Underwriters Laboratories Inc. safety certification standard). Five test pieces were tested, and the total time of the flammable combustion duration after the first and second flame contact (two flames each twice for a total of 10 flames) was expressed in seconds.
Glass transition temperature DSC: Expressed by the DSC extrapolated temperature when measured under a temperature rising condition of 10 ° C./min with a differential scanning calorimeter (EXSTAR DSC6200, manufactured by SII Nano Technology Co., Ltd.).
Glass transition temperature TMA: TMA extrapolated temperature when measured under a temperature rising condition of 5 ° C./min with a thermomechanical analyzer (EXSTAR6000 TMA / SS120U manufactured by SII Nano Technology Co., Ltd.).
As epoxy resin used:
YDF-170C (Bisphenol F type epoxy resin manufactured by Nippon Steel Chemical Co., Ltd., dinuclear content 81.9% by area, trinuclear content 5.3% by area, number average molecular weight as measured by gel permeation chromatography) 254, weight average molecular weight 285, dispersity 1.12, epoxy equivalent 169 g / eq)
YDPN-638 (manufactured by Nippon Steel Chemical Co., Ltd., phenol novolak epoxy resin, dinuclear content 22.1% by area, trinuclear content 10.7% by area, number average molecular weight as measured by gel permeation chromatography 463, weight average molecular weight 1003, dispersity 2.17, epoxy equivalent 176 g / eq)
YDCN-700-2 (manufactured by Nippon Steel Chemical Co., Ltd. Cresol novolac type epoxy resin, dinuclear content 10.5 area%, trinuclear content 10.9 area% as measured by gel permeation chromatography, number (Average molecular weight 633, weight average molecular weight 1187, dispersity 1.88, epoxy equivalent 200 g / eq)
合成例１
攪拌装置、温度計、冷却管、窒素ガス導入装置を備えた４つ口のガラス製セパラブルフラスコに、フェノール ２５００部、シュウ酸二水和物 ７．５部を仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って昇温した。３７．４％ホルマリン ４７４．１部を８０℃で滴下を開始し、３０分で滴下を終了した。更に反応温度を９２℃に保ち３時間反応を行った。昇温を行い反応生成水を系外に除去しながら１１０℃まで昇温した。残存フェノールを１６０℃にて減圧下回収を行い、フェノールノボラック樹脂を得た。更に温度を上げて二核体の一部を回収した。得られたフェノールノボラック樹脂の二核体含有率はゲルパーミエーションクロマトグラフィーによる測定で１０面積％であった。
Synthesis example 1
While introducing nitrogen gas into a four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introduction device, introduce 2500 parts of phenol and 7.5 parts of oxalic acid dihydrate. The mixture was stirred and heated to raise the temperature. Addition of 474.1 parts of 37.4% formalin was started at 80 ° C., and the addition was completed in 30 minutes. Further, the reaction was carried out for 3 hours while maintaining the reaction temperature at 92 ° C. The temperature was raised to 110 ° C. while removing the reaction product water out of the system. Residual phenol was collected at 160 ° C. under reduced pressure to obtain a phenol novolac resin. The temperature was further raised to recover a part of the binuclear body. The dinuclear content of the obtained phenol novolac resin was 10 area% as measured by gel permeation chromatography.
合成例２
合成例１で得られたフェノールノボラック樹脂をＭＩＢＫに溶解し、５％水酸化ナトリウム水溶液で水洗分液を行なった。残存する水酸化ナトリウムを水洗で除去した後、ＭＩＢＫを減圧回収した。得られたフェノールノボラック樹脂の二核体含有率はゲルパーミエーションクロマトグラフィーによる測定で６面積％であった。
Synthesis example 2
The phenol novolak resin obtained in Synthesis Example 1 was dissolved in MIBK and washed with 5% aqueous sodium hydroxide solution. The remaining sodium hydroxide was removed by washing with water, and MIBK was recovered under reduced pressure. The dinuclear content of the obtained phenol novolac resin was 6 area% as measured by gel permeation chromatography.
