JP2010078949A - Alkali developable curable composition and cured product of the same - Google Patents
Alkali developable curable composition and cured product of the same Download PDFInfo
- Publication number
- JP2010078949A JP2010078949A JP2008247539A JP2008247539A JP2010078949A JP 2010078949 A JP2010078949 A JP 2010078949A JP 2008247539 A JP2008247539 A JP 2008247539A JP 2008247539 A JP2008247539 A JP 2008247539A JP 2010078949 A JP2010078949 A JP 2010078949A
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- Prior art keywords
- acid
- group
- epoxy
- curable composition
- carboxyl group
- Prior art date
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- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 91
- 239000003513 alkali Substances 0.000 title claims description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 121
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 83
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 59
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 57
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 48
- -1 acrylate compound Chemical class 0.000 claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 40
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 40
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 20
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 61
- 239000003822 epoxy resin Substances 0.000 claims description 51
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 35
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 21
- 229920003986 novolac Polymers 0.000 claims description 19
- 238000011161 development Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 abstract description 67
- 239000000126 substance Substances 0.000 abstract description 15
- 229910000679 solder Inorganic materials 0.000 abstract description 14
- 239000000047 product Substances 0.000 abstract description 12
- 238000007747 plating Methods 0.000 abstract description 10
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052737 gold Inorganic materials 0.000 abstract description 7
- 239000010931 gold Substances 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 6
- 230000002087 whitening effect Effects 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 57
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 36
- 239000004593 Epoxy Substances 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 25
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 22
- 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 21
- 238000000576 coating method Methods 0.000 description 20
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 20
- 238000007664 blowing Methods 0.000 description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 229920006395 saturated elastomer Polymers 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 9
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 8
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 229930003836 cresol Natural products 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 8
- 239000011976 maleic acid Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical class 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 5
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 5
- 239000013039 cover film Substances 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- FNYWFRSQRHGKJT-UHFFFAOYSA-N 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane Chemical compound C1OCC1(CC)COCC1(CC)COC1 FNYWFRSQRHGKJT-UHFFFAOYSA-N 0.000 description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
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- ZIKLJUUTSQYGQI-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxypropoxy)propane Chemical compound CCOCC(C)OCC(C)OCC ZIKLJUUTSQYGQI-UHFFFAOYSA-N 0.000 description 2
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- 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
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
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Landscapes
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Abstract
Description
本発明は、プリント配線板のソルダーレジスト等の形成に使用される硬化性組成物に関し、特にカルボキシル基含有化合物を含有する硬化性組成物及びその硬化物に関する。 The present invention relates to a curable composition used for forming a solder resist of a printed wiring board, and more particularly to a curable composition containing a carboxyl group-containing compound and a cured product thereof.
現在、プリント配線板のソルダーレジストの形成に使用される硬化性化合物は、環境問題への配慮から、希アルカリ水溶液で現像ができる不飽和基及びカルボキシル基含有化合物が主流になっている。このような化合物としては、エポキシ樹脂と不飽和基含有モノカルボン酸の反応物に酸無水物を付加した硬化性化合物が一般的である。
例えば、特許文献1には、ノボラック型エポキシ樹脂と不飽和基含有モノカルボン酸の反応物に酸無水物を付加した硬化性化合物が開示されている。また、特許文献2には、1分子中に2個のグリシジル基を有する芳香族エポキシ樹脂と1分子中に2個のフェノール性水酸基を有する芳香族アルコール樹脂とを反応させて得られるアルコール性の二級の水酸基にエピハロヒドリンを反応させ、得られた反応物に不飽和基含有モノカルボン酸、次いで酸無水物を付加した硬化性化合物が開示されている。
これらの他、幾つかの硬化性化合物が提案されており、現在、実際のプリント配線板の製造に多く使用されている。
At present, unsaturated group and carboxyl group-containing compounds that can be developed with a dilute aqueous alkali solution are mainly used as curable compounds used for forming a solder resist of a printed wiring board in consideration of environmental problems. As such a compound, a curable compound obtained by adding an acid anhydride to a reaction product of an epoxy resin and an unsaturated group-containing monocarboxylic acid is generally used.
For example, Patent Document 1 discloses a curable compound obtained by adding an acid anhydride to a reaction product of a novolak type epoxy resin and an unsaturated group-containing monocarboxylic acid. Patent Document 2 discloses an alcoholic resin obtained by reacting an aromatic epoxy resin having two glycidyl groups in one molecule with an aromatic alcohol resin having two phenolic hydroxyl groups in one molecule. A curable compound in which an epihalohydrin is reacted with a secondary hydroxyl group and an unsaturated group-containing monocarboxylic acid and then an acid anhydride is added to the resulting reaction product is disclosed.
In addition to these, several curable compounds have been proposed and are currently widely used in the production of actual printed wiring boards.
近年、エレクトロニクス機器の軽薄短小化に伴いプリント配線板が高密度化されており、プリント配線板の高密度化に対応して、ソルダーレジストを形成する硬化性化合物の高性能化が要求されている。即ち、高密度化プリント配線板の製造では、従来市販されている硬化性化合物の現像性が十分でないためにソルダーレジストの極微細なパターンが得られず、また、従来の硬化性化合物を用いてソルダーレジストを形成した高密度化のプリント配線板では、高温及び高湿下での電気絶縁性が低下し、さらに、従来の硬化性化合物を用いて得られたソルダーレジストは、十分な可撓性がないためにフレキシブルプリント配線板に適用できず、これらの問題の解決のために硬化性化合物のいっそうの高性能化が要求されている。 In recent years, printed circuit boards have been densified as electronic devices have become lighter, thinner, and smaller, and higher performance of curable compounds that form solder resists is required in response to the increased density of printed circuit boards. . That is, in the production of a high-density printed wiring board, since the developability of a curable compound that has been commercially available is not sufficient, an extremely fine pattern of a solder resist cannot be obtained, and a conventional curable compound is used. In a high-density printed wiring board on which a solder resist is formed, the electrical insulation under high temperature and high humidity is reduced, and the solder resist obtained using a conventional curable compound is sufficiently flexible. Therefore, in order to solve these problems, higher performance of the curable compound is required.
可撓性の問題を解決する硬化性化合物として、例えば、ビスフェノールA型エポキシ樹脂のアルコール性の二級の水酸基に、エピハロルヒドリンを反応させ、次いで得られた多官能エポキシ樹脂に、エポキシ当量当たり0.2〜1.2モルのエチレン性不飽和カルボン酸を反応させ、さらにエポキシ当量当たり0.2〜1.0モルの多塩基カルボン酸又はその無水物あるいはその両方を反応させて得られるカルボキシル基含有化合物が提案されている(特許文献3参照)。
また、特許文献4には、ノボラック型エポキシ樹脂及びゴム変性ビスフェノールA型エポキシ樹脂の混合物と該混合物のエポキシ当量当たり0.2〜1.2モルのエチレン性不飽和カルボン酸とを反応させ、得られた反応生成物と、上記混合物のエポキシ当量当たり0.2〜1.0モルの多塩基カルボン酸及び/又はその無水物とを反応させて得られるカルボキシル基含有化合物が開示されている。
As a curable compound that solves the problem of flexibility, for example, an alcoholic secondary hydroxyl group of bisphenol A type epoxy resin is reacted with epihalohydrin, and then the resulting polyfunctional epoxy resin has an epoxy equivalent weight. It is obtained by reacting 0.2 to 1.2 mol of ethylenically unsaturated carboxylic acid per unit, and further reacting 0.2 to 1.0 mol of polybasic carboxylic acid or its anhydride or both per epoxy equivalent. A carboxyl group-containing compound has been proposed (see Patent Document 3).
Patent Document 4 discloses that a mixture of a novolac type epoxy resin and a rubber-modified bisphenol A type epoxy resin is reacted with 0.2 to 1.2 mol of ethylenically unsaturated carboxylic acid per epoxy equivalent of the mixture. A carboxyl group-containing compound obtained by reacting the obtained reaction product with 0.2 to 1.0 mol of a polybasic carboxylic acid and / or its anhydride per epoxy equivalent of the above mixture is disclosed.
特許文献3や特許文献4のカルボキシル基含有化合物を用いてレジストを形成した高密度化プリント配線板は、可撓性に優れている。しかし、これらカルボキシル基含有化合物は、多官能エポキシ樹脂や、ノボラック型エポキシ樹脂とゴム変性ビスフェノールA型エポキシ樹脂の混合物に対するエチレン性不飽和カルボン酸の反応割合がある範囲内のときはゲル化したり、高分子化したりするため、十分な現像性が得られない。
即ち、特許文献3や特許文献4のカルボキシル基含有化合物は、多官能エポキシ樹脂や、ノボラック型エポキシ樹脂とゴム変性ビスフェノールA型エポキシ樹脂の混合物に、エポキシ当量当たり0.2〜1.2モルのエチレン性不飽和カルボン酸を反応させて得られる生成物に、エポキシ当量当たり、0.2〜1.0モルの多塩基カルボン酸及び/又はその無水物を反応させて得られるが、多塩基カルボン酸及び/又はその無水物の反応割合が上記範囲内のときに、多官能エポキシ樹脂や、ノボラック型エポキシ樹脂とゴム変性ビスフェノールA型エポキシ樹脂の混合物に対してエポキシ当量当たり1モル未満のエチレン性不飽和カルボン酸を反応させると、多塩基カルボン酸及び/又はその無水物が上記エチレン性不飽和基含有エポキシ樹脂の架橋剤として働き、ゲル化、又は高分子化して現像性が低下する。
The high-density printed wiring board in which a resist is formed using the carboxyl group-containing compounds of Patent Document 3 and Patent Document 4 is excellent in flexibility. However, these carboxyl group-containing compounds are gelled when the reaction ratio of the ethylenically unsaturated carboxylic acid to the polyfunctional epoxy resin or the mixture of the novolac type epoxy resin and the rubber-modified bisphenol A type epoxy resin is within a certain range, Sufficient developability cannot be obtained due to polymerization.
That is, the carboxyl group-containing compounds of Patent Document 3 and Patent Document 4 are 0.2 to 1.2 moles per epoxy equivalent in a polyfunctional epoxy resin or a mixture of a novolac epoxy resin and a rubber-modified bisphenol A epoxy resin. The product obtained by reacting an ethylenically unsaturated carboxylic acid can be obtained by reacting 0.2 to 1.0 mol of a polybasic carboxylic acid and / or its anhydride per epoxy equivalent. When the reaction ratio of the acid and / or anhydride thereof is within the above range, the ethylenic property is less than 1 mol per epoxy equivalent with respect to the polyfunctional epoxy resin or the mixture of the novolac type epoxy resin and the rubber-modified bisphenol A type epoxy resin. When the unsaturated carboxylic acid is reacted, the polybasic carboxylic acid and / or its anhydride is converted into the above ethylenically unsaturated group-containing epoxy resin. As a cross-linking agent, it develops into a gel or polymer and deteriorates the developability.
一方、このような高分子化を利用して硬化性組成物の塗膜のタック(粘着)フリー性を向上させる方法が提案されている(特許文献5参照)。タックフリー性は液状現像型レジストの重要な特性の一つであるが、アルカリ現像性と背反する特性である。そこで、特許文献5に開示された硬化性化合物では、ヒドロキシル基に多塩基酸及び/又は多塩基酸無水物を付加反応させることにより、硬化性組成物の塗膜のタックフリー性と現像性の両立を図っている。しかし、それでもなお、近年のエレクトロニクス機器の軽薄短小化に伴うプリント配線板の高密度化に対応した十分な現像性は得られていない。 On the other hand, a method for improving the tack (adhesion) -free property of the coating film of the curable composition by utilizing such polymerization has been proposed (see Patent Document 5). The tack-free property is one of the important characteristics of the liquid development type resist, but is a characteristic contrary to the alkali developability. Therefore, in the curable compound disclosed in Patent Document 5, the tack-free property and developability of the coating film of the curable composition are obtained by addition reaction of a polybasic acid and / or a polybasic acid anhydride to the hydroxyl group. We are trying to achieve both. However, sufficient developability corresponding to the increase in the density of printed wiring boards accompanying the recent reduction in the thickness and size of electronic devices has not been obtained.
また、可撓性、さらには電気絶縁性の問題を解決するために、ノボラック型フェノール樹脂とアルキレンオキシドとの反応生成物に不飽和基含有モノカルボン酸を反応させ、得られた反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有化合物(特許文献6参照)、ノボラック型フェノール樹脂とアルキレンオキシド又は環状カーボネートとの反応生成物に不飽和基含有モノカルボン酸及び飽和脂肪族モノカルボン酸及び/又は芳香族モノカルボン酸を反応させ、得られた反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有化合物(特許文献7参照)等が提案されている。しかしながら、上記化合物は現像性に劣る。また、上記化合物を用いてレジストを形成したプリント配線板は、高温及び高湿下での電気絶縁性には優れているが、硬度が低い。
本発明は前記のような問題に鑑みなされたものであり、現像性に優れ、且つ、硬度、はんだ耐熱性、耐薬品性、密着性、PCT耐性、無電解金めっき耐性、白化耐性、電気絶縁性、可撓性などの特性に優れる硬化膜を形成できる硬化性組成物及びその硬化物を提供することを目的とするものである。 The present invention has been made in view of the problems as described above, has excellent developability, and has hardness, solder heat resistance, chemical resistance, adhesion, PCT resistance, electroless gold plating resistance, whitening resistance, electrical insulation. It aims at providing the curable composition which can form the cured film excellent in characteristics, such as property and flexibility, and its hardened | cured material.
上記課題を解決するために成された本発明に係るアルカリ現像可能な硬化性組成物は、(A)1分子中に2個以上のエポキシ基を有する樹脂(a)のエポキシ基に、エポキシ基1当量に対してモノカルボン酸(b)を0.3〜0.9モルの割合で反応させ、得られた反応生成物(c)のエポキシ基に、エポキシ基1当量に対して多塩基酸(d)を0.2〜5モルの割合で反応させ、得られた反応生成物(e)のエポキシ基に、エポキシ基1当量に対してモノカルボン酸(f)を0.0〜5.0モルの割合で反応させて得られる酸価18〜180mgKOH/gの反応生成物(g)の2級のアルコール性水酸基に、さらに多塩基酸無水物(h)を反応させて得られる酸価40〜200mgKOH/gのカルボキシル基含有化合物、
(B)カルボキシル基含有化合物(A)以外のカルボキシル基含有化合物、
(C)感光性(メタ)アクリレート化合物、及び
(D)光重合開始剤
を含有することを特徴とする。
The curable composition capable of being developed with an alkali according to the present invention, which has been made to solve the above-mentioned problems, is (A) an epoxy group in the epoxy group of the resin (a) having two or more epoxy groups in one molecule The monocarboxylic acid (b) is reacted at a ratio of 0.3 to 0.9 mol with respect to 1 equivalent, and a polybasic acid is added to the epoxy group of the obtained reaction product (c) with respect to 1 equivalent of the epoxy group. (D) is reacted at a ratio of 0.2 to 5 moles, and the monocarboxylic acid (f) is added to the epoxy group of the obtained reaction product (e) in an amount of 0.0 to 5.5 with respect to 1 equivalent of the epoxy group. Acid value obtained by further reacting polybasic acid anhydride (h) with the secondary alcoholic hydroxyl group of the reaction product (g) having an acid value of 18 to 180 mgKOH / g obtained by reacting at a ratio of 0 mol. 40-200 mg KOH / g carboxyl group-containing compound,
(B) a carboxyl group-containing compound other than the carboxyl group-containing compound (A),
It contains (C) a photosensitive (meth) acrylate compound, and (D) a photopolymerization initiator.
