TW202426518A - Photosensitive thermosetting developing resin composition, its dry film and hardened product, and printed circuit board formed using the same - Google Patents
Photosensitive thermosetting developing resin composition, its dry film and hardened product, and printed circuit board formed using the same Download PDFInfo
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- TW202426518A TW202426518A TW112143632A TW112143632A TW202426518A TW 202426518 A TW202426518 A TW 202426518A TW 112143632 A TW112143632 A TW 112143632A TW 112143632 A TW112143632 A TW 112143632A TW 202426518 A TW202426518 A TW 202426518A
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- Prior art keywords
- resin composition
- photosensitive thermosetting
- weight
- talc
- coating
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 58
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 57
- 229920005989 resin Polymers 0.000 claims abstract description 73
- 239000011347 resin Substances 0.000 claims abstract description 73
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000454 talc Substances 0.000 claims abstract description 45
- 229910052623 talc Inorganic materials 0.000 claims abstract description 45
- -1 phosphate ester Chemical class 0.000 claims abstract description 41
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 40
- 239000003999 initiator Substances 0.000 claims abstract description 36
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 33
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 239000010452 phosphate Substances 0.000 claims abstract description 32
- 239000002270 dispersing agent Substances 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 239000011256 inorganic filler Substances 0.000 claims abstract description 16
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims description 33
- 239000011248 coating agent Substances 0.000 claims description 32
- 239000003822 epoxy resin Substances 0.000 claims description 25
- 229920000647 polyepoxide Polymers 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000000016 photochemical curing Methods 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 5
- 238000001723 curing Methods 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 230000035939 shock Effects 0.000 abstract description 28
- 229910000679 solder Inorganic materials 0.000 abstract description 22
- 239000010408 film Substances 0.000 description 42
- 235000012222 talc Nutrition 0.000 description 37
- 239000000126 substance Substances 0.000 description 28
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 22
- 239000000203 mixture Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 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 15
- 230000000052 comparative effect Effects 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- 239000000945 filler Substances 0.000 description 11
- 239000000976 ink Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 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 9
- 239000004593 Epoxy Substances 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 239000013039 cover film Substances 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002516 radical scavenger Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- JAGHDVYKBYUAFD-UHFFFAOYSA-L cyclopenta-1,3-diene;titanium(4+);dichloride Chemical compound [Cl-].[Cl-].[Ti+4].C1C=CC=[C-]1.C1C=CC=[C-]1 JAGHDVYKBYUAFD-UHFFFAOYSA-L 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000004843 novolac epoxy resin Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 2
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical compound NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- UMLWXYJZDNNBTD-UHFFFAOYSA-N alpha-dimethylaminoacetophenone Natural products CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
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- 238000001816 cooling Methods 0.000 description 2
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- 238000005260 corrosion Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
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- 229960001545 hydrotalcite Drugs 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
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- 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 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000002966 varnish Substances 0.000 description 2
- 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 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- HGCMSCWGVAYWHR-UHFFFAOYSA-N 1,3,5-trimethyl-2-[[phenyl-[(2,4,6-trimethylphenyl)methyl]phosphoryl]methyl]benzene Chemical compound CC1=CC(C)=CC(C)=C1CP(=O)(C=1C=CC=CC=1)CC1=C(C)C=C(C)C=C1C HGCMSCWGVAYWHR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LAVARTIQQDZFNT-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-yl acetate Chemical compound COCC(C)OCC(C)OC(C)=O LAVARTIQQDZFNT-UHFFFAOYSA-N 0.000 description 1
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- ZIKLJUUTSQYGQI-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxypropoxy)propane Chemical compound CCOCC(C)OCC(C)OCC ZIKLJUUTSQYGQI-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- UALAKBZSBJIXBP-UHFFFAOYSA-N 1-phenylethane-1,1,2,2-tetrol Chemical compound OC(O)C(O)(O)C1=CC=CC=C1 UALAKBZSBJIXBP-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 1
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- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
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- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- LESMLVDJJCWZAJ-UHFFFAOYSA-N 2-(diphenylphosphorylmethyl)-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 LESMLVDJJCWZAJ-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
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- IETYNJBCXVFYIQ-UHFFFAOYSA-N [4-(2-tert-butylperoxypropan-2-yl)phenyl]-phenylmethanone Chemical compound C1=CC(C(C)(C)OOC(C)(C)C)=CC=C1C(=O)C1=CC=CC=C1 IETYNJBCXVFYIQ-UHFFFAOYSA-N 0.000 description 1
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- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
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- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- KGGOIDKBHYYNIC-UHFFFAOYSA-N ditert-butyl 4-[3,4-bis(tert-butylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=C1 KGGOIDKBHYYNIC-UHFFFAOYSA-N 0.000 description 1
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- 238000005530 etching Methods 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- FRCAGVUKJQCWBD-UHFFFAOYSA-L iodine green Chemical compound [Cl-].[Cl-].C1=CC(N(C)C)=CC=C1C(\C=1C=CC(=CC=1)[N+](C)(C)C)=C/1C=C(C)C(=[N+](C)C)C=C\1 FRCAGVUKJQCWBD-UHFFFAOYSA-L 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000005267 main chain polymer Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910002055 micronized silica Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WZESLRDFSNLECD-UHFFFAOYSA-N phenyl prop-2-eneperoxoate Chemical compound C=CC(=O)OOC1=CC=CC=C1 WZESLRDFSNLECD-UHFFFAOYSA-N 0.000 description 1
- CCDXIADKBDSBJU-UHFFFAOYSA-N phenylmethanetriol Chemical compound OC(O)(O)C1=CC=CC=C1 CCDXIADKBDSBJU-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
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- 150000007519 polyprotic acids Polymers 0.000 description 1
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- QCTJRYGLPAFRMS-UHFFFAOYSA-N prop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical compound OC(=O)C=C.NC1=NC(N)=NC(N)=N1 QCTJRYGLPAFRMS-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- 238000010992 reflux Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
本發明提供印刷性優異、且能夠形成具有優異的硬度和耐冷熱衝擊性的阻焊層的感光熱硬化顯影性樹脂組合物、其乾膜及其硬化物以及使用其而形成的印刷電路板。所述感光熱硬化顯影性樹脂組合物的特徵在於,含有(A)乙烯基酯樹脂、(B)光聚合起始劑、(C)磷酸酯系分散劑、(D)在一分子中具有兩個以上的乙烯性不飽和基團的化合物及(E)無機填料,所述(C)磷酸酯系分散劑包含(C-1)主鏈中具有磷酸酯結構的聚合物,所述(E)無機填料包含滑石和二氧化矽,相對於以固體成分計的(A)乙烯基酯樹脂100重量份,滑石和二氧化矽兩者的總量為50~180重量份,按滑石和二氧化矽的總重量為100重量%計,滑石的比率為20~80重量%。The present invention provides a photosensitive thermosetting developing resin composition which has excellent printability and can form a solder resist layer having excellent hardness and resistance to cold and hot shocks, a dry film thereof, a cured product thereof, and a printed circuit board formed using the same. The photosensitive thermosetting developing resin composition is characterized in that it contains (A) a vinyl ester resin, (B) a photopolymerization initiator, (C) a phosphate ester dispersant, (D) a compound having two or more ethylenically unsaturated groups in one molecule, and (E) an inorganic filler, wherein the (C) phosphate ester dispersant comprises a polymer having a phosphate ester structure in the main chain (C-1), and the (E) inorganic filler comprises talc and silica, and the total amount of the talc and the silica is 50 to 180 parts by weight relative to 100 parts by weight of the vinyl ester resin (A) calculated as a solid component, and the ratio of the talc is 20 to 80% by weight based on the total weight of the talc and the silica being 100% by weight.
Description
本發明涉及印刷電路板的阻焊劑等的形成中適用的感光熱硬化顯影性樹脂組合物、其乾膜及其硬化物,特別涉及印刷性優異、且能夠形成具有優異的硬度和耐冷熱衝擊性的阻焊層的感光熱硬化顯影性樹脂組合物、其乾膜及其硬化物,以及印刷電路板。The present invention relates to a photosensitive thermosetting developing resin composition suitable for forming a solder resist or the like of a printed circuit board, a dry film thereof and a cured product thereof, and in particular to a photosensitive thermosetting developing resin composition which has excellent printability and can form a solder resist layer having excellent hardness and resistance to cold and hot shocks, a dry film thereof and a cured product thereof, and a printed circuit board.
現在,在一部分民用印刷電路板以及幾乎所有工業用印刷電路板的阻焊劑中,使用紫外線曝光後顯影從而形成圖像、並通過熱和/或光照射進行完全硬化(主硬化)的鹼性顯影型阻焊劑。此外,在用於汽車、火車、船舶和飛機等交通工具的半導體裝置中,作為印刷電路板阻焊劑有使用面向高可靠性電子材料的阻焊劑的傾向。Currently, alkaline developing type solder resists are used in some consumer printed circuit boards and almost all industrial printed circuit boards, which are exposed to ultraviolet light and then developed to form an image, and are completely cured (primary cure) by heat and/or light irradiation. In addition, in semiconductor devices used in vehicles such as automobiles, trains, ships, and airplanes, there is a tendency to use solder resists for high-reliability electronic materials as printed circuit board solder resists.
然而,常規的鹼顯影性阻焊油墨因為熱脹冷縮等的原因,通常冷熱衝擊抗開裂性能較差,對於環境溫度變化的可靠性較差。雖然選擇滑石作為填料可以改善開裂情況,但印刷性和硬度較差。或者採用滑石和硫酸鋇作為填料,以滿足車載用途的阻焊油墨的耐冷熱衝擊性的要求,但印刷性和硬度變差。However, conventional alkali-developable solder resist inks usually have poor resistance to hot and cold shock cracking due to thermal expansion and contraction, and poor reliability for changes in ambient temperature. Although talc can be used as a filler to improve the cracking, the printability and hardness are poor. Alternatively, talc and barium sulfate are used as fillers to meet the requirements for hot and cold shock resistance of solder resist inks for automotive use, but the printability and hardness are deteriorated.
