JP5430884B2 - Curable composition capable of alkali development and cured product thereof - Google Patents
Curable composition capable of alkali development and cured product thereof Download PDFInfo
- Publication number
- JP5430884B2 JP5430884B2 JP2008161553A JP2008161553A JP5430884B2 JP 5430884 B2 JP5430884 B2 JP 5430884B2 JP 2008161553 A JP2008161553 A JP 2008161553A JP 2008161553 A JP2008161553 A JP 2008161553A JP 5430884 B2 JP5430884 B2 JP 5430884B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- curable composition
- group
- monocarboxylic acid
- epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 95
- 239000003513 alkali Substances 0.000 title claims description 4
- 238000011161 development Methods 0.000 title claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 63
- 229920000647 polyepoxide Polymers 0.000 claims description 63
- 239000003822 epoxy resin Substances 0.000 claims description 54
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 40
- 239000007795 chemical reaction product Substances 0.000 claims description 40
- 125000003700 epoxy group Chemical group 0.000 claims description 40
- 229920003986 novolac Polymers 0.000 claims description 39
- -1 acrylate compound Chemical class 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000004593 Epoxy Substances 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 21
- 150000002763 monocarboxylic acids Chemical group 0.000 claims description 19
- 238000007259 addition reaction Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 9
- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 55
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 41
- 239000000243 solution Substances 0.000 description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 24
- 238000000576 coating method Methods 0.000 description 18
- 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 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 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 15
- 238000007664 blowing Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 14
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 229910000679 solder Inorganic materials 0.000 description 13
- 229920001187 thermosetting polymer Polymers 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000010292 electrical insulation Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000007747 plating Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000001476 alcoholic effect Effects 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 150000001252 acrylic acid derivatives Chemical class 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
- 238000010438 heat treatment Methods 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 7
- 229910052737 gold Inorganic materials 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 6
- 239000011976 maleic acid Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 230000002087 whitening effect Effects 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
- 235000011054 acetic acid Nutrition 0.000 description 5
- 150000008065 acid anhydrides Chemical class 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
- 230000000052 comparative effect Effects 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
- 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 5
- 150000007519 polyprotic acids Polymers 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- KVXNKFYSHAUJIA-UHFFFAOYSA-N acetic acid;ethoxyethane Chemical compound CC(O)=O.CCOCC KVXNKFYSHAUJIA-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 150000001875 compounds Chemical class 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 group 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
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000004843 novolac epoxy resin Substances 0.000 description 4
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 3
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-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
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- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 3
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Macromonomer-Based Addition Polymer (AREA)
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ノボラック型樹脂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 or the like of a printed wiring board, and more particularly to a curable composition containing a carboxyl group-containing novolac resin 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組成物としては、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光及び熱硬化性樹脂を用いた組成物が主流になっている。このような硬化性組成物として、例えば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樹脂を用いた硬化性組成物(特許文献1参照)、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樹脂を用いた硬化性組成物(特許文献2参照)等が挙げられる。 Currently, as a curable composition used for forming a solder resist on a printed wiring board, a composition using a light and thermosetting resin that can be developed with a dilute alkaline aqueous solution has become mainstream in consideration of environmental problems. ing. As such a curable composition, for example, a curable composition using a curable resin obtained by adding an acid anhydride to a reaction product of a novolak-type epoxy resin and an unsaturated group-containing monocarboxylic acid (see Patent Document 1), 1 Epihalohydrin is reacted with an alcoholic secondary hydroxyl group obtained by reacting an aromatic epoxy resin having two glycidyl groups in the molecule with an aromatic alcohol resin having two phenolic hydroxyl groups in one molecule. Examples thereof include a curable composition using a curable resin obtained by adding an unsaturated group-containing monocarboxylic acid and then an acid anhydride to the obtained reaction product (see Patent Document 2).
このように、従来より幾つかの硬化性組成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。
近年の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を製造する場合、従来市販されている硬化性組成物では現像性が十分ではなく、高密度化に対応した解像性に乏しい。また、従来の硬化性組成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、可撓性の低下や高温及び高湿下での電気絶縁性の低下及び白化現象が問題となっている。
Thus, several curable compositions have been proposed in the past, and are currently widely used in the production of actual printed wiring boards.
In recent years, printed wiring boards have been densified along with the reduction in size and size of electronic equipment, and higher performance of solder resists is required in response to the higher density of printed wiring boards. That is, when manufacturing a high-density printed wiring board, the curable composition that has been commercially available in the past does not have sufficient developability, and the resolution corresponding to the increase in density is poor. In addition, in a high-density printed wiring board in which a solder resist is formed using a conventional curable composition, there are problems such as a decrease in flexibility, a decrease in electrical insulation under high temperature and high humidity, and a whitening phenomenon. ing.
可撓性の問題を解決する硬化性組成物として、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たカルボキシル基含有感光性プレポリマーを用いた硬化性組成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と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の反応生成物と、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/又はその無水物との反応生成物であってカルボキシル基を有する感光性プレポリマーを用いた硬化性組成物が開示されている。
As a curable composition that solves the problem of flexibility, the alcoholic secondary hydroxyl group of bisphenol A type epoxy resin is reacted with epihalohydrin, and then the resulting polyfunctional epoxy resin is added per epoxy equivalent. Carboxyl obtained by reacting 0.2 to 1.2 mol of ethylenically unsaturated carboxylic acid and further reacting 0.2 to 1.0 mol of polybasic carboxylic acid and / or anhydride thereof per epoxy equivalent A curable composition using a group-containing photosensitive prepolymer has been proposed (see Patent Document 3).
Patent Document 4 discloses a reaction product of a mixture of a novolac type epoxy resin and a rubber-modified bisphenol A type epoxy resin and 0.2 to 1.2 mol of ethylenically unsaturated carboxylic acid per epoxy equivalent of the mixture; A curable composition using a photosensitive prepolymer having a carboxyl group, which is a reaction product of 0.2 to 1.0 mol of a polybasic carboxylic acid and / or an anhydride thereof per epoxy equivalent of the above mixture. It is disclosed.
