CN104379626A - Phosphorus-containing epoxy resin, composition containing phosphorus-containing epoxy resin as essential component, and cured product - Google Patents
Phosphorus-containing epoxy resin, composition containing phosphorus-containing epoxy resin as essential component, and cured product Download PDFInfo
- Publication number
- CN104379626A CN104379626A CN201380030849.7A CN201380030849A CN104379626A CN 104379626 A CN104379626 A CN 104379626A CN 201380030849 A CN201380030849 A CN 201380030849A CN 104379626 A CN104379626 A CN 104379626A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- phosphorous
- phosphorus
- molecular weight
- area
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 187
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 187
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 48
- 239000011574 phosphorus Substances 0.000 title claims abstract description 43
- 239000000203 mixture Substances 0.000 title claims description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title abstract description 19
- -1 phosphorus compound Chemical class 0.000 claims abstract description 65
- 238000009826 distribution Methods 0.000 claims abstract description 23
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 10
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 6
- 125000004437 phosphorous atom Chemical group 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000004843 novolac epoxy resin Substances 0.000 abstract 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 42
- 229910000831 Steel Inorganic materials 0.000 description 25
- 229920003986 novolac Polymers 0.000 description 25
- 239000010959 steel Substances 0.000 description 25
- 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 25
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- 239000004593 Epoxy Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- 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 description 13
- 239000003063 flame retardant Substances 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 150000001299 aldehydes Chemical class 0.000 description 10
- 229930192627 Naphthoquinone Natural products 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000004922 lacquer Substances 0.000 description 9
- 150000002791 naphthoquinones Chemical class 0.000 description 9
- 229920003987 resole Polymers 0.000 description 9
- 230000007704 transition Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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
- 239000000047 product Substances 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 4
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 4
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- 229930185605 Bisphenol Natural products 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 150000004782 1-naphthols Chemical class 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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-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
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 150000001412 amines Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 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 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
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- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
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- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 description 2
- 150000008614 2-methylimidazoles Chemical class 0.000 description 2
- 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 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
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
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- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- HFFLGKNGCAIQMO-UHFFFAOYSA-N trichloroacetaldehyde Chemical compound ClC(Cl)(Cl)C=O HFFLGKNGCAIQMO-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QLAGHGSFXJZWKY-UHFFFAOYSA-N triphenylborane;triphenylphosphane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QLAGHGSFXJZWKY-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
Classifications
-
- 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
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
-
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/3272—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing phosphorus
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
-
- 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
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
- B32B2260/023—Two or more layers
-
- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- 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
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/07—Parts immersed or impregnated in a matrix
- B32B2305/076—Prepregs
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- 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
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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
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/012—Flame-retardant; Preventing of inflammation
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The present invention provides an epoxy resin that has further improved heat resistance, while maintaining conventional adhesion, specifically a phosphorus-containing epoxy resin (A) which is obtained by reacting, as essential components, a phosphorus compound represented by general formula (1), a quinone compound and an epoxy resin (a), and which is characterized in that the epoxy resin (a) is a novolac epoxy resin that has a molecular weight distribution having a dinuclear component content of 15% by area or less, a trinuclear component content of 15-60% by area, and a number average molecular weight of 350-700 as determined by gel permeation chromatography.
Description
Technical field
The present invention relates in molecular skeleton containing phosphorus atom, not halogen-containing fire-retarded epoxy resin, and using this epoxy resin as the composition epoxy resin of essential component, and then relate to the epoxy resin cured product formed by this epoxy resin composition; The invention provides the epoxy resin of applicable following purposes: the thin-film material used in the prepreg used in circuit substrate, copper-coated laminated board or electronic unit, sealing material, shaped material, cast-molding material, caking agent, electrical insulating coating, need the matrix material of flame retardant resistance, powder coating etc.
Background technology
The flame-retarded of epoxy resin was undertaken by halogenation in the past, and representational is using the brominated epoxy resin of tetrabromo-bisphenol as raw material.But, when using halogenated epoxy resin, have following problem: the halogenide finding to produce due to pyrolysis when the burning of cured article strong toxicity.To this, Recent study utilizes the not halogen-containing flame-retarded technology of phosphorus compound, proposes epoxy resin phosphorous disclosed in patent documentation 1 ~ patent documentation 7, phosphorous resol.
Epoxy resin phosphorous disclosed in patent documentation 1, patent documentation 2, although bonding force is high, is that the thermotolerance of representative is not enough with second-order transition temperature; Epoxy resin phosphorous disclosed in patent documentation 3, although improve second-order transition temperature, is difficult to take into account bonding force.In addition, epoxy resin phosphorous disclosed in patent documentation 4, by the raising using naphtoquinone compounds to realize high bonding force and high heat resistance.And then, in patent documentation 5, by and with specific 2 functional epoxy resins, thus realize improving high bonding force and high heat resistance further; About epoxy resin phosphorous disclosed in patent documentation 6, also studied the raising of bonding force and high heat resistance.But, for second-order transition temperature, there is the requirement of more height, require to improve while maintenance bonding force.
The phosphorous epoxy resin obtained by the flame-retarded gimmick of phosphorus compound, is difficult to take into account high heat resistance and high bonding force, if carry out multiple functionalized to improve thermotolerance, bonding force reduces; If carry out the 2 functionalized of phosphorus compound to improve bonding force, thermotolerance reduces.To this, proposing in patent documentation 5, by using specific 2 functional epoxy resins in the scope of 20% ~ 45%, can further improve high heat resistance and high bonding force.
prior art document
patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 04 No. 11662 publications
Patent documentation 2: Japanese Unexamined Patent Publication 2000 No. 309623 publications
Patent documentation 3: Japanese Unexamined Patent Publication 11 No. 166035 publications
Patent documentation 4: Japanese Unexamined Patent Publication 11 No. 279258 publications
Patent documentation 5: No. 4588834th, Japanese Patent
Patent documentation 6: Japanese Unexamined Patent Publication 2001 No. 123049 publications
Patent documentation 7: Japanese Unexamined Patent Publication 2003 No. 040969 publications.
Summary of the invention
the technical problem that invention will solve
Recently, in circuit substrate etc., in order to Reflow Soldering temperature rising, guarantee long-term reliability, thermotolerance, particularly second-order transition temperature require to improve further.The technical problem to be solved in the present invention is to provide a kind of epoxy resin, and it has the characteristic that thermotolerance improves further while keeping bonding force.
the means of technical solution problem
In order to solve the problems of the technologies described above, the present inventor finds, use and there is phenol aldehyde type (the ノ ボ ラ ッ Network type) epoxy resin of specific molecular weight distribution and phosphorus compound, naphtoquinone compounds and the phosphorous epoxy resin that obtains in the epoxy, thermotolerance can be improved while the high bonding force of maintenance, and then find that flame retardant resistance is good, thus complete the present invention.
