JPWO2014034675A1 - Method for producing cyanuric acid-modified phosphorus-containing epoxy resin, resin composition containing cyanuric acid-modified phosphorus-containing epoxy resin, and cured product thereof - Google Patents
Method for producing cyanuric acid-modified phosphorus-containing epoxy resin, resin composition containing cyanuric acid-modified phosphorus-containing epoxy resin, and cured product thereof Download PDFInfo
- Publication number
- JPWO2014034675A1 JPWO2014034675A1 JP2014533024A JP2014533024A JPWO2014034675A1 JP WO2014034675 A1 JPWO2014034675 A1 JP WO2014034675A1 JP 2014533024 A JP2014533024 A JP 2014533024A JP 2014533024 A JP2014533024 A JP 2014533024A JP WO2014034675 A1 JPWO2014034675 A1 JP WO2014034675A1
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- JP
- Japan
- Prior art keywords
- epoxy resin
- cyanuric acid
- phosphorus
- modified
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 182
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 182
- 150000003017 phosphorus Chemical class 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000011342 resin composition Substances 0.000 title abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 78
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000011574 phosphorus Substances 0.000 claims abstract description 73
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 54
- -1 phosphorus compound Chemical class 0.000 claims abstract description 49
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 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 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 6
- 125000004437 phosphorous atom Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 239000003063 flame retardant Substances 0.000 abstract description 6
- 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 abstract description 5
- 230000000704 physical effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 239000004593 Epoxy Substances 0.000 description 69
- 229910000831 Steel Inorganic materials 0.000 description 28
- 239000010959 steel Substances 0.000 description 28
- 238000001723 curing Methods 0.000 description 25
- 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 24
- 229910001873 dinitrogen Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 14
- 239000011521 glass Substances 0.000 description 13
- 229920003986 novolac Polymers 0.000 description 12
- 150000002989 phenols Chemical class 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 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 9
- 239000002904 solvent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 150000004780 naphthols Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 229930003836 cresol Natural products 0.000 description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N alpha-naphthol Natural products C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 150000003018 phosphorus compounds Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- 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 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-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
- JWAZRIHNYRIHIV-UHFFFAOYSA-N beta-hydroxynaphthyl Natural products C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 150000002460 imidazoles Chemical class 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
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- OVAZZMXASSWARN-UHFFFAOYSA-N naphthalen-1-ylmethanediol Chemical compound C1=CC=C2C(C(O)O)=CC=CC2=C1 OVAZZMXASSWARN-UHFFFAOYSA-N 0.000 description 2
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical group C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 1
- UQWJRHXJJRTQCX-UHFFFAOYSA-N 1-(ethoxymethyl)-4-[4-(ethoxymethyl)phenyl]benzene Chemical group C1=CC(COCC)=CC=C1C1=CC=C(COCC)C=C1 UQWJRHXJJRTQCX-UHFFFAOYSA-N 0.000 description 1
- 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
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- NWQWQKUXRJYXFH-UHFFFAOYSA-N 2,2-Dichloroacetaldehyde Chemical compound ClC(Cl)C=O NWQWQKUXRJYXFH-UHFFFAOYSA-N 0.000 description 1
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- LUHXJGDSMBXRAH-UHFFFAOYSA-N 2-(2-hydroxyphenyl)-3-methylphenol Chemical compound CC1=CC=CC(O)=C1C1=CC=CC=C1O LUHXJGDSMBXRAH-UHFFFAOYSA-N 0.000 description 1
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- OISQRSYTOVYXGK-UHFFFAOYSA-N 2-ethyl-5-methyl-1h-imidazole;1h-imidazole Chemical class C1=CNC=N1.CCC1=NC=C(C)N1 OISQRSYTOVYXGK-UHFFFAOYSA-N 0.000 description 1
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 description 1
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical compound CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical group O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 description 1
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- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- 239000005060 rubber Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
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- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- CMLWFCUAXGSMBB-UHFFFAOYSA-N tris(2,6-dimethoxyphenyl)phosphane Chemical compound COC1=CC=CC(OC)=C1P(C=1C(=CC=CC=1OC)OC)C1=C(OC)C=CC=C1OC CMLWFCUAXGSMBB-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
-
- 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
-
- 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
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/304—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing phosphorus
Abstract
シアヌル酸とリン化合物とを用いてエポキシ樹脂を変性した難燃性のシアヌル酸変性リン含有エポキシ樹脂の製造において、短時間での製造を可能とし、かつシアヌル酸の残存が極めて少なく、優れた物性を有するエポキシ樹脂硬化物を得ることができるシアヌル酸変性リン含有エポキシ樹脂の製造方法を提供する。リン化合物、シアヌル酸、及びエポキシ樹脂とを必須成分として反応して得られるシアヌル酸変性リン含有エポキシ樹脂の製造方法であって、特定のリン化合物を、シアヌル酸１モルに対して、該リン化合物を2.5〜50モルにした、シアヌル酸変性リン含有エポキシ樹脂の製造方法とそれから得られるリン含有率が1.0〜5.0質量％、窒素含有率が0.1〜2.0質量％、かつ、リン含有率と窒素含有率の総和が2.5〜5.5質量％であるシアヌル酸変性リン含有エポキシ樹脂と硬化剤を含む樹脂組成物とその硬化物である。In the production of flame retardant cyanuric acid-modified phosphorus-containing epoxy resin modified with epoxy resin using cyanuric acid and phosphorus compound, it can be manufactured in a short time, and there is very little residual cyanuric acid, and excellent physical properties The manufacturing method of the cyanuric acid modified phosphorus containing epoxy resin which can obtain the epoxy resin hardened | cured material which has this is provided. A method for producing a cyanuric acid-modified phosphorus-containing epoxy resin obtained by reacting a phosphorus compound, cyanuric acid, and an epoxy resin as essential components, wherein the specific phosphorus compound is added to 1 mol of cyanuric acid. 2.5 to 50 mol, a method for producing a cyanuric acid-modified phosphorus-containing epoxy resin, and a phosphorus content obtained from 1.0 to 5.0 mass%, a nitrogen content of 0.1 to 2.0 mass%, and a phosphorus content and nitrogen content A resin composition containing a cyanuric acid-modified phosphorus-containing epoxy resin having a total rate of 2.5 to 5.5% by mass and a curing agent, and a cured product thereof.
Description
本発明は分子骨格にリン原子と窒素原子を含有するハロゲンフリー難燃性エポキシ樹脂の製造方法、該製造方法から得られたエポキシ樹脂とその他のエポキシ樹脂を含むエポキシ樹脂組成物、該エポキシ樹脂組成物と硬化剤を含む硬化性エポキシ樹脂組成物、及び該硬化性エポキシ樹脂組成物を硬化したエポキシ樹脂硬化物に関する。 The present invention relates to a method for producing a halogen-free flame-retardant epoxy resin containing a phosphorus atom and a nitrogen atom in the molecular skeleton, an epoxy resin composition containing an epoxy resin obtained from the production method and another epoxy resin, and the epoxy resin composition The present invention relates to a curable epoxy resin composition containing a product and a curing agent, and an epoxy resin cured product obtained by curing the curable epoxy resin composition.
エポキシ樹脂の難燃化は従来テトラブロモビスフェノールＡを原料とした臭素化エポキシ樹脂に代表されるようにハロゲン化により行われていた。しかし、ハロゲン化エポキシ樹脂を用いた場合、硬化物の燃焼時に熱分解反応により毒性の強いハロゲン化物の生成がみられるといった問題があった。これに対して近年リン化合物を利用したハロゲンフリー難燃技術が検討され、特許文献１〜特許文献４で開示されたリン化合物を応用するという提案がされている。しかし、これらのリン化合物はエポキシ樹脂や溶剤との溶解性が低く、エポキシ樹脂に配合したり溶剤に溶解したりして用いることが困難であったため、特許文献５〜特許文献１０で開示されているようにあらかじめエポキシ樹脂類と反応することによってリン含有エポキシ樹脂、リン含有フェノール樹脂として溶剤溶解性を付与して使用されている。 Conventionally, flame retarding of epoxy resins has been performed by halogenation, as represented by brominated epoxy resins using tetrabromobisphenol A as a raw material. However, when a halogenated epoxy resin is used, there is a problem in that a highly toxic halide is generated due to a thermal decomposition reaction when the cured product is burned. In contrast, in recent years, halogen-free flame retardant technology using phosphorus compounds has been studied, and proposals have been made to apply the phosphorus compounds disclosed in Patent Documents 1 to 4. However, these phosphorus compounds have low solubility in epoxy resins and solvents, and are difficult to use by being mixed in an epoxy resin or dissolved in a solvent. As described above, it is used as a phosphorus-containing epoxy resin and a phosphorus-containing phenol resin by previously reacting with epoxy resins to impart solvent solubility.