さらに、特許文献5には、2個以上のグリシジル基を1分子内にもつエポキシ樹脂とエチレン性不飽和モノカルボン酸及び多塩基酸とを所定の割合で反応させ、得られた反応物の1級及び/又は2級のヒドロキシル基の一部をエチレン性不飽和モノカルボン酸の塩化物でエステル化反応させ、さらに得られた反応物に残存するヒドロキシル基の一部または全てを多塩基酸及び/又は多塩基酸無水物でエステル化反応させて得られるビニルエステル樹脂を用いた硬化性組成物が開示されている。
上記硬化性組成物を用いて得られたレジスト膜は、可撓性には優れている。しかし、上記硬化性組成物では、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ない。
Furthermore, in Patent Document 5, an epoxy resin having two or more glycidyl groups in one molecule is reacted with an ethylenically unsaturated monocarboxylic acid and a polybasic acid at a predetermined ratio, and 1 of the obtained reactants. A part of the primary and / or secondary hydroxyl groups are esterified with an ethylenically unsaturated monocarboxylic acid chloride, and some or all of the remaining hydroxyl groups in the resulting reaction product are converted into polybasic acids and A curable composition using a vinyl ester resin obtained by esterification with a polybasic acid anhydride is disclosed.
A resist film obtained using the curable composition is excellent in flexibility. However, with the curable composition, 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 cannot be obtained.
一方、可撓性、さらには電気絶縁性の問題を解決する硬化性組成物として、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感光性樹脂を用いた硬化性組成物(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感光性樹脂を用いた硬化性組成物(特許文献7参照)等が提案されている。しかしながら、これらの組成物は現像性に劣る。また、上記組成物を用いてレジストを形成した高密度化のプリント配線板は、高温及び高湿下での電気絶縁性には優れているが、硬度が低く、白化する。
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(プレッシャー・クッカー・テスト)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 above problems, and has excellent developability, hardness, solder heat resistance, chemical resistance, adhesion, PCT (pressure cooker test) resistance, and electroless gold plating. An object of the present invention is to provide a curable composition capable of forming a cured film having excellent properties such as resistance, whitening resistance, electrical insulation and flexibility, and a cured product thereof.
上記目的を達成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)下記一般式(1)、(2)、(3)及び(4)で示される構造単位から成り、酸価20〜131mgKOH/g、エポキシ当量3000g/eq.以上で、且つ有機溶剤に可溶であるカルボキシル基含有ノボラック型樹脂
(B)感光性(メタ)アクリレート化合物、及び
(C)光重合開始剤
を含有することを特徴とする。
The alkali-developable curable composition according to the present invention, which has been made to achieve the above object,
(A) It consists of structural units represented by the following general formulas (1), (2), (3) and (4), and has an acid value of 20 to 131 mgKOH / g, an epoxy equivalent of 3000 g / eq. A carboxyl group-containing novolac resin that is soluble in an organic solvent as described above
It contains (B) a photosensitive (meth) acrylate compound, and (C) a photopolymerization initiator.
本発明の具体的な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ノボラック型樹脂は、上記一般式(1)、(2)において、X1、X2がそれぞれ不飽和基含有モノカルボン酸残基、又はX1が不飽和基含有モノカルボン酸残基、X2が不飽和基を含有しないモノカルボン酸残基、又はX1、X2がそれぞれ不飽和基を含有しないモノカルボン酸残基である。 According to a specific preferred embodiment of the present invention, the carboxyl group-containing novolak resin, which is one component of the curable composition, is such that in the general formulas (1) and (2), X 1 and X 2 are not present. Saturated group-containing monocarboxylic acid residue, or X 1 is an unsaturated group-containing monocarboxylic acid residue, X 2 is a monocarboxylic acid residue that does not contain an unsaturated group, or X 1 and X 2 are each an unsaturated group. It is a monocarboxylic acid residue not contained.
より具体的な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ノボラック型樹脂は、カルボキシル基含有ノボラック型樹脂は、ノボラック型エポキシ樹脂(a)のエポキシ基に、部分的に不飽和基含有モノカルボン酸(b)及び同一又は異なる不飽和基含有モノカルボン酸(b')を付加反応させ、得られた反応生成物(c)のエポキシ基に、ジカルボン酸(d)を付加反応させて得られる、又は上記ノボラック型エポキシ樹脂(a)のエポキシ基に、部分的に不飽和基含有モノカルボン酸(b)を付加反応させ、次いで得られた反応生成物(c')のエポキシ基に、部分的にジカルボン酸(d)を付加反応させ、さらに得られた反応生成物(e)のエポキシ基に、不飽和基含有モノカルボン酸(b')を付加反応させて得られる、又は上記反応生成物(e)のエポキシ基に、不飽和基を含有しないモノカルボン酸(f)を付加反応させて得られる、又は上記ノボラック型エポキシ樹脂(a)のエポキシ基に、部分的に不飽和基含有モノカルボン酸(b)及び不飽和基を含有しないモノカルボン酸(f)を付加反応させ、次いで得られた反応生成物(g)のエポキシ基に、ジカルボン酸(d)を付加反応させて得られる、又は上記ノボラック型エポキシ樹脂(a)のエポキシ基に、部分的に不飽和基を含有しないモノカルボン酸(f)を付加反応させ、次いで得られた反応生成物(h)のエポキシ基に、部分的にジカルボン酸(d)を付加反応させ、さらに得られた反応生成物(i)のエポキシ基に、不飽和基含有モノカルボン酸(b)を付加反応させて得られるが、上記不飽和基含有モノカルボン酸(b)がアクリル酸又はメタクリル酸であり、上記ジカルボン酸(d)が反応溶媒に可溶及び/又は反応温度で溶媒中に融けるカルボン酸が好ましい。 According to a more specific preferred embodiment, the carboxyl group-containing novolac resin, which is one component of the curable composition, is partially bonded to the epoxy group of the novolac epoxy resin (a). To the unsaturated group-containing monocarboxylic acid (b) and the same or different unsaturated group-containing monocarboxylic acid (b ′), and the epoxy group of the resulting reaction product (c) is added to the dicarboxylic acid (d). Or an epoxy group of the novolak-type epoxy resin (a) partially added with the unsaturated group-containing monocarboxylic acid (b), and then the reaction product (c ′ The dicarboxylic acid (d) is partially added to the epoxy group of (2), and the unsaturated group-containing monocarboxylic acid (b ′) is further added to the epoxy group of the obtained reaction product (e). Gain Or obtained by subjecting the epoxy group of the reaction product (e) to an addition reaction with a monocarboxylic acid (f) not containing an unsaturated group, or a part of the epoxy group of the novolac epoxy resin (a). Then, an unsaturated group-containing monocarboxylic acid (b) and an unsaturated group-free monocarboxylic acid (f) are subjected to an addition reaction, and then the epoxy group of the resulting reaction product (g) is converted to a dicarboxylic acid (d). Or a monocarboxylic acid (f) that does not partially contain an unsaturated group is added to the epoxy group of the novolak-type epoxy resin (a), and then the reaction product ( h) an epoxy group of the dicarboxylic acid (d) is partially subjected to an addition reaction, and an epoxy group of the obtained reaction product (i) is further subjected to an addition reaction of an unsaturated group-containing monocarboxylic acid (b). can get The unsaturated group-containing monocarboxylic acid (b) is acrylic acid or methacrylic acid, the dicarboxylic acid (d) is a carboxylic acid soluble in the solvent soluble and / or the reaction temperature in the reaction solvent preferred.
