JP5720486B2 - Photosensitive resin composition - Google Patents
Photosensitive resin composition Download PDFInfo
- Publication number
- JP5720486B2 JP5720486B2 JP2011177946A JP2011177946A JP5720486B2 JP 5720486 B2 JP5720486 B2 JP 5720486B2 JP 2011177946 A JP2011177946 A JP 2011177946A JP 2011177946 A JP2011177946 A JP 2011177946A JP 5720486 B2 JP5720486 B2 JP 5720486B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- acid
- resin
- epoxy resin
- structural formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011342 resin composition Substances 0.000 title claims description 25
- 239000003822 epoxy resin Substances 0.000 claims description 89
- 229920000647 polyepoxide Polymers 0.000 claims description 89
- 229920005989 resin Polymers 0.000 claims description 69
- 239000011347 resin Substances 0.000 claims description 69
- 229910052698 phosphorus Inorganic materials 0.000 claims description 57
- 125000004437 phosphorous atom Chemical group 0.000 claims description 42
- 239000002253 acid Substances 0.000 claims description 41
- 229920001567 vinyl ester resin Polymers 0.000 claims description 30
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 22
- 150000008065 acid anhydrides Chemical class 0.000 claims description 18
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 150000007519 polyprotic acids Polymers 0.000 claims description 11
- 239000003085 diluting agent Substances 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 238000000576 coating method Methods 0.000 description 29
- 239000011248 coating agent Substances 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 24
- 229920003986 novolac Polymers 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- 239000000976 ink Substances 0.000 description 21
- 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 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 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 17
- 235000014786 phosphorus Nutrition 0.000 description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 16
- 239000011574 phosphorus Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- -1 phosphorus compound Chemical class 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 238000005259 measurement Methods 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- 230000035945 sensitivity Effects 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 238000011161 development Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 8
- 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 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 8
- 229930003836 cresol Natural products 0.000 description 8
- 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 8
- 229910000679 solder Inorganic materials 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 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 4
- 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 4
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical class CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 230000036211 photosensitivity Effects 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- WDGCBNTXZHJTHJ-UHFFFAOYSA-N 2h-1,3-oxazol-2-id-4-one Chemical group O=C1CO[C-]=N1 WDGCBNTXZHJTHJ-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-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 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- 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
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 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
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- XVWNIYLSVLQOFL-UHFFFAOYSA-N [1-(diethylamino)cyclohexa-2,4-dien-1-yl]-[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1(N(CC)CC)C=CC=CC1 XVWNIYLSVLQOFL-UHFFFAOYSA-N 0.000 description 2
- XFSBVAOIAHNAPC-WSORPINJSA-N acetylbenzoylaconine Chemical compound O([C@H]1[C@]2(O)C[C@H]3C45[C@@H]6[C@@H]([C@@]([C@H]31)(OC(C)=O)[C@@H](O)[C@@H]2OC)[C@H](OC)C4[C@]([C@@H](C[C@H]5OC)O)(COC)CN6CC)C(=O)C1=CC=CC=C1 XFSBVAOIAHNAPC-WSORPINJSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 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
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
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- 239000004843 novolac epoxy resin Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 235000001508 sulfur Nutrition 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-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
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Materials For Photolithography (AREA)
Description
本発明は、特に光に対する感度に優れ、かつ、基材への密着性が良好な感光性樹脂組成物に関する。 The present invention relates to a photosensitive resin composition that is particularly excellent in sensitivity to light and has good adhesion to a substrate.
従来、レジストインキ用感光性樹脂組成物として、ノボラック型エポキシ樹脂と不飽和モノカルボン酸の反応物に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂がその優れた耐熱性、耐薬品性、電気絶縁性から広く使用されてきた。しかしながら、近年の電気基板の小型化、高精度化に伴い、これら電子基板材料の表層に用いられるレジストインキに対しても難燃性の向上が必須となり、種々の感光性樹脂が開発されている。 Conventionally, as a photosensitive resin composition for resist ink, a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride with a reaction product of a novolak type epoxy resin and an unsaturated monocarboxylic acid has excellent heat resistance, Widely used from chemical resistance and electrical insulation. However, with the recent miniaturization and high precision of electric substrates, it is essential to improve flame resistance for resist inks used for the surface layer of these electronic substrate materials, and various photosensitive resins have been developed. .
例えば、難燃性、感度、耐熱性、解像度、現像性、耐薬品性、耐メッキ性等に優れたソルダーレジストインキ用カルボキシル基含有感光性樹脂として、ノボラック型エポキシ樹脂等の多官能型エポキシ樹脂に燐化合物であるＨＣＡ(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)を反応させ、更に不飽和基含有モノカルボン酸やそのエステルを反応させ、更に多塩基酸無水物を反応させて得られるカルボキシル基含有感光性樹脂及びその組成物、硬化物が開示されている（下記特許文献１参照）。斯かる特許文献１記載のカルボキシル基含有感光性樹脂は、難燃性については確かに公知のエポキシ樹脂を用いたエポキシアクリレート樹脂と比較した場合は向上がみられるものの、その製造工程において、原料エポキシ樹脂のエポキシ基に前記ＨＣＡを反応させることによりリン原子を樹脂構造に導入する手段を採用している為、リン原子含有率を高められず、依然として難燃性が十分なものでないことに加え、ソルダーレジスト用途におけるプリント配線基板表面の回路パターンを形成する銅箔に対する密着性にも劣るものであった。 For example, as a carboxyl group-containing photosensitive resin for solder resist inks that has excellent flame retardancy, sensitivity, heat resistance, resolution, developability, chemical resistance, plating resistance, etc., a polyfunctional epoxy resin such as a novolac type epoxy resin Is reacted with HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) which is a phosphorus compound, further reacted with an unsaturated group-containing monocarboxylic acid or its ester, and further with a polybasic acid A carboxyl group-containing photosensitive resin obtained by reacting an anhydride, a composition thereof, and a cured product are disclosed (see Patent Document 1 below). Such a carboxyl group-containing photosensitive resin described in Patent Document 1 is certainly improved in terms of flame retardancy when compared with an epoxy acrylate resin using a known epoxy resin. In addition to adopting a means for introducing phosphorus atoms into the resin structure by reacting the HCA with the epoxy group of the resin, the phosphorus atom content cannot be increased, and the flame retardancy is still not sufficient, It was inferior also in the adhesiveness with respect to the copper foil which forms the circuit pattern of the printed wiring board surface in a soldering resist use.
本発明が解決しようとする課題は、高い難燃性と密着性を兼備したアルカリ現像型の感光性樹脂組成物を提供することにある。 The problem to be solved by the present invention is to provide an alkali development type photosensitive resin composition having both high flame retardancy and adhesion.
本発明者等は、上記課題を解決すべく鋭意検討した結果、特定構造のリン原子含有エポキシ樹脂から誘導される酸基含有のビニルエステル樹脂を用いた場合、優れた難燃性と密着性とを発現することを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained excellent flame retardancy and adhesion when using an acid group-containing vinyl ester resin derived from a phosphorus atom-containing epoxy resin having a specific structure. The present invention was completed.
即ち、本発明は、下記構造式（１） That is, the present invention provides the following structural formula (1)
（式中、Ｘは下記構造式（ｘ１）又は（ｘ２）
(Wherein X represents the following structural formula (x1) or (x2)
で表される構造部位であり、Ｙは水素原子、水酸基又は前記構造式（ｘ１）若しくは（ｘ２）で表される構造部位であり、Ｒ１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、又は前記構造式（ｘ１）若しくは（ｘ２）を表し、ｎは繰り返し単位で１以上の整数であり、また、前記構造式（ｘ１）又は（ｘ２）中、Ｒ２、Ｒ３、Ｒ４、Ｒ５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基を表す。）で表される分子構造を有するリン原子含有オリゴマー（α）と、多官能型エポキシ樹脂（β）とを反応させて得られる樹脂構造を有するリン原子含有エポキシ樹脂（Ａ−１）に、不飽和基含有モノカルボン酸（Ａ−２）及び多塩基酸無水物（Ａ−３）を反応させて得られる、ラジカル重合性不飽和二重結合（i）及びカルボキシル基（ii）を有する酸基含有ビニルエステル樹脂（Ａ）、光重合開始剤（Ｂ）、及びエポキシ樹脂（Ｃ）を必須成分とすることを特徴とする感光性樹脂組成物に関する。
Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Represents an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or the structural formula (x1) or (x2), wherein n is a repeating unit and is an integer of 1 or more, and the structural formula (x1) or ( In x2), R 2 , R 3 , R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. The phosphorus atom-containing epoxy resin (A-1) having a resin structure obtained by reacting a phosphorus atom-containing oligomer (α) having a molecular structure represented by (II) with a polyfunctional epoxy resin (β). An acid group having a radical polymerizable unsaturated double bond (i) and a carboxyl group (ii) obtained by reacting a saturated group-containing monocarboxylic acid (A-2) and a polybasic acid anhydride (A-3) The present invention relates to a photosensitive resin composition comprising, as essential components, a vinyl ester resin (A), a photopolymerization initiator (B), and an epoxy resin (C).
本発明によれば、高い難燃性と密着性とを兼備したアルカリ現像型の感光性樹脂組成物を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the alkali development type photosensitive resin composition which has high flame retardance and adhesiveness can be provided.
本発明で用いる酸基含有ビニルエステル樹脂（Ａ）は、下記構造式（１） The acid group-containing vinyl ester resin (A) used in the present invention has the following structural formula (1).
（式中、Ｘは下記構造式（ｘ１）又は（ｘ２）
(Wherein X represents the following structural formula (x1) or (x2)
で表される構造部位であり、Ｙは水素原子、水酸基又は前記構造式（ｘ１）若しくは（ｘ２）で表される構造部位であり、Ｒ１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、又は前記構造式（ｘ１）若しくは（ｘ２）を表し、ｎは繰り返し単位で１以上の整数であり、また、前記構造式（ｘ１）又は（ｘ２）中、Ｒ２、Ｒ３、Ｒ４、Ｒ５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基を表す。）で表される分子構造を有するリン原子含有オリゴマー（α）と、多官能型エポキシ樹脂（β）とを反応させて得られる樹脂構造を有するリン原子含有エポキシ樹脂（Ａ−１）に、不飽和基含有モノカルボン酸（Ａ−２）及び多塩基酸無水物（Ａ−３）を反応させて得られる、ラジカル重合性不飽和二重結合（i）及びカルボキシル基（ii）を有する樹脂構造を有するものである。
Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Represents an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or the structural formula (x1) or (x2), wherein n is a repeating unit and is an integer of 1 or more, and the structural formula (x1) or ( In x2), R 2 , R 3 , R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. The phosphorus atom-containing epoxy resin (A-1) having a resin structure obtained by reacting a phosphorus atom-containing oligomer (α) having a molecular structure represented by (II) with a polyfunctional epoxy resin (β). Resin structure having radically polymerizable unsaturated double bond (i) and carboxyl group (ii) obtained by reacting saturated group-containing monocarboxylic acid (A-2) and polybasic acid anhydride (A-3) It is what has.
ここで、前記酸基含有ビニルエステル樹脂（Ａ）中のラジカル重合性不飽和二重結合（i）は、前記不飽和基含有モノカルボン酸（Ａ−２）に由来するものであり、他方、カルボキシル基（ii）は、多塩基酸無水物（Ａ−３）に由来するものである。前記酸基含有ビニルエステル樹脂（Ａ）中のラジカル重合性不飽和二重結合（i）とカルボキシル基（ii）との存在割合は、［（ii）／（ｉ）］のモル比率が９０／１０〜３０／７０となる割合で有することが、光感度と現像性とのバランスが良好なものとなる点から好ましい。 Here, the radical polymerizable unsaturated double bond (i) in the acid group-containing vinyl ester resin (A) is derived from the unsaturated group-containing monocarboxylic acid (A-2), The carboxyl group (ii) is derived from the polybasic acid anhydride (A-3). In the acid group-containing vinyl ester resin (A), the radically polymerizable unsaturated double bond (i) and the carboxyl group (ii) are present in a molar ratio of [(ii) / (i)] of 90 / It is preferable to have a ratio of 10 to 30/70 from the viewpoint of a good balance between photosensitivity and developability.