リン化合物による難燃化は、難燃性を更に向上しようとするとリン含有率を高めるしかなく、分子量が大きくなり架橋密度が低下してしまうことや、高価なリン含有化合物を使用しなければならなかった。これに対して、本発明者らは非特許文献１に記載されているリンと窒素の難燃性に対する相乗効果に着目し、窒素化合物としてシアヌル酸を使用することにより難燃性の向上を提案した（特許文献11）。しかしながら、製造方法によっては、工ポキシ樹脂とシアヌル酸が十分に反応せず、未反応のシアヌル酸が残存しやすいことが分かった。反応系中に残存したシアヌル酸は非常にゆっくりとした速度でしかエポキシ樹脂と反応せず、また未反応のシアヌル酸は溶剤への溶解性が悪く、硬化物性に悪影響を及ぼす未反応シアヌル酸の低減が更に求められていた。 In order to further improve the flame retardancy, the flame retardancy by the phosphorus compound has only to increase the phosphorus content, the molecular weight increases and the crosslinking density decreases, and an expensive phosphorus-containing compound must be used. There wasn't. On the other hand, the present inventors focused on the synergistic effect on the flame retardancy of phosphorus and nitrogen described in Non-Patent Document 1, and proposed improvement of flame retardancy by using cyanuric acid as a nitrogen compound. (Patent Document 11). However, it has been found that depending on the production method, the engineered epoxy resin and cyanuric acid do not sufficiently react, and unreacted cyanuric acid tends to remain. Cyanuric acid remaining in the reaction system reacts with the epoxy resin only at a very slow rate, and unreacted cyanuric acid has poor solubility in the solvent, and unreacted cyanuric acid has an adverse effect on the cured material properties. There was a further need for reduction.
上記の課題を解決するために、本発明者はエポキシ樹脂とシアヌル酸との反応の際、シアヌル酸に対して一定割合の特定のリン化合物を共存させて反応させることで、シアヌル酸の残存が極めて少なく長時間の反応を要することなくエポキシ樹脂との反応が容易に進行することを見出し、本発明を完成した。 In order to solve the above-mentioned problems, the present inventor made the residual of cyanuric acid by reacting with a certain proportion of a specific phosphorus compound with respect to cyanuric acid in the reaction of epoxy resin and cyanuric acid. The present invention was completed by finding that the reaction with the epoxy resin easily proceeds without requiring a very long reaction.
すなわち、本発明は、
（１）リン化合物、シアヌル酸及びエポキシ樹脂を必須成分として反応して得られるシアヌル酸変性リン含有エポキシ樹脂の製造方法であって、前記リン化合物が、
下記一般式（１）：
(1) A method for producing a cyanuric acid-modified phosphorus-containing epoxy resin obtained by reacting a phosphorus compound, cyanuric acid and an epoxy resin as essential components, wherein the phosphorus compound is
The following general formula (1):
または、下記一般式（２）：
で示されるリン化合物、または、その両者を含むリン化合物であり、シアヌル酸１モルに対して該リン化合物を2.5〜50モル配合した、リン化合物及びシアヌル酸の共存下に、前記エポキシ樹脂を予め混合し、その後に反応を行い、リン含有率が1.0〜5.0質量％、窒素含有率が0.1〜2.0質量％、かつ、リン含有率と窒素含有率の総和が2.5〜5.5質量％であることを特徴とするシアヌル酸変性リン含有エポキシ樹脂の製造方法、Or the following general formula (2):
In the presence of phosphorus compound and cyanuric acid, 2.5 to 50 mol of the phosphorus compound is added to 1 mol of cyanuric acid, and the epoxy resin is preliminarily prepared in advance. The mixture is then reacted, and the phosphorus content is 1.0 to 5.0 mass%, the nitrogen content is 0.1 to 2.0 mass%, and the total of the phosphorus content and nitrogen content is 2.5 to 5.5 mass% A method for producing a cyanuric acid-modified phosphorus-containing epoxy resin,
（２）上記（１）に記載の製造方法により得られるシアヌル酸変性リン含有エポキシ樹脂に、他のエポキシ樹脂を配合したエポキシ樹脂組成物、 (2) An epoxy resin composition in which another epoxy resin is blended with the cyanuric acid-modified phosphorus-containing epoxy resin obtained by the production method described in (1) above,
（３）上記（１）に記載の製造方法により得られるシアヌル酸変性リン含有エポキシ樹脂に、該シアヌル酸変性リン含有エポキシ樹脂のエポキシ基１当量に対して、官能基比で0.4〜2.0当量の硬化剤を含有した硬化性エポキシ樹脂組成物、
（４）上記（２）に記載のエポキシ樹脂組成物に、該エポキシ樹脂組成物のエポキシ基１当量に対して、官能基比で0.4〜2.0当量の硬化剤を含有した硬化性エポキシ樹脂組成物、(3) The cyanuric acid-modified phosphorus-containing epoxy resin obtained by the production method described in (1) above has a functional group ratio of 0.4 to 2.0 equivalents with respect to 1 equivalent of the epoxy group of the cyanuric acid-modified phosphorus-containing epoxy resin. A curable epoxy resin composition containing a curing agent,
(4) A curable epoxy resin composition containing, in the epoxy resin composition according to (2), a curing agent having a functional group ratio of 0.4 to 2.0 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin composition. ,
（５）上記（３）または（４）に記載の硬化性エポキシ樹脂組成物を硬化させたエポキシ樹脂硬化物、
に関する。(5) A cured epoxy resin obtained by curing the curable epoxy resin composition according to (3) or (4) above,
About.
本発明は、シアヌル酸１モルに対して特定のリン化合物を2.5〜50モルのモル比で共存させた後、エポキシ樹脂と反応することによって得られるシアヌル酸変性リン含有エポキシ樹脂であり、短時間での製造を可能とし、かつシアヌル酸の残存が極めて少なく、優れた物性を有するエポキシ樹脂硬化物を得ることができる。 The present invention is a cyanuric acid-modified phosphorus-containing epoxy resin obtained by reacting with a specific phosphorus compound at a molar ratio of 2.5 to 50 moles per mole of cyanuric acid and then reacting with the epoxy resin for a short time. It is possible to produce an epoxy resin cured product having excellent physical properties, which can be produced by the above-mentioned method, and cyanuric acid remains very little.
以下、本発明の実施の形態について、詳細に説明する。本発明の一般式（１）または（２）で示されるリン化合物は、具体的に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（DOPO）、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）等が挙げられる。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。 Hereinafter, embodiments of the present invention will be described in detail. The phosphorus compound represented by the general formula (1) or (2) of the present invention is specifically dimethylphosphine, diethylphosphine, diphenylphosphine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxide (DOPO), dimethylphosphine oxide, diethylphosphine oxide, dibutylphosphine oxide, diphenylphosphine oxide, 1,4-cyclooctylenephosphine oxide, 1,5-cyclooctylenephosphine oxide (CPHO, manufactured by Nippon Chemical Industry Co., Ltd.) Etc. These phosphorus compounds may be used alone or in combination of two or more, and are not limited thereto.
本発明において、シアヌル酸とは互変異性であるｓ−トリアジン−2,4,6−トリオール、及びｓ−トリアジン−2,4,6−トリオンを示すものであり、その比率については特に規定は無い。 In the present invention, cyanuric acid indicates s-triazine-2,4,6-triol and s-triazine-2,4,6-trione which are tautomers, and the ratio thereof is particularly specified. No.
シアヌル酸は窒素系難燃剤として添加される技術が開示されているが、シアヌル酸の溶剤に対する溶解性不良やエポキシ樹脂や硬化剤に対する相溶性不良のため均一な樹脂組成物を得られがたく、難燃性にバラツキが生じていた。本発明の製造方法から得られるシアヌル酸変性リン含有エポキシ樹脂は、シアヌル酸をエポキシ樹脂と反応することで、樹脂組成物中で均一となるため、安定した難燃性が得られる。なお、本発明の樹脂組成物というときは、特に断りがない限り、エポキシ樹脂組成物と硬化性エポキシ樹脂組成物との両者を含む意味で使用されるが、文脈上明らかな場合は、いずれか一方を示す。 Although a technique in which cyanuric acid is added as a nitrogen-based flame retardant is disclosed, it is difficult to obtain a uniform resin composition because of poor solubility in cyanuric acid solvent and poor compatibility with epoxy resin and curing agent, There were variations in flame retardancy. Since the cyanuric acid-modified phosphorus-containing epoxy resin obtained from the production method of the present invention becomes uniform in the resin composition by reacting cyanuric acid with the epoxy resin, stable flame retardancy is obtained. The resin composition of the present invention is used to include both an epoxy resin composition and a curable epoxy resin composition, unless otherwise specified. Show one.