例如專利文獻1的光硬化型阻焊油墨中的填料使用二氧化矽、硫酸鋇和滑石粉。專利文獻2的阻焊層用硬化性樹脂組合物含有含羧基樹脂、熱硬化成分、阻燃劑及離子捕捉劑,所述離子捕捉劑為水滑石系的離子捕捉劑與水滑石系以外的離子捕捉劑的混合物,無機填料使用氫氧化鋁。專利文獻3的硬化性樹脂組合物用於印刷電路板的永久掩膜,其包含:分子內含有烯屬不飽和基團和羧基的樹脂、光聚合起始劑、光聚合性單體、用氧化鋁進行了表面處理的氧化鈦、硫酸鋇和/或滑石、有機溶劑。專利文獻4的紫外光硬化液態感光阻焊軟板油墨記載了填料為硫酸鋇、滑石粉或者二氧化矽。 [先前技術文獻] For example, the fillers in the photocurable solder resist ink of Patent Document 1 include silicon dioxide, barium sulfate and talc. The curable resin composition for the solder resist layer of Patent Document 2 contains a carboxyl resin, a thermosetting component, a flame retardant and an ion scavenger, wherein the ion scavenger is a mixture of a hydrotalcite-based ion scavenger and an ion scavenger other than the hydrotalcite-based ion scavenger, and the inorganic filler is aluminum hydroxide. The curable resin composition of Patent Document 3 is used for a permanent mask of a printed circuit board, and includes: a resin containing an olefinic unsaturated group and a carboxyl group in the molecule, a photopolymerization initiator, a photopolymerizable monomer, titanium oxide surface-treated with aluminum oxide, barium sulfate and/or talc, and an organic solvent. Patent document 4 states that the filler of the UV-curable liquid photosensitive solder resist soft board ink is barium sulfate, talcum powder or silicon dioxide. [Prior technical document]
[專利文獻] [專利文獻1] CN114716868A [專利文獻2] CN108137791A [專利文獻3] CN101798432A [專利文獻4] CN106380929A [Patent document] [Patent document 1] CN114716868A [Patent document 2] CN108137791A [Patent document 3] CN101798432A [Patent document 4] CN106380929A
[發明所欲解決之課題][The problem that the invention wants to solve]
本發明的目的在於,在改善阻焊油墨的印刷性和由其形成的乾膜、硬化物的硬度的同時,進一步改善長期可靠性。 更具體而言,本發明的目的在於,提供印刷性優異、且能夠形成具有優異的硬度和耐冷熱衝擊性的阻焊層的感光熱硬化顯影性樹脂組合物、其乾膜及其硬化物,以及印刷電路板。 [用以解決課題之手段] The purpose of the present invention is to improve the printability of solder resist ink and the hardness of the dry film and cured product formed therefrom, and to further improve the long-term reliability. More specifically, the purpose of the present invention is to provide a photosensitive thermosetting developing resin composition having excellent printability and capable of forming a solder resist layer having excellent hardness and resistance to cold and hot shocks, its dry film and its cured product, and a printed circuit board. [Means for Solving the Problem]
本發明人等為解決所述問題進行反覆深入研究,結果發現,填料和添加劑的種類對耐冷熱衝擊性有很大的影響。如下所述的感光熱硬化顯影性樹脂組合物可解決上述問題,從而完成本發明,所述感光熱硬化顯影性樹脂組合物的特徵在於,含有(A)乙烯基酯樹脂、(B)光聚合起始劑、(C)磷酸酯系分散劑、(D)在一分子中具有兩個以上的乙烯性不飽和基團的化合物及(E)無機填料,所述(C)磷酸酯系分散劑包含(C-1)主鏈中具有磷酸酯結構的聚合物,所述(E)無機填料包含滑石和二氧化矽,相對於以固體成分計的(A)乙烯基酯樹脂100重量份,滑石和二氧化矽兩者的總量為50~180重量份,按滑石和二氧化矽的總重量為100重量%計,滑石的比率為20~80重量%。The inventors of the present invention have conducted repeated and in-depth research to solve the above-mentioned problem and found that the types of fillers and additives have a great influence on the resistance to cold and hot shock. The photosensitive thermosetting developing resin composition described below can solve the above problems, thereby completing the present invention. The photosensitive thermosetting developing resin composition is characterized in that it contains (A) a vinyl ester resin, (B) a photopolymerization initiator, (C) a phosphate ester dispersant, (D) a compound having two or more ethylenically unsaturated groups in one molecule, and (E) an inorganic filler. The (C) phosphate ester dispersant contains (C-1) a polymer having a phosphate ester structure in the main chain, and the (E) inorganic filler contains talc and silica. The total amount of talc and silica is 50 to 180 parts by weight relative to 100 parts by weight of the vinyl ester resin (A) calculated as a solid component. The ratio of talc is 20 to 80% by weight based on the total weight of talc and silica being 100% by weight.
即,本發明的感光熱硬化顯影性樹脂組合物的特徵在於,含有(A)乙烯基酯樹脂、(B)光聚合起始劑、(C)磷酸酯系分散劑、(D)在一分子中具有兩個以上的乙烯性不飽和基團的化合物及(E)無機填料,所述(C)磷酸酯系分散劑包含(C-1)主鏈中具有磷酸酯結構的聚合物,所述(E)無機填料包含滑石和二氧化矽,相對於以固體成分計的(A)乙烯基酯樹脂100重量份,滑石和二氧化矽兩者的總量為50~180重量份,按滑石和二氧化矽的總重量為100重量%計,滑石的比率為20~80重量%。That is, the photosensitive thermosetting developing resin composition of the present invention is characterized in that it contains (A) a vinyl ester resin, (B) a photopolymerization initiator, (C) a phosphate ester dispersant, (D) a compound having two or more ethylenically unsaturated groups in one molecule, and (E) an inorganic filler, wherein the (C) phosphate ester dispersant comprises a polymer having a phosphate ester structure in the main chain (C-1), and the (E) inorganic filler comprises talc and silica, and the total amount of talc and silica is 50 to 180 parts by weight relative to 100 parts by weight of the vinyl ester resin (A) calculated as a solid component, and the ratio of talc is 20 to 80% by weight based on the total weight of talc and silica being 100% by weight.
此外,優選含有除(B)光聚合起始劑和(C)磷酸酯系分散劑以外的(F)其它添加劑。Furthermore, it is preferred to contain (F) other additives in addition to (B) the photopolymerization initiator and (C) the phosphate ester dispersant.
此外,優選含有(G)環氧樹脂。Furthermore, it is preferred to contain (G) an epoxy resin.
此外,優選含有(H)有機溶劑。Furthermore, it is preferred to contain (H) an organic solvent.
此外,優選(C)磷酸酯系分散劑還包含(C-2)側鏈中具有磷酸酯結構的聚合物。Furthermore, it is preferred that the (C) phosphate ester-based dispersant further comprises (C-2) a polymer having a phosphate ester structure in a side chain.
此外,本發明的乾膜的特徵在於,是在載體膜上塗布所述感光熱硬化顯影性樹脂組合物並乾燥而得到的。Furthermore, the dry film of the present invention is characterized in that it is obtained by coating the photosensitive thermosetting developing resin composition on a carrier film and drying it.
此外,本發明的硬化物的特徵在於,是將如下的塗膜光硬化而得到的,所述塗膜為:將所述感光熱硬化顯影性樹脂組合物塗布在銅上並乾燥而得到的塗膜;或將該感光熱硬化顯影性樹脂組合物塗布在載體膜上並乾燥,將所得光硬化性的乾膜層壓在銅上而得到的塗膜。In addition, the cured product of the present invention is characterized in that it is obtained by photocuring the following coating, wherein the coating is: a coating obtained by applying the photosensitive thermosetting developing resin composition on copper and drying; or a coating obtained by applying the photosensitive thermosetting developing resin composition on a carrier film and drying, and pressing the obtained photocurable dry film layer on copper.
此外,本發明的印刷電路板的特徵在於,是將如下的塗膜光硬化後進行熱硬化而得到的,所述塗膜為:將所述感光熱硬化顯影性樹脂組合物塗布在基材上並乾燥而得到的塗膜;或將該感光熱硬化顯影性樹脂組合物塗布在載體膜上並乾燥,將所得光硬化性的乾膜層壓在基材上而得到的塗膜。In addition, the printed circuit board of the present invention is characterized in that it is obtained by photocuring and then thermally curing the following coating, wherein the coating is: a coating obtained by applying the photosensitive thermosetting developing resin composition on a substrate and drying; or a coating obtained by applying the photosensitive thermosetting developing resin composition on a carrier film and drying, and pressing the obtained photocurable dry film layer on the substrate.
本發明的感光熱硬化顯影性樹脂組合物的最大的技術特徵在於,作為(A)乙烯基酯樹脂、(B)光聚合起始劑、(C)磷酸酯系分散劑、(D)在一分子中具有兩個以上的乙烯性不飽和基團的化合物及(E)無機填料,所述(C)磷酸酯系分散劑包含(C-1)主鏈中具有磷酸酯結構的聚合物,所述(E)無機填料包含滑石和二氧化矽。The greatest technical feature of the photosensitive thermosetting developing resin composition of the present invention is that it comprises (A) a vinyl ester resin, (B) a photopolymerization initiator, (C) a phosphate ester dispersant, (D) a compound having two or more ethylenically unsaturated groups in one molecule, and (E) an inorganic filler, wherein the (C) phosphate ester dispersant comprises a polymer having a phosphate ester structure in the main chain (C-1), and the (E) inorganic filler comprises talc and silica.
基於本發明的特徵構成,通過使用主鏈中具有磷酸酯結構的聚合物,並且組合使用滑石及二氧化矽,並優化兩者的配比,以替代傳統的填料硫酸鋇,可在有效提升耐冷熱衝擊性能的基礎上,改善印刷性及鉛筆硬度。Based on the characteristic structure of the present invention, by using a polymer with a phosphate structure in the main chain, and combining talc and silicon dioxide, and optimizing the ratio of the two to replace the traditional filler barium sulfate, the printing property and pencil hardness can be improved on the basis of effectively improving the resistance to cold and hot shocks.
與此相對,同時使用滑石和硫酸鋇作為填料,可以滿足阻焊油墨的耐冷熱衝擊性的要求,但鉛筆硬度會較差(例如專利文獻1等)。In contrast, using talc and barium sulfate as fillers at the same time can meet the requirements of the solder resist ink for resistance to cold and hot shocks, but the pencil hardness will be poor (for example, Patent Document 1, etc.).
如上所述,本發明人等經過反覆深入研究發現,滑石作為填料柔韌性較好,在耐冷熱衝擊循環試驗(Temperature Cycle Test,下文有時簡稱為「TCT試驗」)中,抗開裂性能優異,但表面硬度下降明顯。並且滑石的吸油量較大,使得油墨印刷性變差嚴重。而二氧化矽硬度較高,吸油量也較小。通過同時使用滑石和二氧化矽並優化兩者的配比,從而實現了上述本發明的目的。 [發明的效果] As mentioned above, the inventors of the present invention have found through repeated and in-depth research that talc has better flexibility as a filler and has excellent crack resistance in the temperature cycle test (hereinafter sometimes referred to as the "TCT test"), but the surface hardness decreases significantly. In addition, talc has a large oil absorption, which seriously deteriorates the printing properties of ink. Silica has a higher hardness and a lower oil absorption. By using talc and silica at the same time and optimizing the ratio of the two, the above-mentioned purpose of the present invention is achieved. [Effect of the invention]
如上所述可知,利用本發明,能夠提供印刷性優異、且能夠形成具有優異的硬度和耐冷熱衝擊性的阻焊層的感光熱硬化顯影性樹脂組合物、其乾膜及其硬化物,以及印刷電路板。As described above, the present invention can provide a photosensitive thermosetting developing resin composition having excellent printability and capable of forming a solder resist layer having excellent hardness and resistance to cold and hot shocks, a dry film thereof, a cured product thereof, and a printed circuit board.
以下,對本發明的感光熱硬化顯影性樹脂組合物中的各構成成分進行說明。Hereinafter, each component of the photosensitive thermosetting developing resin composition of the present invention will be described.
本發明的感光熱硬化顯影性樹脂組合物的特徵在於含有(E)無機填料,所述(E)無機填料包含滑石和二氧化矽作為必需成分,因此首先對(E)無機填料進行說明。The photosensitive thermosetting developing resin composition of the present invention is characterized by containing (E) an inorganic filler, wherein the (E) inorganic filler includes talc and silica as essential components, and therefore the (E) inorganic filler will be described first.
(E)無機填料 本發明的感光熱硬化顯影性樹脂組合物中,作為(E)無機填料所使用的滑石是為了提高耐冷熱衝擊性而使用的。作為二氧化矽是為了改善印刷性而使用的。 (E) Inorganic filler In the photosensitive thermosetting developing resin composition of the present invention, talc used as (E) inorganic filler is used to improve resistance to cold and hot shocks. Silica is used to improve printability.
作為滑石,母岩石為碳酸鎂、蛇紋石、二氧化矽/二氧化矽-氧化鋁、鎂沉積物中的任一種即可,為所謂矽酸鹽礦物的一種即可,形狀可以為塊狀也可以為微粉狀。可以進行表面處理也可以不進行。滑石吸油量為20~100ml/100g是合適的,優選30~90ml/100g,更優選40~80ml/100g。滑石的平均粒徑為1.0-20.0μm是合適的,更優選2.0~10μm,進一步優選3.0~8.0μm。As talc, the parent rock can be any one of magnesium carbonate, serpentine, silica/silica-alumina, and magnesium precipitate, and can be one of the so-called silicate minerals, and the shape can be blocky or fine powder. It may or may not be surface treated. The oil absorption of talc is suitable for 20~100ml/100g, preferably 30~90ml/100g, and more preferably 40~80ml/100g. The average particle size of talc is suitable for 1.0-20.0μm, more preferably 2.0~10μm, and further preferably 3.0~8.0μm.
