JP2005097373A - Energy ray-curable resin composition and coating material using the same - Google Patents
Energy ray-curable resin composition and coating material using the same Download PDFInfo
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- JP2005097373A JP2005097373A JP2003330764A JP2003330764A JP2005097373A JP 2005097373 A JP2005097373 A JP 2005097373A JP 2003330764 A JP2003330764 A JP 2003330764A JP 2003330764 A JP2003330764 A JP 2003330764A JP 2005097373 A JP2005097373 A JP 2005097373A
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- 239000011342 resin composition Substances 0.000 title claims abstract description 23
- 238000000576 coating method Methods 0.000 title claims description 13
- 239000011248 coating agent Substances 0.000 title claims description 12
- 239000000463 material Substances 0.000 title claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 44
- -1 diol compound Chemical class 0.000 claims abstract description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 13
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 13
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 125000002993 cycloalkylene group Chemical group 0.000 claims abstract description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 3
- 125000005650 substituted phenylene group Chemical group 0.000 claims abstract description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 12
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 5
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 9
- 150000002009 diols Chemical class 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 125000005442 diisocyanate group Chemical group 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 150000002513 isocyanates Chemical class 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 2
- 0 CN(C(N(*NC(O*)=O)C(N1*NC(O*)=O)=O)=O)C1=O Chemical compound CN(C(N(*NC(O*)=O)C(N1*NC(O*)=O)=O)=O)C1=O 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- AHBNSOZREBSAMG-UHFFFAOYSA-N 1,5-diisocyanato-2-methylpentane Chemical compound O=C=NCC(C)CCCN=C=O AHBNSOZREBSAMG-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- BAASNFXQVLIVQO-UHFFFAOYSA-N 2-methylpentane;3-methylpentane Chemical compound CCCC(C)C.CCC(C)CC BAASNFXQVLIVQO-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
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 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
- 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 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- DWYKRMTVNUXSIM-UHFFFAOYSA-N hexane-1,6-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCCCCCO DWYKRMTVNUXSIM-UHFFFAOYSA-N 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 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
- 239000013638 trimer Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 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
- 238000004383 yellowing Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、エネルギー線の照射によって硬化可能なエネルギー線硬化型樹脂組成物及びこれを用いた塗料に関する。 The present invention relates to an energy ray-curable resin composition that can be cured by irradiation with energy rays, and a coating material using the same.
床や壁に代表される建材用途や、各種構造物、成型物は、基材を保護し、美観を保つために、塗料でコーティングするのが一般的である。 In general, building materials, such as floors and walls, and various structures and molded products are coated with a paint to protect the base material and maintain its beauty.
塗料としては、従来は合成樹脂を溶剤で溶解させた溶剤タイプが一般的であったが、作業環境の改善や、火気に対する危険防止等の点から、エネルギー線照射によって硬化可能な樹脂を用いたエネルギー線硬化型の塗料が種々開発され、化粧板のコーティング、木工塗料、紙コーティング、レジスト用材料、接着剤、電子機器の部品等の幅広い分野で実用化されている。 Conventionally, a solvent type in which a synthetic resin was dissolved in a solvent was generally used as a paint, but a resin that can be cured by irradiation with energy rays was used in order to improve the work environment and prevent danger to fire. Various energy ray curable paints have been developed and put into practical use in a wide range of fields such as decorative board coating, woodwork paint, paper coating, resist materials, adhesives, and electronic device parts.
