JP6780256B2 - Active energy ray-curable resin composition - Google Patents
Active energy ray-curable resin composition Download PDFInfo
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- JP6780256B2 JP6780256B2 JP2016022389A JP2016022389A JP6780256B2 JP 6780256 B2 JP6780256 B2 JP 6780256B2 JP 2016022389 A JP2016022389 A JP 2016022389A JP 2016022389 A JP2016022389 A JP 2016022389A JP 6780256 B2 JP6780256 B2 JP 6780256B2
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- acrylate
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- urethane
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- 239000011342 resin composition Substances 0.000 title claims description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 101
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 34
- 150000002009 diols Chemical class 0.000 claims description 31
- 150000003077 polyols Chemical class 0.000 claims description 27
- 229920001610 polycaprolactone Polymers 0.000 claims description 25
- 239000004632 polycaprolactone Substances 0.000 claims description 25
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 22
- 229920005862 polyol Polymers 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 230000001588 bifunctional effect Effects 0.000 claims description 12
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 30
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 18
- 238000007664 blowing Methods 0.000 description 18
- -1 2-hydroxypropyl Chemical group 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000010408 film Substances 0.000 description 12
- 239000005058 Isophorone diisocyanate Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 11
- 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 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 description 10
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Polymers OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 9
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 6
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 5
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 239000002216 antistatic agent Substances 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000007423 decrease Effects 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
- 238000009826 distribution Methods 0.000 description 2
- JZMPIUODFXBXSC-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCOC(N)=O JZMPIUODFXBXSC-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 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
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- ROHUXHMNZLHBSF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCC(CN=C=O)CC1 ROHUXHMNZLHBSF-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- RESLDRQKMNCSIC-UHFFFAOYSA-N 2-(2-hydroxyethoxycarbonyl)benzoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCOC(=O)C1=CC=CC=C1C(O)=O RESLDRQKMNCSIC-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
- 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
- 229910001369 Brass Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 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
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000000654 additive Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002519 antifouling agent 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
- 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing 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
- 230000008719 thickening Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 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
Landscapes
- Paints Or Removers (AREA)
- 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、強度や耐薬品性に優れた硬化膜を形成することから、各種基材の表面を保護する目的で用いられている。
近年では、携帯電話やパソコン、テレビなどの液晶ディスプレイ等の画像表示装置用保護フィルム、反射防止フィルム、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、スイッチボタンなど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。
このような用途で用いられる硬化性樹脂組成物には、良好な美観を長期間維持するための耐傷つき性、耐薬品性、耐候性、密着性や、成型加工を容易にし、生産性を向上させるための伸張性などの物性が求められる。これらの物性を良好なものとすべく、様々な検討がなされている。
The curable resin composition is used for the purpose of protecting the surface of various base materials because it is immediately cured by irradiation with active energy rays to form a cured film having excellent strength and chemical resistance.
In recent years, protective films for image display devices such as liquid crystal displays of mobile phones, personal computers, and televisions, antireflection films, optical films or sheets such as prism sheets, housings for electronic devices and home appliances, display panels, and switch buttons. The use for insert molding or in-mold transfer film used for such as is expanding.
The curable resin composition used in such applications has scratch resistance, chemical resistance, weather resistance, adhesion to maintain a good appearance for a long period of time, facilitates molding, and improves productivity. Physical properties such as extensibility are required to make it. Various studies have been conducted to improve these physical properties.