本発明のシアヌル酸変性リン含有エポキシ樹脂を製造するために使用するエポキシ樹脂は、エポトート YD-128、エポトート YD-8125（新日鉄住金化学株式会社製、ビスフェノールＡ型エポキシ樹脂）、エポトート YDF-170、エポトート YDF-8170（新日鉄住金化学株式会社製、ビスフェノールＦ型エポキシ樹脂）、YSLV-80XY（新日鉄住金化学株式会社製、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 YX-4000H（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、エポトート YDPN-63X（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（新日鉄住金化学株式会社製、クレゾールノボラック型エポキシ樹脂）、エポトート GK-5855、エポトートTX-1210（新日鉄住金化学株式会社製、置換フェノール型エポキシ樹脂）エポトート ZX-1201（新日鉄住金化学株式会社製、ビスフェノールフルオレン型エポキシ樹脂）、TX-0710（新日鉄住金化学株式会社製、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（新日鉄住金化学株式会社製、ナフタレンジオール型エポキシ樹脂）、エポトート ESN-155（新日鉄住金化学株式会社製、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（新日鉄住金化学株式会社製、ジナフトールアラルキル型エポキシ樹脂）、エポトート ESN-475V、エポトート ESN-485（新日鉄住金化学株式会社製、α−ナフトールアラルキル型エポキシ樹脂）、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）、YSLV-120TE（新日鉄住金化学株式会社製、ビスチオエーテル型エポキシ樹脂）、エポトート ZX-1684（新日鉄住金化学株式会社製、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）、エポトート YDG-414（新日鉄住金化学株式会社製、四官能エポキシ樹脂）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、TX-0929、TX-0934、ZX-1542、TX-1032（新日鉄住金化学株式会社製、アルキレングリコール型エポキシ樹脂）等のアルコ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、セロキサイド2021（ダイセル化学工業株式会社製、脂肪族環状エポキシ樹脂）、エポトート YH-434、（新日鉄住金化学株式会社製、ジアミノジフェニルメタンテトラグリシジルアミン）、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）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、エポトート FX-289B、エポトート FX-305、TX-0940（新日鉄住金化学株式会社製、リン含有エポキシ樹脂）、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等が挙げられるが、これらに限定されるものではない。 The epoxy resins used for producing the cyanuric acid-modified phosphorus-containing epoxy resin of the present invention are Epototo YD-128, Epototo YD-8125 (Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol A type epoxy resin), Epototo YDF-170, Epototo YDF-8170 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol F type epoxy resin), YSLV-80XY (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., tetramethylbisphenol F type epoxy resin), Epototo YDC-1312 (hydroquinone type epoxy resin), jER YX-4000H (manufactured by Mitsubishi Chemical Corporation, biphenyl type epoxy resin), Epototo YDPN-638, Epototo YDPN-63X (manufactured by Nippon Steel Corporation, phenol novolac type epoxy resin), Epototo YDCN-701 (Nippon Steel & Sumikin Chemical Co., Ltd.) Company made, cresol novolac type epoxy resin), Epototo GK-5855, Epototo TX-1210 ( Nippon Steel & Sumikin Chemical Co., Ltd., substituted phenol type epoxy resin) Epototo ZX-1201 (Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol fluorene type epoxy resin), TX-0710 (Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol S type epoxy resin) , NC-3000 (Nippon Kayaku Co., Ltd., biphenylaralkylphenol type epoxy resin), Epototo ZX-1355, Epototo ZX-1711 (Nippon Steel & Sumikin Chemical Co., Ltd., Naphthalenediol type epoxy resin), Epototo ESN-155 (Nippon Steel) Sumikin Chemical Co., Ltd., β-naphthol aralkyl epoxy resin), Epototo ESN-355, Epototo ESN-375 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Dinaphthol aralkyl epoxy resin), Epototo ESN-475V, Epototo ESN-485 ( Nippon Steel & Sumikin Chemical Co., Ltd., α-naphthol aralkyl epoxy resin), E PPN-501H (Nippon Kayaku Co., Ltd., trisphenylmethane type epoxy resin), YSLV-120TE (Nippon Steel & Sumikin Chemical Co., Ltd., bisthioether type epoxy resin), Epototo ZX-1684 (Nippon Steel & Sumikin Chemical Co., Ltd., Resorcinol) Type epoxy resin), Epicron HP-7200H (DIC Corporation, dicyclopentadiene type epoxy resin), Epototo YDG-414 (Nippon Steel & Sumikin Chemical Co., Ltd., tetrafunctional epoxy resin), etc. Epoxy resin produced from epihalohydrin, epoxy resin produced from epihalohydrin and alcohol compounds such as TX-0929, TX-0934, ZX-1542, TX-1032 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., alkylene glycol type epoxy resin) Resin, Celoxide 2021 (Daicel Chemical Industries, Aliphatic cyclic epoxy resin), Epoto Epototo FX, an epoxy resin produced from an amine compound such as YH-434, (Nippon Steel & Sumikin Chemical Co., Ltd., diaminodiphenylmethanetetraglycidylamine), jER 630 (Mitsubishi Chemical Corporation, aminophenol type epoxy resin) and epihalohydrin -289B, Epototo FX-305, TX-0940 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., phosphorus-containing epoxy resin), urethane-modified epoxy resin, oxazolidone ring-containing epoxy resin, and the like, but are not limited thereto.
また、これらのエポキシ樹脂は単独で使用しても２種類以上を併用してもよく、ビスフェノール型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂を好適に用いることができる。 These epoxy resins may be used alone or in combination of two or more, and bisphenol type epoxy resins, phenol novolac type epoxy resins, and cresol novolac type epoxy resins can be suitably used.
一般式（１）または（２）で示されるリン化合物とシアヌル酸とエポキシ樹脂との反応は、リン化合物とシアヌル酸の共存下でエポキシ樹脂と反応させるが、シアヌル酸１モルに対して2.5〜50モルのリン化合物が必要であり、好ましいリン化合物のモル比はシアヌル酸１モルに対して2.7〜25モルであり、望ましくは３〜10モルである。シアヌル酸１モルに対してリン化合物が2.5モル未満ではシアヌル酸とエポキシ樹脂との反応の進行が不十分となり、シアヌル酸の残存量が増える。シアヌル酸１モルに対してリン化合物が５０モルを越えるとシアヌル酸とエポキシ樹脂との反応の十分進行するが、シアヌル酸による窒素原子の導入効果、即ち、難燃性に対するリンと窒素の相乗効果がほとんどなくなる。また、リン化合物とシアヌル酸の共存条件を満たせば、エポキシ樹脂とシアヌル酸との反応の前後のいずれにおいてもエポキシ樹脂とリン化合物とを反応させることができる。 The reaction of the phosphorus compound represented by the general formula (1) or (2), cyanuric acid and the epoxy resin is caused to react with the epoxy resin in the presence of the phosphorus compound and cyanuric acid. 50 mol of phosphorus compound is required, and the preferred molar ratio of the phosphorus compound is 2.7 to 25 mol, preferably 3 to 10 mol, per mol of cyanuric acid. If the phosphorus compound is less than 2.5 moles per mole of cyanuric acid, the reaction between cyanuric acid and the epoxy resin will not proceed sufficiently, and the residual amount of cyanuric acid will increase. When the amount of phosphorus compound exceeds 50 moles per mole of cyanuric acid, the reaction between cyanuric acid and epoxy resin proceeds sufficiently, but the effect of introducing nitrogen atoms by cyanuric acid, that is, the synergistic effect of phosphorus and nitrogen on flame retardancy Almost disappears. Moreover, if the coexistence conditions of a phosphorus compound and cyanuric acid are satisfy | filled, an epoxy resin and a phosphorus compound can be made to react in any before and after reaction of an epoxy resin and cyanuric acid.
本発明のシアヌル酸変性リン含有エポキシ樹脂を得るための反応温度は、エポキシ樹脂の合成に通常設定されている温度でよく、100〜250℃、好ましくは120〜200℃である。 The reaction temperature for obtaining the cyanuric acid-modified phosphorus-containing epoxy resin of the present invention may be a temperature usually set for the synthesis of the epoxy resin, and is 100 to 250 ° C, preferably 120 to 200 ° C.
反応には時間短縮や反応温度低減の為、触媒を使用しても良い。使用できる触媒は特に制限は無く、エポキシ樹脂の合成に通常使用されているものが使用できる。例えば、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可能であり、単独で用いても２種類以上併用してもよく、これらに限定されるものではない。また、分割して数回に分けて使用しても良い。 A catalyst may be used for the reaction to shorten the time and reduce the reaction temperature. The catalyst that can be used is not particularly limited, and those usually used for the synthesis of epoxy resins can be used. For example, tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, ethyltriphenylphosphonium bromide, etc. Various catalysts such as phosphonium salts, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole can be used, and these may be used alone or in combination of two or more. is not. Further, it may be divided and used in several times.
反応に使用する触媒量は特に限定されないが、用いるエポキシ樹脂に対して５質量％以下が好ましく、１質量％以下がより好ましく、0.5質量％以下が更に好ましい。触媒量が５質量％を超える場合にはエポキシ基の自己重合反応が進行しやすくなり、樹脂粘度が高くなる傾向にあるため好ましくない。 The amount of catalyst used in the reaction is not particularly limited, but is preferably 5% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less based on the epoxy resin used. When the amount of the catalyst exceeds 5% by mass, the self-polymerization reaction of the epoxy group tends to proceed and the resin viscosity tends to increase, which is not preferable.
また、反応には不活性溶媒を使用しても良い。具体的にはヘキサン、へプタン、オクタン、デカン、ジメチルブタン、ペンテン、シクロヘキサン、メチルシクロヘキサン、ベンゼン、トルエン、キシレン、エチルベンゼン等の各種炭化水素、エチルエーテル、イソプロピルエーテル、ブチルエーテル、ジイソアミルエーテル、メチルフェニルエーテル、エチルフェニルエーテル、アミルフェニルエーテル、エチルベンジルエーテル、ジオキサン、メチルフラン、テトラヒドロフラン等のエーテル類、メチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブ、セロソルブアセテート、エチレングリコールイソプロピルエーテル、ジエチレングリコールジメチルエーテル、メチルエチルカルビトール、プロピレングリコールモノメチルエーテル、ジメチルホルムアミド、ジメチルスルホキシド等が使用できるが、これらに限定されるものではなく、単独で用いても２種類以上混合して使用しても良い。 Moreover, you may use an inert solvent for reaction. Specifically, various hydrocarbons such as hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethyl ether, isopropyl ether, butyl ether, diisoamyl ether, methylphenyl Ethers, ethyl phenyl ether, amyl phenyl ether, ethyl benzyl ether, dioxane, methyl furan, tetrahydrofuran, and other ethers, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, cellosolve acetate, ethylene glycol isopropyl ether, diethylene glycol dimethyl ether, methyl ethyl carbitol , Propylene glycol monomethyl ether, dimethylformamide, dimethyl Although sulfoxide or the like can be used, is not limited thereto, it may be used by mixing 2 or more kinds may be used alone.
