JP6565613B2 - Active energy ray-curable resin composition - Google Patents
Active energy ray-curable resin composition Download PDFInfo
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- JP6565613B2 JP6565613B2 JP2015217827A JP2015217827A JP6565613B2 JP 6565613 B2 JP6565613 B2 JP 6565613B2 JP 2015217827 A JP2015217827 A JP 2015217827A JP 2015217827 A JP2015217827 A JP 2015217827A JP 6565613 B2 JP6565613 B2 JP 6565613B2
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- acrylate
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- urethane
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- 239000011342 resin composition Substances 0.000 title claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 51
- 229920001610 polycaprolactone Polymers 0.000 claims description 20
- 239000004632 polycaprolactone Substances 0.000 claims description 20
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 19
- 150000003077 polyols Chemical class 0.000 claims description 18
- 229920005862 polyol Polymers 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 230000009477 glass transition Effects 0.000 claims description 7
- 229920001519 homopolymer Polymers 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000000126 substance Substances 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- -1 2-hydroxypropyl Chemical group 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 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 4
- 239000000463 material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 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 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical class O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-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
- HRPUANCEDYZMFT-UHFFFAOYSA-N 2-(1-hydroxycyclohexyl)-1-phenylethanone Chemical class C=1C=CC=CC=1C(=O)CC1(O)CCCCC1 HRPUANCEDYZMFT-UHFFFAOYSA-N 0.000 description 1
- IAMASUILMZETHW-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-phenoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOCC(O)OC1=CC=CC=C1 IAMASUILMZETHW-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- UUSPDEWFJUSHKG-UHFFFAOYSA-N dibutylbismuth Chemical compound CCCC[Bi]CCCC UUSPDEWFJUSHKG-UHFFFAOYSA-N 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
- 238000009826 distribution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- RSVDRWTUCMTKBV-UHFFFAOYSA-N sbb057044 Chemical compound C12CC=CC2C2CC(OCCOC(=O)C=C)C1C2 RSVDRWTUCMTKBV-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing 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
- 238000004383 yellowing Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、活性エネルギー線硬化型樹脂組成物に関する。 The present invention relates to an active energy ray-curable resin composition.
硬化性樹脂組成物は、活性エネルギー線の照射により直ちに硬化して強度や耐薬品性に優れる硬化膜を形成することから、各種の表面を保護するための塗料、コーティング材として用いられている。近年では、液晶ディスプレイ等の画像表示装置に使用される反射防止フィルム、偏光フィルム、プリズムシート等の光学フィルムまたはシートや、電子機器や家電製品の筐体、表示パネル、スイッチボタン等に使用されるインサート成形またはインモールド転写フィルムへの利用が拡大している。このような用途に用いられる硬化性樹脂組成物には、美観を維持するための耐傷つき性、耐薬品性と加工性の点での基材への密着性、伸張性が求められる。耐傷つき性を向上させる方法として多官能モノマーまたはオリゴマーを用いて表面硬度を向上させる方法が知られている。しかしこの方法では伸張性が著しく低下し、加工性が劣る。そこで、耐傷つき性と加工性を両立させる手段として、擦傷が継時的に自己修復する樹脂組成物が開示されている。例えば、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分子量２，０００のポリカプロラクトントリオールとを反応させて得られるウレタンアクリレート（特許文献１）、ヘキサメチレンジイソシアネートのイソシアヌレート変性体とポリエチレングリコールモノアクリレートとを反応させて得られるウレタンアクリレート（特許文献２）が開示されている。しかしながら、これらの方法では良好な自己修復性、表面硬度、伸張性と基材への密着性、耐薬品性を同時に満たすには至っていない。 The curable resin composition is immediately cured by irradiation with active energy rays to form a cured film having excellent strength and chemical resistance. Therefore, the curable resin composition is used as a paint or a coating material for protecting various surfaces. In recent years, it is used for optical films or sheets such as antireflection films, polarizing films, and prism sheets used in image display devices such as liquid crystal displays, as well as housings, display panels, switch buttons, and the like of electronic devices and home appliances. Use in insert molding or in-mold transfer films is expanding. The curable resin composition used for such applications is required to have scratch resistance, chemical resistance, and adhesion to a substrate and stretchability in order to maintain aesthetics. As a method of improving scratch resistance, a method of improving surface hardness using a polyfunctional monomer or oligomer is known. However, in this method, the extensibility is remarkably lowered and the processability is inferior. Therefore, as a means for achieving both scratch resistance and workability, a resin composition in which scratches self-repair over time is disclosed. For example, urethane acrylate (Patent Document 1) obtained by reacting isophorone diisocyanate, 2-hydroxyethyl acrylate, and polycaprolactone triol having a molecular weight of 2,000, isocyanurate-modified hexamethylene diisocyanate and polyethylene glycol monoacrylate are reacted. Urethane acrylate (Patent Document 2) obtained by the above process is disclosed. However, these methods have not yet achieved good self-repairability, surface hardness, extensibility, adhesion to a substrate, and chemical resistance.