作為市售品可以列舉山東省平度市滑石礦業有限公司製HD25、富士滑石工業株式會社製LMP-100等。As commercially available products, HD25 manufactured by Shandong Pingdu Talc Mining Co., Ltd. and LMP-100 manufactured by Fuji Talc Industry Co., Ltd. can be cited.
作為二氧化矽,可以為無定形、晶體中的任意一者,也可以為它們的混合物。特別優選無定形(熔融)二氧化矽。可以進行表面處理也可以不進行。二氧化矽吸油量為15~60ml/100g是合適的,優選20~50ml/100g,更優選27~45ml/100g。二氧化矽的平均粒徑為0.1~10.0μm是合適的,更優選1.0~8.0μm,進一步優選2.0~6.0μm。The silicon dioxide may be any of amorphous and crystalline, or a mixture thereof. Amorphous (fused) silicon dioxide is particularly preferred. Surface treatment may or may not be performed. The silicon dioxide oil absorption is suitably 15 to 60 ml/100 g, preferably 20 to 50 ml/100 g, and more preferably 27 to 45 ml/100 g. The average particle size of the silicon dioxide is suitably 0.1 to 10.0 μm, more preferably 1.0 to 8.0 μm, and further preferably 2.0 to 6.0 μm.
作為二氧化矽的市售品,可以列舉江蘇聯瑞新材料股份有限公司製CS1002和CS1002A等、矽比科Sibelco有限公司製A-8 、Tokuyama Co., Ltd.製 SE-40、龍森製MSV25G、龍森製MLV-2114、ADMATECHS製 SO-E5、ADMATECHS製SO-E2等。 Commercially available products of silicon dioxide include CS1002 and CS1002A manufactured by Jiangsu Lianrui New Materials Co., Ltd., A-8 manufactured by Sibelco Co., Ltd. , SE-40 manufactured by Tokuyama Co., Ltd., MSV25G manufactured by Ronsen, MLV-2114 manufactured by Ronsen, SO-E5 manufactured by ADMATECHS, and SO-E2 manufactured by ADMATECHS.
關於滑石和二氧化矽的配混比率,按兩者總重量為100重量%計,滑石比率的下限為20重量%以上是適宜的,優選25重量%以上,更優選30重量%以上。滑石比率的上限為80重量%以下是適宜的,優選75重量%以下,更優選70重量%以下。滑石的比率位於上述範圍內,則能夠明顯改善耐冷熱衝擊性。當不足20重量%時,不能獲得充分的耐冷熱衝擊性,超過80重量%時,雖然耐冷熱衝擊性仍然優異,但印刷性和阻焊膜的表面硬度有降低的傾向。推測是由於滑石的吸油量較大,其用量過多時導致油墨的印刷性受到較大影響。而二氧化矽硬度較高且吸油量較小,通過將兩者以適合的比例配混,從而實現了在兼顧印刷性和鉛筆硬度(至少4H,優選6H以上)的同時改善耐冷熱衝擊性(在-40℃~160℃冷熱循環條件下耐受至少1000次循環)。Regarding the mixing ratio of talc and silica, based on the total weight of the two as 100 weight%, the lower limit of the talc ratio is preferably 20 weight% or more, preferably 25 weight% or more, and more preferably 30 weight% or more. The upper limit of the talc ratio is preferably 80 weight% or less, preferably 75 weight% or less, and more preferably 70 weight% or less. When the talc ratio is within the above range, the resistance to cold and hot shocks can be significantly improved. When it is less than 20 weight%, sufficient resistance to cold and hot shocks cannot be obtained. When it exceeds 80 weight%, although the resistance to cold and hot shocks is still excellent, the printability and the surface hardness of the solder mask tend to decrease. It is speculated that this is because the oil absorption of talc is large, and when its amount is too much, the printability of the ink is greatly affected. Silica has a higher hardness and a lower oil absorption. By mixing the two in a suitable ratio, it is possible to achieve both printability and pencil hardness (at least 4H, preferably 6H or above) while improving resistance to cold and hot shock (withstanding at least 1,000 cycles under cold and hot cycling conditions of -40°C to 160°C).
另外,相對於以固體成分計的(A)乙烯基酯樹脂100重量份,滑石和二氧化矽兩者的總量為50~180重量份是適宜的,優選60 ~160重量份,更優選80 ~150重量份。若位於上述範圍內,可確保在兼顧印刷性和硬度的同時獲得優異的耐冷熱衝擊性。In addition, the total amount of talc and silica is preferably 50 to 180 parts by weight, preferably 60 to 160 parts by weight, and more preferably 80 to 150 parts by weight, relative to 100 parts by weight of the (A) vinyl ester resin in terms of solid content. Within the above range, excellent resistance to cold and hot shocks can be achieved while taking into account both printability and hardness.
從進一步滿足耐冷熱衝擊性能、鉛筆硬度和印刷性的方面出發,本發明的感光熱硬化顯影性樹脂組合物優選不含硫酸鋇。In order to further satisfy the requirements of resistance to cold and hot impact, pencil hardness and printability, the photosensitive thermosetting developing resin composition of the present invention preferably does not contain barium sulfate.
(A)乙烯基酯樹脂 本發明的光硬化性熱硬化樹脂組合物中的(A)乙烯基酯樹脂可以使用用於賦予鹼顯影性的、分子中含有烯屬不飽和雙鍵的公知的樹脂。從光硬化性、耐顯影性的方面出發,特別優選分子中具有烯屬不飽和雙鍵的含羧基樹脂。此外,更優選該不飽和雙鍵源自丙烯酸或甲基丙烯酸或它們的衍生物。作為(A)乙烯基酯樹脂,優選以環氧樹脂為起始原料的樹脂、具有胺基甲酸酯骨架的聚胺酯樹脂、具有不飽和羧酸的共聚結構的共聚樹脂、以酚化合物為起始原料的樹脂。以下示出(A)乙烯基酯樹脂的具體例子。 (A) Vinyl ester resin The (A) vinyl ester resin in the photocurable thermosetting resin composition of the present invention can use a known resin containing an olefinic unsaturated double bond in the molecule for imparting alkaline development. From the aspects of photocurability and development resistance, a carboxyl-containing resin having an olefinic unsaturated double bond in the molecule is particularly preferred. In addition, it is more preferred that the unsaturated double bond is derived from acrylic acid or methacrylic acid or a derivative thereof. As the (A) vinyl ester resin, a resin using an epoxy resin as a starting material, a polyurethane resin having a urethane skeleton, a copolymer resin having a copolymer structure of an unsaturated carboxylic acid, and a resin using a phenol compound as a starting material are preferred. Specific examples of the (A) vinyl ester resin are shown below.
(1)通過使(甲基)丙烯酸等不飽和羧酸與除此以外的1種以上的具有不飽和雙鍵的化合物共聚而獲得的乙烯基酯樹脂;(1) Vinyl ester resins obtained by copolymerizing unsaturated carboxylic acids such as (meth)acrylic acid with one or more other compounds having unsaturated double bonds;
(2)利用(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧環己基甲酯等具有環氧基和不飽和雙鍵的化合物、(甲基)丙烯醯氯等,在(甲基)丙烯酸等不飽和羧酸與除此以外的1種以上的具有不飽和雙鍵的化合物的共聚物上以側基的形式加成烯屬不飽和基團而獲得的感光性的乙烯基酯樹脂;(2) Photosensitive vinyl ester resins obtained by adding an olefinic unsaturated group as a pendant to a copolymer of an unsaturated carboxylic acid such as (meth)acrylic acid and one or more other compounds having an unsaturated double bond, using compounds having an epoxy group and an unsaturated double bond such as glycidyl (meth)acrylate, 3,4-epoxyhexylmethyl (meth)acrylate, (meth)acrylic acid chloride, etc.;
(3)使(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧環己基甲酯等具有環氧基和不飽和雙鍵的化合物和除此以外的具有不飽和雙鍵的化合物的共聚物、與(甲基)丙烯酸等不飽和羧酸反應,並使多元酸酐與所生成的第二羥基反應而獲得的感光性的乙烯基酯樹脂;(3) A photosensitive vinyl ester resin obtained by reacting a copolymer of a compound having an epoxy group and an unsaturated double bond such as glycidyl (meth)acrylate and 3,4-epoxyhexylmethyl (meth)acrylate, and another compound having an unsaturated double bond with an unsaturated carboxylic acid such as (meth)acrylic acid, and reacting a polyacid anhydride with the generated second hydroxyl group;
(4)使馬來酸酐等具有不飽和雙鍵的酸酐和除此以外的具有不飽和雙鍵的化合物的共聚物、與(甲基)丙烯酸2-羥乙酯等具有羥基和不飽和雙鍵的化合物反應而獲得的感光性的乙烯基酯樹脂;(4) Photosensitive vinyl ester resins obtained by reacting a copolymer of an acid anhydride having an unsaturated double bond such as maleic anhydride and another compound having an unsaturated double bond with a compound having a hydroxyl group and an unsaturated double bond such as 2-hydroxyethyl (meth)acrylate;
(5)使多官能環氧化合物與不飽和單羧酸反應,並使飽和或不飽和多元酸酐與所生成的羥基反應而獲得的乙烯基酯樹脂;(5) Vinyl ester resins obtained by reacting a polyfunctional epoxy compound with an unsaturated monocarboxylic acid and reacting a saturated or unsaturated polyacid anhydride with the resulting hydroxyl group;
(6)使聚乙烯醇衍生物等含羥基聚合物與飽和或不飽和多元酸酐反應之後,使1分子中具有環氧基和不飽和雙鍵的化合物與所生成的羧酸反應而獲得的含有羥基和羧基的乙烯基酯樹脂;(6) A vinyl ester resin containing hydroxyl and carboxyl groups obtained by reacting a hydroxyl-containing polymer such as a polyvinyl alcohol derivative with a saturated or unsaturated polyacid anhydride and then reacting a compound having an epoxy group and an unsaturated double bond in one molecule with the resulting carboxylic acid;
(7)使多官能環氧化合物和不飽和單羧酸與1分子中具有至少1個醇性羥基和與環氧基反應的除醇性羥基以外的1個反應性基團的化合物的反應產物、與飽和或不飽和多元酸酐反應而獲得的乙烯基酯樹脂;(7) A vinyl ester resin obtained by reacting a reaction product of a polyfunctional epoxy compound and an unsaturated monocarboxylic acid with a compound having at least one alcoholic hydroxyl group and one reactive group other than the alcoholic hydroxyl group that reacts with the epoxy group in one molecule, with a saturated or unsaturated polybasic acid anhydride;
(8)使不飽和單羧酸與1分子中具有至少2個氧雜環丁烷環的多官能氧雜環丁烷化合物反應,並使飽和或不飽和多元酸酐與所得改質氧雜環丁烷樹脂中的伯羥基反應而獲得的乙烯基酯樹脂;以及(8) a vinyl ester resin obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional cyclohexane compound having at least two cyclohexane rings in one molecule, and reacting a saturated or unsaturated polyacid anhydride with a primary hydroxyl group in the obtained modified cyclohexane resin; and
(9)對於使不飽和單羧酸與多官能環氧樹脂反應之後與多元酸酐反應所得到的含羧基樹脂,進一步使分子中具有1個氧雜環丙烷環和1個以上烯屬不飽和基團的化合物與其反應而獲得的乙烯基酯樹脂;(9) A vinyl ester resin obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional epoxy resin and then reacting the resulting reaction with a polyacid anhydride, and further reacting the resulting reaction with a compound having one cyclohexane ring and one or more olefinic unsaturated groups in the molecule;
(10)使雙官能團環氧化合物與不飽和單羧酸反應,使飽和或不飽和多元酸酐與所生成的羥基反應而獲得的乙烯基酯樹脂。(10) A vinyl ester resin obtained by reacting a difunctional epoxy compound with an unsaturated monocarboxylic acid and reacting a saturated or unsaturated polyacid anhydride with the resulting hydroxyl group.
作為這些例示中特別優選的物質,為所述(2)、(5)、(7)、(9)的乙烯基酯樹脂。Particularly preferred among these examples are the vinyl ester resins (2), (5), (7) and (9).