本発明で得られるシアヌル酸変性リン含有エポキシ樹脂のエポキシ当量は、100〜700g/eqが好ましく、200〜600g/eqがより好ましい。エポキシ当量が100g/eq未満では、硬化物の接着性が劣るものとなりやすく、700g/eqより大きい場合は硬化物のガラス転移温度（Ｔｇ）が低下し、樹脂組成物が高粘度となり作業性に劣るものとなりやすい。 The epoxy equivalent of the cyanuric acid-modified phosphorus-containing epoxy resin obtained in the present invention is preferably 100 to 700 g / eq, more preferably 200 to 600 g / eq. If the epoxy equivalent is less than 100 g / eq, the adhesiveness of the cured product tends to be inferior, and if it is more than 700 g / eq, the glass transition temperature (Tg) of the cured product is lowered, and the resin composition has a high viscosity and improves workability. It tends to be inferior.
本発明で得られるシアヌル酸変性リン含有エポキシ樹脂のリン含有率は、1.0〜5.0質量％であり、1.5〜4.0質量％が好ましく、2.0〜3.5質量％がより好ましい。窒素含有率は、0.1〜2.0質量％であり、0.5〜1.0質量％が好ましい。また、リン含有率と窒素含有率の総和は、2.5〜5.5質量％であり、3.0〜4.5質量％が好ましく、3.0〜4.0質量％がより好ましい。本発明で得られるシアヌル酸変性リン含有エポキシ樹脂の難燃性は、リンと窒素の相乗効果で発揮されるため、どちらか一方の範囲を規定しても意味がなく、リン含有率と窒素含有率の総和の範囲を規定する必要がある。リン含有率と窒素含有率の総和が２．５質量％未満だと樹脂組成物によっては難燃性が十分発揮できない恐れがある。また、リン含有率と窒素含有率の総和が５．５質量％を越えると難燃性は十分発揮できるが、樹脂組成物が高粘度になり、溶剤溶解性に悪影響がでる恐れがある。そのため、リン含有率と窒素含有率の総和の範囲を2.5〜5.5質量％にすることが好ましい。 The phosphorus content of the cyanuric acid-modified phosphorus-containing epoxy resin obtained in the present invention is 1.0 to 5.0 mass%, preferably 1.5 to 4.0 mass%, and more preferably 2.0 to 3.5 mass%. The nitrogen content is 0.1 to 2.0 mass%, preferably 0.5 to 1.0 mass%. Moreover, the sum total of phosphorus content rate and nitrogen content rate is 2.5-5.5 mass%, 3.0-4.5 mass% is preferable and 3.0-4.0 mass% is more preferable. Since the flame retardancy of the cyanuric acid-modified phosphorus-containing epoxy resin obtained in the present invention is exhibited by the synergistic effect of phosphorus and nitrogen, it is meaningless to define either range, phosphorus content and nitrogen content It is necessary to specify the range of the sum of rates. If the total of the phosphorus content and the nitrogen content is less than 2.5% by mass, the flame retardancy may not be sufficiently exhibited depending on the resin composition. Further, if the total of the phosphorus content and the nitrogen content exceeds 5.5% by mass, the flame retardancy can be sufficiently exerted, but the resin composition has a high viscosity and may adversely affect the solvent solubility. Therefore, it is preferable that the total range of the phosphorus content and the nitrogen content is 2.5 to 5.5% by mass.
本発明のエポキシ樹脂組成物に用いるその他のエポキシ樹脂としては、本発明の特性を損なわない範囲で、前記エポキシ樹脂と同一のエポキシ樹脂をシアヌル酸変性リン含有エポキシ樹脂と併用することができる。 As another epoxy resin used for the epoxy resin composition of the present invention, the same epoxy resin as the above epoxy resin can be used in combination with the cyanuric acid-modified phosphorus-containing epoxy resin as long as the characteristics of the present invention are not impaired.
本発明のシアヌル酸変性リン含有エポキシ樹脂またはエポキシ樹脂組成物は硬化剤を配合することにより、硬化性エポキシ樹脂組成物とすることができる。硬化剤としては各種フェノール化合物、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種類以上併用しても良い。これらのうち、本発明の硬化性エポキシ樹脂組成物が含有する硬化剤としてはジシアンジアミドまたはフェノール化合物が好ましい。 The cyanuric acid-modified phosphorus-containing epoxy resin or epoxy resin composition of the present invention can be made into a curable epoxy resin composition by blending a curing agent. As the curing agent, commonly used curing agents for epoxy resins such as various phenol compounds, acid anhydrides, amines, hydrazides, and acidic polyesters can be used, and only one of these curing agents is used. Or you may use together 2 or more types. Of these, dicyandiamide or a phenol compound is preferable as the curing agent contained in the curable epoxy resin composition of the present invention.
本発明の硬化性エポキシ樹脂組成物において硬化剤の使用量は、エポキシ樹脂の官能基であるエポキシ基１当量に対して硬化剤の官能基0.4〜2.0当量が好ましく、0.5〜1.5当量がより好ましく、0.5〜1.0当量が特に好ましくい。エポキシ基１当量に対して硬化剤が0.4当量に満たない場合、または2.0当量を超える場合は硬化が不完全になり良好な硬化物性が得られない恐れがある。 In the curable epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.4 to 2.0 equivalents, more preferably 0.5 to 1.5 equivalents of the functional group of the curing agent with respect to 1 equivalent of the epoxy group that is a functional group of the epoxy resin. 0.5 to 1.0 equivalent is particularly preferred. When the curing agent is less than 0.4 equivalent or 1 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.
本発明の硬化性エポキシ樹脂組成物に用いることができるフェノール化合物の具体例としては、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、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、4,4'−ビフェノール、テトラメチルビフェノール等のビフェノール類等の２価フェノール類、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のポリ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（新日鉄住金化学株式会社製、クレゾールノボラック樹脂）、ナフトールノボラック樹脂等のフェノール類また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（新日鉄住金化学株式会社製）等のフェノール類またはナフトール類とキシリレングリコールとの縮合物、GK-5855P (新日鉄住金化学株式会社製、置換フェノール樹脂)、フェノール類また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、フェノール類またはナフトール類とジシクロペンタジエンとの反応物、フェノール類またはナフトール類とビフェニル系縮合剤との縮合物等の一分子中に２個以上のフェノール性水酸基と有するフェノール化合物等が例示される。 Specific examples of the phenol compound that can be used in the curable epoxy resin composition of the present invention include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, Tetramethylbisphenol S, tetramethylbisphenol Z, dihydroxydiphenyl sulfide, bisphenols such as 4,4'-thiobis (3-methyl-6-tert-butylphenol), catechol, resorcin, methylresorcin, hydroquinone, monomethylhydroquinone, dimethylhydroquinone Dihydroxybenzenes such as trimethylhydroquinone, mono-tert-butylhydroquinone, di-tert-butylhydroquinone, 4,4'-biphenol, tetra Dihydric phenols such as biphenols such as methylbiphenol, polyhydroxynaphthalenes such as dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxymethylnaphthalene and trihydroxynaphthalene, phenol novolac resin, DC-5 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., cresol) Novolak resin), phenols such as naphthol novolak resin or condensates of naphthols and aldehydes, phenols such as SN-160, SN-395, SN-485 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) or naphthols Condensate with lenglycol, GK-5855P (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., substituted phenol resin), condensate of phenols or naphthols with isopropenylacetophenone, reaction product of phenols or naphthols with dicyclopentadiene Phenolic compounds having two or more phenolic hydroxyl groups in one molecule of the condensate of phenols or naphthols and biphenyl condensing agent and the like.
なお、前記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、前記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。また、前記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挙げられ、前記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）ビフェニル等が挙げられるが、これらに限定されるわけではない。 Examples of the phenols include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol, and phenylphenol. Examples of the naphthols include 1-naphthol and 2-naphthol. Can be mentioned. The aldehydes include formaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chloraldehyde, bromaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipine aldehyde, pimelin aldehyde. , Sebacinaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde and the like. Examples of the biphenyl condensing agent include bis (methylol) biphenyl, bis (methoxymethyl) biphenyl, bis (ethoxymethyl) biphenyl, bis ( Chloromethyl) biphenyl and the like, but are not limited thereto.
