JP5199803B2 - Carboxyl group-containing compound and cured product thereof - Google Patents
Carboxyl group-containing compound and cured product thereof Download PDFInfo
- Publication number
- JP5199803B2 JP5199803B2 JP2008240305A JP2008240305A JP5199803B2 JP 5199803 B2 JP5199803 B2 JP 5199803B2 JP 2008240305 A JP2008240305 A JP 2008240305A JP 2008240305 A JP2008240305 A JP 2008240305A JP 5199803 B2 JP5199803 B2 JP 5199803B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- group
- epoxy
- containing compound
- carboxyl group
- 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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- 150000001875 compounds Chemical class 0.000 title claims description 83
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims description 63
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 73
- 229920000647 polyepoxide Polymers 0.000 claims description 64
- 239000003822 epoxy resin Substances 0.000 claims description 54
- 239000007795 chemical reaction product Substances 0.000 claims description 50
- 125000003700 epoxy group Chemical group 0.000 claims description 50
- 239000002253 acid Substances 0.000 claims description 37
- 150000007519 polyprotic acids Polymers 0.000 claims description 37
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 35
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- 150000008065 acid anhydrides Chemical class 0.000 claims description 22
- 229920003986 novolac Polymers 0.000 claims description 21
- 230000001476 alcoholic effect Effects 0.000 claims description 18
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 34
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 24
- -1 aromatic monocarboxylic acid Chemical class 0.000 description 21
- 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 20
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 19
- 238000007664 blowing Methods 0.000 description 17
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 235000013824 polyphenols Nutrition 0.000 description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 11
- 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 11
- 229930003836 cresol Natural products 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 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 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 9
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 8
- 238000010292 electrical insulation Methods 0.000 description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 8
- 239000011976 maleic acid Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 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 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 229910000679 solder Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000007864 aqueous solution Substances 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
- 239000002904 solvent Substances 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
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- 150000001298 alcohols Chemical class 0.000 description 2
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- 239000003513 alkali Substances 0.000 description 2
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- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
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- Materials For Photolithography (AREA)
- Epoxy Resins (AREA)
- 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化合物に関し、特にカルボキシル基含有化合物及びその硬化物に関する。 The present invention relates to a curable compound used for forming a solder resist or the like of a printed wiring board, and particularly relates to a carboxyl group-containing compound and a cured product thereof.
現在、プリント配線板のソルダーレジストの形成に使用される硬化性化合物は、環境問題への配慮から、希アルカリ水溶液で現像ができる不飽和基及びカルボキシル基含有化合物が主流になっている。このような化合物としては、エポキシ樹脂と不飽和基含有モノカルボン酸の反応物に酸無水物を付加した硬化性化合物が一般的である。
例えば、特許文献１には、ノボラック型エポキシ樹脂と不飽和基含有モノカルボン酸の反応物に酸無水物を付加した硬化性化合物が開示されている。また、特許文献２には、１分子中に２個のグリシジル基を有する芳香族エポキシ樹脂と１分子中に２個のフェノール性水酸基を有する芳香族アルコール樹脂とを反応させて得られるアルコール性の二級の水酸基にエピハロヒドリンを反応させ、得られた反応物に不飽和基含有モノカルボン酸、次いで酸無水物を付加した硬化性化合物が開示されている。
これらの他、幾つかの硬化性化合物が提案されており、現在、実際のプリント配線板の製造に多く使用されている。
At present, unsaturated group and carboxyl group-containing compounds that can be developed with a dilute aqueous alkaline solution are mainly used as curable compounds used for forming a solder resist on a printed wiring board in consideration of environmental problems. As such a compound, a curable compound obtained by adding an acid anhydride to a reaction product of an epoxy resin and an unsaturated group-containing monocarboxylic acid is generally used.
For example,
In addition to these, several curable compounds have been proposed and are currently widely used in the production of actual printed wiring boards.
近年、エレクトロニクス機器の軽薄短小化に伴いプリント配線板が高密度化されており、プリント配線板の高密度化に対応して、ソルダーレジストを形成する硬化性化合物の高性能化が要求されている。しかし、従来市販されている硬化性化合物は、現像性が十分でないためにソルダーレジストの極微細なパターンが得られない。また、従来の硬化性化合物を用いてソルダーレジストを形成した高密度化のプリント配線板は、高温及び高湿下での電気絶縁性が低い。さらに、従来の硬化性化合物を用いて形成されたソルダーレジストは十分な可撓性がないために、フレキシブルプリント配線板に適用できない。 In recent years, printed circuit boards have been densified in accordance with the miniaturization of electronic equipment, and high performance of curable compounds that form solder resists is required in response to the increased density of printed circuit boards. . However, conventionally available curable compounds do not have sufficient developability, so that a very fine pattern of the solder resist cannot be obtained. Moreover, the high-density printed wiring board which formed the soldering resist using the conventional sclerosing | hardenable compound has low electrical insulation at high temperature and high humidity. Furthermore, since the solder resist formed using the conventional curable compound does not have sufficient flexibility, it cannot be applied to a flexible printed wiring board.
これらの問題のうち可撓性の問題を解決する硬化性化合物として、例えば、ビスフェノールＡ型エポキシ樹脂のアルコール性の二級の水酸基に、エピハロルヒドリンを反応させ、次いで得られた多官能エポキシ樹脂に、エポキシ当量当たり０．２〜１．２モルのエチレン性不飽和カルボン酸を反応させ、さらにエポキシ当量当たり０．２〜１．０モルの多塩基カルボン酸又はその無水物あるいはその両方を反応させて得られるカルボキシル基含有化合物が提案されている（特許文献３参照）。
また、特許文献４には、ノボラック型エポキシ樹脂及びゴム変性ビスフェノールＡ型エポキシ樹脂の混合物と、この混合物のエポキシ当量当たり０．２〜１．２モルのエチレン性不飽和カルボン酸とを反応させ、得られた反応生成物と、上記混合物のエポキシ当量当たり０．２〜１．０モルの多塩基カルボン酸及び／又はその無水物とを反応させて得られるカルボキシル基含有化合物が開示されている。
Among these problems, as a curable compound that solves the flexibility problem, for example, an alcoholic secondary hydroxyl group of a bisphenol A type epoxy resin is reacted with epihalohydrin, and then the polyfunctional epoxy obtained. The resin is reacted with 0.2 to 1.2 moles of ethylenically unsaturated carboxylic acid per epoxy equivalent, and 0.2 to 1.0 mole of polybasic carboxylic acid or anhydride or both per epoxy equivalent. A carboxyl group-containing compound obtained by reacting has been proposed (see Patent Document 3).
Further, in Patent Document 4, a mixture of a novolac type epoxy resin and a rubber-modified bisphenol A type epoxy resin is reacted with 0.2 to 1.2 mol of ethylenically unsaturated carboxylic acid per epoxy equivalent of the mixture, A carboxyl group-containing compound obtained by reacting the obtained reaction product with 0.2 to 1.0 mol of a polybasic carboxylic acid and / or its anhydride per epoxy equivalent of the above mixture is disclosed.
特許文献３や特許文献４のカルボキシル基含有化合物を用いてレジストを形成した高密度化プリント配線板は、可撓性に優れている。しかし、これらカルボキシル基含有化合物は、多官能エポキシ樹脂や、ノボラック型エポキシ樹脂とゴム変性ビスフェノールＡ型エポキシ樹脂の混合物に対するエチレン性不飽和カルボン酸の反応割合がある範囲内のときはゲル化したり、高分子化したりするため、十分な現像性が得られない。
即ち、特許文献３や特許文献４のカルボキシル基含有化合物は、多官能エポキシ樹脂や、ノボラック型エポキシ樹脂とゴム変性ビスフェノールＡ型エポキシ樹脂の混合物に、エポキシ当量当たり０．２〜１．２モルのエチレン性不飽和カルボン酸を反応させて得られる生成物に、エポキシ当量当たり、０．２〜１．０モルの多塩基カルボン酸及び／又はその無水物を反応させて得られるが、多塩基カルボン酸及び／又はその無水物の反応割合が上記範囲内のときに、多官能エポキシ樹脂や、ノボラック型エポキシ樹脂とゴム変性ビスフェノールＡ型エポキシ樹脂の混合物に対してエポキシ当量当たり1モル未満のエチレン性不飽和カルボン酸を反応させると、多塩基カルボン酸及び／又はその無水物が上記エチレン性不飽和基含有エポキシ樹脂の架橋剤として働き、ゲル化、又は高分子化して現像性が低下する。
The high-density printed wiring board in which a resist is formed using the carboxyl group-containing compounds of Patent Document 3 and Patent Document 4 is excellent in flexibility. However, these carboxyl group-containing compounds are gelled when the reaction ratio of the ethylenically unsaturated carboxylic acid to the polyfunctional epoxy resin or the mixture of the novolac type epoxy resin and the rubber-modified bisphenol A type epoxy resin is within a certain range, Sufficient developability cannot be obtained due to polymerization.
That is, the carboxyl group-containing compounds of Patent Document 3 and Patent Document 4 are 0.2 to 1.2 moles per epoxy equivalent in a polyfunctional epoxy resin or a mixture of a novolac epoxy resin and a rubber-modified bisphenol A epoxy resin. The product obtained by reacting an ethylenically unsaturated carboxylic acid can be obtained by reacting 0.2 to 1.0 mol of a polybasic carboxylic acid and / or its anhydride per epoxy equivalent. When the reaction ratio of the acid and / or anhydride thereof is within the above range, the ethylenic property is less than 1 mol per epoxy equivalent with respect to the polyfunctional epoxy resin or the mixture of the novolac type epoxy resin and the rubber-modified bisphenol A type epoxy resin. When the unsaturated carboxylic acid is reacted, the polybasic carboxylic acid and / or its anhydride is converted into the above ethylenically unsaturated group-containing epoxy resin. As a cross-linking agent, it develops into a gel or polymer and deteriorates the developability.