需要說明的是,在本說明書中,(甲基)丙烯酸酯是統稱丙烯酸酯、甲基丙烯酸酯及其混合物的術語,對其他類似的表達也同樣。It should be noted that, in this specification, (meth)acrylate is a term that collectively refers to acrylate, methacrylate and mixtures thereof, and the same applies to other similar expressions.
上述那樣的(A)乙烯基酯樹脂由於在主鏈聚合物的側鏈上具有多個游離的羧基,因此可以利用稀鹼水溶液進行顯影。Since the above-mentioned (A) vinyl ester resin has a plurality of free carboxyl groups on the side chains of the main chain polymer, it can be developed using a dilute alkaline aqueous solution.
另外,上述(A)乙烯基酯樹脂的酸值優選為40~200mgKOH/g的範圍,更優選為45~120mgKOH/g的範圍。含羧基樹脂的酸值不足40mgKOH/g時,難以鹼顯影,另一方面,超過200mgKOH/g時,會促進顯影液對曝光部的溶解,因此,線變得比所需要的更細,有時曝光部和未曝光部無區別地被顯影液溶解剝離,難以描繪正常的抗蝕圖案,故不優選。The acid value of the vinyl ester resin (A) is preferably in the range of 40 to 200 mgKOH/g, more preferably in the range of 45 to 120 mgKOH/g. If the acid value of the carboxyl-containing resin is less than 40 mgKOH/g, alkali development is difficult. On the other hand, if it exceeds 200 mgKOH/g, the developer dissolves the exposed part, so that the line becomes thinner than necessary, and sometimes the exposed part and the unexposed part are dissolved and peeled by the developer without distinction, making it difficult to draw a normal resist pattern, so it is not preferred.
此外,上述(A)乙烯基酯樹脂的重均分子量根據樹脂骨架而不同,通常優選為2000~150000、進一步優選為5000~100000的範圍。重均分子量不足2000時,有時向基板的塗布、乾燥後的不黏手性能變差,此外,有時曝光後的塗膜的耐濕性惡化、顯影時產生膜減少、解析度大幅變差。另一方面,重均分子量超過150000時,有時顯影性會顯著劣化、保存穩定性會變差。The weight average molecular weight of the vinyl ester resin (A) varies depending on the resin skeleton, but is generally preferably in the range of 2,000 to 150,000, and more preferably in the range of 5,000 to 100,000. When the weight average molecular weight is less than 2,000, the coating on the substrate and the non-tackiness after drying may be poor, and the moisture resistance of the coating after exposure may deteriorate, and film reduction may occur during development, and the resolution may be greatly deteriorated. On the other hand, when the weight average molecular weight exceeds 150,000, the developability may be significantly deteriorated and the storage stability may be poor.
(A)乙烯基酯樹脂的配混量理想的是以固體成分計的全部組合物的20~60質量%的範圍,優選為25~50質量%。(A)乙烯基酯樹脂的配混量少於所述範圍的情況下,塗膜強度降低故不優選。另一方面,多於所述範圍的情況下、組合物的黏性變高或塗布性等降低故不優選。The blending amount of the vinyl ester resin (A) is preferably in the range of 20 to 60% by mass of the total composition based on the solid content, preferably 25 to 50% by mass. If the blending amount of the vinyl ester resin (A) is less than the above range, the coating film strength is reduced, which is not preferred. On the other hand, if the blending amount is more than the above range, the viscosity of the composition becomes high or the coating property is reduced, which is not preferred.
(B)光聚合起始劑 作為本發明的感光熱硬化顯影性樹脂組合物中使用的光聚合起始劑,只要是通常用於感光熱硬化顯影性樹脂組合物的光聚合起始劑則沒有特別的限制。 (B) Photopolymerization initiator The photopolymerization initiator used in the photosensitive thermosetting developing resin composition of the present invention is not particularly limited as long as it is a photopolymerization initiator commonly used in photosensitive thermosetting developing resin compositions.
作為光聚合起始劑,可以使用公知的物質,可以舉出:苯偶姻、苯偶姻甲醚、苯偶姻乙醚等苯偶姻和其烷醚類;苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、1,1-二氯苯乙酮、4-(1-第三丁基二氧基-1-甲基乙基)苯乙酮等苯乙酮類;2-甲基蒽醌、2-戊基蒽醌、2-第三丁基蒽醌、1-氯蒽醌等蒽醌類;異丙基噻噸酮、2,4-二甲基噻噸酮、2,4-二異丙基噻噸酮、2-氯噻噸酮等噻噸酮類;苯乙酮二甲基縮酮、苯偶醯二甲基縮酮等縮酮類;二苯甲酮、4-(1-第三丁基二氧基-1-甲基乙基)二苯甲酮、3,3’,4,4’-四(第三丁基二氧基羰基)二苯甲酮等二苯甲酮類;和氧雜蒽酮類等。As the photopolymerization initiator, known substances can be used, and examples thereof include: benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-tert-butyldioxy-1-methylethyl)acetophenone; 2-methylanthraquinone, 2-amylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone. Anthraquinones; thiocontanes such as isopropylthiocontanone, 2,4-dimethylthiocontanone, 2,4-diisopropylthiocontanone, and 2-chlorothiocontanone; ketones such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-(1-tert-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(tert-butyldioxycarbonyl)benzophenone; and oxanthrone, etc.
另外,作為光聚合起始劑,也可以使用具有肟酯基的肟酯系光聚合起始劑、烷基苯酮系光聚合起始劑、α-胺基苯乙酮系光聚合起始劑、醯基氧化膦系光聚合起始劑、二茂鈦系光聚合起始劑等。In addition, as the photopolymerization initiator, an oxime ester-based photopolymerization initiator having an oxime ester group, an alkylphenone-based photopolymerization initiator, an α-aminoacetophenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a titanocene-based photopolymerization initiator, or the like can also be used.
作為肟酯系光聚合起始劑的市售品,可以舉出BASF Japan公司製造的Irgacure OXE01、Irgacure OXE02、ADEKA CORPORATION製造的N-1919、NCI-831等。可以優選使用分子內具有2個肟酯基的光聚合起始劑,具體可以列舉具有哢唑環結構的肟酯化合物。Commercially available oxime ester photopolymerization initiators include Irgacure OXE01 and Irgacure OXE02 manufactured by BASF Japan, and N-1919 and NCI-831 manufactured by ADEKA CORPORATION. A photopolymerization initiator having two oxime ester groups in the molecule can be preferably used, and specifically, an oxime ester compound having an oxazole ring structure can be exemplified.
作為烷基苯酮系光聚合起始劑的市售品,可以列舉IGM Resins B.V.公司製造的Omnirad 184、Omnirad 1173、Omnirad 2959、Omnirad 127等α-羥烷基苯酮系。Commercially available products of alkylphenone-based photopolymerization initiators include α-hydroxyalkylphenone-based products such as Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 manufactured by IGM Resins B.V.
作為α-胺基苯乙酮系光聚合起始劑,具體而言,可以舉出2-甲基-1-[4-(甲基硫代)苯基]-2-嗎啉基-1-丙酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁烷-1-酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮、N,N-二甲基胺基苯乙酮等。作為市售品,可以使用IGM Resins B.V.公司製造的Omnirad 907、Omnirad 369、Omnirad 379等。Specific examples of the α-aminoacetophenone-based photopolymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone, and N,N-dimethylaminoacetophenone. As commercially available products, Omnirad 907, Omnirad 369, and Omnirad 379 manufactured by IGM Resins B.V. can be used.
作為醯基氧化膦系光聚合起始劑,具體而言,可以舉出2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基氧化膦、3官能以上的醯基膦系光聚合起始劑等。該3官能以上的醯基膦系光聚合起始劑可以為1分子中具有3個以上的醯基氧化膦骨架的光聚合起始劑,可以由下述式(I)表示。 As the acylphosphine oxide-based photopolymerization initiator, specifically, there can be mentioned 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzyl)-2,4,4-trimethyl-pentylphosphine oxide, trifunctional or higher acylphosphine-based photopolymerization initiators, etc. The trifunctional or higher acylphosphine-based photopolymerization initiator may be a photopolymerization initiator having three or more acylphosphine oxide skeletons in one molecule, and may be represented by the following formula (I).
式中, A彼此獨立地表示單鍵、O、S或NR 3; G是多官能化合物(核芯)G-(A-H) m+n的殘基,其中A-H各自表示醇基或胺基或硫醇基; m及n均為整數,且m+n為3~10之間的整數; m為3~8之間的整數; R 1及R 2彼此獨立地是C 1-C 18的烷基、C 6-C 12的芳基及C 5-C 12的環烷基,各自不斷開或被如下基團斷開:1個以上的氧和/或硫原子和/或1個以上的取代或未取代亞胺基,或者R 1及R 2彼此獨立地是含有氧和/或氮和/或硫原子的五至六元雜環基,其中,前述基團各自任選被芳基、烷基、芳氧基、烷氧基、雜原子和/或雜環基團取代; R 2可以為R 1-(C=O)-; Y為O或S; R 3為氫或C 1~C 4的烷基; wherein A independently represents a single bond, O, S or NR 3 ; G is a residue of a multifunctional compound (core) G-(AH) m+n , wherein AH independently represents an alcohol group, an amine group or a thiol group; m and n are both integers, and m+n is an integer between 3 and 10; m is an integer between 3 and 8; R 1 and R 2 independently represent a C 1 -C 18 alkyl group, a C 6 -C 12 aryl group and a C 5 -C 12 cycloalkyl group, each of which is continuous or interrupted by the following groups: one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or R 1 and R 2 are each independently a C 1 -C 18 alkyl group, a C 6 -C 12 aryl group and a C 5 -C 12 cycloalkyl group, each of which is continuous or interrupted by the following groups: one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups, or R 1 and R 2 are independently a five- to six-membered heterocyclic group containing oxygen and/or nitrogen and/or sulfur atoms, wherein the aforementioned groups are each optionally substituted by an aryl group, an alkyl group, an aryloxy group, an alkoxy group, a heteroatom and/or a heterocyclic group; R 2 may be R 1 -(C=O)-; Y is O or S; R 3 is hydrogen or a C 1 to C 4 alkyl group;
其中,式(I)的光聚合起始劑不含光硬化性烯屬不飽和基團。The photopolymerization initiator of formula (I) does not contain a photocurable ethylenic unsaturated group.
優選的是,式(I)中,m+n為3~8之間的整數、更優選為3~6之間的整數。例如,式I中,m為3~6之間的整數、更優選為3~5之間的整數。Preferably, in formula (I), m+n is an integer between 3 and 8, more preferably an integer between 3 and 6. For example, in formula I, m is an integer between 3 and 6, more preferably an integer between 3 and 5.
式(I)中,A為氧時,G-(A-H) m+n為多羥基(多元羥基)化合物,選自由單體多元醇、低聚物多元醇和聚合物多元醇及其混合物組成的組。A為硫時,G-(A-H) m+n為多硫醇化合物。式(I)中,A為氮時,G-(A-H) m+n為線型或支鏈多胺。A為氧和/或氮和/或硫的混合時,G-(A-H) m+n為包含不同官能團的化合物、例如包含胺基及羥基的化合物。適於本發明的實施的殘基G-不含光硬化性烯屬不飽和基團。A為單鍵時,G-為上述列舉的G-(A-H) m+n中除去羥基和/或胺基和/或巰基後的殘基。 In formula (I), when A is oxygen, G-(AH) m+n is a polyhydroxyl (polyhydroxyl) compound selected from the group consisting of monomer polyols, oligomer polyols and polymer polyols and mixtures thereof. When A is sulfur, G-(AH) m+n is a polythiol compound. In formula (I), when A is nitrogen, G-(AH) m+n is a linear or branched polyamine. When A is a mixture of oxygen and/or nitrogen and/or sulfur, G-(AH) m+n is a compound containing different functional groups, for example, a compound containing an amino group and a hydroxyl group. The residue G- suitable for the implementation of the present invention does not contain a photocurable ethylenic unsaturated group. When A is a single bond, G- is the residue after removing the hydroxyl and/or amino group and/or hydroxyl group from the above-mentioned G-(AH) m+n .