本発明の課題は、良好な自己修復性、表面硬度、伸張性を有し、かつ基材へ密着性と耐薬品性が良好な硬化物を得ることができる活性エネルギー線硬化型樹脂組成物を提供することである。 An object of the present invention is to provide an active energy ray-curable resin composition that has a good self-healing property, surface hardness, and extensibility, and that can obtain a cured product having good adhesion and chemical resistance to a substrate. Is to provide.
本発明者は、上記課題を解決するために鋭意検討した結果、特定構造のウレタン（メタ）アクリレートと特定の単官能（メタ）アクリレートを含有する活性エネルギー線硬化型樹脂組成物が有用であることを見出し、本発明の完成に至った。 As a result of intensive studies in order to solve the above problems, the present inventor has found that an active energy ray-curable resin composition containing a urethane (meth) acrylate having a specific structure and a specific monofunctional (meth) acrylate is useful. As a result, the present invention has been completed.
すなわち、本発明は、次の〔１〕である。
〔１〕下記のウレタン（メタ）アクリレート（Ａ）および単官能（メタ）アクリレート（Ｂ）を含有し、ウレタン（メタ）アクリレート（Ａ）と単官能（メタ）アクリレート（Ｂ）の質量比が（Ａ）／（Ｂ）＝５０／５０〜９５／５である活性エネルギー線硬化型樹脂組成物。
ウレタン（メタ）アクリレート（Ａ）： 数平均分子量３００〜９００のポリカプロラクトンポリオール（ａ１）、脂肪族又は脂環式ジイソシアネート（ａ２）、水酸基含有（メタ）アクリレート（ａ３）を反応させて得られる重量平均分子量３，０００〜３０，０００のウレタン（メタ）アクリレート
単官能（メタ）アクリレート（Ｂ）： 単独重合体としたときのガラス転移温度が−３０〜３５℃であり、下記の式（１）で表される単官能（メタ）アクリレート
[1] The following urethane (meth) acrylate (A) and monofunctional (meth) acrylate (B) are contained, and the mass ratio of urethane (meth) acrylate (A) and monofunctional (meth) acrylate (B) is ( A) / (B) = 50/50 to 95/5 active energy ray-curable resin composition.
Urethane (meth) acrylate (A): Weight obtained by reacting a polycaprolactone polyol (a1) having a number average molecular weight of 300 to 900, an aliphatic or alicyclic diisocyanate (a2), and a hydroxyl group-containing (meth) acrylate (a3). Urethane (meth) acrylate having an average molecular weight of 3,000 to 30,000 Monofunctional (meth) acrylate (B): The glass transition temperature when it is a homopolymer is −30 to 35 ° C., and the following formula (1) Monofunctional (meth) acrylate represented by
本発明の活性エネルギー線硬化型樹脂組成物によれば、良好な自己修復性、表面硬度、伸張性を有し、かつ基材への密着性と耐薬品性が良好な硬化物を得ることができる。 According to the active energy ray-curable resin composition of the present invention, it is possible to obtain a cured product having good self-healing properties, surface hardness, extensibility, and good adhesion to a substrate and chemical resistance. it can.
本発明の活性エネルギー線硬化型樹脂組成物は、ウレタン（メタ）アクリレート（Ａ）、単官能（メタ）アクリレート（Ｂ）を含有することを特徴とする。以下に、各成分について説明する。
なお、本明細書において、「（メタ）アクリレート」とは、アクリレート又はメタクリレートを意味する。
＜ウレタン（メタ）アクリレート（Ａ）＞
The active energy ray-curable resin composition of the present invention is characterized by containing urethane (meth) acrylate (A) and monofunctional (meth) acrylate (B). Below, each component is demonstrated.
In the present specification, “(meth) acrylate” means acrylate or methacrylate.
<Urethane (meth) acrylate (A)>
本発明に用いるウレタン（メタ）アクリレート（Ａ）は、数平均分子量３００〜９００のポリカプロラクトンポリオール（ａ１）と、脂肪族または脂環式ジイソシアネート（ａ２）と、水酸基含有（メタ）アクリレート（ａ３）とを反応させて得られる重量平均分子量が３，０００〜３０，０００のウレタンアクリレートである。
＜ポリカプロラクトンポリオール（ａ１）＞
The urethane (meth) acrylate (A) used in the present invention comprises a polycaprolactone polyol (a1) having a number average molecular weight of 300 to 900, an aliphatic or alicyclic diisocyanate (a2), and a hydroxyl group-containing (meth) acrylate (a3). Is a urethane acrylate having a weight average molecular weight of 3,000 to 30,000 obtained by the reaction.