一方、このような高分子化した樹脂を利用して硬化性組成物の塗膜のタック(粘着)フリー性を向上させる方法が提案されている（特許文献５参照）。タックフリー性は液状現像型レジストの重要な特性の一つであるが、アルカリ現像性と背反する特性である。そこで、特許文献５では、高分子化させた樹脂のヒドロキシル基に多塩基酸及び／又は多塩基酸無水物を付加反応させて得られる硬化性樹脂を用いることにより、硬化性組成物の塗膜のタックフリー性と現像性の両立を図っている。しかし、それでもなお、近年のエレクトロニクス機器の軽薄短小化に伴うプリント配線板の高密度化に対応した十分な現像性は得られていない。
On the other hand, a method for improving the tack-free property of the coating film of the curable composition using such a polymerized resin has been proposed (see Patent Document 5). The tack-free property is one of the important characteristics of the liquid development type resist, but is a characteristic contrary to the alkali developability. Therefore, in
また、可撓性、さらには電気絶縁性の問題を解決するために、ノボラック型フェノール樹脂とアルキレンオキシドとの反応生成物に不飽和基含有モノカルボン酸を反応させ、得られた反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有化合物（特許文献６参照）、ノボラック型フェノール樹脂とアルキレンオキシド又は環状カーボネートとの反応生成物に不飽和基含有モノカルボン酸及び飽和脂肪族モノカルボン酸及び／又は芳香族モノカルボン酸を反応させ、得られた反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有化合物（特許文献７参照）等が提案されている。しかしながら、上記化合物は現像性に劣る。また、上記化合物を用いてレジストを形成したプリント配線板は、高温及び高湿下での電気絶縁性には優れているが、硬度が低い。
本発明は前記のような問題に鑑みなされたものであり、ゲル化することなく、現像性に優れ、また硬度、耐熱性、耐薬品性、電気絶縁性、可撓性等の特性を充分に満足する優れた硬化膜が得られる光及び／又は熱硬化性化合物及びその硬化物を提供することを目的とするものである。 The present invention has been made in view of the problems as described above, is excellent in developability without gelation, and has sufficient properties such as hardness, heat resistance, chemical resistance, electrical insulation, and flexibility. An object of the present invention is to provide a light and / or thermosetting compound and a cured product thereof from which a satisfactory cured film can be obtained.
上記課題を解決するために成された本発明に係るカルボキシル基含有化合物は、１分子中に２個以上のエポキシ基を有する樹脂（ａ）のエポキシ基に、エポキシ基１当量に対して、モノカルボン酸（ｂ）を０．３〜０．９モルの割合で反応させ、得られた反応生成物（ｃ）のエポキシ基に、エポキシ基１当量に対して、多塩基酸（ｄ）を０．２〜５モルの割合で反応させ、得られた反応生成物（ｅ）のエポキシ基に、エポキシ基１当量に対して、モノカルボン酸（ｆ）を０．０〜５．０モルの割合で反応させて得られる酸価１８〜１８０ｍｇＫＯＨ／ｇの反応生成物（ｇ）の２級のアルコール性水酸基に、さらに多塩基酸無水物（ｈ）を反応させて得られる酸価４０〜２００ｍｇＫＯＨ／ｇのカルボキシル基含有化合物であることを特徴とする。 The carboxyl group-containing compound according to the present invention, which has been made to solve the above-mentioned problems, has a mono group on the epoxy group of the resin (a) having two or more epoxy groups in one molecule with respect to 1 equivalent of the epoxy group. Carboxylic acid (b) is reacted at a ratio of 0.3 to 0.9 mol, and polybasic acid (d) is added to the epoxy group of the obtained reaction product (c) with respect to 1 equivalent of epoxy group. The reaction is carried out at a ratio of 2 to 5 mol, and the epoxy group of the obtained reaction product (e) is added at a ratio of 0.0 to 5.0 mol of monocarboxylic acid (f) with respect to 1 equivalent of epoxy group. The secondary alcoholic hydroxyl group of the reaction product (g) having an acid value of 18 to 180 mgKOH / g obtained by reacting with a polybasic acid anhydride (h) and an acid value of 40 to 200 mgKOH / be characterized in that g is a carboxyl group-containing compound .
本発明の具体的な好適な態様によれば、モノカルボン酸（ｂ）及びモノカルボン酸（ｆ）が不飽和基含有モノカルボン酸であり、又はモノカルボン酸（ｂ）が不飽和基含有モノカルボン酸であり、モノカルボン酸（ｆ）が不飽和基を含有しないモノカルボン酸であり、又はモノカルボン酸（ｂ）が不飽和基を含有しないモノカルボン酸であり、モノカルボン酸（ｆ）が不飽和基含有モノカルボン酸であり、又はモノカルボン酸（ｂ）及びモノカルボン酸（ｆ）が不飽和基を含有しないモノカルボン酸であり、又はモノカルボン酸（ｂ）及び／又は（ｆ）が不飽和基含有モノカルボン酸と不飽和基を含有しないモノカルボン酸の混合物であり、又は多塩基酸（ｄ）がマロン酸又はマロン酸と他の二塩基酸との混合物であり、特に１分子中に２個以上のエポキシ基を有する樹脂（ａ）がノボラック型エポキシ樹脂である。 According to a specific preferred embodiment of the present invention, the monocarboxylic acid (b) and the monocarboxylic acid (f) are unsaturated group-containing monocarboxylic acids, or the monocarboxylic acid (b) is an unsaturated group-containing monocarboxylic acid. A carboxylic acid, the monocarboxylic acid (f) is a monocarboxylic acid containing no unsaturated group, or the monocarboxylic acid (b) is a monocarboxylic acid containing no unsaturated group, and the monocarboxylic acid (f) Is an unsaturated group-containing monocarboxylic acid, or the monocarboxylic acid (b) and the monocarboxylic acid (f) are monocarboxylic acids not containing an unsaturated group, or the monocarboxylic acids (b) and / or (f ) Is a mixture of an unsaturated group-containing monocarboxylic acid and a monocarboxylic acid not containing an unsaturated group, or a polybasic acid (d) is malonic acid or a mixture of malonic acid and other dibasic acids, 2 per molecule Resins having an epoxy group (a) above is a novolak epoxy resin.
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化合物に要求される現像性を充分に満足し、且つ硬度、耐熱性、耐薬品性、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 compound capable of increasing the density of printed wiring boards is sufficiently satisfied, and the hardness, heat resistance, chemical resistance, electrical insulation, flexibility, etc. are excellent. A cured film can be obtained.
本発明者らは、前記の課題を解決するため鋭意検討を重ねた結果、１分子中に２個以上のエポキシ基を有する樹脂のエポキシ基にモノカルボン酸を部分的に付加反応させ、次いで残りのエポキシ基に多塩基酸を部分的又は全部に付加反応させ、次いで多塩基酸が部分的に付加されている場合には、残りのエポキシ基にモノカルボン酸を付加反応させ、最後に得られた反応生成物の２級のアルコール性水酸基に、多塩基酸無水物を反応させることによって得られる硬化性化合物であるカルボキシル基含有化合物が、ゲル化することなく、現像性に優れ、また優れた硬度、耐熱性、耐薬品性、電気絶縁性、可撓性を持つ硬化物を与えることを見出し、本発明を完成させるに至ったものである。 As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have made a partial addition reaction of a monocarboxylic acid to an epoxy group of a resin having two or more epoxy groups in one molecule, and then the rest When the polybasic acid is partially or fully added to the epoxy group of the product, and then the polybasic acid is partially added, the remaining epoxy group is added with a monocarboxylic acid, and finally obtained. The carboxyl group-containing compound, which is a curable compound obtained by reacting the secondary alcoholic hydroxyl group of the reaction product with a polybasic acid anhydride, is excellent in developability without gelling. The inventors have found that a cured product having hardness, heat resistance, chemical resistance, electrical insulation, and flexibility can be obtained, and have completed the present invention.
すなわち、１分子中に２個以上のエポキシ基を有する樹脂（ａ）にモノカルボン酸（ｂ）を部分的に付加させることによって、ゲル化させることなく、その反応生成物（ｃ）のエポキシ基に多塩基酸（ｄ）を付加させることができ、さらにモノカルボン酸（ｆ）を残存するエポキシ基に付加させることができ、その結果、その後の２級のアルコール性水酸基への多塩基酸無水物の反応を容易にさせることができる。
このようにして得られる本発明のカルボキシル基含有化合物は、優れた現像性を示し、また反応性にも優れるために、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 epoxy group of the reaction product (c) is not gelled by partially adding the monocarboxylic acid (b) to the resin (a) having two or more epoxy groups in one molecule. Can be added with a polybasic acid (d), and further a monocarboxylic acid (f) can be added to the remaining epoxy group, resulting in subsequent polybasic acid anhydride to a secondary alcoholic hydroxyl group. The reaction of the product can be facilitated.
The carboxyl group-containing compound of the present invention thus obtained exhibits excellent developability and is excellent in reactivity, and therefore gives a cured product having a high crosslinking density and excellent properties.