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, the developability required for a curable composition capable of supporting high density printed wiring boards is sufficiently satisfied, and the hardness, solder heat resistance, chemical resistance, adhesion, and PCT resistance are satisfied. 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、前記一般式(1)、(2)、(3)及び(4)で示される構造単位から成るノボラック型カルボキシル基含有樹脂を含む組成物が、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 to solve the above-mentioned problems, the inventors of the present invention have novolak-type carboxyl group containing the structural unit represented by the general formulas (1), (2), (3) and (4). A resin-containing composition has excellent developability, and has excellent hardness, solder heat resistance, chemical resistance, adhesion, PCT resistance, electroless gold plating resistance, whitening resistance, electrical insulation, and flexibility. The present invention has been found to give a product, and the present invention has been completed.
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ノボラック型樹脂は、二級のアルコール性水酸基がどの側鎖にも存在するために優れた現像性が得られ、しかも不飽和基やカルボキシル基が、それぞれ側鎖の末端に位置するため、反応性に優れる。そして、このようなカルボキシル基含有ノボラック型樹脂に感光性(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 novolac resin, which is a component of the curable composition of the present invention, has excellent developability because a secondary alcoholic hydroxyl group is present in any side chain, and also has an unsaturated group. And the carboxyl group is located at the end of the side chain, so that the reactivity is excellent. And the composition which added the photosensitive (meth) acrylate compound and the photoinitiator to such a carboxyl group-containing novolak-type resin gives the hardened | cured material with a high crosslinking density and the outstanding characteristic.
以下、本発明の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ノボラック型樹脂(A)は、モノカルボン酸残基やカルボキシル基が、それぞれ側鎖の末端に位置し、しかもすべての側鎖に二級のアルコール性水酸基を有するが、どの側鎖にも一級のアルコール性水酸基は存在しないところに特徴がある。このような構造は、種々の方法によって得ることができる。例えば、ノボラック型エポキシ樹脂(a)のエポキシ基に、モノカルボン酸(bf)及び同一又は異なるモノカルボン酸(b'f)を部分的に付加反応させ、次いで得られた反応生成物(ch)の残りのエポキシ基にジカルボン酸(d)を付加反応させる方法(以下、この方法によって得られる構造をKと称す。)、ノボラック型エポキシ樹脂(a)のエポキシ基に、部分的にモノカルボン酸(bf)を付加反応させ、次いで得られた反応生成物(c'h)のエポキシ基に、部分的にジカルボン酸(d)を付加反応させ、さらに得られた反応生成物(ei)の残りのエポキシ基に、モノカルボン酸(b'f)を付加反応させる方法(以下、この方法によって得られる構造をNと称す。)などが挙げられるが、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 curable composition of the present invention will be described in detail.
First, the carboxyl group-containing novolak resin (A), which is a component of the present invention, has a monocarboxylic acid residue and a carboxyl group located at the end of each side chain, and secondary alcoholic groups in all side chains. Although it has a hydroxyl group, it is characterized in that no primary alcoholic hydroxyl group exists in any side chain. Such a structure can be obtained by various methods. For example, a monocarboxylic acid (bf) and the same or different monocarboxylic acid (b′f) are partially added to the epoxy group of the novolak-type epoxy resin (a), and the resulting reaction product (ch) Of the remaining epoxy group of dicarboxylic acid (d) (hereinafter, the structure obtained by this method is referred to as K), and the epoxy group of the novolac epoxy resin (a) is partially monocarboxylic acid (Bf) is subjected to an addition reaction, and then an epoxy group of the obtained reaction product (c′h) is partially subjected to an addition reaction with a dicarboxylic acid (d), and the remaining reaction product (ei) remaining is obtained. And the like, and a method of adding a monocarboxylic acid (b′f) to the epoxy group (hereinafter, the structure obtained by this method is referred to as “N”). It is easily carried out in a solvent or without a solvent.
構造Kを得るために、前記ノボラック型エポキシ樹脂(a)のエポキシ基に、モノカルボン酸(bf)及び同一又は異なるモノカルボン酸(b'f)を部分的に付加反応させて、反応生成物(ch)を得るが、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。上記ノボラック型エポキシ樹脂(a)のエポキシ基1当量に対して、モノカルボン酸(bf)及び(b'f)を合計で0.3〜0.9モルの割合で反応させることが好ましいが、より好ましくは、0.5〜0.8モルである。モノカルボン酸(bf)及び(b'f)が合計で0.3〜0.9モルの範囲を外れると、この後の反応でゲル化、又は最終生成物の現像性が十分に得られない恐れがある。モノカルボン酸(bf)及び/又は(b'f)が、不飽和基含有モノカルボン酸である場合には、最終生成物の光硬化性が得られる。 In order to obtain the structure K, a monocarboxylic acid (bf) and the same or different monocarboxylic acid (b′f) are partially added to the epoxy group of the novolak-type epoxy resin (a) to obtain a reaction product. (Ch) is obtained, and in this case, it is preferable to carry out the reaction in a solvent using a polymerization inhibitor and a catalyst, and the reaction temperature is preferably 50 to 150 ° C, more preferably 70 to 120 ° C. Although it is preferable to react the monocarboxylic acid (bf) and (b′f) at a ratio of 0.3 to 0.9 mol in total with respect to 1 equivalent of the epoxy group of the novolak type epoxy resin (a), More preferably, it is 0.5-0.8 mol. When the monocarboxylic acids (bf) and (b′f) are out of the range of 0.3 to 0.9 mol in total, gelation in the subsequent reaction or developability of the final product cannot be sufficiently obtained. There is a fear. When the monocarboxylic acid (bf) and / or (b′f) is an unsaturated group-containing monocarboxylic acid, the photocurability of the final product is obtained.