優選的是G-(A-H) m+n具有1500以下、更優選800以下、進一步優選500以下的數均分子量。 It is preferred that G-(AH) m+n has a number average molecular weight of 1500 or less, more preferably 800 or less, further preferably 500 or less.
當n不為0時,式(I)的化合物具有醇性游離基和/或胺基和/或巰基。When n is not 0, the compound of formula (I) has an alcoholic free group and/or an amino group and/or a hydroxyl group.
將式(I)中包括的代表性的3官能以上的醯基膦系光聚合起始劑示於表1。這些當中,特別優選PI-3、PI-4、PI-10、PI-11、PI-12、PI-14、PI-17。通過包含這種3官能以上的醯基膦系光聚合起始劑,能夠得到排氣受到抑制、絕緣可靠性更加優異的硬化物。Representative trifunctional or higher acylphosphine photopolymerization initiators included in formula (I) are shown in Table 1. Among these, PI-3, PI-4, PI-10, PI-11, PI-12, PI-14, and PI-17 are particularly preferred. By including such trifunctional or higher acylphosphine photopolymerization initiators, outgassing is suppressed and a cured product with more excellent insulation reliability can be obtained.
表1 Table 1
這種3官能以上的醯基膦系光聚合起始劑例如可以通過日本特許6599446號中記載的方法來製造。Such a trifunctional or higher acylphosphine-based photopolymerization initiator can be produced by the method described in Japanese Patent No. 6599446, for example.
作為醯基氧化膦系光聚合起始劑的市售品,可以使用IGM Resins公司製造的Omnirad TPO、IGM Resins B.V.公司製的Omnirad 819、Omnipol TP等。As commercially available products of acylphosphine oxide-based photopolymerization initiators, Omnirad TPO manufactured by IGM Resins, Omnirad 819 and Omnipol TP manufactured by IGM Resins B.V., etc. can be used.
作為前述二茂鈦系光聚合起始劑,具體而言,可以舉出雙(環戊二烯基)-二苯基鈦、雙(環戊二烯基)-二氯化鈦、雙(環戊二烯基)-雙(2,3,4,5,6五氟苯基)鈦、雙(環戊二烯基)-雙(2,6-二氟-3-(吡咯-1-基)苯基)鈦等。作為市售品,可以舉出IGM Resins B.V.公司製造的Omnirad 784等。Specific examples of the titanocene-based photopolymerization initiator include bis(cyclopentadienyl)-diphenyl titanium, bis(cyclopentadienyl)-titanium dichloride, bis(cyclopentadienyl)-bis(2,3,4,5,6-pentafluorophenyl)titanium, and bis(cyclopentadienyl)-bis(2,6-difluoro-3-(pyrrol-1-yl)phenyl)titanium. Examples of commercially available products include Omnirad 784 manufactured by IGM Resins B.V.
對於這些光聚合起始劑(B)的配混比例,相對於100重量份以固體成分計的所述(A)乙烯基酯樹脂為0.01~30重量份是合適的,優選5~25重量份,更優選10~20重量份。光聚合起始劑的使用量比所述範圍少的情況下,組合物的光硬化性變差,另一方面,過多的情況下,作為阻焊劑的特性降低故不優選。The compounding ratio of the photopolymerization initiator (B) is preferably 0.01 to 30 parts by weight, preferably 5 to 25 parts by weight, and more preferably 10 to 20 parts by weight, relative to 100 parts by weight of the vinyl ester resin (A) in terms of solid content. If the amount of the photopolymerization initiator used is less than the above range, the photocurability of the composition deteriorates, while if it is too much, the properties as a solder resist are deteriorated, which is not preferred.
(C)磷酸酯系分散劑 本發明的感光熱硬化顯影性樹脂組合物中使用的(C)磷酸酯系分散劑是指在主鏈或側鏈中具有如下式(II)所示的磷酸酯結構的化合物或聚合物。 (C) Phosphate Ester Dispersant The (C) phosphate ester dispersant used in the photosensitive thermosetting developing resin composition of the present invention refers to a compound or polymer having a phosphate structure represented by the following formula (II) in the main chain or the side chain.
其中基於與顏料具有良好的親和性、可用於無溶劑型和溶劑型油墨、適合於在低極性的體系(例如醇酸樹脂、丙烯酸酯樹脂、熱塑性丙烯酸系樹脂和環氧樹脂)中使顏料穩定化的角度出發,優選在主鏈或側鏈中具有如式(II)所示的磷酸酯結構的聚合物。Among them, based on the perspective of having good affinity with pigments, being usable in solvent-free and solvent-based inks, and being suitable for stabilizing pigments in low-polarity systems (such as alkyd resins, acrylate resins, thermoplastic acrylic resins and epoxy resins), polymers having a phosphate structure as shown in formula (II) in the main chain or side chain are preferred.
進一步地,本發明人等發現,從兼顧油墨印刷性和阻焊層表面硬度的同時改善耐冷熱衝擊性的角度出發,在滑石配合二氧化矽作為填料的同時,(C)磷酸酯系分散劑更優選同時使用主鏈中具有磷酸酯結構的聚合物(即聚磷酸酯系聚合物)和側鏈中具有磷酸酯結構的聚合物。此時,兩者的配混比例以重量比計,即(C-1)主鏈中具有磷酸酯結構的聚合物:(C-2)側鏈中具有磷酸酯結構的聚合物為1:10~10:1是合適的,優選為1:5~5:1,更優選為1:3~3:1,進一步優選為1:2~2:1。如此,可以獲得油墨印刷性、阻焊層表面硬度和耐冷熱衝擊性均優異的感光熱硬化顯影性樹脂組合物。Furthermore, the inventors have found that, from the perspective of improving the resistance to cold and hot shocks while taking into account both the ink printability and the surface hardness of the solder mask layer, it is more preferable to use a polymer having a phosphate structure in the main chain (i.e., a polyphosphate polymer) and a polymer having a phosphate structure in the side chain as the (C) phosphate ester dispersant while combining talc with silica as a filler. At this time, the mixing ratio of the two is based on a weight ratio, i.e., (C-1) a polymer having a phosphate structure in the main chain: (C-2) a polymer having a phosphate structure in the side chain of 1:10 to 10:1, preferably 1:5 to 5:1, more preferably 1:3 to 3:1, and further preferably 1:2 to 2:1. In this way, a photosensitive thermosetting developing resin composition having excellent ink printability, solder mask surface hardness, and resistance to cold and hot shock can be obtained.
對於(C)磷酸酯系分散劑的配混比例,相對於100重量份以固體成分計的所述(A)乙烯基酯樹脂為0.01~20重量份是合適的,優選為0.1~15重量份,更優選1~10重量份。(C)磷酸酯系分散劑的使用量位於上述範圍內,可確保在兼顧印刷性和硬度的同時獲得優異的耐冷熱衝擊性。在超出上述範圍的情況下,作為阻焊劑的特性降低故不優選。The compounding ratio of (C) phosphate ester dispersant is suitably 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight, and more preferably 1 to 10 parts by weight, relative to 100 parts by weight of the (A) vinyl ester resin in terms of solid content. The amount of (C) phosphate ester dispersant used within the above range can ensure excellent resistance to thermal shock while taking into account both printability and hardness. If the amount exceeds the above range, the properties as a solder resist are reduced, which is not preferred.
作為磷酸酯系分散劑的市售產品,可以列舉:Tech-5011(上海泰格聚合物技術有限公司製造)、BYK-102、BYK-103、BYK-106 、BYK-110、BYK-111、BYK-118、BYK-142、BYK-145(畢克化學公司製造)等。Commercially available products of phosphate ester dispersants include Tech-5011 (manufactured by Shanghai Tiger Polymer Technology Co., Ltd.), BYK-102, BYK-103, BYK-106, BYK-110, BYK-111, BYK-118, BYK-142, BYK-145 (manufactured by Beck Chemical Co., Ltd.), etc.
需要說明的是,在本說明書中,聚合物是統稱均聚物、共聚物及其混合物的術語,對其他類似的表達也同樣。It should be noted that in this specification, polymer is a term generally referring to homopolymers, copolymers and mixtures thereof, and the same applies to other similar expressions.
(D)在一分子中具有兩個以上的乙烯性不飽和基團的化合物 本發明的感光熱硬化顯影性樹脂組合物中使用的(D)在一分子中具有兩個以上的乙烯性不飽和基團的化合物是通過照射活性能量射線進行光硬化使前述(A)乙烯基酯樹脂不溶於鹼水溶液、或有助於前述乙烯基酯樹脂不溶於鹼水溶液的化合物。作為這樣的化合物的具體例子,可列舉出: 丙烯酸2-羥乙酯、丙烯酸2-羥丙酯等丙烯酸羥烷基酯類; 乙二醇、甲氧基四乙二醇、聚乙二醇、丙二醇等二醇的單丙烯酸酯或二丙烯酸酯類; N,N-二甲基丙烯醯胺、N-羥甲基丙烯醯胺、N,N-二甲胺基丙基丙烯醯胺等丙烯醯胺類; 丙烯酸N,N-二甲胺基乙酯、丙烯酸N,N-二甲胺基丙酯等丙烯酸胺基烷基酯類; 己二醇、三羥甲基丙烷、季戊四醇、二季戊四醇、三羥乙基異氰脲酸酯等多元醇或它們的環氧乙烷加成物或環氧丙烷加成物等的多元丙烯酸酯類; 苯氧基丙烯酸酯、雙酚A二丙烯酸酯、及這些酚類的環氧乙烷加成物或環氧丙烷加成物等丙烯酸酯類; 甘油二縮水甘油醚、甘油三縮水甘油醚、三羥甲基丙烷三縮水甘油醚、三縮水甘油基異氰脲酸酯等縮水甘油醚的丙烯酸酯類; 及三聚氰胺丙烯酸酯、及與上述丙烯酸酯對應的各甲基丙烯酸酯類的至少任一種等。 進而,還可以列舉出:使甲酚酚醛清漆型環氧樹脂等多官能環氧樹脂與丙烯酸反應而成的環氧丙烯酸酯樹脂、進一步使該環氧丙烯酸酯樹脂的羥基與季戊四醇三丙烯酸酯等羥基丙烯酸酯和異佛爾酮二異氰酸酯等二異氰酸酯的半胺基甲酸酯(half urethane)化合物反應而成的環氧胺基甲酸酯丙烯酸酯化合物等。 (D) Compounds having two or more ethylenically unsaturated groups in one molecule The compound (D) having two or more ethylenically unsaturated groups in one molecule used in the photosensitive thermosetting developing resin composition of the present invention is a compound that makes the aforementioned (A) vinyl ester resin insoluble in an alkaline aqueous solution by photocuring with active energy rays, or helps the aforementioned vinyl ester resin to be insoluble in an alkaline aqueous solution. Specific examples of such compounds include: Hydroxyl alkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Monoacrylates or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; Acrylamides such as N,N-dimethylacrylamide, N-hydroxymethylacrylamide, and N,N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; Polyacrylates of polyols such as hexanediol, trihydroxymethylpropane, pentaerythritol, dipentaerythritol, and trihydroxyethyl isocyanurate, or their ethylene oxide adducts or propylene oxide adducts; Acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; Acrylates of glycidyl ethers such as glycerol diglycidyl ether, glycerol triglycidyl ether, trihydroxymethylpropane triglycidyl ether, and triglycidyl isocyanurate; and melamine acrylate, and at least one of the methacrylates corresponding to the above acrylates, etc. Furthermore, examples include: epoxy acrylate resins formed by reacting a multifunctional epoxy resin such as a cresol novolac epoxy resin with acrylic acid, and epoxy urethane acrylate compounds formed by reacting the hydroxyl group of the epoxy acrylate resin with a hydroxyl acrylate such as pentaerythritol triacrylate and a half urethane compound of a diisocyanate such as isophorone diisocyanate, etc.
