JP6075687B2 - Active energy ray-curable self-healing coating composition - Google Patents
Active energy ray-curable self-healing coating composition Download PDFInfo
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- JP6075687B2 JP6075687B2 JP2013045108A JP2013045108A JP6075687B2 JP 6075687 B2 JP6075687 B2 JP 6075687B2 JP 2013045108 A JP2013045108 A JP 2013045108A JP 2013045108 A JP2013045108 A JP 2013045108A JP 6075687 B2 JP6075687 B2 JP 6075687B2
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- 125000001033 ether group Chemical group 0.000 claims description 5
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- 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 1
- MWDGNKGKLOBESZ-UHFFFAOYSA-N 2-oxooctanal Chemical compound CCCCCCC(=O)C=O MWDGNKGKLOBESZ-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- VTDMBRAUHKUOON-UHFFFAOYSA-N 4-[(4-carboxyphenyl)methyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C=C1 VTDMBRAUHKUOON-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- ZMDDERVSCYEKPQ-UHFFFAOYSA-N Ethyl (mesitylcarbonyl)phenylphosphinate Chemical compound C=1C=CC=CC=1P(=O)(OCC)C(=O)C1=C(C)C=C(C)C=C1C ZMDDERVSCYEKPQ-UHFFFAOYSA-N 0.000 description 1
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- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
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- 239000004721 Polyphenylene oxide Substances 0.000 description 1
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- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 1
- QHZLCTYHMCNIMS-UHFFFAOYSA-L [2-ethylhexanoyloxy(dioctyl)stannyl] 2-ethylhexanoate Chemical compound CCCCCCCC[Sn](OC(=O)C(CC)CCCC)(OC(=O)C(CC)CCCC)CCCCCCCC QHZLCTYHMCNIMS-UHFFFAOYSA-L 0.000 description 1
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- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 1
- GPDWNEFHGANACG-UHFFFAOYSA-L [dibutyl(2-ethylhexanoyloxy)stannyl] 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)O[Sn](CCCC)(CCCC)OC(=O)C(CC)CCCC GPDWNEFHGANACG-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
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- 239000000654 additive Substances 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
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- 239000003242 anti bacterial agent Substances 0.000 description 1
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- 239000012298 atmosphere Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- MAOSFLAYGYQLBB-UHFFFAOYSA-N butane-1,4-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCCCO MAOSFLAYGYQLBB-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- BMFYCFSWWDXEPB-UHFFFAOYSA-N cyclohexyl(phenyl)methanone Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1 BMFYCFSWWDXEPB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- WUDNUHPRLBTKOJ-UHFFFAOYSA-N ethyl isocyanate Chemical compound CCN=C=O WUDNUHPRLBTKOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- IIRDTKBZINWQAW-UHFFFAOYSA-N hexaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCO IIRDTKBZINWQAW-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- PWGIEBRSWMQVCO-UHFFFAOYSA-N phosphono prop-2-enoate Chemical compound OP(O)(=O)OC(=O)C=C PWGIEBRSWMQVCO-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Description
本発明は、傷が生じても短時間に消失する自己修復性の塗膜を各種基材の表面に形成できる、活性エネルギー線硬化型の塗料組成物に関する。 The present invention relates to an active energy ray-curable coating composition capable of forming a self-repairing coating film that disappears in a short time even when scratches occur on the surface of various substrates.
冷蔵庫、電子レンジ等の家電品や、携帯電話、パーソナルコンピューター等の情報機器といった各種の工業製品は、その表面に、輸送時や特に使用時において擦傷が無数に生じ得る。また、自動車や自動二輪車といった車両の場合には、ボンネットやガソリンタンクの表面に、移動時のチッピング傷や洗浄時のブラシ傷等が発生し得る。 Various industrial products such as household appliances such as refrigerators and microwave ovens, and information devices such as mobile phones and personal computers may have numerous scratches on the surface during transportation and particularly during use. Further, in the case of vehicles such as automobiles and motorcycles, chipping scratches during movement, brush scratches during cleaning, and the like may occur on the surface of the bonnet or gasoline tank.
そこで、それら工業製品の部材をゴム弾性のある塗膜でコーティングし、その表面に生じた傷を自然に消失させる手段が採られることがあり、例えば特許文献１には、所定の水酸基価および数平均分子量を有するポリエステルポリオールとポリイソシアネートとを含有するポリウレタン系の塗料組成物が開示されている。 Therefore, there is a case where means for coating these industrial products with a rubber-elastic coating film and naturally eliminating the scratches generated on the surface is taken. For example, Patent Document 1 discloses a predetermined hydroxyl value and number. A polyurethane-based coating composition containing a polyester polyol having an average molecular weight and a polyisocyanate is disclosed.
しかし、当該組成物は熱硬化性であるため基材の種類が限定される場合があり、また硬化塗膜を得るために比較的長時間を要するため生産性にも劣る。また、得られる塗膜も自己修復性が不十分であり、例えば金属ブラシ等で強く擦ると傷痕が残ってしまう。 However, since the composition is thermosetting, the type of substrate may be limited, and it takes a relatively long time to obtain a cured coating film, so that the productivity is also inferior. Also, the obtained coating film has insufficient self-healing properties, and for example, scratches remain when rubbed strongly with a metal brush or the like.
そこで斯界では、生産性に優れる方法として、製品の部材の表面を紫外線硬化型樹脂等でハードコートし、塗膜に傷自体がつかないようにする方法がとられることもある。例えば特許文献２には、塗膜の表面硬度を保ちつつ自己修復性を発現するものとして、（メタ）アクリル樹脂にジイソシアネート化合物を介して（メタ）アクリロイル基を導入してなる紫外線硬化性の（メタ）アクリル樹脂（以下、ポリマー（メタ）アクリレートという）を用いた表面コーティング剤が開示されている。 Therefore, in this field, as a method with excellent productivity, there is a method in which the surface of a product member is hard-coated with an ultraviolet curable resin or the like so that the coating film is not scratched. For example, Patent Document 2 discloses an ultraviolet curable product in which a (meth) acryloyl group is introduced into a (meth) acrylic resin via a diisocyanate compound as expressing self-repairability while maintaining the surface hardness of the coating film. A surface coating agent using a (meth) acrylic resin (hereinafter referred to as polymer (meth) acrylate) is disclosed.
しかし、ポリマー（メタ）アクリレートは活性エネルギー線の照射により瞬時に硬化するため塗膜が硬化収縮しやすく、基材との密着性が不十分となったり、場合によりクラックが発生したりする懸念がある。 However, since polymer (meth) acrylate cures instantaneously upon irradiation with active energy rays, the coating film tends to cure and shrink, and there is a concern that adhesion to the substrate may be insufficient or cracks may occur in some cases. is there.
本発明は、各種基材との密着性が良好であり、クラックもなく、かつ生じた傷が短時間に消失する自己修復性の塗膜を形成可能な、非ポリマー（メタ）アクリレートタイプの活性エネルギー線硬化型塗料組成物を提供することを課題とする。 The present invention is a non-polymer (meth) acrylate type activity that has good adhesion to various substrates, is free of cracks, and can form a self-repairing coating film in which the generated scratches disappear in a short time. It is an object to provide an energy ray curable coating composition.
本発明者らは鋭意検討した結果、活性エネルギー線硬化型の塗料組成物であっても、ガラス転移温度が異なる二種の（メタ）アクリロイル基含有ポリエステルを組み合わせて得られる塗料であれば、前記課題を解決可能なことを見出した。 As a result of intensive studies, the present inventors have found that the active energy ray-curable coating composition is a coating composition obtained by combining two (meth) acryloyl group-containing polyesters having different glass transition temperatures. I found that the problem could be solved.
即ち本発明は、分子末端に（メタ）アクリロイル基を有し、ガラス転移温度が−４０〜−１０℃であるポリエステル系ウレタン樹脂（Ａ）、分子末端に（メタ）アクリロイル基を有し、ガラス転移温度が５０〜７０℃であるポリエステル系ウレタン樹脂（Ｂ）、および表面調整剤（Ｃ）を含有し、かつ、（Ａ）成分と（Ｂ）成分の使用重量比〔（Ａ）／（Ｂ）〕が６０／４０〜９５／５であることを特徴とする、活性エネルギー線硬化型自己修復性塗料組成物；（Ａ）成分が、ジカルボン酸類（ａ１）、ジオール類（ａ２）およびトリオール類（ａ３）を反応させてなる分岐状のポリエステルポリオール（Ａ’）に、下記一般式（１）〜（４）で表わされるいずれか１種のイソシアネート基含有化合物を反応させて得られるものであり、（Ｂ）成分が、ジカルボン酸類（ｂ１）、ジオール類（ｂ２）および必要に応じてトリオール類（ｂ３）を反応させてなる直鎖状または分岐状のポリエステルポリオール（Ｂ’）に、下記一般式（１）〜（４）で表わされるいずれか１種のイソシアネート基含有化合物を反応させて得られる前記活性エネルギー線硬化型自己修復性塗料組成物
一般式（１）：
一般式（２）：
一般式（３）：
（Ｒ８は水素またはメチル基を、Ｒ９はアルキレン基を示す）
一般式（４）：
（Ｒ１０は水素またはメチル基を、Ｒ１１はアルキレン基を示す））；（Ａ）成分と（Ｂ）成分の（メタ）アクリロイル基の含有量が順に０．５〜２．０ｍｍｏｌ／ｇおよび０．２〜１．５ｍｍｏｌ／ｇである前記活性エネルギー線硬化型自己修復性塗料組成物；（Ａ）成分と（Ｂ）成分の数平均分子量が順に４５００〜８０００および２５００〜６０００である前記活性エネルギー線硬化型自己修復性塗料組成物；表面調整剤（Ｃ）がシリコーン系表面調整剤である前記活性エネルギー線硬化型自己修復性塗料組成物；さらに光重合開始剤（Ｄ）を含有する前記活性エネルギー線硬化型自己修復性塗料組成物；さらに反応性希釈剤（Ｅ）を含有する、請求項１〜６のいずれかの活性エネルギー線硬化型自己修復性塗料組成物；有機溶剤（Ｆ）の溶液として使用する前記活性エネルギー線硬化型自己修復性塗料組成物、に関する。
That is, the present invention comprises a polyester-based urethane resin (A) having a (meth) acryloyl group at the molecular end and a glass transition temperature of −40 to −10 ° C., a (meth) acryloyl group at the molecular end, It contains a polyester-based urethane resin (B) having a transition temperature of 50 to 70 ° C., and a surface conditioner (C), and the weight ratio of the component (A) to the component (B) [(A) / (B )] Is 60/40 to 95/5, the active energy ray-curable self-healing coating composition; the component (A) is dicarboxylic acids (a1), diols (a2) and triols It is obtained by reacting any one isocyanate group-containing compound represented by the following general formulas (1) to (4) with the branched polyester polyol (A ′) obtained by reacting (a3). , (B) A linear or branched polyester polyol (B ′) obtained by reacting a dicarboxylic acid (b1), a diol (b2) and, if necessary, a triol (b3) as a component is represented by the following general formula (1) The active energy ray-curable self-healing coating composition obtained by reacting any one of the isocyanate group-containing compounds represented by (4): General formula (1):
General formula (2):
General formula (3):
(R8 represents hydrogen or a methyl group, and R9 represents an alkylene group)
General formula (4):
(R10 represents hydrogen or a methyl group, and R11 represents an alkylene group.); The content of the (meth) acryloyl group in the components (A) and (B) is 0.5 to 2.0 mmol / g and 0. The active energy ray-curable self-healing coating composition that is 2 to 1.5 mmol / g; the active energy rays in which the number average molecular weights of the component (A) and the component (B) are 4500 to 8000 and 2500 to 6000, respectively. Curing-type self-healing coating composition; The active energy ray-curable self-healing coating composition in which the surface conditioner (C) is a silicone-based surface conditioner; and the active energy further containing a photopolymerization initiator (D) An active energy ray-curable self-healing coating composition according to any one of claims 1 to 6, further comprising a reactive diluent (E); an organic solvent (F) The active energy ray-curable self-healing coating composition of use as a solution, about.