本発明の具体的で好適な態様によれば、硬化性組成物の一成分であるカルボキシル基含有化合物(A)は、モノカルボン酸(b)及びモノカルボン酸(f)が不飽和基含有モノカルボン酸であり、又はモノカルボン酸(b)が不飽和基含有モノカルボン酸であり、モノカルボン酸(f)が不飽和基を含有しないモノカルボン酸であり、又はモノカルボン酸(b)が不飽和基を含有しないモノカルボン酸であり、モノカルボン酸(f)が不飽和基含有モノカルボン酸であり、又はモノカルボン酸(b)及びモノカルボン酸(f)が不飽和基を含有しないモノカルボン酸であり、又はモノカルボン酸(b)及び/又は(f)が不飽和基含有モノカルボン酸と不飽和基を含有しないモノカルボン酸の混合物であり、又は多塩基酸(d)がマロン酸又はマロン酸と他の二塩基酸との混合物であり、特に1分子中に2個以上のエポキシ基を有する樹脂(a)がノボラック型エポキシ樹脂である。 According to a specific and preferred embodiment of the present invention, the carboxyl group-containing compound (A), which is one component of the curable composition, is composed of a monocarboxylic acid (b) and a monocarboxylic acid (f) containing an unsaturated group-containing compound. A carboxylic acid, a monocarboxylic acid (b) is an unsaturated group-containing monocarboxylic acid, a monocarboxylic acid (f) is a monocarboxylic acid not containing an unsaturated group, or a monocarboxylic acid (b) is The monocarboxylic acid does not contain an unsaturated group, the monocarboxylic acid (f) is an unsaturated group-containing monocarboxylic acid, or the monocarboxylic acid (b) and the monocarboxylic acid (f) do not contain an unsaturated group A monocarboxylic acid, or the monocarboxylic acid (b) and / or (f) is a mixture of an unsaturated group-containing monocarboxylic acid and a monocarboxylic acid not containing an unsaturated group, or a polybasic acid (d) Malonic acid or A mixture of malonic acid and other dibasic acids, resins having two or more epoxy groups (a) is a novolak epoxy resin, especially in the molecule.
本発明によれば、プリント配線板の高密度化に対応可能な硬化性組成物に要求される現像性を充分に満足し、且つ硬度、はんだ耐熱性、耐薬品性、密着性、PCT耐性、無電解金めっき耐性、白化耐性、電気絶縁性、可撓性などに優れた硬化膜を得ることができる。 According to the present invention, sufficiently satisfying the developability required for a curable composition capable of supporting high density of printed wiring boards, and hardness, solder heat resistance, chemical resistance, adhesion, PCT resistance, A cured film excellent in electroless gold plating resistance, whitening resistance, electrical insulation, flexibility and the like can be obtained.
本発明者らは、前記の課題を解決するため鋭意検討を重ねた結果、1分子中に2個以上のエポキシ基を有する樹脂のエポキシ基にモノカルボン酸を部分的に付加反応させ、次いで残りのエポキシ基に多塩基酸を部分的又は全部に付加反応させ、次いで多塩基酸が部分的に付加されている場合には、残りのエポキシ基にモノカルボン酸を付加反応させ、最後に得られた反応生成物の2級のアルコール性水酸基に、多塩基酸無水物を反応させることによって得られる硬化性化合物を含む組成物が、ゲル化することなく、現像性に優れ、また優れた硬度、はんだ耐熱性、耐薬品性、密着性、PCT耐性、無電解金めっき耐性、白化耐性、電気絶縁性、可撓性を持つ硬化物を与えることを見出し、本発明を完成させるに至ったものである。 As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have made a partial addition reaction of a monocarboxylic acid to an epoxy group of a resin having two or more epoxy groups in one molecule, and then the rest When the polybasic acid is partially or fully added to the epoxy group of the product, and then the polybasic acid is partially added, the remaining epoxy group is added with a monocarboxylic acid, and finally obtained. The composition containing a curable compound obtained by reacting a secondary alcoholic hydroxyl group of the reaction product with a polybasic acid anhydride is excellent in developability without gelling, and has excellent hardness, Found to give a cured product with solder heat resistance, chemical resistance, adhesion, PCT resistance, electroless gold plating resistance, whitening resistance, electrical insulation, flexibility, and completed the present invention. is there.
すなわち、本発明の硬化性組成物の一成分であるカルボキシル基含有化合物(A)は、1分子中に2個以上のエポキシ基を有する樹脂(a)にモノカルボン酸(b)を部分的に付加させることによって、ゲル化させることなく、その反応生成物(c)のエポキシ基に多塩基酸(d)を付加させることができ、さらにモノカルボン酸(f)を残存するエポキシ基に付加させることができ、その結果、その後の2級のアルコール性水酸基への多塩基酸無水物の反応を容易にさせることができることで、得られるが、優れた現像性を示し、また反応性にも優れるため、このカルボキシル基含有化合物(A)に他のカルボキシル基含有化合物(B)、感光性(メタ)アクリレート化合物及び光重合開始剤を加えた組成物は、架橋密度の高い、優れた特性を持つ硬化物を与える。 That is, the carboxyl group-containing compound (A), which is one component of the curable composition of the present invention, partially converts the monocarboxylic acid (b) to the resin (a) having two or more epoxy groups in one molecule. By adding, the polybasic acid (d) can be added to the epoxy group of the reaction product (c) without gelation, and the monocarboxylic acid (f) is further added to the remaining epoxy group. As a result, it can be obtained by facilitating the subsequent reaction of the polybasic acid anhydride with the secondary alcoholic hydroxyl group, but it exhibits excellent developability and excellent reactivity. Therefore, a composition obtained by adding another carboxyl group-containing compound (B), a photosensitive (meth) acrylate compound, and a photopolymerization initiator to this carboxyl group-containing compound (A) has a high crosslinking density and an excellent characteristic. Give a cured product with.
尚、カルボキシル基含有化合物(A)の製造において、反応生成物(c)のエポキシ基に対する多塩基酸(d)の付加によってカルボキシル基が得られるが、反応生成物(c)に多塩基酸(d)がすべて反応するとは限らない。その場合、未反応のエポキシ基の存在において、反応生成物(e)と多塩基酸(d)の混合物が得られる。その後、それらの混合物の反応生成物(e)にモノカルボン酸(f)を反応させることができる。それで、カルボキシル基含有化合物(A)は未反応の多塩基酸(d)及び未反応のモノカルボン酸(f)と混合した状態で得られる場合があるが、未反応の多塩基酸(d)及び未反応のモノカルボン酸(f)の存在・非存在に関係なく、ゲル化することなく、保存安定性に優れる。 In the production of the carboxyl group-containing compound (A), a carboxyl group is obtained by adding a polybasic acid (d) to the epoxy group of the reaction product (c), but the reaction product (c) has a polybasic acid ( Not all d) react. In that case, a mixture of the reaction product (e) and the polybasic acid (d) is obtained in the presence of an unreacted epoxy group. Thereafter, the monocarboxylic acid (f) can be reacted with the reaction product (e) of the mixture. Thus, the carboxyl group-containing compound (A) may be obtained in a state where it is mixed with the unreacted polybasic acid (d) and the unreacted monocarboxylic acid (f), but the unreacted polybasic acid (d) In addition, regardless of the presence / absence of the unreacted monocarboxylic acid (f), it is excellent in storage stability without gelation.
以下、本発明に係る光及び/又は熱硬化性組成物について詳細に説明する。
まず、本発明の一成分であるカルボキシル基含有化合物(A)は、前記したように、1分子中に2個以上のエポキシ基を有する樹脂(a)のエポキシ基に、エポキシ基1当量に対して、モノカルボン酸(b)を0.3〜0.9モルの割合で反応させ、得られた反応生成物(c)のエポキシ基に、エポキシ基1当量に対して、多塩基酸(d)を0.2〜5モルの割合で反応させ、得られた反応生成物(e)のエポキシ基に、エポキシ基1当量に対して、モノカルボン酸(f)を0.0〜5.0モルの割合で反応させて得られる酸価18〜180mgKOH/gの反応生成物(g)の2級のアルコール性水酸基に、さらに多塩基酸無水物(h)を反応させて得られるが、各反応は、後述するような触媒を用い、溶媒中又は無溶媒下で容易に行なわれる。
Hereinafter, the light and / or thermosetting composition according to the present invention will be described in detail.
First, as described above, the carboxyl group-containing compound (A) which is one component of the present invention is added to the epoxy group of the resin (a) having two or more epoxy groups in one molecule with respect to 1 equivalent of the epoxy group. Then, the monocarboxylic acid (b) is reacted at a ratio of 0.3 to 0.9 mol, and the polybasic acid (d) is added to the epoxy group of the obtained reaction product (c) with respect to 1 equivalent of the epoxy group. ) At a ratio of 0.2 to 5 mol, and the epoxy group of the obtained reaction product (e) is added to the monocarboxylic acid (f) in an amount of 0.0 to 5.0 with respect to 1 equivalent of the epoxy group. It can be obtained by reacting polybasic acid anhydride (h) with the secondary alcoholic hydroxyl group of the reaction product (g) having an acid value of 18 to 180 mgKOH / g obtained by reacting at a molar ratio. The reaction is easily carried out in a solvent or without solvent using a catalyst as described below. That.
1分子中に2個以上のエポキシ基を有する樹脂(a)としては、例えば、ジャパンエポキシレジン(株)製のエピコート828、エピコート834、エピコート1001、エピコート1004、大日本インキ化学工業(株)製のエピクロン840、エピクロン850、エピクロン1050、エピクロン2055、東都化成(株)製のエポトートYD−011、YD−013、YD−127、YD−128、ダウケミカル(株)製のD.E.R.317、D.E.R.331、D.E.R.661、D.E.R.664、住友化学工業(株)製のスミ−エポキシESA−011、ESA−014、ELA−115、ELA−128(何れも商品名)等のビスフェノールA型エポキシ樹脂;ジャパンエポキシレジン(株)製のエピコートYL903、大日本インキ化学工業(株)製のエピクロン152、エピクロン165、東都化成(株)製のエポトートYDB−400、YDB−500、ダウケミカル(株)製のD.E.R.542、住友化学工業(株)製のスミ−エポキシESB−400、ESB−700(何れも商品名)等のブロム化エポキシ樹脂;ジャパンエポキシレジン(株)製のエピコート152、エピコート154、ダウケミカル(株)製のD.E.N.431、D.E.N.438、大日本インキ化学工業(株)製のエピクロンN−730、エピクロンN−770、エピクロンN−865、東都化成(株)製のエポトートYDCN−701、YDCN−704、日本化薬(株)製のEPPN−201、EOCN−1025、EOCN−1020,EOCN−104S、RE−306、住友化学工業(株)製のスミ−エポキシESCN−195X、ESCN−220(何れも商品名)等のノボラック型エポキシ樹脂;大日本インキ化学工業(株)製のエピクロン830、ジャパンエポキシレジン製エピコート807、東都化成(株)製のエポトートYDF−170、YDF−175、YDF−2004(何れも商品名)等のビスフェノールF型エポキシ樹脂;東都化成(株)製のエポトートST−2004、ST−2007、ST−3000(何れも商品名)等の水添ビスフェノールA型エポキシ樹脂;ジャパンエポキシレジン(株)製のエピコート604、東都化成(株)製のエポトートYH−434、住友化学工業(株)製のスミ−エポキシELM−120(何れも商品名)等のグリシジルアミン型エポキシ樹脂;ダイセル化学工業(株)製のセロキサイド2021(商品名)等の脂環式エポキシ樹脂;ジャパンエポキシレジン(株)製のYL−933、日本化薬(株)製のEPPN−501、EPPN−502(何れも商品名)等のトリヒドロキシフェニルメタン型エポキシ樹脂;ジャパンエポキシレジン(株)製のYL−6056、YX−4000、YL−6121(何れも商品名)等のビキシレノール型もしくはビフェノール型エポキシ樹脂又はそれらの混合物;日本化薬(株)製のEBPS−200、旭電化工業(株)製のEPX−30、大日本インキ化学工業(株)製のEXA−1514(何れも商品名)等のビスフェノールS型エポキシ樹脂;ジャパンエポキシレジン(株)製のエピコート157S(商品名)等のビスフェノールAノボラック型エポキシ樹脂;ジャパンエポキシレジン(株)製のエピコートYL−931(商品名)等のテトラフェニロールエタン型エポキシ樹脂;日産化学(株)製のTEPIC(商品名)等の複素環式エポキシ樹脂;日本油脂(株)製のブレンマーDGT(商品名)等のジグリシジルフタレート樹脂;東都化成(株)製のZX−1063(商品名)等のテトラグリシジルキシレノイルエタン樹脂;新日鉄化学(株)製のESN−190、ESN−360、大日本インキ化学工業(株)製のHP−4032、EXA−4750、EXA−4700(何れも商品名)等のナフタレン基含有エポキシ樹脂;大日本インキ化学工業(株)製のHP−7200、HP−7200H(何れも商品名)等のジシクロペンタジエン骨格を有するエポキシ樹脂;日本油脂(株)製のCP−50S、CP−50M(何れも商品名)等のグリシジルメタアクリレート共重合系エポキシ樹脂;シクロヘキシルマレイミドとグリシジルメタアクリレートの共重合エポキシ樹脂;1,5−ジヒドロキシナフタレンとビスフェノールA型エポキシ樹脂とを反応させて得られるアルコール性の二級の水酸基に、エピハロルヒドリンを反応させて得られる多官能エポキシ樹脂(国際公開WO 01/024774号公報);エポキシ基の一部にケトンを付加反応させて得られる1,3−ジオキソラン環を有するエポキシ樹脂(特開2007−176987号公報)等を挙げることができるが、これらに限られるものではない。これらのエポキシ樹脂は、単独で又は2種類以上を混合して用いることができる。 Examples of the resin (a) having two or more epoxy groups in one molecule include, for example, Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, and Dainippon Ink and Chemicals, manufactured by Japan Epoxy Resin Co., Ltd. Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Tohto Kasei Co., Ltd., D. Chemicals manufactured by Dow Chemical Co., Ltd. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Sumitomo Chemical Co., Ltd. bisphenol A type epoxy resins such as Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128 (all trade names); manufactured by Japan Epoxy Resin Co., Ltd. Epicort YL903, Daikoku Ink Chemical Co., Ltd. Epicron 152, Epicron 165, Toto Kasei Co., Ltd. Epototo YDB-400, YDB-500, Dow Chemical Co., Ltd. E. R. 542, brominated epoxy resins such as Sumi-epoxy ESB-400 and ESB-700 (both trade names) manufactured by Sumitomo Chemical Co., Ltd .; Epicoat 152, Epicoat 154, Dow Chemical (manufactured by Japan Epoxy Resin Co., Ltd.) D. manufactured by Co., Ltd. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, manufactured by Dainippon Ink & Chemicals, Inc. Epototo YDCN-701, YDCN-704, manufactured by Tohto Kasei Co., Ltd., manufactured by Nippon Kayaku Co., Ltd. Novolak type epoxy such as EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Epoxy ESCN-195X, ESCN-220 (all trade names) manufactured by Sumitomo Chemical Co., Ltd. Resins; Bisphenols such as Epiklon 830 manufactured by Dainippon Ink & Chemicals, Ltd., Epicoat 807 manufactured by Japan Epoxy Resin, Epototo YDF-170, YDF-175, YDF-2004 manufactured by Toto Kasei Co., Ltd. (all trade names) F-type epoxy resin; Epototo ST-2004, ST-2 manufactured by Tohto Kasei Co., Ltd. Hydrogenated bisphenol A type epoxy resin such as 07 and ST-3000 (all are trade names); Epicoat 604 manufactured by Japan Epoxy Resin Co., Ltd., Epototo YH-434 manufactured by Toto Kasei Co., Ltd., Sumitomo Chemical Co., Ltd. Glycidylamine type epoxy resin such as Sumi-Epoxy ELM-120 (both trade names) manufactured by Daicel Chemical Industries Ltd. Alicyclic epoxy resin such as Celoxide 2021 (trade name) manufactured by Daicel Chemical Industries, Ltd .; Japan Epoxy Resin Co., Ltd. YL-933 manufactured by Nippon Kayaku Co., Ltd., EPPN-501 manufactured by Nippon Kayaku Co., Ltd., trihydroxyphenylmethane type epoxy resin such as EPPN-502 (both trade names); YL-6056 manufactured by Japan Epoxy Resin Co., Ltd., YX -4000, YL-6121 (both trade names) and other bixylenol type or biphenol type epoxy resins or EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by Dainippon Ink & Chemicals Co., Ltd. (all trade names), etc. Bisphenol S type epoxy resin; Bisphenol A novolac type epoxy resin such as Epicoat 157S (trade name) manufactured by Japan Epoxy Resin Co., Ltd .; Tetraphenylol such as Epicoat YL-931 (trade name) manufactured by Japan Epoxy Resin Co., Ltd. Ethane type epoxy resin; heterocyclic epoxy resin such as TEPIC (trade name) manufactured by Nissan Chemical Co., Ltd .; diglycidyl phthalate resin such as Blemmer DGT (trade name) manufactured by Nippon Oil &Fats; Toto Kasei Co., Ltd. Tetraglycidylxylenoylethane resin such as ZX-1063 (trade name) manufactured by Nippon Steel Chemical Co., Ltd .; ESN-190, ESN- manufactured by Nippon Steel Chemical Co., Ltd. 360, Naphthalene group-containing epoxy resins such as HP-4032, EXA-4750, EXA-4700 (all trade names) manufactured by Dainippon Ink & Chemicals, Inc .; HP-7200 manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin having a dicyclopentadiene skeleton such as HP-7200H (all trade names); Glycidyl methacrylate copolymer epoxy such as CP-50S and CP-50M (all trade names) manufactured by NOF Corporation Resin; Copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epihalohydrin is reacted with an alcoholic secondary hydroxyl group obtained by reacting 1,5-dihydroxynaphthalene and bisphenol A type epoxy resin. Polyfunctional epoxy resin obtained (International Publication WO 01/024774); Examples thereof include, but are not limited to, epoxy resins having a 1,3-dioxolane ring obtained by addition reaction of a ketone with a part of a poxy group (Japanese Patent Laid-Open No. 2007-176987). These epoxy resins can be used individually or in mixture of 2 or more types.