That is, main points of the present invention are,
(1) phosphorous epoxy resin (A), it is characterized in that, it is that phosphorus compound, naphtoquinone compounds and the epoxy resin (a) represented by general formula (1) carries out reacting as essential component and the phosphorous epoxy resin obtained, wherein, epoxy resin (a) is in the mensuration of following gel permeation chromatography, has the phenol aldehyde type epoxy resin that two nucleomes (two nucleomes) containing ratio is 15 below area %, three nucleome containing ratios are 15 area % ~ 60 area %, number-average molecular weight is the molecular weight distribution of 350 ~ 700;
(gel permeation chromatography condition)
Use and possess (East ソ ー Co., Ltd. of TOSOH Co., Ltd in upright arrangemently) equipment of TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL processed, make column temperature be 40 DEG C.Elutriant uses tetrahydrofuran (THF) (THF), and flow velocity is 1ml/min, and detector uses RI (differential refractometer) detector.Mensuration test portion is, sample 0.1g is dissolved in the THF of 10ml.Adopt chromatographic computation two nucleome containing ratio and the three nucleome containing ratios of gained, utilize the standard curve determination number-average molecular weight of polystyrene standard;
(in formula, R1 and R2 represents alkyl, can be the same or different, and R1, R2 can form ring texture together with phosphorus atom.N represents 0 or 1.);
(2) phosphorous composition epoxy resin, wherein, the phosphorous epoxy resin (A) recorded using above-mentioned (1) and solidifying agent are as essential component, relative to epoxy group(ing) 1 equivalent of phosphorous epoxy resin (A), active group 0.3 equivalent ~ 1.5 equivalent of solidifying agent is coordinated to form;
(3) epoxy resin cured product, it is formed by the phosphorous epoxy resin composition that above-mentioned (2) are recorded;
(4) prepreg, it is soaked into by the phosphorous composition epoxy resin that above-mentioned (2) are recorded to form in the substrate;
(5) laminated plate, it is formed by the phosphorous epoxy resin composition that above-mentioned (2) are recorded;
(6) circuit substrate, it is formed by the phosphorous epoxy resin composition that above-mentioned (2) are recorded.
invention effect
The present invention is, by the phosphorous epoxy resin that will there is the phenol aldehyde type epoxy resin of specific molecular weight distribution, phosphorus compound and naphtoquinone compounds carry out reacting as essential component and obtain, by using the phenol aldehyde type epoxy resin with specific molecular weight distribution, the phosphorous epoxy resin demonstrating the cured article physical property that second-order transition temperature is high while maintaining bonding force can be obtained.And then the viscosity of epoxy resin is low, operability and also good to the impregnability of base material, flame retardant resistance is also good.
Accompanying drawing explanation
Fig. 1 represents gel permeation chromatography (GPC) figure of universal novolac type epoxy resin and YDPN 638.Transverse axis represents elution time, left longitudinal axis expression signal intensity.The right longitudinal axis represents number-average molecular weight M with log.Using use reference material number-average molecular weight measured value with black circle draw and as typical curve.Peak shown in A represents that the peak shown in two nucleomes, B represents three nucleomes.
Fig. 2 represents the GPC figure of the phenol aldehyde type epoxy resin of synthesis example 2.Peak shown in A represents that the peak shown in two nucleomes, B represents three nucleomes.
Embodiment
Below embodiments of the present invention are described in detail.
The epoxy resin (a) used in the present invention is the reaction product of phenols and aldehydes, is the polyfunctional phenol aldehyde type epoxy resin having the resol of specific molecular weight distribution and epoxyhalopropane reaction and obtain.As the phenols used, can enumerate: phenol, cresols, ethylphenol, butylphenol, styrenated phenol, cumenyl phenol, naphthols, catechol, Resorcinol, naphthalenediol, dihydroxyphenyl propane etc.; As aldehydes, formalin (formalin), formaldehyde (formaldehyde), hydroxy benzaldehyde, salicylic aldehyde etc. can be enumerated.In addition, substitute aldehydes, use the aralkyl resol of xylylene dimethanol (xylylene dimethanol), two (chloromethyl) benzene (xylylene dichloride), dichloride methyl naphthalene, dichloride methyl biphenyl etc. to be also contained in resol of the present invention.By using epoxyhalopropane to carry out epoxidation to above-mentioned resol, thus obtain phenol aldehyde type epoxy resin.
As the concrete example of conventional phenol aldehyde type epoxy resin, can enumerate: エ ポ ト ー ト YDPN 638 (Nippon Steel Chemical Co., Ltd's novolac type epoxy resin), エ ピ コ ー ト 152, エ ピ コ ー ト 154 (Mitsubishi chemical Co., Ltd's novolac type epoxy resin), エ ピ Network ロ Application N 740, エ ピ Network ロ Application N 770, エ ピ Network ロ Application N 775 (Dainippon Ink Chemicals's novolac type epoxy resin), エ ポ ト ー ト YDCN 700 series (Nippon Steel Chemical Co., Ltd's cresoform type epoxy resin), エ ピ Network ロ Application N 660, エ ピ Network ロ Application N 665, エ ピ Network ロ Application N 670, エ ピ Network ロ Application N 673, エ ピ Network ロ Application N 695 (Dainippon Ink Chemicals's cresoform type epoxy resin), EOCN 1020, EOCN 102S, EOCN 104S (Nippon Kayaku K. K's cresoform type epoxy resin), エ ポ ト ー ト ZX 1071T, ZX 1270, ZX 1342 (Nippon Steel Chemical Co., Ltd's alkyl phenolic type epoxy resin), エ ポ ト ー ト ZX 1247, GK 5855 (Nippon Steel Chemical Co., Ltd's preparation of styrene novolac type epoxy resin), エ ポ ト ー ト ZX 1142L (Nippon Steel Chemical Co., Ltd's naphthol novolac type epoxy resin), ESN 155, ESN 185V, ESN 175 (Nippon Steel Chemical Co., Ltd's Beta Naphthol 99MIN aralkyl-type epoxy resin), the ESN 355 of ESN 300 series, ESN 375 (Nippon Steel Chemical Co., Ltd's bisnaphthol aralkyl-type epoxy resin), the ESN 475V of ESN 400 series, ESN 485 (Nippon Steel Chemical Co., Ltd α naphthols aralkyl-type epoxy resin) bis-phenol phenol aldehyde type epoxy resin etc., but these epoxy resin do not have the specific molecular weight distribution in the present invention.
For the epoxy resin (a) with specific molecular weight distribution obtaining using in the present invention, by regulating the mol ratio of phenols and aldehydes, and the method for low molecular weight compositions can be removed from the resol of gained and obtain.In addition, phenolic aldehyde (the ノ ボ ラ ッ Network) resin utilizing the manufacture method as shown in patent documentation 8, patent documentation 9 to obtain can also be carried out asphalt mixtures modified by epoxy resin esterified;
Patent documentation 8: Japanese Unexamined Patent Publication 2002 No. 194041 publications
Patent documentation 9: Japanese Unexamined Patent Publication 2007 No. 126683 publications.