<Polycaprolactone polyol (a1)>
本発明に用いるポリカプロラクトンポリオールとしてはポリカプロラクトンジオールまたはポリカプロラクトントリオールが挙げられ、２種以上を組み合わせて使用することもできる。ポリカプロラクトンポリオールの数平均分子量が３００未満の場合は自己修復性が不十分となり、９００を超えると自己修復性と表面硬度、密着性、耐薬品性が不十分となる。好ましくは５００〜８５０である。ポリカプロラクトンポリオールの入手可能な市販品としては、（株）ダイセル製の「プラクセル２０５」、「プラクセル２０５Ｈ」、「プラクセル２０５Ｕ」、「プラクセルＬ２０５ＡＬ」、「プラクセル２０８」、「プラクセル２１０」、「プラクセル２１０Ｎ」、「プラクセル２１０ＣＰ」等が挙げられる。
＜脂肪族または脂環式ジイソシアネート（ａ２）＞
Examples of the polycaprolactone polyol used in the present invention include polycaprolactone diol and polycaprolactone triol, and two or more kinds can be used in combination. When the number average molecular weight of the polycaprolactone polyol is less than 300, the self-healing property is insufficient, and when it exceeds 900, the self-healing property, surface hardness, adhesion, and chemical resistance are insufficient. Preferably it is 500-850. Examples of commercially available products of polycaprolactone polyol include “Placcel 205”, “Placcel 205H”, “Placcel 205U”, “Placcel L205AL”, “Placcel 208”, “Placcel 210”, and “Placcel” manufactured by Daicel Corporation. 210N "," Placcel 210CP "and the like.
<Aliphatic or alicyclic diisocyanate (a2)>
本発明に用いる脂肪族ジイソシアネートとしては、トリメチレンジイソシアネート、ヘキサメチレンジイソシアネート等が挙げられ、脂環式ジイソシアネートとしては、１，４−シクロヘキサンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート、ノルボルナンジイソシアネート等が挙げられる。硬化物の表面硬度、伸張性および耐薬品性に優れるという点で脂環式ジイソシアネートが好ましい。
＜水酸基含有（メタ）アクリレート（ａ３）＞
Examples of the aliphatic diisocyanate used in the present invention include trimethylene diisocyanate and hexamethylene diisocyanate, and examples of the alicyclic diisocyanate include 1,4-cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and norbornane diisocyanate. An alicyclic diisocyanate is preferable in that the cured product has excellent surface hardness, extensibility, and chemical resistance.
<Hydroxyl group-containing (meth) acrylate (a3)>
本発明で用いる水酸基含有（メタ）アクリレート（ｃ）は、１分子中に少なくとも１個以上の水酸基と、１個以上の（メタ）アクリロイル基を有する水酸基含有（メタ）アクリレートである。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、４−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレートのε−カプロラクトン付加物（平均付加モル数１〜１０）、ポリエチレングリコール（平均付加モル数１〜１０）モノ（メタ）アクリレート、ポリプロピレングリコール（平均付加モル数１〜１０）モノ（メタ）アクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレート等が挙げられる。これら水酸基含有（メタ）アクリレートは、一種単独で用いてもよく、２種以上を組み合わせてもよい。自己修復性と伸張性に優れるという観点から、２−ヒドロキシエチルアクリレート、２−ヒドロキシプロピルアクリレート、４−ヒドロキシブチルアクリレートが好ましい。 The hydroxyl group-containing (meth) acrylate (c) used in the present invention is a hydroxyl group-containing (meth) acrylate having at least one hydroxyl group and one or more (meth) acryloyl groups in one molecule. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate Ε-caprolactone adduct (average addition mole number 1 to 10), polyethylene glycol (average addition mole number 1 to 10) mono (meth) acrylate, polypropylene glycol (average addition mole number 1 to 10) mono (meth) acrylate, Examples include pentaerythritol triacrylate and dipentaerythritol pentaacrylate. These hydroxyl group-containing (meth) acrylates may be used alone or in combination of two or more. 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate are preferable from the viewpoint of excellent self-repairability and extensibility.
本発明に用いるウレタンアクリレート（Ａ）の重量平均分子量は３，０００〜３０，０００である。重量平均分子量が３，０００未満では自己修復性と伸張性が不十分であり、３０，０００を超えると自己修復性と表面硬度が不十分である。好ましくは４，０００〜１５，０００である。 The weight average molecular weight of the urethane acrylate (A) used in the present invention is 3,000 to 30,000. When the weight average molecular weight is less than 3,000, the self-healing property and the stretchability are insufficient, and when it exceeds 30,000, the self-healing property and the surface hardness are insufficient. Preferably it is 4,000-15,000.
ウレタン（メタ）アクリレート（Ａ）の製造において、ポリカプロラクトンポリオール（ａ１）、水酸基含有（メタ）アクリレート（ａ３）の水酸基の合計とジイソシアネート（ａ２）のイソシアネート基の当量比は０．９〜１．１であり、好ましくは０．９５〜１．０５である。 In the production of urethane (meth) acrylate (A), the equivalent ratio of the total hydroxyl groups of polycaprolactone polyol (a1) and hydroxyl group-containing (meth) acrylate (a3) to the isocyanate group of diisocyanate (a2) is 0.9 to 1. 1, preferably 0.95 to 1.05.