本発明の塗料組成物によれば、金属やプラスチック等の各種基材の表面に、密着性に優れる自己修復性の塗膜を短時間で形成できる。また、この塗膜は適度な柔軟性を有しているためクラックも生じない。また、この塗膜は耐ブロッキング性に優れているため、例えば本発明の塗料組成物を塗工したフィルムを巻きとった後、巻戻しの際に塗膜の剥がれや巻戻し音が低減する等の利点がある。その他、耐スリップ性や耐湿熱性が良好であり、例えば高温高湿の使用環境下においても欠陥が生じにくい。 According to the coating composition of the present invention, a self-repairing coating film having excellent adhesion can be formed in a short time on the surface of various substrates such as metals and plastics. Moreover, since this coating film has a moderate softness | flexibility, a crack does not arise. Moreover, since this coating film is excellent in blocking resistance, for example, after winding a film coated with the coating composition of the present invention, the peeling of the coating film and the unwinding sound are reduced during rewinding. There are advantages. In addition, slip resistance and heat-and-moisture resistance are good, and defects are less likely to occur even in high-temperature and high-humidity environments.
それゆえ、本発明の塗料組成物は、自動車や自動二輪車といった車両のボディー部材（ボンネット、ガソリンタンク等）や冷蔵庫や電子レンジ等の家電製品の部材（側板、ドア材等）、携帯電話やパーソナルコンピューター等の情報機器の筐体といった各種工業製品の上塗り塗料として有用である。 Therefore, the coating composition of the present invention is used for vehicle body members such as automobiles and motorcycles (bonnets, gasoline tanks, etc.), household appliance members such as refrigerators and microwave ovens (side plates, door materials, etc.), mobile phones and personal computers. It is useful as a top coating for various industrial products such as the casing of information equipment such as computers.
本発明の塗料組成物は、分子末端に（メタ）アクリロイル基を有し、ガラス転移温度が−４０〜−１０℃であるポリエステル系ウレタン樹脂（Ａ）（以下、（Ａ）成分という）、分子末端に（メタ）アクリロイル基を有し、ガラス転移温度が５０〜７０℃であるポリエステル系ウレタン樹脂（Ｂ）（以下、（Ｂ）成分という）、および表面調整剤（Ｃ）（以下、（Ｃ）成分という）を含有する。 The coating composition of the present invention comprises a polyester-based urethane resin (A) (hereinafter referred to as component (A)) having a (meth) acryloyl group at the molecular end and a glass transition temperature of -40 to -10 ° C, molecule Polyester urethane resin (B) (hereinafter referred to as (B) component) having a (meth) acryloyl group at the terminal and having a glass transition temperature of 50 to 70 ° C., and a surface conditioner (C) (hereinafter referred to as (C ) Component)).
（Ａ）成分は、前記ガラス転移温度を有し、分子末端が（メタ）アクリロイル基であるポリエステル系ウレタン樹脂であれば、各種公知のものを特に制限なく使用できる。具体的には、ジカルボン酸類（ａ１）（以下、（ａ１）成分という）、ジオール類（ａ２）（以下、（ａ２）成分という）、およびトリオール類（ａ３）（以下、（ａ３）成分という）を反応させてなる分岐状のポリエステルポリオール（Ａ’）に、一般式（１）〜（４）のイソシアネート基含有化合物のうち少なくとも１種類を反応させて得られる（メタ）アクリロイル基含有ポリエステル系ウレタン樹脂が好ましい。 As the component (A), various known resins can be used without particular limitation as long as they are polyester-based urethane resins having the glass transition temperature and the molecular terminals of which are (meth) acryloyl groups. Specifically, dicarboxylic acids (a1) (hereinafter referred to as component (a1)), diols (a2) (hereinafter referred to as component (a2)), and triols (a3) (hereinafter referred to as component (a3)) (Meth) acryloyl group-containing polyester urethane obtained by reacting at least one of the isocyanate group-containing compounds of the general formulas (1) to (4) with the branched polyester polyol (A ′) obtained by reacting Resins are preferred.
（ａ１）成分としては、例えば、イソフタル酸、テレフタル酸、フタル酸、ジフェニルメタン−４，４’−ジカルボン酸、２，６−ナフタレンジカルボン酸等の芳香族ジカルボン酸；シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、アゼライン酸、ピメリン酸、スベリン酸、セバシン酸、ウンデカン二酸、ドデカン二酸、トリデカン二酸等の脂肪族ジカルボン酸；ヘキサヒドロフタル酸、ヘキサヒドロフタル酸無水物、１，４−シクロヘキサンジカルボン酸、１，２−シクロヘキサンジカルボン酸等の脂環族ジカルボン酸；これらのジエステル化合物等が挙げられ、１種を単独で、或いは２種以上を組み合わせて使用することができる。 Examples of the component (a1) include aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, phthalic acid, diphenylmethane-4,4′-dicarboxylic acid, and 2,6-naphthalenedicarboxylic acid; oxalic acid, malonic acid, and succinic acid , Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, azelaic acid, pimelic acid, suberic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid; hexahydrophthalic acid, hexahydrophthalic anhydride, 1 , 4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and the like alicyclic dicarboxylic acids; these diester compounds and the like can be mentioned, and one kind can be used alone, or two or more kinds can be used in combination.
（ａ２）成分としては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、１，３−プロパンジオール、１，３−ブタンジオール、１，４−ブタンジオール、ペンタンジオール、１，６−ヘキサンジオール等の直鎖状脂肪族ジオール；ネオペンチルグリコール、３−メチル−１，５−ペンタンジオール、２−メチル−１，３−プロパンジオール、１，２−プロパンジオール等の分岐状脂肪族ジオール；１，４−シクロヘキサンジメタノール、ダイマー酸を水素化して得られるジオール、水添ビスフェノールＡのエチレンオキシド付加物等の脂環状ジオール等の低分子ジオール、ビスフェノールＡのエチレンオキサイド付加物の他、オリゴマーポリオール、ポリカプロラクトンポリオール、ポリカーボネートポリオール、ポリエーテルポリオールなどの高分子ポリオールが挙げられ、１種を単独で、或いは２種以上を組み合わせて使用することができる。（ａ２）成分としては、（Ａ）成分のガラス転移温度を考慮すると、直鎖状脂肪族ジオールおよび／または分岐状脂肪族ジオールのみを使用するのが好ましい。 As component (a2), linear chains such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, pentanediol, and 1,6-hexanediol Branched aliphatic diols; branched aliphatic diols such as neopentyl glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 1,2-propanediol; 1,4-cyclohexane Dimer, diol obtained by hydrogenating dimer acid, low molecular diol such as alicyclic diol such as ethylene oxide adduct of hydrogenated bisphenol A, ethylene oxide adduct of bisphenol A, oligomer polyol, polycaprolactone polyol, polycarbonate Polyol, They include polymeric polyols such as Li polyether polyols can be singly or in combination of two or more used. As the component (a2), in consideration of the glass transition temperature of the component (A), it is preferable to use only a linear aliphatic diol and / or a branched aliphatic diol.
（ａ３）成分としては、グリセリン、ペンタエリスリトール、トリメチロールプロパン、トリメチロールエタン、１，２，６−ヘキサントリオール、１，２，４−ブタントリオール等が挙げられ、１種を単独で、或いは２種以上を組み合わせて使用することができる。 Examples of the component (a3) include glycerin, pentaerythritol, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, and the like. More than one species can be used in combination.
（Ａ’）成分は、各種公知の方法で製造できる。具体的には、（ａ１）成分〜（ａ３）成分を、常圧下または減圧下において、通常１５０〜２８０℃程度および５〜１０時間程度の条件で、一括的にまたは逐次的に反応させる方法が挙げられる。また、（Ａ’）成分の諸物性は（ａ１）成分〜（ａ３）成分の種類を変更したり、圧力条件を変更したりすることによって調節可能である。また、反応の際には、三酸化アンチモンや酸化ジブチルスズ等のエステル化触媒や、反応溶媒として後述の有機溶剤を使用することができる。 The component (A ′) can be produced by various known methods. Specifically, there is a method in which the components (a1) to (a3) are reacted collectively or sequentially under conditions of about 150 to 280 ° C. and about 5 to 10 hours under normal pressure or reduced pressure. Can be mentioned. Various physical properties of the component (A ′) can be adjusted by changing the types of the components (a1) to (a3) or changing the pressure conditions. In the reaction, an esterification catalyst such as antimony trioxide or dibutyltin oxide, or an organic solvent described later can be used as a reaction solvent.
（ａ１）成分〜（ａ３）成分の使用量は、（Ａ）成分のガラス転移温度を考慮して適宜決定すればよく、通常は、（ａ１）成分と（ａ２）成分および（ａ３）成分とのモル比、即ち（ａ１）：（ａ２+ａ３）が１：１程度であり、かつ、（ａ２）成分および（ａ３）成分の合計モル数における（ａ３）成分のモル数、即ち（ａ３）／（ａ２＋ａ３）が５〜３０％程度、好ましくは１０〜２５％となる範囲である。 The amount of component (a1) to component (a3) used may be appropriately determined in consideration of the glass transition temperature of component (A). Usually, component (a1), component (a2) and component (a3) (A1) :( a2 + a3) is about 1: 1, and the number of moles of component (a3) in the total number of moles of component (a2) and component (a3), ie (a3) / (A2 + a3) is about 5 to 30%, preferably 10 to 25%.
前記イソシアネート基含有化合物としては、各種公知のものを特に制限なく用いることができる。具体的には、前記一般式（１）〜（４）で表されるイソシアネート基含有化合物のうち１種類を単独でまたは２種類以上を組み合わせて使用できる。なお、式（１）および（２）中、Ｒ２、Ｒ４およびＲ６のアルキレン基は炭素数が通常１〜３程度、アルキレンエーテル基も炭素数は通常２〜６程度である。 As the isocyanate group-containing compound, various known compounds can be used without particular limitation. Specifically, one of the isocyanate group-containing compounds represented by the general formulas (1) to (4) can be used alone or in combination of two or more. In formulas (1) and (2), the alkylene group of R 2 , R 4 and R 6 usually has about 1 to 3 carbon atoms, and the alkylene ether group also usually has about 2 to 6 carbon atoms.
前記一般式（１）で表されるイソシアネート基含有化合物としては、例えば、Ｘがイソシアネート基のものとして２−アクリロイルオキシエチルイソシアネート、２−メタクリロイルオキシエチルイソシアネート、メタクリル酸２−（２−イソシアネートエトキシ）エチル、アクリル酸２−（２−イソシアネートエトキシ）エチル等が挙げられ、１種を単独で、或いは２種以上を組み合わせて使用することができる。また、市販品としては、例えば、カレンズＭＯＩ、カレンズＡＯＩ、カレンズＭＯＩ−ＥＧ（いずれも昭和電工（株）製、商標）等が挙げられる。 Examples of the isocyanate group-containing compound represented by the general formula (1) include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 2- (2-isocyanatoethoxy) methacrylate, where X is an isocyanate group. Examples thereof include ethyl, 2- (2-isocyanatoethoxy) ethyl acrylate and the like, and one can be used alone or two or more can be used in combination. Moreover, as a commercial item, Karenz MOI, Karenz AOI, Karenz MOI-EG (all are trademarks made by Showa Denko KK) etc. are mentioned, for example.