合成例３
合成例１の３７．４％ホルマリンを７１１．１部とした以外は合成例１と同様な操作を行った。得られたフェノールノボラック樹脂の二核体含有率はゲルパーミエーションクロマトグラフィーによる測定で１０面積％であった。
Synthesis example 3
The same operation as in Synthesis Example 1 was carried out except that 37.4% formalin in Synthesis Example 1 was changed to 711.1 parts. The dinuclear content of the obtained phenol novolac resin was 10 area% as measured by gel permeation chromatography.
合成例４
合成例１と同様な装置に、合成例１のフェノールノボラック樹脂 ６６５．８部、エピクロロヒドリン ２１１０．８部、水 １７部を仕込み、攪拌しながら５０℃まで昇温した。４９％水酸化ナトリウム水溶液 １４．２部を仕込み３時間反応を行った。６４℃まで昇温し、水の還流が起きる程度に減圧を引き、４９％水酸化ナトリウム水溶液 ４５７．７部を３時間かけて滴下し反応をおこなった。温度を７０℃まで上げ脱水を行い、温度を１３５℃として残存するエピクロロヒドリンを回収した。常圧に戻し、ＭＩＢＫ １２３２部を加えて溶解した。イオン交換水１２００部を加え、攪拌静置して副生した食塩を水に溶解して除去した。次に４９％水酸化ナトリウム水溶液 ３７．４部を仕込み８０℃で９０分間攪拌反応して精製反応を行った。ＭＩＢＫを追加、水洗を数回行いイオン性不純物を除去した。溶剤を回収し、ノボラック型エポキシ樹脂を得た。ゲルパーミエーションクロマトグラフィーによる測定で二核体含有率９面積％、三核体含有率３７．０面積％、数平均分子量４４０、重量平均分子量６０５、分散度１．３８、エポキシ当量１７６ｇ／ｅｑであった。
Synthesis example 4
In a device similar to Synthesis Example 1, 665.8 parts of the phenol novolak resin of Synthesis Example 1, 2110.8 parts of epichlorohydrin, and 17 parts of water were charged, and the temperature was raised to 50 ° C. with stirring. A 49% aqueous sodium hydroxide solution (14.2 parts) was charged and the reaction was carried out for 3 hours. The temperature was raised to 64 ° C., the pressure was reduced to such an extent that water was refluxed, and 457.7 parts of 49% aqueous sodium hydroxide solution was added dropwise over 3 hours to carry out the reaction. The temperature was raised to 70 ° C. to perform dehydration, and the remaining epichlorohydrin was recovered at a temperature of 135 ° C. The pressure was returned to normal pressure, and 1232 parts of MIBK was added and dissolved. 1200 parts of ion-exchanged water was added, and the mixture was left standing with stirring, and the salt produced as a by-product was dissolved in water and removed. Next, 37.4 parts of a 49% aqueous sodium hydroxide solution was added, and the mixture was stirred and reacted at 80 ° C. for 90 minutes to carry out a purification reaction. MIBK was added and washed with water several times to remove ionic impurities. The solvent was recovered to obtain a novolac type epoxy resin. As measured by gel permeation chromatography, the dinuclear content is 9 area%, the trinuclear content is 37.0 area%, the number average molecular weight is 440, the weight average molecular weight is 605, the dispersity is 1.38, and the epoxy equivalent is 176 g / eq. there were.
合成例５
合成例４で使用した合成例１のフェノールノボラック樹脂の代わりに合成例２のフェノールノボラック樹脂を用いた以外は合成例４と同様な操作を行い、ノボラック型エポキシ樹脂を得た。ゲルパーミエーションクロマトグラフィーによる測定で二核体含有率５．５面積％、三核体含有率３４．６面積％、数平均分子量４８５、重量平均分子量６８４、分散度１．４１、エポキシ当量１７６ｇ／ｅｑであった。
Synthesis example 5
A novolac epoxy resin was obtained in the same manner as in Synthesis Example 4 except that the phenol novolak resin of Synthesis Example 2 was used instead of the phenol novolak resin of Synthesis Example 1 used in Synthesis Example 4. As measured by gel permeation chromatography, the binuclear content is 5.5 area%, the trinuclear content is 34.6 area%, the number average molecular weight is 485, the weight average molecular weight is 684, the degree of dispersion is 1.41, the epoxy equivalent is 176 g / eq.