前記酸基含有ビニルエステル樹脂（Ａ）は、その不飽和二重結合当量が２５０〜２０００の範囲であることが光感度の点から好ましい。 The acid group-containing vinyl ester resin (A) preferably has an unsaturated double bond equivalent in the range of 250 to 2000 from the viewpoint of photosensitivity.
また、前記酸基含有ビニルエステル樹脂（Ａ）は、固形分酸価が３０〜１５０ＫＯＨ／ｇの範囲であることが優れた現像性を発現できる点から好ましい。 In addition, the acid group-containing vinyl ester resin (A) is preferable because the solid content acid value is in the range of 30 to 150 KOH / g because excellent developability can be exhibited.
ここで、前記酸基含有ビニルエステル樹脂（Ａ）の前駆体であるリン原子含有オリゴマー（α）は、具体的には、下記構造式（１） Here, the phosphorus atom-containing oligomer (α), which is a precursor of the acid group-containing vinyl ester resin (A), specifically has the following structural formula (1).
（式中、Ｘは下記構造式（ｘ１）又は（ｘ２）
(Wherein X represents the following structural formula (x1) or (x2)
で表される構造部位であり、Ｙは水素原子、水酸基又は前記構造式（ｘ１）若しくは（ｘ２）で表される構造部位であり、Ｒ１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、又は前記構造式（ｘ１）若しくは（ｘ２）を表し、ｎは繰り返し単位で１以上の整数であり、また、前記構造式（ｘ１）又は（ｘ２）中、Ｒ２、Ｒ３、Ｒ４、Ｒ５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基を表す。）で表される分子構造を有するリン原子含有オリゴマー（α）と、多官能型エポキシ樹脂（β）とを反応させて得られる樹脂構造を有することを特徴とするものである。
Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Represents an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or the structural formula (x1) or (x2), wherein n is a repeating unit and is an integer of 1 or more, and the structural formula (x1) or ( In x2), R 2 , R 3 , R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. It has a resin structure obtained by reacting a phosphorus atom-containing oligomer (α) having a molecular structure represented by (II) and a polyfunctional epoxy resin (β).
ここで用いるリン原子含有オリゴマー（α）は、前記した通り、前記構造式（１）中に下記構造式（２） As described above, the phosphorus atom-containing oligomer (α) used here has the following structural formula (2) in the structural formula (1).
（式中、Ｘは下記構造式（ｘ１）又は（ｘ２）
(Wherein X represents the following structural formula (x1) or (x2)
で表される構造部位であり、Ｒ１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、又は前記構造式（ｘ１）若しくは（ｘ２）を表し、ｎは繰り返し単位で１以上の整数であり、また、前記構造式（ｘ１）又は（ｘ２）中、Ｒ２、Ｒ３、Ｒ４、Ｒ５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基を表す。）で表される構造部位を有することから、最終的に得られる酸基含有ビニルエステル樹脂（Ａ）の硬化物における難燃性と、銅箔に対する密着性とが優れたものとなる。
R 1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or the structural formula (x1) or (x2). N represents a repeating unit and is an integer of 1 or more. In the structural formula (x1) or (x2), R 2 , R 3 , R 4 and R 5 are each independently a hydrogen atom, carbon An alkyl group having 1 to 4 atoms, a phenyl group, or an aralkyl group is represented. ), The flame retardancy in the cured product of the finally obtained acid group-containing vinyl ester resin (A) and the adhesion to the copper foil are excellent.
ここで、前記構造式（２）中で表される構造部位は、具体的には、下記構造式（２−１）〜（２−１０）で表されるものが挙げられる。 Here, specific examples of the structural portion represented in the structural formula (2) include those represented by the following structural formulas (2-1) to (2-10).
本発明では、前記構造式（１）中のＸは構造式（ｘ１）及び構造式（ｘ２）から選択されるものであるが、特に難燃性の点から構造式（ｘ１）であることが好ましく、よって、前記構造式（２）で表される構造部位のなかでも、前記構造式（ｘ−１）に対応する構造式（２−１）、（２−２）、（２−３）、（２−４）及び（２−９）が好ましい。 In the present invention, X in the structural formula (1) is selected from the structural formula (x1) and the structural formula (x2), and may be the structural formula (x1) particularly from the viewpoint of flame retardancy. Therefore, among the structural sites represented by the structural formula (2), the structural formulas (2-1), (2-2), and (2-3) corresponding to the structural formula (x-1). , (2-4) and (2-9) are preferred.
また、前記構造式（１）において、Ｙは、水素原子、水酸基又は前記構造式（ｘ１）若しくは（ｘ２）で表される構造部位であるが、該リン原子含有オリゴマー中にこれらが共存していてもよい。Ｙとして前記構造式（ｘ１）又は（ｘ２）で表される構造部位を有する場合、難燃性の点から構造式（ｘ１）であることが好ましい。 In the structural formula (1), Y is a hydrogen atom, a hydroxyl group, or a structural site represented by the structural formula (x1) or (x2), and these coexist in the phosphorus atom-containing oligomer. May be. When Y has the structural moiety represented by the structural formula (x1) or (x2), the structural formula (x1) is preferable from the viewpoint of flame retardancy.
また、前記リン原子含有オリゴマー（α）は、上記した構造式（１）においてｎが２以上の成分の含有率が、ＧＰＣ測定におけるピーク面積基準で５〜９０％の範囲にあるものが、とりわけ有機溶剤への溶解性に優れ、かつ、最終的に得られる酸基含有ビニルエステル樹脂（Ａ）の硬化物における難燃性に優れる点から好ましい。 In addition, the phosphorus atom-containing oligomer (α) has a content of components having n of 2 or more in the above structural formula (1) in the range of 5 to 90% on the basis of the peak area in GPC measurement. It is preferable from the viewpoint of excellent solubility in an organic solvent and excellent flame retardancy in a cured product of the finally obtained acid group-containing vinyl ester resin (A).
ここで、前記構造式（１）におけるｎが２以上の成分の含有率とは、下記の条件で測定されたＧＰＣのチャートにおいて、３６．０分未満のピーク面積の割合をいうものである。 Here, the content ratio of the component having n of 2 or more in the structural formula (1) refers to the ratio of the peak area of less than 36.0 minutes in the GPC chart measured under the following conditions.
＜ＧＰＣ測定条件＞
測定装置 ：東ソー株式会社製「ＨＬＣ−８２２０ ＧＰＣ」、
カラム：東ソー株式会社製ガードカラム「ＨＸＬ−Ｌ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ３０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ４０００ＨＸＬ」
検出器： ＲＩ（示差屈折径）
データ処理：東ソー株式会社製「ＧＰＣ−８０２０モデルIIバージョン４．１０」
測定条件： カラム温度 ４０℃
展開溶媒 テトラヒドロフラン
流速 １．０ｍｌ／分
標準 ： 前記「ＧＰＣ−８０２０モデルIIバージョン４．１０」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
（使用ポリスチレン）
東ソー株式会社製「Ａ−５００」
東ソー株式会社製「Ａ−１０００」
東ソー株式会社製「Ａ−２５００」
東ソー株式会社製「Ａ−５０００」
東ソー株式会社製「Ｆ−１」
東ソー株式会社製「Ｆ−２」
東ソー株式会社製「Ｆ−４」
東ソー株式会社製「Ｆ−１０」
東ソー株式会社製「Ｆ−２０」
東ソー株式会社製「Ｆ−４０」
東ソー株式会社製「Ｆ−８０」
東ソー株式会社製「Ｆ−１２８」
試料 ： 樹脂固形分換算で１．０質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（５０μｌ）。
<GPC measurement conditions>
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).
本発明では、ｎが２以上の成分の含有率が、ＧＰＣ測定におけるピーク面積基準で５％以上の場合、溶剤溶解性が良好なものとなり、他方、９０％以下の場合には溶融時の流動性或いはワニスにした場合の流動性が良好なものとなる。かかる溶剤溶解性と流動性とのバランスに優れる点からとりわけ４０〜７５％となる範囲であることが好ましい。 In the present invention, when the content of the component having n of 2 or more is 5% or more on the basis of the peak area in GPC measurement, the solvent solubility is good. On the other hand, when the content is 90% or less, the flow during melting Or fluidity when made into a varnish. From the viewpoint of excellent balance between the solvent solubility and the fluidity, a range of 40 to 75% is particularly preferable.
また、上記したリン原子含有オリゴマー（α）は、該オリゴマー中のリン原子含有率が９〜１２質量％の範囲であることが酸基含有ビニルエステル樹脂（Ａ）の硬化物における難燃性及び密着性に優れる点から好ましい。かかるリン原子含有率は、ＪＩＳ規格Ｋ０１０２ ４６に準拠して測定した値である。 In addition, the phosphorus atom-containing oligomer (α) described above has a flame retardancy in a cured product of the acid group-containing vinyl ester resin (A) that the phosphorus atom content in the oligomer is in the range of 9 to 12% by mass. It is preferable from the point which is excellent in adhesiveness. The phosphorus atom content is a value measured in accordance with JIS standard K010246.
次に、前記リン原子含有オリゴマー（α）と反応させる多官能型エポキシ樹脂（β）は後述する本発明の製造方法で用いる多官能型エポキシ樹脂（β）が挙げられる。その中でも、ビスフェノール型エポキシ樹脂が溶剤溶解性の点から好ましく、また、硬化物の耐熱性の点からはナフタレン骨格含有エポキシ樹脂であることが好ましい。前者のビスフェノール型エポキシ樹脂を用いる場合、とりわけエポキシ当量１６０〜２３０ｇ／ｅｑ．のビスフェノール型エポキシ樹脂であることが溶剤溶解性と耐熱性とのバランスが良好なものとなる点から好ましく、また、後者のナフタレン骨格含有エポキシ樹脂は、流動性及び耐熱性に優れる点からジグリシジルオキシナフタレンであることが好ましい。 Next, examples of the polyfunctional epoxy resin (β) to be reacted with the phosphorus atom-containing oligomer (α) include the polyfunctional epoxy resin (β) used in the production method of the present invention described later. Among these, a bisphenol type epoxy resin is preferable from the viewpoint of solvent solubility, and from the viewpoint of heat resistance of the cured product, a naphthalene skeleton-containing epoxy resin is preferable. When the former bisphenol type epoxy resin is used, an epoxy equivalent of 160 to 230 g / eq. The bisphenol-type epoxy resin is preferable from the viewpoint of good balance between solvent solubility and heat resistance, and the latter naphthalene skeleton-containing epoxy resin is diglycidyl from the viewpoint of excellent fluidity and heat resistance. Oxynaphthalene is preferred.
上記した新規リン原子含有エポキシ樹脂（Ａ−１）は、そのエポキシ当量が２００〜１０００ｇ／ｅｑ．の範囲にあるものが、硬化物の耐熱性がより良好なものとなる点から好ましく、なかでも、３００〜８００ｇ／ｅｑ．の範囲にあるものが特に好ましい。また、その軟化点（Ｂ＆Ｒ法）は、５０〜１１０℃の範囲であることが流動性、溶剤溶解性、及び耐熱性に優れる点から好ましい。また。溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は５〜５０ｄＰａ・ｓの範囲であることが、流動性、溶剤溶解性に優れる点から好ましく、更に、そのリン原子含有率は、２．０〜７．０質量％の範囲、特に３．５〜７．０質量％の範囲であることが、硬化物における酸基含有ビニルエステル樹脂（Ａ）の硬化物における難燃性及び密着性に優れる点から好ましい。 The above-described novel phosphorus atom-containing epoxy resin (A-1) has an epoxy equivalent of 200 to 1000 g / eq. Is preferable from the point that the heat resistance of the cured product becomes better, and in particular, 300 to 800 g / eq. Those within the range are particularly preferred. Further, the softening point (B & R method) is preferably in the range of 50 to 110 ° C. from the viewpoint of excellent fluidity, solvent solubility, and heat resistance. Also. The melt viscosity (measurement method: ICI viscometer, measurement temperature: 150 ° C.) is preferably in the range of 5 to 50 dPa · s from the viewpoint of excellent fluidity and solvent solubility, and the phosphorus atom content is The flame retardancy in the cured product of the acid group-containing vinyl ester resin (A) in the cured product is in the range of 2.0 to 7.0% by mass, particularly in the range of 3.5 to 7.0% by mass. It is preferable from the point which is excellent in adhesiveness.