本発明の硬化性エポキシ樹脂組成物に用いることができるその他の公知の硬化剤としては、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、無水メチルナジック酸等の酸無水物類、ジシアンジアミド、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、メタキシレンジアミン、イソホロンジアミン等の脂肪族アミン類、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、ジアミノエチルベンゼン等の芳香族アミン類、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、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、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、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド等のヒドラジド類、アミノ安息香酸エステル類、トリフェニルホスフィン等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、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またはヨードニウム塩等が挙げられるが、これらに限定されるわけではない。また、これらを２種類以上併用してもよい。 Other known curing agents that can be used in the curable epoxy resin composition of the present invention include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, phthalic anhydride, trimellitic anhydride, methyl anhydride Acid anhydrides such as nadic acid, aliphatic amines such as dicyandiamide, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, metaxylenediamine, and isophoronediamine, aromatics such as diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, and diaminoethylbenzene Amines, benzyldimethylamine, amines such as 2,4,6-tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole Imidazoles such as 2-undecylimidazole and 1-cyanoethyl-2-methylimidazole, and imidazole salts which are salts thereof with trimellitic acid, isocyanuric acid, boron and the like, acids such as dimer acid and polyamines Condensates such as amine-based compounds such as polyamidoamine, hydrazides such as adipic acid dihydrazide, sebacic acid dihydrazide, aminobenzoic acid esters, phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, trimethyl Quaternary ammonium salts such as ammonium chloride, diazabicyclo compounds and salts thereof with phenols, phenol novolac resins, etc. Complex compounds of boron trifluoride with amines, ether compounds, aromatic phosphonium or iodine Salts and the like, but is not limited thereto. Two or more of these may be used in combination.
本発明の硬化性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。用いることができ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る。これらの溶剤のうちの単独または複数種を混合したものを、樹脂組成物中のエポキシ樹脂成分100質量部に対し25〜250質量部の範囲で配合することができる。 In the curable 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, toluene and the like. Aromatic hydrocarbons etc. are mentioned. One of these solvents or a mixture of a plurality of them can be blended in the range of 25 to 250 parts by mass with respect to 100 parts by mass of the epoxy resin component in the resin composition.
本発明の硬化性エポキシ樹脂組成物には必要に応じて硬化促進剤を使用することができる。使用できる硬化促進剤の例としては、2−メチルイミダゾール、2−エチルイミダゾール、2−エチル−4−メチルイミダゾール等のイミダゾール類、2−（ジメチルアミノメチル）フェノール、1,8−ジアザ−ビシクロ（5,4,0）ウンデセン−7等の第３級アミン類、トリフェニルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフィントリフェニルボラン当のホスフィン類、オクチル酸スズ等の金属化合物が挙げられる。硬化促進剤を用いる場合の使用量は、本発明の樹脂組成物中のエポキシ樹脂成分100質量部に対して0.02〜5.0質量部が好ましい。硬化促進剤を用いることにより、硬化温度を下げ、硬化時間を短縮することができる。 A curing accelerator can be used in the curable epoxy resin composition of the present invention as necessary. Examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo ( 5,4,0) tertiary amines such as undecene-7, triphenylphosphine, tricyclohexylphosphine, phosphines such as triphenylphosphine triphenylborane, and metal compounds such as tin octylate. When the curing accelerator is used, the amount used is preferably 0.02 to 5.0 parts by mass with respect to 100 parts by mass of the epoxy resin component in the resin composition of the present invention. By using a curing accelerator, the curing temperature can be lowered and the curing time can be shortened.
本発明の硬化性エポキシ樹脂組成物には必要に応じてフィラーを用いることができる。具体的には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、酸化チタン、ガラス粉末、ベーマイト、シリカバルーン等の無機フィラーが挙げられるが、顔料等を配合しても良い。一般的無機充填材を用いる理由として、耐衝撃性の向上が挙げられる。また、水酸化アルミニウム、水酸化マグネシウム等の金属水酸化物を用いた場合、難燃助剤として作用し、樹脂組成物中のリン含有率が少なくても難燃性を確保することができる。特にエポキシ樹脂成分100質量部に対し配合量が１０質量部以上でないと、耐衝撃性の効果は少ない。しかしながら、配合量が150質量部を越えると積層板用途として必要な項目である接着性が低下する。また、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や微粒子ゴム、熱可塑性エラストマー等の有機充填材を上記樹脂組成物に含有することもできる。 A filler can be used in the curable epoxy resin composition of the present invention as necessary. Specific examples include inorganic fillers such as aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium oxide, glass powder, boehmite, and silica balloon, but pigments may also be blended. The reason for using a general inorganic filler is an improvement in impact resistance. Moreover, when metal hydroxides, such as aluminum hydroxide and magnesium hydroxide, are used, it acts as a flame retardant aid, and flame retardancy can be ensured even if the phosphorus content in the resin composition is small. In particular, if the blending amount is not more than 10 parts by mass with respect to 100 parts by mass of the epoxy resin component, the effect of impact resistance is small. However, if the blending amount exceeds 150 parts by mass, the adhesiveness, which is a necessary item for the use of laminates, is lowered. Moreover, fiber fillers such as glass fibers, pulp fibers, synthetic fibers, and ceramic fibers, and organic fillers such as fine particle rubbers and thermoplastic elastomers can also be contained in the resin composition.
本発明の硬化性エポキシ樹脂組成物を硬化することによってリン及び窒素含有エポキシ樹脂硬化物を得ることができる。硬化の際には例えば樹脂シート、樹脂付き銅箔、プリプレグ等の形態とし、積層して加熱加圧硬化することで積層板としてのリン含有エポキシ樹脂硬化物を得ることができる。 By curing the curable epoxy resin composition of the present invention, a cured product of phosphorus and nitrogen-containing epoxy resin can be obtained. At the time of curing, for example, a resin sheet, a copper foil with resin, a prepreg, and the like are laminated, and cured by heating and pressing to obtain a cured phosphorus-containing epoxy resin as a laminate.
本発明のシアヌル酸変性リン含有エポキシ樹脂を用いた硬化性エポキシ樹脂組成物を作成し、リン及び窒素含有エポキシ樹脂硬化物の特性を加熱硬化により得られた積層板として評価した結果、本発明のモル比の範囲外のリン化合物とシアヌル酸を用いてエポキシ樹脂を反応したシアヌル酸変性リン含有エポキシ樹脂、及び、リン化合物とエポキシ樹脂から得られる従来公知のリン含有エポキシ樹脂と比較して、高い接着力、難燃性を示した。 As a result of making a curable epoxy resin composition using the cyanuric acid-modified phosphorus-containing epoxy resin of the present invention and evaluating the properties of the phosphorus and nitrogen-containing epoxy resin cured product as a laminate obtained by heat curing, Higher than cyanuric acid-modified phosphorus-containing epoxy resin obtained by reacting an epoxy resin with a phosphorus compound outside the molar ratio and cyanuric acid, and a conventionally known phosphorus-containing epoxy resin obtained from the phosphorus compound and epoxy resin Adhesive strength and flame retardancy were exhibited.
実施例及び比較例を挙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。実施例及び比較例において、特に断りがない限り「部」は質量部を表し、「％」は質量％を表す。 EXAMPLES The present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these. In Examples and Comparative Examples, unless otherwise specified, “part” represents part by mass, and “%” represents mass%.
実施例及び比較例で測定するエポキシ樹脂のエポキシ当量はJIS K 7236にて測定を行った。
窒素含有率はシアヌル酸の窒素含有率と配合量から、シアヌル酸変性リン含有エポキシ樹脂に対する百分率を算出した。
実施例及び比較例で合成されたエポキシ樹脂のリン含有率は以下の方法で測定を行った。すなわち、試料150mgに硫酸3mLを加え３０分加熱する。室温に戻し、硝酸3.5 mL及び過塩素酸0.5 mLを加えて内容物が透明又は黄色になるまで加熱分解する。この液を100mLメスフラスコに純水で希釈する。この試料液10mLを50mLメスフラスコに入れ、フェノールフタレイン指示薬を１滴加え、2mol/Lアンモニア水を微赤色になるまで加える。50%硫酸液2mLを加え、純水を加える。2.5g/Lのメタバナジン酸アンモニウム水溶液を5mL及び50g/Lモリブデン酸アンモニウム水溶液5mLを加えた後、純水で定容とする。室温で４０分放置した後、分光光度計を用いて波長440nmの条件で純水を対照として測定し、吸光度からリン含有率を求めた。The epoxy equivalent of the epoxy resin measured in Examples and Comparative Examples was measured according to JIS K 7236.
The nitrogen content was calculated as a percentage of the cyanuric acid-modified phosphorus-containing epoxy resin from the nitrogen content and the blending amount of cyanuric acid.
The phosphorus content of the epoxy resins synthesized in the examples and comparative examples was measured by the following method. That is, 3 mL of sulfuric acid is added to 150 mg of sample and heated for 30 minutes. Return to room temperature, add 3.5 mL of nitric acid and 0.5 mL of perchloric acid and heat decompose until the contents are clear or yellow. Dilute this solution with pure water in a 100 mL volumetric flask. Add 10 mL of this sample solution to a 50 mL volumetric flask, add 1 drop of phenolphthalein indicator, and add 2 mol / L aqueous ammonia until it becomes slightly red. Add 2mL of 50% sulfuric acid solution and add pure water. Add 5 mL of 2.5 g / L ammonium metavanadate aqueous solution and 5 mL of 50 g / L ammonium molybdate aqueous solution, and make up to volume with pure water. After standing at room temperature for 40 minutes, a spectrophotometer was used to measure pure water under the condition of a wavelength of 440 nm, and the phosphorus content was determined from the absorbance.