前記モノカルボン酸(bf)及び(b'f)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。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。ここで好ましいのは、アクリル酸、メタクリル酸、及び酢酸である。 Representative examples of the monocarboxylic acids (bf) and (b′f) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-furfurylacrylic. Monocarboxylic acids containing unsaturated groups such as acids, 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, tridecyl Acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid and other saturated aliphatic monocarboxylic acids, benzoic acid, alkylbenzoic acid, alkylaminobenzoic acid, halogenated benzoic acid , Aromatic monocarboxylic acids such as phenylacetic acid, anisic acid, benzoylbenzoic acid, naphthoic acid, etc. And the like. These monocarboxylic acids can be used alone or in admixture of two or more. Preference is given here to acrylic acid, methacrylic 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。これらの反応用剤(有機溶剤)は、単独で又は2種類以上の混合物として使用することができる。 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. These reaction agents (organic solvents) can be used alone or as a mixture 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く、単独で又は2種類以上を混合して使用してもかまわない。 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 metal salts of organic acids such as lithium, chromium, zirconium, potassium, and sodium of acid, stearic acid, oleic acid, and octoenoic acid, but are not limited to these, alone or in combination of two or more. May be used.
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く、単独で又は2種類以上を混合して使用することができる。 Examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and phenothiazine, but are not limited to these and may be used alone or in combination of two or more. it can.
前記反応生成物(ch)のエポキシ基に、エポキシ基1当量に対して、ジカルボン酸(d)を1.0モル以上の割合で付加反応させて、本発明の組成物の一成分であるカルボキシル基含有ノボラック型樹脂の構造Kが得られるが、その際ジカルボン酸(d)は、反応溶媒に可溶及び/又は反応温度で溶媒中に融けるものが好ましい。反応溶媒に不溶及び/又は反応温度で溶媒中に融けないジカルボン酸(d)を反応生成物(ch)に付加反応させようとすると、ジカルボン酸(d)が反応生成物(ch)に十分に付加しない、又はゲル化する恐れがあるからである。反応温度は、好ましくは50〜150℃、より好ましくは70〜120℃である。前記ノボラック型エポキシ樹脂(a)、モノカルボン酸(bf)及びジカルボン酸(d)の反応量は、ノボラック型エポキシ樹脂(a)のエポキシ基1当量に対して、モノカルボン酸(bf)及びジカルボン酸(d)の合計で0.94〜1モルが好ましい。また、反応生成物のエポキシ当量は3000g/eq.以上であるが、好ましくは、5000g/eq.以上である。エポキシ当量が3000g/eq.以下では、ゲル化し有機溶剤に不溶となり、又は高分子化により最終生成物の現像性が十分に得られない。 Carboxyl which is one component of the composition of the present invention is obtained by subjecting the epoxy group of the reaction product (ch) to addition reaction of 1.0 mol or more of dicarboxylic acid (d) with respect to 1 equivalent of epoxy group. The structure K of the group-containing novolac resin is obtained, and the dicarboxylic acid (d) is preferably soluble in the reaction solvent and / or melted in the solvent at the reaction temperature. When dicarboxylic acid (d) that is insoluble in the reaction solvent and / or does not melt in the solvent at the reaction temperature is added to the reaction product (ch), the dicarboxylic acid (d) is sufficiently contained in the reaction product (ch). This is because they may not be added or gelled. The reaction temperature is preferably 50 to 150 ° C, more preferably 70 to 120 ° C. The reaction amount of the novolak-type epoxy resin (a), monocarboxylic acid (bf) and dicarboxylic acid (d) is such that the monocarboxylic acid (bf) and dicarboxylic acid (bf) and dicarboxylic acid (d) are equivalent to 1 equivalent of the epoxy group of the novolak-type epoxy resin (a). The total amount of the acid (d) is preferably 0.94 to 1 mol. The epoxy equivalent of the reaction product was 3000 g / eq. Above, but preferably 5000 g / eq. That's it. Epoxy equivalent is 3000 g / eq. Below, it gels and becomes insoluble in an organic solvent, or developability of the final product is not sufficiently obtained due to polymerization.
前記ジカルボン酸(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等が挙げられる。これらジカルボン酸は、単独で又は2種類以上を混合して用いることができる。ここで好ましいのは、反応溶媒に可溶及び/又は反応温度で溶媒中に融けるジカルボン酸(d)であり、より好ましいのは、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、特に好ましいのは、マレイン酸、テトラヒドロフタル酸及びフタル酸である。 Representative examples of the dicarboxylic 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 isophthalic acid, terephthalic acid, and tetrahydrophthalic acid. These dicarboxylic acids can be used alone or in admixture of two or more. Preference is given here to dicarboxylic acids (d) which are soluble in the reaction solvent and / or melt into the solvent at the reaction temperature, more preferred are malonic acid, glutaric acid, maleic acid, tetrahydrophthalic acid and phthalic acid, Particularly preferred are maleic acid, tetrahydrophthalic acid and phthalic acid.
また、ノボラック型エポキシ樹脂(a)のエポキシ基に、部分的にモノカルボン酸(bf)を付加反応させ、得られた反応生成物(c'h)のエポキシ基に、部分的にジカルボン酸(d)を付加反応させ、さらに得られた反応生成物(ei)の残りのエポキシ基に、モノカルボン酸(b'f)を付加反応させて、本発明のカルボキシル基含有ノボラック型樹脂の構造Nが得られるが、モノカルボン酸(bf)及び(b'f)の付加の役割は、ジカルボン酸(d)の反応生成物(c'h)に対する架橋反応を抑制するためである。それ故、反応生成物(c'h)とジカルボン酸(d)の反応時間を長くしてはならない。これらの反応時間が長いとジカルボン酸(d)が、反応生成物(c'h)の架橋剤として働く恐れがあるからである。反応温度は、好ましくは50〜150℃、より好ましくは70〜120℃である。又、上記ノボラック型エポキシ樹脂(a)のエポキシ基1当量に対して、モノカルボン酸(bf)を0.3〜0.85モルの割合で反応させ、得られた反応生成物(c'h)のエポキシ基に、エポキシ基1当量に対して、ジカルボン酸(d)を0.3〜0.95モルの割合で反応させることが好ましい。このようにして得られた反応生成物(ei)の残りのエポキシ基に、エポキシ基1当量に対して、モノカルボン酸(b'f)を1.0モル以上の割合で反応させることが好ましい。 In addition, the monocarboxylic acid (bf) is partially added to the epoxy group of the novolak-type epoxy resin (a), and the dicarboxylic acid (c′h) is partially added to the epoxy group of the obtained reaction product (c′h). d) is subjected to an addition reaction, and the remaining epoxy group of the obtained reaction product (ei) is further subjected to an addition reaction with a monocarboxylic acid (b′f) to obtain the structure N of the carboxyl group-containing novolak resin of the present invention. However, the role of the addition of the monocarboxylic acids (bf) and (b′f) is to suppress the crosslinking reaction of the dicarboxylic acid (d) with respect to the reaction product (c′h). Therefore, the reaction time of the reaction product (c′h) and the dicarboxylic acid (d) must not be increased. If these reaction times are long, the dicarboxylic acid (d) may act as a crosslinking agent for the reaction product (c′h). The reaction temperature is preferably 50 to 150 ° C, more preferably 70 to 120 ° C. Further, the monocarboxylic acid (bf) is reacted at a ratio of 0.3 to 0.85 mol with respect to 1 equivalent of the epoxy group of the novolac type epoxy resin (a), and the reaction product (c′h) It is preferable to react the dicarboxylic acid (d) at a ratio of 0.3 to 0.95 mol with respect to 1 equivalent of the epoxy group. The remaining epoxy groups of the reaction product (ei) thus obtained are preferably reacted with a monocarboxylic acid (b′f) at a ratio of 1.0 mol or more per 1 equivalent of the epoxy groups. .