次に、前記したリン原子含有オリゴマー（α）は、下記構造式（ａ１−１）又は（ａ１−２） Next, the phosphorus atom-containing oligomer (α) described above has the following structural formula (a1-1) or (a1-2)
（式中、Ｒ２、Ｒ３、Ｒ４、Ｒ５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基を表す。）で表される化合物（ａ１）と、
下記構造式（ａ２）
(Wherein R 2 , R 3 , R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group) a1)
The following structural formula (a2)
（式中、Ｒ６は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基を表す。）で表される化合物（ａ２）とを反応させてリン原子含有オリゴマー（α）を得（工程１）、次いで、得られたリン原子含有オリゴマー（α）と多官能型エポキシ樹脂（β）とを反応させる（工程２）ことにより製造することができる。
(Wherein R 6 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group) and is reacted with a compound (a2) represented by phosphorus. An atom-containing oligomer (α) can be obtained (step 1), and then the obtained phosphorus atom-containing oligomer (α) can be reacted with a polyfunctional epoxy resin (β) (step 2).
工程１において、前記構造式（ａ１−１）又は（ａ１−２）中の、Ｒ２、Ｒ３、Ｒ４、Ｒ５を構成する炭素原子数１〜５のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｔ−ブチル基が挙げられるが、本発明で用いる化合物（ａ１）は、Ｒ２、Ｒ３、Ｒ４、Ｒ５の全てが水素原子であるものが難燃性の点から好ましい。更に化合物（ａ１）は、硬化物の難燃性に優れる点から構造式（ａ１−１）を有するものが好ましい。他方、化合物（ａ２）における前記構造式（ａ２）中のＲ１は、メチル基、エチル基、ｎ−プロピル基、メトキシ基等が挙げられるが、化合物（ａ１）との反応性及び酸基含有ビニルエステル樹脂（Ａ）の硬化物における難燃性に優れる点からＲ１は水素原子であることが好ましい。 In step 1, as the alkyl group having 1 to 5 carbon atoms constituting R 2 , R 3 , R 4 , and R 5 in the structural formula (a1-1) or (a1-2), a methyl group, Examples include an ethyl group, an n-propyl group, an i-propyl group, and a t-butyl group. In the compound (a1) used in the present invention, all of R 2 , R 3 , R 4 , and R 5 are hydrogen atoms. A thing is preferable from a flame-retardant point. Further, the compound (a1) preferably has the structural formula (a1-1) from the viewpoint that the cured product is excellent in flame retardancy. On the other hand, examples of R 1 in the structural formula (a2) in the compound (a2) include a methyl group, an ethyl group, an n-propyl group, and a methoxy group, but the reactivity with the compound (a1) and the acid group content are included. From the viewpoint of excellent flame retardancy in the cured product of the vinyl ester resin (A), R 1 is preferably a hydrogen atom.
工程１の具体的な反応方法としては、前記化合物（ａ１）と前記化合物（ａ２）とを、モル比［化合物（ａ１）／化合物（ａ２）］が０．０１／１．０〜０．９９／１．０となる割合で配合し、酸触媒の存在下、８０〜１８０℃で反応を行い、次いで、前記化合物（ａ２）の仕込み量に対して、モル基準で合計１．０１〜３．０倍量となる前記化合物（ａ１）を加え、１２０〜２００℃にて反応を行う方法が、反応中間体の析出を良好に抑制でき、高分子量化し易くなる点から好ましい。 As a specific reaction method of Step 1, the compound (a1) and the compound (a2) are mixed in a molar ratio [compound (a1) / compound (a2)] of 0.01 / 1.0 to 0.99. /1.0, and the reaction is carried out at 80 to 180 ° C. in the presence of an acid catalyst. Then, the total amount of 1.01 to 3.3 on a molar basis with respect to the charged amount of the compound (a2). A method of adding the compound (a1) in a 0-fold amount and carrying out the reaction at 120 to 200 ° C. is preferable in that precipitation of the reaction intermediate can be satisfactorily suppressed and the molecular weight is easily increased.
また、ここで使用し得る触媒としては、塩酸、硫酸、リン酸などの無機酸、メタンスルホン酸、ｐ−トルエンスルホン酸、シュウ酸などの有機酸、三弗化ホウ素、無水塩化アルミニウム、塩化亜鉛などのルイス酸などが挙げられる。その使用量は硬化物の電気絶縁の低下を防ぐ観点から仕込み原料の総重量に対して、０．１〜５.０質量％の範囲であることが好ましい。 Examples of catalysts that can be used here include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Lewis acids such as The amount used is preferably in the range of 0.1 to 5.0% by mass with respect to the total weight of the charged raw materials from the viewpoint of preventing a decrease in electrical insulation of the cured product.
該反応は前記化合物（ａ２）が液状であるため、これを有機溶媒として用い反応を行うことができるが、作業性等の向上という観点から他の有機溶媒を使用してもよい。ここで、用いる有機溶媒としては、アルコール系有機溶媒、炭化水素系有機溶媒などの非ケトン系有機溶媒が挙げられ、具体的には、前記アルコール系有機溶媒としてはプロピレングリコールモノメチルエーテル等が挙げられ、前記炭化水素系有機溶媒としてはトルエン、キシレン等が挙げられる。 In the reaction, since the compound (a2) is in a liquid state, it can be used as an organic solvent, but another organic solvent may be used from the viewpoint of improving workability and the like. Here, examples of the organic solvent used include non-ketone organic solvents such as alcohol-based organic solvents and hydrocarbon-based organic solvents. Specifically, examples of the alcohol-based organic solvent include propylene glycol monomethyl ether. Examples of the hydrocarbon organic solvent include toluene, xylene and the like.
反応終了後は、減圧下で乾燥することによって目的とするリン原子含有オリゴマー（α）を得ることができる。 After completion of the reaction, the desired phosphorus atom-containing oligomer (α) can be obtained by drying under reduced pressure.
次に、工程２として、工程１で得らリン原子含有オリゴマー（α）を、多官能型エポキシ樹脂（β）と反応させることにより、リン原子含有エポキシ樹脂（ａ１）を得ることができる。 Next, as step 2, the phosphorus atom-containing epoxy resin (a1) can be obtained by reacting the phosphorus atom-containing oligomer (α) obtained in step 1 with the polyfunctional epoxy resin (β).
ここで用いる多官能型エポキシ樹脂（β）としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等の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、ビスフェノールＡノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、下記構造式（β−ａ） Examples of the polyfunctional epoxy resin (β) used here include bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins; phenol novolac type epoxy resins, cresol novolac type epoxy resins, and bisphenol A novolak types. Epoxy resin, biphenyl novolac type epoxy resin, the following structural formula (β-a)
（前記式中、Ｇはグリシジル基、Ｒａは水素原子又は炭素原子数１〜６の炭化水素基を表し、ｌａは繰り返し単位で０〜１０の整数である。）で表されるノボラック型エポキシ樹脂；ジグリシジルオキシナフタレン、１，１−ビス（２，７−ジグリシジルオキシ−１−ナフチル）アルカン；ナフトールノボラック型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ナフトール−フェノール共縮ノボラック型エポキシ樹脂、ナフトール−クレゾール共縮ノボラック型エポキシ樹脂等のナフトールノボラック系エポキシ樹脂；キサンテン型エポキシ樹脂；下記構造式（β−ｂ）
(In the above formula, G represents a glycidyl group, Ra represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and la is an integer of 0 to 10 in terms of repeating units). Diglycidyloxynaphthalene, 1,1-bis (2,7-diglycidyloxy-1-naphthyl) alkane; naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol- Naphthol novolak epoxy resin such as cresol co-condensed novolac epoxy resin; xanthene epoxy resin; structural formula (β-b) below
（前記式中、Ｇはグリシジル基、Ｒｂは水素原子又は炭素原子数１〜６の炭化水素基、ｌｂは繰り返し単位で０〜１０の整数である。）で表されるアラルキル型エポキシ樹脂；
下記構造式（β−ｃ）、
(In the above formula, G is a glycidyl group, Rb is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and lb is an integer of 0 to 10 in terms of repeating units);
The following structural formula (β-c),
（前記式中、Ｇはグリシジル基、Ｒｃは水素原子又は炭素原子数１〜６の炭化水素基、ｌｃは繰り返し単位で０〜１０の整数である。）で表されるアラルキル型エポキシ樹脂；下記構造式（β−ｄ）
(In the above formula, G is a glycidyl group, Rc is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and lc is an integer of 0 to 10 in terms of repeating units); Structural formula (β-d)
（前記式中、Ｇはグリシジル基、Ｒｄは水素原子又は炭素原子数１〜６の炭化水素基、ｌｄは繰り返し単位で０〜１０の整数である。）で表されるアラルキル型エポキシ樹脂；
下記構造式（β−ｅ）
(In the above formula, G is a glycidyl group, Rd is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and ld is an integer of 0 to 10 in terms of repeating units);
The following structural formula (β-e)
（前記式中、Ｇはグリシジル基、Ｒｅは水素原子又は炭素原子数１〜６の炭化水素基、ｌｅは繰り返し単位で０〜１０の整数である。）で表されるアラルキル型エポキシ樹脂；下記構造式（β−ｆ）
(In the above formula, G is a glycidyl group, Re is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and le is an integer of 0 to 10 in terms of repeating units); Structural formula (β-f)
（前記式中、Ｇはグリシジル基、Ｒｅは水素原子又は炭素原子数１〜６の炭化水素基、ｌｆは繰り返し単位で０〜１０の整数である。）で表されるアラルキル型エポキシ樹脂；下記構造式（β−ｇ）
(In the above formula, G is a glycidyl group, Re is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and lf is an integer of 0 to 10 in terms of repeating units); Structural formula (β-g)
（前記式中、Ｇはグリシジル基、Ｒｇは水素原子又は炭素原子数１〜６の炭化水素基、ｌｇは繰り返し単位で０〜１０の整数である。）で表されるアラルキル型エポキシ樹脂；前記構造式（β−ｈ）
(Wherein G is a glycidyl group, Rg is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and lg is an integer of 0 to 10 in terms of repeating units); Structural formula (β-h)
（式中、Ｇはグリシジル基、Ｒｈはそれぞれ独立的に水素原子、炭素原子数１〜４のアルキル基である。）で表されるビフェノール型エポキシ樹脂；下記構造式（β−ｉ）
(Wherein G is a glycidyl group, and Rh is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms); the following structural formula (β-i)
（式中、Ｇはグリシジル基、Ｒｉはそれぞれ独立的に水素原子、炭素原子数１〜４のアルキル基である。）
で表されるエポキシ樹脂；トリフェニルメタン型エポキシ樹脂；テトラフェニルエタン型エポキシ樹脂；ジシクロペンタジエン、テトラヒドロインデン、４−ビニルシクロヘキセン、５−ビニルノルボナ−２−エン、α−ピネン、β−ピネン、及びリモネンからなる群から選択される脂肪族環状炭化水素基を介してフェノール化合物が結節された分子構造をもつフェノール樹脂のポリグリシジルエーテル等が挙げられる。
(In the formula, G is a glycidyl group, and Ri is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
An epoxy resin represented by: triphenylmethane type epoxy resin; tetraphenylethane type epoxy resin; dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorborna-2-ene, α-pinene, β-pinene, and And a polyglycidyl ether of a phenol resin having a molecular structure in which a phenol compound is knotted through an aliphatic cyclic hydrocarbon group selected from the group consisting of limonene.