得られたシアヌル酸変性リン含有エポキシ樹脂について、外観の目視による濁りの有無で残存シアヌル酸の有無の確認を行った。濁り無しを残存シアヌル酸無し（○）とし、濁り有りを残存シアヌル酸有り（×）とした。 About the obtained cyanuric acid modification phosphorus containing epoxy resin, the presence or absence of residual cyanuric acid was confirmed by the presence or absence of the turbidity by visual appearance. No turbidity was defined as no residual cyanuric acid (O), and turbidity was defined as residual cyanuric acid present (X).
硬化物のガラス転移温度はセイコーインスツルメンツ株式会社製、Exster 6000を使用し、DSCでは最初の変曲点の値をガラス転移温度とし、TMAでは変曲点をガラス転移温度とした。
銅箔剥離強さはJIS C 6481 5.7に準じて、層間接着力はJIS C 6481 5.7に準じてプリプレグ１枚と残りの３枚の間で剥離を行い測定した。
難燃性はUL（Underwriter Laboratorics）規格に準じて測定を行った。また、残炎時間は試験片５本の有炎燃焼持続時間を合計して示した。The glass transition temperature of the cured product was Exster 6000 manufactured by Seiko Instruments Inc., DSC used the first inflection point as the glass transition temperature, and TMA used the inflection point as the glass transition temperature.
Copper foil peel strength was measured according to JIS C 6481 5.7, and interlayer adhesion was measured by peeling between one prepreg and the remaining three sheets according to JIS C 6481 5.7.
Flame retardancy was measured according to UL (Underwriter Laboratorics) standards. Further, the afterflame time is the sum of the flammable combustion durations of five test pieces.
シアヌル酸の反応率は、初期エポキシ当量、理論エポキシ当量及びシアヌル酸変性リン含有エポキシ樹脂のエポキシ当量（最終エポキシ当量）の値を用いて、以下の式により求めた。
［（最終エポキシ当量−初期エポキシ当量）／（理論エポキシ当量−初期エポキシ当量）]×１００
ただし、最終エポキシ当量が理論エポキシ当量より大きい場合は、反応率は100％とした。The reaction rate of cyanuric acid was determined by the following equation using values of initial epoxy equivalent, theoretical epoxy equivalent and epoxy equivalent (final epoxy equivalent) of cyanuric acid-modified phosphorus-containing epoxy resin.
[(Final epoxy equivalent−initial epoxy equivalent) / (theoretical epoxy equivalent−initial epoxy equivalent)] × 100
However, when the final epoxy equivalent was larger than the theoretical epoxy equivalent, the reaction rate was 100%.
実施例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、エポトートYDPN-638（新日鉄住金化学株式会社製、フェノールノボラック型エポキシ樹脂：エポキシ当量177g/eq）を850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％）を127部、シアヌル酸（東京化成工業株式会社製）を23部仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って130℃まで昇温した。混合状態での初期エポキシ当量は207g/eqであった、初期エポキシ当量測定後、触媒としてトリフェニルホスフィンを0.14部添加して160℃で４時間反応を行った。得られたシアヌル酸変性リン含有エポキシ樹脂（Ａ−１）のリン含有率は1.8％、理論エポキシ当量は270g/eq、最終エポキシ当量は272g/eq、シアヌル酸の反応率は100％であった。結果を表１に示した。 Example 1.
Epototo YDPN-638 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., phenol novolac type epoxy resin: epoxy equivalent of 177 g / eq) with a four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet ), 850 parts, HCA (manufactured by Sanko Co., Ltd., 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorus content 14.2%) 127 parts, cyanuric acid (Tokyo Chemical Industry Co., Ltd.) 23 parts) was added, stirred while introducing nitrogen gas, heated and heated to 130 ° C. The initial epoxy equivalent in the mixed state was 207 g / eq. After measuring the initial epoxy equivalent, 0.14 part of triphenylphosphine was added as a catalyst, and the reaction was performed at 160 ° C. for 4 hours. The obtained cyanuric acid-modified phosphorus-containing epoxy resin (A-1) had a phosphorus content of 1.8%, a theoretical epoxy equivalent of 270 g / eq, a final epoxy equivalent of 272 g / eq, and a reaction rate of cyanuric acid of 100%. . The results are shown in Table 1.
実施例２．
エポトートYDPN-638を758部に、シアヌル酸を3部にHCAを239部に変更した以外は実施例１と同様の操作を行った。得られたシアヌル酸変性リン含有エポキシ樹脂（A-2）のリン含有率は3.4％、初期エポキシ当量は232g/eq、理論エポキシ当量は320g/eq、最終エポキシ当量は332g/eq、シアヌル酸の反応率は100％であった。結果を表１に示した。 Example 2
The same operation as in Example 1 was performed, except that Epototo YDPN-638 was changed to 758 parts, cyanuric acid was changed to 3 parts, and HCA was changed to 239 parts. The resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-2) has a phosphorus content of 3.4%, an initial epoxy equivalent of 232 g / eq, a theoretical epoxy equivalent of 320 g / eq, a final epoxy equivalent of 332 g / eq, The reaction rate was 100%. The results are shown in Table 1.
実施例３．
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、エポトートYDPN-63X（新日鉄住金化学株式会社製、狭分散フェノールノボラック型エポキシ樹脂：エポキシ当量176g/eq）を692部、HCAを250部、シアヌル酸を58部仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って130℃まで昇温した。混合状態での初期エポキシ当量は254g/eqであった、初期エポキシ当量測定後、触媒としてトリフェニルホスフィンを0.33部添加して160℃で４時間反応を行った。得られたシアヌル酸変性リン含有エポキシ樹脂（A-3）のリン含有率は3.6％、理論エポキシ当量は701g/eq、最終エポキシ当量は669g/eq、シアヌル酸の反応率は93％であった。結果を表１に示した。 Example 3
Epototo YDPN-63X (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., narrowly dispersed phenol novolac type epoxy resin: epoxy equivalent 176 g), equipped with a stirrer, thermometer, condenser, and nitrogen gas introduction device / eq) was charged with 692 parts, HCA with 250 parts, and cyanuric acid with 58 parts. The mixture was stirred while introducing nitrogen gas and heated to 130 ° C. The initial epoxy equivalent in the mixed state was 254 g / eq. After measuring the initial epoxy equivalent, 0.33 part of triphenylphosphine was added as a catalyst, and the reaction was performed at 160 ° C. for 4 hours. The obtained cyanuric acid-modified phosphorus-containing epoxy resin (A-3) had a phosphorus content of 3.6%, a theoretical epoxy equivalent of 701 g / eq, a final epoxy equivalent of 669 g / eq, and a reaction rate of cyanuric acid of 93%. . The results are shown in Table 1.
実施例４．
エポトートYDPN-63Xを640部に、シアヌル酸を15部にHCAを345部に変更した以外は実施例３と同様の操作を行った。得られたシアヌル酸変性リン含有エポキシ樹脂（A-4）のリン含有率は4.9％、初期エポキシ当量は275g/eq、理論エポキシ当量は592g/eq、最終エポキシ当量は594g/eq、シアヌル酸の反応率は100％であった。結果を表１に示した。 Example 4
The same operation as in Example 3 was performed, except that Epototo YDPN-63X was changed to 640 parts, cyanuric acid was changed to 15 parts, and HCA was changed to 345 parts. The resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-4) has a phosphorus content of 4.9%, an initial epoxy equivalent of 275 g / eq, a theoretical epoxy equivalent of 592 g / eq, a final epoxy equivalent of 594 g / eq, The reaction rate was 100%. The results are shown in Table 1.
実施例５．
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、エポトートYDPN-638を507部、エポトート YD-128（新日鉄住金化学株式会社製、ビスフェノールＡ型液状エポキシ樹脂：エポキシ当量186g/eq）を300部、HCAを162部、シアヌル酸を31部仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って130℃まで昇温した。混合状態での初期エポキシ当量は223g/eqであった、初期エポキシ当量測定後、触媒としてトリフェニルホスフィンを0.25部添加して160℃で４時間反応を行った。得られたシアヌル酸変性リン含有エポキシ樹脂（A-5）のリン含有率は2.3％、理論エポキシ当量は333g/eq、最終エポキシ当量は330g/eq、シアヌル酸の反応率は97％であった。結果を表１に示した。 Example 5 FIG.
A four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introduction device, 507 parts of Epototo YDPN-638, Epotot YD-128 (Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol A type) Liquid epoxy resin: 300 parts of epoxy equivalent (186 g / eq), 162 parts of HCA and 31 parts of cyanuric acid were added, stirred while introducing nitrogen gas, heated and heated to 130 ° C. The initial epoxy equivalent in the mixed state was 223 g / eq. After measuring the initial epoxy equivalent, 0.25 part of triphenylphosphine was added as a catalyst, and the reaction was performed at 160 ° C. for 4 hours. The resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-5) had a phosphorus content of 2.3%, a theoretical epoxy equivalent of 333 g / eq, a final epoxy equivalent of 330 g / eq, and a cyanuric acid reaction rate of 97%. . The results are shown in Table 1.