これらのエポキシ樹脂の中でも好ましいのは、1分子中に3個以上のエポキシ基を有する樹脂であり、より好ましくは、ノボラック型エポキシ樹脂である。 Among these epoxy resins, a resin having 3 or more epoxy groups in one molecule is preferable, and a novolac type epoxy resin is more preferable.
上記エポキシ樹脂(a)に、部分的にモノカルボン酸(b)を付加反応させるが、その際、重合禁止剤及び触媒を用いて溶媒中で反応を行うことが好ましく、反応温度は好ましくは50〜150℃、より好ましくは70〜120℃である。上記エポキシ樹脂(a)のエポキシ基に、エポキシ基1当量に対して、モノカルボン酸(b)を0.3〜0.9モルの割合で反応させるが、好ましくは、0.5〜0.9モルである。モノカルボン酸(b)が0.3モル未満では、この後の反応でゲル化する。 The epoxy resin (a) is partially reacted with the monocarboxylic acid (b). In this case, the reaction is preferably performed in a solvent using a polymerization inhibitor and a catalyst, and the reaction temperature is preferably 50. It is -150 degreeC, More preferably, it is 70-120 degreeC. The monocarboxylic acid (b) is reacted with the epoxy group of the epoxy resin (a) at a ratio of 0.3 to 0.9 mol with respect to 1 equivalent of the epoxy group. 9 moles. When the monocarboxylic acid (b) is less than 0.3 mol, gelation occurs in the subsequent reaction.
前記モノカルボン酸(b)の代表的なものとしては、アクリル酸、メタクリル酸、クロトン酸、桂皮酸、α−シアノ桂皮酸、β−スチリルアクリル酸、β−フルフリルアクリル酸などの不飽和基含有モノカルボン酸、ギ酸、酢酸、プロピオン酸、n-酪酸、イソ酪酸、バレリアン酸、トリメチル酢酸、カプロン酸、カプリル酸、ペラルゴン酸、カプリン酸、ウンデシル酸、ラウリン酸、トリデシル酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、ヘプタデシル酸、ステアリン酸、ノナデカン酸、アラキン酸、ベヘン酸などの飽和脂肪族モノカルボン酸、安息香酸、アルキル安息香酸、アルキルアミノ安息香酸、ハロゲン化安息香酸、フェニル酢酸、アニス酸、ベンゾイル安息香酸、ナフトエ酸などの芳香族モノカルボン酸などが挙げられるが、これらに限られるものではない。これらモノカルボン酸は、単独で又は2種類以上を混合して用いることができる。ここで特に好ましいのはアクリル酸、メタクリル酸、安息香酸、及び酢酸である。 Representative examples of the monocarboxylic acid (b) include unsaturated groups such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Containing monocarboxylic acid, formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, valeric acid, trimethylacetic acid, caproic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecyl Acids, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid and other saturated aliphatic monocarboxylic acids, benzoic acid, alkylbenzoic acid, alkylaminobenzoic acid, halogenated benzoic acid, phenylacetic acid, anisic acid Aromatic monocarboxylic acids such as benzoylbenzoic acid and naphthoic acid The present invention is not limited to these. These monocarboxylic acids can be used alone or in admixture of two or more. Particularly preferred here are acrylic acid, methacrylic acid, benzoic acid and acetic acid.
反応溶媒としては、例えば、メチルエチルケトン、シクロヘキサノン等のケトン類;トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類;エチレングリコールモノエチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類;酢酸エチル、酢酸ブチル、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート等の酢酸エステル類;エタノール、プロパノール、エチレングリコール、プロピレングリコール等のアルコール類;オクタン、デカン等の脂肪族炭化水素;石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤などが挙げられるが、これらに限られるものではない。これらの有機溶剤は、単独で又は2種類以上を混合して用いることができる。 Examples of the reaction solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether , Glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate , Ethylene glycol monobutyl ether Acetates such as cetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; octane, decane, etc. Aliphatic hydrocarbons: Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha are exemplified, but not limited thereto. These organic solvents can be used alone or in admixture of two or more.
反応触媒としては、例えば、トリエチルアミン等の三級アミン、トリエチルベンジルアンモニウムクロライド等の4級アンモニウム塩、2−エチル−4−メチルイミダゾール等のイミダゾール化合物、トリフェニルホスフィン等のリン化合物、ナフテン酸、ラウリン酸、ステアリン酸、オレイン酸やオクトエン酸のリチウム、クロム、ジルコニウム、カリウム、ナトリウム等の有機酸の金属塩などが挙げられるが、これらに限られるものではない。これらの反応触媒は、単独で又は2種類以上を混合して用いることができる。 Examples of the reaction catalyst include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, phosphorus compounds such as triphenylphosphine, naphthenic acid, and laurin. Examples include, but are not limited to, metal salts of organic acids such as lithium, chromium, zirconium, potassium, and sodium of acid, stearic acid, oleic acid, and octoenoic acid. These reaction catalysts can be used alone or in admixture of two or more.
重合禁止剤としては、例えば、ハイドロキノン、メチルハイドロキノン、ハイドロキノンモノメチルエーテル、カテコール、ピロガロール、フェノチアジンなどが挙げられるが、これらに限られるものではない。これらの重合禁止剤は、単独で又は2種類以上を混合して用いることができる。 Examples of the polymerization inhibitor include, but are not limited to, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, phenothiazine, and the like. These polymerization inhibitors can be used alone or in admixture of two or more.
さらに、前記反応生成物(c)のエポキシ基に多塩基酸(d)を付加させるが、反応温度は、好ましくは50〜150℃、より好ましくは70〜120℃である。前記反応生成物(c)のエポキシ基に、エポキシ基1当量に対して、多塩基酸(d)を0.2〜5.0モルの割合で反応させるが、好ましくは、0.2〜2.0モルである。多塩基酸(d)が0.2〜5.0モルの範囲を外れると、多量の未反応の多塩基酸(d)が残り、本発明の硬化性組成物の硬化膜に悪影響を及ぼす。 Furthermore, polybasic acid (d) is added to the epoxy group of the reaction product (c), and the reaction temperature is preferably 50 to 150 ° C, more preferably 70 to 120 ° C. The polybasic acid (d) is reacted with the epoxy group of the reaction product (c) at a ratio of 0.2 to 5.0 mol with respect to 1 equivalent of the epoxy group, preferably 0.2 to 2 0.0 mole. When the polybasic acid (d) is out of the range of 0.2 to 5.0 mol, a large amount of unreacted polybasic acid (d) remains and adversely affects the cured film of the curable composition of the present invention.
多塩基酸(d)の代表的なものとしては、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、マレイン酸、フマル酸、フタル酸、イソフタル酸、テレフタル酸、テトラヒドロフタル酸、メタントリカルボン酸、トリカルバリル酸、ベンゼントリカルボン酸、ベンゼンテトラカルボン酸等が挙げられるが、これらに限られるものではない。これらの多塩基酸は、単独で又は2種類以上を混合して用いることができる。これらの中でも、二塩基酸が好ましく、より好ましくは、マロン酸、グルタル酸、マレイン酸、テトラヒドロフタル酸及びフタル酸であり、特に好ましくは、マロン酸、マロン酸と他の二塩基酸との混合物である。但し、前記反応生成物(c)のマロン酸と他の二塩基酸との混合物の反応において、(N1)マロン酸と他の二塩基酸との混合物は前記反応生成物(c)に同時に、又は(N2)マロン酸と他の二塩基酸とは時間差で前記反応生成物(c)に、反応させることができる。特に、(N2)は、マロン酸と他の二塩基酸の反応容器への投入時間をずらすことでなされる。 Representative examples of the polybasic acid (d) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, Examples include, but are not limited to, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, methanetricarboxylic acid, tricarballylic acid, benzenetricarboxylic acid, and benzenetetracarboxylic acid. These polybasic acids can be used alone or in admixture of two or more. Among these, dibasic acid is preferable, more preferably malonic acid, glutaric acid, maleic acid, tetrahydrophthalic acid and phthalic acid, and particularly preferable is malonic acid, a mixture of malonic acid and other dibasic acids. It is. However, in the reaction of the mixture of malonic acid and other dibasic acid of the reaction product (c), the mixture of (N1) malonic acid and other dibasic acid is simultaneously added to the reaction product (c). Alternatively, (N2) malonic acid and another dibasic acid can be reacted with the reaction product (c) with a time difference. In particular, (N2) is made by shifting the charging time of malonic acid and another dibasic acid into the reaction vessel.
前記エポキシ樹脂(a)にモノカルボン酸(b)、次いで多塩基酸(d)を付加させた後、残存するエポキシ基にモノカルボン酸(f)を付加させるが、モノカルボン酸(f)の付加の役割は、反応生成物(e)の重合を抑制するためである。しかし、反応条件及び/又は多塩基酸(d)の種類によっては、モノカルボン酸(f)は必要ない。これは、多塩基酸(d)の反応生成物(c)への付加により、エポキシ基が無くなることによる。反応生成物(e)とモノカルボン酸(f)を反応させる際の温度は、好ましくは50〜150℃、より好ましくは70〜120℃である。上記反応生成物(e)のエポキシ基に、エポキシ基1当量に対して、モノカルボン酸(f)を0.0〜5.0モルの割合で反応させるが、好ましくは、0.0〜2.0モルである。モノカルボン酸(f)が5.0モルを超えると、多量の未反応のモノカルボン酸(f)が残り、本発明の硬化性組成物の硬化膜に悪影響を及ぼす。 After the monocarboxylic acid (b) and then the polybasic acid (d) are added to the epoxy resin (a), the monocarboxylic acid (f) is added to the remaining epoxy group. The role of the addition is to suppress the polymerization of the reaction product (e). However, depending on the reaction conditions and / or the type of polybasic acid (d), the monocarboxylic acid (f) is not necessary. This is because the epoxy group disappears due to the addition of the polybasic acid (d) to the reaction product (c). The temperature at which the reaction product (e) and the monocarboxylic acid (f) are reacted is preferably 50 to 150 ° C, more preferably 70 to 120 ° C. The epoxy group of the reaction product (e) is reacted with the monocarboxylic acid (f) at a ratio of 0.0 to 5.0 mol with respect to 1 equivalent of the epoxy group, preferably 0.0 to 2 0.0 mole. When the monocarboxylic acid (f) exceeds 5.0 mol, a large amount of unreacted monocarboxylic acid (f) remains, which adversely affects the cured film of the curable composition of the present invention.
モノカルボン酸(f)としては、モノカルボン酸(b)と同じものが挙げられる。これらモノカルボン酸は、単独で又は2種類以上を混合して用いることができる。ここで特に好ましいのはアクリル酸、メタクリル酸、安息香酸、及び酢酸である。 As monocarboxylic acid (f), the same thing as monocarboxylic acid (b) is mentioned. These monocarboxylic acids can be used alone or in admixture of two or more. Particularly preferred here are acrylic acid, methacrylic acid, benzoic acid and acetic acid.