一般式（２）で表わされるイソシアネート基含有化合物としては、例えばＸがイソシアネート基のものとして、１，１−（ビス（メタ）アクリロイルオキシメチル）エチルイソシアネート等が挙げられ、市販品としては、例えば、カレンズＢＥＩ等が挙げられる。 Examples of the isocyanate group-containing compound represented by the general formula (2) include 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate, where X is an isocyanate group. , Karenz BEI and the like.
一般式（３）および（４）で表わされるイソシアネート基含有化合物としては、例えばイソホロンジイソシアネートと少なくとも１種類以上の水酸基含有（メタ）アクリレートとの反応生成物等が挙げられる。水酸基含有（メタ）アクリレートとしては、水酸基と（メタ）アクリレート基とを有するものであれば特に制限なく用いることができ、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、２−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシ−３−フェニルオキシプロピル（メタ）アクリレート、１，４−ブタンジオールモノ（メタ）アクリレート、２−ヒドロキシアルキル（メタ）アクリロイルホスフェート、４−ヒドロキシシクロヘキシル（メタ）アクリレート、１，６−ヘキサンジオールモノ（メタ）アクリレート、ネオペンチルグリコールモノ（メタ）アクリレート、（ポリ）エチレングリコールモノアクリレート、（ポリ）プロピレングリコールモノアクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等を挙げることができる。 Examples of the isocyanate group-containing compound represented by the general formulas (3) and (4) include a reaction product of isophorone diisocyanate and at least one hydroxyl group-containing (meth) acrylate. As the hydroxyl group-containing (meth) acrylate, any hydroxyl group and (meth) acrylate group can be used without particular limitation. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (Meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, (poly) ethylene glycol monoacrylate, (poly) propylene glycol monoacrylate, Data pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.
なお、一般式（１）〜（４）におけるＸがブロックドイソシアネートの場合は、所望の温度に加熱することにより脱離する化合物であれば特に制限なく使用することができる。ブロック化剤としては、メチルエチルケトオキシム等のオキシム化合物、ε−カプロラクタム等のラクタム化合物、フェノール、マロン酸ジエチルエステル、アセト酢酸エステル、アセチルアセトン、亜硫酸ナトリウム、エチレンイミンなどが挙げられる。これらのブロック化剤は１種単独で、または２種以上を組み合わせて使用することができる。具体的には、アクリル酸２−（０−［１’−メチルプロピリデンアミノ］カルボキシアミノ）エチル、メタクリル酸２−（０−［１’−メチルプロピリデンアミノ］カルボキシアミノ）エチル等が挙げられ、１種を単独で、或いは２種以上を組み合わせて使用することができる。また、ブロックドイソシアネートの市販品としては、例えば、カレンズＭＯＩ−ＢＭ等が挙げられる。 In addition, when X in General formula (1)-(4) is blocked isocyanate, if it is a compound detach | desorbed by heating to desired temperature, it can be especially used without a restriction | limiting. Examples of the blocking agent include oxime compounds such as methyl ethyl ketoxime, lactam compounds such as ε-caprolactam, phenol, malonic acid diethyl ester, acetoacetic acid ester, acetylacetone, sodium sulfite, and ethyleneimine. These blocking agents can be used alone or in combination of two or more. Specific examples include 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl acrylate, 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate, and the like. One kind can be used alone, or two or more kinds can be used in combination. Moreover, as a commercial item of blocked isocyanate, Karenz MOI-BM etc. are mentioned, for example.
（Ａ’）成分とイソシアネート基含有化合物は、各種公知の方法で反応させることができる。具体的には、例えば、（Ａ’）成分と前記イソシアネート基含有化合物を通常５０〜１５０℃程度の温度でウレタン化反応させればよく、その際、各種公知のウレタン化触媒や、反応溶媒として後述の有機溶剤を使用することができる。また、（Ａ’）成分は１種類のみを使用しても２種類以上の混合物として使用しても良い。 The component (A ′) and the isocyanate group-containing compound can be reacted by various known methods. Specifically, for example, the component (A ′) and the isocyanate group-containing compound may be urethanated usually at a temperature of about 50 to 150 ° C. In this case, as various known urethanization catalysts and reaction solvents. The organic solvent mentioned later can be used. The component (A ′) may be used alone or as a mixture of two or more.
ウレタン化触媒としては、例えば、オクチル酸錫、ジブチル錫ジ（２−エチルヘキサノエート）、ジオクチル錫ジ（２−エチルヘキサノエート）、ジオクチル錫ジアセテート、ジブチル錫ジラウレート、ジブチル錫オキサイド、ジオクチル錫オキサイド、ジブチル錫ジオクテート、モノブチル錫トリオクテート、ジブチル錫脂肪酸塩が挙げられ、これらは１種を単独で、或いは２種以上を組み合わせて使用できる。ウレタン化触媒の使用量は特に限定されないが、（Ａ’）成分とイソシアネート基含有化合物の合計重量に対して固形分換算で通常０〜２重量％程度、好ましくは０．０１〜０．１重量％となる範囲で使用できる。 Examples of the urethanization catalyst include tin octylate, dibutyltin di (2-ethylhexanoate), dioctyltin di (2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, and dioctyl. Examples thereof include tin oxide, dibutyltin dioctate, monobutyltin trioctate, and dibutyltin fatty acid salt, and these can be used alone or in combination of two or more. Although the usage-amount of a urethanization catalyst is not specifically limited, About 0 to 2 weight% normally in conversion of solid content with respect to the total weight of (A ') component and an isocyanate group containing compound, Preferably it is 0.01 to 0.1 weight % Can be used.
イソシアネート基含有化合物の使用量は特に限定されないが、通常、該イソシアネート基含有化合物のイソシアネート基の当量値（ＮＣＯ）と、（Ａ’）成分の水酸基の当量値（ＯＨ）との比率（ＮＣＯ／ＯＨ）が０．５〜１程度、好ましくは０．８〜１程度となる範囲であればよい。 The amount of the isocyanate group-containing compound used is not particularly limited. Usually, however, the ratio of the isocyanate group equivalent value (NCO) of the isocyanate group-containing compound to the hydroxyl group equivalent value (OH) of the component (A ′) (NCO / OH) may be in the range of about 0.5 to 1, preferably about 0.8 to 1.
こうして得られる（Ａ）成分は、主に塗膜の自己修復性の観点より、ガラス転移温度が−４０〜−１０℃、好ましくは−３０〜−１５℃である。 The component (A) thus obtained has a glass transition temperature of −40 to −10 ° C., preferably −30 to −15 ° C., mainly from the viewpoint of self-healing properties of the coating film.
（Ｂ）成分も、所定のガラス転移温度を有し、分子末端が（メタ）アクリロイル基であるポリエステル系ウレタン樹脂であれば、各種公知のものを特に制限なく使用できる。具体的には、ジカルボン酸類（ｂ１）（以下、（ｂ１）成分という）、ジオール類（ｂ２）（以下、（ｂ２）成分という）、およびトリオール類（ｂ３）（以下、（ｂ３）成分という）を反応させてなる直鎖または分岐状のポリエステルポリオール（Ｂ’）（以下、（Ｂ’）成分という）に、前記一般式（１）〜（４）で表されるイソシアネート基含有化合物のうち少なくとも１種類を反応させることにより得られるものが好ましい。なお、（ｂ１）成分〜（ｂ３）成分としては、前記（ａ１）成分〜（ａ３）成分と同一のものを使用でき、（Ｂ’）成分としては、直鎖のものが好ましい。 As the component (B), various known resins can be used without particular limitation as long as they are polyester-based urethane resins having a predetermined glass transition temperature and having molecular ends that are (meth) acryloyl groups. Specifically, dicarboxylic acids (b1) (hereinafter referred to as component (b1)), diols (b2) (hereinafter referred to as component (b2)), and triols (b3) (hereinafter referred to as component (b3)) To the linear or branched polyester polyol (B ′) (hereinafter referred to as component (B ′)) obtained by reacting at least one of the isocyanate group-containing compounds represented by the general formulas (1) to (4) What is obtained by making 1 type react is preferable. In addition, as (b1) component-(b3) component, the same thing as said (a1) component-(a3) component can be used, and (B ') component has a preferable linear thing.
（Ｂ’）成分も、（Ａ’）成分と同様の方法で製造できる。また、（ｂ１）成分〜（ｂ３）成分の使用量は、（Ｂ）成分のガラス転移温度を考慮して適宜決定すればよく、通常は、（ｂ１）成分と（ｂ２）成分および（ｂ３）成分とのモル比、即ち（ｂ１）：（ｂ２＋ｂ３）が１：１程度であり、かつ、（ｂ２）成分および（ｂ３）成分のモル数、即ち（ｂ３）／（ｂ２＋ｂ３）が０〜３０％程度、好ましくは０〜５％、さらに好ましくは０％となる範囲である。 The component (B ′) can also be produced in the same manner as the component (A ′). Moreover, the usage-amount of (b1) component-(b3) component should just be determined suitably in consideration of the glass transition temperature of (B) component, Usually, (b1) component, (b2) component, and (b3) The molar ratio with the component, that is, (b1) :( b2 + b3) is about 1: 1, and the number of moles of the component (b2) and the component (b3), that is, (b3) / (b2 + b3) is 0 to 30%. The degree is preferably in the range of 0 to 5%, more preferably 0%.
また、（Ｂ’）成分と前記イソシアネート基含有化合物の反応条件（温度、使用量等）も、（Ａ’）成分のそれと同様である。その際、（Ｂ’）成分は１種類のみを使用しても２種類以上の混合物として使用しても良い。 The reaction conditions (temperature, amount used, etc.) of the component (B ′) and the isocyanate group-containing compound are the same as those of the component (A ′). At that time, the component (B ′) may be used alone or as a mixture of two or more.
こうして得られる（Ｂ）成分は、主に塗膜の自己修復性の観点より、ガラス転移温度が５０〜７０℃、好ましくは５５〜６５℃である。 The component (B) thus obtained has a glass transition temperature of 50 to 70 ° C., preferably 55 to 65 ° C., mainly from the viewpoint of self-healing properties of the coating film.
なお、（Ａ）成分と（Ｂ）成分の他の物性は特に限定されないが、例えば（メタ）アクリロイル基の含有量は、主に塗膜の自己修復性の観点より、順に０．５〜２．０ｍｍｏｌ／ｇ程度および０．２〜１．５ｍｍｏｌ／ｇ程度であるのが好ましく、１．０〜１．５ｍｍｏｌ／ｇおよび０．５〜１．０ｍｍｏｌ／ｇであるのがより好ましい。 In addition, although the other physical property of (A) component and (B) component is not specifically limited, For example, content of (meth) acryloyl group is 0.5-2 in order from the viewpoint of the self-restoration property of a coating film mainly. It is preferably about 0.0 mmol / g and about 0.2 to 1.5 mmol / g, more preferably 1.0 to 1.5 mmol / g and 0.5 to 1.0 mmol / g.
また、（Ａ）成分と（Ｂ）成分の数平均分子量（ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定によるポリスチレン換算値をいう。以下、同様。）も特に限定されないが、主に塗膜傷の自己修復性の点より、順に４５００〜８０００程度および２５００〜６０００程度であるのが好ましく、５０００〜７０００および３０００〜５０００であるのがより好ましい。 In addition, the number average molecular weight of the component (A) and the component (B) (referred to polystyrene conversion value by gel permeation chromatography (GPC) measurement; hereinafter the same) is not particularly limited, but mainly the self-damage of the coating film. From the point of restorability, it is preferable that it is about 4500-8000 and about 2500-6000 in order, and it is more preferable that they are 5000-7000 and 3000-5000.