尚、本発明のカルボキシル基含有化合物の製造において、反応生成物（ｃ）のエポキシ基に対する多塩基酸（ｄ）の付加によってカルボキシル基が得られるが、反応生成物（ｃ）に多塩基酸（ｄ）がすべて反応するとは限らない。その場合、未反応のエポキシ基の存在において、反応生成物（ｅ）と多塩基酸（ｄ）の混合物が得られる。その後、反応生成物（ｅ）のエポキシ基にモノカルボン酸（ｆ）を反応させることができる。本発明のカルボキシル基含有化合物は未反応の多塩基酸（ｄ）及び未反応のモノカルボン酸（ｆ）と混合した状態で得られる場合があるが、未反応の多塩基酸（ｄ）及び未反応のモノカルボン酸（ｆ）の存在・非存在に関係なく、ゲル化することなく、保存安定性に優れる。 In the production of the carboxyl group-containing compound of the present invention, a carboxyl group is obtained by adding a polybasic acid (d) to the epoxy group of the reaction product (c). Not all d) react. In that case, a mixture of the reaction product (e) and the polybasic acid (d) is obtained in the presence of an unreacted epoxy group. Thereafter, the monocarboxylic acid (f) can be reacted with the epoxy group of the reaction product (e). The carboxyl group-containing compound of the present invention may be obtained in a state of being mixed with an unreacted polybasic acid (d) and an unreacted monocarboxylic acid (f). Regardless of the presence or absence of the monocarboxylic acid (f) in the reaction, it is excellent in storage stability without gelation.
以下、本発明に係る光及び／又は熱硬化性化合物について詳細に説明する。
本発明のカルボキシル基含有化合物は、前記したように、１分子中に２個以上のエポキシ基を有する樹脂（ａ）のエポキシ基に、エポキシ基１当量に対して、モノカルボン酸（ｂ）を０．３〜０．９モルの割合で反応させ、得られた反応生成物（ｃ）のエポキシ基に、エポキシ基１当量に対して、多塩基酸（ｄ）を０．２〜５モルの割合で反応させ、得られた反応生成物（ｅ）のエポキシ基に、エポキシ基１当量に対して、モノカルボン酸（ｆ）を０．０〜５．０モルの割合で反応させて得られる酸価１８〜１８０ｍｇＫＯＨ／ｇの反応生成物（ｇ）の２級のアルコール性水酸基に、さらに多塩基酸無水物（ｈ）を反応させて得られるが、各反応は、後述するような触媒を用い、溶媒中又は無溶媒下で容易に行なわれる。
Hereinafter, the light and / or thermosetting compound according to the present invention will be described in detail.
As described above, in the carboxyl group-containing compound of the present invention, the monocarboxylic acid (b) is added to the epoxy group of the resin (a) having two or more epoxy groups in one molecule with respect to 1 equivalent of the epoxy group. The polybasic acid (d) is reacted in an amount of 0.3 to 0.9 mol, and the polybasic acid (d) is added to the epoxy group of the obtained reaction product (c) with respect to 1 equivalent of the epoxy group. It is obtained by reacting the epoxy group of the obtained reaction product (e) with a monocarboxylic acid (f) at a ratio of 0.0 to 5.0 mol with respect to 1 equivalent of the epoxy group. The secondary alcoholic hydroxyl group of the reaction product (g) having an acid value of 18 to 180 mg KOH / g is further reacted with a polybasic acid anhydride (h). Used easily in a solvent or without a solvent.
１分子中に２個以上のエポキシ基を有する樹脂（ａ）としては、例えば、ジャパンエポキシレジン（株）製のエピコート８２８、エピコート８３４、エピコート１００１、エピコート１００４、大日本インキ化学工業（株）製のエピクロン８４０、エピクロン８５０、エピクロン１０５０、エピクロン２０５５、東都化成（株）製のエポトートＹＤ−０１１、ＹＤ−０１３、ＹＤ−１２７、ＹＤ−１２８、ダウケミカル（株）製のＤ．Ｅ．Ｒ．３１７、Ｄ．Ｅ．Ｒ．３３１、Ｄ．Ｅ．Ｒ．６６１、Ｄ．Ｅ．Ｒ．６６４、住友化学工業（株）製のスミ−エポキシＥＳＡ−０１１、ＥＳＡ−０１４、ＥＬＡ−１１５、ＥＬＡ−１２８（何れも商品名）等のビスフェノールＡ型エポキシ樹脂；ジャパンエポキシレジン（株）製のエピコートＹＬ９０３、大日本インキ化学工業（株）製のエピクロン１５２、エピクロン１６５、東都化成（株）製のエポトートＹＤＢ−４００、ＹＤＢ−５００、ダウケミカル（株）製のＤ．Ｅ．Ｒ．５４２、住友化学工業（株）製のスミ−エポキシＥＳＢ−４００、ＥＳＢ−７００（何れも商品名）等のブロム化エポキシ樹脂；ジャパンエポキシレジン（株）製のエピコート１５２、エピコート１５４、ダウケミカル（株）製のＤ．Ｅ．Ｎ．４３１、Ｄ．Ｅ．Ｎ．４３８、大日本インキ化学工業（株）製のエピクロンＮ−７３０、エピクロンＮ−７７０、エピクロンＮ−８６５、東都化成（株）製のエポトートＹＤＣＮ−７０１、ＹＤＣＮ−７０４、日本化薬（株）製のＥＰＰＮ−２０１、ＥＯＣＮ−１０２５、ＥＯＣＮ−１０２０，ＥＯＣＮ−１０４Ｓ、ＲＥ−３０６、住友化学工業（株）製のスミ−エポキシＥＳＣＮ−１９５Ｘ、ＥＳＣＮ−２２０（何れも商品名）等のノボラック型エポキシ樹脂；大日本インキ化学工業（株）製のエピクロン８３０、ジャパンエポキシレジン製エピコート８０７、東都化成（株）製のエポトートＹＤＦ−１７０、ＹＤＦ−１７５、ＹＤＦ−２００４（何れも商品名）等のビスフェノールＦ型エポキシ樹脂；東都化成（株）製のエポトートＳＴ−２００４、ＳＴ−２００７、ＳＴ−３０００（何れも商品名）等の水添ビスフェノールＡ型エポキシ樹脂；ジャパンエポキシレジン（株）製のエピコート６０４、東都化成（株）製のエポトートＹＨ−４３４、住友化学工業（株）製のスミ−エポキシＥＬＭ−１２０（何れも商品名）等のグリシジルアミン型エポキシ樹脂；ダイセル化学工業（株）製のセロキサイド２０２１（商品名）等の脂環式エポキシ樹脂；ジャパンエポキシレジン（株）製のＹＬ−９３３、日本化薬（株）製のＥＰＰＮ−５０１、ＥＰＰＮ−５０２（何れも商品名）等のトリヒドロキシフェニルメタン型エポキシ樹脂；ジャパンエポキシレジン（株）製のＹＬ−６０５６、ＹＸ−４０００、ＹＬ−６１２１（何れも商品名）等のビキシレノール型もしくはビフェノール型エポキシ樹脂又はそれらの混合物；日本化薬（株）製のＥＢＰＳ−２００、旭電化工業（株）製のＥＰＸ−３０、大日本インキ化学工業（株）製のＥＸＡ−１５１４（何れも商品名）等のビスフェノールＳ型エポキシ樹脂；ジャパンエポキシレジン（株）製のエピコート１５７Ｓ（商品名）等のビスフェノールＡノボラック型エポキシ樹脂；ジャパンエポキシレジン（株）製のエピコートＹＬ−９３１（商品名）等のテトラフェニロールエタン型エポキシ樹脂；日産化学（株）製のＴＥＰＩＣ（商品名）等の複素環式エポキシ樹脂；日本油脂（株）製のブレンマーＤＧＴ（商品名）等のジグリシジルフタレート樹脂；東都化成（株）製のＺＸ−１０６３（商品名）等のテトラグリシジルキシレノイルエタン樹脂；新日鉄化学（株）製のＥＳＮ−１９０、ＥＳＮ−３６０、大日本インキ化学工業（株）製のＨＰ−４０３２、ＥＸＡ−４７５０、ＥＸＡ−４７００（何れも商品名）等のナフタレン基含有エポキシ樹脂；大日本インキ化学工業（株）製のＨＰ−７２００、ＨＰ−７２００Ｈ（何れも商品名）等のジシクロペンタジエン骨格を有するエポキシ樹脂；日本油脂（株）製のＣＰ−５０Ｓ、ＣＰ−５０Ｍ（何れも商品名）等のグリシジルメタアクリレート共重合系エポキシ樹脂；シクロヘキシルマレイミドとグリシジルメタアクリレートの共重合エポキシ樹脂；１，５−ジヒドロキシナフタレンとビスフェノールＡ型エポキシ樹脂とを反応させて得られるアルコール性の二級の水酸基に、エピハロルヒドリンを反応させて得られる多官能エポキシ樹脂（国際公開ＷＯ ０１／０２４７７４号公報）；エポキシ基の一部にケトンを付加反応させて得られる１，３−ジオキソラン環を有するエポキシ樹脂（特開２００７−１７６９８７号公報）等を挙げることができるが、これらに限られるものではない。これらのエポキシ樹脂は、単独で又は２種類以上を混合して用いることができる。 Examples of the resin (a) having two or more epoxy groups in one molecule include, for example, Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, and Dainippon Ink and Chemicals, manufactured by Japan Epoxy Resin Co., Ltd. Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Tohto Kasei Co., Ltd., D. Chemicals manufactured by Dow Chemical Co., Ltd. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Sumitomo Chemical Co., Ltd. bisphenol A type epoxy resins such as Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128 (all trade names); manufactured by Japan Epoxy Resin Co., Ltd. Epicort YL903, Daikoku Ink Chemical Co., Ltd. Epicron 152, Epicron 165, Toto Kasei Co., Ltd. Epototo YDB-400, YDB-500, Dow Chemical Co., Ltd. E. R. 542, brominated epoxy resins such as Sumi-epoxy ESB-400 and ESB-700 (both trade names) manufactured by Sumitomo Chemical Co., Ltd .; Epicoat 152, Epicoat 154, Dow Chemical (manufactured by Japan Epoxy Resin Co., Ltd.) D. manufactured by Co., Ltd. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, manufactured by Dainippon Ink & Chemicals, Inc. Epototo YDCN-701, YDCN-704, manufactured by Tohto Kasei Co., Ltd., manufactured by Nippon Kayaku Co., Ltd. Novolak type epoxy such as EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Epoxy ESCN-195X, ESCN-220 (all trade names) manufactured by Sumitomo Chemical Co., Ltd. Resins; Bisphenols such as Epiklon 830 manufactured by Dainippon Ink & Chemicals, Ltd., Epicoat 807 manufactured by Japan Epoxy Resin, Epototo YDF-170, YDF-175, YDF-2004 manufactured by Toto Kasei Co., Ltd. (all trade names) F type epoxy resin; Epototo ST-2004, ST-2 manufactured by Tohto Kasei Co., Ltd. Hydrogenated bisphenol A type epoxy resin such as 07 and ST-3000 (all are trade names); Epicoat 604 manufactured by Japan Epoxy Resin Co., Ltd., Epototo YH-434 manufactured by Toto Kasei Co., Ltd., Sumitomo Chemical Co., Ltd. Glycidylamine type epoxy resin such as Sumi-Epoxy ELM-120 (both trade names) manufactured by Daicel Chemical Industries