得られた反応生成物(g)の酸価は18〜180mgKOH/gであるが、好ましくは30〜150mgKOH/g、より好ましくは40〜120mgKOH/gである。反応生成物(g)の酸価が18〜180mgKOH/gの範囲を外れると、最終生成物の特性が十分に得られない恐れがある。 Although the acid value of the obtained reaction product (g) is 18 to 180 mgKOH / g, it is preferably 30 to 150 mgKOH / g, more preferably 40 to 120 mgKOH / g. If the acid value of the reaction product (g) is out of the range of 18 to 180 mgKOH / g, the properties of the final product may not be sufficiently obtained.
前記反応生成物(g)の2級のアルコール性水酸基に、多塩基酸無水物(h)を反応させて、カルボキシル基含有化合物(A)が得られるが、この反応において、多塩基酸無水物(h)の使用量は、生成するカルボキシル基含有化合物(A)の酸価が、40〜200mgKOH/g、好ましくは40〜150mgKOH/gとなるような付加量とする。反応は、ハイドロキノンや酸素等の重合禁止剤の存在下で、通常、約50〜150℃で行なう。このとき必要に応じて、トリエチルアミン等の三級アミン、トリエチルベンジルアンモニウムクロライド等の4級アンモニウム塩、2−エチル−4−メチルイミダゾール等のイミダゾール化合物、トリフェニルホスフィン等のリン化合物等を触媒として添加してもよい。 The secondary alcoholic hydroxyl group of the reaction product (g) is reacted with the polybasic acid anhydride (h) to obtain the carboxyl group-containing compound (A). In this reaction, the polybasic acid anhydride is obtained. The amount of (h) used is such that the acid value of the carboxyl group-containing compound (A) to be produced is 40 to 200 mgKOH / g, preferably 40 to 150 mgKOH / g. The reaction is usually carried out at about 50 to 150 ° C. in the presence of a polymerization inhibitor such as hydroquinone or oxygen. At this time, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, a phosphorus compound such as triphenylphosphine is added as a catalyst, if necessary. May be.
上記多塩基酸無水物(h)としては、メチルテトラヒドロ無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、無水ナジック酸、3,6−エンドメチレンテトラヒドロ無水フタル酸、メチルエンドメチレンテトラヒドロ無水フタル酸、テトラブロモ無水フタル酸等の脂環式二塩基酸無水物;無水コハク酸、無水マレイン酸、無水イタコン酸、オクテニル無水コハク酸、ペンタドデセニル無水コハク酸、無水フタル酸、無水トリメリット酸等の脂肪族又は芳香族二塩基酸無水物、あるいはビフェニルテトラカルボン酸二無水物、ジフェニルエーテルテトラカルボン酸二無水物、ブタンテトラカルボン酸二無水物、シクロペンタンテトラカルボン酸二無水物、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸二無水物等の脂肪族又は芳香族四塩基酸二無水物が挙げられが、これらに限られるものではない。これらの多塩基酸無水物は、単独で又は2種類以上を混合して用いることができる。これらの中でも、脂環式二塩基酸無水物が特に好ましい。 Examples of the polybasic acid anhydride (h) include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, Alicyclic dibasic acid anhydrides such as methylendomethylenetetrahydrophthalic anhydride and tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, anhydrous Aliphatic or aromatic dibasic acid anhydrides such as trimellitic acid, or biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, Pyromellitic anhydride, benzofu Aliphatic or aromatic tetrabasic acid dianhydride, such as non-tetracarboxylic acid dianhydride can be mentioned but not limited thereto. These polybasic acid anhydrides can be used alone or in admixture of two or more. Among these, alicyclic dibasic acid anhydrides are particularly preferable.
カルボキシル基含有化合物(A)の酸価は、40〜200mgKOH/gであるが、未反応の多塩基酸(d)及びモノカルボン酸(f)が存在する場合には、固形分酸価は、カルボン酸全体として、200mgKOH/gを超える場合がある。しかし未反応のカルボン酸は、多量に含まれていなければ、本発明の硬化性組成物の硬化膜に悪影響を及ばさない。 The acid value of the carboxyl group-containing compound (A) is 40 to 200 mg KOH / g, but when unreacted polybasic acid (d) and monocarboxylic acid (f) are present, the solid content acid value is The carboxylic acid as a whole may exceed 200 mg KOH / g. However, unless the unreacted carboxylic acid is contained in a large amount, the cured film of the curable composition of the present invention will not be adversely affected.
尚、カルボキシル基含有化合物(A)のある一つの構造(これを構造1とする)に近い化合物を得ることは可能である。例えば、ノボラック型クレゾール樹脂のフェノール性水酸基に部分的にグリシジルメタクリレートを反応させ、得られた反応生成物の残りのフェノール性水酸基にグリシドールをフェノール性水酸基を残さないような量で反応させ、さらに得られた反応生成物の一級及び二級のアルコール性水酸基に酸無水物を反応させて得られる構造(これを構造2とする)である。しかし、構造1と構造2とは違いがある。つまり、ノボラック型クレゾール樹脂のフェノール性水酸基に部分的にグリシジルメタクリレートを反応させて得られた生成物の残りのフェノール性水酸基にグリシドールを反応させようとすると、各フェノール性水酸基にグリシドール1分子ずつを付加させることはできない。即ち、フェノール性水酸基にグリシドール1分子が付加したところにさらに他のグリシドールが付加した構造も得られる。従って、一般的にはフェノール性水酸基にグリシドールをフェノール性水酸基を残さないように反応させるためには、フェノール性水酸基1当量に対して、グリシドールを1モルを超える割合で反応させる。その結果、構造1と構造2とは、異なる化合物となる。また、構造1は1級のアルコール性水酸基は存在しないが、構造2はグリシドール由来の1級のアルコール性水酸基が存在する又は存在する可能性が大きい。1級のアルコール性水酸基は電気特性を低下させる。従って、1級のアルコール性水酸基を有しないカルボキシル基含有化合物(A)を含有する本発明の硬化性組成物の硬化膜は、優れた電気特性を示す。 In addition, it is possible to obtain a compound close to a certain structure of the carboxyl group-containing compound (A) (this is referred to as structure 1). For example, the glycidyl methacrylate is partially reacted with the phenolic hydroxyl group of the novolak-type cresol resin, and the remaining phenolic hydroxyl group of the obtained reaction product is reacted with glycidol in an amount that does not leave the phenolic hydroxyl group. It is a structure obtained by reacting an acid anhydride with primary and secondary alcoholic hydroxyl groups of the obtained reaction product (this structure is referred to as structure 2). However, there is a difference between Structure 1 and Structure 2. That is, when trying to react glycidol with the remaining phenolic hydroxyl group of the product obtained by partially reacting the phenolic hydroxyl group of the novolak-type cresol resin with glycidyl methacrylate, one molecule of glycidol is added to each phenolic hydroxyl group. It cannot be added. That is, a structure in which one glycidol molecule is added to the phenolic hydroxyl group and another glycidol is added can also be obtained. Therefore, generally, in order to make glycidol react with the phenolic hydroxyl group so as not to leave the phenolic hydroxyl group, glycidol is reacted at a ratio exceeding 1 mol with respect to 1 equivalent of the phenolic hydroxyl group. As a result, Structure 1 and Structure 2 are different compounds. In Structure 1, there is no primary alcoholic hydroxyl group, but in Structure 2, a primary alcoholic hydroxyl group derived from glycidol is present or likely to exist. Primary alcoholic hydroxyl groups reduce electrical properties. Therefore, the cured film of the curable composition of the present invention containing the carboxyl group-containing compound (A) having no primary alcoholic hydroxyl group exhibits excellent electrical characteristics.
次に、カルボキシル基含有化合物(A)以外のカルボキシル基含有化合物(B)は、1分子中に少なくとも1個、好ましくは2個以上のカルボキシル基を有する化合物である。具体的には、それ自体がエチレン性不飽和二重結合を有さないカルボキシル基含有化合物及びエチレン性不飽和二重結合を有するカルボキシル基含有感光性化合物のいずれも使用可能であり、特定のものに限定されるものではないが、特に以下に列挙するような化合物を好適に使用できる。 Next, the carboxyl group-containing compound (B) other than the carboxyl group-containing compound (A) is a compound having at least one, preferably two or more carboxyl groups in one molecule. Specifically, both a carboxyl group-containing compound that itself does not have an ethylenically unsaturated double bond and a carboxyl group-containing photosensitive compound that has an ethylenically unsaturated double bond can be used. Although not limited to these, the compounds listed below can be particularly preferably used.
(1)不飽和カルボン酸と不飽和二重結合を有する化合物を共重合させることによって得られるカルボキシル基含有化合物、
(2)不飽和カルボン酸と不飽和二重結合を有する化合物の共重合体にエチレン性不飽和基をペンダントとして付加させることによって得られるカルボキシル基含有感光性化合物、
(3)エポキシ基と不飽和二重結合を有する化合物と不飽和二重結合を有する化合物の共重合体に、不飽和カルボン酸を反応させ、生成した二級の水酸基に飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有感光性化合物、
(4)不飽和二重結合を有する酸無水物と不飽和二重結合を有する化合物の共重合体に、水酸基と不飽和二重結合を有する化合物を反応させて得られるカルボキシル基含有感光性化合物、
(5)1分子中に少なくとも2個のエポキシ基を有する多官能エポキシ化合物のエポキシ基と不飽和モノカルボン酸のカルボキシル基をエステル化反応させ、生成した水酸基にさらに飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有感光性化合物、
(6)不飽和二重結合を有する化合物とグリシジル(メタ)アクリレートの共重合体のエポキシ基に、1分子中に1つのカルボキシル基を有し、エチレン性不飽和結合を持たない有機酸を反応させ、生成した二級の水酸基に飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有化合物、
(7)水酸基含有ポリマーに飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有化合物、
(8)水酸基含有ポリマーに飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有化合物に、エポキシ基と不飽和二重結合を有する化合物をさらに反応させて得られるカルボキシル基含有感光性化合物、
(9)1分子中に少なくとも2個のエポキシ基を有する多官能エポキシ化合物と、不飽和モノカルボン酸と、1分子中に少なくとも2個の水酸基と、エポキシ基と反応する水酸基以外の1個の他の反応性基を有する化合物との反応生成物に、飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有感光性化合物、
(10)1分子中に少なくとも2個のエポキシ基を有する多官能エポキシ化合物と、不飽和モノカルボン酸と、1分子中に少なくとも2個の水酸基と、エポキシ基と反応する水酸基以外の1個の他の反応性基を有する化合物との反応生成物と、飽和又は不飽和多塩基酸無水物と、不飽和基含有モノイソシアネートとの反応生成物からなる不飽和基含有ポリカルボン酸ウレタン化合物、
(11)1分子中に少なくとも2個のオキセタン環を有する多官能オキセタン化合物に不飽和モノカルボン酸を反応させ、得られた変性オキセタン化合物中の一級水酸基に対して飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有感光性化合物、
(12)ビスエポキシ化合物とジカルボン酸との反応生成物に、不飽和二重結合を導入し、引き続き飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有感光性化合物、
(13)ビスエポキシ化合物とビスフェノール類との反応生成物に、不飽和二重結合を導入し、引き続き飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有感光性化合物、及び
(14)ノボラック型フェノール樹脂とアルキレンオキシド及び/又は環状カーボネートとの反応生成物に不飽和モノカルボン酸を反応させ、得られた反応生成物に飽和又は不飽和多塩基酸無水物を反応させて得られるカルボキシル基含有感光性化合物。
(1) a carboxyl group-containing compound obtained by copolymerizing an unsaturated carboxylic acid and a compound having an unsaturated double bond,
(2) a carboxyl group-containing photosensitive compound obtained by adding an ethylenically unsaturated group as a pendant to a copolymer of an unsaturated carboxylic acid and a compound having an unsaturated double bond,
(3) A copolymer of an epoxy group, a compound having an unsaturated double bond and a compound having an unsaturated double bond is reacted with an unsaturated carboxylic acid, and the resulting secondary hydroxyl group is saturated or unsaturated polybasic. A carboxyl group-containing photosensitive compound obtained by reacting an acid anhydride,
(4) A carboxyl group-containing photosensitive compound obtained by reacting a copolymer of an acid anhydride having an unsaturated double bond and a compound having an unsaturated double bond with a compound having a hydroxyl group and an unsaturated double bond. ,
(5) An esterification reaction of an epoxy group of a polyfunctional epoxy compound having at least two epoxy groups in one molecule and a carboxyl group of an unsaturated monocarboxylic acid, and the resulting hydroxyl group is further saturated or unsaturated polybasic acid anhydride Carboxyl group-containing photosensitive compound obtained by reacting a product,
(6) Reaction of an organic acid having one carboxyl group in one molecule and not having an ethylenically unsaturated bond with the epoxy group of a copolymer of a compound having an unsaturated double bond and glycidyl (meth) acrylate A carboxyl group-containing compound obtained by reacting the produced secondary hydroxyl group with a saturated or unsaturated polybasic acid anhydride,
(7) a carboxyl group-containing compound obtained by reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride,
(8) A carboxyl group-containing photosensitivity obtained by further reacting a carboxyl group-containing compound obtained by reacting a hydroxyl group-containing polymer with a saturated or unsaturated polybasic acid anhydride and a compound having an epoxy group and an unsaturated double bond. Sex compounds,
(9) A polyfunctional epoxy compound having at least two epoxy groups in one molecule, an unsaturated monocarboxylic acid, at least two hydroxyl groups in one molecule, and one hydroxyl group that reacts with an epoxy group A carboxyl group-containing photosensitive compound obtained by reacting a reaction product with a compound having another reactive group with a saturated or unsaturated polybasic acid anhydride,
(10) One polyfunctional epoxy compound having at least two epoxy groups in one molecule, unsaturated monocarboxylic acid, at least two hydroxyl groups in one molecule, and one hydroxyl group that reacts with an epoxy group An unsaturated group-containing polycarboxylic acid urethane compound comprising a reaction product of a compound having another reactive group, a reaction product of a saturated or unsaturated polybasic acid anhydride and an unsaturated group-containing monoisocyanate,
(11) A polyfunctional oxetane compound having at least two oxetane rings in one molecule is reacted with an unsaturated monocarboxylic acid, and a saturated or unsaturated polybasic acid anhydride with respect to the primary hydroxyl group in the resulting modified oxetane compound Carboxyl group-containing photosensitive compound obtained by reacting a product,
(12) A carboxyl group-containing photosensitive compound obtained by introducing an unsaturated double bond into a reaction product of a bisepoxy compound and a dicarboxylic acid and subsequently reacting with a saturated or unsaturated polybasic acid anhydride,
(13) A carboxyl group-containing photosensitive compound obtained by introducing an unsaturated double bond into a reaction product of a bisepoxy compound and a bisphenol and subsequently reacting with a saturated or unsaturated polybasic acid anhydride, and ( 14) obtained by reacting a reaction product of a novolak type phenolic resin with an alkylene oxide and / or a cyclic carbonate with an unsaturated monocarboxylic acid, and reacting the resulting reaction product with a saturated or unsaturated polybasic acid anhydride. Carboxyl group-containing photosensitive compound.