相對於100重量份以固體成分計的前述(A)乙烯基酯樹脂,這樣的在一分子中具有兩個以上的乙烯性不飽和基團的化合物(D)的配混量期望為5~100重量份的比例,更優選為10~70重量份的比例。所述配混量相對於100重量份所述(A)乙烯基酯樹脂不足5重量份的情況下,所得到的感光熱硬化顯影性樹脂組合物的光硬化性降低,難以通過活性能量射線照射後的鹼顯影形成圖案,因此不優選。另一方面,超過100重量份時,對鹼水溶液的溶解性降低、硬化塗膜變脆,故不優選。The compound (D) having two or more ethylenically unsaturated groups in one molecule is preferably added in an amount of 5 to 100 parts by weight, more preferably 10 to 70 parts by weight, relative to 100 parts by weight of the aforementioned (A) vinyl ester resin in terms of solid content. If the amount is less than 5 parts by weight relative to 100 parts by weight of the aforementioned (A) vinyl ester resin, the photocurability of the resulting photosensitive thermosetting developing resin composition is reduced, and it is difficult to form a pattern by alkaline development after irradiation with active energy rays, which is not preferred. On the other hand, if the amount exceeds 100 parts by weight, the solubility in alkaline aqueous solutions is reduced, and the cured coating becomes brittle, which is not preferred.
(F)其它添加劑 如上所述,本發明中的其它添加劑是指除(B)光聚合起始劑和(C)磷酸酯系分散劑以外的添加劑。 (F) Other additives As mentioned above, the other additives in the present invention refer to additives other than (B) photopolymerization initiator and (C) phosphate dispersant.
作為這樣的添加劑,可列舉出:酞菁藍、酞菁綠、碘綠、雙偶氮黃、結晶紫、氧化鈦、炭黑、萘黑等公知慣用的著色劑,氫醌、氫醌單甲醚、第三丁基兒茶酚、鄰苯三酚、吩噻嗪等公知慣用的熱聚合抑制劑,微粉矽石、有機膨潤土、蒙脫土等公知慣用的增稠劑、有機矽系、氟系、高分子系等的消泡劑和流平劑的至少任意一種,咪唑系、噻唑系、三唑系等的密合性賦予劑、矽烷偶聯劑、苯酚系、磷系、硫系等抗氧化劑、受阻胺類光穩定劑等這樣的公知慣用的添加劑類。Examples of such additives include: phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and other commonly used coloring agents; hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, pyrogallol, phenothiazine and other commonly used thermal polymerization inhibitors; micronized silica, organic bentonite, montmorillonite and other commonly used Well-known and commonly used additives such as descaling thickeners, at least one of organic silicon-based, fluorine-based, polymer-based defoaming agents and leveling agents, imidazole-based, thiazole-based, triazole-based adhesion agents, silane coupling agents, phenol-based, phosphorus-based, sulfur-based antioxidants, hindered amine-based light stabilizers, etc.
這樣的(F)其它添加劑的配混比率在感光熱硬化顯影性樹脂組合物總量的0.01重量%以上且20重量%以下是合適的。不足0.01重量%時,不能充分得到相應的效果,超過20重量%時,感光熱硬化顯影性樹脂組合物的印刷性、硬度變差,因此不優選。The compounding ratio of such (F) other additives is preferably 0.01 wt % or more and 20 wt % or less of the total amount of the photosensitive thermosetting developing resin composition. If it is less than 0.01 wt %, the corresponding effect cannot be fully obtained, and if it exceeds 20 wt %, the printing property and hardness of the photosensitive thermosetting developing resin composition deteriorate, which is not preferred.
(G)環氧樹脂 為了賦予耐熱性,本發明中使用的感光熱硬化顯影性樹脂組合物中優選配混分子中具有至少2個環氧基的環氧樹脂,即多官能環氧樹脂(G)。 (G) Epoxy resin In order to impart heat resistance, the photosensitive thermosetting developing resin composition used in the present invention preferably contains an epoxy resin having at least two epoxy groups in the molecule, i.e., a multifunctional epoxy resin (G).
作為市售品,例如可以舉出:三菱化學公司製造的jER828、jER834、jER1001、jER1004、DIC株式會社製的EPICLON 840、850、850S、1050、2055、NIPPON STEEL Chemical & Material Co., Ltd.製造的EPOTOTE YD-011、YD-013、YD-127、YD-128、Dow Chemical Company製造的D.E.R.317、D.E.R.331、D.E.R.661、D.E.R.664、住友化學工業公司製造製的Sumi-Epoxy ESA-011、ESA-014、ELA-115、ELA-128等(均為商品名)雙酚A型環氧樹脂;三菱化學公司製造的jERYL903、DIC公司製造的EPICLON 152、EPICLON 165、NIPPON STEEL Chemical & Material Co., Ltd.製造的EPOTOTE YDB-400、YDB-500、Dow Chemical Company製的D.E.R.542、住友化學工業公司製造的Sumi-Epoxy ESB-400、ESB-700等(均為商品名)溴化環氧樹脂;三菱化學公司製造的jER152、jER154、Dow Chemical Company製的D.E.N.431、D.E.N.438、DIC公司製造的EPICLON N-730、EPICLON N-770、EPICLON N-865、NIPPON STEEL Chemical & Material Co., Ltd.製造的EPOTOTE YDCN-701、YDCN-704、日本化藥公司製造的EPPN-201、EOCN-1025、EOCN-1020、EOCN-104S、RE-306、NC-3000、住友化學工業公司製造的Sumi-Epoxy ESCN-195X、ESCN-220、NIPPON STEEL Chemical & Material Co., Ltd.製造的YDCN-700-2、YDCN-700-3、YDCN-700-5、YDCN-700-7、YDCN-700-10、YDCN-704、YDCN-704A、DIC株式會社製的EPICLON N-680、N-690、N-695等(均為商品名)酚醛清漆型環氧樹脂;DIC公司製造的EPICLON 830、三菱化學公司製造jER807、NIPPON STEEL Chemical & Material Co., Ltd.製造的EPOTOTE YDF-170、YDF-175、YDF-2004等(均為商品名)雙酚F型環氧樹脂;NIPPON STEEL Chemical & Material Co., Ltd.製造的EPOTOTE ST-2004、ST-2007、ST-3000(商品名)、三菱化學公司製造的YX8034等氫化雙酚A型環氧樹脂;三菱化學公司製造的jER604、NIPPON STEEL Chemical & Material Co., Ltd.製造的EPOTOTE YH-434、住友化學工業公司製造的Sumi-Epoxy ELM-120等(均為商品名)縮水甘油胺型環氧樹脂;乙內醯脲型環氧樹脂;Daicel Corporation製的CELLOXIDE 2021P等(商品名)脂環式環氧樹脂;三菱化學公司製造的YL-933、日本化藥公司製造的EPPN-501、EPPN-502等(均為商品名)三羥基苯基甲烷型環氧樹脂;三菱化學公司製造的YL-6056、YX-4000、YL-6121(均為商品名)等聯二甲苯酚型或聯苯酚型環氧樹脂或它們的混合物;日本化藥公司製造EBPS-200、ADEKA CORPORATION製EPX-30、DIC公司製造的EXA-1514(商品名)等雙酚S型環氧樹脂;三菱化學公司製造的jER157S(商品名)等雙酚A酚醛清漆型環氧樹脂;三菱化學公司製造的jERYL-931等(商品名)四羥苯基乙烷型環氧樹脂;日產化學工業公司製造的TEPIC等(商品名)雜環式環氧樹脂;日油公司製造BRENMAR DGT等苯二甲酸二縮水甘油酯樹脂;NIPPON STEEL Chemical & Material Co., Ltd.製造ZX-1063等四縮水甘油基二甲苯醯基乙烷樹脂;NIPPON STEEL Chemical & Material Co., Ltd.製造ESN-190、ESN-360、DIC公司製造HP-4032、EXA-4750、EXA-4700等含萘骨架氧樹脂;日油公司製造CP-50S、CP-50M等甲基丙烯酸縮水甘油酯共聚系環氧樹脂;進而環己基馬來醯亞胺與甲基丙烯酸縮水甘油酯的共聚環氧樹脂;CTBN改質環氧樹脂(例如NIPPON STEEL Chemical & Material Co., Ltd.製造的YR-102、YR-450等)等,但不限定於這些。這些環氧樹脂可以使用1種或組合2種以上而使用。Examples of commercially available products include jER828, jER834, jER1001, and jER1004 manufactured by Mitsubishi Chemical Corporation, EPICLON 840, 850, 850S, 1050, and 2055 manufactured by DIC Corporation, EPOTOTE YD-011, YD-013, YD-127, and YD-128 manufactured by NIPPON STEEL Chemical & Material Co., Ltd., D.E.R.317, D.E.R.331, D.E.R.661, and D.E.R.664 manufactured by Dow Chemical Company, and Sumi-Epoxy manufactured by Sumitomo Chemical Industries, Ltd. ESA-011, ESA-014, ELA-115, ELA-128, etc. (all trade names) bisphenol A type epoxy resins; jERYL903 manufactured by Mitsubishi Chemical Corporation, EPICLON 152, EPICLON 165 manufactured by DIC Corporation, EPOTOTE YDB-400, YDB-500 manufactured by NIPPON STEEL Chemical & Material Co., Ltd., D.E.R.542 manufactured by Dow Chemical Company, Sumi-Epoxy ESB-400, ESB-700, etc. (all trade names) brominated epoxy resins; jER152, jER154 manufactured by Mitsubishi Chemical Corporation, D.E.N.431, D.E.N.438 manufactured by Dow Chemical Company, EPICLON N-730, EPICLON N-770, EPICLON N-865, EPOTOTE YDCN-701, YDCN-704 manufactured by NIPPON STEEL Chemical & Material Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000 manufactured by Nippon Kayaku Co., Ltd., Sumi-Epoxy ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Industries, Ltd., YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704, YDCN-704A manufactured by NIPPON STEEL Chemical & Material Co., Ltd., EPICLON Novolac epoxy resins such as N-680, N-690, and N-695 (all trade names); bisphenol F epoxy resins such as EPICLON 830 manufactured by DIC Corporation, jER807 manufactured by Mitsubishi Chemical Corporation, and EPOTOTE YDF-170, YDF-175, and YDF-2004 manufactured by NIPPON STEEL Chemical & Material Co., Ltd. (all trade names); hydrogenated bisphenol A epoxy resins such as EPOTOTE ST-2004, ST-2007, and ST-3000 (trade names) manufactured by NIPPON STEEL Chemical & Material Co., Ltd., and YX8034 manufactured by Mitsubishi Chemical Corporation; jER604 manufactured by Mitsubishi Chemical Corporation, and EPOTOTE YH-434, Sumi-Epoxy ELM-120, etc. (all trade names) manufactured by Sumitomo Chemical Industries, Ltd. Glycidylamine type epoxy resins; hydantoin type epoxy resins; CELLOXIDE 2021P, etc. (trade names) manufactured by Daicel Corporation; YL-933 manufactured by Mitsubishi Chemical Corporation, EPPN-501, EPPN-502, etc. (all trade names) manufactured by Nippon Kayaku Co., Ltd. Trihydroxyphenylmethane type epoxy resins; YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation Bixylenol type or biphenol type epoxy resins or mixtures thereof; EBPS-200, ADEKA manufactured by Nippon Kayaku Co., Ltd. EPX-30 manufactured by KOMOBILE CORPORATION, EXA-1514 (trade name) manufactured by DIC Corporation, etc. bisphenol S type epoxy resins; jER157S (trade name) manufactured by Mitsubishi Chemical Corporation, etc. bisphenol A novolac type epoxy resins; jERYL-931 (trade name) manufactured by Mitsubishi Chemical Corporation, etc. tetrahydroxyphenylethane type epoxy resins; TEPIC (trade name) manufactured by Nissan Chemical Industries, Ltd., etc. hybrid epoxy resins; BRENMAR DGT (trade name) manufactured by NOF Corporation, etc. diglycidyl phthalate resins; ZX-1063 (trade name) manufactured by NIPPON STEEL Chemical & Material Co., Ltd., etc. tetraglycidyl dimethylbenzene ether resins; NIPPON STEEL Chemical & Material Co., Ltd., etc. Ltd., ESN-190, ESN-360, HP-4032, EXA-4750, EXA-4700, etc., made by DIC Corporation; methacrylate glycidyl copolymer epoxy resins such as CP-50S, CP-50M, etc. made by NOF Corporation; furthermore, copolymer epoxy resins of cyclohexylmaleimide and methacrylate glycidyl; CTBN modified epoxy resins (such as YR-102, YR-450, etc. made by NIPPON STEEL Chemical & Material Co., Ltd.), etc., but not limited to these. These epoxy resins can be used alone or in combination of two or more.