かかるコーティング用途の中には耐熱性が要求される用途があり、耐熱性を有するエネルギー線硬化型塗料としては、水酸基を有するジペンタエリスリトールの多官能アクリレートとイソシアヌレート型ポリイソシアネートとの反応物（特開平７−２６１６７号公報）や、ヘキサメチレンジイソシアネートの三量化物とヒドロキシエチル（メタ）アクリレートとの反応物（特開平５−２３９３４２号公報）のような、イソシアヌレート環を導入したウレタン（メタ）アクリレートが提案されている。
上記のようにウレタン（メタ）アクリレートの構造中にイソシアヌレート環を導入して得られる硬化樹脂は高い耐熱性を有することが知られている。ところが、イソシアヌレート型ポリイソシアネートと水酸基を含有する（メタ）アクリレート系化合物のみを反応させたウレタン（メタ）アクリレートは耐熱性は非常に優れているが、硬化収縮が大きいため、硬化樹脂にひび割れが生じやすいという問題点があった。また、可とう性を付与しにくいという問題点もあった。そのため、従来のウレタン（メタ）アクリレートのもつ優れた特性である耐熱性を維持しつつ、硬化収縮を小さくすることや、可とう性を向上させることが望まれているのが実状である。 As described above, it is known that a cured resin obtained by introducing an isocyanurate ring into the structure of urethane (meth) acrylate has high heat resistance. However, although urethane (meth) acrylate obtained by reacting only an isocyanurate-type polyisocyanate and a (meth) acrylate compound containing a hydroxyl group is very excellent in heat resistance, the cured resin has large shrinkage, so that the cured resin is cracked. There was a problem that it was likely to occur. There is also a problem that it is difficult to impart flexibility. Therefore, in reality, it is desired to reduce curing shrinkage and improve flexibility while maintaining heat resistance, which is an excellent characteristic of conventional urethane (meth) acrylates.
本発明は、上記に鑑みてなされたものであり、耐熱性が良好で硬化収縮が小さく、さらに可とう性を付与することもできる、ウレタン（メタ）アクリレートを含有するエネルギー線硬化型樹脂組成物を提供することを目的とする。 The present invention has been made in view of the above, and has an energy ray-curable resin composition containing urethane (meth) acrylate, which has good heat resistance, small curing shrinkage, and can also impart flexibility. The purpose is to provide.
請求項１のエネルギー線硬化型樹脂組成物は、上記の課題を解決するためにイソシアヌレート型ポリイソシアネート化合物（Ａ）と、ジオール化合物（Ｂ）と、分子内に１個以上の水酸基を含有する（メタ）アクリレート系化合物（Ｃ）とを反応して得られる、次の一般式（１）で表される構造を有するウレタン（メタ）アクリレートを含有してなるものとする。
但し、一般式（１）において、Ｒ１は前記イソシアヌレート型ポリイソシアネート化合物（Ａ）に由来する、炭素数４〜１２のアルキレン基、シクロアルキレン基、ジシクロアルキレン基、フェニレン基又は置換フェニレン基を示す。Ｒ２は前記ジオール化合物（Ｂ）から水酸基を除いた残基を示す。Ｙ１及びＹ２は前記分子内に１個以上の水酸基を含有する（メタ）アクリレート系化合物（Ｃ）から水酸基を除いた残基であり、次の一般式（２）で表される基を示す。Ｙ１とＹ２とは同一でも異なっていてもよい。また、２個のＹ１同士及びＹ２同士も、それぞれ同一でも異なっていてもよい。
上記エネルギー線硬化樹脂組成物において、ウレタン（メタ）アクリレートは、（Ａ）成分と（Ｂ）成分とを、（Ａ）成分中のイソシアネート基と（Ｂ）成分中の水酸基のモル比が３．００／１．００〜７．００／１．００の範囲となる割合で反応させて反応物（Ｄ）を得て、さらにこの反応物（Ｄ）と（Ｃ）成分とを、反応物（Ｄ）中のイソシアネート基と（Ｃ）成分中の水酸基のモル比が１．００／１．００〜１．００／２．００の範囲となる割合で反応させて得ることが望ましい（請求項２）。 In the energy ray curable resin composition, the urethane (meth) acrylate comprises (A) component and (B) component, and the molar ratio of isocyanate group in (A) component to hydroxyl group in (B) component is 3. The reaction product (D) is obtained by reacting at a ratio in the range of 00 / 1.00 to 7.00 / 1.00. It is desirable to obtain it by reacting at a ratio such that the molar ratio of the isocyanate group in (C) to the hydroxyl group in the component (C) is in the range of 1.00 / 1.00 to 1.00 / 2.00. .
上記エネルギー線硬化樹脂組成物は、光重合開始剤をさらに含有するものとすることができる（請求項３）。 The energy beam curable resin composition may further contain a photopolymerization initiator (claim 3).
本発明の塗料は、上記いずれかのエネルギー線硬化型樹脂組成物を用いてなるものとする（請求項４）。 The coating material of the present invention uses any one of the above energy beam curable resin compositions (claim 4).