（Ｃ）成分は、主に塗膜の自己修復性および耐ブロッキング性や耐スリップ性を確保する目的で使用する。具体例としては、ポリエーテル変性シリコーン、ポリエステル変性シリコーン、ポリジメチルシロキサン、ポリメチルアルキルシロキサン等のシリコーン系表面調整剤や、フルオロアルキルカルボン酸、パーフルオロアルキルカルボン酸等のフッ素系表面調整剤、パーフルオロ変性シリコーン等のシリコーン−フッ素系表面調整剤、ポリエーテル変性アクリルポリマー、ポリエステル変性アクリルポリマー、パーフルオロアルキル変性アクリルポリマー等のアクリル系表面調整剤が挙げられ、これらは１種を単独で、或いは２種以上を組み合わせて使用できる。これらの中でも耐ブロッキング性およびスリップ性の観点より、シリコーン系表面調整剤が好ましい。 The component (C) is mainly used for the purpose of securing the self-restoring property, blocking resistance and slip resistance of the coating film. Specific examples include silicone-based surface conditioners such as polyether-modified silicone, polyester-modified silicone, polydimethylsiloxane, and polymethylalkylsiloxane; fluorine-based surface conditioners such as fluoroalkylcarboxylic acid and perfluoroalkylcarboxylic acid; Examples include silicone-fluorine-based surface conditioners such as fluoro-modified silicones, polyether-modified acrylic polymers, polyester-modified acrylic polymers, and acrylic surface conditioners such as perfluoroalkyl-modified acrylic polymers. Two or more types can be used in combination. Among these, a silicone-based surface conditioner is preferable from the viewpoint of blocking resistance and slipping property.
本発明の組成物には、必要に応じて各種の光重合開始剤（Ｄ）（以下、（Ｄ）成分という）を含めることができる。具体的には、例えば、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、１−シクロヘキシルフェニルケトン、１−ヒドロキシ−シクロヘキシル−フェニルケトン、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、オリゴ（２−ヒドロキシ−２−メチル−１−（４−（１−メチルビニル）フェニル）プロパノン）、２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチル−プロピオニル）−ベンジル］−フェニル｝−２−メチル−プロパン−１−オン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１、ビス（２，４，６−トリメチルベンゾイル）−フェニルホスフィンオキサイド、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、ビス（２，６−ジメトキシベンゾイル）−２，４，４−トリメチル−ペンチルホスフィンオキサイド、エチル−（２，４，６−トリメチルベンゾイル）フェニルフォスフィネート、１，２−オクタンジオン，１−［４−（フェニルチオ）−，２−（Ｏ−ベンゾイルオキシム）］、メチルベンゾイルホルメート、４−メチルベンゾフェノン、４−フェニルベンソフェノン、２，４，６−トリメチルベンゾフェノン、４−ベンゾイル−４’−メチルジフェニルスルフィド、１−［４−（４−ベンゾイルフェニルスルファニル）フェニル］−２−メチル−２−（４−メチルフェニルスルホニル）プロパン−１−オン等が挙げられ、これらは１種を単独で、或いは２種以上を組み合わせて使用できる。 In the composition of this invention, various photoinitiators (D) (henceforth (D) component) can be included as needed. Specifically, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl -Propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane- 1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1 (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,6-dimethoxybenzoyl) ) -2,4,4-trimethyl-pentylphosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenyl phosphinate, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], methylbenzoylformate, 4-methylbenzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 1- [4- (4-Benzoylphenylsulfanyl) phenyl]- - methyl-2- (4-methyl-phenylsulfonyl) propan-1-one and the like, and these alone, or may be used in combination of two or more.
また、本発明の組成物には、必要に応じてさらに各種公知の反応性希釈剤（Ｅ）（以下、（Ｅ）成分という）を含めることができる。具体的には、例えば、単官能（メタ）アクリレート化合物〔スチレン、ｎ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、イソステアリル（メタ）アクリレート、ｎ−オクタデシル（メタ）アクリレート、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、３−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、（メタ）アクリル酸と多価アルコールとのエステル等〕、２官能（メタ）アクリレート化合物〔ヘキサメチレングリコールジアクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ヘキサエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ブチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，３−ブタンジオールジ（メタ）アクリレート、１，４ーブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、２，２’−ビス（４−アクリロキシジエトキシフェニル）プロパン、１，９−ノナンジオールジ（メタ）アクリレート、ビスフェノールＡテトラエチレングリコールジアクリレート等〕、３官能（メタ）アクリレート化合物〔トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、エチレンオキシド変性グリセロールトリアクリレート、プロピレンオキシド変性グリセロールトリアクリレート、εカプロラクトン変性トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート等〕、４官能（メタ）アクリレート化合物〔ジトリメチロールプロパンテトラアクリレート、ペンタエリスリトールエトキシテトラアクリレート、ペンタエリスリトールテトラアクリレート〕、５官能以上の（メタ）アクリレート化合物〔ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、ポリペンタエリスリトールポリアクリレート等〕などが挙げられ、これらは１種を単独で、或いは２種以上を組み合わせて用いることができる。 Moreover, the composition of this invention can contain various well-known reactive diluents (E) (henceforth (E) component) as needed. Specifically, for example, monofunctional (meth) acrylate compounds [styrene, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, isostearyl (meta ) Acrylate, n-octadecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, isobornyl (meth) ) Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ester of (meth) acrylic acid and polyhydric alcohol, etc.], bifunctional (meth) acrylate compound [hexa Tylene glycol diacrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2,2′-bis (4-acryloxydi) Toxiphenyl) propane, 1,9-nonanediol di (meth) acrylate, bisphenol A tetraethylene glycol diacrylate, etc.], trifunctional (meth) acrylate compounds [trimethylolpropane tri (meth) acrylate, tetramethylol methanetri (meta ) Acrylate, ethylene oxide modified glycerol triacrylate, propylene oxide modified glycerol triacrylate, epsilon caprolactone modified trimethylolpropane triacrylate, pentaerythritol triacrylate, etc.] tetrafunctional (meth) acrylate compounds [ditrimethylolpropane tetraacrylate, pentaerythritol ethoxytetra Acrylate, pentaerythritol tetraacrylate], (meth) acrylates with 5 or more functions Compound [dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, poly pentaerythritol polyacrylate, etc.] and the like, which may be used alone or in combination one or two or more kinds.
本発明の塗料組成物は、各種公知の有機溶剤（Ｆ）（以下、（Ｆ）成分という）の溶液（ワニス）として利用できる。（Ｆ）成分としては、例えば、ソルベッソ＃１００、ソルベッソ＃１５０（いずれもエクソン化学（株）製）、トルエン、キシレン等の炭化水素系有機溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系有機溶剤；酢酸メチル、酢酸エチル、酢酸イソプロピル、酢酸ブチル、酢酸アミル、ぎ酸エチル、プロピオン酸ブチル、メチルセロソルブアセテート、セロソルブアセテート等のエステル系有機溶剤；ジオキサン、ジエチルエーテル、テトラヒドロフラン等のエーテル系有機溶剤が挙げられる。これらの中でも（Ａ）成分および（Ｂ）成分に対する溶解力の点より炭化水素系有機溶剤および／またはケトン系有機溶剤が好ましい。 The coating composition of this invention can be utilized as a solution (varnish) of various well-known organic solvents (F) (henceforth (F) component). Examples of component (F) include Solvesso # 100, Solvesso # 150 (both manufactured by Exxon Chemical Co., Ltd.), hydrocarbon organic solvents such as toluene and xylene; ketone organics such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Solvent: Ester organic solvents such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, ethyl formate, butyl propionate, methyl cellosolve acetate, cellosolve acetate, etc. Ether organic solvents such as dioxane, diethyl ether, tetrahydrofuran, etc. Is mentioned. Among these, hydrocarbon organic solvents and / or ketone organic solvents are preferable from the viewpoint of the dissolving power with respect to the component (A) and the component (B).
本発明の塗料組成物における各成分の含有量は特に限定されないが、（Ａ）〜（Ｆ）成分の全量を１００重量％（固形分換算）とした場合において、通常は以下の通りである。
（Ａ）成分および（Ｂ）成分の合計：３０〜６０重量％、好ましくは３５〜５５重量％
（Ｃ）成分：０．１〜２重量％程度、好ましくは０．１〜１重量％
（Ｄ）成分：０〜１０重量％程度、好ましくは１〜５重量％
（Ｅ）成分：０〜２０重量％程度、好ましくは０〜１０重量％
（Ｆ）成分：３９．９〜６５重量％程度、好ましくは４３．９〜６０重量％程度
Although content of each component in the coating composition of this invention is not specifically limited, When the whole quantity of (A)-(F) component is 100 weight% (solid content conversion), it is as follows normally.
Total of component (A) and component (B): 30 to 60% by weight, preferably 35 to 55% by weight
Component (C): about 0.1 to 2% by weight, preferably 0.1 to 1% by weight
Component (D): about 0 to 10% by weight, preferably 1 to 5% by weight
Component (E): about 0 to 20% by weight, preferably 0 to 10% by weight
Component (F): about 39.9 to 65% by weight, preferably about 43.9 to 60% by weight
但し、（Ａ）成分と（Ｂ）成分の使用重量比〔（Ａ）／（Ｂ）〕は、主に塗膜の自己修復性の点より、通常６０／４０〜９５／５程度、好ましくは７５／３５〜９５／５程度、いっそう好ましくは８０／２０〜９５／５（いずれも固形分換算）の必要がある。 However, the weight ratio [(A) / (B)] of the component (A) and the component (B) is usually about 60/40 to 95/5, preferably from the viewpoint of self-healing properties of the coating film, It is necessary to be about 75/35 to 95/5, more preferably 80/20 to 95/5 (all in terms of solid content).
なお、（Ａ）成分と（Ｂ）成分には水酸基が残存している場合があり、この水酸基と反応させることにより塗膜の硬度を調整する目的で、各種公知のジイソシアネート化合物を用いることができる。具体的には、例えば、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート等の脂肪族ジイソシアネートや、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、キシリレンジイソシアネート等の芳香族ジイソシアネート、イソホロンジイソシアネート等の脂環族ジイソシアネート、それらの三量体等が挙げられ、これらは１種を単独で、或いは２種以上を組み合わせて使用できる。 In addition, a hydroxyl group may remain in the component (A) and the component (B), and various known diisocyanate compounds can be used for the purpose of adjusting the hardness of the coating film by reacting with the hydroxyl group. . Specifically, for example, aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate, These trimers and the like can be mentioned, and these can be used alone or in combination of two or more.
また、本発明の組成物には、充填剤、離型剤、難燃剤、粘度調節剤、可塑剤、抗菌剤、防黴剤、消泡剤、着色剤、安定剤等の添加剤も適宜配合できる。 In addition, the composition of the present invention also contains additives such as fillers, mold release agents, flame retardants, viscosity modifiers, plasticizers, antibacterial agents, antifungal agents, antifoaming agents, colorants, and stabilizers as appropriate. it can.
本発明の塗料組成物は、金属、プラスチック、ガラス等の各種基材に適用できる。金属としては、鉄、アルミニウム、アルミめっき鋼板、チンフリー鋼板（ＴＦＳ）、ステンレス鋼板、リン酸亜鉛処理鋼板、亜鉛・亜鉛合金めっき鋼板（ボンデ鋼板）等の処理鋼板が挙げられる。また、プラスチックとしては、ポリカーボネート（ＰＣ）、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、ポリエステル（ＰＥ）、ＡＢＳ、ＦＲＰ等が挙げられる。 The coating composition of the present invention can be applied to various substrates such as metals, plastics, and glass. Examples of the metal include treated steel plates such as iron, aluminum, aluminum-plated steel plates, chin-free steel plates (TFS), stainless steel plates, zinc phosphate-treated steel plates, and zinc / zinc alloy-plated steel plates (bonded steel plates). Examples of the plastic include polycarbonate (PC), polyethylene (PE), polypropylene (PP), polyester (PE), ABS, and FRP.