ウレタン（メタ）アクリレート（Ａ）の製造において、ウレタン化反応の方法は一般的には公知の方法に従って製造することができる。例えば、反応容器中にポリカプロラクトンポリオール（ａ１）、ジイソシアネート（ａ２）を投入し、必要に応じてウレタン化触媒、重合禁止剤、黄変防止剤、有機溶剤を投入し、３０〜１００℃の温度において反応させ、その後に水酸基含有（メタ）アクリレートを投入して、さらに３０〜１００℃の温度において反応させる。 In the production of the urethane (meth) acrylate (A), the urethanization reaction method can be generally produced according to a known method. For example, a polycaprolactone polyol (a1) and a diisocyanate (a2) are charged into a reaction vessel, and a urethanization catalyst, a polymerization inhibitor, a yellowing inhibitor, and an organic solvent are charged as necessary, and a temperature of 30 to 100 ° C. Then, a hydroxyl group-containing (meth) acrylate is added, and further reacted at a temperature of 30 to 100 ° C.
ウレタン化反応において、反応時間を短縮することができることから、ウレタン化触媒を使用することが好ましい。ウレタン化触媒としては、ジブチルスズジラウレートなどの有機スズ化合物、ジブチルビスマスジラウレートなどの有機ビスマス化合物、トリエチルアミンなどの３級アミン、テトラアルキルアンモニウムブロマイドなどの４級アンモニウムなどを用いることができる。これらのウレタン化触媒は、反応原料の総量に対して０．００５〜１．０重量％の量で用いられる。
＜単官能（メタ）アクリレート（Ｂ）＞
In the urethanization reaction, it is preferable to use a urethanization catalyst because the reaction time can be shortened. As the urethanization catalyst, organic tin compounds such as dibutyltin dilaurate, organic bismuth compounds such as dibutylbismuth dilaurate, tertiary amines such as triethylamine, quaternary ammonium such as tetraalkylammonium bromide, and the like can be used. These urethanization catalysts are used in an amount of 0.005 to 1.0% by weight based on the total amount of reaction raw materials.
<Monofunctional (meth) acrylate (B)>
式（１）で表され、単独重合体としたときのガラス転移温度が−３０〜３５℃である。単独重合体としたときのガラス転移温度が−３０℃未満では自己修復性、表面硬度、耐薬品性が不十分となり、３５℃を超えると、自己修復性と伸張性が不十分となる。具体的にはフェノキシエチルアクリレート、フェノキシジエチレングリコールアクリレート、ジシクロペンテニルオキシエチルアクリレート、環状トリメチロールプロパンホルマールアクリレートが挙げられる。これらの内１種類を用いてもよく、２種類以上を用いてもよい。自己修復性と表面硬度に優れるという観点からフェノキシエチルアクリレートが好ましい。 It is represented by the formula (1) and has a glass transition temperature of −30 to 35 ° C. when it is a homopolymer. When the glass transition temperature is less than −30 ° C. when the homopolymer is used, the self-healing property, the surface hardness and the chemical resistance are insufficient, and when it exceeds 35 ° C., the self-healing property and the extensibility are insufficient. Specific examples include phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, dicyclopentenyloxyethyl acrylate, and cyclic trimethylolpropane formal acrylate. One of these may be used, or two or more may be used. Phenoxyethyl acrylate is preferable from the viewpoint of excellent self-repairability and surface hardness.
本発明の活性エネルギー線硬化型樹脂組成物は、ウレタン（メタ）アクリレート（Ａ）と環状構造を有する（メタ）アクリレート（Ｂ）を質量比（Ａ）／（Ｂ）＝５０／５０〜９５／５で含有する。５０／５０未満では自己修復性、伸張性、耐薬品性が十分でなく、９５／５を超えると硬化物の自己修復性と表面硬度が不十分となる。好ましくは（Ａ）／（Ｂ）＝５０／５０〜８０／２０である。 The active energy ray-curable resin composition of the present invention comprises a urethane (meth) acrylate (A) and a (meth) acrylate (B) having a cyclic structure in a mass ratio (A) / (B) = 50/50 to 95 /. 5 to contain. If it is less than 50/50, the self-healing property, extensibility, and chemical resistance are not sufficient, and if it exceeds 95/5, the self-healing property and surface hardness of the cured product become insufficient. Preferably (A) / (B) = 50/50 to 80/20.
本発明の活性エネルギー線硬化型樹脂組成物には光重合開始剤を配合しても良い。前記光重合開始剤としては、例えば、ベンゾイン、ベンゾインメチルエーテル等のベンゾインまたはベンゾインアルキルエーテル；ベンゾフェノン、ベンゾイル安息香酸等の芳香族ケトン；ベンジルジメチルケタール、ベンジルジエチルケタール等のベンジルケタール；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−１−プロパン−１−オン等のアセトフェノン；２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキシド、ビス（２，４，６−トリメチルベンゾイル）フェニルフォスフィンオキシド等のアシルフォスフィンオキシドが挙げられる。 You may mix | blend a photoinitiator with the active energy ray hardening-type resin composition of this invention. Examples of the photopolymerization initiator include benzoin and benzoin alkyl ethers such as benzoin and benzoin methyl ether; aromatic ketones such as benzophenone and benzoylbenzoic acid; benzyl ketals such as benzyldimethyl ketal and benzyldiethyl ketal; 1-hydroxycyclohexyl Acetophenones such as phenyl ketone and 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) An acyl phosphine oxide such as phenyl phosphine oxide may be mentioned.