本発明のエネルギー線硬化型樹脂組成物によれば、耐熱性に優れ、かつ硬化収縮の小さな硬化物が得られる。また、必要に応じて、硬度、強度、伸びの設計が自由にできるので、可とう性の大きな硬化物も得られる。 According to the energy beam curable resin composition of the present invention, a cured product having excellent heat resistance and small curing shrinkage can be obtained. Moreover, since the design of hardness, intensity | strength, and elongation can be made freely as needed, a hardened | cured material with a large flexibility is also obtained.
従って、本発明の樹脂組成物を用いた塗料によれば、これらの性能を具備した塗膜が得られる。 Therefore, according to the paint using the resin composition of the present invention, a coating film having these performances can be obtained.
イソシアヌレート型ポリイソシアネート化合物（Ａ）としては、脂肪族ジイソシアネート、脂環族ジイソシアネート、芳香族ジイソシアネートや芳香脂肪族ジイソシアネート等の有機ジイソシアネートを３量化したものを用いることができる。中でも、黄変の低減を必要とする場合には、脂肪族ジイソシアネートや脂環族ジイソシアネートを３量化したイソシアヌレート型ポリイソシアネート化合物が好ましい。イソシアヌレート型ポリイソシアネート化合物（Ａ）は１種を単独で使用してもよく、複数種を併用することもできる。 As the isocyanurate type polyisocyanate compound (A), those obtained by trimerizing organic diisocyanates such as aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate and araliphatic diisocyanate can be used. Among these, when it is necessary to reduce yellowing, an isocyanurate type polyisocyanate compound obtained by trimerizing aliphatic diisocyanate or alicyclic diisocyanate is preferable. An isocyanurate type polyisocyanate compound (A) may be used individually by 1 type, and can also use multiple types together.
脂肪族ジイソシアネートの例としては、テトラメチレンジイソシアネート、ドデカメチレンジイソシアネート、１，４−ブタンジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４−トリメチルヘキサメチレンジイソシアネート、２，４，４−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、２−メチルペンタン−１，５−ジイソシアネート、３−メチルペンタン−１，５−ジイソシアネート等が挙げられる。 Examples of aliphatic diisocyanates include tetramethylene diisocyanate, dodecamethylene diisocyanate, 1,4-butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine. Examples include diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate.
脂環族ジイソシアネートの例としては、イソホロンジイソシアネート、水添キシリレンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、１，４−シクロヘキサンジイソシアネート、メチルシクロヘキシレンジイソシアネート、１，３−ビス（イソシアネートメチル）シクロヘキサン等が挙げられる。 Examples of alicyclic diisocyanates include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and the like. Is mentioned.
芳香族ジイソシアネートの例としては、トリレンジイソシアネート、２，２’−ジフェニルメタンジイソシアネート、２，４’−ジフェニルメタンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、４，４’−ジフェニルジメチルメタンジイソシアネート、４，４’−ジベンジルジイソシアネート、１，５−ナフチレンジイソシアネート、キシリレンジイソシアネート、１，３−フェニレンジイソシアネート、１，４−フェニレンジイソシアネート等が挙げられる。 Examples of aromatic diisocyanates include tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4 ′. -Dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and the like.
芳香脂肪族ジイソシアネートの例としては、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、α，α，α，α−テトラメチルキシリレンジイソシアネート等が挙げられる。 Examples of the araliphatic diisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α, α, α-tetramethylxylylene diisocyanate and the like.
また、ジオール化合物（Ｂ）としては、ポリエステルジオール、ポリカーボネートジオール、ポリエーテルジオール、脂肪族炭化水素系ジオール、脂環族炭化水素系ジオール、ジヒドロキシ（メタ）アクリレート化合物等を用いることができ、これらは１種を単独で使用してもよく、複数種を併用することもできる。これらジオール化合物は、目的とする物性が得られるように適宜選択すればよい。 As the diol compound (B), polyester diol, polycarbonate diol, polyether diol, aliphatic hydrocarbon diol, alicyclic hydrocarbon diol, dihydroxy (meth) acrylate compound, etc. can be used. 1 type may be used independently and multiple types can also be used together. These diol compounds may be appropriately selected so as to obtain desired physical properties.