合成例６
合成例４で使用した合成例１のフェノールノボラック樹脂の代わりに合成例３のフェノールノボラック樹脂を用いた以外は合成例４と同様な操作を行い、ノボラック型エポキシ樹脂を得た。ゲルパーミエーションクロマトグラフィーによる測定で二核体含有率９．１面積％、三核体含有率２４．２面積％、数平均分子量５９３、重量平均分子量９５４、分散度１．６１、エポキシ当量１７７ｇ／ｅｑであった。
Synthesis Example 6
A novolac-type epoxy resin was obtained in the same manner as in Synthesis Example 4 except that the phenol novolac resin of Synthesis Example 3 was used instead of the phenol novolak resin of Synthesis Example 1 used in Synthesis Example 4. As measured by gel permeation chromatography, dinuclear content 9.1 area%, trinuclear content 24.2 area%, number average molecular weight 593, weight average molecular weight 954, dispersity 1.61, epoxy equivalent 177 g / eq.
合成例７
合成例４で使用した合成例１のフェノールノボラック樹脂の代わりにＬＶ−７０Ｓ（群栄化学工業株式会社製 フェノールノボラック樹脂、二核体成分２％、三核体成分７５％）を用いた以外は合成例４と同様な操作を行い、ノボラック型エポキシ樹脂を得た。ゲルパーミエーションクロマトグラフィーによる測定で二核体含有率１．４面積％、三核体含有率５６．１面積％、数平均分子量４８６、重量平均分子量６１７、分散度１．２７、エポキシ当量１７６ｇ／ｅｑであった。
Synthesis example 7
Except for using LV-70S (Phenol novolac resin,
合成例８
合成例４で使用した合成例１のフェノールノボラック樹脂の代わりにＴＲＩ−００２（昭和電工株式会社製 トリフェニルメタン型ノボラック樹脂、二核体成分４．６％、三核体成分２９．７％）を２３２６．５部、４，４−メチレンビスクレゾール１７３．６部用いた以外は合成例４と同様な操作を行い、ノボラック型エポキシ樹脂を得た。ゲルパーミエーションクロマトグラフィーによる測定で二核体含有率９．２面積％、三核体含有率２１．８面積％、数平均分子量６４０、重量平均分子量１１０９、分散度１．８０、エポキシ当量１７７ｇ／ｅｑであった。
Synthesis Example 8
TRI-002 (Triphenylmethane type novolak resin, manufactured by Showa Denko KK, dinuclear component 4.6%, trinuclear component 29.7%) instead of the phenol novolak resin of Synthesis Example 1 used in Synthesis Example 4 Was used in the same manner as in Synthesis Example 4 except that 2326.5 parts and 17-36 parts of 4,4-methylenebiscresol were used to obtain a novolac type epoxy resin. As measured by gel permeation chromatography, dinuclear content 9.2 area%, trinuclear content 21.8 area%, number average molecular weight 640, weight average molecular weight 1109, dispersity 1.80, epoxy equivalent 177 g / eq.
合成例９
合成例４で使用した合成例１のフェノールノボラック樹脂の代わりにＢＲＧ−５５８（群栄化学株式会社製 フェノールノボラック樹脂、二核体成分１２．０％、三核体成分１０．０％）を用いた以外は合成例４と同様な操作を行い、ノボラック型エポキシ樹脂を得た。ゲルパーミエーションクロマトグラフィーによる測定で二核体含有率１０．４面積％、三核体含有率５．８面積％、数平均分子量８１８、重量平均分子量２４３６、分散度２．９８、エポキシ当量１７７ｇ／ｅｑであった。
Synthesis Example 9
BRG-558 (Phenol novolac resin, dinuclear component 12.0%, trinuclear component 10.0%, manufactured by Gunei Chemical Co., Ltd.) was used instead of the phenol novolak resin of Synthesis Example 1 used in Synthesis Example 4. A novolac epoxy resin was obtained in the same manner as in Synthesis Example 4 except that. As measured by gel permeation chromatography, the dinuclear content was 10.4 area%, the trinuclear content was 5.8 area%, the number average molecular weight 818, the weight average molecular weight 2436, the dispersity 2.98, and the epoxy equivalent 177 g / eq.