Ltd. Alicyclic epoxy resin such as Celoxide 2021 (trade name) manufactured by Daicel Chemical Industries, Ltd .; Japan Epoxy Resin Co., Ltd. YL-933 manufactured by Nippon Kayaku Co., Ltd., EPPN-501 manufactured by Nippon Kayaku Co., Ltd., trihydroxyphenylmethane type epoxy resin such as EPPN-502 (both trade names); YL-6056 manufactured by Japan Epoxy Resin Co., Ltd., YX -4000, YL-6121 (both trade names) and other bixylenol type or biphenol type epoxy resins or EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by Dainippon Ink & Chemicals Co., Ltd. (all trade names), etc. Bisphenol S type epoxy resin; Bisphenol A novolac type epoxy resin such as Epicoat 157S (trade name) manufactured by Japan Epoxy Resin Co., Ltd .; Tetraphenylol such as Epicoat YL-931 (trade name) manufactured by Japan Epoxy Resin Co., Ltd. Ethane type epoxy resin; heterocyclic epoxy resin such as TEPIC (trade name) manufactured by Nissan Chemical Co., Ltd .; diglycidyl phthalate resin such as Blemmer DGT (trade name) manufactured by Nippon Oil &Fats; Toto Kasei Co., Ltd. Tetraglycidylxylenoylethane resin such as ZX-1063 (trade name) manufactured by Nippon Steel Chemical Co., Ltd .; ESN-190, ESN- manufactured by Nippon Steel Chemical Co., Ltd. 360, Naphthalene group-containing epoxy resins such as HP-4032, EXA-4750, EXA-4700 (all trade names) manufactured by Dainippon Ink & Chemicals, Inc .; HP-7200 manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin having a dicyclopentadiene skeleton such as HP-7200H (all trade names); Glycidyl methacrylate copolymer epoxy such as CP-50S and CP-50M (all trade names) manufactured by NOF Corporation Resin; Copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epihalohydrin is reacted with an alcoholic secondary hydroxyl group obtained by reacting 1,5-dihydroxynaphthalene and bisphenol A type epoxy resin. Polyfunctional epoxy resin obtained (International Publication WO 01/024774); Examples thereof include, but are not limited to, epoxy resins having a 1,3-dioxolane ring obtained by addition reaction of a ketone with a part of a poxy group (Japanese Patent Laid-Open No. 2007-176987). These epoxy resins can be used individually or in mixture of 2 or more types.
これらのエポキシ樹脂の中でも好ましいのは、１分子中に３個以上のエポキシ基を有する樹脂であり、より好ましくは、ノボラック型エポキシ樹脂である。 Among these epoxy resins, a resin having 3 or more epoxy groups in one molecule is preferable, and a novolac type epoxy resin is more preferable.
上記エポキシ樹脂（ａ）に、部分的にモノカルボン酸（ｂ）を付加反応させるが、その際、重合禁止剤及び触媒を用いて溶媒中で反応を行うことが好ましく、反応温度は好ましくは５０〜１５０℃、より好ましくは７０〜１２０℃である。上記エポキシ樹脂（ａ）のエポキシ基に、エポキシ基１当量に対して、モノカルボン酸（ｂ）を０．３〜０．９モルの割合で反応させるが、好ましくは、０．５〜０．９モルである。モノカルボン酸（ｂ）が０．３モル未満では、この後の反応でゲル化する。 The epoxy resin (a) is partially reacted with the monocarboxylic acid (b). In this case, the reaction is preferably performed in a solvent using a polymerization inhibitor and a catalyst, and the reaction temperature is preferably 50. It is -150 degreeC, More preferably, it is 70-120 degreeC. The monocarboxylic acid (b) is reacted with the epoxy group of the epoxy resin (a) at a ratio of 0.3 to 0.9 mol with respect to 1 equivalent of the epoxy group. 9 moles. When the monocarboxylic acid (b) is less than 0.3 mol, gelation occurs in the subsequent reaction.
前記モノカルボン酸（ｂ）の代表的なものとしては、アクリル酸、メタクリル酸、クロトン酸、桂皮酸、α−シアノ桂皮酸、β−スチリルアクリル酸、β−フルフリルアクリル酸などの不飽和基含有モノカルボン酸、ギ酸、酢酸、プロピオン酸、n-酪酸、イソ酪酸、バレリアン酸、トリメチル酢酸、カプロン酸、カプリル酸、ペラルゴン酸、カプリン酸、ウンデシル酸、ラウリン酸、トリデシル酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、ヘプタデシル酸、ステアリン酸、ノナデカン酸、アラキン酸、ベヘン酸などの飽和脂肪族モノカルボン酸、安息香酸、アルキル安息香酸、アルキルアミノ安息香酸、ハロゲン化安息香酸、フェニル酢酸、アニス酸、ベンゾイル安息香酸、ナフトエ酸などの芳香族モノカルボン酸などが挙げられるが、これらに限られるものではない。これらモノカルボン酸は、単独で又は２種類以上を混合して用いることができる。ここで特に好ましいのはアクリル酸、メタクリル酸、安息香酸、及び酢酸である。 Representative examples of the monocarboxylic acid (b) include unsaturated groups such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Containing monocarboxylic acid, formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, valeric acid, trimethylacetic acid, caproic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecyl Acids, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid and other saturated aliphatic monocarboxylic acids, benzoic acid, alkylbenzoic acid, alkylaminobenzoic acid, halogenated benzoic acid, phenylacetic acid, anisic acid Aromatic monocarboxylic acids such as benzoylbenzoic acid and naphthoic acid The present invention is not limited to these. These monocarboxylic acids can be used alone or in admixture of two or more. Particularly preferred here are acrylic acid, methacrylic acid, benzoic acid and acetic acid.
反応溶媒としては、例えば、メチルエチルケトン、シクロヘキサノン等のケトン類；トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類；エチレングリコールモノエチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類；酢酸エチル、酢酸ブチル、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート等の酢酸エステル類；エタノール、プロパノール、エチレングリコール、プロピレングリコール等のアルコール類；オクタン、デカン等の脂肪族炭化水素；石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤などが挙げられるが、これらに限られるものではない。これらの有機溶剤は、単独で又は２種類以上を混合して用いることができる。 Examples of the reaction solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether , Glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate , Ethylene glycol monobutyl ether Acetates such as cetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; octane, decane, etc. Aliphatic hydrocarbons: Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha are exemplified, but not limited thereto. These organic solvents can be used alone or in admixture of two or more.
反応触媒としては、例えば、トリエチルアミン等の三級アミン、トリエチルベンジルアンモニウムクロライド等の４級アンモニウム塩、２−エチル−４−メチルイミダゾール等のイミダゾール化合物、トリフェニルホスフィン等のリン化合物、ナフテン酸、ラウリン酸、ステアリン酸、オレイン酸やオクトエン酸のリチウム、クロム、ジルコニウム、カリウム、ナトリウム等の有機酸の金属塩などが挙げられるが、これらに限られるものではない。これらの反応触媒は、単独で又は２種類以上を混合して用いることができる。 Examples of the reaction catalyst include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, phosphorus compounds such as triphenylphosphine, naphthenic acid, and laurin. Examples include, but are not limited to, metal salts of organic acids such as lithium, chromium, zirconium, potassium, and sodium of acid, stearic acid, oleic acid, and octoenoic acid. These reaction catalysts can be used alone or in admixture of two or more.
重合禁止剤としては、例えば、ハイドロキノン、メチルハイドロキノン、ハイドロキノンモノメチルエーテル、カテコール、ピロガロール、フェノチアジンなどが挙げられるが、これらに限られるものではない。これらの重合禁止剤は、単独で又は２種類以上を混合して用いることができる。 Examples of the polymerization inhibitor include, but are not limited to, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, phenothiazine, and the like. These polymerization inhibitors can be used alone or in admixture of two or more.