For the mol ratio of phenols and aldehydes, adopt phenols to represent relative to the mol ratio of 1 mole of aldehydes, the ratio with more than 1 manufactures, but when mol ratio is larger, generates a large amount of two nucleomes, three nucleomes; When mol ratio is less, generate a large amount of high molecular body, two nucleomes, three nucleomes tail off.
For the epoxy resin (a) with specific molecular weight distribution obtaining using in the present invention, can adopt and obtain with the following method: utilize the solvability difference of all kinds of SOLVENTS to remove the method for two nucleomes from the resol class of gained; Two nucleomes are dissolved in the method etc. of removing in alkali aqueous solution, also can adopt other known separation method.
Use known epoxidizing method can obtain having the phenol aldehyde type epoxy resin of specific molecular weight distribution to the resol controlling molecular weight.Or, by utilizing various method to remove two nucleome compositions from commercially available phenol aldehyde type epoxy resin, the phenol aldehyde type epoxy resin with specific molecular weight distribution also can be obtained.Also other known separation method can be adopted.
The epoxy resin (a) with specific molecular weight distribution used in the present invention, preferably two nucleome containing ratios are 15 below area %, more preferably 5 area % ~ 12 area %.By containing two a small amount of nucleomes, the physical property such as bonding force can be improved.Three nucleome containing ratios are preferably 15 area % ~ 60 area %, are more preferably 20 area % ~ 50 area %.When the containing ratio of three nucleomes is less than 15 area %, thermotolerance is easily deteriorated; During more than 60 area %, cementability is easily deteriorated.Should illustrate, not specify especially about scopes more than four nucleomes and five nucleomes, but total containing ratio of three nucleomes and four nucleomes is preferably 30 area % ~ 70 area %.When total containing ratio of three nucleomes and four nucleomes is in the scope of 30 area % ~ 70 area %, improve flame retardant resistance further.Containing ratios more than five nucleomes is preferably 45 below area %, is more preferably 40 below area %.If containing ratio 45 below area % more than five nucleomes, then can obtain the higher cured article of bonding force.Number-average molecular weight is preferably 350 ~ 700, is more preferably 380 ~ 600.When number-average molecular weight is more than 700, the viscosity of the phosphorous epoxy resin (A) of gained uprises, and may produce detrimentally affect to operability, base material impregnability.For utilizing these conditions, thus make the reason that the flame retardant resistance of the phosphorous epoxy resin (A) obtained is improved, think the Young's modulus step-down of the cured article due to gained, thus the carbon (チ ャ ー generated when burning) become more strong, bring higher insulation effect, but invalidated.
The phosphorus compound that the general formula (1) used in the present invention represents, specifically, can enumerate: dimethyl phosphine, diethyl phosphine, diphenylphosphine, 9,10 dihydro 9 oxa-10 phospho hetero phenanthrene 10 oxide compounds (HCA Sanko Co., Ltd. system), dimethyl phosphine oxide compound, diethyl phosphine oxide, dibutyl phosphine oxide, diphenyl phosphine oxide, 1,4 cyclooctene phosphine oxides, 1,5 cyclooctene phosphine oxides (CPHO Nippon Chemical Ind system) etc.These phosphorus compounds can be used alone also can two or more be used in combination, is not limited to these.
Naphtoquinone compounds in the present invention, can enumerate: benzoquinones, naphthoquinones, toluquinone, anthraquinone and their isomer, have the naphtoquinone compounds etc. of hydrocarbyl substituent, and can be used alone also can two or more be used in combination, is not limited to these.The molar ratio of the phosphorus compound that general formula (1) represents and naphtoquinone compounds, is preferably phosphorus compound: naphtoquinone compounds=below 1:1, be more preferably 1:0.99 ~ 0.2, expect for 1:0.98 ~ 0.40.When naphtoquinone compounds becomes surplus, remain in phosphorous epoxy resin (A) as unreacted component, therefore easily cause physical property to reduce; Lower than 0.2 time, may to thermotolerance, flame retardant resistance produce detrimentally affect.In addition, after phosphorus compound and naphtoquinone compounds react, can use and only take out the material after reacted constituent by purifying.
Phosphorous epoxy resin (A) of the present invention is that phosphorus compound, naphtoquinone compounds and the epoxy resin (a) with specific molecular weight distribution represented by general formula (1) obtains as essential component reaction, but not having in influential scope to action effect of the present invention, other known conventional epoxy resin, properties-correcting agent can also be used further.
The reaction of the phosphorus compound that general formula (1) represents, naphtoquinone compounds and the epoxy resin (a) with specific molecular weight distribution can adopt known method to carry out.There is following method: after phosphorus compound and naphtoquinone compounds being reacted, and then the method for reacting with epoxy resin (a); After phosphorus compound and naphtoquinone compounds are reacted in epoxy resin (a), and then the method for reacting with epoxy resin (a); Obtain product phosphorus compound and naphtoquinone compounds reacted in advance, then the method etc. of reacting with epoxy resin (a), in the present invention, to reactions steps, there is no particular limitation.
Temperature of reaction can be the temperature of setting usually in the synthesis of indirect method epoxy resin, is 100 DEG C ~ 250 DEG C, is preferably 120 DEG C ~ 200 DEG C.
In reaction, in order to shorten the time, reduce temperature of reaction, catalyzer can be used.Spendable catalyzer has no particular limits, and can use normally used catalyzer in the synthesis of indirect method epoxy resin.Such as, the quaternary ammonium salt such as tertiary amines, tetramethyl ammonium chloride, the triphenylphosphines, three (2 such as benzyl dimethyl amine, 6 Dimethoxyphenyls) the various catalyzer such as imidazoles such as phosphonium salt class, glyoxal ethyline, 2-ethyl-4-methylimidazole such as phosphine class, second base three phenyl phosphonium bromide such as phosphine, can be used alone, also can two or more and use, be not limited to these.In addition, can also separate to be divided into and use for several times.
Catalytic amount is not particularly limited, relative to epoxy resin (a) and can and the gross weight of other known conventional epoxy resin be below 5 quality %, be more preferably below 1 quality %, more preferably below 0.5 quality %.When catalytic amount is more, according to circumstances carry out the auto-polymerization reaction of epoxy group(ing), therefore resin viscosity uprises, not preferably.