例えば、耐熱性と硬度を維持しつつ、硬化収縮を低減させることを目的とする場合には、脂肪族炭化水素系ジオール、脂環族炭化水素系ジオール、ジヒドロキシ（メタ）アクリレート化合物を用いることが好ましく、中でも脂環族炭化水素系ジオールが好ましい。 For example, when the purpose is to reduce curing shrinkage while maintaining heat resistance and hardness, an aliphatic hydrocarbon diol, an alicyclic hydrocarbon diol, or a dihydroxy (meth) acrylate compound may be used. Among them, alicyclic hydrocarbon diols are preferable.
また、可とう性の付与と硬化収縮の低減を目的とする場合には、ポリエステルジオール、ポリカーボネートジオール、ポリエーテルジオールを用いることが好ましく、さらに耐熱性維持の目的も加わる場合には、このうち、ポリエステルジオール、ポリカーボネートジオールを用いることがより好ましい。 In addition, in the case of aiming to impart flexibility and reduce cure shrinkage, it is preferable to use polyester diol, polycarbonate diol, polyether diol, and when the purpose of maintaining heat resistance is further added, It is more preferable to use polyester diol and polycarbonate diol.
分子量の点からは、硬度維持を目的とする場合には、低分子量のものが好ましく、可とう性の付与を目的とする場合には、高分子量のものが好ましい。 From the viewpoint of molecular weight, a low molecular weight is preferable for the purpose of maintaining hardness, and a high molecular weight is preferable for the purpose of imparting flexibility.
次に、水酸基を含有する（メタ）アクリレート系化合物（Ｃ）の例としては、上記式（２）におけるＲ３が炭素数２〜６のアルコール残基の場合では、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、４−ヒドロキシブチル（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、グリセリンジ（メタ）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、ソルビトールペンタ（メタ）アクリレート等が挙げられる。 Next, as an example of the (meth) acrylate compound (C) containing a hydroxyl group, when R 3 in the above formula (2) is an alcohol residue having 2 to 6 carbon atoms, 2-hydroxyethyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, sorbitol penta (meth) acrylate Etc.
Ｒ３が炭素数３〜６であるポリオールの脱水縮合物のアルコール残基の場合では、ジグリセリントリ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等が挙げられる。 In the case of an alcohol residue of a dehydration condensate of a polyol having 3 to 6 carbon atoms, R 3 is diglycerin tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. Can be mentioned.
Ｒ３がポリアルキレングリコール又はポリカプロラクトンのアルコール残基の場合では、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、（ポリ）カプロラクトン変性２−ヒドロキシエチル（メタ）アクリレート、エチレンオキシド／カプロラクトン共重合体のモノ（メタ）アクリレート等が挙げられる。 When R 3 is an alcohol residue of polyalkylene glycol or polycaprolactone, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (poly) caprolactone modified 2-hydroxyethyl (meth) acrylate, ethylene oxide / caprolactone Examples thereof include mono (meth) acrylate of a copolymer.
Ｒ３がフェニルグリシジルエーテルの開環物のアルコール残基である場合では、フェニルグリシジルエーテル（メタ）アクリレート等が挙げられる。 In the case where R 3 is an alcohol residue of a ring-opened product of phenyl glycidyl ether, phenyl glycidyl ether (meth) acrylate and the like can be mentioned.
上記の中でも、２−ヒドロキシエチルアクリレート及び２−ヒドロキシプロピルアクリレートが特に好適に用いられる。なお、アクリロイル基を有する化合物とメタクリロイル基を有する化合物とでは、アクリロイル基を有する化合物の方が硬化速度がより速い傾向にある。これら水酸基を含有する（メタ）アクリレート系化合物も１種を単独で使用してもよく、複数種を併用することもできる。 Among the above, 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate are particularly preferably used. In addition, between the compound having an acryloyl group and the compound having a methacryloyl group, the compound having an acryloyl group tends to have a faster curing rate. These (meth) acrylate compounds containing a hydroxyl group may be used alone or in combination of two or more.