実施例１
合成例１と同様な装置に合成例４のフェノールノボラック型エポキシ樹脂 ８２４部、ＨＣＡ（三光株式会社製 ９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド リン含有率１４．２重量％）１７６部を仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って昇温した。１３０℃にてトリフェニルホスフィンを触媒として０．１８部を添加して１６０℃で３時間反応を行った。得られたエポキシ樹脂のエポキシ当量は２６６ｇ／ｅｑ、リン含有率は２．５％であった。結果を表１にまとめる。
Example 1
In the same apparatus as in Synthesis Example 1, 824 parts of phenol novolac type epoxy resin of Synthesis Example 4 and HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide phosphorus content by Sanko Co., Ltd. 14. 2 wt%) 176 parts were charged, stirred while introducing nitrogen gas, and heated to raise the temperature. At 130 ° C, 0.18 part of triphenylphosphine was added as a catalyst, and the reaction was carried out at 160 ° C for 3 hours. The epoxy equivalent of the obtained epoxy resin was 266 g / eq, and the phosphorus content was 2.5%. The results are summarized in Table 1.
実施例２
合成例４のフェノールノボラック型エポキシ樹脂 ８３８部、ＨＣＡ １６２部とした以外は実施例１と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は２５６ｇ／ｅｑ、リン含有率は２．３％であった。結果を表１にまとめる。
Example 2
The same operation as in Example 1 was performed except that 838 parts of the phenol novolac type epoxy resin of Synthesis Example 4 and 162 parts of HCA were used. The epoxy equivalent of the obtained epoxy resin was 256 g / eq, and the phosphorus content was 2.3%. The results are summarized in Table 1.
実施例３
合成例４のフェノールノボラック型エポキシ樹脂 ８８０部、ＨＣＡ １２０部とした以外は実施例１と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は２２６ｇ／ｅｑ、リン含有率は１．７％であった。結果を表１にまとめる。
Example 3
The same operation as in Example 1 was carried out except that 880 parts of the phenol novolac type epoxy resin of Synthesis Example 4 and 120 parts of HCA were used. The epoxy equivalent of the obtained epoxy resin was 226 g / eq, and the phosphorus content was 1.7%. The results are summarized in Table 1.
実施例４
合成例４のフェノールノボラック型エポキシ樹脂の代わりに合成例５のフェノールノボラック型エポキシ樹脂 ８２４部、ＨＣＡ １７６部とした以外は実施例１と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は２６４ｇ／ｅｑ、リン含有率は２．５％であった。結果を表１にまとめる。
Example 4
The same operation as in Example 1 was carried out except that 824 parts of the phenol novolac type epoxy resin of Synthesis Example 5 and 176 parts of HCA were used instead of the phenol novolak type epoxy resin of Synthesis Example 4. The epoxy equivalent of the obtained epoxy resin was 264 g / eq, and the phosphorus content was 2.5%. The results are summarized in Table 1.
実施例５
合成例４のフェノールノボラック型エポキシ樹脂の代わりに合成例６のフェノールノボラック型エポキシ樹脂 ８２４部、ＨＣＡ １７６部とした以外は実施例１と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は２５６ｇ／ｅｑ、リン含有率は２．５％であった。結果を表１にまとめる。
Example 5
The same operation as in Example 1 was carried out except that 824 parts of the phenol novolac type epoxy resin of Synthesis Example 6 and 176 parts of HCA were used instead of the phenol novolak type epoxy resin of Synthesis Example 4. The epoxy equivalent of the obtained epoxy resin was 256 g / eq, and the phosphorus content was 2.5%. The results are summarized in Table 1.