When the phosphorus compound represented by general formula (1), naphtoquinone compounds and the epoxy resin (a) with specific molecular weight distribution react, as required, in the scope not damaging characteristic of the present invention, can also and with various epoxy resin modification agent.As properties-correcting agent, can enumerate: dihydroxyphenyl propane, Bisphenol F, dihydroxyphenyl propane D, tetrabutyl dihydroxyphenyl propane, quinhydrones, toluhydroquinone, dimethyl hydroquinone, dibutyl quinhydrones, Resorcinol, methylresorcinol, biphenol (PVC Off ェ ノ ー Le), tetramethyl-biphenol, dihydroxy naphthlene, dihydroxydiphenyl ether, dihydroxyl stibene class, lacquer resins, Cresol Formaldehyde Resin, bisphenol A phenolic resin, dicyclopentadiene phenolic resin, phenol aralkyl resin, naphthol novolac resin, terpene phenolic resin, heavy oil modified phenolic resins, the various phenols such as bromination lacquer resins, various phenols and hydroxy benzaldehyde, crotonic aldehyde, the condensation reaction of the various aldehydes of oxalic dialdehyde etc. and the polyphenol urea formaldehyde obtained, aniline, phenylenediamine, Tolylamine, xylidene(s), diethyl toluene diamine, diaminodiphenyl-methane, diamino-diphenyl ethane, diamino-diphenyl propane, diamino-diphenyl ketone, diamino-diphenyl sulfide, diamino diphenyl sulfone, two (aminophenyl) fluorenes, diamino diethyl-dimethyl ditan, diamino-diphenyl ether, diaminobenzene formylaniline, benzidine, tolidine, biphenyl tetramine, two aminophenyl anthracene, two amino-benzene oxygen benzene, two aminophenoxy phenyl ether, two amino-benzene oxygen biphenyl, two aminophenoxy phenyl sulfone, two aminophenoxy phenyl propane, the amine compound such as diaminonaphthalene, are not limited to these, and two or more kinds may be used.
When the phosphorus compound represented by general formula (1), naphtoquinone compounds and the epoxy resin (a) with specific molecular weight distribution react, as required, the degree of characteristic of the present invention can also do not damaged and with other various epoxy resins.As can and epoxy resin, specifically can enumerate: エ ポ ト ー ト YDC 1312, ZX 1027 (Nippon Steel Chemical Co., Ltd's hydrogen manufacturing quinoid epoxy resin), YX 4000 (Mitsubishi chemical Co., Ltd's system) ZX 1251 (Nippon Steel Chemical Co., Ltd's bisphenol-type epoxy resin), 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 (Nippon Steel Chemical Co., Ltd BPA type epoxy resin), 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 (Nippon Steel Chemical Co., Ltd BPF type epoxy resin), エ ポ ト ー ト YDPN 638 (Nippon Steel Chemical Co., Ltd's novolac type epoxy resin), エ ポ ト ー ト YDCN 701 (Nippon Steel Chemical Co., Ltd's cresoform type epoxy resin), ZX 1201 (Nippon Steel Chemical Co., Ltd's bisphenol fluorene type epoxy resin), NC 3000 (Nippon Kayaku K. K's biphenyl aralkyl phenol aldehyde type epoxy resin), EPPN 501H, EPPN 502H (Nippon Kayaku K. K's polyfunctional epoxy resin) ZX 1355 (Nippon Steel Chemical Co., Ltd's naphthalenediol type epoxy resin), ESN 155, ESN 185V, ESN 175 (Nippon Steel Chemical Co., Ltd's Beta Naphthol 99MIN aralkyl-type epoxy resin), ESN 355, ESN 375 (Nippon Steel Chemical Co., Ltd's bisnaphthol aralkyl-type epoxy resin), ESN 475V, the epoxy resin that ESN 485 (Nippon Steel Chemical Co., Ltd α naphthols aralkyl-type epoxy resin) etc. is manufactured by the oxybenzene compounds such as polyphenol urea formaldehyde and epoxyhalopropane, エ ポ ト ー ト YH 434, the epoxy resin that エ ポ ト ー ト YH 434GS (Nippon Steel Chemical Co., Ltd's diaminodiphenyl-methane four glycidyl group ether) etc. is manufactured by amine compound and epoxyhalopropane, the epoxy resin etc. that YD 171 (Nippon Steel Chemical Co., Ltd's dimer acid type epoxy resin) etc. is manufactured by carboxylic-acid and epoxyhalopropane, but be not limited to these, two or more kinds may be used.
When the phosphorus compound represented by general formula (1), naphtoquinone compounds and the epoxy resin (a) with specific molecular weight distribution react, as required, inert solvent can also be used.Specifically hexane can be used, heptane, octane, decane, dimethylbutane, amylene, hexanaphthene, methylcyclohexane, benzene, toluene, dimethylbenzene, the various hydrocarbon such as ethylbenzene, ether, isopropyl ether, butyl ether, diisoamyl ether, methyl phenyl ether, ethylphenyl ether, amyl group phenyl ether, ethyl benzyl ether, diox, methyl furan, the ethers such as tetrahydrofuran (THF), methylcyclohexane (methyl cellosolve), methylcellosolve acetate, ethyl cellosolve, cellosolve acetate, ethylene glycol isopropyl ether, diethylene glycol dimethyl ether, methylethyl Trivalin SF, propylene glycol monomethyl ether, dimethyl formamide, dimethyl sulfoxide (DMSO) etc., but be not limited to these, can two or more be used in combination.
Phosphorous epoxy resin (A) of the present invention, by the phosphorous composition epoxy resin coordinating solidifying agent can obtain solidified nature.As solidifying agent, can use the normally used hardener for epoxy resin such as various resol class, anhydrides, amine, hydrazides class, acidic polyester class, these solidifying agent only can use a kind, also can use two or more.Wherein, as the solidifying agent contained in curable epoxy resin composition of the present invention, particularly preferably Dyhard RU 100 or phenol system solidifying agent.In curable epoxy resin composition of the present invention, the usage quantity of solidifying agent is, relative to functional group and epoxy group(ing) 1 equivalent of epoxy resin, the functional group of solidifying agent is preferably 0.4 ~ 2.0 equivalent, is more preferably 0.5 ~ 1.5 equivalent, is particularly preferably 0.5 ~ 1.0 equivalent.Relative to epoxy group(ing) 1 equivalent, when solidifying agent is less than 0.4 equivalent, or during more than 2.0 equivalent, solidification becomes incomplete, possibly cannot obtain good solidification physical property.
As the concrete example of the phenol system solidifying agent that can use in curable epoxy resin composition of the present invention, can example: dihydroxyphenyl propane, Bisphenol F, bisphenol-c, bis-phenol K, bisphenol Z, bisphenol S, tetramethyl-dihydroxyphenyl propane, tetramethyl-Bisphenol F, tetramethyl-bisphenol S, tetramethyl-bisphenol Z, dihydroxydiphenyl sulfide, the bisphenols such as 4,4 ' thiobis (3 methyl 6 tert.-butyl phenol), and, catechol, Resorcinol, methylresorcinol, quinhydrones, monomethyl quinhydrones, dimethyl hydroquinone, Trimethylhydroquinone, single tertiary butylated hydroquinone, the dihydroxy-benzene classes such as di-tert-butyl hydroquinone, dihydroxy naphthlene, bishydroxymethyl naphthalene, bishydroxymethyl naphthalene, the hydroxyl naphthalene classes such as trihydroxynaphthalene, lacquer resins, DC 5 (Nippon Steel Chemical Co., Ltd's Cresol Formaldehyde Resin), the condenses of the phenol such as naphthol novolac resin and/or aphthols and aldehydes, SN 160, SN 395, the condenses of the phenol such as SN 485 (Nippon Steel Chemical Co., Ltd's system) and/or aphthols and xylyl alcohol, the condenses of phenol and/or aphthols and pseudoallyl methyl phenyl ketone, the reactant of phenol and/or aphthols and Dicyclopentadiene (DCPD), the oxybenzene compounds etc. such as the condenses of phenol and/or aphthols and biphenyl system condensing agent.