実施例６．
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、エポトートYDPN-638を433部、エポトート YDCN-704（新日鉄住金化学株式会社製、クレゾールノボラック型エポキシ樹脂：エポキシ当量209g/eq）を300部、HCAを250部、シアヌル酸を17部仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って130℃まで昇温した。混合状態での初期エポキシ当量は258g/eqであった、初期エポキシ当量測定後、触媒としてトリフェニルホスフィンを0.25部添加して160℃で４時間反応を行った。得られたシアヌル酸変性リン含有エポキシ樹脂（A-6）のリン含有率は3.6％、理論エポキシ当量は429g/eq、最終エポキシ当量は428g/eq、シアヌル酸の反応率は99％であった。結果を表１に示した。 Example 6
A four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet, 433 parts of Epotot YDPN-638, Epotot YDCN-704 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., cresol novolak type) Epoxy resin: Epoxy equivalent: 209 g / eq) 300 parts, HCA 250 parts, cyanuric acid 17 parts were charged, stirred while introducing nitrogen gas, heated and heated to 130 ° C. The initial epoxy equivalent in the mixed state was 258 g / eq. After measuring the initial epoxy equivalent, 0.25 part of triphenylphosphine was added as a catalyst, and the reaction was performed at 160 ° C. for 4 hours. The obtained cyanuric acid-modified phosphorus-containing epoxy resin (A-6) had a phosphorus content of 3.6%, a theoretical epoxy equivalent of 429 g / eq, a final epoxy equivalent of 428 g / eq, and a reaction rate of cyanuric acid of 99%. . The results are shown in Table 1.
実施例７．
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、エポトートYDPN-638を442部、YSLV-80XY（新日鉄住金化学株式会社製、テトラメチルビスフェノールＦ型エポキシ樹脂：エポキシ当量190g/eq）を300部、HCAを250部、シアヌル酸を6部仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って130℃まで昇温した。混合状態での初期エポキシ当量は245g/eqであった、初期エポキシ当量測定後、触媒としてトリフェニルホスフィンを0.25部添加して160℃で４時間反応を行った。得られたシアヌル酸変性リン含有エポキシ樹脂（A-7）のリン含有率は3.6％、理論エポキシ当量は360g/eq、最終エポキシ当量は360/eq、シアヌル酸の反応率は100％であった。結果を表１に示した。 Example 7
A four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet, 442 parts of Epototo YDPN-638, YSLV-80XY (Nippon Steel & Sumikin Chemical Co., Ltd., Tetramethylbisphenol F) Type epoxy resin: Epoxy equivalent 190g / eq) 300 parts, HCA 250 parts, cyanuric acid 6 parts were charged, stirred while introducing nitrogen gas, heated and heated to 130 ° C. The initial epoxy equivalent in the mixed state was 245 g / eq. After measuring the initial epoxy equivalent, 0.25 part of triphenylphosphine was added as a catalyst, and the reaction was performed at 160 ° C. for 4 hours. The obtained cyanuric acid-modified phosphorus-containing epoxy resin (A-7) had a phosphorus content of 3.6%, a theoretical epoxy equivalent of 360 g / eq, a final epoxy equivalent of 360 / eq, and a reaction rate of cyanuric acid of 100%. . The results are shown in Table 1.
実施例８．
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、エポトートYDPN-638を860部、CPHO（日本化学工業株式会社製、1,5−シクロオクチレンホスフィンオキサイド、リン含有率19.6％）を110部、シアヌル酸を30部仕込み、窒素ガスを導入しながら攪拌を行い、加熱を行って130℃まで昇温した。混合状態での初期エポキシ当量は206g/eqであった、初期エポキシ当量測定後、触媒としてトリフェニルホスフィンを0.14部添加して160℃で４時間反応を行った。得られたシアヌル酸変性リン含有エポキシ樹脂（A-8）のリン含有率は2.2％、理論エポキシ当量は289g/eq、最終エポキシ当量は290/eq、シアヌル酸の反応率は100％であった。結果を表１に示した。 Example 8 FIG.
Into a four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet, 860 parts of Epototo YDPN-638, CPHO (Nippon Chemical Industry Co., Ltd., 1,5-cyclooctyl) Lenphosphine oxide (phosphorus content 19.6%) (110 parts) and cyanuric acid (30 parts) were charged, stirred while introducing nitrogen gas, heated and heated to 130 ° C. The initial epoxy equivalent in the mixed state was 206 g / eq. After measuring the initial epoxy equivalent, 0.14 part of triphenylphosphine was added as a catalyst, and the reaction was performed at 160 ° C. for 4 hours. The resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-8) had a phosphorus content of 2.2%, a theoretical epoxy equivalent of 289 g / eq, a final epoxy equivalent of 290 / eq, and a cyanuric acid reaction rate of 100%. . The results are shown in Table 1.
比較例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、エポトートYDPN-638を954部、シアヌル酸を46部仕込み、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℃まで昇温した。混合状態での初期エポキシ当量は185g/eqであった、初期エポキシ当量測定後、触媒としてトリフェニルホスフィンを0.05部を添加して160℃で４時間反応を行った。得られたシアヌル酸変性エポキシ樹脂（A-9）の最終エポキシ当量は194g/eq、リン含有率は0％であった。理論エポキシ当量は230g/eq、シアヌル酸の反応率は20％であった。結果を表１に示した。 Comparative Example 1
A four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introduction device was charged with 954 parts of Epototo YDPN-638 and 46 parts of cyanuric acid, and stirred while introducing nitrogen gas. And heated to raise the temperature. The temperature was raised to 130 ° C. The initial epoxy equivalent in the mixed state was 185 g / eq. After measuring the initial epoxy equivalent, 0.05 part of triphenylphosphine was added as a catalyst, and the reaction was performed at 160 ° C. for 4 hours. The final epoxy equivalent of the obtained cyanuric acid-modified epoxy resin (A-9) was 194 g / eq, and the phosphorus content was 0%. The theoretical epoxy equivalent was 230 g / eq, and the reaction rate of cyanuric acid was 20%. The results are shown in Table 1.
比較例２．
エポトートYDPN-638を843部に、シアヌル酸を31部に変更した以外は実施例１と同様の操作を行った。得られたシアヌル酸変性リン含有エポキシ樹脂（A-10）のリン含有率は1.8％、初期エポキシ当量は209g/eq、理論エポキシ当量は287g/eq、最終エポキシ当量は263g/eq、シアヌル酸の反応率は69％であった。結果を表１に示した。 Comparative Example 2
The same operation as in Example 1 was performed, except that Epototo YDPN-638 was changed to 843 parts and cyanuric acid was changed to 31 parts. The resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-10) has a phosphorus content of 1.8%, an initial epoxy equivalent of 209 g / eq, a theoretical epoxy equivalent of 287 g / eq, and a final epoxy equivalent of 263 g / eq. The reaction rate was 69%. The results are shown in Table 1.
比較例３．
エポトートYDPN-638を882部に、シアヌル酸を23部に、HCAを95部に変更した以外は実施例１と同様の操作を行った。得られたシアヌル酸変性リン含有エポキシ樹脂（A-11）のリン含有率は1.35％、初期エポキシ当量は200g/eq、理論エポキシ当量は248g/eq、最終エポキシ当量は231g/eq、シアヌル酸の反応率は65％であった。結果を表１に示した。 Comparative Example 3
The same operation as in Example 1 was conducted except that Epototo YDPN-638 was changed to 882 parts, cyanuric acid was changed to 23 parts, and HCA was changed to 95 parts. The resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-11) has a phosphorus content of 1.35%, initial epoxy equivalent of 200 g / eq, theoretical epoxy equivalent of 248 g / eq, final epoxy equivalent of 231 g / eq, cyanuric acid The reaction rate was 65%. The results are shown in Table 1.
比較例４．
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、エポトートYDPN-638を788部、シアヌル酸を23部、HCA-HQ（三光株式会社製、10−（2,5−ジヒドロキシフェニル）−10H−9−オキサ−10−ホスファフェナントレン−10−オキシド、リン含有率9.6％）を189部仕込み、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℃まで昇温した。混合状態での初期エポキシ当量を測定したら223g/eqであった、初期エポキシ当量測定後、触媒としてトリフェニルホスフィンを0.2部添加して160℃で４時間反応を行った所、ゲル化してしまいエポキシ樹脂は得られなかった。また、ゲル化物中にはシアヌル酸が固形で残存していた。 Comparative Example 4
In a four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet, 788 parts of Epototo YDPN-638, 23 parts of cyanuric acid, HCA-HQ (manufactured by Sanko Co., Ltd., 189 parts of 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorus content 9.6%) was charged, stirred while introducing nitrogen gas, and heated. Went and warmed up. The temperature was raised to 130 ° C. The initial epoxy equivalent in the mixed state was 223 g / eq. After measuring the initial epoxy equivalent, 0.2 parts of triphenylphosphine was added as a catalyst and reacted at 160 ° C. for 4 hours. Resin was not obtained. Moreover, cyanuric acid remained solid in the gelled product.
比較例５．
エポトートYDPN-638を855部に、シアヌル酸を15部に、HCA-HQを130部に変更した以外は比較例４と同様の操作を行った。得られたシアヌル酸変性リン含有エポキシ樹脂（A-12）のリン含有率は1.2％、初期エポキシ当量は206g/eq、理論エポキシ当量は271g/eq、最終エポキシ当量は224g/eq、シアヌル酸の反応率は28％であった。結果を表１に示した。 Comparative Example 5
The same operation as in Comparative Example 4 was performed except that epototo YDPN-638 was changed to 855 parts, cyanuric acid was changed to 15 parts, and HCA-HQ was changed to 130 parts. The resulting cyanuric acid-modified phosphorus-containing epoxy resin (A-12) has a phosphorus content of 1.2%, an initial epoxy equivalent of 206 g / eq, a theoretical epoxy equivalent of 271 g / eq, and a final epoxy equivalent of 224 g / eq. The reaction rate was 28%. The results are shown in Table 1.