さらに、前記反応生成物（ｃ）のエポキシ基に多塩基酸（ｄ）を付加反応させるが、反応温度は、好ましくは５０〜１５０℃、より好ましくは７０〜１２０℃である。前記反応生成物（ｃ）のエポキシ基に、エポキシ基１当量に対して、多塩基酸（ｄ）を０．２〜５．０モルの割合で反応させるが、好ましくは、０．２〜２．０モルである。多塩基酸（ｄ）が５．０モルを超えると、多量の未反応の多塩基酸（ｄ）が残り、最終生成物の硬化膜に悪影響を及ぼす。 Further, the polybasic acid (d) is added to the epoxy group of the reaction product (c), and the reaction temperature is preferably 50 to 150 ° C, more preferably 70 to 120 ° C. The polybasic acid (d) is reacted with the epoxy group of the reaction product (c) at a ratio of 0.2 to 5.0 mol with respect to 1 equivalent of the epoxy group, preferably 0.2 to 2 0.0 mole. When the polybasic acid (d) exceeds 5.0 mol, a large amount of unreacted polybasic acid (d) remains, which adversely affects the cured film of the final product.
多塩基酸（ｄ）の代表的なものとしては、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、マレイン酸、フマル酸、フタル酸、イソフタル酸、テレフタル酸、テトラヒドロフタル酸、メタントリカルボン酸、トリカルバリル酸、ベンゼントリカルボン酸、ベンゼンテトラカルボン酸等が挙げられるが、これらに限られるものではない。これらの多塩基酸は、単独で又は２種類以上を混合して用いることができる。これらの中でも、二塩基酸が好ましく、より好ましくは、マロン酸、グルタル酸、マレイン酸、テトラヒドロフタル酸及びフタル酸であり、特に好ましくは、マロン酸、マロン酸と他の二塩基酸との混合物である。但し、前記反応生成物（ｃ）のマロン酸と他の二塩基酸との混合物の反応において、（Ｎ１）マロン酸と他の二塩基酸は前記反応生成物（ｃ）に同時に、又は、（Ｎ２）マロン酸と他の二塩基酸は時間差で前記反応生成物（ｃ）に、反応させることができる。特に、（Ｎ２）の反応は、マロン酸と他の二塩基酸の反応容器への投入時間をずらすことでなされる。 Representative examples of the polybasic acid (d) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, Examples include, but are not limited to, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, methanetricarboxylic acid, tricarballylic acid, benzenetricarboxylic acid, and benzenetetracarboxylic acid. These polybasic acids can be used alone or in admixture of two or more. Among these, dibasic acid is preferable, more preferably malonic acid, glutaric acid, maleic acid, tetrahydrophthalic acid and phthalic acid, and particularly preferable is malonic acid, a mixture of malonic acid and other dibasic acids. It is. However, in the reaction of the mixture of malonic acid and other dibasic acid of the reaction product (c), (N1) malonic acid and the other dibasic acid are simultaneously with the reaction product (c) or ( N2) Malonic acid and other dibasic acids can be reacted with the reaction product (c) with a time difference. In particular, the reaction of (N2) is performed by shifting the charging time of malonic acid and another dibasic acid into the reaction vessel.
前記エポキシ樹脂（ａ）にモノカルボン酸（ｂ）、次いで多塩基酸（ｄ）を付加させた後、残存するエポキシ基にモノカルボン酸（ｆ）を付加させるが、モノカルボン酸（ｆ）の付加の役割は、反応生成物（ｅ）の重合を抑制するためである。しかし、反応条件及び／又は多塩基酸（ｄ）の種類によっては、モノカルボン酸（ｆ）は必要ない。これは、多塩基酸（ｄ）の反応生成物（ｃ）への付加により、エポキシ基が無くなることによる。反応生成物（ｅ）とモノカルボン酸（ｆ）を反応させる際の温度は、好ましくは５０〜１５０℃、より好ましくは７０〜１２０℃である。上記反応生成物（ｅ）のエポキシ基に、エポキシ基１当量に対して、モノカルボン酸（ｆ）を０．０〜５．０モルの割合で反応させるが、好ましくは、０．０〜２．０モルである。モノカルボン酸（ｆ）が５．０モルを超えると、多量の未反応のモノカルボン酸（ｆ）が残り、最終生成物の硬化膜に悪影響を及ぼす。 After the monocarboxylic acid (b) and then the polybasic acid (d) are added to the epoxy resin (a), the monocarboxylic acid (f) is added to the remaining epoxy group. The role of the addition is to suppress the polymerization of the reaction product (e). However, depending on the reaction conditions and / or the type of polybasic acid (d), the monocarboxylic acid (f) is not necessary. This is because the epoxy group disappears due to the addition of the polybasic acid (d) to the reaction product (c). The temperature at which the reaction product (e) and the monocarboxylic acid (f) are reacted is preferably 50 to 150 ° C, more preferably 70 to 120 ° C. The epoxy group of the reaction product (e) is reacted with the monocarboxylic acid (f) at a ratio of 0.0 to 5.0 mol with respect to 1 equivalent of the epoxy group, preferably 0.0 to 2 0.0 mole. When the monocarboxylic acid (f) exceeds 5.0 mol, a large amount of unreacted monocarboxylic acid (f) remains, which adversely affects the cured film of the final product.
モノカルボン酸（ｆ）としては、モノカルボン酸（ｂ）と同じものが挙げられる。これらモノカルボン酸は、単独で又は２種類以上を混合して用いることができる。ここで特に好ましいのはアクリル酸、メタクリル酸、安息香酸、及び酢酸である。 As monocarboxylic acid (f), the same thing as monocarboxylic acid (b) is mentioned. These monocarboxylic acids can be used alone or in admixture of two or more. Particularly preferred here are acrylic acid, methacrylic acid, benzoic acid and acetic acid.
得られた反応生成物（ｇ）の酸価は１８〜１８０ｍｇＫＯＨ／ｇであるが、好ましくは３０〜１５０ｍｇＫＯＨ／ｇである。反応生成物（ｇ）の酸価が１８〜１８０ｍｇＫＯＨ／ｇの範囲を外れると、最終生成物の特性が十分に得られない恐れがある。 The acid value of the obtained reaction product (g) is 18 to 180 mgKOH / g, preferably 30 to 150 mgKOH / g. If the acid value of the reaction product (g) is out of the range of 18 to 180 mgKOH / g, the properties of the final product may not be sufficiently obtained.
前記反応生成物（ｇ）の２級のアルコール性水酸基に、多塩基酸無水物（ｈ）を反応させて、本発明のカルボキシル基含有化合物が得られるが、この反応において、多塩基酸無水物（ｈ）の使用量は、生成するカルボキシル基含有化合物の酸価が、４０〜２００ｍｇＫＯＨ／ｇ、好ましくは４０〜１５０ｍｇＫＯＨ／ｇとなるような付加量とする。反応は、ハイドロキノンや酸素等の重合禁止剤の存在下で、通常、約５０〜１５０℃で行なう。このとき必要に応じて、トリエチルアミン等の三級アミン、トリエチルベンジルアンモニウムクロライド等の４級アンモニウム塩、２−エチル−４−メチルイミダゾール等のイミダゾール化合物、トリフェニルホスフィン等のリン化合物等を触媒として添加してもよい。 The secondary alcoholic hydroxyl group of the reaction product (g) is reacted with the polybasic acid anhydride (h) to obtain the carboxyl group-containing compound of the present invention. In this reaction, the polybasic acid anhydride is obtained. The amount of (h) used is such that the acid value of the resulting carboxyl group-containing compound is 40 to 200 mgKOH / g, preferably 40 to 150 mgKOH / g. The reaction is usually carried out at about 50 to 150 ° C. in the presence of a polymerization inhibitor such as hydroquinone or oxygen. At this time, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, and a phosphorus compound such as triphenylphosphine are added as a catalyst. May be.
上記多塩基酸無水物（ｈ）としては、メチルテトラヒドロ無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、無水ナジック酸、３，６−エンドメチレンテトラヒドロ無水フタル酸、メチルエンドメチレンテトラヒドロ無水フタル酸、テトラブロモ無水フタル酸等の脂環式二塩基酸無水物；無水コハク酸、無水マレイン酸、無水イタコン酸、オクテニル無水コハク酸、ペンタドデセニル無水コハク酸、無水フタル酸、無水トリメリット酸等の脂肪族又は芳香族二塩基酸無水物、あるいはビフェニルテトラカルボン酸二無水物、ジフェニルエーテルテトラカルボン酸二無水物、ブタンテトラカルボン酸二無水物、シクロペンタンテトラカルボン酸二無水物、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸二無水物等の脂肪族又は芳香族四塩基酸二無水物が挙げられが、これらに限られるものではない。これらの多塩基酸無水物は、単独で又は２種類以上を混合して用いることができる。これらの中でも、脂環式二塩基酸無水物が特に好ましい。 Examples of the polybasic acid anhydride (h) include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, Cycloaliphatic dibasic acid anhydrides such as methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, anhydrous Aliphatic or aromatic dibasic acid anhydrides such as trimellitic acid, or biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, Pyromellitic anhydride, benzofu Aliphatic or aromatic tetrabasic acid dianhydride, such as non-tetracarboxylic acid dianhydride can be mentioned but not limited thereto. These polybasic acid anhydrides can be used alone or in admixture of two or more. Among these, alicyclic dibasic acid anhydrides are particularly preferable.