As above-mentioned phenol, can enumerate: phenol, cresols, xylenol, butylphenol, amyl phenol, nonylphenol, butyl methyl phenol, pseudocuminol, phenylphenol etc.; As aphthols, can enumerate: 1 naphthols, 2 naphthols etc.
As aldehydes, can example: formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, phenyl aldehyde, chloral, bromal, oxalic dialdehyde, mda, suceinic aldehyde, glutaraldehyde, hexanedial, heptan dialdehyde, decanedial, propenal, crotonic aldehyde, salicylic aldehyde, phthalaldehyde, hydroxy benzaldehyde etc.As biphenyl system condensing agent, can example: two (methylol) biphenyl, two (methoxymethyl) biphenyl, two (ethoxyl methyl) biphenyl, two (chloromethyl) biphenyl etc.
As other known conventional solidifying agent that can use in curable epoxy resin composition of the present invention, can enumerate: the amine compounds etc. such as the condenses of the acids such as anhydrides, diethylenetriamine, Triethylenetetramine (TETA), m-xylene diamine, isophorone diamine, diaminodiphenyl-methane, diamino diphenyl sulfone, diamino-diphenyl ether, Dyhard RU 100, dimeracid such as methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, methyl Na Dike acid and polyamines class and daiamid.
And then, as causing the polymerization of epoxy group(ing) and making the solidifying agent of solidification, can example: the phosphine compounds such as triphenylphosphine, the phosphonium salts such as 4-phenyl phosphonium bromide, 2 Methylimidazoles, 2 phenylimidazoles, 2 ethyl 4 Methylimidazoles, 2 undecyl imidazoles, the imidazoles such as 1 cyano ethyl 2 Methylimidazole and they and trimellitic acid, tricarbimide, the salt of boron etc. and imidazole salt, benzyl dimethyl amine, 2, 4, the amines such as 6 three (dimethylaminomethyl) phenol, the quaternary ammonium salts such as trimethyl ammonium chloride, diazabicylo compound and they and phenols, salt 3 boron fluoride of lacquer resins class etc. and amine, the complex compound of ether compound etc., Fang Xiang Zu Phosphonium or salt compounded of iodine etc.These solidifying agent may be used alone, two or more kinds can also be used.
The mixing ratio of other the known conventional epoxy curing agent used in composition epoxy resin of the present invention is, relative to epoxy group(ing) 1 equivalent, the functional group of solidifying agent is 0.5 ~ 1.5 equivalent, the ratio being preferably 0.8 ~ 1.2 equivalent.In addition, cause the polymerization of epoxy group(ing) and make the mixing ratio of the solidifying agent of solidification be relative to epoxy resin 100 mass parts, be 0.1 ~ 10 mass parts, be more preferably 0.2 ~ 5 mass parts.
In flame-retardant epoxy resin omposition containing phosphorous epoxy resin (A) of the present invention, as viscosity adjustment use, can also be with an organic solvent.As spendable organic solvent, do not specify especially, can enumerate: N, the alcohols such as the ketones such as the ethers such as the amidess such as N dimethyl formamide, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl alcohol, ethanol, benzene, toluene etc. are aromatic hydrocarbon based, one or more solvents mixed in these solvents can be coordinated with the scope that epoxy resin concentration is 20 ~ 90 quality %.
In the present composition, as required, curing catalyst can be used.As the example of spendable curing catalyst, can enumerate: imidazoles, 2 (dimethylaminomethyl) phenol, 1 such as 2 Methylimidazoles, 2 ethyl imidazol(e)s, 2 ethyl 4 Methylimidazoles, 8 diazabicyclos (5,4,0) metallic compounds such as phosphine class, stannous octoate such as tertiary amines, triphenylphosphine, tricyclohexyl phosphine, triphenylphosphine triphenylborane such as undecylene 7.Relative to epoxy resin ingredient 100 mass parts in composition epoxy resin of the present invention, the curing catalyst of 0.02 ~ 5.0 mass parts can be used as required.By using curing catalyst, solidification value can be reduced or shorten set time.
Filler can be used as required in the present composition.Specifically can enumerate: the mineral fillers such as aluminium hydroxide, magnesium hydroxide, talcum, calcination of talc, clay, kaolin, boehmite, titanium oxide, glass powder, silicon-dioxide air bag (シ リ カ バ ル ー Application), can also coordinate pigment etc.As the reason usually using inorganic filling material, raising shock-resistance can be enumerated.In addition, when using the metal hydroxides such as aluminium hydroxide, magnesium hydroxide, work as flame retardant, even if phosphorus containing ratio also can guarantee flame retardant resistance less.If particularly use level is not more than 10 quality %, then the effect of shock-resistance is little.But, if use level is more than 150 quality %, then reduce as the necessary project of laminated plate purposes and cementability.In addition, the organic filler materials such as the cellulosic packing materials such as glass fibre, pulp fibers, synthon, ceramic fiber, particulate rubber, thermoplastic elastomer can also be contained in above-mentioned resin combination.
By solidifying composition epoxy resin of the present invention, epoxy resin cured product can be obtained.During solidification, such as, by becoming the form such as Copper Foil, prepreg of resin sheet, resin, lamination can be carried out and heat-pressure curing, thus the phosphorous epoxy resin cured product as laminated plate can be obtained.
Make the phosphorous composition epoxy resin employing phosphorous epoxy resin (A) of the present invention, be heating and curing, the result evaluating the phosphorous epoxy resin cured product of laminated plate is by this, by phosphorus compound, the phosphorous epoxy resin (A) that naphtoquinone compounds reacts with the epoxy resin (a) with specific molecular weight distribution and obtains, as compared to the phosphorous epoxy resin obtained by known phosphorus compound and epoxy resin, be not only low viscosity, operability is good, and high heat resistance and high adhesion can be had concurrently, and then can also flame retardant resistance be improved.
Embodiment
Enumerate embodiment and comparative example to specifically describe the present invention, but the present invention is not limited to these.In case of no particular description, " part " represents mass parts, " % " represent quality %.Measuring method adopts following method to measure respectively.
Measuring method is as follows.
Epoxy equivalent (weight): according to JIS K7236.
Two nucleome containing ratios, three nucleome containing ratios, four nucleome containing ratios, the above containing ratio of five nucleomes, number-average molecular weight (Mn), weight-average molecular weight (Mw), with dispersity (Mw/Mn): use gel permeation chromatography molecular weight distribution, two nucleome containing ratios, three nucleome containing ratios, four nucleome containing ratios, the above containing ratio of five nucleomes is calculated by the area % at peak, number-average molecular weight, weight-average molecular weight, dispersity is by monodisperse polystyrene (the TOSOH Co., Ltd A 500 utilizing standard, A 1000, A 2500, A 5000, F 1, F 2, F 4, F 10, F 20, F 40) typical curve obtained converts.Particularly, be used in main body (TOSOH Co., Ltd HLC 8220GPC) upper possess post (TOSOH Co., Ltd TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL) in upright arrangemently equipment, make column temperature be 40 DEG C.In addition, elutriant uses tetrahydrofuran (THF), and flow velocity is 1ml/min, and detector uses RI (differential refractometer) detector.