これらの中でも、クレゾールノボラック型エポキシ樹脂が耐熱性の点から、ナフトールノボラック型エポキシ樹脂が、硬化物における耐熱性及び難燃性に優れる点から、また、脂肪族環状炭化水素基を介してフェノール化合物が結節された分子構造をもつフェノール樹脂のポリグリシジルエーテルが、最終的に得られる酸基含有ビニルエステル樹脂（Ａ）の硬化物における耐熱性及び耐湿性に優れる点から好ましい。 Among these, cresol novolac type epoxy resins are heat resistant, naphthol novolac type epoxy resins are excellent in heat resistance and flame retardancy in cured products, and phenolic compounds via aliphatic cyclic hydrocarbon groups. Polyglycidyl ether of a phenol resin having a molecular structure with knots is preferable from the viewpoint of excellent heat resistance and moisture resistance in a cured product of the finally obtained acid group-containing vinyl ester resin (A).
工程２の具体的な反応方法は、例えば、リン原子含有フェノール化合物（α）と、多官能型エポキシ樹脂（β）とを、反応容器に仕込み、反応触媒を加え、不活性ガス封入下で撹拌しながら加熱し、撹拌しながら反応させる方法が挙げられる。ここで用いる、反応触媒としては、例えば、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸ナトリウム等のアルカリ金属塩類、トリブチルアミン等のアミン類、トリフェニルホスフィン等のホスフィン類等が挙げられる。反応温度は、１００〜２５０℃の範囲が挙げられる。 The specific reaction method in Step 2 is, for example, charging a phosphorus atom-containing phenol compound (α) and a polyfunctional epoxy resin (β) into a reaction vessel, adding a reaction catalyst, and stirring under inert gas filling. Heating while stirring and reacting with stirring. Examples of the reaction catalyst used here include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal salts such as sodium carbonate, amines such as tributylamine, and phosphines such as triphenylphosphine. Can be mentioned. As for reaction temperature, the range of 100-250 degreeC is mentioned.
また、リン原子含有フェノール化合物（α）と、多官能型エポキシ樹脂（β）との反応割合は、得られるリン原子含有エポキシ樹脂（ａ１）のエポキシ当量が２００〜１０００ｇ／ｅｑ．の範囲、好ましくは３００〜８００ｇ／ｅｑ．の範囲となるように適宜選択すればよい。 The reaction rate of the phosphorus atom-containing phenol compound (α) and the polyfunctional epoxy resin (β) was such that the epoxy equivalent of the resulting phosphorus atom-containing epoxy resin (a1) was 200 to 1000 g / eq. , Preferably 300 to 800 g / eq. What is necessary is just to select suitably so that it may become this range.
次いで、得られたリン原子含有エポキシ樹脂（Ａ−１）に、不飽和基含有モノカルボン酸（Ａ−２）及び多塩基酸無水物（Ａ−３）を反応させて目的とする酸基含有ビニルエステル樹脂（Ａ）を製造することができる。斯かる方法は、具体的には、リン原子含有エポキシ樹脂（Ａ−１）に、不飽和基含有モノカルボン酸（Ａ−２）を反応させ、次いで、多塩基酸無水物（Ａ−３）を反応させる方法（方法１）、リン原子含有エポキシ樹脂（Ａ−１）と不飽和基含有モノカルボン酸（Ａ−２）と多塩基酸無水物（Ａ−３）とを一括で仕込み反応させる方法（方法２）が挙げられる。 Next, the resulting phosphorus atom-containing epoxy resin (A-1) is reacted with an unsaturated group-containing monocarboxylic acid (A-2) and a polybasic acid anhydride (A-3) to contain the desired acid group. A vinyl ester resin (A) can be produced. Specifically, such a method comprises reacting a phosphorus atom-containing epoxy resin (A-1) with an unsaturated group-containing monocarboxylic acid (A-2), and then polybasic acid anhydride (A-3). (Method 1), a phosphorus atom-containing epoxy resin (A-1), an unsaturated group-containing monocarboxylic acid (A-2), and a polybasic acid anhydride (A-3) are charged and reacted together. A method (method 2) is mentioned.
本発明では、上記方法１及び方法２の何れにおいても、リン原子含有エポキシ樹脂（Ａ−１）と不飽和基含有モノカルボン酸（Ａ−２）との反応により生成した２級水酸基に多塩基酸無水物（Ａ−３）が反応し、最終的に得られる酸基含有ビニルエステル樹脂（Ａ）の樹脂構造中に、前記不飽和基含有モノカルボン酸（Ａ−２）に由来するラジカル重合性不飽和二重結合（i）と、前記多塩基酸無水物（Ａ−３）に由来するカルボキシル基（ii）とを樹脂構造中に導入することができる。 In the present invention, in any of the above method 1 and method 2, a polybasic hydroxyl group is produced by reacting the phosphorus atom-containing epoxy resin (A-1) with the unsaturated group-containing monocarboxylic acid (A-2). Radical polymerization derived from the unsaturated group-containing monocarboxylic acid (A-2) in the resin structure of the acid group-containing vinyl ester resin (A) finally obtained by the reaction of the acid anhydride (A-3). The unsaturated double bond (i) and the carboxyl group (ii) derived from the polybasic acid anhydride (A-3) can be introduced into the resin structure.
また、前記方法１及び方法２における反応温度は、５０〜１２０℃の範囲であり、特に７０〜１１０℃の範囲であることが反応制御の点から好ましい。 Moreover, the reaction temperature in the said method 1 and the method 2 is the range of 50-120 degreeC, and it is preferable from the point of reaction control that it is the range of 70-110 degreeC especially.
ここで、不飽和基含有モノカルボン酸（Ａ−２）は、例えば、（メタ）アクリル酸（Ａ−２−１）、或いは、１分子内に２つ以上のエステル結合を有し、かつ、分子片末端にカルボキシル基を有する不飽和化合物（Ａ−２−２）が挙げられる。ラジカル重合性不飽和二重結合の濃度が高くなって感度が良好となる点からは（メタ）アクリル酸（Ａ−２−１）が好ましい。一方、後者の１分子内に２つ以上のエステル結合を有し、かつ、分子片末端にカルボキシル基を有する不飽和化合物（Ａ−２−２）は、最終的に得られる酸基含有ビニルエステル樹脂（Ａ）の極性が高くなって、アルカリ現像性が良好となる点から好ましい。当該不飽和化合物（Ａ−２−２）としては、例えば、エチレングリコール、プロピレングリコール、トリメチレングリコール、１，３−ブタンジオール、１，３−プロパンジオール、１，４−ブタンジオール、１，２−エタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコール等の脂肪族ジオールと、コハク酸、アジピン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカン二酸等の脂肪族ジカルボン酸とを反応させて得られる脂肪族ポリエステルポリオールに、コハク酸無水物、マレイン酸無水物、テトラヒドロフタル酸無水物などの二塩基酸無水物を反応させてハーフエステルを得、これを（メタ）アクリル酸と反応させた化合物や、下記構造式（１） Here, the unsaturated group-containing monocarboxylic acid (A-2) has, for example, (meth) acrylic acid (A-2-1), or two or more ester bonds in one molecule, and An unsaturated compound (A-2-2) having a carboxyl group at one end of the molecule is mentioned. (Meth) acrylic acid (A-2-1) is preferred from the viewpoint that the concentration of the radical polymerizable unsaturated double bond is increased and the sensitivity is improved. On the other hand, the unsaturated compound (A-2-2) having two or more ester bonds in one molecule and having a carboxyl group at one end of the molecule is an acid group-containing vinyl ester finally obtained. It is preferable from the point that the polarity of the resin (A) becomes high and the alkali developability becomes good. Examples of the unsaturated compound (A-2-2) include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,2 -Aliphatic diols such as ethanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol and aliphatics such as succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid The aliphatic polyester polyol obtained by reacting with a dicarboxylic acid is reacted with a dibasic acid anhydride such as succinic anhydride, maleic anhydride, or tetrahydrophthalic anhydride to obtain a half ester. ) A compound reacted with acrylic acid or the following structural formula (1)
で表される化合物が挙げられる。前記一般式（１）で表される化合物としては、（メタ）アクリル酸にε−カプロラクトンを反応させ分子伸長したポリラクトン（メタ）アクリレートや、（メタ）アクリル酸ダイマーが挙げられる。
The compound represented by these is mentioned. Examples of the compound represented by the general formula (1) include polylactone (meth) acrylate obtained by reacting (meth) acrylic acid with ε-caprolactone and molecular extension, and (meth) acrylic acid dimer.
前記不飽和化合物（Ａ−２−２）のなかでも、特にアルカリ現像性が良好である点から前記一般式（１）で表される化合物が好ましく、特に、一般式（１）中、ｎが１乃至６である場合には、硬化物に十分な柔軟性が付与され、近年、需要が伸びているフレキシブル基板へ適用することが可能となる。 Among the unsaturated compounds (A-2-2), the compound represented by the general formula (1) is preferable from the viewpoint of particularly good alkali developability, and in particular, in the general formula (1), n is In the case of 1 to 6, sufficient flexibility is imparted to the cured product, and it becomes possible to apply to a flexible substrate whose demand is increasing in recent years.
また、一般式（１）で表され、かつ、該一般式（１）中ｎが１乃至６である化合物は、（メタ）アクリル酸と併用することが好ましく、この際、前者：後者のモル比が２０：８０〜９９：１となる範囲であることが、最終的に得られる酸基含有ビニルエステル樹脂（Ａ）をレジストインキとして用いる場合の感度、現像性、及び予備乾燥時の乾燥性とのバランスに優れる点から好ましい。 Further, the compound represented by the general formula (1) and n in the general formula (1) is preferably 1 to 6 is preferably used in combination with (meth) acrylic acid. When the ratio is 20:80 to 99: 1, the final acid group-containing vinyl ester resin (A) used as a resist ink has sensitivity, developability, and drying property during preliminary drying. From the point of being excellent in balance with.
次に、前記多塩基酸無水物（Ａ−３）は、例えば無水マレイン酸、無水コハク酸、無水イタコン酸、ドデシル無水コハク酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、３−メチルテトラヒドロ無水フタル酸、４−メチルテトラヒドロ無水フタル酸、３−メチルヘキサヒドロ無水フタル酸、４−メチルヘキサヒドロ無水フタル酸、３，４−ジメチルテトラヒドロ無水フタル酸、４−（４−メチル−３−ペンテニル）テトラヒドロ無水フタル酸、３−ブテニル−５，６−ジメチルテトラヒドロ無水フタル酸、３，６−エンドメチレン−テトラヒドロ無水フタル酸、７−メチル−３，６−エンドメチレンテトラヒドロ無水フタル酸、ベンゾフェノンテトラカルボン酸無水物等の脂肪族酸無水類；無水フタル酸、テトラクロロ無水フタル酸、テトラブロモ無水フタル酸、無水クロレンド酸、無水トリメリット酸、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸無水物等の芳香物酸無水物が挙げられる。 Next, the polybasic acid anhydride (A-3) is, for example, maleic anhydride, succinic anhydride, itaconic anhydride, dodecyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride. Acid, 4-methyltetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 4- (4-methyl-3-pentenyl) tetrahydro Phthalic anhydride, 3-butenyl-5,6-dimethyltetrahydrophthalic anhydride, 3,6-endomethylene-tetrahydrophthalic anhydride, 7-methyl-3,6-endomethylenetetrahydrophthalic anhydride, benzophenonetetracarboxylic anhydride Aliphatic acid anhydrides; phthalic anhydride, tetrachloroanhydride Acid, tetrabromophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, aromatic monoacid anhydride such as benzophenone tetracarboxylic acid anhydride.
これらの中でも酸基含有ビニルエステル樹脂（Ａ）の溶剤溶解性が良好となる点からテトラヒドロ無水フタル酸又はヘキサヒドロ無水フタル酸が好ましい。 Among these, tetrahydrophthalic anhydride or hexahydrophthalic anhydride is preferable from the viewpoint of good solvent solubility of the acid group-containing vinyl ester resin (A).