本発明のカルボキシル基含有化合物の酸価は、４０〜２００ｍｇＫＯＨ／ｇであるが、未反応の多塩基酸（ｄ）及びモノカルボン酸（ｆ）が存在する場合には、固形分酸価は、カルボン酸全体として、２００ｍｇＫＯＨ／ｇを超える場合がある。しかし未反応のカルボン酸は、多量に含まれていなければ、本発明のカルボキシル基含有化合物の硬化膜に悪影響を及ばさない。 The acid value of the carboxyl group-containing compound of the present invention is 40 to 200 mg KOH / g. When unreacted polybasic acid (d) and monocarboxylic acid (f) are present, the solid content acid value is The carboxylic acid as a whole may exceed 200 mg KOH / g. However, unless the unreacted carboxylic acid is contained in a large amount, the cured film of the carboxyl group-containing compound of the present invention is not adversely affected.
尚、本発明のカルボキシル基含有化合物のある一つの構造（これを構造１とする）に近い化合物を得ることは可能である。例えば、ノボラック型クレゾール樹脂のフェノール性水酸基に部分的にグリシジルメタクリレートを反応させ、得られた反応生成物の残りのフェノール性水酸基にグリシドールをフェノール性水酸基を残さないような量で反応させ、さらに得られた反応生成物の一級及び二級のアルコール性水酸基に酸無水物を反応させて得られる構造（これを構造２とする）である。しかし、構造１と構造２とは違いがある。つまり、ノボラック型クレゾール樹脂のフェノール性水酸基に部分的にグリシジルメタクリレートを反応させて得られた生成物の残りのフェノール性水酸基にグリシドールを反応させようとすると、各フェノール性水酸基にグリシドール１分子ずつを付加させることはできない。即ち、フェノール性水酸基にグリシドール１分子が付加したところにさらに他のグリシドールが付加した構造も得られる。従って、一般的にはフェノール性水酸基にグリシドールをフェノール性水酸基を残さないように反応させるためには、フェノール性水酸基１当量に対して、グリシドールを１モルを超える割合で反応させる。その結果、構造１と構造２とは、異なる化合物となる。また、構造１は１級のアルコール性水酸基は存在しないが、構造２はグリシドール由来の１級のアルコール性水酸基が存在する又は存在する可能性が大きい。１級のアルコール性水酸基は電気特性を低下させる。従って、１級のアルコール性水酸基を有しない本発明のカルボキシル基含有化合物の硬化膜は、優れた電気特性を示す。
In addition, it is possible to obtain a compound close to a certain structure of the carboxyl group-containing compound of the present invention (hereinafter referred to as structure 1). For example, glycidyl methacrylate is partially reacted with the phenolic hydroxyl group of the novolac-type cresol resin, and glycidol is reacted with the remaining phenolic hydroxyl group of the obtained reaction product in an amount that does not leave the phenolic hydroxyl group, and further obtained. It is a structure obtained by reacting an acid anhydride with primary and secondary alcoholic hydroxyl groups of the obtained reaction product (this structure is referred to as structure 2). However, there is a difference between
本発明のカルボキシル基含有化合物は、光重合開始剤、感光性（メタ）アクリレート化合物、エポキシ樹脂、熱硬化触媒などを配合して、硬化させることができる。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。 The carboxyl group-containing compound of the present invention can be cured by blending a photopolymerization initiator, a photosensitive (meth) acrylate compound, an epoxy resin, a thermosetting catalyst, and the like. In this specification, “(meth) acrylate” is a term that collectively refers to acrylate and methacrylate, and the same applies to other similar expressions.
光重合開始剤としては、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。 Examples of the photopolymerization initiator 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, 2,2-diethoxy- Acetophenones such as 2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 Aminoacetophenones such as-(4-morpholinophenyl) -butan-1-one and N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthracone Anthraquinones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, thioxanthones such as 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzoyl par 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'-bisdiethylamino Benzophenones or xanthones such as benzophenone; and 2,4,6-trimethylbenzoyl diphenylphosphine oxide.
感光性（メタ）アクリレート化合物としては、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、及び上記アクリレート類に対応するメタクリレート類などが挙げられる。 Examples of the photosensitive (meth) acrylate compound include hydroxyl group-containing acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate; polyethylene glycol Water-soluble acrylates such as diacrylate and polypropylene glycol diacrylate; polyfunctional polyester acrylates of polyhydric alcohols such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate; trimethylolpropane; Ethylene of polyfunctional alcohols such as hydrogenated bisphenol A or polyphenols such as bisphenol A and biphenol Acrylates of propylene oxide adducts; polyfunctional or monofunctional polyurethane acrylates which are isocyanate modified products of the above hydroxyl group-containing acrylates; bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or phenol novolac epoxy Examples thereof include epoxy acrylates which are (meth) acrylic acid adducts of resins, and methacrylates corresponding to the above acrylates.
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、メラミン、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が挙げられる。 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, melamine, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N- Examples include amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid hydrazide and sebacic acid hydrazide; and phosphorus compounds such as triphenylphosphine.
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。
実施例１
クレゾールノボラック型エポキシ樹脂のＹＤＣＮ−７００−５（東都化成（株）製、エポキシ当量：２０３ｇ／ｅｑ．）２０３部を温度計、撹拌機、還流冷却器及び空気吹き込み管を備えた反応容器に入れ、ジエチレングリコールモノエチルエーテルアセテート１０８部を加え、加熱溶解した。次に、アクリル酸５０．４部、メチルハイドロキノン０．３部及びトリフェニルホスフィン１部を加え、空気を吹き込みながら９５〜１０５℃で７時間反応させた。その後、マレイン酸４０．６部、ジエチレングリコールモノエチルエーテルアセテート５０部及びメチルハイドロキノン０．２部を加え９５〜１０５℃で４時間反応させ、エポキシ当量４４６３６ｇ／ｅｑ．の反応生成物を得た。次いでテトラヒドロ無水フタル酸３０．４部、ジエチレングリコールモノエチルエーテルアセテート３３部を加え９５〜１０５℃で４時間反応させて、不揮発分６３％の溶液を得た。このようにして得られたカルボキシル基含有化合物は、酸価１１６ｍｇＫＯＨ／ｇ、であった。以下、この溶液をＡ−１と称す。得られたカルボキシル基含有化合物のＩＲスペクトルを図１、ゲルクロマトグラムを図２にそれぞれ示す。
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.
Example 1
203 parts of cresol novolac type epoxy resin YDCN-700-5 (manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 203 g / eq.) Is placed in a reaction vessel equipped with a thermometer, stirrer, reflux condenser and air blowing tube. Then, 108 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 50.4 parts of acrylic acid, 0.3 part of methylhydroquinone and 1 part of triphenylphosphine were added and reacted at 95-105 ° C. for 7 hours while blowing air. Thereafter, 40.6 parts of maleic acid, 50 parts of diethylene glycol monoethyl ether acetate and 0.2 part of methylhydroquinone were added and reacted at 95 to 105 ° C. for 4 hours to obtain an epoxy equivalent of 44636 g / eq. The reaction product was obtained. Next, 30.4 parts of tetrahydrophthalic anhydride and 33 parts of diethylene glycol monoethyl ether acetate were added and reacted at 95 to 105 ° C. for 4 hours to obtain a solution having a nonvolatile content of 63%. The carboxyl group-containing compound thus obtained had an acid value of 116 mgKOH / g. Hereinafter, this solution is referred to as A-1. The IR spectrum of the resulting carboxyl group-containing compound is shown in FIG. 1, and the gel chromatogram is shown in FIG.
実施例２
クレゾールノボラック型エポキシ樹脂のＹＤＣＮ−７００−５（東都化成（株）製、エポキシ当量：２０３ｇ／ｅｑ．）２０３部を温度計、撹拌機、還流冷却器及び空気吹き込み管を備えた反応容器に入れ、ジエチレングリコールモノエチルエーテルアセテート１０８部を加え、加熱溶解した。次に、アクリル酸５０．４部、メチルハイドロキノン０．３部及びトリフェニルホスフィン１部を加え、空気を吹き込みながら９５〜１０５℃で６時間反応させた。その後、マレイン酸４０．６部、ジエチレングリコールモノエチルエーテルアセテート５０部及びメチルハイドロキノン０．２部を加え９５〜１０５℃で４時間反応させ、エポキシ当量５５５００ｇ／ｅｑ．の反応生成物を得た。次いで無水フタル酸２９．６部、ジエチレングリコールモノエチルエーテルアセテート３２部を加え９５〜１０５℃で４時間反応させて、不揮発分６３％の溶液を得た。このようにして得られたカルボキシル基含有化合物は、酸価１１５ｍｇＫＯＨ／ｇ、であった。以下、この溶液をＡ−２と称す。得られたカルボキシル基含有化合物のＩＲスペクトルを図３、ゲルクロマトグラムを図４にそれぞれ示す。
Example 2
203 parts of cresol novolac type epoxy resin YDCN-700-5 (manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 203 g / eq.) Is placed in a reaction vessel equipped with a thermometer, stirrer, reflux condenser and air blowing tube. Then, 108 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 50.4 parts of acrylic acid, 0.3 part of methylhydroquinone and 1 part of triphenylphosphine were added and reacted at 95-105 ° C. for 6 hours while blowing air. Thereafter, 40.6 parts of maleic acid, 50 parts of diethylene glycol monoethyl ether acetate and 0.2 part of methylhydroquinone were added and reacted at 95 to 105 ° C. for 4 hours to obtain an epoxy equivalent of 55500 g / eq. The reaction product was obtained. Subsequently, 29.6 parts of phthalic anhydride and 32 parts of diethylene glycol monoethyl ether acetate were added and reacted at 95 to 105 ° C. for 4 hours to obtain a solution having a nonvolatile content of 63%. The carboxyl group-containing compound thus obtained had an acid value of 115 mgKOH / g. Hereinafter, this solution is referred to as A-2. The IR spectrum of the resulting carboxyl group-containing compound is shown in FIG. 3, and the gel chromatogram is shown in FIG.