Phosphorus containing ratio: add sulfuric acid, hydrochloric acid, perchloric acid in test portion, carries out heating and carries out wet combustion, makes whole phosphorus atom become ortho-phosphoric acid.Metavanadate and molybdate reaction is made in sulfuric acid solution, measure phosphovanadomolybdic acid complex compound (the リ Application バ ナ ー De モ リ Block デ ン Suan Wrong body) absorbancy at 420nm place generated, adopt in advance with the typical curve that potassium primary phosphate is made, the phosphorus atom containing ratio obtained represents with %.The phosphorus containing ratio of laminated plate represents as the containing ratio of the resinous principle relative to laminated plate.
Peel strength of copper foil and layers cementing power: measure according to JIS C 6481, layers cementing power carries out avulsing measuring between the 7th layer and the 8th layer.
Incendivity: according to UL94 (the safety certification specification of Underwriters Laboratories Inc.).5 test films are tested, by the 1st time with the 2nd time contact flame (connecing inflammation) (5 difference each twice altogether 10 contact flames) after the showing with stopwatch total time of flaming combustion time length.
Second-order transition temperature DSC: use Differential Scanning Calorimetry determinator (エ ス ア イ ア イ Na ノ テ Network ノ ロ ジ ー Co., Ltd. EXSTAR6000 DSC6200), measure with the Elevated Temperature Conditions of 10 DEG C/min, represent with the temperature of DSC extrapolated value now.
Second-order transition temperature TMA: use thermo-mechanical analysis device (エ ス ア イ ア イ Na ノ テ Network ノ ロ ジ ー Co., Ltd. EXSTAR6000 TMA/SS120U), measure with the Elevated Temperature Conditions of 5 DEG C/min, represent with the temperature of TMA extrapolated value now.
The epoxy resin used in embodiment and comparative example is as follows.
エ Port ト ー ト YDPN 638 (the adding up to 25 area %, five nucleomes above containing ratio 53 area %, number-average molecular weight 528, weight-average molecular weight 1127, dispersity 2.13, epoxy equivalent (weight) 176g/eq of the universal novolac type epoxy resin of Nippon Steel Chemical Co., Ltd's system, two nucleome containing ratio 22 area %, three nucleome containing ratio 15 area %, three nucleomes and four nucleome containing ratios) (with reference to Fig. 1)
エ ポ ト ー ト YDF 170 (Nippon Steel Chemical Co., Ltd bisphenol f type epoxy resin epoxy equivalent (weight) 170g/eq).
Synthesis example 1 (synthesis of lacquer resins)
In the detachable flask of glass system of 4 mouthfuls possessing whipping appts, thermometer, prolong, nitrogen gatherer, add phenol 2500 parts, oxalic acid dihydrate 7.5 parts, import nitrogen and stir, carry out heat temperature raising.Start to drip 37.4% formalin 474.1 parts at 80 DEG C, spend and complete dropping in 30 minutes.And then make temperature of reaction remain on 92 DEG C, carry out reaction in 3 hours.Heat up, water generation reaction is got rid of to outside system, while be warming up to 110 DEG C.By residual phenol 160 DEG C, decompression under reclaim, obtain lacquer resins.And then raised temperature, reclaim a part of two nucleomes.Utilize two nucleome containing ratios and the three nucleome containing ratios of the lacquer resins of gel permeation chromatography gained, be respectively 10 area % and 38 area %.
Synthesis example 2 (synthesis of novolac type epoxy resin)
To in the device same with synthesis example 1, add the lacquer resins 665.8 parts of synthesis example 1, Epicholorohydrin 2110.8 parts, 17 parts, water, stir and be warming up to 50 DEG C.Add 49% aqueous sodium hydroxide solution 14.2 parts, carry out reaction in 3 hours.Be warming up to 64 DEG C, reduce pressure with the degree of the backflow causing water, spend 3 hours and drip 49% aqueous sodium hydroxide solution 457.7 parts, react.Temperature is increased to 70 DEG C, dewaters, make temperature be 135 DEG C, reclaim residual Epicholorohydrin.Return to normal pressure, add MIBK 1232 parts and make dissolving.Add ion exchanged water 1200 parts, stir and leave standstill, by product salt to be dissolved in water and to remove.Then add 49% aqueous sodium hydroxide solution 37.4 parts, 80 DEG C of stirring reactions 90 minutes, carry out purification reaction.Add MIBK, carry out several washing, deionizing impurity.Recycling design, obtains phenol aldehyde type epoxy resin.Two nucleome containing ratio 9 area %, three nucleome containing ratio 36 area %, three nucleomes and four nucleome containing ratios add up to 53 area %, five nucleomes above containing ratio 38 area %, number-average molecular weight 513, weight-average molecular weight 713, dispersity 1.39, epoxy equivalent (weight) 174g/eq (with reference to Fig. 2).
Embodiment 1
To in the device same with synthesis example 1, add HCA (Sanko Co., Ltd.'s system 9,10 dihydro 9 oxa-10 phospho hetero phenanthrene 10 oxide compound phosphorus containing ratio 14.2%) 127 parts, toluene 270 parts, carry out heating for dissolving.Then note heat release while add Isosorbide-5-Nitrae naphthoquinones (Tokyo HuaCheng Industry Co., Ltd's purity more than 98%) 70 parts, temperature is remained on less than 90 DEG C, keep 30 minutes.And then slowly raised temperature, at a reflux temperature maintenance 2 hours.After reclaiming a part of toluene, add the novolac type epoxy resin 804 parts of synthesis example 2, import nitrogen and stir, be warming up to 130 DEG C.Triphenylphosphine is added 0.20 part as catalyzer, at 160 DEG C, carries out reaction in 3 hours.The epoxy equivalent (weight) of the epoxy resin of gained is 276g/eq, phosphorus containing ratio is 1.8%.The results are summarized in table 1.
Embodiment 2
HCA 141 parts, Isosorbide-5-Nitrae naphthoquinones 77 parts, the novolac type epoxy resin 782 parts of synthesis example 2, triphenylphosphine 0.22 part, carry out same operation with embodiment 1 in addition.The epoxy equivalent (weight) of the epoxy resin of gained is 294g/eq, phosphorus containing ratio is 2.0%.The results are summarized in table 1.
Embodiment 3
HCA 155 parts, Isosorbide-5-Nitrae naphthoquinones 85 parts, the novolac type epoxy resin 760 parts of synthesis example 2, triphenylphosphine 0.24 part, carry out same operation with embodiment 1 in addition.The epoxy equivalent (weight) of the epoxy resin of gained is 317g/eq, phosphorus containing ratio is 2.2%.The results are summarized in table 1.