次に、本発明で用いる光重合開始剤（Ｂ）は、例えば、アセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、ｐ−ジメチルアミノプロピオフェノン、シクロロアセトフェノン、２−メチル−１−〔４−（メチルチオ）フェニル〕−２−モルホリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１等のアセトフェノン類；ベンゾフェノン、２−クロロベンゾフェノン、ｐ，ｐ−ビスジエチルアミノベンゾフェノン、ｐ，ｐ−ビスジエチルアミノベンゾフェノン、４−ベンゾイル−４’−メチルジフェニルサルファイド等のベンゾフェノン類；ベンジル、ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソブチルエーテル等のベンゾインエーテル類；ベンジルジメチルケタール等のケタール類；チオキサントン、２−クロロチオキサントン、２，４−ジエチルチオキサントン、２−イソプロピルチオキサントン等のチオキサントン類；アントラキノン、２，４，５−トリアリールイミダゾール二量体、２，４，６−トリス−Ｓ−トリアジン、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド等が挙げられる。これらのなかでも、２−メチル−１−〔４−（メチルチオ）フェニル〕−２−モルホリノプロパン−１−オンや２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１が反応性が高く好ましい。これらの光重合開始剤（Ｂ）は、単独又は２種以上を組み合わせて使用することができる。 Next, the photopolymerization initiator (B) used in the present invention is, for example, acetophenone, 2,2-diethoxy-2-phenylacetophenone, p-dimethylaminopropiophenone, cycloacetophenone, 2-methyl-1- [ Acetophenones such as 4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; benzophenone, 2-chlorobenzophenone, benzophenones such as p, p-bisdiethylaminobenzophenone, p, p-bisdiethylaminobenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide; benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isobutyl ether; Ketals such as tilketal; thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone; anthraquinone, 2,4,5-triarylimidazole dimer, 2,4,6- Examples include tris-S-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Among these, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 Is preferred because of its high reactivity. These photopolymerization initiators (B) can be used alone or in combination of two or more.
前記光重合開始剤（Ｂ）の配合量は、酸基含有ビニルエステル樹脂（Ａ）１００質量部に対して、通常０．５〜５０質量部の範囲であることが好ましい。即ち、０．５質量部以上においては、酸基含有ビニルエステル樹脂（Ａ）の光硬化反応が良好に進行し、また、５０質量部以下では硬化物の機械物性が良好なものとなる。光に対する感度、硬化物の機械物性などに優れる点から、光重合開始剤（Ｂ）のより好ましい配合量としては酸基含有ビニルエステル樹脂（Ａ）１００質量部に対して、２〜３０質量部の範囲である。 It is preferable that the compounding quantity of the said photoinitiator (B) is the range of 0.5-50 mass parts normally with respect to 100 mass parts of acid group containing vinyl ester resin (A). That is, at 0.5 parts by mass or more, the photocuring reaction of the acid group-containing vinyl ester resin (A) proceeds well, and at 50 parts by mass or less, the cured product has good mechanical properties. From the point which is excellent in the sensitivity with respect to light, the mechanical property of hardened | cured material, etc., as a more preferable compounding quantity of a photoinitiator (B), 2-30 mass parts with respect to 100 mass parts of acid group containing vinyl ester resin (A) Range.
また、本発明で用いるエポキシ樹脂（Ｃ）は、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂、ビスフェノールＳノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、レゾルシン・クレゾール共縮合ノボラック型エポキシ樹脂、脂環式エポキシ樹脂、トリスフェノールメタン型エポキシ樹脂、ゴム変性エポキシ樹脂、トリス（２，３−エポキシプロピル）イソシアヌレート、ジフェニルジグリシジルエーテル、テトラメチルジフェニルジグリシジルエーテル、オキサゾリドン環を含有するエポキシ樹脂、ジシクロペンタジエン等の不飽和脂環式化合物とフェノール類との重付加反応物のポリグリシジルエーテル等が挙げられる。 The epoxy resin (C) used in the present invention is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, bisphenol S novolak. Type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, resorcinol / cresol co-condensation novolak type epoxy resin, alicyclic epoxy resin, trisphenol methane type epoxy resin, rubber modified epoxy resin, tris (2,3- Epoxypropyl) isocyanurate, diphenyldiglycidyl ether, tetramethyldiphenyldiglycidyl ether, epoxy resin containing oxazolidone ring, dicyclopentadiene Polyglycidyl ethers of the polyaddition reaction product of an unsaturated alicyclic compound and phenols of.
これらの中でも、レジストインキとして用いた際の熱管理幅が広く、熱硬化後の硬化物の耐熱性等に優れる面からクレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、レゾルシン・クレゾール共縮合ノボラック型エポキシ樹脂、オキサゾリドン環を含有するエポキシ樹脂、ジシクロペンタジエン等の不飽和脂環式化合物とフェノール類との重付加反応物のポリグリシジルエーテルが好ましく、レジストインキとして用いた際の光感度、反応性に優れる面からはビスフェノールＡ型エポキシ樹脂やトリス（２，３−エポキシプロピル）イソシアヌレートを用いることが好ましい。これらの樹脂は用途に合わせて単独又は２種以上を組み合わせて使用可能である。 Among these, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin from the aspect of having a wide thermal management range when used as a resist ink and excellent heat resistance of the cured product after heat curing, Resorcin / cresol co-condensed novolak type epoxy resin, epoxy resin containing oxazolidone ring, polyglycidyl ether of polyaddition reaction product of unsaturated cycloaliphatic compound such as dicyclopentadiene and phenols is preferable and used as resist ink It is preferable to use bisphenol A type epoxy resin or tris (2,3-epoxypropyl) isocyanurate from the viewpoint of excellent photosensitivity and reactivity. These resins can be used alone or in combination of two or more according to the application.
前記オキサゾリドン環を含有するエポキシ樹脂は特に制限はないが、例えば、多官能型エポキシ樹脂と芳香族モノイソシアネート類とを反応させて得られるエポキシ樹脂等が挙げられる。 The epoxy resin containing the oxazolidone ring is not particularly limited, and examples thereof include an epoxy resin obtained by reacting a polyfunctional epoxy resin with aromatic monoisocyanates.
また、本発明では、更に、硬化促進剤を使用することが好ましい。硬化促進剤としては、例えば、メラミン及びその誘導体、イミダゾール及びその誘導体、ジシアンジアミド、フェノール及びその誘導体などの種々のエポキシ樹脂用硬化促進剤等が挙げられる。 In the present invention, it is further preferable to use a curing accelerator. Examples of the curing accelerator include various curing accelerators for epoxy resins such as melamine and derivatives thereof, imidazole and derivatives thereof, dicyandiamide, phenol and derivatives thereof, and the like.
エポキシ樹脂（Ｃ）の配合量としては、前記酸基含有ビニルエステル樹脂（Ａ）１００質量部に対して５〜４０質量部が好ましい。即ち、５質量部以上用いることにより、最終的に得られる硬化物の耐熱性、耐溶剤性、耐酸性、密着性等の諸物性に優れたものとなる他、絶縁抵抗等の電気特性に十分な性能が得られ、一方、４０質量部以下とすることにより、光に対する感度に優れ、レジストインキとして用いた際の感光性、現像性に優れたものとなる。 As a compounding quantity of an epoxy resin (C), 5-40 mass parts is preferable with respect to 100 mass parts of said acid group containing vinyl ester resins (A). That is, by using 5 parts by mass or more, the cured product finally obtained has excellent physical properties such as heat resistance, solvent resistance, acid resistance, and adhesion, and is sufficient for electrical characteristics such as insulation resistance. On the other hand, when the amount is 40 parts by mass or less, the sensitivity to light is excellent, and the sensitivity and developability when used as a resist ink are excellent.
本発明の感光性樹脂組成物には、特にレジストインキ用樹脂組成物として用いる際には、上記各成分に加え、希釈剤（Ｄ）を配合することが好ましい。 In particular, when used as a resist ink resin composition, the photosensitive resin composition of the present invention preferably contains a diluent (D) in addition to the above components.
前記希釈剤（Ｄ）としては、特に限定されるものではないが、例えば、エチルメチルケトン、シクロヘキサノン等のケトン；トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類；メチルセロソルブ、ブチルセロソルブ、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールジエチルエーテル等のグリコールエーテル類；酢酸エチル、酢酸ブチル、ブチルセロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート等のエステル；エタノール、プロパノール、エチレングリコール、プロピレングリコール等のアルコール；オクタン、デカン等の脂肪族炭化水素；石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤等の有機溶剤や、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、Ｎ−ビニルピロリドン、Ｎ−ビニルカプロラクタム、アクリロイルモルホリン、メトキシテトラエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、Ｎ，Ｎ−ジメチルアクリルアミド、メラミン（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、グリセリンジグリシジルエーテルジ（メタ）アクリレート、イソボルニル（メタ）アクリレート、ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトールジトリメチロールプロパン、ジペンタエリスリトール、トリス−ヒドロキシエチルイソシアヌレート等の多価アルコール、又はこれらのエチレンオキサイド、プロピレンオキサイド付加物の多価（メタ）アクリレート類等の光重合性反応性希釈剤等を挙げることができる。これらの中でもレジストインキとして用いた際の予備乾燥後の平滑性が良好となる点からエステルの単独使用、エステルと石油系溶剤との併用物が好ましく、これらと光重合性反応性希釈剤の併用物が更に好ましい。前記エステル類の中でもプロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテートを用いることが好ましい。 The diluent (D) is not particularly limited, but examples thereof include ketones such as ethyl methyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; methyl cellosolve, butyl cellosolve, methyl Glycol ethers such as carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether; ethyl acetate, butyl acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate Esters such as ethanol; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; fats such as octane and decane Hydrocarbons; organic solvents such as petroleum ethers such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, N, N-dimethylacrylamide, melamine (meth) acrylate, diethylene glycol di (meth) ) Acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, glycerin di Polyhydric alcohols such as ricidyl ether di (meth) acrylate, isobornyl (meth) acrylate, hexanediol, trimethylolpropane, pentaerythritol ditrimethylolpropane, dipentaerythritol, tris-hydroxyethyl isocyanurate, or ethylene oxide thereof, And photopolymerizable reactive diluents such as polyvalent (meth) acrylates of propylene oxide adducts. Among these, from the point that smoothness after preliminary drying when used as a resist ink is good, the use of an ester alone, a combination of an ester and a petroleum solvent is preferable, and the combined use of these and a photopolymerizable reactive diluent More preferred are. Among the esters, propylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate are preferably used.
希釈剤（Ｄ）は単独又は２種以上の混合物として用いられ、その配合量としては、酸基含有重合性樹脂（Ａ）１００質量部当り、３０〜３００質量部であることが好ましく、特に５０〜２００質量部であることが好ましい。 The diluent (D) is used alone or as a mixture of two or more thereof, and the blending amount thereof is preferably 30 to 300 parts by mass, particularly 50 parts per 100 parts by mass of the acid group-containing polymerizable resin (A). It is preferable that it is -200 mass parts.
本発明の感光性樹脂組成物をレジストインキ用樹脂組成物とするためには、前記酸基含有ビニルエステル樹脂（Ａ）、光重合開始剤（Ｂ）、エポキシ樹脂（Ｃ）、及び希釈剤（Ｄ）を混合し、３本ロールや自転公転型撹拌機等の手段により均一に混合させることにより得られる。 In order to use the photosensitive resin composition of the present invention as a resist ink resin composition, the acid group-containing vinyl ester resin (A), photopolymerization initiator (B), epoxy resin (C), and diluent ( It is obtained by mixing D) and mixing them uniformly by means of a three-roll or rotating / revolving stirrer.
ここで、酸基含有ビニルエステル樹脂（Ａ）の配合量としては、特に制限されるものではないが、レジストインキの光感度、予備乾燥後の乾燥性の改善効果が良好なものとなり、更に熱硬化後に得られる塗膜の耐熱性、耐溶剤性に優れる点からレジストインキ用樹脂組成物中１０〜７０質量％であることが好ましく、特に３０〜６０質量％となる範囲であることが好ましい。 Here, the blending amount of the acid group-containing vinyl ester resin (A) is not particularly limited, but the effect of improving the photosensitivity of resist ink and the drying property after preliminary drying becomes favorable, and further the heat It is preferable that it is 10-70 mass% in the resin composition for resist inks from the point which is excellent in the heat resistance of the coating film obtained after hardening, and solvent resistance, and it is especially preferable that it is the range used as 30-60 mass%.