比較例６．
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、エポトートYDPN-638を683部、エポトート YDF-2001（新日鉄住金化学株式会社製、ビスフェノールＦ型固形エポキシ樹脂：エポキシ当量469g/eq）を190部、HCAを127部仕込み、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℃まで昇温した。混合状態での初期エポキシ当量は235g/eqであった、初期エポキシ当量測定後、触媒としてトリフェニルホスフィンを0.13部を添加して160℃で４時間反応を行った。得られたリン含有エポキシ樹脂（A-13）の最終エポキシ当量は272g/eq、リン含有率は1.8％であった。理論エポキシ当量は272g/eqであった。結果を表１に示した。 Comparative Example 6
A four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet, 683 parts of Epototo YDPN-638, Epotot YDF-2001 (Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol F type) Solid epoxy resin: 190 parts of epoxy equivalent (469 g / eq) and 127 parts of HCA were charged, stirred while introducing nitrogen gas, heated and heated. The temperature was raised to 130 ° C. The initial epoxy equivalent in the mixed state was 235 g / eq. After measuring the initial epoxy equivalent, 0.13 part of triphenylphosphine was added as a catalyst, and the reaction was performed at 160 ° C. for 4 hours. The final epoxy equivalent of the obtained phosphorus-containing epoxy resin (A-13) was 272 g / eq, and the phosphorus content was 1.8%. The theoretical epoxy equivalent weight was 272 g / eq. The results are shown in Table 1.
実施例９〜12及び14〜16、並びに比較例７〜11．
実施例１〜５、比較例１〜３、及び比較例５のシアヌル酸変性リン含有エポキシ樹脂、並びに比較例６のリン含有エポキシ樹脂と、硬化剤としてDICY（日本カーバイト株式会社製、ジシアンジアミド）を使用して硬化性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２に示した。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、N,N−ジメチルホルムアミドに溶解して使用した。2E4MZ（四国化成工業株式会社製、2−エチル−4−メチルイミダゾール）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、均一溶液な樹脂ワニスを得た。 Examples 9-12 and 14-16, and Comparative Examples 7-11.
Examples 1-5, Comparative Examples 1-3, and Cyanuric Acid Modified Phosphorus-Containing Epoxy Resin of Comparative Example 5, and Phosphorus-Containing Epoxy Resin of Comparative Example 6 and DICY (Dicyandiamide, manufactured by Nippon Carbide Corporation) Was used to prepare a curable epoxy resin composition. Table 2 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 dissolved in methoxypropanol and N, N-dimethylformamide and used. 2E4MZ (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2-ethyl-4-methylimidazole) was dissolved in methoxypropanol and used. After blending, the solution was adjusted with methyl ethyl ketone and methoxypropanol so that the non-volatile content was 50% to obtain a uniform resin varnish.
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４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２に示した。
なお、表中のTX-1210-90は、エポトートTX-1210-90（新日鉄住金化学株式会社製、置換フェノール型エポキシ樹脂:エポキシ当量293g/eq）を示す。The obtained resin varnish was impregnated into glass cloth WEA 7628 XS13 (manufactured by Nitto Boseki Co., Ltd., thickness 0.18 mm). The impregnated glass cloth was dried in a hot air circulating furnace at 150 ° C. for 8 minutes to obtain a prepreg. 4 sheets of prepreg obtained are stacked, and copper foil (Mitsui Metal Mining Co., Ltd., 3EC) is stacked on top and bottom, and heated and pressed at 130 ° C x 15 min and 170 ° C x 20 kg / cm 2 x 70 min. Got. Table 2 shows the physical properties of the obtained laminate.
In addition, TX-1210-90 in the table represents Epototo TX-1210-90 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., substituted phenol type epoxy resin: epoxy equivalent 293 g / eq).
実施例13及び17．
実施例２と８で得られたシアヌル酸変性リン含有エポキシ樹脂と、硬化剤としてBRG-557（昭和電工株式会社製、フェノールノボラック樹脂）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２に示した。配合の際にエポキシ樹脂及びBRG-557はメチルエチルケトンに溶解して用いた。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、均一溶液な樹脂ワニスを得た。 Examples 13 and 17.
An epoxy resin composition was prepared using the cyanuric acid-modified phosphorus-containing epoxy resin obtained in Examples 2 and 8 and BRG-557 (manufactured by Showa Denko KK, phenol novolac resin) as a curing agent. Table 2 shows the formulation of the solid content. At the time of blending, the epoxy resin and BRG-557 were dissolved in methyl ethyl ketone and used. 2E4MZ was used by dissolving in methoxypropanol. After blending, the solution was adjusted with methyl ethyl ketone and methoxypropanol so that the non-volatile content was 50% to obtain a uniform resin varnish.
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４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190℃×20kg/cm2×80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２に示した。The obtained resin varnish was impregnated into glass cloth WEA 7628 XS13 (manufactured by Nitto Boseki Co., Ltd., thickness 0.18 mm). The impregnated glass cloth was dried in a hot air circulating furnace at 150 ° C. for 8 minutes to obtain a prepreg. Laminate 4 sheets of prepregs obtained, stack copper foil (Mitsui Metal Mining Co., Ltd., 3EC) on top and bottom, heat and press at 130 ° C x 15 min and 190 ° C x 20 kg / cm 2 x 80 min. Got. Table 2 shows the physical properties of the obtained laminate.
実施例から判るようにシアヌル酸１モルに対して所定のモル比範囲のリン化合物とエポキシ樹脂を反応することで、短時間の反応でシアヌル酸が十分反応し、濁りの無いシアヌル酸変性リン含有エポキシ樹脂を得ることができる。また、シアヌル酸が十分反応した濁りの無いシアヌル酸変性リン含有エポキシ樹脂を使用して積層板評価を行ったところ、未反応で濁りがある比較例のシアヌル酸変性エポキシ樹脂を使用した場合よりも高い耐熱性、接着性、難燃性を示した。 As can be seen from the examples, by reacting a phosphorus compound in a predetermined molar ratio range with 1 mol of cyanuric acid and an epoxy resin, cyanuric acid sufficiently reacts in a short reaction, and there is no turbid cyanuric acid modified phosphorus containing An epoxy resin can be obtained. Moreover, when the laminated board evaluation was performed using cyanuric acid-modified phosphorus-containing epoxy resin without turbidity that cyanuric acid reacted sufficiently, compared to the case of using a cyanuric acid-modified epoxy resin of comparative example that is unreacted and turbid. High heat resistance, adhesiveness and flame retardancy were exhibited.
本発明は、特定のリン化合物とシアヌル酸とを特定のモル比で共存させてエポキシ樹脂と反応させる製造方法であって、その製造方法から得られるシアヌル酸変性リン含有エポキシ樹脂は、難燃性、耐熱性、接着性に優れた電子回路基板用のエポキシ樹脂として利用することができる。 The present invention is a manufacturing method in which a specific phosphorus compound and cyanuric acid coexist in a specific molar ratio and react with an epoxy resin, and the cyanuric acid-modified phosphorus-containing epoxy resin obtained from the manufacturing method is flame retardant. It can be used as an epoxy resin for electronic circuit boards having excellent heat resistance and adhesiveness.
Claims (5)
下記一般式（１）：
または、下記一般式（２）：
で示されるリン化合物、または、その両者を含むリン化合物であり、シアヌル酸１モルに対して、該リン化合物を2.5〜50モルにした、リン化合物及びシアヌル酸の共存下に、前記エポキシ樹脂を予め混合し、その後に反応を行い、リン含有率が1.0〜5.0質量％、窒素含有率が0.1〜2.0質量％、かつ、リン含有率と窒素含有率の総和が2.5〜5.5質量％であることを特徴とするシアヌル酸変性リン含有エポキシ樹脂の製造方法。A method for producing a cyanuric acid-modified phosphorus-containing epoxy resin obtained by reacting a phosphorus compound, cyanuric acid, and an epoxy resin as essential components, wherein the phosphorus compound is
The following general formula (1):
Or the following general formula (2):
Or a phosphorus compound containing both of them, wherein the epoxy resin is used in the presence of a phosphorus compound and cyanuric acid, with 2.5 to 50 moles of the phosphorus compound per mole of cyanuric acid. Mixing in advance, followed by reaction, phosphorus content is 1.0-5.0 mass%, nitrogen content is 0.1-2.0 mass%, and the total of phosphorus content and nitrogen content is 2.5-5.5 mass% A process for producing a cyanuric acid-modified phosphorus-containing epoxy resin.
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- 2013-08-27 CN CN201380044287.1A patent/CN104583263B/en active Active
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| JP2002284850A (en) * | 2001-03-26 | 2002-10-03 | Sanko Kk | Phosphorus and nitrogen modified flame-retardant epoxy resin composition, prepreg and laminate |
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| Publication number | Publication date |
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| CN104583263B (en) | 2018-02-13 |
| WO2014034675A1 (en) | 2014-03-06 |
| TW201418309A (en) | 2014-05-16 |
| JP6246126B2 (en) | 2017-12-13 |
| KR20150052011A (en) | 2015-05-13 |
| KR101954484B1 (en) | 2019-03-05 |
| TWI620762B (en) | 2018-04-11 |
| CN104583263A (en) | 2015-04-29 |
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