実施例６
合成例４のフェノールノボラック型エポキシ樹脂の代わりに合成例７のフェノールノボラック型エポキシ樹脂 ７１１．９部、とＹＤＦ−１７０Ｃ １１２．１部とした以外は実施例１と同様な操作を行なった。使用したエポキシ樹脂の二核体含有率は１１．９面積％、三核体含有率は４９．０面積％だった。得られたエポキシ樹脂のエポキシ当量は２５７ｇ／ｅｑ、リン含有率は２．５％であった。結果を表１にまとめる。
Example 6
The same operation as in Example 1 was performed except that 711.9 parts of phenol novolac type epoxy resin of Synthesis Example 7 and 112.1 parts of YDF-170C were used instead of the phenol novolak type epoxy resin of Synthesis Example 4. The epoxy resin used had a dinuclear content of 11.9 area% and a trinuclear content of 49.0 area%. The epoxy equivalent of the obtained epoxy resin was 257 g / eq, and the phosphorus content was 2.5%. The results are summarized in Table 1.
実施例７
合成例４のフェノールノボラック型エポキシ樹脂 ８０４部、ビスフェノールＦ（本州化学製）５５部を仕込み、１２０℃に加熱した。トリフェニルホスフィン０．０６部を添加し、１５０℃で２．５時間反応した。更にＨＣＡ １４１部追加し、トリフェニルホスフィン０．１４部を添加して１６０℃で３時間反応を行った。得られたエポキシ樹脂のエポキシ当量は３０１ｇ／ｅｑ、リン含有率は２．０％であった。結果を表１にまとめる。
Example 7
804 parts of a phenol novolac type epoxy resin of Synthesis Example 4 and 55 parts of bisphenol F (manufactured by Honshu Chemical) were charged and heated to 120 ° C. 0.06 part of triphenylphosphine was added and reacted at 150 ° C. for 2.5 hours. Furthermore, 141 parts of HCA was added, 0.14 part of triphenylphosphine was added, and the reaction was carried out at 160 ° C. for 3 hours. The epoxy equivalent of the obtained epoxy resin was 301 g / eq, and the phosphorus content was 2.0%. The results are summarized in Table 1.
実施例８
実施例７の合成例４のフェノールノボラック型エポキシ樹脂 ７９９部、ビスフェノールＦの代わりにビスフェノールＡを ６０部とした以外は実施例７と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は２９５ｇ／ｅｑ、リン含有率は２．０％であった。結果を表１にまとめる。
Example 8
The same operation as in Example 7 was carried out except that 799 parts of the phenol novolac type epoxy resin of Synthesis Example 4 of Example 7 and 60 parts of bisphenol A instead of bisphenol F were used. The epoxy equivalent of the obtained epoxy resin was 295 g / eq, and the phosphorus content was 2.0%. The results are summarized in Table 1.
実施例９
合成例４のフェノールノボラック型エポキシ樹脂の代わりに合成例８のフェノールノボラック型エポキシ樹脂 ８２４部とした以外は実施例１と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は２６０ｇ／ｅｑ、リン含有率は２．５％であった。結果を表１にまとめる。
Example 9
The same operation as in Example 1 was performed except that 824 parts of the phenol novolac type epoxy resin of Synthesis Example 8 was used instead of the phenol novolak type epoxy resin of Synthesis Example 4. The epoxy equivalent of the obtained epoxy resin was 260 g / eq, and the phosphorus content was 2.5%. The results are summarized in Table 1.
比較例１
合成例４のフェノールノボラック型エポキシ樹脂の代わりにＹＤＰＮ−６３８ ８１０部、ＨＣＡ １９０部とした以外は実施例１と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は２７１ｇ／ｅｑ、リン含有率は２．７％であった。結果を表２にまとめる。
Comparative Example 1
The same operation as in Example 1 was carried out except that 810 parts of YDPN-638 and 190 parts of HCA were used instead of the phenol novolac type epoxy resin of Synthesis Example 4. The epoxy equivalent of the obtained epoxy resin was 271 g / eq, and the phosphorus content was 2.7%. The results are summarized in Table 2.
比較例２
合成例４のフェノールノボラック型エポキシ樹脂の代わりにＹＤＰＮ−６３８ ８２４部とした以外は実施例１と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は２５１ｇ／ｅｑ、リン含有率は２．５％であった。結果を表２にまとめる。
Comparative Example 2
The same operation as in Example 1 was performed except that 824 parts of YDPN-638 were used instead of the phenol novolac type epoxy resin of Synthesis Example 4. The epoxy equivalent of the obtained epoxy resin was 251 g / eq, and the phosphorus content was 2.5%. The results are summarized in Table 2.