上記カルボキシル基含有ノボラック型樹脂の酸価は、20〜131mgKOH/gであるが、好ましくは33〜111mgKOH/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 acid value of the carboxyl group-containing novolac resin is 20 to 131 mgKOH / g, preferably 33 to 111 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(B)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、これらは単独で又は2種類以上を組み合わせて使用することができる。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ノボラック型樹脂(A)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(B)の配合量は、前記カルボキシル基含有ノボラック型樹脂(A)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 (B) 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 novolac 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. Can be used alone or in combination of two or more. Among these, a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in one molecule is preferable. The purpose of using these photosensitive (meth) acrylate compounds is to increase the photoreactivity of the carboxyl group-containing novolac resin (A). 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. The compounding amount of the photosensitive (meth) acrylate compound (B) is preferably 100 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing novolac resin (A). 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(C)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種類以上の混合物として使用でき、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、単独であるいは複数併用して使用できる。そして、その使用量は前記カルボキシル基含有ノボラック型樹脂(A)100質量部(合計量又は単独使用の場合には単独量)に対して0. 5〜25質量部の割合が好ましい。 Examples of the photopolymerization initiator (C) 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 as a mixture of two or more thereof. Further, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4- Photoinitiator aids such as tertiary amines such as 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 combination. And the usage-amount is the ratio of 0.5-25 mass parts with respect to 100 mass parts (total amount or single amount in the case of single use) of said carboxyl group-containing novolak-type resin (A).
また、本発明の硬化性組成物は、カルボキシル基含有ノボラック型樹脂(A)の熱硬化性を促進させる目的で、熱硬化成分を配合させることができる。前記熱硬化成分は前記カルボキシル基含有ノボラック型樹脂(A)のカルボキシル基と熱によって反応するものであれば、どのようなものでも良い。一般的には、エポキシ樹脂、オキセタン樹脂などが挙げられる。
エポキシ樹脂としては、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;さらにヒダントイン型エポキシ樹脂、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等が挙げられる。
Moreover, the curable composition of this invention can mix | blend a thermosetting component in order to accelerate | stimulate the thermosetting of carboxyl group-containing novolak-type resin (A). The thermosetting component may be anything as long as it reacts with the carboxyl group of the carboxyl group-containing novolac resin (A) by heat. Generally, an epoxy resin, an oxetane resin, etc. are mentioned.
As the epoxy resin, for example, Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, Epiklone 840, Epicron 850, Epicron 1050, Epicron 1050, Epicron 2055, Toto from Japan Epoxy Resin Co., Ltd. Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Kasei Chemical Co., Ltd., D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.E. 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; Furthermore, hydantoin type epoxy resin, copolymer epoxy resin of cyclohexyl maleimide and glycidyl methacrylate, alcoholic secondary hydroxyl group obtained by reacting 1,5-dihydroxynaphthalene and bisphenol A type epoxy resin, epihalo Polyfunctional epoxy resin obtained by reacting hydrin (International publication) O 01/024774 discloses), epoxy resins having a 1,3-dioxolane ring obtained ketone by the addition reaction in a part of the epoxy groups.
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。 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.
前記したような熱硬化成分は、単独であるいは2種類以上を組み合わせて用いることができる。これらの熱硬化成分は、前記カルボキシル基含有ノボラック型樹脂(A)との熱硬化により、レジストの密着性、耐熱性等の特性を向上させる。その配合量は、前記カルボキシル基含有ノボラック型樹脂(A)100質量部に対して10質量部以上、100質量部以下の割合で充分であり、好ましくは15〜60質量部の割合である。熱硬化成分の配合量が上記範囲未満の場合、硬化膜の吸湿性が高くなってPCT耐性が低下し易くなり、また、はんだ耐熱性や無電解めっき耐性も低くなり易い。一方、上記範囲を超えると、塗膜の現像性や硬化膜の無電解めっき耐性が悪くなり、またPCT耐性も劣ったものとなる。電子材料用としては、熱硬化成分は、エポキシ樹脂が好ましいが、その中でも、1分子中にエポキシ基を2個以上有する多官能エポキシ樹脂が好ましい。 The aforementioned thermosetting components can be used alone or in combination of two or more. These thermosetting components improve characteristics such as resist adhesion and heat resistance by thermosetting with the carboxyl group-containing novolac resin (A). The compounding quantity is sufficient with the ratio of 10 mass parts or more and 100 mass parts or less with respect to 100 mass parts of said carboxyl group containing novolak-type resin (A), Preferably it is a ratio of 15-60 mass parts. When the blending amount of the thermosetting component is less than the above range, the hygroscopicity of the cured film becomes high and the PCT resistance tends to decrease, and the solder heat resistance and electroless plating resistance tend to decrease. On the other hand, when the above range is exceeded, the developability of the coating film and the electroless plating resistance of the cured film are deteriorated, and the PCT resistance is also inferior. For electronic materials, the thermosetting component is preferably an epoxy resin, and among them, a polyfunctional epoxy resin having two or more epoxy groups in one molecule is preferable.