Embodiment 4
HCA 141 parts, Isosorbide-5-Nitrae naphthoquinones 83 parts, the novolac type epoxy resin 726 parts of synthesis example 2, triphenylphosphine 0.22 part and then coordinate YDF 170B 50 parts with novolac type epoxy resin, carry out same operation with embodiment 1 simultaneously in addition.The epoxy equivalent (weight) of the epoxy resin of gained is 297g/eq, phosphorus containing ratio is 2.0%.The results are summarized in table 1.
Embodiment 5
HCA 155 parts, Isosorbide-5-Nitrae naphthoquinones 57 parts, the novolac type epoxy resin 638 parts of synthesis example 2, triphenylphosphine 0.21 part and then coordinate YDF 170 150 parts with novolac type epoxy resin, carry out same operation with embodiment 1 simultaneously in addition.The epoxy equivalent (weight) of the epoxy resin of gained is 286g/eq, phosphorus containing ratio is 2.2%.The results are summarized in table 1.
Embodiment 6
HCA 155 parts, 1,4 naphthoquinones 34 parts, the novolac type epoxy resin 777 parts of synthesis example 2, triphenylphosphine 0.19 part, and then coordinate BRG 555 (Showa Denko K. K's lacquer resins) 34 parts with novolac type epoxy resin simultaneously, carry out same operation with embodiment 1 in addition.The epoxy equivalent (weight) of the epoxy resin of gained is 310g/eq, phosphorus containing ratio is 2.2%.The results are summarized in table 1.
Embodiment 7
HCA 155 parts, Isosorbide-5-Nitrae naphthoquinones 23 parts, the novolac type epoxy resin 779 parts of synthesis example 2, triphenylphosphine 0.18 part and then coordinate BRG 555 43 parts with novolac type epoxy resin, carry out same operation with embodiment 1 simultaneously in addition.The epoxy equivalent (weight) of the epoxy resin of gained is 310g/eq, phosphorus containing ratio is 2.2%.The results are summarized in table 1.
[table 1]
。
Comparative example 1
In the device same with synthesis example 1, add YDPN 638 824 parts, HCA 176 parts, import nitrogen and stir, carry out heat temperature raising.At 130 DEG C, triphenylphosphine is added 0.18 part as catalyzer, at 160 DEG C, carry out reaction in 3 hours.The epoxy equivalent (weight) of the epoxy resin of gained is 263g/eq, phosphorus containing ratio is 2.5%.The results are summarized in table 1.
Comparative example 2
The novolac type epoxy resin 824 parts of synthesis example 2, HCA 176 parts, carries out same operation with comparative example 1 in addition.The epoxy equivalent (weight) of the epoxy resin of gained is 266g/eq, phosphorus containing ratio is 2.5%.The results are summarized in table 1.
Comparative example 3
HCA 141 parts, Isosorbide-5-Nitrae naphthoquinones 77 parts, YDPN 638 782 parts, triphenylphosphine 0.22 part, carry out same operation with embodiment 1 in addition.The epoxy equivalent (weight) of the epoxy resin of gained is 303g/eq, phosphorus containing ratio is 2.0%.The results are summarized in table 1.
Comparative example 4
HCA 155 parts, Isosorbide-5-Nitrae naphthoquinones 80 parts, YDPN 638 465 parts, triphenylphosphine 0.23 part and then coordinate YDF 170 300 parts with novolac type epoxy resin, carry out same operation with embodiment 1 simultaneously in addition.The epoxy equivalent (weight) of the epoxy resin of gained is 311g/eq, phosphorus containing ratio is 2.2%.The results are summarized in table 1.
Embodiment 8 ~ embodiment 14 and comparative example 5 ~ comparative example 8
Using the epoxy resin of embodiment 1 ~ embodiment 7, comparative example 1 ~ comparative example 4, coordinate as the Dyhard RU 100 of solidifying agent according to the prescription of table 2, be dissolved in methyl ethyl ketone, propylene glycol monomethyl ether, N, in the mixed solvent of N dimethyl formamide modulation, obtain composition epoxy resin varnish.
The resin composition Chinese varnish of gained is soaked in woven fiber glass WEA 7628 XS13 (Nitto Boseki Co. Ltd 0.18mm is thick).Woven fiber glass through soaking into being carried out drying with the recirculation furnace of 150 DEG C, obtaining prepreg.By prepreg 8 overlaps of gained, lower overlapping Copper Foil (Mitsu Mining & Smelting Co., Ltd 3EC) thereon, carries out 130 DEG C × 15 minutes and 170 DEG C × 20Kg/cm2 × 70 minute are heated, pressurization, obtains laminated plate.Laminated plate by TMA, DSC, DMS measure second-order transition temperature, peel strength of copper foil, layers cementing power, flame retardant test the results are summarized in table 2.
[table 2]
。
As shown in table 1, table 2, the phosphorus compound that general formula (1) is represented, naphtoquinone compounds and there is epoxy resin (a) reaction of specific molecular weight distribution and the phosphorous epoxy resin (A) that obtains, with use the epoxy resin not carried out by naphtoquinone compounds reacting, the situation of the novolac type epoxy resin without specific molecular weight distribution compares, for low viscosity and second-order transition temperature, bonding force are high, and obtain flame retardant resistance with low phosphorus containing ratio.
utilizability in industry
Specific phosphorus compound, naphtoquinone compounds and the epoxy resin (a) with specific molecular weight distribution carry out reacting as essential component and the phosphorous epoxy resin (A) obtained by the present invention, can be used as the epoxy resin of flame retardant resistance, thermotolerance, circuit board use excellent in adhesion.
Claims (6)
1. phosphorous epoxy resin (A), it is characterized in that, it is that phosphorus compound, naphtoquinone compounds and the epoxy resin (a) represented by general formula (1) carries out reacting as essential component and the phosphorous epoxy resin obtained, wherein, epoxy resin (a) is in the mensuration of gel permeation chromatography, has the phenol aldehyde type epoxy resin that two nucleome containing ratios are 15 below area %, three nucleome containing ratios are 15 area % ~ 60 area %, number-average molecular weight is the molecular weight distribution of 350 ~ 700;
Gel permeation chromatography condition:
Use the equipment possessing TOSOH Co., Ltd TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL in upright arrangemently, make column temperature be 40 DEG C; Elutriant uses tetrahydrofuran (THF), and flow velocity is 1ml/min, and detector uses RI (differential refractometer) detector; Measuring test portion is THF sample 0.1g being dissolved in 10ml; Adopt chromatographic computation two nucleome containing ratio and the three nucleome containing ratios of gained, utilize the standard curve determination number-average molecular weight of polystyrene standard;
In formula, R1 and R2 represents alkyl, can be the same or different, and R1, R2 can form ring texture together with phosphorus atom, and n represents 0 or 1.