塗工方法としては、スプレー法、ナチュラルロールコート法、リバースロールコート、カーテンフローコート法等が挙げられ、塗工量は通常１０〜３０ｇ／ｍ２程度である。 Examples of the coating method include a spray method, a natural roll coating method, a reverse roll coating method, and a curtain flow coating method, and the coating amount is usually about 10 to 30 g / m 2 .
前記基材に塗工した本発明の塗料組成物は、乾燥させた後、活性エネルギー線を照射することにより、自己修復性の塗膜を与える。活性エネルギー線としては紫外線や電子線が挙げられ、紫外線光源としては、キセノンランプ、高圧水銀灯、メタルハライドランプを有する紫外線照射装置が挙げられる。また、光量、光源、搬送速度等の条件は適宜調整すればよく、例えば高圧水銀灯を使用する場合には、照度が通常１００〜２００ｍＷ／ｃｍ２程度、照射時間は通常１〜１０秒程度である。 The coating composition of the present invention applied to the base material is dried and then irradiated with active energy rays to give a self-repairing coating film. Examples of the active energy ray include ultraviolet rays and electron beams, and examples of the ultraviolet light source include an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, and a metal halide lamp. In addition, conditions such as the amount of light, the light source, and the conveyance speed may be adjusted as appropriate. For example, when a high-pressure mercury lamp is used, the illuminance is usually about 100 to 200 mW / cm 2 and the irradiation time is usually about 1 to 10 seconds. .
以下、合成例、実施例および比較例をあげて本発明を詳細に説明するが、これらによって何ら限定されるものではない。なお、各例中、部は特記しない限り重量基準である。 EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated in detail, it is not limited at all by these. In each example, parts are based on weight unless otherwise specified.
なお、各合成例において、ガラス転移温度は市販の測定装置（製品名「ＤＳＣ ８２３０Ｂ」、理学電機（株）製）を用いて得た値である。また、数平均分子量は、ゲルパーメーションクロマトグラフィー法（測定装置：東ソー（株）製ＨＬＣ-８１２０、カラム：ＴＳＫｇｅｌＧ２０００Ｈ、ＴＳＫｇｅｌＧ４０００Ｈ）によるポリスチレン換算値である。 In each synthesis example, the glass transition temperature is a value obtained using a commercially available measuring device (product name “DSC 8230B”, manufactured by Rigaku Corporation). The number average molecular weight is a polystyrene-converted value by gel permeation chromatography (measuring device: HLC-8120 manufactured by Tosoh Corporation, column: TSKgel G2000H, TSKgel G4000H).
［（Ａ）成分の製造］
合成例１
撹拌機、温度計および窒素ガス導入管、還流脱水装置を備えたフラスコに、イソフタル酸４５６．３部及びアジピン酸４０１．３部、ならびにエチレングリコール６６．５部、１，６−ヘキサンジオール５４８．２部およびトリメチロールプロパン１２７．８部を仕込んだ。次いで、加熱溶融して留出する水を系外に除きながら反応系を２５０℃まで徐々に昇温させ、さらに３時間保持した。次に、このフラスコに真空減圧装置を接続し、さらにテトラブチルチタネート０．１８部を加え３０分保温した後、１．３ｋＰａで２時間減圧重縮合反応を行った。その後、トルエン１５７４．５ｇを仕込み、ワニスとした後、イソシアネート基含有化合物（商品名「カレンズＡＯＩ」、昭和電工（株）製）を２５７．４部ならびにオクチル酸錫（商品名「スタノクト」、（株）エーピーアイコーポレーション）５．１部を仕込み、窒素雰囲気下、８０℃で３時間保持し、ガラス転移点が−２５℃、（メタ）アクリロイル基の含有量が１．２ｍｍｏｌ／ｇ、数平均分子量が５４００、不揮発分が５０重量％であるポリエステル系ウレタン樹脂（Ａ−１）のワニスを得た。
[Production of component (A)]
Synthesis example 1
In a flask equipped with a stirrer, a thermometer and a nitrogen gas inlet tube, and a reflux dehydrator, 456.3 parts of isophthalic acid and 401.3 parts of adipic acid, 66.5 parts of ethylene glycol, and 1,6-hexanediol 548. 2 parts and 127.8 parts of trimethylolpropane were charged. Next, the temperature of the reaction system was gradually raised to 250 ° C. while removing water distilled by heating and melting out, and was further maintained for 3 hours. Next, a vacuum decompression apparatus was connected to the flask, 0.18 part of tetrabutyl titanate was further added and the mixture was kept warm for 30 minutes, and then a reduced pressure polycondensation reaction was performed at 1.3 kPa for 2 hours. Thereafter, 1574.5 g of toluene was charged to make a varnish, and then 257.4 parts of an isocyanate group-containing compound (trade name “Karenz AOI”, manufactured by Showa Denko KK) and tin octylate (trade name “STANOCTO”, ( AIP Corporation) 5.1 parts, charged under nitrogen atmosphere at 80 ° C. for 3 hours, glass transition point of −25 ° C., (meth) acryloyl group content of 1.2 mmol / g, number average A varnish of a polyester urethane resin (A-1) having a molecular weight of 5400 and a nonvolatile content of 50% by weight was obtained.
合成例２
合成例１と同様のフラスコにイソフタル酸５５０．６部およびアジピン酸３２２．８部、ならびにエチレングリコール８９．１部、ネオペンチルグリコール７４．７部、１，６−ヘキサンジオール４６６．４部およびトリメチロールプロパン９６．４部を仕込んだ。次いで、加熱溶融して留出する水を系外に除きながら反応系を２５０℃まで徐々に昇温させ、さらに３時間保温した。次に、このフラスコに真空減圧装置を接続し、さらにテトラブチルチタネート０．１８部を加え３０分保温した後、１．３ｋＰａで２時間減圧重縮合反応を行った。その後、トルエン１５４４．３部を仕込み、ワニスとした後、カレンズAOIを２２２．７部ならびにスタノクトを４．６部仕込み、窒素雰囲気下、８０℃で３時間保持し、ガラス転移点が−１６℃、（メタ）アクリロイル基の含有量が１．０mmol／g、数平均分子量が４９００、不揮発分が５０重量％であるポリエステル系ウレタン樹脂（A−２）のワニスを得た。
Synthesis example 2
In a flask similar to Synthesis Example 1, 550.6 parts of isophthalic acid and 322.8 parts of adipic acid, 89.1 parts of ethylene glycol, 74.7 parts of neopentyl glycol, 466.4 parts of 1,6-hexanediol and 96.4 parts of methylolpropane were charged. Next, the temperature of the reaction system was gradually raised to 250 ° C. while removing water distilled by heating and melting out, and the temperature was further maintained for 3 hours. Next, a vacuum decompression apparatus was connected to the flask, 0.18 part of tetrabutyl titanate was further added and the mixture was kept warm for 30 minutes, and then a reduced pressure polycondensation reaction was performed at 1.3 kPa for 2 hours. Thereafter, 1544.3 parts of toluene was added to form a varnish, 222.7 parts of Karenz AOI and 4.6 parts of stanocto were added, and kept at 80 ° C. for 3 hours in a nitrogen atmosphere, with a glass transition point of −16 ° C. A varnish of a polyester-based urethane resin (A-2) having a (meth) acryloyl group content of 1.0 mmol / g, a number average molecular weight of 4900, and a nonvolatile content of 50% by weight was obtained.
合成例３
合成例１と同様のフラスコにイソフタル酸３２２．７部およびアジピン酸５２７．１部、ならびにエチレングリコール６７．２部、１，６−ヘキサンジオール５５３．９部およびトリメチロールプロパン１２９．１部を仕込んだ。次いで、加熱溶融して留出する水を系外に除きながら反応系を２５０℃まで徐々に昇温させ、さらに３時間保温した。次に、このフラスコに真空減圧装置を接続し、さらにテトラブチルチタネート０．１８部を加え３０分保温した後、１．３ｋＰａで２時間減圧重縮合反応を行った。その後、トルエン１５６７．８部を仕込み、ワニスとした後、カレンズAOIを２５０．８部ならびにスタノクトを ５．０部仕込み、窒素雰囲気下、８０℃で３時間保持し、ガラス転移点が−３５℃、（メタ）アクリロイル基の含有量が１．１mmol／g、数平均分子量が５６００、不揮発分が５０重量％であるポリエステル系ウレタン樹脂（A−３）のワニスを得た。
Synthesis example 3
The same flask as in Synthesis Example 1 was charged with 322.7 parts of isophthalic acid and 527.1 parts of adipic acid, 67.2 parts of ethylene glycol, 553.9 parts of 1,6-hexanediol, and 129.1 parts of trimethylolpropane. It is. Next, the temperature of the reaction system was gradually raised to 250 ° C. while removing water distilled by heating and melting out, and the temperature was further maintained for 3 hours. Next, a vacuum decompression apparatus was connected to the flask, 0.18 part of tetrabutyl titanate was further added and the mixture was kept warm for 30 minutes, and then a reduced pressure polycondensation reaction was performed at 1.3 kPa for 2 hours. Thereafter, 1567.8 parts of toluene was charged to form a varnish, and then 250.8 parts of Karenz AOI and 5.0 parts of stanocto were charged and held at 80 ° C. for 3 hours in a nitrogen atmosphere, and the glass transition point was −35 ° C. A varnish of a polyester-based urethane resin (A-3) having a (meth) acryloyl group content of 1.1 mmol / g, a number average molecular weight of 5600, and a nonvolatile content of 50% by weight was obtained.
合成例４
合成例１と同様のポリエステル樹脂を合成し、その後、トルエン１６００．７部を仕込み、ワニスとした後、イソシアネート基含有化合物（商品名「カレンズMOI」、昭和電工（株）製）を２８３．０部ならびにスタノクトを５．７部仕込み、窒素雰囲気下、８０℃で３時間保持し、ガラス転移点が−２５℃、（メタ）アクリロイル基の含有量が１．１mmol／g、数平均分子量が５４００、不揮発分が５０重量％であるポリエステル系ウレタン樹脂（A−４）のワニスを得た。
Synthesis example 4
After synthesizing the same polyester resin as in Synthesis Example 1, and then adding 1600.7 parts of toluene to make a varnish, 283.0% of an isocyanate group-containing compound (trade name “Karenz MOI”, Showa Denko KK) was prepared. Part and 5.7 parts of stanocto were charged, kept at 80 ° C. for 3 hours under nitrogen atmosphere, glass transition point of −25 ° C., (meth) acryloyl group content of 1.1 mmol / g, number average molecular weight of 5400 A varnish of a polyester-based urethane resin (A-4) having a nonvolatile content of 50% by weight was obtained.