また、本発明の硬化性組成物は、カルボキシル基含有ノボラック型樹脂(A)及び熱硬化成分を溶解させ、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種類以上の混合物として使用することができる。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。
In addition, the curable composition of the present invention contains an organic solvent in order to dissolve the carboxyl group-containing novolac resin (A) and the thermosetting component, and to adjust 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 as a mixture 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使用してもかまわない。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ノボラック型樹脂(A)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, You may 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 to be blended is a normal quantitative ratio, for example, 0.1 to 20 parts by mass, preferably 0.5 to 15.0 parts per 100 parts by mass of the carboxyl group-containing novolac resin (A). It is a ratio of 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ノボラック型樹脂(A)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 of the carboxyl group-containing novolac resin (A).
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ノボラック型樹脂(A)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 100 mass parts of said carboxyl group-containing novolak-type resin (A), 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ノボラック型樹脂(A)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. In the case of adding water, the carboxyl group of the carboxyl group-containing novolak resin (A) is replaced with amines such as trimethylamine and triethylamine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl. It is preferable to make the curable composition of the present invention conform to water by salt formation with a (meth) acrylate resin having a tertiary amino group such as (meth) acrylamide and acryloylmorpholine.
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、実施例等を示して本発明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。 EXAMPLES Hereinafter, although an Example etc. are shown and this invention is demonstrated more concretely, this invention is not limited to these Examples. In the following description, “part” means part by mass unless otherwise specified.
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:203)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293部を加え、加熱溶解した。次に、アクリル酸43.2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3時間反応させた。その後、マレイン酸46.4部及びメチルハイドロキノン0.3部を加え95〜105℃で4時間反応させ、不揮発分50%の溶液を得た。このようにして得られた溶液中のカルボキシル基含有ノボラック型樹脂は、酸価78mgKOH/g、エポキシ当量9013g/eq.であった。以下、この溶液をA−1と称す。
Synthesis example 1
203 parts of cresol novolac type epoxy resin YDCN-700-5 (manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 203) was put in a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and an air blowing tube, and diethylene glycol mono 293 parts of ethyl ether acetate was added and dissolved by heating. Next, 43.2 parts of acrylic acid, 0.2 part of methylhydroquinone and 3 parts of triphenylphosphine were added and reacted at 95 to 105 ° C. for 3 hours while blowing air. Thereafter, 46.4 parts of maleic acid and 0.3 part of methylhydroquinone 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 novolak resin in the solution thus obtained has an acid value of 78 mgKOH / g and an epoxy equivalent of 9013 g / eq. Met. 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:203)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305部を加え、加熱溶解した。次に、アクリル酸43.2、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3時間反応させた。その後、フタル酸66.4部及びメチルハイドロキノン0.3部を加え95〜105℃で4時間反応させ、不揮発分51%の溶液を得た。このようにして得られた溶液中のカルボキシル基含有ノボラック型樹脂は、酸価72mgKOH/g、エポキシ当量6744g/eq.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) was put in a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and an air blowing tube, and diethylene glycol mono 305 parts of ethyl ether acetate was added and dissolved by heating. Next, 43.2 acrylic acid, 0.2 part of methylhydroquinone and 3 parts of triphenylphosphine were added and reacted at 95 to 105 ° C. for 3 hours while blowing air. Thereafter, 66.4 parts of phthalic acid and 0.3 part of methylhydroquinone were added and reacted at 95 to 105 ° C. for 4 hours to obtain a solution having a nonvolatile content of 51%. The carboxyl group-containing novolak resin in the solution thus obtained has an acid value of 72 mgKOH / g and an epoxy equivalent of 6744 g / eq. Met. 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:203)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292部を加え、加熱溶解した。次に、アクリル酸36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3時間反応させた。その後、マレイン酸46.4部及びメチルハイドロキノン0.3部を加え95〜105℃で2時間、さらに酢酸6部を加え95〜105℃で4時間反応させ、不揮発分50%の溶液を得た。このようにして得られた溶液中のカルボキシル基含有ノボラック型樹脂は、酸価77mgKOH/g、エポキシ当量5194g/eq.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) was put in a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and an air blowing tube, and diethylene glycol mono 292 parts of ethyl ether acetate was added and dissolved by heating. Next, 36 parts of acrylic acid, 0.2 part of methylhydroquinone and 3 parts of triphenylphosphine were added and reacted at 95 to 105 ° C. for 3 hours while blowing air. Thereafter, 46.4 parts of maleic acid and 0.3 part of methylhydroquinone were added and the mixture was reacted at 95 to 105 ° C. for 2 hours, and further 6 parts of acetic acid was 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 novolac resin in the solution thus obtained has an acid value of 77 mgKOH / g and an epoxy equivalent of 5194 g / eq. Met. Hereinafter, this solution is referred to as A-3.
合成例4
合成例3の酢酸6部に代えてアクリル酸7.2部を用い、合成例3と同じようにして反応させ、不揮発分50%の溶液を得た。このようにして得られた溶液中のカルボキシル基含有ノボラック型樹脂は、酸価79mgKOH/g、エポキシ当量5530g/eq.であった。以下、この溶液をA−4と称す。
Synthesis example 4
Instead of 6 parts of acetic acid in Synthesis Example 3, 7.2 parts of acrylic acid was used and reacted in the same manner as in Synthesis Example 3 to obtain a solution having a nonvolatile content of 50%. The carboxyl group-containing novolak resin in the solution thus obtained has an acid value of 79 mgKOH / g and an epoxy equivalent of 5530 g / eq. Met. Hereinafter, this solution is referred to as A-4.
合成例5
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:203)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291部を加え、加熱溶解した。次に、アクリル酸36部、酢酸6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3時間反応させた。その後、マレイン酸46.4部及びメチルハイドロキノン0.3部を加え95〜105℃で4時間反応させ、不揮発分50%の溶液を得た。このようにして得られた溶液中のカルボキシル基含有ノボラック型樹脂は、酸価77mgKOH/g、エポキシ当量7911g/eq.であった。以下、この溶液をA−5と称す。
Synthesis example 5
203 parts of cresol novolac type epoxy resin YDCN-700-5 (manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 203) was put in a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and an air blowing tube, and diethylene glycol mono 291 parts of ethyl ether acetate was added and dissolved by heating. Next, 36 parts of acrylic acid, 6 parts of acetic acid, 0.2 part of methylhydroquinone and 3 parts of triphenylphosphine were added and reacted at 95 to 105 ° C. for 3 hours while blowing air. Thereafter, 46.4 parts of maleic acid and 0.3 part of methylhydroquinone 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 novolak resin in the solution thus obtained has an acid value of 77 mgKOH / g and an epoxy equivalent of 7911 g / eq. Met. Hereinafter, this solution is referred to as A-5.