2. phosphorous composition epoxy resin, wherein, using phosphorous epoxy resin (A) according to claim 1 and solidifying agent as essential component, relative to epoxy group(ing) 1 equivalent of phosphorous epoxy resin (A), active group 0.3 equivalent ~ 1.5 equivalent of solidifying agent is coordinated to form.
3. epoxy resin cured product, it is formed by phosphorous epoxy resin composition according to claim 2.
4. prepreg, it is soaked into by phosphorous composition epoxy resin according to claim 2 to form in the substrate.
5. laminated plate, it is formed by phosphorous epoxy resin composition according to claim 2.
6. circuit substrate, it is formed by phosphorous epoxy resin composition according to claim 2.
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CN201811147674.9A CN109293881B (en) | 2012-06-15 | 2013-05-13 | Phosphorus-containing epoxy resin, composition containing the epoxy resin as essential component, and cured product |
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CN201380030849.7A Active CN104379626B (en) | 2012-06-15 | 2013-05-13 | Phosphorous epoxy resin and using the epoxy resin as the composition of essential component, solidfied material |
CN201810193561.6A Active CN108314774B (en) | 2012-06-15 | 2013-05-13 | Phosphorus-containing epoxy resin, composition containing the epoxy resin as essential component, and cured product |
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JP (1) | JP6067699B2 (en) |
KR (1) | KR102038173B1 (en) |
CN (3) | CN109293881B (en) |
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TW (1) | TWI598371B (en) |
WO (1) | WO2013187184A1 (en) |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04220422A (en) * | 1990-12-20 | 1992-08-11 | Nippon Kayaku Co Ltd | Epoxy resin, resin composition containing same, and cured article prepared from the composition |
JP2002012739A (en) * | 2000-06-29 | 2002-01-15 | Nippon Kayaku Co Ltd | Flame-retardant epoxy resin composition and use thereof |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3268498B2 (en) | 1990-05-01 | 2002-03-25 | 東都化成株式会社 | Phosphorus-containing flame-retardant epoxy resin |
JP3092009B2 (en) | 1990-05-01 | 2000-09-25 | 東都化成株式会社 | Flame retardant and thermosetting flame-retardant resin composition containing the flame retardant |
JP3613724B2 (en) | 1997-09-09 | 2005-01-26 | 東都化成株式会社 | Phosphorus-containing epoxy resin composition |
JP3533973B2 (en) | 1998-01-27 | 2004-06-07 | 東都化成株式会社 | Phosphorus-containing epoxy resin composition |
JP2001123049A (en) | 1999-10-28 | 2001-05-08 | Dainippon Ink & Chem Inc | Flame-retardant epoxy resin composition |
JP3651843B2 (en) * | 1999-12-16 | 2005-05-25 | 住友ベークライト株式会社 | Method for producing phenolic resin |
JP4588834B2 (en) | 2000-04-06 | 2010-12-01 | パナソニック電工株式会社 | Phosphorus-containing epoxy resin composition, flame-retardant resin sheet using the phosphorus-containing epoxy resin, metal foil with resin, prepreg and laminate, multilayer board |
JP4837175B2 (en) * | 2001-02-23 | 2011-12-14 | 新日鐵化学株式会社 | Phosphorus-containing epoxy resin composition |
JP4906020B2 (en) | 2001-07-26 | 2012-03-28 | 新日鐵化学株式会社 | Phosphorus-containing phenol resin and epoxy resin composition using the phenol resin |
JP4435791B2 (en) * | 2001-11-16 | 2010-03-24 | 旭有機材工業株式会社 | Method for producing novolac-type phenolic resin and resin-coated sand |
WO2006001445A1 (en) * | 2004-06-29 | 2006-01-05 | Asahi Kasei Chemicals Corporation | Flame-retardant epoxy resin composition |
US20090143511A1 (en) * | 2004-07-13 | 2009-06-04 | Hitachi Chemical Co., Ltd. | Encapsulated epoxy-resin molding compound, and electronic component device |
JP5632163B2 (en) * | 2007-11-09 | 2014-11-26 | 新日鉄住金化学株式会社 | Phosphorus-containing epoxy resin and phosphorus-containing epoxy resin composition, production method thereof, curable resin composition and cured product using the resin, and resin composition |
JP5547386B2 (en) * | 2008-09-25 | 2014-07-09 | パナソニック株式会社 | Epoxy resin composition for prepreg, prepreg, and multilayer printed wiring board |
JP5441477B2 (en) * | 2009-04-01 | 2014-03-12 | 新日鉄住金化学株式会社 | Flame retardant phosphorus-containing epoxy resin composition and cured product thereof |
JP5686512B2 (en) * | 2009-11-05 | 2015-03-18 | 新日鉄住金化学株式会社 | Phosphorus-containing epoxy resin, resin composition, and flame-retardant cured product thereof |
JP5544184B2 (en) * | 2010-02-08 | 2014-07-09 | 新日鉄住金化学株式会社 | Method for producing phosphorus-containing epoxy resin, epoxy resin composition and cured product thereof |
JP5579008B2 (en) * | 2010-09-29 | 2014-08-27 | 新日鉄住金化学株式会社 | Phosphorus-containing epoxy resin |
-
2013
- 2013-05-13 KR KR1020147034499A patent/KR102038173B1/en active IP Right Grant
- 2013-05-13 SG SG11201408343TA patent/SG11201408343TA/en unknown
- 2013-05-13 WO PCT/JP2013/063865 patent/WO2013187184A1/en active Application Filing
- 2013-05-13 CN CN201811147674.9A patent/CN109293881B/en active Active
- 2013-05-13 CN CN201380030849.7A patent/CN104379626B/en active Active
- 2013-05-13 CN CN201810193561.6A patent/CN108314774B/en active Active
- 2013-05-13 JP JP2014521221A patent/JP6067699B2/en active Active
- 2013-06-03 TW TW102119560A patent/TWI598371B/en active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04220422A (en) * | 1990-12-20 | 1992-08-11 | Nippon Kayaku Co Ltd | Epoxy resin, resin composition containing same, and cured article prepared from the composition |
JP2002012739A (en) * | 2000-06-29 | 2002-01-15 | Nippon Kayaku Co Ltd | Flame-retardant epoxy resin composition and use thereof |
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CN110003616B (en) * | 2017-12-12 | 2024-01-09 | 日铁化学材料株式会社 | Epoxy resin composition and cured product thereof |
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Also Published As
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KR20150031237A (en) | 2015-03-23 |
CN109293881B (en) | 2021-04-13 |
JP6067699B2 (en) | 2017-01-25 |
JPWO2013187184A1 (en) | 2016-02-04 |
CN104379626B (en) | 2019-03-22 |
WO2013187184A1 (en) | 2013-12-19 |
TWI598371B (en) | 2017-09-11 |
CN108314774B (en) | 2021-02-12 |
CN109293881A (en) | 2019-02-01 |
SG11201408343TA (en) | 2015-01-29 |
TW201402632A (en) | 2014-01-16 |
CN108314774A (en) | 2018-07-24 |
KR102038173B1 (en) | 2019-10-29 |
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