実施例３
クレゾールノボラック型エポキシ樹脂のＹＤＣＮ−７００−５（東都化成（株）製、エポキシ当量：２０３ｇ／ｅｑ．）２０３部を温度計、撹拌機、還流冷却器及び空気吹き込み管を備えた反応容器に入れ、ジエチレングリコールモノエチルエーテルアセテート１０８部を加え、加熱溶解した。次に、アクリル酸４３．２部、酢酸６部、メチルハイドロキノン０．３部及びトリフェニルホスフィン１部を加え、空気を吹き込みながら９５〜１０５℃で６時間反応させた。その後、マレイン酸４０．６部、ジエチレングリコールモノエチルエーテルアセテート５０部及びメチルハイドロキノン０．２部を加え９５〜１０５℃で４時間反応させ、エポキシ当量４４１１５ｇ／ｅｑ．の反応生成物を得た。次いでテトラヒドロ無水フタル酸１５．２部、ジエチレングリコールモノエチルエーテルアセテート２３部を加え９５〜１０５℃で４時間反応させて、不揮発分６３％の溶液を得た。このようにして得られたカルボキシル基含有化合物は、酸価９４ｍｇＫＯＨ／ｇであった。以下、この溶液をＡ−３と称す。得られたカルボキシル基含有化合物のＩＲスペクトルを図５、ゲルクロマトグラムを図６にそれぞれ示す。
Example 3
203 parts of cresol novolac type epoxy resin YDCN-700-5 (manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 203 g / eq.) Is placed in a reaction vessel equipped with a thermometer, stirrer, reflux condenser and air blowing tube. Then, 108 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 43.2 parts of acrylic acid, 6 parts of acetic acid, 0.3 part of methylhydroquinone and 1 part of triphenylphosphine were added and reacted at 95-105 ° C. for 6 hours while blowing air. Thereafter, 40.6 parts of maleic acid, 50 parts of diethylene glycol monoethyl ether acetate and 0.2 part of methylhydroquinone were added and reacted at 95 to 105 ° C. for 4 hours to obtain an epoxy equivalent of 44115 g / eq. The reaction product was obtained. Next, 15.2 parts of tetrahydrophthalic anhydride and 23 parts of diethylene glycol monoethyl ether acetate were added and reacted at 95 to 105 ° C. for 4 hours to obtain a solution having a nonvolatile content of 63%. The carboxyl group-containing compound thus obtained had an acid value of 94 mgKOH / g. Hereinafter, this solution is referred to as A-3. The IR spectrum of the obtained carboxyl group-containing compound is shown in FIG. 5, and the gel chromatogram is shown in FIG.
実施例４
クレゾールノボラック型エポキシ樹脂のＹＤＣＮ−７００−５（東都化成（株）製、エポキシ当量：２０３ｇ／ｅｑ．）１５９．５部及びビスフェノールＡ型エポキシ樹脂のエピコート８２８（ジャパンエポキシレジン（株）製、エポキシ当量：１８６ｇ／ｅｑ．）３９．９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１０７部を加え、加熱溶解した。次に、アクリル酸５０．４部、メチルハイドロキノン０．３部及びトリフェニルホスフィン１部を加え、空気を吹き込みながら９５〜１０５℃で６時間反応させた。その後、マレイン酸４０．６部、ジエチレングリコールモノエチルエーテルアセテート７９部及びメチルハイドロキノン０．２部を加え９５〜１０５℃で４時間反応させ、エポキシ当量４８２３２ｇ／ｅｑ．の反応生成物を得た。次いでテトラヒドロ無水フタル酸１５．２部、ジエチレングリコールモノエチルエーテルアセテート９部を加え９５〜１０５℃で４時間反応させて、不揮発分６１％の溶液を得た。このようにして得られたカルボキシル基含有化合物は、酸価１０７ｍｇＫＯＨ／ｇであった。以下、この溶液をＡ−４と称す。得られたカルボキシル基含有化合物のＩＲスペクトルを図７、ゲルクロマトグラムを図８にそれぞれ示す。
Example 4
159.5 parts of cresol novolac type epoxy resin YDCN-700-5 (manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 203 g / eq.) And Epicoat 828 of bisphenol A type epoxy resin (manufactured by Japan Epoxy Resins Co., Ltd., epoxy) (Equivalent: 186 g / eq.) 39.9 parts was put into a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and an air blowing tube, and 107 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 50.4 parts of acrylic acid, 0.3 part of methylhydroquinone and 1 part of triphenylphosphine were added and reacted at 95-105 ° C. for 6 hours while blowing air. Thereafter, 40.6 parts of maleic acid, 79 parts of diethylene glycol monoethyl ether acetate and 0.2 part of methylhydroquinone were added and reacted at 95-105 ° C. for 4 hours to give an epoxy equivalent of 48232 g / eq. The reaction product was obtained. Next, 15.2 parts of tetrahydrophthalic anhydride and 9 parts of diethylene glycol monoethyl ether acetate were added and reacted at 95 to 105 ° C. for 4 hours to obtain a solution having a nonvolatile content of 61%. The carboxyl group-containing compound thus obtained had an acid value of 107 mgKOH / g. Hereinafter, this solution is referred to as A-4. The IR spectrum of the obtained carboxyl group-containing compound is shown in FIG. 7, and the gel chromatogram is shown in FIG.
実施例５
グリシジルメタクリレート、メチルメタクリレート、ｔ−ブチルアクリレート、２−エチルヘキシルメタクリレート及びｔ−ブチルメタクリレートの共重合体溶液（ジエチレングリコールモノエチルエーテルアセテート、不揮発分５０％、重量平均分子量５８３６、固形分のエポキシ当量：２１４ｇ／ｅｑ．）４２８部、アクリル酸５７．６部、メチルハイドロキノン０．３部及びトリフェニルホスフィン０．５部を温度計、撹拌機、還流冷却器及び空気吹き込み管を備えた反応容器に入れ、空気を吹き込みながら９５〜１０５℃で１０時間反応させた。その後、マレイン酸２６．７部及びメチルハイドロキノン０．２部を加えて８５〜９５℃で３時間反応させ、エポキシ当量２９４７９ｇ／ｅｑ．の反応生成物を得た。次いでテトラヒドロ無水フタル酸３０．４部を加え９５〜１０５℃で４時間反応させて、不揮発分６１％の溶液を得た。このようにして得られたカルボキシル基含有化合物は、酸価１０１ｍｇＫＯＨ／ｇであった。以下、この溶液をＡ−５と称す。得られたカルボキシル基含有化合物のＩＲスペクトルを図９、ゲルクロマトグラムを図１０にそれぞれ示す。
Example 5
Copolymer solution of glycidyl methacrylate, methyl methacrylate, t-butyl acrylate, 2-ethylhexyl methacrylate and t-butyl methacrylate (diethylene glycol monoethyl ether acetate,
実施例６
クレゾールノボラック型エポキシ樹脂のＹＤＣＮ−７００−１０（東都化成（株）製、エポキシ当量：２０６．４ｇ／ｅｑ．）２０６．４部を温度計、撹拌機、還流冷却器及び空気吹き込み管を備えた反応容器に入れ、ジエチレングリコールモノエチルエーテルアセテート１１３部を加え、加熱溶解した。次に、アクリル酸５７．６部、メチルハイドロキノン０．３部及びトリフェニルホスフィン１部を加え、空気を吹き込みながら９５〜１０５℃で１０時間反応させた。次いで、マロン酸２６部、ジエチレングリコールモノエチルエーテルアセテート１７７部及びメチルハイドロキノン０．２部を加え９５〜１０５℃で６時間反応させ、エポキシ当量２５２０ｇ／ｅｑ．の反応生成物を得た。さらに、マレイン酸１３．９部、ジエチレングリコールモノエチルエーテルアセテート１３．９部を加え９５〜１０５℃で６時間反応させ、エポキシ当量２１５７７ｇ／ｅｑ．の反応生成物を得た。その後、テトラヒドロ無水フタル酸４５．６部、ジエチレングリコールモノエチルエーテルアセテート４５．６部を加え９５〜１０５℃で４時間反応させて、不揮発分５０％の溶液を得た。このようにして得られたカルボキシル基含有化合物は、酸価１３２ｍｇＫＯＨ／ｇであった。以下、この溶液をＡ−６と称す。得られたカルボキシル基含有化合物のＩＲスペクトルを図１１、ゲルクロマトグラムを図１２にそれぞれ示す。
Example 6
A cresol novolac type epoxy resin YDCN-700-10 (manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 206.4 g / eq.) 206.4 parts was equipped with a thermometer, stirrer, reflux condenser and air blowing tube. In a reaction vessel, 113 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 57.6 parts of acrylic acid, 0.3 part of methylhydroquinone and 1 part of triphenylphosphine were added and reacted at 95 to 105 ° C. for 10 hours while blowing air. Next, 26 parts of malonic acid, 177 parts of diethylene glycol monoethyl ether acetate and 0.2 part of methylhydroquinone were added and reacted at 95 to 105 ° C. for 6 hours to give an epoxy equivalent of 2520 g / eq. The reaction product was obtained. Furthermore, 13.9 parts of maleic acid and 13.9 parts of diethylene glycol monoethyl ether acetate were added and reacted at 95 to 105 ° C. for 6 hours to give an epoxy equivalent of 21777 g / eq. The reaction product was obtained. Thereafter, 45.6 parts of tetrahydrophthalic anhydride and 45.6 parts of diethylene glycol monoethyl ether acetate were added and reacted at 95 to 105 ° C. for 4 hours to obtain a solution having a nonvolatile content of 50%. The carboxyl group-containing compound thus obtained had an acid value of 132 mgKOH / g. Hereinafter, this solution is referred to as A-6. FIG. 11 shows an IR spectrum of the obtained carboxyl group-containing compound, and FIG. 12 shows a gel chromatogram.