本発明の活性エネルギー線硬化型樹脂組成物には、単独重合体としたときのガラス転移温度が８０〜２００℃である単官能（メタ）アクリレート（Ｃ）を１〜３０質量％配合することで硬化物の伸張性がさらに良好な樹脂組成物が得られる。具体的には、イソボニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、アクリロイルモルホリン、Ｎ，Ｎ−ジメチルアクリルアミドを配合することが好ましい。さらには、アクリロイルモルホリン、Ｎ，Ｎ−ジメチルアクリルアミドを配合することよりが好ましい。 In the active energy ray-curable resin composition of the present invention, 1 to 30% by mass of a monofunctional (meth) acrylate (C) having a glass transition temperature of 80 to 200 ° C. as a homopolymer is blended. A resin composition having a further excellent extensibility of the cured product can be obtained. Specifically, it is preferable to blend isobonyl (meth) acrylate, dicyclopentanyl (meth) acrylate, acryloylmorpholine, and N, N-dimethylacrylamide. Furthermore, it is more preferable to mix acryloylmorpholine and N, N-dimethylacrylamide.
さらに、任意成分として、（メタ）アクリル重合体、表面調整剤、レベリング剤、充填剤、顔料、シランカップリング剤、帯電防止剤、消泡剤、防汚剤、酸化防止剤、紫外線吸収剤、光安定剤、光重合開始剤、有機溶剤等を配合することができる。 Furthermore, as an optional component, (meth) acrylic polymer, surface conditioner, leveling agent, filler, pigment, silane coupling agent, antistatic agent, antifoaming agent, antifouling agent, antioxidant, UV absorber, A light stabilizer, a photopolymerization initiator, an organic solvent, and the like can be blended.
本発明の硬化性樹脂組成物を硬化させる方法としては、赤外線、可視光線、紫外線、Ｘ線、γ線および電子線などの活性エネルギー線の群より選ばれる光線を選択することができる。活性エネルギー線の照射方法は、通常の硬化性樹脂組成物の硬化方法を用いることができる。活性エネルギー線照射装置として紫外線を用いる場合、波長が２００〜４５０ｎｍの領域にスペクトル分布を有するフュージョンＵＶシステムズ（株）製Ｈバルブ等の無電極ランプ、低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、キセノンランプ、ガリウムランプ、メタルハライドランプ等が挙げられる。活性エネルギー線の照射量は、積算光量として通常１０〜３，０００ｍＪ／ｃｍ2であり、５０〜２，０００ｍＪ／ｃｍ2が好ましく、１００〜１，０００ｍＪ／ｃｍ2がより好ましい。照射時の雰囲気は空気中でもよく、窒素やアルゴン等の不活性ガス中で硬化してもよい。 As a method for curing the curable resin composition of the present invention, a light ray selected from the group of active energy rays such as infrared rays, visible rays, ultraviolet rays, X-rays, γ rays and electron beams can be selected. As a method of irradiating active energy rays, a normal curing method of a curable resin composition can be used. When ultraviolet rays are used as the active energy ray irradiation device, electrodeless lamps such as H bulbs manufactured by Fusion UV Systems Co., Ltd. having a spectral distribution in the wavelength range of 200 to 450 nm, low pressure mercury lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps Xenon lamp, gallium lamp, metal halide lamp and the like. The dose of the active energy rays are usually 10~3,000mJ / cm 2 as the accumulated light quantity is preferably 50~2,000mJ / cm 2, 100~1,000mJ / cm 2 is more preferable. The atmosphere at the time of irradiation may be air or may be cured in an inert gas such as nitrogen or argon.
本発明の活性エネルギー線硬化型樹脂組成物はディスプレイ画面、モバイル機器の筐体、加飾フィルム等の各種コーティング剤に有用である。 The active energy ray-curable resin composition of the present invention is useful for various coating agents such as display screens, mobile device casings, and decorative films.
以下、実施例を示して本発明をさらに詳細に説明する。なお、以下において特に規定しない限り、「部」は「質量部」、「％」は「質量％」を示す。
＜合成例１：ウレタン（メタ）アクリレート（ＵＡ−１）の製造＞
Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “parts” means “parts by mass” and “%” means “mass%”.
<Synthesis Example 1: Production of urethane (meth) acrylate (UA-1)>
攪拌装置、空気導入管、温度計を備えた四つ口フラスコに、数平均分子量５３０のポリカプロラクトンジオール（（株）ダイセル製プラクセル２０５Ｕ）を１５９ｇ、イソホロンジイソシアネート（住化バイエルウレタン（株）製デスモジュールＩ）を８８．９ｇ、酢酸ブチルを６７．８ｇ、ジブチルスズジラウレートを０．０３ｇ投入し、窒素を吹き込みながら内温を６０℃に保持して４時間反応させた後、ＪＩＳ Ｋ ７３０１の方法でイソシアネート基含有量が３．５％以下でなることを確認した。次に、２−ヒドロキシエチルアクリレートを２３．２ｇ、メトキシハイドロキノンを０．１ｇ投入した。空気を吹き込みながら内温を６０℃に保持して３時間反応させた後、イソシアネート基含有量が０．２％以下でなることを確認し、重量平均分子量４，４５０のウレタン（メタ）アクリレート（ＵＡ−１）を３２２．１ｇ得た。
＜合成例２〜５、比較合成例１〜４＞
In a four-necked flask equipped with a stirrer, an air inlet tube, and a thermometer, 159 g of polycaprolactone diol having a number average molecular weight of 530 (Placcel 205U, manufactured by Daicel Corporation), and isophorone diisocyanate (Death manufactured by Sumika Bayer Urethane Co., Ltd.) 88.9 g of module I), 67.8 g of butyl acetate, and 0.03 g of dibutyltin dilaurate were added, and the reaction was carried out for 4 hours while maintaining the internal temperature at 60 ° C. while blowing nitrogen, followed by the method of JIS K 7301. It was confirmed that the isocyanate group content was 3.5% or less. Next, 23.2 g of 2-hydroxyethyl acrylate and 0.1 g of methoxyhydroquinone were added. After reacting for 3 hours while maintaining the internal temperature at 60 ° C. while blowing air, it was confirmed that the isocyanate group content was 0.2% or less, and a urethane (meth) acrylate having a weight average molecular weight of 4,450 ( 322.1 g of UA-1) was obtained.