上記各成分を反応させることにより、一般式（１）で表されるウレタン（メタ）アクリレートが得られるが、好ましくは、まず（Ａ）成分と（Ｂ）成分とを、（Ａ）成分中のイソシアネート基と（Ｂ）成分中の水酸基のモル比が３．００／１．００〜７．００／１．００の範囲となる割合で反応させて反応物（Ｄ）を得て、さらにこの反応物（Ｄ）と（Ｃ）成分とを、反応物（Ｄ）中のイソシアネート基と（Ｃ）成分中の水酸基のモル比が１．００／１．００〜１．００／２．００の範囲となる割合で反応させる。（Ａ）成分中のイソシアネート基のモル比が（Ｂ）成分中の水酸基のモル比に対して３．００未満の場合は、ウレタン化物が架橋してゲル化し易い。一方、（Ａ）成分中のイソシアネート基のモル比が（Ｂ）成分中の水酸基のモル比に対して７．００より大きい場合は、硬化収縮を抑制する効果が十分に得られない。 By reacting each of the above components, the urethane (meth) acrylate represented by the general formula (1) is obtained. Preferably, the component (A) and the component (B) are first combined in the component (A). A reaction product (D) is obtained by reacting the isocyanate group with a hydroxyl group in the component (B) at a ratio of 3.00 / 1.00 to 7.00 / 1.00. The product (D) and the component (C) are in a range where the molar ratio of the isocyanate group in the reaction product (D) and the hydroxyl group in the component (C) is 1.00 / 1.00 to 1.00 / 2.00. It is made to react in the ratio which becomes. When the molar ratio of the isocyanate group in the component (A) is less than 3.00 with respect to the molar ratio of the hydroxyl group in the component (B), the urethanized product is easily crosslinked and gelled. On the other hand, when the molar ratio of the isocyanate group in the component (A) is larger than 7.00 relative to the molar ratio of the hydroxyl group in the component (B), the effect of suppressing curing shrinkage cannot be sufficiently obtained.
上記のウレタンアクリレートは、公知の方法で合成することが可能であり、例えば、所定量の（Ａ）成分と（Ｂ）成分を一括で仕込み、７０〜８０℃に加温しつつ攪拌し、遊離ＮＣＯ濃度が所定値になったところでハイドロキノンモノメチルエーテル等の重合禁止剤の存在下、所定量の（Ｃ）成分を仕込み、７０〜８０℃で遊離イソシアネートがなくなるまで攪拌することにより得られる。 The urethane acrylate can be synthesized by a known method. For example, a predetermined amount of the components (A) and (B) are charged in a lump and stirred while heating to 70 to 80 ° C. When the NCO concentration reaches a predetermined value, it is obtained by charging a predetermined amount of the component (C) in the presence of a polymerization inhibitor such as hydroquinone monomethyl ether and stirring at 70 to 80 ° C. until there is no free isocyanate.
また、本発明の樹脂組成物を塗料化する場合には、酢酸エチル、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有機溶剤及び／又はモノマー類で希釈することができる。モノマー類で希釈する場合は、ウレタンアクリレートとモノマー類の総和量中のウレタンアクリレートの含有率を５０重量％以上にすることが望ましい。 In addition, when the resin composition of the present invention is made into a paint, it can be diluted with an organic solvent and / or monomers such as ethyl acetate and propylene glycol monomethyl ether acetate. When diluting with monomers, the content of urethane acrylate in the total amount of urethane acrylate and monomers is preferably 50% by weight or more.
希釈に用いるモノマー類としては、公知慣用のものが使用可能であるが、中でも代表的なものとして、２−エチルヘキシルアクリレート、スチレン、メチルメタクリレート、テトラヒドロフルフリル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（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、ポリプロピレングリコールジ（メタ）アクリレート、１，４−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、エチレンオキサイド変性ビスフェノールジ（メタ）アクリレート、プロピレンオキサイド変性ビスフェノールジ（メタ）アクリレート、エチレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、プロピレンオキサイド変性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トリ（メタ）アクリレート、トリス（（メタ）アクリロキシエチル）イソシアヌレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等が挙げられる。これらは１種を単独で用いてもよく、複数種を併用してもよい。 As the monomers used for dilution, known and commonly used monomers can be used. Among them, typical examples include 2-ethylhexyl acrylate, styrene, methyl methacrylate, tetrahydrofurfuryl (meth) acrylate, and phenoxyethyl (meth) acrylate. , Isobornyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate 1,6-hexanediol di (meth) acrylate, ethylene oxide modified bisphenol di (meth) acrylate, propylene oxide modified bisphenol di (meth) acrylate Ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, dipentaerythritol hexa (meta) ) Acrylate, dipentaerythritol penta (meth) acrylate, and the like. These may be used individually by 1 type and may use multiple types together.