比較合成例1
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:220)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3.0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溶液中のカルボキシル基含有ノボラック型樹脂は、酸価100mgKOH/gであった。以下、この溶液をB−1と称す。
Comparative Synthesis Example 1
Cresol novolac type epoxy resin Epicron N-695 (Dainippon Ink Chemical Co., Ltd., epoxy equivalent: 220) 220 parts was put in a reaction vessel equipped with a thermometer, stirrer, reflux condenser and air blowing tube, 220 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 0.46 parts of methylhydroquinone and 3.0 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 novolak resin in the solution thus obtained had an acid value of 100 mgKOH / g. Hereinafter, this solution is referred to as B-1.
比較合成例2
ガス導入管、撹拌装置、冷却管、温度計、及びアルカリ金属水酸化物水溶液の連続滴下用の滴下ロートを備えた反応容器に、フェノール性水酸基当量80g/eq.の1,5−ジヒドロキシナフタレン224部とビスフェノールA型エポキシ樹脂(ジャパンエポキシレジン(株)製、エピコート828、エポキシ当量189g/eq.)1075部を仕込み、窒素雰囲気下にて、撹拌下110℃で溶解させた。その後、トリフェニルホスフィン0.65部を添加し、反応容器内の温度を150℃まで昇温し、温度を150℃に保持しながら、約90分間反応させ、エポキシ当量452g/当量のエポキシ樹脂(a)を得た。次にフラスコ内の温度を40℃まで冷却し、エピクロルヒドリン1920部、トルエン1690部、テトラメチルアンモニウムブロマイド70部を加え、撹拌下45℃まで昇温し保持した。その後、48wt%水酸化ナトリウム水溶液364部を60分間かけて連続滴下し、その後、さらに6時間反応させた。反応終了後、過剰のエピクロルヒドリン及びトルエンの大半を減圧蒸留して回収し、副生塩とトルエンを含む反応生成物をメチルイソブチルケトンに溶解させ水洗した。有機溶媒層と水層を分離後、有機溶媒層よりメチルイソブチルケトンを減圧蒸留して留去し、エポキシ当量277g/eq.の多核エポキシ樹脂(b)を得た。得られた多核エポキシ樹脂(b)は、エポキシ当量から計算すると、エポキシ樹脂(a)におけるアルコール性水酸基1.98個のうち約1.59個がエポキシ化されている。従って、アルコール性水酸基のエポキシ化率は約80%である。次に、多核エポキシ樹脂(b)277部を撹拌装置、冷却管及び温度計を備えたフラスコに入れ、プロピレングリコールモノメチルエーテルアセテート290部を加え、加熱溶解し、メチルハイドロキノン0.46部と、トリフェニルホスフィン1.38部を加え、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129部を加え、5時間反応させ、不揮発分62%の溶液を得た。このようにして得られた溶液中のカルボキシル基含有樹脂は、酸価100mgKOH/gであった。以下、この溶液をB−2と称す。
Comparative Synthesis Example 2
In a reaction vessel equipped with a gas introduction tube, a stirring device, a cooling tube, a thermometer, and a dropping funnel for continuous dropping of an alkali metal hydroxide aqueous solution, a phenolic hydroxyl group equivalent of 80 g / eq. 224 parts of 1,5-dihydroxynaphthalene and 1075 parts of bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., Epicoat 828, epoxy equivalent 189 g / eq.) Were added at 110 ° C. with stirring in a nitrogen atmosphere. Dissolved. Thereafter, 0.65 part of triphenylphosphine was added, the temperature in the reaction vessel was raised to 150 ° C., the reaction was continued for about 90 minutes while maintaining the temperature at 150 ° C., and an epoxy resin having an epoxy equivalent of 452 g / equivalent ( a) was obtained. Next, the temperature in the flask was cooled to 40 ° C., 1920 parts of epichlorohydrin, 1690 parts of toluene, and 70 parts of tetramethylammonium bromide were added, and the temperature was raised to 45 ° C. and maintained with stirring. Thereafter, 364 parts of a 48 wt% aqueous sodium hydroxide solution were continuously added dropwise over 60 minutes, and then reacted for another 6 hours. After completion of the reaction, excess epichlorohydrin and most of toluene were recovered by distillation under reduced pressure, and the reaction product containing by-product salt and toluene was dissolved in methyl isobutyl ketone and washed with water. After the organic solvent layer and the aqueous layer were separated, methyl isobutyl ketone was distilled off from the organic solvent layer under reduced pressure to obtain an epoxy equivalent of 277 g / eq. The polynuclear epoxy resin (b) was obtained. When the obtained polynuclear epoxy resin (b) is calculated from the epoxy equivalent, about 1.59 of 1.98 alcoholic hydroxyl groups in the epoxy resin (a) are epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl group is about 80%. Next, 277 parts of the polynuclear epoxy resin (b) is placed in a flask equipped with a stirrer, a cooling tube and a thermometer, 290 parts of propylene glycol monomethyl ether acetate is added, and dissolved by heating, 0.46 part of methyl hydroquinone, 1.38 parts of phenylphosphine was added, 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., 129 parts of tetrahydrophthalic anhydride was added and reacted for 5 hours to obtain a solution having a nonvolatile content of 62%. The carboxyl group-containing resin in the solution thus obtained had an acid value of 100 mgKOH / g. Hereinafter, this solution is referred to as B-2.