<Synthesis Examples 2-5, Comparative Synthesis Examples 1-4>
表１に記載の原料を用いて、実施例１と同様にしてウレタン（メタ）アクリレートＵＡ−２〜ＵＡ−５及びＵＡ’−１〜ＵＡ’−４を製造した。ウレタン（メタ）アクリレートの重量平均分子量を表１に記載する。 Using the raw materials shown in Table 1, urethane (meth) acrylates UA-2 to UA-5 and UA′-1 to UA′-4 were produced in the same manner as in Example 1. Table 1 shows the weight average molecular weight of urethane (meth) acrylate.
表中に略記した配合材料の詳細は次の通りである。
ポリカプロラクトンジオール（数平均分子量５３０）：（株）ダイセル製「プラクセル２０５Ｕ」
ポリカプロラクトンジオール（数平均分子量８３０）：（株）ダイセル製「プラクセル２０８」
ポリカプロラクトントリオール（数平均分子量８５０）：（株）ダイセル製「プラクセル３０８」
ポリカプロラクトンジオール（数平均分子量２，０００）：（株）ダイセル製「プラクセル２２０」
ポリテトラメチレングリコール（数平均分子量６５０）：保土ヶ谷化学工業（株）製「ＰＴＧ６５０」
ポリプロピレングリコール（数平均分子量７００）：日油（株）製「ユニオールＤ−７００」
イソホロンジイソシアネート：住化バイエルウレタン製（株）「デスモジュールＩ」
ビス（４−イソシアナトシクロヘキシル）メタン：住化バイエルウレタン（株）「デスモジュールＷ」
２−ヒドロキシエチルアクリレート：大阪有機化学工業（株）製「ＨＥＡ」
ペンタエリスリトールトリアクリレート：大阪有機化学工業（株）製「ビスコート＃３００」
＜実施例１〜９、比較例１〜８＞
Details of the compounding materials abbreviated in the table are as follows.
Polycaprolactone diol (number average molecular weight 530): “Placcel 205U” manufactured by Daicel Corporation
Polycaprolactone diol (number average molecular weight 830): “Placcel 208” manufactured by Daicel Corporation
Polycaprolactone triol (number average molecular weight 850): “Placcel 308” manufactured by Daicel Corporation
Polycaprolactone diol (number average molecular weight 2,000): “Placcel 220” manufactured by Daicel Corporation
Polytetramethylene glycol (number average molecular weight 650): “PTG650” manufactured by Hodogaya Chemical Co., Ltd.
Polypropylene glycol (number average molecular weight 700): “Uniol D-700” manufactured by NOF Corporation
Isophorone diisocyanate: Sumika Bayer Urethane Co., Ltd. “Desmodur I”
Bis (4-isocyanatocyclohexyl) methane: Sumika Bayer Urethane Co., Ltd. “Desmodur W”
2-hydroxyethyl acrylate: “HEA” manufactured by Osaka Organic Chemical Industry Co., Ltd.
Pentaerythritol triacrylate: “Biscoat # 300” manufactured by Osaka Organic Chemical Industry Co., Ltd.
<Examples 1-9, Comparative Examples 1-8>
合成例１〜５、比較合成例１〜４で得られたウレタンアクリレート、表２記載の単官能モノマーおよび表３又は表４記載の添加剤、溶剤を表３又は表４記載の重量で５０ｍＬ褐色スクリュー管に量りとり、ボルテックスミキサーにて１分間混合させ活性エネルギー線硬化型樹脂組成物を得た。得られた活性エネルギー線硬化型樹脂組成物を、１２５μｍＰＥＴフィルム（東洋紡績（株）製コスモシャインＡ４３００）上に乾燥膜厚が２５μｍとなるよう塗工し、８０℃にて５分間乾燥して有機溶剤を蒸発させた。続いて、８０Ｗ／ｃｍの無電極ＵＶランプ（Ｈバルブ）を用いて積算光量１，０００ｍＪ／ｃｍ2のエネルギー量を照射することで硬化物試験片を得た。この硬化物試験片を用いて以下の評価を行った。 The urethane acrylate obtained in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 4, the monofunctional monomer described in Table 2, the additive described in Table 3 or Table 4, and the solvent are 50 mL brown in the weight described in Table 3 or Table 4. The active energy ray-curable resin composition was obtained by weighing into a screw tube and mixing with a vortex mixer for 1 minute. The obtained active energy ray-curable resin composition was applied onto a 125 μm PET film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) so that the dry film thickness was 25 μm, and dried at 80 ° C. for 5 minutes to form an organic material. The solvent was evaporated. Then, the cured | curing material test piece was obtained by irradiating the energy amount of 1000 mJ / cm < 2 > of integrated light quantities using an 80W / cm electrodeless UV lamp (H bulb). The following evaluation was performed using this hardened | cured material test piece.