(G)環氧樹脂的含量優選相對於以固體成分計的(A)乙烯基酯樹脂100質量份為10~100重量份,優選20~90重量份,更優選30~80重量份。The content of the (G) epoxy resin is preferably 10 to 100 parts by weight, more preferably 20 to 90 parts by weight, and more preferably 30 to 80 parts by weight, based on 100 parts by weight of the (A) vinyl ester resin in terms of solid content.
(H)有機溶劑 對於本發明的感光熱硬化顯影性樹脂組合物中可使用的有機溶劑(H),為了合成前述含羧基樹脂(A)、製備組合物、或為了調整黏度以便塗布在基板、載體膜上,可使用有機溶劑。 (H) Organic solvent The organic solvent (H) that can be used in the photosensitive thermosetting developing resin composition of the present invention can be used to synthesize the aforementioned carboxyl-containing resin (A), prepare the composition, or adjust the viscosity for coating on a substrate or a carrier film.
作為這樣的有機溶劑,可列舉出:酮類、芳香族烴類、二醇醚類、二醇醚乙酸酯類、酯類、醇類、脂肪族烴、石油系溶劑等。更具體而言,為甲乙酮、環己酮等酮類;甲苯、二甲苯、四甲苯等芳香族烴類;溶纖劑、甲基溶纖劑、丁基溶纖劑、卡必醇、甲基卡必醇、丁基卡必醇、丙二醇單甲醚、二丙二醇單甲醚、二丙二醇二乙醚、三乙二醇單乙醚等二醇醚類;醋酸乙酯、醋酸丁酯、二丙二醇甲醚乙酸酯、丙二醇甲醚乙酸酯、丙二醇乙醚乙酸酯、丙二醇丁醚乙酸酯等酯類;乙醇、丙醇、乙二醇、丙二醇等醇類;辛烷、癸烷等脂肪族烴;石油醚、石腦油、氫化石腦油、溶劑石腦油等石油系溶劑等。上述有機溶劑可以單獨使用或以兩種以上的混合物的形式使用。Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum-based solvents. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as solvent, methyl solvent, butyl solvent, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha, etc. The above organic solvents can be used alone or in the form of a mixture of two or more.
在形成印刷電路板的阻焊劑時使用本發明的感光熱硬化顯影性樹脂組合物的情況下,根據需要調整至與塗布方法適應的黏度後,通過絲網印刷法、簾幕印刷法、噴塗法、輥塗法等方法將其塗布在例如在預先形成有電路的印刷電路板上,根據需要例如通過以約60~100℃的溫度進行乾燥處理,可形成不黏手的塗膜。然後,透過形成有規定的曝光圖案的光掩模,選擇性地利用活性光線進行曝光,通過鹼性水溶液顯影未曝光部,可以形成抗蝕圖案,進而,例如通過加熱至約140~180℃的溫度使其熱硬化,從而可以促進環氧樹脂的硬化反應和乙烯基酯樹脂的聚合,提高得到的抗蝕覆膜的硬度、耐冷熱衝擊性、耐熱性、耐溶劑性、耐酸性、耐吸濕性、PCT耐受性、密合性、電特性等各種特性。When the photosensitive thermosetting developing resin composition of the present invention is used to form a solder resist for a printed circuit board, the composition is adjusted to a viscosity suitable for the coating method as needed, and then coated on, for example, a printed circuit board on which a circuit is pre-formed by a method such as screen printing, curtain printing, spray coating, or roller coating. If necessary, a non-sticky coating film can be formed by drying the composition at a temperature of about 60 to 100°C. Then, by selectively exposing with active light through a photomask having a prescribed exposure pattern, and developing the unexposed portion with an alkaline aqueous solution, an anti-corrosion pattern can be formed. Furthermore, by, for example, heating to a temperature of about 140 to 180° C. to thermally cure the film, the curing reaction of the epoxy resin and the polymerization of the vinyl ester resin can be promoted, thereby improving the hardness, thermal shock resistance, heat resistance, solvent resistance, acid resistance, moisture absorption resistance, PCT tolerance, adhesion, electrical properties, and other properties of the resulting anti-corrosion coating.
作為上述顯影時使用的鹼水溶液,可以使用氫氧化鉀、氫氧化鈉、碳酸鈉、碳酸鉀、磷酸鈉、矽酸鈉、氨、胺類等的鹼水溶液。此外,作為用於光硬化的照射光源,低壓汞燈、中壓汞燈、高壓汞燈、超高壓汞燈、半導體雷射器、固體雷射、氙氣燈或金屬鹵化物燈等是合適的。As the alkaline aqueous solution used in the above-mentioned development, there can be used alkaline aqueous solutions of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc. In addition, as the irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a semiconductor laser, a solid laser, a xenon lamp, or a metal halide lamp is suitable.
本發明的感光熱硬化顯影性樹脂組合物除了以液態直接塗布於基材的方法之外,還可以以預先將感光熱硬化顯影性樹脂組合物塗布在載體膜上並乾燥而得到的光硬化性的乾膜的形態來使用。以下示出將本發明的感光熱硬化顯影性樹脂組合物以光硬化性的乾膜的形式使用的情況。In addition to the method of directly applying the photosensitive thermosetting developing resin composition of the present invention to a substrate in a liquid state, the photosensitive thermosetting developing resin composition can also be used in the form of a photocurable dry film obtained by applying the photosensitive thermosetting developing resin composition on a carrier film in advance and drying it. The following shows the case where the photosensitive thermosetting developing resin composition of the present invention is used in the form of a photocurable dry film.
光硬化性的乾膜具有將載體膜、樹脂層、和根據需要而使用的可剝離的覆蓋膜依次層疊而成的結構。樹脂層是將本發明的感光熱硬化顯影性樹脂組合物塗布在載體膜或覆蓋膜上並乾燥而得到的層。在載體膜上形成樹脂層後,將覆蓋膜層疊於其上,或者在覆蓋膜上形成樹脂層,將該積層體層疊於載體膜,即可得到乾膜。The photocurable dry film has a structure in which a carrier film, a resin layer, and a peelable cover film used as needed are stacked in sequence. The resin layer is a layer obtained by applying the photosensitive thermosetting developing resin composition of the present invention on a carrier film or a cover film and drying it. After forming a resin layer on a carrier film, a cover film is stacked thereon, or a resin layer is formed on a cover film and the stacked body is stacked on a carrier film to obtain a dry film.
作為載體膜,可使用2~150μm的厚度的聚酯薄膜等熱塑性薄膜。樹脂層是將感光熱硬化顯影性樹脂組合物用刮刀塗布機、唇口塗布機、逗點塗布機、薄膜塗布機等在載體膜或覆蓋膜上以10~150μm的厚度均勻地塗布並乾燥而形成的。作為覆蓋膜,可以使用聚乙烯薄膜、聚丙烯薄膜等,與樹脂層的黏接力小於載體膜與樹脂層的黏接力的覆蓋膜較好。As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm can be used. The resin layer is formed by uniformly applying a photosensitive thermosetting developing resin composition to a carrier film or a covering film at a thickness of 10 to 150 μm using a doctor blade coater, a lip coater, a comma coater, a film coater, etc. and drying. As the covering film, a polyethylene film, a polypropylene film, etc. can be used. A covering film having a smaller adhesive force to the resin layer than the carrier film and the resin layer is preferred.
本申請的硬化物是將如下的塗膜光硬化而得到的,所述塗膜為:將感光熱硬化顯影性樹脂組合物塗布在銅上並乾燥而得到的塗膜;或將該感光熱硬化顯影性樹脂組合物塗布在載體膜上並乾燥,將所得光硬化性的乾膜層壓在銅上而得到的塗膜。The cured product of the present application is obtained by photocuring the following coating, wherein the coating is: a coating obtained by applying a photosensitive thermosetting developing resin composition on copper and drying it; or a coating obtained by applying the photosensitive thermosetting developing resin composition on a carrier film and drying it, and pressing the obtained photocurable dry film layer on copper.
對於使用光硬化性的乾膜在具有銅電路的印刷電路板上製作硬化物,剝離覆蓋膜,將樹脂層與形成有電路的基材重疊,使用層壓機等進行貼合,在形成有電路的基材上形成樹脂層。對所形成的樹脂層與前述同樣地進行曝光、顯影、加熱硬化時,可以形成硬化物。載體膜在曝光前或曝光後剝離均可。When a photocurable dry film is used to produce a cured product on a printed circuit board having a copper circuit, the cover film is peeled off, and the resin layer is overlapped with the substrate having the circuit formed thereon, and the resin layer is formed on the substrate having the circuit formed thereon by laminating them using a laminating press or the like. When the formed resin layer is exposed, developed, and heat-cured in the same manner as described above, a cured product can be formed. The carrier film can be peeled off before or after exposure.
感光熱硬化顯影性樹脂組合物適宜用於在印刷電路板上形成硬化覆膜。作為硬化覆膜,優選為永久絕緣覆膜,特別優選為阻焊層。The photosensitive thermosetting developing resin composition is suitable for forming a hardened film on a printed circuit board. As the hardened film, a permanent insulating film is preferred, and a solder resist layer is particularly preferred.
實施例 基於實施例及比較例更詳細地對本發明進行說明,但本發明的保護範圍及其實施方式並不限定於這些。實施例及比較例中的「份」或「%」若無特別說明則為重量基準。通過以下敘述的方法,進行本實施例的組合物的性狀值試驗。 Examples The present invention is described in more detail based on the examples and comparative examples, but the scope of protection of the present invention and its implementation are not limited to these. "Parts" or "%" in the examples and comparative examples are based on weight unless otherwise specified. The property value test of the composition of this example was carried out by the method described below.
合成例 向具有攪拌器及回流冷凝管的四口燒瓶中投入214份甲酚酚醛清漆型環氧樹脂EPICLON N-695(DIC製造、環氧當量=214),添加103份卡必醇醋酸酯、103份石油系烴溶劑(Japan Energy Corporation製造 商品名:Cactus Fines SF-01)加熱溶解。接著,添加作為阻聚劑的0.1份氫醌和作為反應催化劑的2.0份三苯基膦。將該混合物加熱至95~105℃,緩慢滴加72份丙烯酸,使其反應16小時。將得到的反應生成物冷卻至80~90℃,添加91.2份四氫鄰苯二甲酸酐使其反應8小時,冷卻後取出。如此操作得到的含羧基乙烯基酯樹脂的不揮發成分為65%,固體成分的酸值為87.5mgKOH/g。 Synthesis Example 214 parts of cresol novolac epoxy resin EPICLON N-695 (manufactured by DIC, epoxide equivalent = 214) were added to a four-necked flask equipped with a stirrer and a reflux condenser, and 103 parts of carbitol acetate and 103 parts of petroleum-based hydrocarbon solvent (manufactured by Japan Energy Corporation, trade name: Cactus Fines SF-01) were added and heated to dissolve. Next, 0.1 parts of hydroquinone as a polymerization inhibitor and 2.0 parts of triphenylphosphine as a reaction catalyst were added. The mixture was heated to 95-105°C, 72 parts of acrylic acid were slowly added dropwise, and the mixture was reacted for 16 hours. The obtained reaction product was cooled to 80-90°C, 91.2 parts of tetrahydrophthalic anhydride were added, the mixture was reacted for 8 hours, and the mixture was taken out after cooling. The carboxyl vinyl ester resin obtained in this way has a non-volatile content of 65% and an acid value of 87.5 mgKOH/g in solid components.