比較例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：２２０ｇ／ｅｑ．）２２０部を温度計、撹拌機、還流冷却器及び空気吹き込み管を備えた反応容器に入れ、ジエチレングリコールモノエチルエーテルアセテート２２０部を加え、加熱溶解した。次に、メチルハイドロキノン０．４６部、トリフェニルフホスフィン３．０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カルボキシル基含有化合物は、酸価１００ｍｇＫＯＨ／ｇであった。以下、この溶液をＢ−１と称す。
Comparative Example 1
A reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and an air blowing tube, 220 parts of cresol novolak type epoxy resin Epicron N-695 (manufactured by Dainippon Ink & Chemicals, Inc., epoxy equivalent: 220 g / eq.) Into this, 220 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 0.46 parts of methylhydroquinone and 3.0 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 compound thus obtained had an acid value of 100 mgKOH / g. Hereinafter, this solution is referred to as B-1.
比較例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℃で保持しながら、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カルボキシル基含有化合物は、酸価１００ｍｇＫＯＨ／ｇであった。以下、この溶液をＢ−２と称す。
Comparative 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 compound thus obtained had an acid value of 100 mgKOH / g. Hereinafter, this solution is referred to as B-2.
比較例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化合物溶液を得た。次に、得られたノボラック型アクリレート化合物溶液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カルボキシル基含有化合物は、酸価８４ｍｇＫＯＨ／ｇであった。以下、この溶液をＢ−３と称す。
Comparative 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 compound solution. Next, 332.5 parts of the obtained novolak acrylate compound 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 compound thus obtained had an acid value of 84 mgKOH / g. Hereinafter, this solution is referred to as B-3.
硬化性化合物の評価
（１）現像性
前記実施例１〜６及び比較例１〜３の各溶液をバーコーターを用いて、３０〜４０μｍの厚さになるように、パターン形成されている銅スルーホールプリント配線基板に全面塗布し、塗膜を８０℃の熱風循環式乾燥炉で３０分間乾燥し、１％の炭酸ナトリウム水溶液で２０秒間、２．０ｋｇ／ｃｍ２のスプレー圧で現像し、現像後の状態を目視判定した。
○：塗膜が除去された。
×：現像されない部分があった。
結果を表１に記す。
○: The coating film was removed.
X: There was a portion that was not developed.
The results are shown in Table 1.
光硬化性・熱硬化性組成物の調製及び各組成物の特性値
前記実施例１〜６及び比較例１〜３の各溶液を表２に示す成分及び成分比で配合し、３本ロールミルでそれぞれ混練して、光硬化性・熱硬化性組成物を調整した。
各組成物の特性値を表３に示す。
各特性値は以下の方法で評価した。 Each characteristic value was evaluated by the following method.
（２）鉛筆硬度
前記組成例１〜６及び比較組成例１〜３の調整した各硬化性組成物を、スクリーン印刷法により、１００メッシュのポリエステルスクリーンを用いて３０〜４０μｍの厚さになるように、パターン形成されている銅スルーホールプリント配線基板に全面塗布し、塗膜を８０℃の熱風循環式乾燥炉で３０分間乾燥させた。そして、レジストパターンを有するネガフィルムを乾燥させた塗膜に密着させ、紫外線露光装置（（株）オーク製作所製、型式ＨＭＷ−６８０ＧＷ）を用いて、紫外線を照射した（露光量４００ｍＪ／ｃｍ２）。次いで１％の炭酸ナトリウム水溶液で６０秒間、２．０ｋｇ／ｃｍ２のスプレー圧で現像し、未露光部分を溶解除去した。その後、１５０℃の熱風循環式乾燥炉で６０分間加熱硬化を行ない、得られた硬化膜を有する評価基板について、ＪＩＳ Ｋ ５４００に準拠して、鉛筆硬度の試験を行なった。
(2) Pencil hardness Each of the curable compositions prepared in Composition Examples 1 to 6 and Comparative Composition Examples 1 to 3 has a thickness of 30 to 40 μm using a 100 mesh polyester screen by screen printing. Next, the entire surface of the copper through-hole printed wiring board on which the pattern was formed was applied, and the coating film was dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. And the negative film which has a resist pattern was stuck to the dried coating film, and it irradiated with the ultraviolet-ray using the ultraviolet-ray exposure apparatus (Corporation | KK Oak Seisakusho make, model HMW-680GW) (exposure amount 400mJ / 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秒間浸漬を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 The said evaluation board | substrate was immersed in a 260 degreeC solder bath for 10 second 3 times according to the test method of JISC6481, 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分間浸漬し、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 immersed in 10 volume% sulfuric acid aqueous solution for 30 minutes at 20 degreeC, taken out, and the state and adhesiveness of the cured film were comprehensively evaluated. The judgment criteria are as follows.
○: No change is observed Δ: Only a slight change ×: The coating has blisters or swelling drops
（５）耐アルカリ性
１０容量％硫酸水溶液を１０容量％水酸化ナトリウム水溶液に代えた以外は耐酸性試験と同様の試験を行い評価した。
(5) Alkali resistance An evaluation similar to the acid resistance test was conducted except that the 10 vol% sulfuric acid aqueous solution was replaced with a 10 vol% sodium hydroxide aqueous solution.
（６）電気絶縁性
パターン形成されている銅スルーホールプリント配線基板の代わりに、ＩＰＣで定められたプリント回路基板（厚さ１．６ｍｍ）のＢパターンを用い、前記の方法にて硬化性組成物の塗布、硬化を行ない、得られた硬化膜の電気絶縁性を以下の基準にて評価した。
加湿条件：温度１２１℃、湿度８５％ＲＨ、印加電圧５Ｖ、１００時間。
測定条件：測定時間６０秒、印加電圧５００Ｖ。
○：加湿後の絶縁抵抗値１０９Ω以上、銅のマイグレーションなし。
△：加湿後の絶縁抵抗値１０９Ω以上、銅のマイグレーションあり。
×：加湿後の絶縁抵抗値１０８Ω以下、銅のマイグレーションあり。
(6) Electrical insulation In place of the copper through-hole printed wiring board on which the pattern is formed, a B pattern of a printed circuit board (thickness: 1.6 mm) defined by IPC is used, and the curable composition is obtained by the above method Application | coating and hardening of the thing were performed and the electrical insulation of the obtained cured film was evaluated on the following references | standards.
Humidification conditions: temperature 121 ° C.,
Measurement conditions:
○: 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.
（７）可撓性
パターン形成されている銅スルーホールプリント配線基板の代わりに、ポリエステルフィルムを用い、前記の方法にて硬化性組成物の塗布、硬化を行ない、その後ポリエステルフィルムから硬化塗膜をはがし、長さ５ｃｍ、幅２ｃｍの評価フィルムを得た。得られたフィルムを折り曲げ、以下の基準にて評価した。
○：フィルムを１７０°折り曲げて割れなかったもの。
△：フィルムを１７０°折り曲げると割れるが、１６０°折り曲げて割れなかったもの。
×：フィルムを１６０°折り曲げて割れたもの。
(7) Instead of a copper through-hole printed wiring board on which a flexible pattern is formed, a polyester film is used, and the curable composition is applied and cured by the method described above, and then a cured coating film is formed from the polyester film. An evaluation film having a length of 5 cm and a width of 2 cm was obtained. The obtained film was bent and evaluated according to the following criteria.
○: The film was bent by 170 ° and not cracked.
(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.
本発明のカルボキシル基含有化合物は、保存安定性に優れ、且つ、前記したような諸特性に優れた硬化物が得られるため、ソルダーレジスト、エッチングレジスト、メッキレジスト、多層配線板の層間絶縁層、テープキャリアパッケージの製造に用いられる永久マスク、フレキシブル配線基板用レジスト、カラーフィルター用レジスト、ドライフィルム用レジスト、インクジェト用レジストなどの用途にも有用である。 Since the carboxyl group-containing compound of the present invention is excellent in storage stability and a cured product having excellent properties as described above is obtained, a solder resist, an etching resist, a plating resist, an interlayer insulating layer of a multilayer wiring board, It is also useful for applications such as permanent masks, flexible wiring board resists, color filter resists, dry film resists, and inkjet resists used in the manufacture of tape carrier packages.
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| JP5254723B2 (en) * | 2008-09-26 | 2013-08-07 | 互応化学工業株式会社 | Curable composition capable of alkali development and cured product thereof |
| JP2012163735A (en) * | 2011-02-07 | 2012-08-30 | Toyo Ink Sc Holdings Co Ltd | Photosensitive resin composition, and protective film and insulating film for touch panel using the composition |
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