本発明のエネルギー線硬化型樹脂組成物には、必要に応じて光重合開始剤を添加する。光重合開始剤の種類は特に限定されず、公知のものが使用可能であるが、代表的な例としては、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、ベンジルジメチルケタール、ベンゾインイソプロピルエーテル、ベンゾフェノン等が挙げられる。これらは１種を単独で用いてもよく、複数種併用してもよい。 If necessary, a photopolymerization initiator is added to the energy beam curable resin composition of the present invention. The type of the photopolymerization initiator is not particularly limited, and known ones can be used. Typical examples include 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropane-1. -One, benzyl dimethyl ketal, benzoin isopropyl ether, benzophenone and the like. These may be used alone or in combination of two or more.
また、光重合開始剤を使用する場合のその添加量は、ウレタン（メタ）アクリレートと上記必要に応じて用いられるモノマーの総和量に対し、１〜１０重量％程度であり、約３〜５重量％が好ましい。 Moreover, the addition amount in the case of using a photoinitiator is about 1 to 10 weight% with respect to the total amount of a urethane (meth) acrylate and the said monomer used as needed, About 3 to 5 weight % Is preferred.
さらに、本発明のエネルギー線硬化樹脂組成物には、必要に応じて、光安定剤、紫外線吸収剤、触媒、着色剤、帯電防止剤、滑剤、レベリング剤、消泡剤、重合促進剤、酸化防止剤、難燃剤、赤外線吸収剤、界面活性剤、表面改質剤等を添加することができる。 Further, the energy ray curable resin composition of the present invention includes a light stabilizer, an ultraviolet absorber, a catalyst, a colorant, an antistatic agent, a lubricant, a leveling agent, an antifoaming agent, a polymerization accelerator, an oxidation agent, if necessary. Inhibitors, flame retardants, infrared absorbers, surfactants, surface modifiers and the like can be added.
なお、本発明のエネルギー線硬化型樹脂組成物を硬化させるエネルギー線源は特に限定されないが、例としては、高圧水銀灯、電子線、γ線、カーボンアーク灯、キセノン灯、メタルハライド灯等が挙げられる。 The energy ray source for curing the energy ray curable resin composition of the present invention is not particularly limited, and examples include high pressure mercury lamp, electron beam, γ ray, carbon arc lamp, xenon lamp, metal halide lamp and the like. .
以下、本発明を実施例および比較例によりさらに具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。なお、以下において、配合比率及び「％」は、特に断らないかぎり、全て重量基準であるものとする。また、残存イソシアネート濃度は、ＪＩＳ Ｋ７３０１−１９９５の６．３に準拠して測定した数値を示す。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples at all. In the following, the blending ratio and “%” are all based on weight unless otherwise specified. Moreover, a residual isocyanate density | concentration shows the numerical value measured based on 6.3 of JISK7301-1995.
［合成例１］
フラスコにヘキサメチレンジイソシアネートのイソシアヌレート型ポリイソシアネート１４３２g（７．２６ＮＣＯ当量）とビス（ヒドロキシメチル）−トリシクロデカン２００ｇ（２ＯＨ当量）を仕込み、７０〜８０℃の条件にて残存イソシアネート濃度が１３．５％になるまで反応させた。残存イソシアネート濃度が１３．５％になったら、２−ヒドロキシプロピルアクリレート７５４ｇ（５．８ＯＨ当量）及びハイドロキノンモノメチルエーテル１．２ｇを仕込み、７０〜８０℃の条件にて残存イソシアネート濃度が０．１％になるまで反応させ、ウレタンアクリレートＥを得た。
[Synthesis Example 1]
A flask is charged with 1432 g (7.26 NCO equivalent) of isocyanurate-type polyisocyanate of hexamethylene diisocyanate and 200 g (2OH equivalent) of bis (hydroxymethyl) -tricyclodecane, and the residual isocyanate concentration is 13. under the conditions of 70 to 80 ° C. The reaction was allowed to reach 5%. When the residual isocyanate concentration reached 13.5%, 754 g of 2-hydroxypropyl acrylate (5.8 OH equivalent) and 1.2 g of hydroquinone monomethyl ether were charged, and the residual isocyanate concentration was 0.1% under the conditions of 70 to 80 ° C. To give urethane acrylate E.