合成例５
合成例１と同様のポリエステル樹脂を合成し、その後、トルエン１７５３．１部を仕込み、ワニスとした後、イソシアネート基含有化合物（商品名「カレンズBEI」、昭和電工（株）製）を４３６．０部ならびにスタノクトを ５．１部仕込み、窒素雰囲気下、８０℃で３時間保持し、ガラス転移点が−２５℃、（メタ）アクリロイル基の含有量が２．１mmol／g、数平均分子量が５４００、不揮発分が５０重量％であるポリエステル系ウレタン樹脂（A−５）のワニスを得た。
Synthesis example 5
After synthesizing the same polyester resin as in Synthesis Example 1, and then charging 1753.1 parts of toluene to make a varnish, an isocyanate group-containing compound (trade name “Karenz BEI”, Showa Denko Co., Ltd.) 436.0 Parts and stanocto 5.1 parts, kept under nitrogen atmosphere at 80 ° C. for 3 hours, glass transition point −25 ° C., (meth) acryloyl group content 2.1 mmol / g, number average molecular weight 5400 A varnish of a polyester-based urethane resin (A-5) having a nonvolatile content of 50% by weight was obtained.
合成例６
予め、攪拌機、温度計、および窒素ガス導入管を備えたフラスコに、トルエン３０９．６部、イソホロンジイソシアネート２０２．７部、２−ヒドロキシエチルアクリレート１０５．９部、スタノクト１．０部を仕込み、１００℃で４時間保持し、イソホロンジイソシアネートと２−ヒドロキシエチルアクリレートとの反応生成物の不揮発分５０重量％の溶液（Ｉ）を得た。
その後、合成例１と同様のポリエステル樹脂を合成し、トルエン１３１２．０部を仕込み、ワニスとした後、上記（Ｉ）を６１９．２部ならびにスタノクトを３．１部加え、８０℃で３時間保持し、ガラス転移点が−２５℃、（メタ）アクリロイル基の含有量が０．５mmol／g、数平均分子量が５４００、不揮発分が５０重量％であるポリエステル系ウレタン樹脂（A−６）のワニスを得た。
Synthesis Example 6
In advance, a flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube was charged with 309.6 parts of toluene, 202.7 parts of isophorone diisocyanate, 105.9 parts of 2-hydroxyethyl acrylate, and 1.0 part of stanocto. The solution was kept at 4 ° C. for 4 hours to obtain a solution (I) having a nonvolatile content of 50% by weight of the reaction product of isophorone diisocyanate and 2-hydroxyethyl acrylate.
Thereafter, the same polyester resin as in Synthesis Example 1 was synthesized, and 1312.0 parts of toluene was added to make a varnish. Then, 619.2 parts of the above (I) and 3.1 parts of stannoct were added, and the mixture was heated at 80 ° C. for 3 hours. Of the polyester-based urethane resin (A-6) having a glass transition point of −25 ° C., a (meth) acryloyl group content of 0.5 mmol / g, a number average molecular weight of 5400, and a nonvolatile content of 50% by weight. A varnish was obtained.
合成例７
合成例１と同様のポリエステル樹脂を合成し、その後、トルエン１５９３．８部を仕込み、ワニスとした後、カレンズAOI１０３．０部、カレンズMOI８４．９部、カレンズBEI８７．２部および前記（Ｉ）を１２３．４部ならびにスタノクトを６．７部仕込み、窒素雰囲気下、８０℃で３時間保持し、ガラス転移点が−２５℃、（メタ）アクリロイル基の含有量が１．３mmol／g、数平均分子量が５４００、不揮発分が５０重量％であるポリエステル系ウレタン樹脂（A−７）のワニスを得た。
Synthesis example 7
After synthesizing the same polyester resin as in Synthesis Example 1, and then charging 1593.8 parts of toluene into a varnish, 103.0 parts of Karenz AOI, 84.9 parts of Karenz MOI, 87.2 parts of Karenz BEI and the above (I) Charge 123.4 parts and 6.7 parts of stanocto, hold under nitrogen atmosphere at 80 ° C. for 3 hours, have a glass transition point of −25 ° C., (meth) acryloyl group content of 1.3 mmol / g, number average A varnish of polyester urethane resin (A-7) having a molecular weight of 5400 and a nonvolatile content of 50% by weight was obtained.
合成例８
合成例１と同様のフラスコにイソフタル酸１８７．９部およびセバチン酸８１０．８部、ならびに２−メチル−１，３−プロパンジオール４８１．７部およびトリメチロールプロパン１１９．６部を仕込んだ。次いで、加熱溶融して留出する水を系外に除きながら反応系を２５０℃まで徐々に昇温させ、さらに３時間保温した。次に、このフラスコに真空減圧装置を接続し、さらにテトラブチルチタネート０．１８部を加え３０分保温した後、１．３ｋＰａで２時間減圧重縮合反応を行った。その後、酢酸ブチル１５００．５部を仕込み、ワニスとした後、カレンズAOIを１８４．８部ならびにスタノクトを３．７部仕込み、窒素雰囲気下、８０℃で３時間保持し、ガラス転移点が−２５℃、（メタ）アクリロイル基の含有量が０．９mmol／g、数平均分子量が７４００、不揮発分が５０重量％であるポリエステル系ウレタン樹脂（A−８）のワニスを得た。
Synthesis Example 8
The same flask as in Synthesis Example 1 was charged with 187.9 parts of isophthalic acid and 810.8 parts of sebacic acid, 481.7 parts of 2-methyl-1,3-propanediol, and 119.6 parts of trimethylolpropane. Next, the temperature of the reaction system was gradually raised to 250 ° C. while removing water distilled by heating and melting out, and the temperature was further maintained for 3 hours. Next, a vacuum decompression apparatus was connected to the flask, 0.18 part of tetrabutyl titanate was further added and the mixture was kept warm for 30 minutes, and then a reduced pressure polycondensation reaction was performed at 1.3 kPa for 2 hours. Thereafter, 1500.5 parts of butyl acetate was added to make a varnish, and then 184.8 parts of Karenz AOI and 3.7 parts of stanocto were added and maintained at 80 ° C. for 3 hours in a nitrogen atmosphere, with a glass transition point of −25. A varnish of a polyester-based urethane resin (A-8) having a (meth) acryloyl group content of 0.9 mmol / g, a number average molecular weight of 7400, and a nonvolatile content of 50% by weight was obtained.
合成例９ （Ａ）の比較合成例
[（メタ）アクリロイル基を有さないポリエステルポリオールの製造]
合成例１と同様のフラスコに、イソフタル酸５１６．５部、アジピン酸４５４．３部、エチレングリコール１００．３部、１，６−ヘキサンジオール６２０．５部、トリメチロールプロパン１０８．５部を仕込んだ。加熱溶融して留出する水を系外に除きながら２５０℃まで徐々に昇温し、さらに３時間保持した。次に、装置を真空減圧装置に替え、さらにテトラブチルチタネート０．１８部を加え３０分保温後、１．３ｋＰａで２時間減圧重縮合反応を行い、その後、トルエンを１４００部仕込み、ガラス転移点が−２５℃、水酸基価が５２ｍｇＫＯＨ／ｇ、および数平均分子量が７０００である、（メタ）アクリロイル基を有さないポリエステルポリオール（イ）の淡黄色透明溶液を得た。
Synthesis Example 9 Comparative Synthesis Example of (A)
[Production of polyester polyol having no (meth) acryloyl group]
A flask similar to Synthesis Example 1 was charged with 516.5 parts of isophthalic acid, 454.3 parts of adipic acid, 100.3 parts of ethylene glycol, 620.5 parts of 1,6-hexanediol, and 108.5 parts of trimethylolpropane. It is. While removing water distilled by heating and melting out of the system, the temperature was gradually raised to 250 ° C., and further maintained for 3 hours. Next, the device was changed to a vacuum decompression device, 0.18 part of tetrabutyl titanate was further added, and the mixture was kept warm for 30 minutes, and then subjected to a reduced pressure polycondensation reaction at 1.3 kPa for 2 hours. A pale yellow transparent solution of polyester polyol (I) having no (meth) acryloyl group, having a -25 ° C., a hydroxyl value of 52 mg KOH / g, and a number average molecular weight of 7000 was obtained.
［（Ｂ）成分の製造］
合成例１０
合成例１と同様のフラスコに、テレフタル酸４５２．２部およびイソフタル酸８３９．９部、エチレングリコール９４．１部、ネオペンチルグリコール３６８．３部、ビスフェノールＡのエチレンオキシド２ｍｏｌ付加物１７４５．５部を仕込んだ。次いで、加熱溶融して留出する水を系外に除きながら２５０℃まで反応系を徐々に昇温させ、さらに３時間保持した。次に、このフラスコに真空減圧装置を接続し、さらにテトラブチルチタネート０．１８部を加え３０分保温した後、１．３ｋＰａで１時間減圧重縮合反応を行った。その後、トルエン３１８６．６ｇを仕込み、ワニスとした後、カレンズＡＯＩを３１０．４部ならびにスタノクト６．２部を仕込み、窒素雰囲気下、８０℃で３時間保持し、ガラス転移点が５９℃、（メタ）アクリロイル基の含有量が０．７ｍｍｏｌ／ｇ、数平均分子量が４４００、不揮発分が重量％のポリエステル系ウレタン樹脂（Ｂ−１）のワニスを得た。
[Production of component (B)]
Synthesis Example 10
In a flask similar to Synthesis Example 1, 452.2 parts of terephthalic acid and 839.9 parts of isophthalic acid, 94.1 parts of ethylene glycol, 368.3 parts of neopentyl glycol, and 1745.5 parts of ethylene oxide 2 mol adduct of bisphenol A were added. Prepared. Next, the temperature of the reaction system was gradually raised to 250 ° C. while removing water distilled by heating and melting out, and was further maintained for 3 hours. Next, a vacuum decompression apparatus was connected to the flask, 0.18 part of tetrabutyl titanate was added and the temperature was kept for 30 minutes, and then a reduced pressure polycondensation reaction was performed at 1.3 kPa for 1 hour. Thereafter, 3186.6 g of toluene was charged to make a varnish, and then 310.4 parts of Karenz AOI and 6.2 parts of stanocto were charged and maintained at 80 ° C. for 3 hours in a nitrogen atmosphere, with a glass transition point of 59 ° C. ( A varnish of a polyester urethane resin (B-1) having a content of a (meth) acryloyl group of 0.7 mmol / g, a number average molecular weight of 4400, and a nonvolatile content of wt% was obtained.
合成例１１
合成例と同様のポリエステル樹脂を合成し、その後、トルエン３２１８．１部を仕込み、ワニスとした後、カレンズMOIを３４１．３部ならびにスタノクトを６．８部仕込み、窒素雰囲気下、８０℃で３時間保持し、ガラス転移点が５９℃、（メタ）アクリロイル基の含有量が０．７mmol／g、数平均分子量が４４００、不揮発分が５０重量％であるポリエステル系ウレタン樹脂（B−２）のワニスを得た。
Synthesis Example 11
After synthesizing the same polyester resin as in the synthesis example, 3218.1 parts of toluene was added to make a varnish, 341.3 parts of Karenz MOI and 6.8 parts of stanocto were added, and the mixture was added at 80 ° C. under nitrogen atmosphere. Of a polyester-based urethane resin (B-2) having a glass transition point of 59 ° C., a (meth) acryloyl group content of 0.7 mmol / g, a number average molecular weight of 4400, and a nonvolatile content of 50% by weight. A varnish was obtained.
合成例１２
合成例９と同様のポリエステル樹脂を合成し、その後、トルエン３４０２．０部を仕込み、ワニスとした後、カレンズBEIを５２５．８部ならびにスタノクトを６．２部仕込み、窒素雰囲気下、８０℃で３時間保持し、ガラス転移点が５９℃、（メタ）アクリロイル基の含有量が１．３mmol／g、数平均分子量が４４００、不揮発分が５０重量％であるポリエステル系ウレタン樹脂（B−３）のワニスを得た。
Synthesis Example 12
After synthesizing the same polyester resin as in Synthesis Example 9, 3402.0 parts of toluene was added to make a varnish, then 525.8 parts of Karenz BEI and 6.2 parts of stanocto were added, and at 80 ° C. in a nitrogen atmosphere. Polyester urethane resin (B-3) having a glass transition point of 59 ° C., a (meth) acryloyl group content of 1.3 mmol / g, a number average molecular weight of 4400, and a nonvolatile content of 50% by weight, maintained for 3 hours The varnish was obtained.