本発明の感光性樹脂組成物には、その用途に応じて顔料、充填剤、添加剤等が使用できる。具体的には、キナクリドン系、アゾ系、フタロシアニン系等の有機顔料；酸化チタン、金属箔状顔料、防錆顔料等の無機顔料；硫酸バリウム、炭酸カルシウム、球状溶融シリカ、破砕状溶融シリカ、結晶シリカ、アルミナ、窒化珪素、水酸化アルミ、カーボンブラック、タルク、クレー等の充填剤；ヒンダードアミン系、ベンゾトリアゾール系、ベンゾフェノン系等の紫外線吸収剤；ヒンダードフェノール系、リン系、イオウ系、ヒドラジド系等の酸化防止剤；シラン系、チタン系等のカップリング剤；フッ素系界面活性剤等のレベリング剤；アエロジル等のレオロジーコントロール剤；顔料分散剤：ハジキ防止剤；消泡剤等の添加剤等が挙げられる。また必要に応じてガラス繊維、ガラス布、炭素繊維等の強化材を含有させることができる。また必要に応じて難燃付与剤も添加できる。この難燃付与剤としては種々のものが使用できるが、例えば、デカブロモジフェニルエーテル、テトラブロモビスフェノールＡなどのハロゲン化合物；赤リンや各種燐酸エステル化合物などの燐原子含有化合物；メラミン或いはその誘導体などの窒素原子含有化合物；水酸化アルミニウム、水酸化マグネシウム、硼酸亜鉛、硼酸カルシウムなどの無機系難燃化合物が例示できる。 In the photosensitive resin composition of the present invention, pigments, fillers, additives and the like can be used depending on the application. Specifically, organic pigments such as quinacridone, azo, and phthalocyanine; inorganic pigments such as titanium oxide, metal foil pigments, rust preventive pigments; barium sulfate, calcium carbonate, spherical fused silica, crushed fused silica, crystals Fillers such as silica, alumina, silicon nitride, aluminum hydroxide, carbon black, talc and clay; UV absorbers such as hindered amines, benzotriazoles, benzophenones; hindered phenols, phosphoruss, sulfurs, hydrazides Antioxidants such as silanes, coupling agents such as titanium, leveling agents such as fluorine surfactants, rheology control agents such as Aerosil, pigment dispersants: anti-repellent agents, additives such as antifoaming agents, etc. Is mentioned. Moreover, reinforcing materials, such as glass fiber, glass cloth, and carbon fiber, can be contained as needed. Moreover, a flame retardant imparting agent can be added as necessary. Various flame retardants can be used as the flame retardant, such as halogen compounds such as decabromodiphenyl ether and tetrabromobisphenol A; phosphorus atom-containing compounds such as red phosphorus and various phosphate compounds; melamine or derivatives thereof Nitrogen atom-containing compounds; inorganic flame retardant compounds such as aluminum hydroxide, magnesium hydroxide, zinc borate and calcium borate can be exemplified.
このようにして得られた感光性樹脂組成物は、紫外線などの光を照射することによって、硬化物を得ることが出来る。特にレジストインキ用樹脂組成物として用いる場合には、例えば、スクリーン印刷、カーテンコート法、ロールコート法、スピンコート法、ディップコート法等によりプリント基板上に１０〜１５０μｍ（液膜厚）の厚さに塗布した後、６０〜９０℃で１５〜９０分予備乾燥し有機溶剤等の揮発分を揮発させ（塗布と予備乾燥工程を複数回繰り返して積層させる場合もある）、その乾燥塗膜に所望のマスクパターンのネガフィルムを密着させ、その上から紫外線を照射し露光を行い（或いはレーザー光などを用いて直接パターンを露光しても良く、この場合、マスクパターンは必要としない。）、その後希アルカリ水溶液を現像液として現像することにより非露光領域の塗膜は除去され、露光部分の塗膜は光硬化しているので除去されず残留することにより、パターンを形成させることが出来る。この際の希アルカリ水溶液としては、０．５〜５質量％の炭酸ナトリウム水溶液や水酸化ナトリウム水溶液が一般的であるが、他のアルカリ溶液も使用可能である。次いで、１３０〜１６０℃で２０〜９０分熱風乾燥機等で熱硬化させることにより、電気特性、耐マイグレーション性、耐熱性、耐溶剤性等に優れた硬化塗膜を得ることが出来る。 The photosensitive resin composition thus obtained can obtain a cured product by irradiation with light such as ultraviolet rays. In particular, when used as a resin composition for resist ink, for example, a thickness of 10 to 150 μm (liquid film thickness) on a printed board by screen printing, curtain coating method, roll coating method, spin coating method, dip coating method or the like. After coating, it is pre-dried at 60-90 ° C. for 15-90 minutes to volatilize volatile components such as organic solvents (the coating and pre-drying steps may be repeated multiple times) and desired for the dried coating film A negative film of the mask pattern is brought into close contact, and ultraviolet light is irradiated from above to perform exposure (or the pattern may be directly exposed using a laser beam or the like. In this case, the mask pattern is not necessary), and thereafter. By developing with a dilute alkaline aqueous solution as a developing solution, the coating film in the non-exposed area is removed, and the coating film in the exposed part is not removed because it is photocured. The Rukoto can to form a pattern. In this case, the dilute alkaline aqueous solution is generally 0.5 to 5% by mass of sodium carbonate aqueous solution or sodium hydroxide aqueous solution, but other alkaline solutions can also be used. Subsequently, the cured coating film excellent in electrical characteristics, migration resistance, heat resistance, solvent resistance, and the like can be obtained by thermosetting with a hot air dryer or the like at 130 to 160 ° C. for 20 to 90 minutes.
本発明の感光性樹脂組成物は、例えばプリント配線板等の回路基板のソルダーレジストインキ用樹脂組成物、層間絶縁層、液晶カラーフィルタ用のレジスト材料、例えばオーバーコート、液晶用スペーサー、カラーフィルタ用顔料レジスト、ブラックマトリクス用レジスト等に好ましく使用される。 The photosensitive resin composition of the present invention is, for example, a resin composition for solder resist ink of a circuit board such as a printed wiring board, an interlayer insulating layer, a resist material for a liquid crystal color filter, such as an overcoat, a spacer for liquid crystal, and a color filter. It is preferably used for pigment resist, black matrix resist and the like.
以下、本発明を実施例により更に具体的に説明する。例中部及び％は断りのない限り質量基準である。尚、合成例１におけるリン原子含有オリゴマー（Ａ−１）中のｎ＝２以上の成分は、下記の条件でＧＰＣ測定を行い、ＧＰＣのチャートにおいて、３６．０分未満のピーク面積の割合を算出したものである。 Hereinafter, the present invention will be described more specifically with reference to examples. Unless otherwise indicated, the middle part and% in the examples are based on mass. In addition, the component of n = 2 or more in the phosphorus atom-containing oligomer (A-1) in Synthesis Example 1 is subjected to GPC measurement under the following conditions, and the ratio of the peak area of less than 36.0 minutes is shown in the GPC chart. It is calculated.
＜ＧＰＣ測定条件＞
測定装置 ：東ソー株式会社製「ＨＬＣ−８２２０ ＧＰＣ」、
カラム：東ソー株式会社製ガードカラム「ＨＸＬ−Ｌ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ３０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ４０００ＨＸＬ」
検出器： ＲＩ（示差屈折径）
データ処理：東ソー株式会社製「ＧＰＣ−８０２０モデルIIバージョン４．１０」
測定条件： カラム温度 ４０℃
展開溶媒 テトラヒドロフラン
流速 １．０ｍｌ／分
標準 ： 前記「ＧＰＣ−８０２０モデルIIバージョン４．１０」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
（使用ポリスチレン）
東ソー株式会社製「Ａ−５００」
東ソー株式会社製「Ａ−１０００」
東ソー株式会社製「Ａ−２５００」
東ソー株式会社製「Ａ−５０００」
東ソー株式会社製「Ｆ−１」
東ソー株式会社製「Ｆ−２」
東ソー株式会社製「Ｆ−４」
東ソー株式会社製「Ｆ−１０」
東ソー株式会社製「Ｆ−２０」
東ソー株式会社製「Ｆ−４０」
東ソー株式会社製「Ｆ−８０」
東ソー株式会社製「Ｆ−１２８」
試料 ： 樹脂固形分換算で１．０質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（５０μｌ）。
<GPC measurement conditions>
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).
合成例１〔リン原子含有オリゴマー（Ａ−１）の合成〕
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、２−ヒドロキシベンズアルデヒド１２２０ｇ（１０．０モル）と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（以下、「ＨＣＡ」と略記する。）１５１２ｇ（７．０モル）、シュウ酸２２．３ｇ（０．１９モル）を仕込み、１２０℃まで昇温し１時間反応させた。次いで、ＨＣＡ１７２８ｇ（８．０モル）を添加し、１８０℃まで昇温して、３時間反応させた。次いで、水を加熱減圧下に除去し、下記構造式
Synthesis Example 1 [Synthesis of phosphorus atom-containing oligomer (A-1)]
To a flask equipped with a thermometer, condenser, fractionator, nitrogen gas inlet, and stirrer, 1220 g (10.0 mol) of 2-hydroxybenzaldehyde and 9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-oxide (hereinafter abbreviated as “HCA”) 1512 g (7.0 mol) and oxalic acid 22.3 g (0.19 mol) were charged, heated to 120 ° C. and reacted for 1 hour. Next, 1728 g (8.0 mol) of HCA was added, the temperature was raised to 180 ° C., and the reaction was carried out for 3 hours. Next, water is removed under reduced pressure by heating, and the following structural formula
で表される構造単位を有するリン原子含有オリゴマー（Ａ−１）４１００ｇを得た。得られたリン原子含有オリゴマーの軟化点は１３８℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１８０℃）は６６ｄＰａ・ｓ、水酸基当量は４２８ｇ／ｅｑ．リン含有量１０．５％であり、ｎ＝２以上の成分比率は４９．０％であった。
4100 g of a phosphorus atom-containing oligomer (A-1) having a structural unit represented by The resulting phosphorus atom-containing oligomer had a softening point of 138 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 180 ° C.) of 66 dPa · s, and a hydroxyl group equivalent of 428 g / eq. The phosphorus content was 10.5%, and the component ratio of n = 2 or more was 49.0%.
合成例２〔リン原子含有エポキシアクリレート樹脂溶液（ＥＡ−１）の合成〕
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、リン含有オリゴマー（Ａ−１）２５２ｇとクレゾールノボラック型エポキシ樹脂（ＤＩＣ製「Ｎ−６５５−ＥＸＰ−Ｓ」）２７３ｇ、トリフェニルホスフィン５．３ｇを仕込み、１５０℃まで昇温し５時間反応させて、リン含有エポキシ樹脂（Ｅ−１）を得た。この樹脂のエポキシ当量は５２５ｇ／ｅｑ．であった。ここにジエチレングリコールモノエチルエーテルアセテート（ＥＤＧＡＣ）３８７ｇとアクリル酸７２．０ｇ（１．０モル）、及びハイドロキノン０．３０ｇを仕込み、１００℃に加熱攪拌し、均一溶解した。次いで、トリフェニルホスフィン１．７９ｇを仕込み、１２０℃に昇温して８時間反応を行った。更にテトラヒドロ無水フタル酸１２２ｇ（０．８０モル）を仕込み、１１０℃で４時間反応を行い、固形分６５％、固形分の二重結合当量は７１９、固形分酸価６６ｍｇＫＯＨ／ｇ、固形分のリン含有量３．７質量％の樹脂溶液を得た。これを樹脂溶液ＥＡ−１とする。
Synthesis Example 2 [Synthesis of phosphorus atom-containing epoxy acrylate resin solution (EA-1)]
A flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer was charged with 252 g of a phosphorus-containing oligomer (A-1) and a cresol novolac-type epoxy resin (“N-655-EXP-S” manufactured by DIC). ) 273 g and 5.3 g of triphenylphosphine were added, and the temperature was raised to 150 ° C. and reacted for 5 hours to obtain a phosphorus-containing epoxy resin (E-1). The epoxy equivalent of this resin is 525 g / eq. Met. Here, 387 g of diethylene glycol monoethyl ether acetate (EDGAC), 72.0 g (1.0 mol) of acrylic acid, and 0.30 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to be uniformly dissolved. Next, 1.79 g of triphenylphosphine was charged, the temperature was raised to 120 ° C., and the reaction was performed for 8 hours. Further, 122 g (0.80 mol) of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 4 hours. The solid content was 65%, the double bond equivalent of the solid content was 719, the solid content acid value was 66 mgKOH / g, the solid content was A resin solution having a phosphorus content of 3.7% by mass was obtained. This is designated as resin solution EA-1.