上記カルボキシル基含有化合物(A)とカルボキシル基含有化合物(B)の配合割合は、質量比でA:B=10:90〜90:10が好ましいが、より好ましくは、A:B=30:70〜70:30である。A:B=10:90〜90:10の範囲外では、十分な特性が得られない恐れがある。また、上記カルボキシル基含有化合物(A)とカルボキシル基含有化合物(B)の混合物の酸価は、好ましくは40〜200mgKOH/gであるが、より好ましくは40〜150mgKOH/gである。これらの範囲により、本発明の硬化性組成物は、現像性のみならず、他の諸特性においても優れた特性をもつことになる。 The mixing ratio of the carboxyl group-containing compound (A) and the carboxyl group-containing compound (B) is preferably A: B = 10: 90 to 90:10 by mass ratio, more preferably A: B = 30: 70. ~ 70: 30. If the ratio is outside the range of A: B = 10: 90 to 90:10, sufficient characteristics may not be obtained. The acid value of the mixture of the carboxyl group-containing compound (A) and the carboxyl group-containing compound (B) is preferably 40 to 200 mgKOH / g, more preferably 40 to 150 mgKOH / g. From these ranges, the curable composition of the present invention has excellent characteristics not only in developability but also in other various characteristics.
前記感光性(メタ)アクリレート化合物(C)としては、例えば、2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレートなどの水酸基含有のアクリレート類;ポリエチレングリコールジアクリレート、ポリプロピレングリコールジアクリレートなどの水溶性のアクリレート類;トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレートなどの多価アルコールの多官能ポリエステルアクリレート類;トリメチロールプロパン、水添ビスフェノールA等の多官能アルコールもしくはビスフェノールA、ビフェノールなどの多価フェノールのエチレンオキサイド付加物及び/又はプロピレンオキサイド付加物のアクリレート類;上記水酸基含有アクリレートのイソシアネート変成物である多官能もしくは単官能ポリウレタンアクリレート;ビスフェノールAジグリシジルエーテル、水添ビスフェノールAジグリシジルエーテル又はフェノールノボラックエポキシ樹脂の(メタ)アクリル酸付加物であるエポキシアクリレート類;カプロラクトン変性ジトリメチロールプロパンテトラアクリレート、ε―カプロラクロン変性ジペンタエリスリトールのアクリレート、カプロラクトン変性ヒドロキシピバリン酸ネオペンチルグリコールエステルジアクリレートなどのカプロラクトン変性のアクリレート類、及び上記アクリレート類に対応するメタクリレート類などが挙げられる。これらの中でも、1分子中に2個以上の(メタ)アクリロイル基を有する多官能(メタ)アクリレート化合物が好ましい。これらの感光性(メタ)アクリレート化合物は、単独で又は2種類以上を混合して用いることができる。これら感光性(メタ)アクリレート化合物の使用目的は、前記カルボキシル基含有化合物(A)及びカルボキシル基含有化合物(B)の光反応性を上げることにある。室温で液状の感光性(メタ)アクリレート化合物は、光反応性を上げる目的の他、組成物を各種の塗布方法に適した粘度に調整したり、アルカリ水溶液への溶解性を助ける役割も果たす。しかし、室温で液状の感光性(メタ)アクリレート化合物を多量に使用すると、塗膜の指触乾燥性が得られず、また塗膜の特性も悪化する傾向があるので、多量に使用することは好ましくない。感光性(メタ)アクリレート化合物(C)の配合量は、前記カルボキシル基含有化合物(A)及びカルボキシル基含有化合物(B)の合計100質量部に対して100質量部以下が好ましい。なお、本明細書において、「(メタ)アクリレート」とは、アクリレートとメタクリレートを総称する用語であり、他の類似の表現についても同様である。 Examples of the photosensitive (meth) acrylate compound (C) include hydroxyl group-containing acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate. Water-soluble acrylates such as polyethylene glycol diacrylate and polypropylene glycol diacrylate; polyfunctional polyester acrylates of polyhydric alcohols such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate; Multifunctional alcohols such as trimethylolpropane and hydrogenated bisphenol A or polyhydric phenols such as bisphenol A and biphenol Acrylates of ethylene oxide adduct and / or propylene oxide adduct; polyfunctional or monofunctional polyurethane acrylate which is an isocyanate modification of the above hydroxyl group-containing acrylate; bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or phenol Epoxy acrylates that are (meth) acrylic acid adducts of novolak epoxy resins; caprolactone-modified ditrimethylolpropane tetraacrylate, ε-caprolaclone-modified dipentaerythritol acrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol ester diacrylate, etc. Acrylates, and methacrylates corresponding to the above acrylates. Among these, a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in one molecule is preferable. These photosensitive (meth) acrylate compounds can be used alone or in admixture of two or more. The purpose of using these photosensitive (meth) acrylate compounds is to increase the photoreactivity of the carboxyl group-containing compound (A) and the carboxyl group-containing compound (B). The photosensitive (meth) acrylate compound which is liquid at room temperature plays a role of adjusting the composition to a viscosity suitable for various coating methods and assisting in solubility in an alkaline aqueous solution, in addition to the purpose of increasing photoreactivity. However, if a large amount of liquid photosensitive (meth) acrylate compound is used at room temperature, the dryness of the coating film cannot be obtained, and the characteristics of the coating film tend to deteriorate. It is not preferable. As for the compounding quantity of the photosensitive (meth) acrylate compound (C), 100 mass parts or less are preferable with respect to a total of 100 mass parts of the said carboxyl group-containing compound (A) and a carboxyl group-containing compound (B). In this specification, “(meth) acrylate” is a term that collectively refers to acrylate and methacrylate, and the same applies to other similar expressions.
前記光重合開始剤(D)としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインとベンゾインアルキルエーテル類;アセトフェノン、2,2−ジメトキシ−2−フェニルアセトフェノン、2,2−ジエトキシ−2−フェニルアセトフェノン、1,1−ジクロロアセトフェノン等のアセトフェノン類;2−メチル−1−[4−(メチルチオ)フェニル]−2−モルホリノプロパン−1−オン、2−ベンジル−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタン−1−オン、N,N- ジメチルアミノアセトフェノン等のアミノアセトフェノン類;2−メチルアントラキノン、2−エチルアントラキノン、2−t−ブチルアントラキノン、1−クロロアントラキノン等のアントラキノン類;2,4−ジメチルチオキサントン、2,4−ジエチルチオキサントン、2−クロロチオキサントン、2,4−ジイソプロピルチオキサントン等のチオキサントン類;アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類;ベンゾイルパーオキシド、クメンパーオキシド等の有機過酸化物;2,4,5−トリアリールイミダゾール二量体;リボフラビンテトラブチレート;2−メルカプトベンゾイミダゾール、2−メルカプトベンゾオキサゾール、2−メルカプトベンゾチアゾール等のチオール化合物;2,4,6−トリス−s−トリアジン、2,2,2−トリブロモエタノール、トリブロモメチルフェニルスルホン等の有機ハロゲン化合物;ベンゾフェノン、4,4´−ビスジエチルアミノベンゾフェノン等のベンゾフェノン類又はキサントン類;2,4,6−トリメチルベンゾイルジフェニルホスフィンオキサイドなどが挙げられる。これら公知慣用の光重合開始剤は、単独で又は2種類以上を混合して用いることができ、さらにはN,N−ジメチルアミノ安息香酸エチルエステル、N,N−ジメチルアミノ安息香酸イソアミルエステル、ペンチル−4−ジメチルアミノベンゾエート、トリエチルアミン、トリエタノールアミン等の三級アミン類などの光開始助剤を加えることができる。また可視光領域に吸収のあるCGI−784等(チバ・スペシャルティ・ケミカルズ(株)製)のチタノセン化合物等も、光反応を促進するために添加することもできる。特に好ましい光重合開始剤は、2,4,6−トリメチルベンゾイルジフェニルホスフィンオキサイド、2−メチル−1−[4−(メチルチオ)フェニル]−2−モルホリノプロパン−1−オン、2−ベンジル−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタン−1−オン等であるが、特にこれらに限られるものではなく、紫外光もしくは可視光領域で光を吸収し、(メタ)アクリロイル基等の不飽和基をラジカル重合させるものであれば、光重合開始剤、光開始助剤に限らず、単独で又は2種類以上を混合して用いることができる。そして、その使用量は前記カルボキシル基含有化合物(A)及びカルボキシル基含有化合物(B)の合計100質量部に対して0. 5〜25質量部の割合が好ましい。 Examples of the photopolymerization initiator (D) include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, Acetophenones such as 2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- Aminoacetophenones such as dimethylamino-1- (4-morpholinophenyl) -butan-1-one, N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1- Chloro Anthraquinones such as nthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzoylper Organic peroxides such as oxide and cumene peroxide; 2,4,5-triarylimidazole dimer; Riboflavin tetrabutyrate; Thiols such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole Compound; Organic halogen compounds such as 2,4,6-tris-s-triazine, 2,2,2-tribromoethanol, tribromomethylphenylsulfone; benzophenone, 4,4'-bisdie Benzophenones or xanthones such as Le aminobenzophenone; and 2,4,6-trimethylbenzoyl diphenylphosphine oxide. These known and commonly used photopolymerization initiators can be used alone or in admixture of two or more. Further, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl Photoinitiator aids such as tertiary amines such as -4-dimethylaminobenzoate, triethylamine, triethanolamine can be added. A titanocene compound such as CGI-784 (manufactured by Ciba Specialty Chemicals Co., Ltd.) having absorption in the visible light region can also be added to promote the photoreaction. Particularly preferred photopolymerization initiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butan-1-one and the like, but is not particularly limited thereto, and absorbs light in the ultraviolet light or visible light region, such as (meth) acryloyl group As long as the unsaturated group is radically polymerized, it is not limited to a photopolymerization initiator and a photoinitiator aid, and can be used alone or in admixture of two or more. And the usage-amount is the ratio of 0.5-25 mass parts with respect to a total of 100 mass parts of the said carboxyl group-containing compound (A) and a carboxyl group-containing compound (B).
また、本発明の硬化性組成物は、熱硬化成分を配合させることができる。例えば、オキセタン樹脂、前記したエポキシ樹脂などが挙げられる。
オキセタン樹脂としては、例えば、3,7−ビス(3−オキセタニル)−5−オキサ−ノナン、3,3´−(1,3−(2−メチレニル)プロパンジイルビス(オキシメチレン))ビス−(3−エチルオキセタン)、1,4−ビス〔(3−エチル−3−オキセタニルメトキシ)メチル〕ベンゼン、1,2−ビス[(3−エチル−3−オキセタニルメトキシ)メチル]エタン、1,3−ビス[(3−エチル−3−オキセタニルメトキシ)メチル]プロパン、エチレングリコールビス(3−エチル−3−オキセタニルメチル)エーテル、ジシクロペンテニルビス(3−エチル−3−オキセタニルメチル)エーテル、トリエチレングリコールビス(3−エチル−3−オキセタニルメチル)エーテル、テトラエチレングリコールビス(3−エチル−3−オキセタニルメチル)エーテル、トリシクロデカンジイルジメチレン(3−エチル−3−オキセタニルメチル)エーテル、トリメチロールプロパントリス(3−エチル−3−オキセタニルメチル)エーテル、1,4−ビス(3−エチル−3−オキセタニルメトキシ)ブタン、1,6−ビス(3−エチル−3−オキセタニルメトキシ)ヘキサン、ペンタエリスリトールトリス(3−エチル−3−オキセタニルメチル)エーテル、ペンタエリスリトールテトラキス(3−エチル−3−オキセタニルメチル)エーテルなどが挙げられる。これらの熱硬化成分は、単独で又は2種類以上を混合して用いることができる。その配合量は、前記カルボキシル基含有化合物(A)及びカルボキシル基含有化合物(B)の合計100質量部に対して5〜100質量部の割合が好ましい。
Moreover, the curable composition of this invention can mix | blend a thermosetting component. For example, oxetane resin, the above-mentioned epoxy resin, etc. are mentioned.
Examples of the oxetane resin include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis- ( 3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3- Bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol Bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3 Oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3) -Oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ) Ether. These thermosetting components can be used alone or in admixture of two or more. The compounding quantity has the preferable ratio of 5-100 mass parts with respect to a total of 100 mass parts of the said carboxyl group-containing compound (A) and a carboxyl group-containing compound (B).
また、本発明の硬化性組成物は、カルボキシル基含有化合物(A)及びカルボキシル基含有化合物(B)を溶解させ、また組成物を塗布方法に適した粘度に調整するために、有機溶剤を配合することができる。
有機溶剤としては、例えば、トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類;エチレングリコールモノエチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類;酢酸エチル、酢酸ブチル、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート等の酢酸エステル類;エタノール、プロパノール、エチレングリコール、プロピレングリコール等のアルコール類;オクタン、デカン等の脂肪族炭化水素;石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤などが挙げられる。これらの有機溶剤は、単独で又は2種類以上を混合して用いることができる。有機溶剤の配合量は、用途等に応じた任意の量とすることができる。
Further, the curable composition of the present invention contains an organic solvent for dissolving the carboxyl group-containing compound (A) and the carboxyl group-containing compound (B) and adjusting the composition to a viscosity suitable for the coating method. can do.
Examples of the organic solvent include aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether , Glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol Monoethyl ether Acetates such as cetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate and dipropylene glycol monomethyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum Examples include petroleum solvents such as ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These organic solvents can be used alone or in admixture of two or more. The compounding quantity of the organic solvent can be made into arbitrary quantity according to a use etc.