［合成例２］
フラスコにヘキサメチレンジイソシアネートのイソシアヌレート型ポリイソシアネート１４３２ｇ（７．２６ＮＣＯ当量）とポリカプロラクトンジオール５００ｇ（２ＯＨ当量）を仕込み、７０〜８０℃の条件にて残存イソシアネート濃度が１１．４％になるまで反応させた。残存イソシアネート濃度が１１．４％になったら、２−ヒドロキシプロピルアクリレート７５４ｇ（５．８ＯＨ当量）及びハイドロキノンモノメチルエーテル１．３ｇを仕込み、７０〜８０℃の条件にて残存イソシアネート濃度が０．１％になるまで反応させ、ウレタンアクリレートＦを得た。
[Synthesis Example 2]
A flask is charged with 1432 g (7.26 NCO equivalent) of isocyanurate-type polyisocyanate of hexamethylene diisocyanate and 500 g (2 OH equivalent) of polycaprolactone diol, and reacted until the residual isocyanate concentration becomes 11.4% at 70 to 80 ° C. I let you. When the residual isocyanate concentration reached 11.4%, 754 g (5.8 OH equivalent) of 2-hydroxypropyl acrylate and 1.3 g of hydroquinone monomethyl ether were charged, and the residual isocyanate concentration was 0.1% at 70 to 80 ° C. To give urethane acrylate F.
［比較合成例１］
フラスコにヘキサメチレンジイソシアネートのイソシアヌレート型ポリイソシアネート５９２ｇ（３ＮＣＯ当量）、２−ヒドロキシプロピルアクリレート５０４ｇ（３．９ＯＨ当量）およびハイドロキノンモノメチルエーテル０．５５ｇを仕込み、合成例１と同様にして反応させ、ウレタンアクリレートＧを得た。
[Comparative Synthesis Example 1]
A flask was charged with 592 g (3 NCO equivalent) of isocyanurate-type polyisocyanate of hexamethylene diisocyanate, 504 g (3.9 OH equivalent) of 2-hydroxypropyl acrylate and 0.55 g of hydroquinone monomethyl ether, reacted in the same manner as in Synthesis Example 1, and urethane. Acrylate G was obtained.
以上の合成例及び比較合成例の、（Ａ）成分、（Ｂ）成分、及び（Ｃ）成分の種類と当量比を表１に示す。
［実施例１，２、比較例１］
上記合成例および比較合成例で得られたウレタンアクリレート、光重合開始剤、及び希釈溶剤を表２に示す比率で配合して均一に溶解させ、計３種の樹脂組成物を調製した。
[Examples 1 and 2 and Comparative Example 1]
The urethane acrylate, photopolymerization initiator, and dilution solvent obtained in the above synthesis examples and comparative synthesis examples were blended in the ratios shown in Table 2 and uniformly dissolved to prepare a total of three types of resin compositions.
得られた樹脂組成物について、以下の要領で、耐熱性、硬化収縮、鉛筆硬度及び引張り強さ、伸びを測定した。結果を表２に併記する。 About the obtained resin composition, heat resistance, cure shrinkage, pencil hardness, tensile strength, and elongation were measured in the following manner. The results are also shown in Table 2.
・硬化条件
各樹脂組成物をガラス板状に１００μｍのアプリケーターバーで塗布し、８０℃のオーブンで３０分間溶剤を揮発させたものに、８０Ｗ／ｃｍの高圧水銀灯を用いて積算照度１７０ｍＪ／ｃｍ２の紫外線を照射した。
Curing conditions Each resin composition was applied to a glass plate with a 100 μm applicator bar, and the solvent was volatilized in an oven at 80 ° C. for 30 minutes. An integrated illuminance of 170 mJ / cm 2 using an 80 W / cm high-pressure mercury lamp. The ultraviolet rays were irradiated.
・耐熱性
上記条件で硬化させた樹脂を１５０℃で６時間加熱し、色差計を用いて加熱前後のΔＹＩ（Yellow Index）として測定した。
-Heat resistance The resin hardened | cured on the said conditions was heated at 150 degreeC for 6 hours, and measured as (DELTA) YI (Yellow Index) before and behind a heating using the color difference meter.