合成例３〔リン原子含有エポキシアクリレート樹脂溶液（ＥＡ−２）の合成〕
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、リン含有オリゴマー（Ａ−１）２８４ｇとナフトールノボラック型エポキシ樹脂（エポキシ当量：２３０ｇ／ｅｑ、軟化点：１００℃）３０７ｇ、トリフェニルホスフィン５．９ｇを仕込み、１５０℃まで昇温し５時間反応させて、リン含有エポキシ樹脂（Ｅ−２）を得た。この樹脂のエポキシ当量は５９１ｇ／ｅｑ．であった。ここにＥＤＧＡＣ４２７ｇとアクリル酸７２．０ｇ（１．０モル）、及びハイドロキノン０．３３ｇを仕込み、１００℃に加熱攪拌し、均一溶解した。次いで、トリフェニルホスフィン１．９９ｇを仕込み、１２０℃に昇温して８時間反応を行った。更にテトラヒドロ無水フタル酸１２９ｇ（０．８５モル）を仕込み、１１０℃で４時間反応を行い、固形分６５％、固形分の二重結合当量は７９２、固形分酸価６３ｍｇＫＯＨ／ｇ、固形分のリン含有量３．７質量％の樹脂溶液を得た。これを樹脂溶液ＥＡ−２とする。
Synthesis Example 3 [Synthesis of phosphorus atom-containing epoxy acrylate resin solution (EA-2)]
To a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer, 284 g of a phosphorus-containing oligomer (A-1) and a naphthol novolac type epoxy resin (epoxy equivalent: 230 g / eq, softening point: 100) 307 g) and 5.9 g of triphenylphosphine were charged, and the temperature was raised to 150 ° C. and reacted for 5 hours to obtain a phosphorus-containing epoxy resin (E-2). The epoxy equivalent of this resin is 591 g / eq. Met. EDGAC427g, acrylic acid 72.0g (1.0mol), and hydroquinone 0.33g were prepared here, and it heated and stirred at 100 degreeC, and melt | dissolved uniformly. Next, 1.99 g of triphenylphosphine was charged, the temperature was raised to 120 ° C., and the reaction was performed for 8 hours. Further, 129 g (0.85 mol) of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 4 hours. The solid content was 65%, the solid double bond equivalent was 792, the solid content acid value was 63 mgKOH / g, the solid content was A resin solution having a phosphorus content of 3.7% by mass was obtained. This is designated as resin solution EA-2.
合成例４〔リン原子含有エポキシアクリレート樹脂溶液（ＥＡ−３）の合成〕
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、リン含有オリゴマー（Ａ−１）３８５ｇとジシクロペンタジエン型エポキシ樹脂（ＤＩＣ製「ＨＰ−７２００Ｈ」）４１５ｇ、トリフェニルホスフィン８．０ｇを仕込み、１５０℃まで昇温し５時間反応させて、リン含有エポキシ樹脂（Ｅ−３）を得た。この樹脂のエポキシ当量は８００ｇ／ｅｑ．であった。ここにＥＤＧＡＣ５５１ｇとアクリル酸７２．０ｇ（１．０モル）、及びハイドロキノン０．４４ｇを仕込み、１００℃に加熱攪拌し、均一溶解した。次いで、トリフェニルホスフィン２．６２ｇを仕込み、１２０℃に昇温して８時間反応を行った。更にテトラヒドロ無水フタル酸１５２ｇ（１．０モル）を仕込み、１１０℃で４時間反応を行い、固形分６５％、固形分の二重結合当量は１０２４、固形分酸価６０ｍｇＫＯＨ／ｇ、固形分のリン含有量３．９質量％の樹脂溶液を得た。これを樹脂溶液ＥＡ−３とする。
Synthesis Example 4 [Synthesis of phosphorus atom-containing epoxy acrylate resin solution (EA-3)]
To a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer, 385 g of a phosphorus-containing oligomer (A-1) and 415 g of a dicyclopentadiene type epoxy resin (“HP-7200H” manufactured by DIC), The triphenylphosphine 8.0g was prepared, and it heated up to 150 degreeC, and was made to react for 5 hours, and the phosphorus containing epoxy resin (E-3) was obtained. The epoxy equivalent of this resin is 800 g / eq. Met. EDGAC551g, acrylic acid 72.0g (1.0mol), and hydroquinone 0.44g were prepared here, and it heated and stirred at 100 degreeC, and melt | dissolved uniformly. Next, 2.62 g of triphenylphosphine was charged, the temperature was raised to 120 ° C., and the reaction was performed for 8 hours. Further, 152 g (1.0 mol) of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 4 hours. The solid content was 65%, the solid double bond equivalent was 1024, the solid content acid value was 60 mgKOH / g, the solid content was A resin solution having a phosphorus content of 3.9% by mass was obtained. This is designated as resin solution EA-3.
合成例５〔リン原子含有エポキシアクリレート樹脂溶液（ＥＡ−４）の合成〕
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、リン含有オリゴマー（Ａ−１）２３５ｇとビスフェノールＡ型エポキシ樹脂（ＤＩＣ製「ＥＰＩＣＬＯＮ ８５０−Ｓ」）２５４ｇ、トリフェニルホスフィン４．９ｇを仕込み、１５０℃まで昇温し５時間反応させて、リン含有エポキシ樹脂（Ｅ−４）を得た。この樹脂のエポキシ当量は４８９ｇ／ｅｑ．であった。ここにＥＤＧＡＣ３６０ｇとアクリル酸７２．０ｇ（１．０モル）、及びハイドロキノン０．２８ｇを仕込み、１００℃に加熱攪拌し、均一溶解した。次いで、トリフェニルホスフィン１．６８ｇを仕込み、１２０℃に昇温して８時間反応を行った。更にテトラヒドロ無水フタル酸１０８ｇ（０．７１モル）を仕込み、１１０℃で４時間反応を行い、固形分６５％、固形分の二重結合当量は６６９、固形分酸価６４ｍｇＫＯＨ／ｇ、固形分のリン含有量３．７質量％の樹脂溶液を得た。これを樹脂溶液ＥＡ−４とする。
Synthesis Example 5 [Synthesis of phosphorus atom-containing epoxy acrylate resin solution (EA-4)]
To a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer, 235 g of a phosphorus-containing oligomer (A-1) and bisphenol A type epoxy resin (“EPICLON 850-S” manufactured by DIC) 254 g, 4.9 g of triphenylphosphine was charged, heated to 150 ° C. and reacted for 5 hours to obtain a phosphorus-containing epoxy resin (E-4). The epoxy equivalent of this resin is 489 g / eq. Met. Here, 360 g of EDGAC, 72.0 g (1.0 mol) of acrylic acid, and 0.28 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to be uniformly dissolved. Next, 1.68 g of triphenylphosphine was charged, the temperature was raised to 120 ° C., and the reaction was performed for 8 hours. Furthermore, 108 g (0.71 mol) of tetrahydrophthalic anhydride was added and reacted at 110 ° C. for 4 hours. The solid content was 65%, the double bond equivalent of the solid content was 669, the solid content acid value was 64 mgKOH / g, the solid content was A resin solution having a phosphorus content of 3.7% by mass was obtained. This is designated as resin solution EA-4.
比較合成例１ 〔リン原子含有エポキシアクリレート樹脂溶液（ＥＡ−５）の合成〕
温度計、冷却管、分留管、窒素ガス導入管、撹拌器を取り付けたフラスコに、ＥＤＧＡＣ９４．５ｇ、ビスフェノールＦ型エポキシ樹脂２５０重量部とノボラック型エポキシ樹脂６００重量部と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１５０重量部を反応させて、リン含有エポキシ樹脂（Ｅ−５）を得た。この樹脂のエポキシ当量は３６２ｇ／ｅｑ．であった。この樹脂３１５ｇにアクリル酸６３．３ｇとメチルハイドロキノン０．２４ｇ、トリフェニルホスフィン１．２２ｇを仕込み、９８℃で２４時間反応させた。更にテトラヒドロ無水フタル酸１２２ｇと２−メチルハイドロキノン０．３ｇとＥＤＧＡＣ２３９ｇを加え、９５℃で６時間反応させ、固形分６０％、樹脂溶液の酸価が５４ｍｇＫＯＨ／ｇ（固形分酸価９０）のの樹脂溶液を得た。これを樹脂溶液ＥＡ−５とする。
Comparative Synthesis Example 1 [Synthesis of phosphorus atom-containing epoxy acrylate resin solution (EA-5)]
In a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer, 94.5 g of EDGAC, 250 parts by weight of a bisphenol F type epoxy resin, 600 parts by weight of a novolac type epoxy resin, and 9,10-dihydro- A phosphorus-containing epoxy resin (E-5) was obtained by reacting 150 parts by weight of 9-oxa-10-phosphaphenanthrene-10-oxide. The epoxy equivalent of this resin is 362 g / eq. Met. 315 g of this resin was charged with 63.3 g of acrylic acid, 0.24 g of methylhydroquinone, and 1.22 g of triphenylphosphine, and reacted at 98 ° C. for 24 hours. Further, 122 g of tetrahydrophthalic anhydride, 0.3 g of 2-methylhydroquinone and 239 g of EDGAC were added and reacted at 95 ° C. for 6 hours. The solid content was 60%, and the acid value of the resin solution was 54 mg KOH / g (solid acid value 90). A resin solution was obtained. This is designated as resin solution EA-5.
比較例６〔熱反応性硬化剤の調製〕
ジエチレングリコールモノエチルエーテルアセテート９０．４ｇを１００℃に加熱し、オルソクレゾールノボラック型エポキシ樹脂〔大日本インキ化学工業株式会社製、ＥＰＩＣＬＯＮ Ｎ−６８０、軟化点９５℃、エポキシ当量２１１〕２１１ｇを均一溶解し固形分７０％の樹脂溶液を得た。この樹脂溶液をＢ−１とする。
Comparative Example 6 [Preparation of heat-reactive curing agent]
Heat 90.4 g of diethylene glycol monoethyl ether acetate to 100 ° C., and uniformly dissolve 211 g of orthocresol novolac type epoxy resin (Dainippon Ink & Chemicals, EPICLON N-680, softening point 95 ° C., epoxy equivalent 211). A resin solution having a solid content of 70% was obtained. This resin solution is designated as B-1.
実施例１〜４、比較例１
表１に示す配合組成（数値は質量部である）に従って感光性樹脂組成物を配合し、冷却装置をつけた自転公転型撹拌機で混合して、レジストインキ樹脂の溶液を調製した。得られたレジストインキ用樹脂組成物の乾燥性、感度、アルカリ現像性及び塗膜性能を表２に示す。なお、レジストインキ用樹脂組成物の乾燥性、感度、アルカリ現像性及び塗膜性能は、以下に示す方法で評価した。ただし、下記「（７）密着性」の他の塗膜性能は、ポリイミドフィルム基板に、レジストインキ樹脂組成物を６０μｍの厚さ（乾燥前）に塗布し、８０℃で３０分間予備乾燥後、２００ｍＪ／ｃｍ２の露光量で紫外線を照射し、次いで３０℃の１重量％炭酸ナトリウム水溶液を用い、２．０ｋｇ／ｃｍ２のスプレー圧で６０秒間現像処理したのち、１５０℃で３０分後硬化することにより、硬化塗膜を作成して評価を行い、「（７）密着性」については当該方法に従い評価を行った。結果を表２に示す。
Examples 1-4, Comparative Example 1
A photosensitive resin composition was blended according to the blending composition shown in Table 1 (the numerical value is parts by mass) and mixed with a rotation / revolution stirrer equipped with a cooling device to prepare a resist ink resin solution. Table 2 shows the drying property, sensitivity, alkali developability and coating film performance of the resulting resist ink resin composition. The drying property, sensitivity, alkali developability and coating film performance of the resist ink resin composition were evaluated by the methods shown below. However, the following "(7) Adhesiveness" other coating film performance is that the resist ink resin composition is applied to a polyimide film substrate to a thickness of 60 μm (before drying), and after preliminary drying at 80 ° C. for 30 minutes, Irradiate ultraviolet rays at an exposure amount of 200 mJ / cm 2 , then develop using a 1 wt% sodium carbonate aqueous solution at 30 ° C. for 60 seconds at a spray pressure of 2.0 kg / cm 2 , and then post-cure at 150 ° C. for 30 minutes. Thus, a cured coating film was prepared and evaluated, and “(7) Adhesion” was evaluated according to the method. The results are shown in Table 2.