合成例１３
予め、攪拌機、温度計、および窒素ガス導入管を備えたフラスコに、トルエン３８８．８部、イソホロンジイソシアネート２４４．５部、２−ヒドロキシエチルメタクリレート１４３．１部、スタノクト１．２部を仕込み、１００℃で４時間保持し、イソホロンジイソシアネートと２−ヒドロキシエチルメタクリレートとの反応生成物の不揮発分５０重量％の溶液（II）を得た。
その後、合成例９と同様のポリエステル樹脂を合成し、トルエン２８７０．０部を仕込み、ワニスとした後、上記（II）を７７７．６部ならびにスタノクトを２．７部加え、８０℃で３時間保持し、ガラス転移点が５９℃、（メタ）アクリロイル基の含有量が０．３mmol／g、数平均分子量が４４００、不揮発分が５０重量％であるポリエステル系ウレタン樹脂（B−４）のワニスを得た。
Synthesis Example 13
In advance, a flask equipped with a stirrer, a thermometer, and a nitrogen gas introduction tube was charged with 388.8 parts of toluene, 244.5 parts of isophorone diisocyanate, 143.1 parts of 2-hydroxyethyl methacrylate, and 1.2 parts of stanocto, The mixture was kept at 4 ° C. for 4 hours to obtain a solution (II) having a nonvolatile content of 50% by weight of the reaction product of isophorone diisocyanate and 2-hydroxyethyl methacrylate.
Thereafter, the same polyester resin as in Synthesis Example 9 was synthesized, and 2870.0 parts of toluene was added to make a varnish. Then, 777.6 parts of the above (II) and 2.7 parts of stanocto were added, and the mixture was heated at 80 ° C. for 3 hours. A varnish of polyester urethane resin (B-4) having a glass transition point of 59 ° C., a (meth) acryloyl group content of 0.3 mmol / g, a number average molecular weight of 4400, and a nonvolatile content of 50% by weight Got.
合成例１４
合成例９と同様のポリエステル樹脂を合成し、その後、トルエン３２０９．８部を仕込み、ワニスとした後、カレンズAOI１２４．２部、カレンズMOI１０２．４部、カレンズBEI１０５．２部および前記（Ｉ）を１４８．９部ならびにスタノクトを８．１部仕込み、窒素雰囲気下、８０℃で３時間保持し、ガラス転移点が５９℃、（メタ）アクリロイル基の含有量が０．８mmol／g、数平均分子量が４４００、不揮発分が５０重量％であるポリエステル系ウレタン樹脂（B−５）のワニスを得た。
Synthesis Example 14
After synthesizing the same polyester resin as in Synthesis Example 9, and then charging 3209.8 parts of toluene into a varnish, 124.2 parts of Karenz AOI, 102.4 parts of Karenz MOI, 105.2 parts of Karenz BEI and the above (I) 148.9 parts and 8.1 parts of stanocto were charged, kept under nitrogen atmosphere at 80 ° C. for 3 hours, glass transition point 59 ° C., (meth) acryloyl group content 0.8 mmol / g, number average molecular weight Of 4400 and a non-volatile content of 50% by weight of a polyester urethane resin (B-5) was obtained.
合成例１５
合成例１と同様のフラスコにテレフタル酸４５３．０部およびイソフタル酸８４１．３部、ならびにエチレングリコール９４．３部、ネオペンチルグリコール３２６．８部、ビスフェノールＡのエチレンオキサイド２モル付加物１７４８．４部およびトリメチロールプロパン３６．２部を仕込んだ。次いで、加熱溶融して留出する水を系外に除きながら反応系を２５０℃まで徐々に昇温させ、さらに３時間保温した。次に、このフラスコに真空減圧装置を接続し、さらにテトラブチルチタネート０．１８部を加え３０分保温した後、１．３ｋＰａで１時間減圧重縮合反応を行った。その後、トルエン３３３７．５部を仕込み、ワニスとした後、カレンズAOIを４６２．０部ならびにスタノクトを９．２部仕込み、窒素雰囲気下、８０℃で３時間保持し、ガラス転移点が６４℃、（メタ）アクリロイル基の含有量が１．０mmol／g、数平均分子量が４３００、不揮発分が５０重量％であるポリエステル系ウレタン樹脂（B−６）のワニスを得た。
Synthesis Example 15
In the same flask as in Synthesis Example 1, 453.0 parts of terephthalic acid and 841.3 parts of isophthalic acid, 94.3 parts of ethylene glycol, 326.8 parts of neopentyl glycol, and 1748.4 ethylene oxide 2-mol adduct of bisphenol A Part and 36.2 parts trimethylolpropane. Next, the temperature of the reaction system was gradually raised to 250 ° C. while removing water distilled by heating and melting out, and the temperature was further maintained for 3 hours. Next, a vacuum decompression apparatus was connected to the flask, 0.18 part of tetrabutyl titanate was added and the temperature was kept for 30 minutes, and then a reduced pressure polycondensation reaction was performed at 1.3 kPa for 1 hour. Thereafter, 3337.5 parts of toluene was charged to form a varnish, and then 462.0 parts of Karenz AOI and 9.2 parts of stanocto were charged and maintained at 80 ° C. for 3 hours in a nitrogen atmosphere, with a glass transition point of 64 ° C., A varnish of a polyester urethane resin (B-6) having a (meth) acryloyl group content of 1.0 mmol / g, a number average molecular weight of 4300, and a nonvolatile content of 50% by weight was obtained.
合成例１６
合成例１と同様のフラスコに、２，６−ナフタレンジカルボン酸ジメチル９６３．８部、エチレングリコール２７２．９部およびネオペンチルグリコール１０６１．８部を仕込んだ。次いで、加熱溶融して留出するメタノールを系外に除きながら２１０℃まで反応系を徐々に昇温させ、さらに１時間保持した。その後、イソフタル酸１０３０．４部およびアジピン酸１６４．８部を仕込み、加熱溶融して留出する水を系外に除きながら２５０℃まで反応系を徐々に昇温させ、さらに３時間保持した。次に、このフラスコに真空減圧装置を接続し、さらにテトラブチルチタネート０．１８部を加え３０分保温した後、１．３ｋＰａで１時間減圧重縮合反応を行った。その後、酢酸ブチル３１７１．９部を仕込み、ワニスとした後、カレンズAOIを２９６．０部ならびにスタノクトを５．９部仕込み、窒素雰囲気下、８０℃で３時間保持し、ガラス転移点が５６℃、（メタ）アクリロイル基の含有量が０．７mmol／g、数平均分子量が４６００、不揮発分が５０重量％であるポリエステル系ウレタン樹脂（B−７）のワニスを得た。
Synthesis Example 16
In the same flask as in Synthesis Example 1, 963.8 parts of dimethyl 2,6-naphthalenedicarboxylate, 272.9 parts of ethylene glycol and 1061.8 parts of neopentyl glycol were charged. Next, the temperature of the reaction system was gradually raised to 210 ° C. while removing methanol that was heated and melted and distilled out of the system, and was further maintained for 1 hour. Thereafter, 1030.4 parts of isophthalic acid and 164.8 parts of adipic acid were added, the temperature of the reaction system was gradually raised to 250 ° C. while removing water distilled out by heating and melting, and maintained for another 3 hours. Next, a vacuum decompression apparatus was connected to the flask, 0.18 part of tetrabutyl titanate was added and the temperature was kept for 30 minutes, and then a reduced pressure polycondensation reaction was performed at 1.3 kPa for 1 hour. Thereafter, 3171.9 parts of butyl acetate was added to prepare a varnish, and then 296.0 parts of Karenz AOI and 5.9 parts of stanocto were added and maintained at 80 ° C. for 3 hours in a nitrogen atmosphere, with a glass transition point of 56 ° C. A varnish of a polyester-based urethane resin (B-7) having a (meth) acryloyl group content of 0.7 mmol / g, a number average molecular weight of 4600, and a nonvolatile content of 50% by weight was obtained.
合成例１７ （Ｂ）の比較合成例
[（メタ）アクリロイル基を有さないポリエステルポリオールの製造]
合成例１と同様のフラスコに、テレフタル酸４５２．２部、イソフタル酸８３９．９部、エチレングリコール９４．１部、ネオペンチルグリコール３６８．３部、ビスフェノールＡのエチレンオキシド１：２ｍｏｌ付加物１７４５．５部を仕込んだ。加熱溶融して留出する水を系外に除きながら２５０℃まで徐々に昇温し、さらに３時間保持した。次に、装置を真空減圧装置に替え、さらにテトラブチルチタネート０．１８部を加え３０分保温後、１．３ｋＰａで１時間減圧重縮合反応を行い、その後、トルエンを２８００部仕込み、ガラス転移点が５９℃、水酸基価が４３ｍｇＫＯＨ／ｇ、および数平均分子量が４０００である、（メタ）アクリロイル基を有さないポリエステルポリオール（Ｂ−８）の淡黄色透明溶液を得た。
Synthesis example 17 Comparative synthesis example of (B)
[Production of polyester polyol having no (meth) acryloyl group]
In a flask similar to Synthesis Example 1, 452.2 parts of terephthalic acid, 839.9 parts of isophthalic acid, 94.1 parts of ethylene glycol, 368.3 parts of neopentyl glycol, 1745.5 ethylene oxide 1: 2 mol adduct of bisphenol A Prepared the department. While removing water distilled by heating and melting out of the system, the temperature was gradually raised to 250 ° C., and further maintained for 3 hours. Next, the device was changed to a vacuum decompression device, 0.18 part of tetrabutyl titanate was further added, and the mixture was kept warm for 30 minutes, and then subjected to a reduced pressure polycondensation reaction at 1.3 kPa for 1 hour. A pale yellow transparent solution of polyester polyol (B-8) having no (meth) acryloyl group, having a hydroxyl value of 59 ° C., a hydroxyl value of 43 mg KOH / g, and a number average molecular weight of 4000 was obtained.
［塗料組成物の調製］
実施例１
合成例１と同様のフラスコに、各々固形分換算で（Ａ−１）成分４２．５部、（Ｂ−１）成分７．５部、光開始剤（商品名「イルガキュア１８４」、チバ・ジャパン（株）製）を３．５部、シリコン系表面調整剤（商品名「ＢＹＫ−ＵＶ３５００」、ビッグケミー・ジャパン（株）製）を０．４部、トルエン５０．０部、メチルエチルケトンを１５．８部仕込み、２５℃で１時間撹拌し、不揮発分が４５重量％の光硬化性塗料組成物を調製した。その組成を表３に示す。
[Preparation of coating composition]
Example 1
In a flask similar to Synthesis Example 1, 42.5 parts of component (A-1), 7.5 parts of component (B-1), photoinitiator (trade name “Irgacure 184”, Ciba Japan, respectively) Co., Ltd.), 3.5 parts, silicon surface conditioner (trade name “BYK-UV3500”, produced by Big Chemie Japan Co., Ltd.) 0.4 parts, toluene 50.0 parts, methyl ethyl ketone 15.8 A photocurable coating composition having a nonvolatile content of 45% by weight was prepared by charging a part thereof and stirring at 25 ° C. for 1 hour. The composition is shown in Table 3.