・硬化収縮
上記条件で硬化させた樹脂の硬化前後の比重を測定し、次式により体積収縮率として求めた。
体積収縮率（％）＝〔（硬化後の比重−硬化前の比重）／硬化後の比重〕×１００
-Curing shrinkage Specific gravity before and behind hardening of the resin hardened | cured on the said conditions was measured, and it calculated | required as a volume shrinkage rate by following Formula.
Volume shrinkage (%) = [(specific gravity after curing−specific gravity before curing) / specific gravity after curing] × 100
・鉛筆硬度
上記条件でガラス板上で硬化させた樹脂をそのまま鉛筆引っかき試験機を用いて試験し、塗膜に擦り傷のつかない硬度を求めた。
-Pencil hardness The resin cured on the glass plate under the above conditions was tested as it was using a pencil scratch tester, and the hardness at which the coating film was not scratched was determined.
・引張り強さ及び伸び
上記条件で硬化させた樹脂から幅５ｍｍ、長さ１００ｍｍの短冊型試験片を作製し、オートグラフを用いて、温度２０℃、相対湿度６０％の恒温・恒湿室にて、チャック間距離を５０ｍｍとし、５ｍｍ／分の速さで引張り、引張り強さ（ＭＰａ）と破断時の伸び（％）を求めた。
表２から分かるように、実施例１、２ともに比較例１と比較して耐熱性について同等の性能を示し、硬化収縮は比較例１と比較して小さくなった。さらに、実施例１では鉛筆硬度は比較例１と同等であり、引っ張り強度と伸びについては同等又はそれ以上の性能を示した。また、実施例２では比較例１に対して伸びが大きくなった。 As can be seen from Table 2, both Examples 1 and 2 showed the same performance with respect to heat resistance as compared with Comparative Example 1, and the curing shrinkage was smaller than that of Comparative Example 1. Furthermore, in Example 1, the pencil hardness was equivalent to that of Comparative Example 1, and the tensile strength and elongation were equivalent or better. In Example 2, the elongation was larger than that in Comparative Example 1.
本発明の樹脂組成物は、塗料として各種建材、構造物、成型物等のコーティングに用いられるほか、紙コーティング、レジスト用材料、接着剤、電子機器の部品等にも用いることができる。 The resin composition of the present invention can be used as a coating material for coating various building materials, structures, molded articles and the like, as well as paper coatings, resist materials, adhesives, electronic device parts, and the like.
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Cited By (6)
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| JP2008038067A (en) * | 2006-08-09 | 2008-02-21 | Dai Ichi Kogyo Seiyaku Co Ltd | Nonyellowing adhesive composition |
| JP2011122119A (en) * | 2009-12-14 | 2011-06-23 | Fujikura Kasei Co Ltd | Active energy ray-curable coating composition and composite coating film |
| KR101198456B1 (en) * | 2008-09-09 | 2012-11-06 | 삼화페인트공업주식회사 | Radiation-Curable Composition and Anti-fingerprinting Composition comprising the same |
| JP2017057353A (en) * | 2015-09-18 | 2017-03-23 | 日本化薬株式会社 | Polyurethane compound and resin composition containing the same |
| JP2017095692A (en) * | 2015-11-18 | 2017-06-01 | 中国塗料株式会社 | Energy ray curable sealer composition for housing material, housing material with coated film and manufacturing method therefor |
| CN115491164A (en) * | 2022-09-30 | 2022-12-20 | 韦尔通(厦门)科技股份有限公司 | Acrylate modified reactive polyurethane hot melt adhesive, and preparation method, application and use method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008038067A (en) * | 2006-08-09 | 2008-02-21 | Dai Ichi Kogyo Seiyaku Co Ltd | Nonyellowing adhesive composition |
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| JP2017095692A (en) * | 2015-11-18 | 2017-06-01 | 中国塗料株式会社 | Energy ray curable sealer composition for housing material, housing material with coated film and manufacturing method therefor |
| CN115491164A (en) * | 2022-09-30 | 2022-12-20 | 韦尔通(厦门)科技股份有限公司 | Acrylate modified reactive polyurethane hot melt adhesive, and preparation method, application and use method thereof |
| CN115491164B (en) * | 2022-09-30 | 2024-02-02 | 韦尔通科技股份有限公司 | Acrylic ester modified reactive polyurethane hot melt adhesive and preparation method and application and use method thereof |
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