比較合成例3
温度計、窒素導入装置兼アルキレンオキシド導入装置及び撹拌装置を備えたオートクレーブに、昭和高分子(株)製ノボラック型クレゾール樹脂(商品名「ショーノールCRG951」、フェノール性水酸基当量:119.4g/eq.)119.4部、水酸化カリウム1.19部、トルエン119.4部を仕込み、撹拌しつつ系内を窒素置換し、加熱昇温した。次に、プロピレンオキシド63.8部を徐々に滴下し、125〜132℃、0〜4.8kg/cm2で16時間反応させた。その後、室温まで冷却し、この反応溶液に89%リン酸1.56部を添加混合し、水酸化カリウムを中和し、不揮発分62.1%、アルコール性水酸基当量が182.2g/eq.であるノボラック型クレゾール樹脂のプロピレンオキシド反応溶液を得た。これは、フェノール性水酸基1当量当りアルキレンオキシドが平均約1.08モル付加しているものであった。得られたノボラック型クレゾール樹脂のプロピレンオキシド反応溶液293.0部、アクリル酸43.2部、メタンスルホン酸11.53部、メチルハイドロキノン0.18部、トルエン252.9部を、撹拌機、温度計、空気吹き込み管を備えた反応容器に仕込み、空気を10ml/分の速度で吹き込み、撹拌しながら、110℃で12時間反応させた。反応により生成した水はトルエンとの共沸混合物として、12.6部の水が留出した。その後、室温まで冷却し、得られた反応溶液を15%水酸化ナトリウム水溶液35.35部で中和し、次いで水洗した。その後、エバポレーターにてトルエンをプロピレングリコールモノメチルエーテルアセテート149部で置換しつつ留去し、ノボラック型アクリレート樹脂溶液を得た。次に、得られたノボラック型アクリレート樹脂溶液332.5部、トリフェニルホスフィン1.22部を、撹拌器、温度計、空気吹き込み管を備えた反応器に仕込み、空気を10ml/分の速度で吹き込み、撹拌しながら、テトラヒドロフタル酸無水物60.8部を徐々に加え、95〜101℃で6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溶液中のカルボキシル基含有ノボラック型樹脂は、酸価84mgKOH/gであった。以下、この溶液をB−3と称す。
Comparative Synthesis Example 3
To an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device, a novolac type cresol resin (trade name “Shonol CRG951” manufactured by Showa Polymer Co., Ltd., phenolic hydroxyl group equivalent: 119.4 g / eq) .) 119.4 parts, 1.19 parts of potassium hydroxide, and 119.4 parts of toluene were charged, and the system was purged with nitrogen while stirring and heated. Next, 63.8 parts of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm 2 for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the alcoholic hydroxyl group equivalent was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of about 1.08 mole of alkylene oxide added per equivalent of phenolic hydroxyl group. 293.0 parts of a propylene oxide reaction solution of the obtained novolac-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 part of methylhydroquinone, and 252.9 parts of toluene were mixed with a stirrer and a temperature. A reaction vessel equipped with a total and an air blowing tube was charged, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring. 12.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while substituting 149 parts of propylene glycol monomethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 parts of the obtained novolak acrylate resin solution and 1.22 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was supplied at a rate of 10 ml / min. While blowing and stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours to obtain a solution having a nonvolatile content of 65%. The carboxyl group-containing novolac resin in the solution thus obtained had an acid value of 84 mgKOH / g. Hereinafter, this solution is referred to as B-3.
硬化性組成物の評価
(1)現像性
前記合成例1〜5及び比較合成例1〜3で得られた溶液を、表1に示す成分及び配合組成(数値は質量部である)に従ってそれぞれ配合し、3本ロールミルでそれぞれ別々に混練して各硬化性組成物を調製した。表1中、イルガキュアー907は重合開始剤、DPHAは感光性アクリレート化合物である。
Evaluation of curable composition (1) Developability The solutions obtained in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 3 were blended in accordance with the components and blending compositions (numerical values are parts by mass) shown in Table 1, respectively. Each curable composition was prepared by kneading separately with a three-roll mill. In Table 1, Irgacure 907 is a polymerization initiator, and DPHA is a photosensitive acrylate compound.
○:塗膜が除去された。
×:現像されない部分があった。
判定結果を表2に記す。
○: The coating film was removed.
X: There was a portion that was not developed.
The determination results are shown in Table 2.
また、各硬化性組成物について、(2)鉛筆硬度、(3)はんだ耐熱性、(4)耐酸性、(5)耐アルカリ性、(6)、密着性、(7)PCT耐性、(8)無電解金めっき耐性、(9)白化耐性、(10)電気絶縁性、(11)可撓性に関する性能試験を行った。試験結果を表3に示す。
各性能試験の評価方法は以下の通りである。
(2)鉛筆硬度
前記組成例1〜5及び比較組成例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50〜60μm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分間乾燥し、レジストパターンを有するネガフィルムを塗膜に密着させ、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600mJ/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。
The evaluation method for each performance test is as follows.
(2) Pencil hardness A pattern so that each of the curable compositions of Composition Examples 1 to 5 and Comparative Composition Examples 1 to 3 has a thickness of 50 to 60 μm using a 100 mesh polyester screen by screen printing. The entire surface of the copper through-hole printed wiring board is applied, and the coating film is dried for 30 minutes in a hot air circulation drying oven at 80 ° C., and a negative film having a resist pattern is adhered to the coating film. Ultraviolet rays were irradiated using a model HMW-680GW manufactured by Oak Manufacturing Co., Ltd. (exposure amount 600 mJ / cm 2). 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 was performed for 60 minutes in a hot air circulation drying oven at 150 ° C., and the pencil hardness test was performed on the evaluation substrate having the obtained cured film 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変えた以外は耐酸性試験と同様の試験を上記評価基板について行い、評価した。
(5) Alkali resistance A test similar to the acid resistance test was conducted on the evaluation substrate, except that the 10 volume% sulfuric acid aqueous solution was changed to a 10 volume% sodium hydroxide aqueous solution, and evaluation was performed.
(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。判定基準は以下の通りである。
○: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. Judgment criteria are as follows.
○: 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し、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。判定基準は以下の通りである。
○: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) Resistance to electroless gold plating 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. Judgment criteria are as follows.
○: 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条件及び基準にて評価した。
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. The product was applied and cured, and the electrical insulation of the resulting cured film was evaluated under the following conditions and 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樹脂組成物の塗布、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 A polyester film is used in place of the patterned copper through-hole printed wiring board, and the curable resin composition is applied and cured by the above method, and then the cured coating film is formed from the polyester film. And 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.
(Triangle | delta): When a film is bend | folded 170 degree | times, it cracks, but it is a 160 degree bend | fold and was not cracked.
X: The film was bent by 160 ° and cracked.
前述したような本発明の硬化性組成物は、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、ドライフィルム、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、インクジェト用レジストなどの用途に有用である。 Since the curable composition of the present invention as described above is excellent in developability and obtains a cured product excellent in various properties as described above, a solder resist, a dry film, an etching resist, a plating resist, a multilayer wiring It is useful for applications such as an interlayer insulating layer of a plate, a permanent mask used in the manufacture of a tape carrier package, a resist for a flexible wiring board, a resist for a color filter, an ink resist, and the like.
Claims (10)
(B)感光性(メタ)アクリレート化合物、及び
(C)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) It consists of structural units represented by the following general formulas (1), (2), (3) and (4), an acid value of 20 to 131 mgKOH / g, and an epoxy equivalent of 3000 g / eq. A carboxyl group-containing novolak resin characterized by being soluble in an organic solvent as described above
A curable composition capable of alkali development, comprising (B) a photosensitive (meth) acrylate compound, and (C) a photopolymerization initiator.
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