例えば特許文献１では、特定範囲の分子量のポリカプロラクトンポリオールを用いてウレタンアクリレートを合成し、さらに単独でポリマーとしたときに高いＴｇを示すアクリレートモノマーを配合する方法が開示されている。この組成物はポリオレフィン系フィルムに対して良好な密着性を示すが、高分子量のポリオールを用いるために硬化膜の強度が低く、傷付きやすいという課題があった。
特許文献２では、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カプロラクトン変性ヒドロキシエチルアクリレートを用いて合成したウレタンアクリレートが開示されている。また、特許文献３では、ポリカプロラクトン変性ポリオールと、ポリイソシアネートと、水酸基含有アクリレートを用いて合成したウレタンアクリレートが開示されている。これらの組成物は剛直な構造と柔軟な構造をバランス良く有し、硬化膜表面についた凹み傷を経時的に修復する自己修復性を示すことで、高い耐傷つき性を実現している。しかし、用途はレンズシートを想定しているためにＰＥＴフィルムへの密着性にのみ言及しており、ＡＢＳに対する密着性は十分でなかった。また、伸張性も未だ十分ではない。
特許文献４では、ポリカプロラクトン変性ポリオールと、ポリイソシアネートと、水酸基含有アクリレートを用いて合成したウレタンアクリレートと、これ以外のウレタンジアクリレート、およびアクリレートモノマーを配合する方法が開示されている。この組成物は良好な硬度を示すものの、硬度を上げるためにウレタンジアクリレートの割合を増やすと伸張性が著しく低下するため、耐傷つき性と伸張性の両立が困難であった。
このように、従来の方法では、指触り性、耐傷つき性、硬度、伸張性、基材への密着性、および耐カール性を同時に満たすことが困難であった。
For example, Patent Document 1 discloses a method of synthesizing urethane acrylate using a polycaprolactone polyol having a molecular weight in a specific range, and further blending an acrylate monomer showing a high Tg when made into a polymer alone. Although this composition exhibits good adhesion to a polyolefin-based film, there is a problem that the strength of the cured film is low due to the use of a high molecular weight polyol and it is easily damaged.
Patent Document 2 discloses a urethane acrylate synthesized by using an isocyanurate modified product of hexamethylene diisocyanate and a polycaprolactone-modified hydroxyethyl acrylate. Further, Patent Document 3 discloses a urethane acrylate synthesized by using a polycaprolactone-modified polyol, a polyisocyanate, and a hydroxyl group-containing acrylate. These compositions have a well-balanced rigid structure and a flexible structure, and exhibit high scratch resistance by exhibiting self-healing property for repairing dents on the surface of the cured film over time. However, since the application is intended for a lens sheet, only the adhesion to the PET film is mentioned, and the adhesion to the ABS is not sufficient. Also, the extensibility is still insufficient.
Patent Document 4 discloses a method of blending a polycaprolactone-modified polyol, a polyisocyanate, a urethane acrylate synthesized using a hydroxyl group-containing acrylate, another urethane diacrylate, and an acrylate monomer. Although this composition exhibits good hardness, it is difficult to achieve both scratch resistance and extensibility because the extensibility is remarkably lowered when the proportion of urethane diacrylate is increased in order to increase the hardness.
As described above, it has been difficult to simultaneously satisfy the touch property, scratch resistance, hardness, extensibility, adhesion to the substrate, and curl resistance by the conventional method.
本発明の課題は、良好な指触り性、自己修復性、表面硬度、伸張性、各種プラスチック基材への密着性、耐カール性を示す硬化物を得ることの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 an active energy ray-curable resin composition capable of obtaining a cured product exhibiting good touch property, self-healing property, surface hardness, extensibility, adhesion to various plastic substrates, and curl resistance. To provide things.
本発明者らは、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構造の単官能（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上記の課題を解決することの知見を見出し、本発明を完成するに至った。
すなわち、本発明は次の〔１〕〜〔２〕である。
As a result of diligent studies to solve the above problems, the present inventors have found an active energy ray-curable resin composition containing a urethane (meth) acrylate having a specific structure and a monofunctional (meth) acrylate having a specific structure. We have found the knowledge to solve the problems and have completed the present invention.
That is, the present invention is the following [1] to [2].
〔１〕下記のウレタン（メタ）アクリレート（Ａ）、および、下記の単官能または二官能（メタ）アクリレート（Ｂ）を含有し、前記ウレタン（メタ）アクリレート（Ａ）と前記単官能または二官能（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）、数平均分子量５０〜３００のジオール（ａ２）、脂肪族または脂環式ジイソシアネート（ａ３）、および水酸基含有（メタ）アクリレート（ａ４）のウレタン化反応物であり、
前記ジオール（ａ２）に対する前記ポリカプロラクトンポリオール（ａ１）のモル比（ａ１）／（ａ２）が０．２〜１０．０であり、
前記ポリカプロラクトンポリオール（ａ１）と前記ジオール（ａ２）の水酸基の合計と、前記脂肪族または脂環式ジイソシアネート（ａ３）のイソシアネート基の当量比（（ａ１）＋（ａ２））／（ａ３）が０．６５〜０．８５であり、
重量平均分子量が２，０００〜３０，０００であるウレタン（メタ）アクリレート
＜単官能または二官能（メタ）アクリレート（Ｂ）＞
脂環式構造、芳香族環、複素環構造の内少なくとも一つの構造を有する、単官能または二官能（メタ）アクリレート
[1] The following urethane (meth) acrylate (A) and the following monofunctional or bifunctional (meth) acrylate (B) are contained, and the urethane (meth) acrylate (A) and the monofunctional or bifunctional are contained. An active energy ray-curable resin composition having a mass ratio of (meth) acrylate (B) of (A) / (B) = 50/50 to 95/5.