比較例３
合成例４のフェノールノボラック型エポキシ樹脂の代わりにＹＤＰＮ−６３８ ８３８部、ＨＣＡ １６２部とした以外は実施例１と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は２５５ｇ／ｅｑ、リン含有率は２．３％であった。結果を表２にまとめる。
Comparative Example 3
The same operation as in Example 1 was performed except that 8DP part of YDPN-638 and 162 parts of HCA were used instead of the phenol novolac type epoxy resin of Synthesis Example 4. The epoxy equivalent of the obtained epoxy resin was 255 g / eq, and the phosphorus content was 2.3%. The results are summarized in Table 2.
比較例４
実施例７の合成例４のフェノールノボラック型エポキシ樹脂の変わりにＹＤＰＮ−６３８ ８０４部とした以外は実施例７と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は３０６ｇ／ｅｑ、リン含有率は２．０％であった。結果を表２にまとめる。
Comparative Example 4
The same operation as in Example 7 was carried out except that 804 parts of YDPN-638 was used instead of the phenol novolac type epoxy resin of Synthesis Example 4 in Example 7. The epoxy equivalent of the obtained epoxy resin was 306 g / eq, and the phosphorus content was 2.0%. The results are summarized in Table 2.
比較例５
実施例８の合成例４のフェノールノボラック型エポキシ樹脂の変わりにＹＤＰＮ−６３８ ７９９部とした以外は実施例７と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は３０８ｇ／ｅｑ、リン含有率は２．０％であった。結果を表２にまとめる。
Comparative Example 5
The same operation as in Example 7 was carried out except that 799 parts of YDPN-638 was used instead of the phenol novolac type epoxy resin of Synthesis Example 4 in Example 8. The epoxy equivalent of the obtained epoxy resin was 308 g / eq, and the phosphorus content was 2.0%. The results are summarized in Table 2.
比較例６
合成例４のフェノールノボラック型エポキシ樹脂の代わりに合成例９のフェノールノボラック型エポキシ樹脂 ８２４部とした以外は実施例１と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は２５６ｇ／ｅｑ、リン含有率は２．５％であった。結果を表２にまとめる。
Comparative Example 6
The same operation as in Example 1 was performed except that 824 parts of the phenol novolac type epoxy resin of Synthesis Example 9 was used instead of the phenol novolak type epoxy resin of Synthesis Example 4. The epoxy equivalent of the obtained epoxy resin was 256 g / eq, and the phosphorus content was 2.5%. The results are summarized in Table 2.
比較例７
合成例４のフェノールノボラック型エポキシ樹脂の代わりにＹＤＣＮ−７００−２ ８２４部とした以外は実施例１と同様な操作を行なった。得られたエポキシ樹脂のエポキシ当量は３０３ｇ／ｅｑ、リン含有率は２．５％であった。結果を表２にまとめる。
Comparative Example 7
The same operation as in Example 1 was carried out except that 824 parts of YDCN-700-2 was used instead of the phenol novolac type epoxy resin of Synthesis Example 4. The epoxy equivalent of the obtained epoxy resin was 303 g / eq, and the phosphorus content was 2.5%. The results are summarized in Table 2.