さらに、本発明の硬化性組成物は、熱硬化触媒を配合することができる。熱硬化触媒としては、例えば、イミダゾール、2−メチルイミダゾール、2−エチルイミダゾール、2−エチル−4−メチルイミダゾール、2−フェニルイミダゾール、4−フェニルイミダゾール、1−シアノエチル−2−フェニルイミダゾール、1−(2−シアノエチル)−2−エチル−4−メチルイミダゾール等のイミダゾール誘導体;ジシアンジアミド、ベンジルジメチルアミン、4−(ジメチルアミノ)−N,N−ジメチルベンジルアミン、4−メトキシ−N,N−ジメチルベンジルアミン、4−メチル−N,N−ジメチルベンジルアミン等のアミン化合物;アジピン酸ヒドラジド、セバシン酸ヒドラジド等のヒドラジン化合物;トリフェニルホスフィン等のリン化合物などを用いることができる。市販されているものとしては、例えば四国化成(株)製の2MZ−A、2MZ−OK、2PHZ、2P4BHZ、2P4MHZ(いずれもイミダゾール系化合物の商品名)、サンアプロ(株)製のU−CAT3503N、U−CAT3502T(いずれもジメチルアミンのブロックイソシアネート化合物の商品名)、DBU、DBN、U−CATSA102、U−CAT5002(いずれも二環式アミジン化合物及びその塩)などが挙げられる。特に、熱硬化特性を向上させるためであれば、これらに限られるものではなく、環状エーテルを有する化合物の硬化触媒、もしくは環状エーテルを有する化合物とカルボン酸の反応を促進するものであればよく、単独で又は2種類以上を混合して用いることができる。また、密着性付与剤としても機能するグアナミン、アセトグアナミン、ベンゾグアナミン、メラミン、2,4−ジアミノ−6−メタクリロイルオキシエチル−S−トリアジン、2−ビニル−4,6−ジアミノ−S−トリアジン、2−ビニル−4,6−ジアミノ−S−トリアジン・イソシアヌル酸付加物、2,4−ジアミノ−6−メタクリロイルオキシエチル−S−トリアジン・イソシアヌル酸付加物等のS−トリアジン誘導体を用いることもでき、好ましくはこれらの化合物を前記硬化触媒と併用する。上記硬化触媒の配合量は通常の量的割合で充分であり、例えばカルボキシル基含有化合物(A)及びカルボキシル基含有化合物(B)の合計100質量部に対して0.1〜20質量部、好ましくは0.5〜15.0質量部の割合である。 Furthermore, the curable composition of this invention can mix | blend a thermosetting catalyst. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Imidazole derivatives such as (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzyl Amine compounds such as amine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid hydrazide and sebacic acid hydrazide; and phosphorus compounds such as triphenylphosphine can be used. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Co., Ltd., U-CAT3503N manufactured by San Apro Co., Ltd. U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, as long as it is for improving thermosetting properties, it is not limited to these, as long as it is a curing catalyst for a compound having a cyclic ether, or a compound that promotes the reaction between a compound having a cyclic ether and a carboxylic acid, It can use individually or in mixture of 2 or more types. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2 S-triazine derivatives such as -vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used, These compounds are preferably used in combination with the curing catalyst. The amount of the curing catalyst is sufficient at a normal quantitative ratio, for example, 0.1 to 20 parts by mass, preferably 100 parts by mass with respect to a total of 100 parts by mass of the carboxyl group-containing compound (A) and the carboxyl group-containing compound (B). Is a ratio of 0.5 to 15.0 parts by mass.
本発明の硬化性組成物には、さらに必要に応じて、硫酸バリウム、チタン酸バリウム、無定形シリカ、結晶性シリカ、溶融シリカ、球状シリカ、タルク、クレー、炭酸マグネシウム、炭酸カルシウム、酸化アルミニウム、水酸化アルミニウム、マイカ等の公知慣用の無機フィラーを単独で又は2種類以上を配合することができる。これらは塗膜の硬化収縮を抑制し、密着性、硬度などの特性を向上させる目的で用いられる。無機フィラーの配合量は、前記カルボキシル基含有化合物(A)及びカルボキシル基含有化合物(B)の合計100質量部に対して、10〜300質量部、好ましくは30〜200質量部の割合が適当である。 The curable composition of the present invention further contains, as necessary, barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, Known or commonly used inorganic fillers such as aluminum hydroxide and mica can be used alone or in combination of two or more. These are used for the purpose of suppressing curing shrinkage of the coating film and improving properties such as adhesion and hardness. The blending amount of the inorganic filler is 10 to 300 parts by mass, preferably 30 to 200 parts by mass with respect to 100 parts by mass in total of the carboxyl group-containing compound (A) and the carboxyl group-containing compound (B). is there.
また、本発明の硬化性組成物は、さらに必要に応じてフタロシアニン・ブルー、フタロシアニン・グリーン、アイオジン・グリーン、ジスアゾイエロー、クリスタルバイオレット、酸化チタン、カーボンブラック、ナフタレンブラックなどの公知慣用の着色剤、ハイドロキノン、ハイドロキノンモノメチルエーテル、t−ブチルカテコール、ピロガロール、フェノチアジンなどの公知慣用の熱重合禁止剤、微粉シリカ、有機ベントナイト、モンモリロナイトなどの公知慣用の増粘剤、シリコーン系、フッ素系、高分子系などの消泡剤及び/又はレベリング剤、イミダゾール系、チアゾール系、トリアゾール系等のシランカップリング剤などのような公知慣用の添加剤類を配合することができる。 Further, the curable composition of the present invention may further include a known and commonly used colorant such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, if necessary. Known and commonly used thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol and phenothiazine, known and commonly used thickeners such as fine silica, organic bentonite and montmorillonite, silicones, fluorines, polymers, etc. Known and conventional additives such as a defoaming agent and / or a leveling agent, an imidazole series, a thiazole series, a triazole series silane coupling agent, and the like can be blended.
さらに本発明の硬化性組成物は、難燃性を得る目的で、必要に応じて、ハロゲン系難燃剤、リン系難燃剤、及びアンチモン系難燃剤等の難燃剤を配合することができる。難燃剤の配合量は、前記カルボキシル基含有化合物(A)及びカルボキシル基含有化合物(B)の合計100質量部に対して、通常1〜200質量部、好ましくは5〜50質量部である。難燃剤の配合量が上記範囲にあると、組成物の難燃性、はんだ耐熱性及び電気絶縁性とが、高度にバランスされて好適である。 Furthermore, the curable composition of this invention can mix | blend flame retardants, such as a halogenated flame retardant, a phosphorus flame retardant, and an antimony flame retardant, for the purpose of obtaining a flame retardance. The compounding quantity of a flame retardant is 1-200 mass parts normally with respect to a total of 100 mass parts of the said carboxyl group-containing compound (A) and a carboxyl group-containing compound (B), Preferably it is 5-50 mass parts. When the blending amount of the flame retardant is in the above range, the flame retardancy, solder heat resistance, and electrical insulation of the composition are highly balanced and suitable.
また、本発明の硬化性組成物は、引火性の低下のために、水を添加することもできる。水を添加する場合には、前記カルボキシル基含有化合物(A)及びカルボキシル基含有化合物(B)のカルボキシル基を、トリメチルアミン、トリエチルアミン等のアミン類、N,N−ジメチルアミノエチル(メタ)アクリレート、N,N−ジメチルアミノプロピル(メタ)アクリルアミド、アクリロイルモルホリン等の3級アミノ基を有する(メタ)アクリレート樹脂で造塩することにより、本発明の硬化性組成物を水になじむようにすることが好ましい。 Moreover, water can also be added to the curable composition of this invention for the fall of flammability. When water is added, the carboxyl groups of the carboxyl group-containing compound (A) and the carboxyl group-containing compound (B) are converted to amines such as trimethylamine and triethylamine, N, N-dimethylaminoethyl (meth) acrylate, N , N-dimethylaminopropyl (meth) acrylamide, acryloylmorpholine, etc., it is preferable to make the curable composition of the present invention compatible with water by salt formation with a (meth) acrylate resin having a tertiary amino group. .
本発明の硬化性組成物は、支持体と、該支持体上に形成された上記硬化性組成物からなる層とを備えたドライフィルムの形態とすることもできる。好ましくは、上記フィルムの硬化性組成物層上に、さらに剥離可能なカバーフィルムを積層する。 The curable composition of this invention can also be made into the form of the dry film provided with the support body and the layer which consists of the said curable composition formed on this support body. Preferably, a peelable cover film is further laminated on the curable composition layer of the film.
支持体としては、プラスチックフィルムが用いられ、ポリエチレンテレフタレート等のポリエステルフィルム、ポリイミドフィルム、ポリアミドイミドフィルム、ポリプロピレンフィルム、ポリスチレンフィルム等のプラスチックフィルムを用いることが好ましい。ここで、支持体の厚さは、10〜150μmの範囲で適宜選択される。 A plastic film is used as the support, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used. Here, the thickness of the support is appropriately selected within a range of 10 to 150 μm.
支持体上の上記硬化性組成物層は、上記硬化性組成物をコンマコータ、ブレードコータ、リップコータ、ロッドコータ、スクイズコータ、リバースコータ、トランスファロールコータ等で支持体上に均一な厚さに塗布し、加熱・乾燥して溶剤を揮発させて得られる。上記硬化性組成物層の厚さは特に制限がなく、10〜150μmの範囲で適宜選択される。 The curable composition layer on the support is coated with a uniform thickness on the support with a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater or the like. It is obtained by evaporating the solvent by heating and drying. The thickness of the curable composition layer is not particularly limited and is appropriately selected within a range of 10 to 150 μm.
前記カバーフィルムには、一般にポリエチレンフィルム、ポリプロピレンフィルム、テフロン(登録商標)フィルム、表面処理した紙等が用いられる。カバーフィルムは、上記硬化性組成物層との接着力が、上記硬化性組成物層と支持体との接着力よりも小さいものであればよく、特定のものに限定されない。 Generally, a polyethylene film, a polypropylene film, a Teflon (registered trademark) film, a surface-treated paper, or the like is used as the cover film. The cover film is not limited to a specific one as long as the adhesive strength with the curable composition layer is smaller than the adhesive strength between the curable composition layer and the support.
本発明の硬化性組成物は、必要に応じて希釈して塗布方法に適した粘度に調製される。粘度が調製された硬化性組成物を、例えば、スクリーン印刷法、カーテンコート法、スプレーコート法、ロールコート法等の方法により回路形成されたプリント配線板に塗布し、例えば約60〜100℃で組成物中に含まれる有機溶剤を揮発乾燥させることにより、タックフリーの塗膜を形成できる。
支持体と該支持体上に形成された上記硬化性組成物からなる層とを備えたドライフィルムの形態の場合、回路形成されたプリント配線板にホットロールラミネーター等を用いて前記ドライフィルムを貼り合わせる。このとき、硬化性組成物層が回路形成されたプリント配線板に接触するように該プリント配線板にドライフィルムを貼り合わせる。これにより、前記プリント配線板上に上記硬化性組成物の塗膜を形成することができる。前記硬化性組成物層の上に、さらに剥離可能なカバーフィルムを備えたドライフィルムの場合、前記カバーフィルムを剥がした後、上記硬化性組成物層と回路形成されたプリント配線板が接触するようにホットロールラミネーター等を用いてドライフィルムとプリント配線板を貼り合わせる。これにより、回路形成されたプリント配線板上に上記硬化性組成物の塗膜を形成することができる。
The curable composition of the present invention is prepared to have a viscosity suitable for the coating method by dilution as necessary. The curable composition having a adjusted viscosity is applied to a printed wiring board formed with a circuit by a method such as a screen printing method, a curtain coating method, a spray coating method, or a roll coating method, for example, at about 60 to 100 ° C. A tack-free coating film can be formed by evaporating and drying the organic solvent contained in the composition.
In the case of a dry film comprising a support and a layer made of the curable composition formed on the support, the dry film is pasted on a printed wiring board formed with a circuit using a hot roll laminator or the like. Match. At this time, a dry film is bonded to the printed wiring board so that the curable composition layer contacts the printed wiring board on which the circuit is formed. Thereby, the coating film of the said curable composition can be formed on the said printed wiring board. In the case of a dry film provided with a peelable cover film on the curable composition layer, after the cover film is peeled off, the curable composition layer and the printed wiring board formed with a circuit are in contact with each other. A dry film and a printed wiring board are bonded together using a hot roll laminator or the like. Thereby, the coating film of the said curable composition can be formed on the printed wiring board by which the circuit was formed.
回路形成されたプリント配線板上に塗膜を形成した後、レーザー光等の活性エネルギー線をパターン通りに直接照射するか、又はパターンを形成したフォトマスクを通して活性エネルギー線を照射して選択的に露光することにより、未露光部を希アルカリ水溶液により現像してレジストパターンを形成できる。なお、上記ドライフィルムを用いた場合は、支持体を剥がさずに選択的に露光した後、支持体を剥がして、現像する。
レジストパターンを形成した後、さらに、加熱硬化させることにより、または、活性エネルギー線の照射後加熱硬化させることにより、あるいは、加熱硬化させた後、活性エネルギー線を照射して最終硬化(本硬化)させることにより、電気絶縁性、PCT耐性,密着性、はんだ耐熱性、耐薬品性、無電解金めっき耐性などに優れた硬化膜(硬化物)を形成することができる。
After the coating film is formed on the printed circuit board on which the circuit is formed, the active energy rays such as laser light are directly irradiated according to the pattern, or the active energy rays are selectively irradiated through the photomask on which the pattern is formed. By exposing, an unexposed part can be developed with dilute alkaline aqueous solution to form a resist pattern. In the case of using the dry film, after selectively exposing without peeling off the support, the support is peeled off and developed.
After the resist pattern is formed, it is further cured by heating, or by heat curing after irradiation with active energy rays, or after heat curing, it is irradiated with active energy rays and finally cured (main curing). By doing so, a cured film (cured product) excellent in electrical insulation, PCT resistance, adhesion, solder heat resistance, chemical resistance, electroless gold plating resistance and the like can be formed.
前記アルカリ水溶液としては、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、リン酸ナトリウム、ケイ酸ナトリウム、アンモニア、アミン類などのアルカリ水溶液が使用できる。
光硬化させるための照射光源としては、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライドランプなどが適当である。また、レーザー光線なども活性エネルギー線として利用できる。
As the alkaline aqueous solution, alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia and amines can be used.
As an irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is appropriate. A laser beam or the like can also be used as an active energy ray.
以下、カルボキシル基含有化合物の合成例、硬化性組成物の組成例等を示して本発明の実施例についてより具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお、以下において特に断りのない限り、「部」は質量部を意味するものとする。
合成例1
クレゾールノボラック型エポキシ樹脂のYDCN−700−5(東都化成(株)製、エポキシ当量:203g/eq.)203部を温度計、撹拌機、還流冷却器及び空気吹き込み管を備えた反応容器に入れ、ジエチレングリコールモノエチルエーテルアセテート108部を加え、加熱溶解した。次に、アクリル酸50.4部、メチルハイドロキノン0.3部及びトリフェニルホスフィン1部を加え、空気を吹き込みながら95〜105℃で7時間反応させた。その後、マレイン酸40.6部、ジエチレングリコールモノエチルエーテルアセテート50部及びメチルハイドロキノン0.2部を加え95〜105℃で4時間反応させ、エポキシ当量44636g/eq.の反応生成物を得た。次いでテトラヒドロ無水フタル酸30.4部、ジエチレングリコールモノエチルエーテルアセテート33部を加え95〜105℃で4時間反応させて、不揮発分63%の溶液を得た。このようにして得られたカルボキシル基含有化合物は、酸価116mgKOH/g、であった。以下、この溶液をA−1と称す。
Hereinafter, although the synthesis example of a carboxyl group-containing compound, the composition example of a curable composition, etc. are shown and it demonstrates more concretely about the Example of this invention, this invention is not limited to these Examples. In the following description, “part” means part by mass unless otherwise specified.