使用所述合成例的乙烯基酯樹脂溶液(清漆),以表1中所示的各種成分和比例(重量份)配混,用攪拌機預混合後,用3輥磨混煉,製備感光熱硬化顯影性樹脂組合物。並根據下述方法評價印刷性、鉛筆硬度和耐冷熱衝擊性。 The vinyl ester resin solution (varnish) of the above-mentioned synthesis example was mixed with the various components and proportions (weight parts) shown in Table 1, pre-mixed with a stirrer, and then kneaded with a 3-roll mill to prepare a photosensitive thermosetting developing resin composition. The printability, pencil hardness, and resistance to cold and hot shock were evaluated according to the following methods.
A 如下合成例製備的甲酚酚醛清漆型的環氧改質丙烯酸類樹脂(固體成分65%) F 顏料:酞菁綠,DIC株式會社製Pigment A 消泡劑:KS-66,信越化學工業公司製造 C-1 磷酸酯系分散劑:BYK-110,聚合磷酸酯,聚磷酸酯系聚合物,畢克化學公司製造,固體成分52質量%,吸油量63ml/100g C-2 磷酸酯系分散劑:BYK-142,2-丙烯酸-2-乙基己酯與(乙二胺和乙撐亞胺聚合物)的反應產物與聚乙烯聚丙二醇單丁醚磷酸酯的化合物),畢克化學公司製造,固體成分60質量%,吸油量29ml/100g B 光聚合起始劑:Omnirad 369 E, IGM製造 E 滑石:LMP-100, FUJI TALC INDUSTRIAL公司製造 二氧化矽:A-8矽比科Sibelco公司製造 硫酸鋇:B-30, Sakai Chemical Industry Co., Ltd.製造 H 溶劑:PGMEA,丙二醇單甲醚乙酸酯CC G 環氧樹脂:N-770-75EA,DIC公司製造,酚醛清漆型的多官能環氧樹脂,固體成分75質量% D 一分子中具有兩個以上的乙烯性不飽和基團的化合物:MT-3501G,張家港東亞迪愛生化學有限公司製 A Cresol novolac type epoxy modified acrylic resin (solid content 65%) prepared in the following synthesis example F Pigment: Phthalocyanine Green, Pigment A manufactured by DIC Corporation Defoamer: KS-66 manufactured by Shin-Etsu Chemical Co., Ltd. C-1 Phosphate ester dispersant: BYK-110, polyphosphate, polyphosphate polymer, manufactured by Beck Chemical Co., Ltd., solid content 52% by mass, oil absorption 63ml/100g C-2 Phosphate ester dispersant: BYK-142, a compound of the reaction product of 2-ethylhexyl acrylate and (polymer of ethylenediamine and ethyleneimine) and polyethylene polypropylene glycol monobutyl ether phosphate), manufactured by Beck Chemical Co., Ltd., solid content 60% by mass, oil absorption 29ml/100g B Photopolymerization initiator: Omnirad 369 E, manufactured by IGM E Talc: LMP-100, manufactured by FUJI TALC INDUSTRIAL Silica: A-8 manufactured by Sibelco Barium sulfate: B-30, manufactured by Sakai Chemical Industry Co., Ltd. H Solvent: PGMEA, propylene glycol monomethyl ether acetate CC G Epoxy resin: N-770-75EA, manufactured by DIC, a phenolic varnish type multifunctional epoxy resin, solid content 75 mass% D Compounds having two or more ethylenically unsaturated groups in one molecule: MT-3501G, manufactured by Zhangjiagang Dongya Di Ai Biochemical Co., Ltd.
性能評價: (1)印刷性 在形成有銅厚100μm的φ400μm、間距600μm的開口圖案的基板上用絲網印刷整面塗布實施例及比較例的感光熱硬化顯影性樹脂組合物,室溫靜置30分鐘後,用熱風循環式乾燥爐在80℃乾燥30分鐘,製作印刷性評價基板。使用100倍的光學顯微鏡觀察印刷性評價基板,對銅開口部的氣泡發生率進行了評價(參照圖1)。評價基準如下。 〇:氣泡發生率低於40% △:氣泡發生率40%以上低於50% ×:氣泡發生率50%以上 Performance evaluation: (1) Printability The photosensitive thermosetting developing resin composition of the embodiment and the comparative example was applied to the entire surface of a substrate with a φ400μm opening pattern with a copper thickness of 100μm and a pitch of 600μm by screen printing. After standing at room temperature for 30 minutes, it was dried in a hot air circulation drying furnace at 80°C for 30 minutes to prepare a printability evaluation substrate. The printability evaluation substrate was observed using a 100x optical microscope, and the bubble occurrence rate of the copper opening was evaluated (see Figure 1). The evaluation criteria are as follows. 0: Bubble occurrence rate less than 40% △: Bubble occurrence rate of more than 40% and less than 50% ×: Bubble occurrence rate of more than 50%
(2)鉛筆硬度 將上述實施例和比較例的感光熱硬化顯影性樹脂組合物通過絲網印刷而整面塗布到通過拋光研磨進行了前處理的敷銅箔層積板基板上,在80℃下乾燥30分鐘,冷卻至室溫,形成厚度40μm的樹脂層。對於樹脂層,使用搭載高壓水銀燈的曝光裝置以400mJ/cm 2進行圖案曝光,使用30℃的1質量%的碳酸鈉水溶液,以噴霧壓力0.15MPa的條件進行50秒顯影。根據JIS K 5600-5-4測定得到的樹脂塗膜熱硬化後的樹脂表面的鉛筆硬度。評價基準如下。 〇:鉛筆硬度6H以上 △:鉛筆硬度4H以上且低於6H ×:鉛筆硬度低於4H (2) Pencil hardness The photosensitive thermosetting developing resin composition of the above-mentioned embodiment and comparative example was applied to the entire surface of a copper foil laminate substrate that had been pre-treated by polishing and grinding by screen printing, dried at 80°C for 30 minutes, and cooled to room temperature to form a resin layer with a thickness of 40 μm. The resin layer was pattern-exposed at 400 mJ/ cm2 using an exposure device equipped with a high-pressure mercury lamp, and developed for 50 seconds using a 1 mass % sodium carbonate aqueous solution at 30°C and a spray pressure of 0.15 MPa. The pencil hardness of the resin surface of the obtained resin coating after thermal curing was measured in accordance with JIS K 5600-5-4. The evaluation criteria are as follows: ○: Pencil hardness 6H or higher △: Pencil hardness 4H or higher and lower than 6H ×: Pencil hardness lower than 4H
(3)耐冷熱衝擊性 將實施例及比較例的感光熱硬化顯影性樹脂組合物,用絲網印刷以使厚度成為40μm的方式整面塗布在形成了2mm的銅線圖案的基板上,用熱風循環乾燥爐在80℃乾燥30分鐘。冷卻至室溫後,使用搭載高壓水銀燈的曝光裝置以400mJ/cm 2進行圖案曝光,接著在1wt%的碳酸鈉水溶液、0.2MPa的壓力、液溫30℃進行60秒顯影後,在熱風循環乾燥爐中進行150℃、60分鐘硬化。通過在UV輸送爐中以累計曝光量2000mJ/cm 2的條件照射紫外線,製作形成了17個具有直角形狀的抗蝕劑圖案的冷熱循環耐裂紋性評價基板。將多個如上製作的評價基板放入在-40℃和160℃之間進行溫度循環的冷熱循環機中並設定不同循環次數,進行了耐冷熱衝擊循環試驗(TCT試驗)。然後,觀察在各個循環次數下的外觀,記錄沒有發生裂紋的最大循環次數,其評價基準如下所示(產生和未產生裂紋的示意圖參見圖2、圖3)。 ○:經過1000次循環沒有裂紋 ×:低於1000次循環時產生裂紋 (3) Resistance to thermal shock The photosensitive thermosetting developing resin composition of the embodiment and the comparative example was applied to the entire surface of a substrate having a 2 mm copper wire pattern formed thereon by screen printing so as to have a thickness of 40 μm, and dried in a hot air circulation drying oven at 80°C for 30 minutes. After cooling to room temperature, the pattern was exposed at 400 mJ/ cm2 using an exposure device equipped with a high-pressure mercury lamp, and then developed in a 1 wt% sodium carbonate aqueous solution, a pressure of 0.2 MPa, and a liquid temperature of 30°C for 60 seconds, and then cured in a hot air circulation drying oven at 150°C for 60 minutes. By irradiating ultraviolet rays in a UV conveyor furnace with a cumulative exposure of 2000mJ/ cm2 , 17 hot and cold cycle crack resistance evaluation substrates with rectangular anti-etching patterns were produced. A number of evaluation substrates produced as above were placed in a hot and cold cycler that cycles the temperature between -40°C and 160°C and set different cycles to conduct a hot and cold shock cycle test (TCT test). Then, the appearance at each cycle number was observed, and the maximum cycle number without cracks was recorded. The evaluation criteria are as follows (see Figures 2 and 3 for schematic diagrams of cracks and non-cracks). ○: No cracks after 1000 cycles ×: Cracks occurred after less than 1000 cycles
由以上可知,通過調整為實施例1~6的組成,可以得到印刷性、鉛筆硬度和耐冷熱衝擊性均優異的感光熱硬化顯影性樹脂組合物。與此相對,比較例1中,由於填料僅使用硫酸鋇,雖然印刷性和鉛筆硬度均優異,但耐冷熱衝擊性很低。比較例2中,由於填料僅使用滑石,雖然耐冷熱衝擊性優異,但印刷性和鉛筆硬度大幅惡化。比較例3使用滑石和硫酸鋇的組合,比較例4使用二氧化矽和硫酸鋇的組合,但均無法在兼顧印刷性和鉛筆硬度的基礎上實現優異的耐冷熱衝擊性。比較例5~比較例8同時使用滑石和二氧化矽,比較例5中兩者配比位於本申請範圍以外,比較例6~8中將兩者的總量增加至200重量份,耐冷熱衝擊性均無法滿足要求,比較例6和比較例8甚至有時影響印刷性或鉛筆硬度。比較例9是在實施例2的基礎上使用等量的一種磷酸酯系分散劑BYK-145,印刷性和鉛筆硬度大幅惡化。As can be seen from the above, by adjusting the composition to Examples 1 to 6, a photosensitive thermosetting developing resin composition with excellent printability, pencil hardness, and resistance to cold and hot shocks can be obtained. In contrast, in Comparative Example 1, since only barium sulfate is used as a filler, although the printability and pencil hardness are excellent, the resistance to cold and hot shocks is very low. In Comparative Example 2, since only talc is used as a filler, although the resistance to cold and hot shocks is excellent, the printability and pencil hardness are greatly deteriorated. Comparative Example 3 uses a combination of talc and barium sulfate, and Comparative Example 4 uses a combination of silica and barium sulfate, but neither can achieve excellent resistance to cold and hot shocks while taking into account both printability and pencil hardness. Comparative Examples 5 to 8 use talc and silicon dioxide at the same time. The ratio of the two in Comparative Example 5 is outside the scope of this application. In Comparative Examples 6 to 8, the total amount of the two is increased to 200 parts by weight. The cold and hot impact resistance cannot meet the requirements. Comparative Examples 6 and 8 sometimes even affect the printability or pencil hardness. Comparative Example 9 uses an equal amount of a phosphate dispersant BYK-145 on the basis of Example 2, and the printability and pencil hardness are greatly deteriorated.
[圖1]為示出實施例中用於評價印刷性的基板的圖。 [圖2]為實施例中用於評價耐冷熱衝擊性時產生裂紋的示意圖。 [圖3]為實施例中用於評價耐冷熱衝擊性時未產生裂紋的示意圖。 [Figure 1] is a diagram showing a substrate used for evaluating printability in an embodiment. [Figure 2] is a schematic diagram showing cracks generated when used for evaluating heat and cold shock resistance in an embodiment. [Figure 3] is a schematic diagram showing no cracks generated when used for evaluating heat and cold shock resistance in an embodiment.
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