比較例８
実施例１と同様な装置にＨＣＡ １４１部とトルエン ３３０部を仕込み、加熱して溶解した。その後、１，４−ナフトキノン ８７．５部を反応熱による昇温に注意しながら分割投入した。このとき１，４−ナフトキノンとＨＣＡのモル比は１，４−ナフトキノン／ＨＣＡ＝０．８５であった。８５℃で３０分保持した後、昇温して還流温度で２時間反応を継続した。更に温度を上げ、トルエンを２００部回収し、ＹＤＰＮ−６３８ ７７１．５部を仕込み、窒素ガスを導入しながら攪拌を行い、１２０℃まで加熱を行った。トリフェニルホスフィンを０．２３重量部添加して１６５℃で４時間反応した。得られたエポキシ樹脂のエポキシ当量は３２７ｇ／ｅｑ、リン含有率は２．０％であった。結果を表２にまとめる。
Comparative Example 8
In the same apparatus as in Example 1, 141 parts of HCA and 330 parts of toluene were charged and dissolved by heating. Thereafter, 87.5 parts of 1,4-naphthoquinone was added in portions while paying attention to the temperature rise by reaction heat. At this time, the molar ratio of 1,4-naphthoquinone to HCA was 1,4-naphthoquinone / HCA = 0.85. After maintaining at 85 ° C. for 30 minutes, the temperature was raised and the reaction was continued at the reflux temperature for 2 hours. The temperature was further raised, 200 parts of toluene was recovered, 771.5 parts of YDPN-638 was charged, stirred while introducing nitrogen gas, and heated to 120 ° C. 0.23 parts by weight of triphenylphosphine was added and reacted at 165 ° C. for 4 hours. The epoxy equivalent of the obtained epoxy resin was 327 g / eq, and the phosphorus content was 2.0%. The results are summarized in Table 2.
実施例１０〜実施例１８
実施例１〜実施例９のリン含有エポキシ樹脂と硬化剤としてジシアンジアミド（日本カーバイト株式会社製）を使用してエポキシ樹脂組成物を作成した。固形分での配合処方を表３に示す。配合の際にエポキシ樹脂はメチルエチルケトンに溶解して用いた。ＤＩＣＹはメトキシプロパノール、ＤＭＦに溶解して使用した。２Ｅ４ＭＺはメトキシプロパノールに溶解して使用した。配合後、メチルエチルケトン、メトキシプロパノールにて不揮発分５０％となるように調整して、均一溶液とした。
Examples 10 to 18
Epoxy resin compositions were prepared using the phosphorus-containing epoxy resins of Examples 1 to 9 and dicyandiamide (manufactured by Nippon Carbide Corporation) as a curing agent. Table 3 shows the formulation of the solid content. At the time of blending, the epoxy resin was dissolved in methyl ethyl ketone and used. DICY was used by dissolving in methoxypropanol and DMF. 2E4MZ was used by dissolving in methoxypropanol. After blending, the mixture was adjusted with methyl ethyl ketone and methoxypropanol so that the nonvolatile content was 50% to obtain a uniform solution.
得られた樹脂ワニスをガラスクロスＷＥＡ ７６２８ ＸＳ１３（日東紡績株式会社製 ０．１８ｍｍ厚）に含浸した。含浸したガラスクロスを１５０℃の熱風循環炉で８分間乾燥を行い、プリプレグを得た。得られたプリプレグ８枚を重ね、上下に銅箔（三井金属鉱業株式会社製 ３ＥＣ）を重ね、１３０℃×１５分及び１７０℃×２０ｋｇ／ｃｍ2 ×７０分間加熱、加圧を行い積層板を得た。得られた積層板の物性を表３に示す。
The obtained resin varnish was impregnated into glass cloth WEA 7628 XS13 (Nittobo Co., Ltd., 0.18 mm thickness). The impregnated glass cloth was dried in a hot air circulating furnace at 150 ° C. for 8 minutes to obtain a prepreg. 8 sheets of the obtained prepregs are stacked, and copper foil (3EC manufactured by Mitsui Mining & Smelting Co., Ltd.) is stacked on the top and bottom, and heated and pressed at 130 ° C. for 15 minutes and 170 ° C. × 20 kg /
比較例９〜比較例１６
実施例１０〜実施例１８と同様に比較例１〜比較例８のリン含有エポキシ樹脂を用いて積層板を作成した。配合処方及び積層板の物性を表４に示す。
Comparative Example 9 to Comparative Example 16
Laminates were made using the phosphorus-containing epoxy resins of Comparative Examples 1 to 8 as in Examples 10 to 18. The formulation and physical properties of the laminate are shown in Table 4.