温度２５℃、相対湿度６０ＲＨ％の雰囲気下、硬化物表面に対して真鍮ブラシで１ｋｇ荷重で１０往復擦り、硬化物表面に入った傷が復元するか否か、または傷が復元するまでの時間を測定し、下記の基準により判定した。
傷が１０秒以内に復元する。（評価：◎）
１０秒後に傷が認められるが、５分経過後には復元する。（評価：○）
５分経過しても傷が復元しない。（評価：×）
＜表面硬度＞
In an atmosphere of 25 ° C. and relative humidity of 60 RH%, the cured product surface is rubbed 10 times with a brass brush with a 1 kg load to determine whether or not the scratches that have entered the cured product surface are restored or the time until the scratches are restored. Was measured and judged according to the following criteria.
The wound is restored within 10 seconds. (Evaluation: ◎)
Scratches are observed after 10 seconds, but will recover after 5 minutes. (Evaluation: ○)
The wound does not recover after 5 minutes. (Evaluation: ×)
<Surface hardness>
ＪＩＳ Ｋ５６００に準拠して、荷重７５０ｇの条件で引っ掻き硬度（鉛筆法）を測定し、下記の基準で評価した。
鉛筆硬度が２Ｈ以上（評価：◎）
鉛筆硬度がＦ〜Ｈ（評価：○）
鉛筆硬度が２Ｂ以下（評価：×）
＜伸張性＞
Based on JIS K5600, the scratch hardness (pencil method) was measured under the condition of a load of 750 g and evaluated according to the following criteria.
Pencil hardness is 2H or more (Evaluation: ◎)
Pencil hardness is F ~ H (evaluation: ○)
Pencil hardness is 2B or less (evaluation: x)
<Extension>
得られた硬化物試験片を基材から剥離し、を１０ｃｍ幅に切断し、オートグラフ試験機（（株）島津製作所製ＡＧＳ−Ｊ）を用いて、温度２５℃、相対湿度６０ＲＨ％、引張速度５０ｍｍ／ｍｉｎ、チャック間距離５０ｍｍの条件で引張試験を行い、測定した破断伸度を下記の基準で評価した。
破断伸度が２００％以上（評価：◎）
破断伸度が１００％以上〜２００％未満（評価：○）
破断伸度が１００％未満（評価：×）
＜密着性＞
The obtained cured product test piece was peeled off from the substrate, cut to a width of 10 cm, and using an autograph tester (AGS-J, manufactured by Shimadzu Corporation), temperature 25 ° C., relative humidity 60 RH%, tensile A tensile test was performed under the conditions of a speed of 50 mm / min and a distance between chucks of 50 mm, and the measured elongation at break was evaluated according to the following criteria.
Breaking elongation is 200% or more (evaluation: ◎)
Elongation at break is 100% or more and less than 200% (evaluation: ○)
Breaking elongation is less than 100% (evaluation: x)
<Adhesion>
ＪＩＳ Ｋ５６００に準拠して、碁盤目剥離試験を行い、下記の基準で評価した（これを、「初期密着性」とする）。また、硬化膜試験片を温度８０℃、相対湿度９０ＲＨ％の条件下で４８時間静置した後、初期密着性と同様の方法で密着性を評価した（これを、「耐湿熱密着性」とする）。
◎：残存した碁盤目の面積が１００％（評価：◎）
○：残存した碁盤目の面積が９０％以上〜９９％未満（評価：○）
△：残存した碁盤目の面積が９０％未満（評価：×）
＜耐薬品性＞
In accordance with JIS K5600, a cross-cut peel test was performed and evaluated according to the following criteria (this is referred to as “initial adhesion”). Moreover, after leaving the cured film test piece to stand for 48 hours under the conditions of a temperature of 80 ° C. and a relative humidity of 90 RH%, the adhesion was evaluated by the same method as the initial adhesion (this is referred to as “moisture and heat resistant adhesion”). To do).
A: The area of the remaining grid is 100% (evaluation: A)
○: The area of the remaining grid is 90% to less than 99% (evaluation: ○)
Δ: The area of the remaining grid is less than 90% (evaluation: x)
<Chemical resistance>
硬化膜表面に５％ＮａＯＨ水溶液又は５％塩酸をスポイトで０．１ｇ滴下し、温度２５℃で２４時間静置した後、水を含んだ脱脂綿で薬品を拭き取ったあとの表面状態を目視で観察し、下記の基準で評価した。
薬品による痕がまったく確認されない。（評価：○）
薬品による痕など硬化膜に異常が確認できる。（評価：×）
Drop 0.1g of 5% NaOH aqueous solution or 5% hydrochloric acid on the surface of the cured film with a dropper, leave it at a temperature of 25 ° C for 24 hours, and then visually observe the surface condition after wiping off the chemical with absorbent cotton containing water And evaluated according to the following criteria.