試験方法及び評価方法
（１）乾燥性
塗膜を８０℃で３０分間予備乾燥した。次に、塗膜を室温に冷却した状態でソルダーマスクパターンを塗膜面に接触させ、塗膜よりソルダーマスクパターンを剥離しその状態を評価した。
○：塗膜とパターンが全く付着せず、剥離できるもの
×：剥離時ソルダーマスクパターンに付着するもの
Test Method and Evaluation Method (1) Dryability The coating film was pre-dried at 80 ° C. for 30 minutes. Next, with the coating film cooled to room temperature, the solder mask pattern was brought into contact with the coating film surface, the solder mask pattern was peeled off from the coating film, and the state was evaluated.
○: The coating film and the pattern do not adhere at all and can be peeled ×: The one that adheres to the solder mask pattern at the time of peeling
（２）感度
８０℃３０分間予備乾燥後の塗膜に、２１段ステップタブレット（コダック社製）を密着させ、オーク製作所製メタルハライドランプ露光装置を用いて、アイグラフィック社製紫外線積算強度計を用い２００ｍＪ／ｃｍ２の紫外線を照射露光した。次いで、３０℃の１重量％炭酸ナトリウム水溶液を用い、２．０ｋｇ／ｃｍ２のスプレー圧で６０秒間現像を行った後の露光部分の除去されない部分の段数を数字にて示した。数字が大きい方が高感度であることを表す。
(2) Sensitivity A 21-step tablet (manufactured by Kodak) was brought into close contact with the coating film after preliminary drying at 80 ° C. for 30 minutes, and an ultraviolet integrated intensity meter manufactured by Igraphic was used using an oak metal halide lamp exposure device. Irradiation exposure was performed with 200 mJ / cm 2 ultraviolet rays. Next, the number of the unexposed portions of the exposed portion after development for 60 seconds at a spray pressure of 2.0 kg / cm 2 using a 1 wt% sodium carbonate aqueous solution at 30 ° C. is shown by numeral. Higher numbers indicate higher sensitivity.
（３）現像時間
８０℃３０分間予備乾燥後の塗膜にソルダーマスクパターンを密着させ、２００ｍＪ／ｃｍ２の紫外線を照射露光した。次いで３０℃の１重量％炭酸ナトリウム水溶液を用い、２．０ｋｇ／ｃｍ２のスプレー圧で現像を行った。現像時、１５秒毎に未露光部分の現像状態を拡大鏡にて目視判定し、完全にインキが除去され、完全な現像ができた時間を現像時間とした。
(3) Development time A solder mask pattern was brought into close contact with the coating film after preliminary drying at 80 ° C. for 30 minutes, and was exposed to 200 mJ / cm 2 of ultraviolet rays. Next, development was performed using a 1% by weight aqueous sodium carbonate solution at 30 ° C. and a spray pressure of 2.0 kg / cm 2 . At the time of development, the development state of the unexposed part was visually determined with a magnifying glass every 15 seconds, and the time when the ink was completely removed and development was complete was defined as the development time.
（４）熱管理幅
８０℃２０分から８０℃９０分まで１０分間隔で予備乾燥時間を変更した各々の塗膜に前記「（３）現像時間」と同様の評価を実施し、６０秒で現像可能な最大の予備乾燥時間（分）を熱管理幅とした。
(4) Thermal management width Each coating film whose pre-drying time was changed at intervals of 10 minutes from 80 ° C. for 20 minutes to 80 ° C. for 90 minutes was subjected to the same evaluation as “(3) Development time” and developed in 60 seconds. The maximum possible predrying time (minutes) was defined as the thermal management width.
（５）半田耐熱性
硬化塗膜をＪＩＳ Ｃ ６４８１の試験方法に従って、２６０℃で半田浴へ１０秒間浸漬を最大３回繰り返し、外観変化の現れない最大回数を記した。
(5) Solder heat resistance According to the test method of JIS C 6481, the cured coating film was repeatedly immersed in a solder bath at 260 ° C. for 10 seconds at a maximum of 3 times, and the maximum number of appearances without appearance change was noted.
（６）鉛筆硬度
硬化塗膜をＪＩＳ Ｋ ５４００の試験方法に従って試験し、塗膜に傷のつかない最も高い硬度を観測した。
(6) Pencil hardness The cured coating film was tested according to the test method of JIS K 5400, and the highest hardness at which the coating film was not damaged was observed.
（７）密着性
表１の組成にて調整したレジストインキ樹脂溶液を、銅張積層板上に６０μｍの厚さ（乾燥前）に塗布し、８０℃で３０分間予備乾燥後、２００ｍＪ／ｃｍ２の露光量で紫外線を照射し、次いで、１５０℃で３０分後硬化することにより、硬化塗膜を作成した、
硬化塗膜に巾１ｍｍで１０×１０のクロスカットを入れ、セロハンテープで剥離テストを行い剥がれの状態を目視観察した。
○：剥がれが認められないもの
△：１〜１０箇所に剥がれが認められるもの
×：１０箇所以上剥がれたもの
(7) Adhesiveness The resist ink resin solution prepared with the composition shown in Table 1 was applied on a copper clad laminate to a thickness of 60 μm (before drying), preliminarily dried at 80 ° C. for 30 minutes, and then 200 mJ / cm 2. A cured coating film was created by irradiating with ultraviolet rays at an exposure amount of, and then post-curing at 150 ° C. for 30 minutes,
A 10 × 10 cross cut with a width of 1 mm was put into the cured coating film, and a peel test was performed with a cellophane tape, and the peeled state was visually observed.
○: No peeling is observed Δ: 1-10 peeling is observed x: 10 or more peeling
（８）耐薬品性
硬化塗膜を１０重量％の塩酸に３０分間浸漬した後の塗膜状態を評価した。
○：全く変化が認められないもの
×：塗膜が膨潤して剥離したもの
(8) Chemical resistance The state of the coating film after the cured coating film was immersed in 10% by weight hydrochloric acid for 30 minutes was evaluated.
○: No change at all ×: The film was swollen and peeled
（９）耐溶剤性
硬化塗膜を塩化メチレンに３０分間浸漬した後の塗膜状態を評価した。
○：全く変化が認められないもの
×：塗膜が膨潤して剥離したもの
(9) Solvent resistance The state of the coating film after the cured coating film was immersed in methylene chloride for 30 minutes was evaluated.
○: No change at all ×: The film was swollen and peeled
（１０）難燃性
ＡＳＴＭ Ｄ４８０４−０３に準拠し、難燃性を評価した。サンプル数ｎ＝５で、各サンプル２回、３秒間ずつ接炎し、計１０回の燃焼時間を測定し、下記の基準に沿って判定した。
ＶＴＭ−０：個々の燃焼時間１０秒以下、かつトータル燃焼時間５０秒以下
ＶＴＭ−１：個々の燃焼時間３０秒以下、かつトータル燃焼時間２５０秒以下
ＶＴＭ−２：個々の燃焼時間３０秒以下、かつトータル燃焼時間２５０秒以下、かつ燃焼物が落下
ＢＵＲＮ：個々の燃焼時間３０秒以上、またはトータル燃焼時間２５０秒以上
(10) Flame retardancy Flame retardancy was evaluated according to ASTM D4804-03. With the number of samples n = 5, each sample was contacted twice for 3 seconds, and the burning time was measured 10 times in total, and judged according to the following criteria.
VTM-0: individual combustion time of 10 seconds or less and total combustion time of 50 seconds or less VTM-1: individual combustion time of 30 seconds or less and total combustion time of 250 seconds or less VTM-2: individual combustion time of 30 seconds or less, And the total combustion time is 250 seconds or less, and the burned material falls BURN: individual combustion time is 30 seconds or more, or total combustion time is 250 seconds or more
Claims (5)
（式中、Ｘは下記構造式（ｘ１）又は（ｘ２）
で表される構造部位であり、Ｙは水素原子、水酸基又は前記構造式（ｘ１）若しくは（ｘ２）で表される構造部位であり、Ｒ１は水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基、又は前記構造式（ｘ１）若しくは（ｘ２）を表し、ｎは繰り返し単位で１以上の整数であり、また、前記構造式（ｘ１）又は（ｘ２）中、Ｒ２、Ｒ３、Ｒ４、Ｒ５は、それぞれ独立的に、水素原子、炭素原子数１〜４のアルキル基、フェニル基、アラルキル基を表す。）で表される分子構造を有するリン原子含有オリゴマー（α）と、多官能型エポキシ樹脂（β）とを反応させて得られる樹脂構造を有するリン原子含有エポキシ樹脂（Ａ−１）に、不飽和基含有モノカルボン酸（Ａ−２）及び多塩基酸無水物（Ａ−３）を反応させて得られる、ラジカル重合性不飽和二重結合（i）及びカルボキシル基（ii）を有する酸基含有ビニルエステル樹脂（Ａ）、光重合開始剤（Ｂ）、及びエポキシ樹脂（Ｃ）を必須成分とすることを特徴とする感光性樹脂組成物。 The following structural formula (1)
(Wherein X represents the following structural formula (x1) or (x2)
Y is a hydrogen atom, a hydroxyl group, or a structural moiety represented by the structural formula (x1) or (x2), and R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Represents an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or the structural formula (x1) or (x2), wherein n is a repeating unit and is an integer of 1 or more, and the structural formula (x1) or ( In x2), R 2 , R 3 , R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or an aralkyl group. The phosphorus atom-containing epoxy resin (A-1) having a resin structure obtained by reacting a phosphorus atom-containing oligomer (α) having a molecular structure represented by (II) with a polyfunctional epoxy resin (β). An acid group having a radical polymerizable unsaturated double bond (i) and a carboxyl group (ii) obtained by reacting a saturated group-containing monocarboxylic acid (A-2) and a polybasic acid anhydride (A-3) A photosensitive resin composition comprising, as essential components, a vinyl ester resin (A), a photopolymerization initiator (B), and an epoxy resin (C).
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| JP5880921B2 (en) * | 2011-08-17 | 2016-03-09 | Dic株式会社 | Curable resin composition, cured product thereof, printed wiring board |
| WO2022107380A1 (en) * | 2020-11-17 | 2022-05-27 | 昭和電工マテリアルズ株式会社 | Photosensitive resin composition, photosensitive resin film, multilayered printed wiring board, semiconductor package, and method for producing multilayered printed wiring board |
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| JPH08325339A (en) * | 1995-05-31 | 1996-12-10 | Dainippon Ink & Chem Inc | Interlaminar insulating material for multi-layer printed circuit board |
| US5512607A (en) * | 1995-06-06 | 1996-04-30 | W. R. Grace & Co.-Conn. | Unsaturated epoxy ester with quaternary ammonium and phosphate groups |
| JP2001048955A (en) * | 1999-08-05 | 2001-02-20 | Nippon Kayaku Co Ltd | Flame retardant type energy beam photosensitive resin, photosensitive resin composition by using the same resin, and its cured material |
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| US8206832B2 (en) * | 2006-12-01 | 2012-06-26 | Kyocera Chemical Corporation | Photosensitive thermosetting resin composition and flexible printed circuit board |
| KR101141305B1 (en) * | 2009-03-31 | 2012-05-04 | 코오롱인더스트리 주식회사 | Phosphorus containing phenol novolac resin, hardener comprising the same and epoxy resin composition |
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