実施例２〜１８、比較例１〜６
原料および使用量を表３（実施例）および表４（比較例）に示すよう変更した他は実施例１と同様にして不揮発分が４５重量％の光硬化性塗料組成物をそれぞれ調製した。
Examples 2-18, Comparative Examples 1-6
A photocurable coating composition having a nonvolatile content of 45% by weight was prepared in the same manner as in Example 1 except that the raw materials and the amounts used were changed as shown in Table 3 (Example) and Table 4 (Comparative Example).
比較例７
実施例１１と同様のフラスコに、各々固形分換算で合成例９で得られた（Ａ−９）成分（（Ａ）成分の比較合成例）成分を３７．５部、合成例１７で得られた（Ｂ−８）成分（（Ｂ）成分の比較合成例）を１２．５部、ヘキサメチレンジイソシアネートヌレート３量体（商品名「ＳＤＣ１１１」、日本ポリウレタン工業（株）製）を４．８部、シリコン系レベリング剤（商品名「ＢＹＫ３７５」、ビッグケミー・ジャパン（株）製）を０．５部、トルエン／メチルエチルケトンの混合溶剤（重量比７５／２５）を８２．９部仕込み、２５℃で１０分間撹拌し、不揮発分が４０重量％の熱硬化性塗料組成物を調製した。その組成を表４に示す。
Comparative Example 7
In the same flask as in Example 11, 37.5 parts of the component (A-9) obtained in Synthesis Example 9 in terms of solid content (comparative synthesis example of component (A)) were obtained in Synthesis Example 17. 12.5 parts of component (B-8) (comparative synthesis example of component (B)) and 4.8 parts of hexamethylene diisocyanurate trimer (trade name “SDC111”, manufactured by Nippon Polyurethane Industry Co., Ltd.) , 0.5 part silicon leveling agent (trade name “BYK375”, manufactured by Big Chemie Japan Co., Ltd.) and 82.9 parts toluene / methyl ethyl ketone mixed solvent (75/25 by weight) were charged at 25 ° C. The mixture was stirred for minutes to prepare a thermosetting coating composition having a nonvolatile content of 40% by weight. The composition is shown in Table 4.
比較例８および９
原料および使用量を表４に示すよう変更した他は実施例１と同様にして不揮発分が４０重量％の熱硬化性塗料組成物を調製した。
Comparative Examples 8 and 9
A thermosetting coating composition having a nonvolatile content of 40% by weight was prepared in the same manner as in Example 1 except that the raw materials and the amounts used were changed as shown in Table 4.
＜塗膜の作製＞
実施例１の光硬化性塗料組成物を、乾燥膜厚が１５μｍとなるようにポリカーボネート（ＰＣ）板（７０ｍｍ×１２０ｍｍ、厚さ２ｍｍ）にバーコーターで塗布し８０℃の乾燥機で５分間乾燥させて後、紫外線照射装置（商品名「ＵＶ−１５２」、ウシオ電機（株）製）を用い、３６５ｎｍの紫外線検出器で積算光量が４００ｍＪ／ｃｍ２となるよう紫外線を照射し、試験片を得た。また、ＡＢＳ樹脂板（７０ｍｍ×１５０ｍｍ、厚さ２ｍｍ）、ボンデ鋼板（１２０ｍｍ×２００ｃｍ、厚さ０．３ｍｍ）についても同様の条件で試験片を得た。実施例２〜１８および比較例１〜６の塗料組成物についても同様にして試験片を得た。
<Preparation of coating film>
The photocurable coating composition of Example 1 was applied to a polycarbonate (PC) plate (70 mm × 120 mm, thickness 2 mm) with a bar coater so that the dry film thickness was 15 μm, and dried for 5 minutes with an 80 ° C. dryer. Then, using a UV irradiation device (trade name “UV-152”, manufactured by Ushio Electric Co., Ltd.), a 365 nm UV detector was used to irradiate UV light so that the integrated light amount was 400 mJ / cm 2 , Obtained. Moreover, the test piece was obtained on the same conditions also about the ABS resin plate (70 mm x 150 mm, thickness 2 mm) and the bonde steel plate (120 mm x 200 cm, thickness 0.3 mm). Test pieces were similarly obtained for the coating compositions of Examples 2 to 18 and Comparative Examples 1 to 6.
また、比較例７〜９の熱硬化性塗料組成物については、乾燥膜厚が１５μｍとなるように上記ポリカーボネート板およびボンデ鋼板（１２０ｍｍ×２００ｃｍ、厚さ０．３ｍｍ）にバーコーターで塗布し１００℃の乾燥機で３０分間乾燥させて試験片を得た。 Moreover, about the thermosetting coating composition of Comparative Examples 7-9, it apply | coats to the said polycarbonate plate and a bonde steel plate (120 mm x 200 cm, thickness 0.3mm) with a bar coater so that a dry film thickness may be set to 15 micrometers. A test piece was obtained by drying for 30 minutes with a dryer at 0C.
＜塗膜の自己修復性＞
実施例１〜１８と比較例１〜９についてはポリカーボネート（ＰＣ）試験片を用い、室温下、各塗膜の表面を真鍮ブラシ（アズワン（株）製）で強く擦り、傷をつけた後、塗膜の自己修復性を以下の基準で目視評価した。
<Self-healing property of coating film>
About Examples 1-18 and Comparative Examples 1-9, after using a polycarbonate (PC) test piece, the surface of each coating film was rubbed strongly with a brass brush (manufactured by ASONE Co., Ltd.) at room temperature, and scratched. The self-healing property of the coating film was visually evaluated according to the following criteria.
５：１０秒以内に傷が修復する。
４：１０秒を超え、２０秒以内に傷が修復する。
３：１０分経過した後も擦傷痕が若干認められる。
１：１０分経過した後においても明らかな擦傷痕が認められる。
5: The wound is repaired within 10 seconds.
4: The wound is repaired within 20 seconds over 10 seconds.
3: Some scratch marks are observed even after 10 minutes.
1:10 Even after 10 minutes, clear scratch marks are observed.
＜塗膜のクラック＞
実施例と比較例の各塗膜を目視確認したが、いずれもクラックは生じていなかった。
<Coat crack>
Although each coating film of an Example and a comparative example was confirmed visually, all were not cracking.
＜密着性試験＞
実施例および比較例のポリカーボネート（ＰＣ）試験片、ＡＢＳ試験片およびボンデ鋼板試験片を用い、それぞれの試験片についてＪＩＳ Ｋ５６００に準じて碁盤目剥離試験を行い、塗膜の剥離状態を以下の基準で評価した。
<Adhesion test>
Using the polycarbonate (PC) test piece, the ABS test piece, and the bonded steel plate test piece of Examples and Comparative Examples, a cross-cut peel test was performed on each test piece in accordance with JIS K5600, and the peeling state of the coating film was determined according to the following criteria: It was evaluated with.
５：１００／１００〜９５／１００
３：９４／１００〜６０／１００
１：５９／１００〜０／１００
5: 100/100 to 95/100
3: 94/100 to 60/100
1: 59 / 100-0 / 100
＜耐ブロッキング性試験＞
実施例および比較例のボンデ鋼板試験板を、２０℃の雰囲気下で１時間放置した後、塗面を指で触って、塗面のタック感を以下の基準で評価した。数値が大きいほど耐ブロッキング性に優れることを意味する。
<Blocking resistance test>
The bonded steel plate test plates of Examples and Comparative Examples were left for 1 hour in an atmosphere of 20 ° C., and then the coated surface was touched with a finger, and the tackiness of the coated surface was evaluated according to the following criteria. It means that it is excellent in blocking resistance, so that a numerical value is large.
５：塗面にタックを感じない。
３：塗面に若干のタックを感じる。
１：塗面に著しいタックを感じる。
5: There is no tack on the paint surface.
3: A slight tack is felt on the paint surface.
1: A marked tack is felt on the paint surface.
＜塗膜の耐湿熱性＞
実施例１〜１８と比較例１〜９についてはポリカーボネート（ＰＣ）試験片を用い、５０℃、９５％の高温高湿下で４００時間保管した後、常温に戻した際の塗膜の外観を以下の評価基準に基づき目視で評価した。
（外観）
５：変化なし
３：白濁している
また、高温高湿処理した後の塗膜の自己修復性についても前記と同様の基準により目視評価した。
<Moisture and heat resistance of coating film>
About Examples 1-18 and Comparative Examples 1-9, after using a polycarbonate (PC) test piece and storing at 50 ° C. under high temperature and high humidity of 95% for 400 hours, the appearance of the coating film when returned to normal temperature Visual evaluation was performed based on the following evaluation criteria.
(appearance)
5: No change 3: Cloudy In addition, the self-healing property of the coating film after high-temperature and high-humidity treatment was also visually evaluated according to the same criteria as described above.
表１のモノマー組成の数値はモル比（モル％）である。 The numerical values of the monomer composition in Table 1 are molar ratios (mol%).
表２のモノマー組成の数値はモル比（モル％）である。
The numerical values of the monomer composition in Table 2 are molar ratios (mol%).
表３中、成分種の数値は、固形分換算の部数である。
In Table 3, the numerical value of the component type is the number of parts in terms of solid content.
表３中、成分種の数値は、固形分換算の部数である。 In Table 3, the numerical value of the component type is the number of parts in terms of solid content.
Claims (8)
一般式（１）：
一般式（２）：
一般式（３）：
（Ｒ８は水素またはメチル基を、Ｒ９はアルキレン基を示す）
一般式（４）：
（Ｒ１０は水素またはメチル基を、Ｒ１１はアルキレン基を示す） The branched polyester polyol (A ′) obtained by reacting the dicarboxylic acid (a1), the diol (a2), and the triol (a3) with the component (A) is represented by the following general formulas (1) to (4) . It is obtained by reacting any one of the represented isocyanate group-containing compounds, and component (B) reacts with dicarboxylic acids (b1), diols (b2) and, if necessary, triols (b3). The linear or branched polyester polyol (B ') obtained is obtained by reacting one type of isocyanate group-containing compound represented by the following general formulas (1) to (4) . An active energy ray-curable self-healing coating composition.
General formula (1):
General formula (2):
General formula (3):
(R8 represents hydrogen or a methyl group, and R9 represents an alkylene group)
General formula (4):
(R10 represents hydrogen or a methyl group, and R11 represents an alkylene group)
The active energy ray-curable self-healing coating composition according to any one of claims 1 to 7, which is used as a solution of an organic solvent (F).
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|---|---|---|---|---|
| JPH02618A (en) * | 1987-12-16 | 1990-01-05 | Toyobo Co Ltd | Radiation-curable resin and recording medium prepared by using same |
| JP3213981B2 (en) * | 1991-09-24 | 2001-10-02 | 凸版印刷株式会社 | Radiation curable coating agent |
| JP3019294B2 (en) * | 1996-05-24 | 2000-03-13 | 日本合成化学工業株式会社 | Photocurable resin composition and use thereof |
| JP2005162908A (en) * | 2003-12-03 | 2005-06-23 | Natoko Kk | Active energy ray-curable urethane (meth)acrylate, active energy ray-curable composition containing the same and functional member using them |
| CN102076797B (en) * | 2008-07-01 | 2014-03-12 | 昭和电工株式会社 | Coating composition and coating film formation method using same |
-
2013
- 2013-03-07 JP JP2013045108A patent/JP6075687B2/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110145841A (en) * | 2019-05-06 | 2019-08-20 | 青岛海尔空调器有限总公司 | A kind of control method, control device and the electronic equipment of air-conditioning group |
| CN110145841B (en) * | 2019-05-06 | 2021-07-30 | 重庆海尔空调器有限公司 | Control method and control device of air conditioning unit and electronic equipment |
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| JP2013213207A (en) | 2013-10-17 |
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