Synthesis example 1
203 parts of cresol novolac type epoxy resin YDCN-700-5 (manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 203 g / eq.) Is placed in a reaction vessel equipped with a thermometer, stirrer, reflux condenser and air blowing tube. Then, 108 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 50.4 parts of acrylic acid, 0.3 part of methylhydroquinone and 1 part of triphenylphosphine were added and reacted at 95-105 ° C. for 7 hours while blowing air. Thereafter, 40.6 parts of maleic acid, 50 parts of diethylene glycol monoethyl ether acetate and 0.2 part of methylhydroquinone were added and reacted at 95 to 105 ° C. for 4 hours to obtain an epoxy equivalent of 44636 g / eq. The reaction product was obtained. Next, 30.4 parts of tetrahydrophthalic anhydride and 33 parts of diethylene glycol monoethyl ether acetate were added and reacted at 95 to 105 ° C. for 4 hours to obtain a solution having a nonvolatile content of 63%. The carboxyl group-containing compound thus obtained had an acid value of 116 mgKOH / g. Hereinafter, this solution is referred to as A-1.
合成例2
クレゾールノボラック型エポキシ樹脂のYDCN−700−5(東都化成(株)製、エポキシ当量:203g/eq.)203部を温度計、撹拌機、還流冷却器及び空気吹き込み管を備えた反応容器に入れ、ジエチレングリコールモノエチルエーテルアセテート108部を加え、加熱溶解した。次に、アクリル酸50.4部、メチルハイドロキノン0.3部及びトリフェニルホスフィン1部を加え、空気を吹き込みながら95〜105℃で6時間反応させた。その後、マレイン酸40.6部、ジエチレングリコールモノエチルエーテルアセテート50部及びメチルハイドロキノン0.2部を加え95〜105℃で4時間反応させ、エポキシ当量55500g/eq.の反応生成物を得た。次いで無水フタル酸29.6部、ジエチレングリコールモノエチルエーテルアセテート32部を加え95〜105℃で4時間反応させて、不揮発分63%の溶液を得た。このようにして得られたカルボキシル基含有化合物は、酸価115mgKOH/g、であった。以下、この溶液をA−2と称す。
Synthesis example 2
203 parts of cresol novolac type epoxy resin YDCN-700-5 (manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 203 g / eq.) Is placed in a reaction vessel equipped with a thermometer, stirrer, reflux condenser and air blowing tube. Then, 108 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 50.4 parts of acrylic acid, 0.3 part of methylhydroquinone and 1 part of triphenylphosphine were added and reacted at 95-105 ° C. for 6 hours while blowing air. Thereafter, 40.6 parts of maleic acid, 50 parts of diethylene glycol monoethyl ether acetate and 0.2 part of methylhydroquinone were added and reacted at 95 to 105 ° C. for 4 hours to obtain an epoxy equivalent of 55500 g / eq. The reaction product was obtained. Subsequently, 29.6 parts of phthalic anhydride and 32 parts of diethylene glycol monoethyl ether acetate were added and reacted at 95 to 105 ° C. for 4 hours to obtain a solution having a nonvolatile content of 63%. The carboxyl group-containing compound thus obtained had an acid value of 115 mgKOH / g. Hereinafter, this solution is referred to as A-2.
合成例3
クレゾールノボラック型エポキシ樹脂のYDCN−700−5(東都化成(株)製、エポキシ当量:203g/eq.)203部を温度計、撹拌機、還流冷却器及び空気吹き込み管を備えた反応容器に入れ、ジエチレングリコールモノエチルエーテルアセテート108部を加え、加熱溶解した。次に、アクリル酸43.2部、酢酸6部、メチルハイドロキノン0.3部及びトリフェニルホスフィン1部を加え、空気を吹き込みながら95〜105℃で6時間反応させた。その後、マレイン酸40.6部、ジエチレングリコールモノエチルエーテルアセテート50部及びメチルハイドロキノン0.2部を加え95〜105℃で4時間反応させ、エポキシ当量44115g/eq.の反応生成物を得た。次いでテトラヒドロ無水フタル酸15.2部、ジエチレングリコールモノエチルエーテルアセテート23部を加え95〜105℃で4時間反応させて、不揮発分63%の溶液を得た。このようにして得られたカルボキシル基含有化合物は、酸価94mgKOH/gであった。以下、この溶液をA−3と称す。
Synthesis example 3
203 parts of cresol novolac type epoxy resin YDCN-700-5 (manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 203 g / eq.) Is placed in a reaction vessel equipped with a thermometer, stirrer, reflux condenser and air blowing tube. Then, 108 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 43.2 parts of acrylic acid, 6 parts of acetic acid, 0.3 part of methylhydroquinone and 1 part of triphenylphosphine were added and reacted at 95-105 ° C. for 6 hours while blowing air. Thereafter, 40.6 parts of maleic acid, 50 parts of diethylene glycol monoethyl ether acetate and 0.2 part of methylhydroquinone were added and reacted at 95 to 105 ° C. for 4 hours to obtain an epoxy equivalent of 44115 g / eq. The reaction product was obtained. Next, 15.2 parts of tetrahydrophthalic anhydride and 23 parts of diethylene glycol monoethyl ether acetate were added and reacted at 95 to 105 ° C. for 4 hours to obtain a solution having a nonvolatile content of 63%. The carboxyl group-containing compound thus obtained had an acid value of 94 mgKOH / g. Hereinafter, this solution is referred to as A-3.
合成例4
クレゾールノボラック型エポキシ樹脂のYDCN−700−5(東都化成(株)製、エポキシ当量:203g/eq.)159.5部及びビスフェノールA型エポキシ樹脂のエピコート828(ジャパンエポキシレジン(株)製、エポキシ当量:186g/eq.)39.9を温度計、撹拌機、還流冷却器及び空気吹き込み管を備えた反応容器に入れ、ジエチレングリコールモノエチルエーテルアセテート107部を加え、加熱溶解した。次に、アクリル酸50.4部、メチルハイドロキノン0.3部及びトリフェニルホスフィン1部を加え、空気を吹き込みながら95〜105℃で6時間反応させた。その後、マレイン酸40.6部、ジエチレングリコールモノエチルエーテルアセテート79部及びメチルハイドロキノン0.2部を加え95〜105℃で4時間反応させ、エポキシ当量48232g/eq.の反応生成物を得た。次いでテトラヒドロ無水フタル酸15.2部、ジエチレングリコールモノエチルエーテルアセテート9部を加え95〜105℃で4時間反応させて、不揮発分61%の溶液を得た。このようにして得られたカルボキシル基含有化合物は、酸価107mgKOH/gであった。以下、この溶液をA−4と称す。
Synthesis example 4
159.5 parts of cresol novolac type epoxy resin YDCN-700-5 (manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 203 g / eq.) And Epicoat 828 of bisphenol A type epoxy resin (manufactured by Japan Epoxy Resins Co., Ltd., epoxy) (Equivalent: 186 g / eq.) 39.9 was put in a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and an air blowing tube, and 107 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 50.4 parts of acrylic acid, 0.3 part of methylhydroquinone and 1 part of triphenylphosphine were added and reacted at 95-105 ° C. for 6 hours while blowing air. Thereafter, 40.6 parts of maleic acid, 79 parts of diethylene glycol monoethyl ether acetate and 0.2 part of methylhydroquinone were added and reacted at 95-105 ° C. for 4 hours to give an epoxy equivalent of 48232 g / eq. The reaction product was obtained. Next, 15.2 parts of tetrahydrophthalic anhydride and 9 parts of diethylene glycol monoethyl ether acetate were added and reacted at 95 to 105 ° C. for 4 hours to obtain a solution having a nonvolatile content of 61%. The carboxyl group-containing compound thus obtained had an acid value of 107 mgKOH / g. Hereinafter, this solution is referred to as A-4.
合成例5
グリシジルメタクリレート、メチルメタクリレート、t−ブチルアクリレート、2−エチルヘキシルメタクリレート及びt−ブチルメタクリレートの共重合体溶液(ジエチレングリコールモノエチルエーテルアセテート、不揮発分50%、重量平均分子量5836、固形分のエポキシ当量:214g/eq.)428部、アクリル酸57.6部、メチルハイドロキノン0.3部及びトリフェニルホスフィン0.5部を温度計、撹拌機、還流冷却器及び空気吹き込み管を備えた反応容器に入れ、空気を吹き込みながら95〜105℃で10時間反応させた。その後、マレイン酸26.7部及びメチルハイドロキノン0.2部を加えて85〜95℃で3時間反応させ、エポキシ当量29479g/eq.の反応生成物を得た。次いでテトラヒドロ無水フタル酸30.4部を加え95〜105℃で4時間反応させて、不揮発分61%の溶液を得た。このようにして得られたカルボキシル基含有化合物は、酸価101mgKOH/gであった。以下、この溶液をA−5と称す。
Synthesis example 5
Copolymer solution of glycidyl methacrylate, methyl methacrylate, t-butyl acrylate, 2-ethylhexyl methacrylate and t-butyl methacrylate (diethylene glycol monoethyl ether acetate, non-volatile content 50%, weight average molecular weight 5836, solid content epoxy equivalent: 214 g / eq.) 428 parts, 57.6 parts of acrylic acid, 0.3 part of methylhydroquinone and 0.5 part of triphenylphosphine are put in a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and an air blowing tube. Was allowed to react at 95 to 105 ° C. for 10 hours. Thereafter, 26.7 parts of maleic acid and 0.2 part of methylhydroquinone were added and reacted at 85 to 95 ° C. for 3 hours to obtain an epoxy equivalent of 29479 g / eq. The reaction product was obtained. Next, 30.4 parts of tetrahydrophthalic anhydride was added and reacted at 95 to 105 ° C. for 4 hours to obtain a solution having a nonvolatile content of 61%. The carboxyl group-containing compound thus obtained had an acid value of 101 mgKOH / g. Hereinafter, this solution is referred to as A-5.
合成例6
クレゾールノボラック型エポキシ樹脂のYDCN−700−10(東都化成(株)製、エポキシ当量:206.4g/eq.)206.4部を温度計、撹拌機、還流冷却器及び空気吹き込み管を備えた反応容器に入れ、ジエチレングリコールモノエチルエーテルアセテート113部を加え、加熱溶解した。次に、アクリル酸57.6部、メチルハイドロキノン0.3部及びトリフェニルホスフィン1部を加え、空気を吹き込みながら95〜105℃で10時間反応させた。次いで、マロン酸26部、ジエチレングリコールモノエチルエーテルアセテート177部及びメチルハイドロキノン0.2部を加え95〜105℃で6時間反応させ、エポキシ当量2520g/eq.の反応生成物を得た。さらに、マレイン酸13.9部、ジエチレングリコールモノエチルエーテルアセテート13.9部を加え95〜105℃で6時間反応させ、エポキシ当量21577g/eq.の反応生成物を得た。その後、テトラヒドロ無水フタル酸45.6部、ジエチレングリコールモノエチルエーテルアセテート45.6部を加え95〜105℃で4時間反応させて、不揮発分50%の溶液を得た。このようにして得られたカルボキシル基含有化合物は、酸価132mgKOH/gであった。以下、この溶液をA−6と称す。
Synthesis Example 6
A cresol novolac type epoxy resin YDCN-700-10 (manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 206.4 g / eq.) 206.4 parts was equipped with a thermometer, stirrer, reflux condenser and air blowing tube. In a reaction vessel, 113 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 57.6 parts of acrylic acid, 0.3 part of methylhydroquinone and 1 part of triphenylphosphine were added and reacted at 95 to 105 ° C. for 10 hours while blowing air. Next, 26 parts of malonic acid, 177 parts of diethylene glycol monoethyl ether acetate and 0.2 part of methylhydroquinone were added and reacted at 95 to 105 ° C. for 6 hours to give an epoxy equivalent of 2520 g / eq. The reaction product was obtained. Furthermore, 13.9 parts of maleic acid and 13.9 parts of diethylene glycol monoethyl ether acetate were added and reacted at 95 to 105 ° C. for 6 hours to give an epoxy equivalent of 21777 g / eq. The reaction product was obtained. Thereafter, 45.6 parts of tetrahydrophthalic anhydride and 45.6 parts of diethylene glycol monoethyl ether acetate were added and reacted at 95 to 105 ° C. for 4 hours to obtain a solution having a nonvolatile content of 50%. The carboxyl group-containing compound thus obtained had an acid value of 132 mgKOH / g. Hereinafter, this solution is referred to as A-6.
合成例7
クレゾールノボラック型エポキシ樹脂のエピクロンN−695(大日本インキ化学工業(株)製、エポキシ当量:220g/eq.)220部を温度計、撹拌機、還流冷却器及び空気吹き込み管を備えた反応容器に入れ、ジエチレングリコールモノエチルエーテルアセテート220部を加え、加熱溶解した。次に、メチルハイドロキノン0.46部、トリフェニルフホスフィン3部を加えた。この混合物を95〜105℃に加熱し、アクリル酸72部を徐々に滴下し、空気を吹き込みながら4時間反応させた。この反応生成物を、80〜90℃まで冷却し、テトラヒドロフタル酸無水物106部を加え、5時間反応させ、不揮発分65%の溶液を得た。このようにして得られたカルボキシル基含有化合物は、酸価100mgKOH/gであった。以下、この溶液をA−7と称す。
Synthesis example 7
A reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and an air blowing tube, 220 parts of cresol novolak type epoxy resin Epicron N-695 (manufactured by Dainippon Ink & Chemicals, Inc., epoxy equivalent: 220 g / eq.) Into this, 220 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 0.46 parts of methylhydroquinone and 3 parts of triphenylphosphine were added. This mixture was heated to 95 to 105 ° C., 72 parts of acrylic acid was gradually added dropwise, and reacted for 4 hours while blowing air. The reaction product was cooled to 80 to 90 ° C., 106 parts of tetrahydrophthalic anhydride was added and reacted for 5 hours to obtain a solution having a nonvolatile content of 65%. The carboxyl group-containing compound thus obtained had an acid value of 100 mgKOH / g. Hereinafter, this solution is referred to as A-7.
合成例8
ビスフェノールA型エポキシ樹脂のエピコート1001(ジャパンエポキシレジン(株)製、エポキシ当量:483g/eq.)483部を温度計、撹拌機、還流冷却器及び空気吹き込み管を備えた反応容器に入れ、ジエチレングリコールモノエチルエーテルアセテート238部を加え、加熱溶解した。次に、アクリル酸72部、メチルハイドロキノン0.2部及びトリフェニルホスフィン3部を加え、空気を吹き込みながら95〜105℃で7時間反応させた。その後、テトラヒドロフタル酸無水物107部、ジエチレングリコールモノエチルエーテルアセテート204部及びメチルハイドロキノン0.3部を加え90〜100℃で8時間反応させ、不揮発分60%の溶液を得た。このようにして得られたカルボキシル基含有化合物は、酸価60mgKOH/gであった。以下、この溶液をA−8と称す。
Synthesis example 8
483 parts of bisphenol A type epoxy resin Epicoat 1001 (manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 483 g / eq.) Is put in a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and an air blowing tube, and diethylene glycol 238 parts of monoethyl ether acetate was added and dissolved by heating. Next, 72 parts of acrylic acid, 0.2 part of methylhydroquinone and 3 parts of triphenylphosphine were added and reacted at 95-105 ° C. for 7 hours while blowing air. Thereafter, 107 parts of tetrahydrophthalic anhydride, 204 parts of diethylene glycol monoethyl ether acetate and 0.3 part of methylhydroquinone were added and reacted at 90 to 100 ° C. for 8 hours to obtain a solution having a nonvolatile content of 60%. The carboxyl group-containing compound thus obtained had an acid value of 60 mgKOH / g. Hereinafter, this solution is referred to as A-8.