There are no traces of chemicals. (Evaluation: ○)
Abnormalities can be confirmed in the cured film such as chemical marks. (Evaluation: ×)
表３に示すように、実施例１〜９は自己修復性、表面硬度、伸張性、密着性、耐薬品性がいずれも良好な樹脂組成物である。
比較例１はウレタンアクリレート（Ａ）の重量平均分子量が本発明の範囲より小さいために硬化物の自己修復性と伸張性が不十分である。比較例２はウレタンアクリレート（Ａ）の原料に用いるポリカプロラクトンポリオールの分子量が本発明の範囲より大きいために硬化物の自己修復性、表面硬度、湿熱試験後の密着性、耐薬品性が不十分である。比較例３はウレタンアクリレート（Ａ）の原料にポリカプロラクトンポリオールでなくポリテトラメチレングリコールを用いているために表面硬度、湿熱試験後の密着性、耐薬品性が不十分である。比較例４はウレタンアクリレート（Ａ）の原料にポリカプロラクトンポリオールでなくポリプロピレングリコールを用いているために自己修復性、表面硬度、伸張性、湿熱試験後の密着性、耐薬品性が不十分である。比較例５は単独重合体としたときのガラス転移点が本発明の範囲より低い単官能モノマーを用いているために自己修復性、表面硬度、湿熱試験後の密着性、耐薬品性が不十分である。比較例６は単独重合体としたときのガラス転移点が本発明の範囲より高い単官能モノマーを用いているために自己修復性と伸張性が不十分である。比較例７単官能モノマー（Ｂ）を用いていないために自己修復性と表面硬度が不十分である。比較例８はウレタンアクリレート（Ａ）と単官能モノマー（Ｂ）の質量比が本発明の範囲を外れるために自己修復性、表面硬度、伸張性、湿熱試験後の密着性、耐薬品性が不十分である。
As shown in Table 3, Examples 1 to 9 are resin compositions having good self-healing properties, surface hardness, extensibility, adhesion, and chemical resistance.
In Comparative Example 1, since the weight average molecular weight of the urethane acrylate (A) is smaller than the range of the present invention, the self-healing property and stretchability of the cured product are insufficient. In Comparative Example 2, since the molecular weight of the polycaprolactone polyol used as a raw material for the urethane acrylate (A) is larger than the range of the present invention, the self-healing property of the cured product, the surface hardness, the adhesion after the wet heat test, and the chemical resistance are insufficient. It is. Since Comparative Example 3 uses polytetramethylene glycol instead of polycaprolactone polyol as a raw material for urethane acrylate (A), surface hardness, adhesion after a wet heat test, and chemical resistance are insufficient. Since Comparative Example 4 uses polypropylene glycol instead of polycaprolactone polyol as a raw material for urethane acrylate (A), self-healing property, surface hardness, extensibility, adhesion after wet heat test, and chemical resistance are insufficient. . Since Comparative Example 5 uses a monofunctional monomer having a glass transition point lower than the range of the present invention when a homopolymer is used, self-repairability, surface hardness, adhesion after wet heat test, and chemical resistance are insufficient. It is. In Comparative Example 6, since a monofunctional monomer having a glass transition point higher than the range of the present invention when used as a homopolymer is used, self-repairability and extensibility are insufficient. Comparative Example 7 Since the monofunctional monomer (B) is not used, the self-repairing property and the surface hardness are insufficient. In Comparative Example 8, since the mass ratio of the urethane acrylate (A) and the monofunctional monomer (B) is out of the range of the present invention, the self-healing property, surface hardness, extensibility, adhesion after wet heat test, and chemical resistance are not good. It is enough.
Claims (1)
ウレタン（メタ）アクリレート（Ａ）： 数平均分子量３００〜９００のポリカプロラクトンポリオール（ａ１）、脂肪族又は脂環式ジイソシアネート（ａ２）、水酸基含有（メタ）アクリレート（ａ３）を反応させて得られる重量平均分子量３，０００〜３０，０００のウレタン（メタ）アクリレート
単官能（メタ）アクリレート（Ｂ）： 単独重合体としたときのガラス転移温度が−３０〜３５℃であり、下記の式（１）で表される単官能（メタ）アクリレート
Urethane (meth) acrylate (A): Weight obtained by reacting a polycaprolactone polyol (a1) having a number average molecular weight of 300 to 900, an aliphatic or alicyclic diisocyanate (a2), and a hydroxyl group-containing (meth) acrylate (a3). Urethane (meth) acrylate having an average molecular weight of 3,000 to 30,000 Monofunctional (meth) acrylate (B): The glass transition temperature when it is a homopolymer is −30 to 35 ° C., and the following formula (1) Monofunctional (meth) acrylate represented by
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