特定の分子量分布を持つフェノールノボラックエポキシ樹脂と特定のリン化合物を反応して得られるリン含有エポキシ樹脂は、リン含有率が１．７％でも難燃性が得られており（実施例１２）、リン含有率を２．３％、２．５％と上げた場合（実施例１０，１１）残炎時間が短くなることから難燃性は良好である。一方従来型のフェノールノボラックエポキシ樹脂と特定のリン化合物を反応して得られるリン含有エポキシ樹脂は、リン含有率２．６％（比較例１）としないと難燃性が得られず、硬化物物性も悪くなっている。リン含有率２．５％，２．３％とした比較例２、比較例３では硬化物物性は改良されるものの難燃性が得られていない。実施例６、実施例７、実施例８においてその他のエポキシ樹脂やエポキシ樹脂変性剤を用い接着性を改良することが出来るが、従来型のフェノールノボラックエポキシ樹脂を用いた比較例４、比較例５ではエポキシ樹脂変性剤を用いたところ、難燃性が非常に悪い結果であった。 The phosphorus-containing epoxy resin obtained by reacting a phenol novolac epoxy resin having a specific molecular weight distribution with a specific phosphorus compound has obtained flame retardancy even when the phosphorus content is 1.7% (Example 12). When the phosphorus content is increased to 2.3% and 2.5% (Examples 10 and 11), the flame retardancy is good because the afterflame time is shortened. On the other hand, a phosphorus-containing epoxy resin obtained by reacting a conventional phenol novolac epoxy resin with a specific phosphorus compound does not provide flame retardancy unless the phosphorus content is 2.6% (Comparative Example 1). The physical properties are also getting worse. In Comparative Examples 2 and 3 in which the phosphorus content is 2.5% and 2.3%, the cured product properties are improved, but flame retardancy is not obtained. In Example 6, Example 7, and Example 8, other epoxy resins and epoxy resin modifiers can be used to improve adhesion, but Comparative Examples 4 and 5 using conventional phenol novolac epoxy resins. Then, when an epoxy resin modifier was used, the flame retardancy was very bad.
また、リン含有エポキシ樹脂の反応時間は３時間から５時間であるが、難燃性及び硬化物物性の良好な比較例８では９時間必要であり、生産性においても良好である。 Further, the reaction time of the phosphorus-containing epoxy resin is 3 to 5 hours. However, Comparative Example 8 having good flame retardancy and cured material properties requires 9 hours, and the productivity is also good.
本発明のリン含有エポキシ樹脂は原料であるフェノールノボラック型エポキシ樹脂の分子量分布を制御することによって、高価なリン化合物の使用量を低減しつつ難燃性を向上し、生産性を高めながら硬化物物性を向上することが出来、電子回路基板に用いられるプリプレグ、銅張り積層板や電子部品に用いられるフィルム材・封止材・成形材・注型材・接着剤・電気絶縁塗料、難燃性の必要な複合材、粉体塗料などに有用である。 The phosphorus-containing epoxy resin of the present invention controls the molecular weight distribution of the phenol novolac type epoxy resin that is a raw material, thereby improving the flame retardancy while reducing the amount of expensive phosphorus compound used, and increasing the productivity. Can improve physical properties, prepregs used for electronic circuit boards, copper-clad laminates and film materials, sealing materials, molding materials, casting materials, adhesives, electrical insulation paints used in electronic components, flame retardant It is useful for the necessary composite materials and powder coatings.
Claims (5)
（ゲルパーミエーションクロマトグラフィー測定条件）
東ソー株式会社製 ＴＳＫｇｅｌＧ４０００ＨＸＬ、ＴＳＫｇｅｌＧ３０００ＨＸＬ、ＴＳＫｇｅｌＧ２０００ＨＸＬを直列に備えたものを使用し、カラム温度は４０℃にした。また、溶離液にはテトラヒドロフランを用い、１ｍｌ／ｍｉｎの流速とし、検出器はＲＩ（示差屈折計）検出器を用いた。サンプル０．１ｇを１０ｍｌのＴＨＦに溶解した。標準ポリスチレンによる検量線により数平均分子量を測定する。
(Gel permeation chromatography measurement conditions)
Tosoh Corporation TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL were used in series, and the column temperature was 40 ° C. Tetrahydrofuran was used as the eluent, the flow rate was 1 ml / min, and an RI (differential refractometer) detector was used as the detector. 0.1 g of sample was dissolved in 10 ml of THF. The number average molecular weight is measured with a standard polystyrene calibration curve.
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