合成例9
グリシジルメタクリレート、メチルメタクリレート、t−ブチルアクリレート、2−エチルヘキシルメタクリレート及びt−ブチルメタクリレートの共重合体溶液(ジエチレングリコールモノエチルエーテルアセテート、不揮発分50%、重量平均分子量5836、固形分のエポキシ当量:214g/eq.)428部、アクリル酸72部、メチルハイドロキノン0.2部及びトリフェニルホスフィン1部を温度計、撹拌機、還流冷却器及び空気吹き込み管を備えた反応容器に入れ、空気を吹き込みながら95〜105℃で8時間反応させた。その後、テトラヒドロフタル酸無水物55部及びメチルハイドロキノン0.2部を加え90〜100℃で10時間させ、不揮発分62%の溶液を得た。このようにして得られたカルボキシル基含有化合物は、酸価60mgKOH/gであった。以下、この溶液をA−9と称す。
Synthesis Example 9
Copolymer solution of glycidyl methacrylate, methyl methacrylate, t-butyl acrylate, 2-ethylhexyl methacrylate and t-butyl methacrylate (diethylene glycol monoethyl ether acetate, non-volatile content 50%, weight average molecular weight 5836, solid content epoxy equivalent: 214 g / eq.) 428 parts, 72 parts of acrylic acid, 0.2 part of methylhydroquinone and 1 part of triphenylphosphine were put into a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and an air blowing tube, and 95 while blowing air. The reaction was carried out at ˜105 ° C. for 8 hours. Thereafter, 55 parts of tetrahydrophthalic anhydride and 0.2 part of methylhydroquinone were added and allowed to stand at 90 to 100 ° C. for 10 hours to obtain a solution having a nonvolatile content of 62%. The carboxyl group-containing compound thus obtained had an acid value of 60 mgKOH / g. Hereinafter, this solution is referred to as A-9.
光硬化性・熱硬化性組成物の調製及び各組成物の特性値
前記合成例1〜9の各溶液を表1に示す成分及び成分比で配合し、3本ロールミルでそれぞれ混練して、実施例1〜6、比較例1〜3の光硬化性・熱硬化性樹脂組成物を調整した。
各組成物の特性値を表2に示す。
各特性値は以下の方法で評価した。
(1)現像性
表1に示す実施例1〜6及び比較例1〜3の各硬化性組成物を、スクリーン印刷法により、100メッシュのポリエステルスクリーンを用いて30〜40μmの厚さになるように、パターン形成されている銅スルホールプリント配線基板に全面塗布し、塗膜を80℃の熱風乾燥器を用いて30分間乾燥し、1wt%炭酸ナトリウム水溶液で20秒間、2.0kg/cm2のスプレー圧で現像し、現像後の状態を目視判定した。
○:塗膜が除去された。
×:現像されない部分があった。
Each characteristic value was evaluated by the following method.
(1) Developability Each of the curable compositions of Examples 1 to 6 and Comparative Examples 1 to 3 shown in Table 1 has a thickness of 30 to 40 μm by a screen printing method using a 100 mesh polyester screen. Then, the entire surface of the patterned copper through hole printed wiring board was coated, and the coating film was dried for 30 minutes using a hot air drier at 80 ° C., and 2.0 kg / cm 2 for 20 seconds with a 1 wt% sodium carbonate aqueous solution. Development was performed with a spray pressure, and the state after development was visually determined.
○: The coating film was removed.
X: There was a portion that was not developed.
(2)鉛筆硬度
表1に示す実施例1〜6及び比較例1〜3の各硬化性組成物を、スクリーン印刷法により、100メッシュのポリエステルスクリーンを用いて30〜40μmの厚さになるように、パターン形成されている銅スルーホールプリント配線基板に全面塗布し、塗膜を80℃の熱風循環式乾燥炉で30分間乾燥させた。そして、レジストパターンを有するネガフィルムを乾燥させた塗膜に密着させ、紫外線露光装置((株)オーク製作所製、型式HMW−680GW)を用いて、紫外線を照射した(露光量500mJ/cm2)。次いで1%の炭酸ナトリウム水溶液で60秒間、2.0kg/cm2のスプレー圧で現像し、未露光部分を溶解除去した。その後、150℃の熱風循環式乾燥炉で60分間加熱硬化を行ない、得られた硬化膜を有する評価基板について、
JIS K 5400に準拠して、鉛筆硬度の試験を行なった。
(2) Pencil hardness Each of the curable compositions of Examples 1 to 6 and Comparative Examples 1 to 3 shown in Table 1 has a thickness of 30 to 40 μm using a 100 mesh polyester screen by screen printing. Next, the entire surface of the copper through-hole printed wiring board on which the pattern was formed was applied, and the coating film was dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. And the negative film which has a resist pattern was closely_contact | adhered to the dried coating film, and the ultraviolet-ray was irradiated using the ultraviolet-ray exposure apparatus (Corporation | KK Oak Seisakusho make, model HMW-680GW) (exposure amount 500mJ / cm2). Subsequently, development was performed with a 1% aqueous sodium carbonate solution for 60 seconds at a spray pressure of 2.0 kg / cm 2 to dissolve and remove unexposed portions. Thereafter, heat curing is performed for 60 minutes in a hot air circulation drying oven at 150 ° C., and the evaluation substrate having the obtained cured film,
A pencil hardness test was performed in accordance with JIS K 5400.
(3)耐熱性
上記評価基板を、JIS C 6481の試験方法に従って、260℃のはんだ浴へ10秒浸漬を3回行ない、外観の変化を以下の基準で評価した。ポストフラックス(ロジン系)としては、JIS C 6481に従ったフラックスを使用した。
○:外観変化なし
△:硬化膜の変色が認められるもの
×:硬化膜の浮き、剥れ、はんだ潜りあり
(3) Heat resistance According to the test method of JIS C 6481, the said evaluation board | substrate was immersed in a 260 degreeC solder bath for 10 second 3 times, and the change of the external appearance was evaluated on the following references | standards. As the post flux (rosin type), a flux according to JIS C 6481 was used.
○: No change in appearance △: Discoloration of the cured film is observed ×: Hardened film is lifted, peeled off, or soldered
(4)耐酸性
上記評価基板を10容量%硫酸水溶液に20℃で30分間浸漬後取り出し、硬化膜の状態と密着性とを総合的に判定評価した。判定基準は以下のとおりである。
○:変化が認められないもの
△:ほんの僅か変化しているもの
×:塗膜にフクレあるいは膨潤脱落があるもの
(4) Acid resistance The said evaluation board | substrate was taken out after 30-minute immersion at 10 degreeC sulfuric acid aqueous solution for 30 minutes, and the state and adhesiveness of the cured film were comprehensively evaluated. The judgment criteria are as follows.
○: No change is observed Δ: Only a slight change ×: The coating has blisters or swelling drops
(5)耐アルカリ性
10容量%硫酸水溶液を10容量%水酸化ナトリウム水溶液に代えた以外は耐酸性試験と同様の試験を行い評価した。
(5) Alkali resistance An evaluation similar to the acid resistance test was performed except that the 10 vol% sulfuric acid aqueous solution was replaced with a 10 vol% sodium hydroxide aqueous solution.
(6)密着性
上記評価基板を、JIS D 0202の試験方法に従って、碁盤目状にクロスカットを入れ、次いでセロハン粘着テープによるピーリングテスト後の剥れの状態を目視判定した。
○:100/100
△:50/100〜90/100
×:0/100〜50/100
(6) Adhesiveness According to the test method of JIS D 0202, the evaluation board | substrate was cross-cut into a grid shape, and then the state of peeling after the peeling test with a cellophane adhesive tape was visually determined.
○: 100/100
Δ: 50/100 to 90/100
X: 0/100 to 50/100
(7)PCT耐性
上記評価基板の硬化膜のPCT耐性を、121℃、飽和水蒸気中50時間の条件にて以下の基準で評価した。
○:硬化膜にふくれ、剥がれ、変色がないもの。
△:硬化膜に若干ふくれ、剥がれ、変色があるもの。
×:硬化膜にふくれ、剥がれ、変色があるもの。
(7) PCT resistance The PCT resistance of the cured film of the evaluation substrate was evaluated under the following criteria under the conditions of 121 ° C. and 50 hours in saturated steam.
○: The cured film does not blister, peel off or discolor.
Δ: The cured film has some swelling, peeling, and discoloration.
X: The cured film has blistering, peeling and discoloration.
(8)無電解金めっき耐性
上記評価基板を、無電解ニッケルめっき、次いで無電解金めっきを行い、外観の変化及びセロハン粘着テープを用いたピーリング試験を行ない、硬化膜の剥離状態を判定した。
○:外観変化もなく、硬化膜の剥離も全くない。
△:外観の変化はないが、硬化膜にわずかに剥れがある。
×:硬化膜の浮きが見られ、めっき潜りが認められ、ピーリング試験で硬化膜の剥れが大
きい。
(8) Electroless gold plating resistance The evaluation substrate was subjected to electroless nickel plating and then electroless gold plating, and a change in appearance and a peeling test using a cellophane adhesive tape were performed to determine the peeled state of the cured film.
○: No change in appearance and no peeling of the cured film.
(Triangle | delta): Although there is no change of an external appearance, there exists slight peeling in a cured film.
X: Lifting of the cured film is observed, plating stagnation is observed, and peeling of the cured film is large in the peeling test.
(9)白化耐性
上記評価基板を60℃の湯の中に10分間浸漬し、取り出した後、室温まで自然冷却したときの硬化膜の表面状態を以下の基準で評価した。
○:外観の変化がない。
△:外観が僅かに白く濁っている。
×:外観が白く濁っている。
(9) Whitening resistance After the said evaluation board | substrate was immersed in 60 degreeC hot water for 10 minutes and taken out, the surface state of the cured film when naturally cooled to room temperature was evaluated on the following references | standards.
○: No change in appearance.
Δ: Appearance is slightly white and cloudy.
X: The appearance is white and cloudy.
(10)電気絶縁性
パターン形成されている銅スルーホールプリント配線基板の代わりに、IPCで定められたプリント回路基板(厚さ1.6mm)のBパターンを用い、前記の方法にて硬化性組成物の塗布、硬化を行ない、得られた硬化膜の電気絶縁性を以下の基準にて評価した。
加湿条件:温度121℃、湿度85%RH、印加電圧5V、100時間。
測定条件:測定時間60秒、印加電圧500V。
○:加湿後の絶縁抵抗値109Ω以上、銅のマイグレーションなし。
△:加湿後の絶縁抵抗値109Ω以上、銅のマイグレーションあり。
×:加湿後の絶縁抵抗値108Ω以下、銅のマイグレーションあり。
(10) Electrical insulation In place of the copper through-hole printed wiring board on which the pattern is formed, the B pattern of the printed circuit board (thickness 1.6 mm) defined by the IPC is used, and the curable composition is formed by the above method. Application | coating and hardening of the thing were performed and the electrical insulation of the obtained cured film was evaluated in accordance with the following criteria.
Humidification conditions: temperature 121 ° C., humidity 85% RH, applied voltage 5 V, 100 hours.
Measurement conditions: measurement time 60 seconds, applied voltage 500V.
○: Insulation resistance value after humidification of 10 9 Ω or more, no copper migration.
Δ: Insulation resistance value after humidification of 10 9 Ω or more, copper migration.
X: Insulation resistance value after humidification of 10 8 Ω or less, copper migration.
(11)可撓性
パターン形成されている銅スルーホールプリント配線基板の代わりに、ポリエステルフィルムを用い、前記の方法にて硬化性組成物の塗布、硬化を行ない、その後ポリエステルフィルムから硬化塗膜をはがし、長さ5cm、幅2cmの評価フィルムを得た。得られたフィルムを折り曲げ、以下の基準にて評価した。
○:フィルムを170°折り曲げて割れなかったもの。
△:フィルムを170°折り曲げると割れるが、160°折り曲げて割れなかったもの
×:フィルムを160°折り曲げて割れたもの。
(11) Flexibility Instead of a patterned copper through-hole printed wiring board, a polyester film is used, and the curable composition is applied and cured by the above method, and then a cured coating film is formed from the polyester film. An evaluation film having a length of 5 cm and a width of 2 cm was obtained. The obtained film was bent and evaluated according to the following criteria.
○: The film was bent by 170 ° and not cracked.
Δ: The film was cracked when it was folded 170 °, but it was not cracked when it was folded 160 °. X: The film was cracked when it was folded 160 °.
本発明の光硬化性・熱硬化性組成物は、現像性に優れ、且つ、前記したような諸特性に優れた硬化物が得られるため、ソルダーレジスト、エッチングレジスト、メッキレジスト、多層配線板の層間絶縁層、テープキャリアパッケージの製造に用いられる永久マスク、フレキシブル配線基板用レジスト、カラーフィルター用レジスト、ドライフィルム用レジスト、インクジェト用レジストなどの用途にも有用である。 Since the photocurable / thermosetting composition of the present invention is excellent in developability and can provide a cured product having excellent properties as described above, a solder resist, an etching resist, a plating resist, a multilayer wiring board It is also useful for applications such as interlayer insulating layers, permanent masks used in the manufacture of tape carrier packages, flexible wiring board resists, color filter resists, dry film resists, and inkjet resists.
Claims (9)
(B)前記カルボキシル基含有化合物(A)以外のカルボキシル基含有化合物、
(C)感光性(メタ)アクリレート化合物、及び
(D)光重合開始剤
を含有することを特徴とするアルカリ現像可能な硬化性組成物。 (A) The monocarboxylic acid (b) is reacted with the epoxy group of the resin (a) having two or more epoxy groups in one molecule at a ratio of 0.3 to 0.9 mol with respect to 1 equivalent of the epoxy group. The polybasic acid (d) is reacted with the epoxy group of the obtained reaction product (c) at a ratio of 0.2 to 5 mol per 1 equivalent of the epoxy group, and the reaction product (e The reaction product (g) having an acid value of 18 to 180 mgKOH / g obtained by reacting the epoxy group of) with a monocarboxylic acid (f) at a ratio of 0.0 to 5.0 mol with respect to 1 equivalent of the epoxy group. A carboxyl group-containing compound having an acid value of 40 to 200 mgKOH / g, obtained by further reacting the secondary alcoholic hydroxyl group with a polybasic acid anhydride (h),
(B) a carboxyl group-containing compound other than the carboxyl group-containing compound (A),
A curable composition capable of alkali development, comprising (C) a photosensitive (meth) acrylate compound, and (D) a photopolymerization initiator.
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JP2015011256A (en) * | 2013-07-01 | 2015-01-19 | 互応化学工業株式会社 | Composition for solder resist and printed wiring board |
US9128375B2 (en) | 2011-08-11 | 2015-09-08 | Goo Chemical Co., Ltd. | Resin composition for masks |
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