<Urethane (meth) acrylate (A)>
Urethaneization of polycaprolactone polyols (a1) with a number average molecular weight of 300 to 900, diols (a2) with a number average molecular weight of 50 to 300, aliphatic or alicyclic diisocyanates (a3), and hydroxyl group-containing (meth) acrylates (a4). It is a reactant and
The molar ratio (a1) / (a2) of the polycaprolactone polyol (a1) to the diol (a2) is 0.2 to 10.0.
The sum of the hydroxyl groups of the polycaprolactone polyol (a1) and the diol (a2) and the equivalent ratio of the isocyanate groups of the aliphatic or alicyclic diisocyanate (a3) ((a1) + (a2)) / (a3) It is 0.65 to 0.85,
Urethane (meth) acrylate having a weight average molecular weight of 2,000 to 30,000 <monofunctional or bifunctional (meth) acrylate (B)>
A monofunctional or bifunctional (meth) acrylate having at least one of an alicyclic structure, an aromatic ring, and a heterocyclic structure.
〔２〕前記の〔１〕に記載の活性エネルギー線硬化型樹脂組成物を活性エネルギー線で硬化させて得られる硬化物。 [2] A cured product obtained by curing the active energy ray-curable resin composition according to the above [1] with an active energy ray.
本発明の活性エネルギー線硬化型樹脂組成物によれば、良好な指触り性、自己修復性、硬度、伸張性を有し、かつ基材への密着性と耐カール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, a cured product having good touch property, self-healing property, hardness, extensibility, and good adhesion to a substrate and curl resistance can be obtained. Obtainable.
以下、本発明をさらに詳細に説明する。
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）および単官能または二官能（メタ）アクリレート（Ｂ）を含有する。以下に、各成分について説明する。
Hereinafter, the present invention will be described in more detail.
The active energy ray-curable resin composition of the present invention contains urethane (meth) acrylate (A) and monofunctional or bifunctional (meth) acrylate (B). Each component will be described below.
＜ウレタン（メタ）アクリレート（Ａ）＞
本発明に用いるウレタン（メタ）アクリレート（Ａ）は、次の（ａ１）〜（ａ４）の成分のウレタン化反応物である。
・数平均分子量３００〜９００のポリカプロラクトンポリオール（ａ１）、
・数平均分子量５０〜３００のジオール（ａ２）、
・脂肪族または脂環式ジイソシアネート（ａ３）、および
・水酸基含有（メタ）アクリレート（ａ４）
<Urethane (meth) acrylate (A)>
The urethane (meth) acrylate (A) used in the present invention is a urethanization reaction product of the following components (a1) to (a4).
Polycaprolactone polyol (a1) with a number average molecular weight of 300 to 900,
A diol (a2) having a number average molecular weight of 50 to 300,
-Aliphatic or alicyclic diisocyanate (a3), and-Hydroxy group-containing (meth) acrylate (a4)
［ポリカプロラクトンポリオール（ａ１）］
ポリカプロラクトンポリオール（ａ１）は、本発明の組成物に柔軟性を付与し、良好な伸張性を持たせるために用いる。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などが挙げられ、単独または２種以上を組み合わせて使用することができる。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、伸張性が十分でなく、自己修復性も損なわれる。一方、数平均分子量が９００を超えると伸張性は十分であるが、柔らかくなりすぎるために表面硬度が低下する。傷付きに弱くなるために自己修復性が不十分となる。以上の傾向から、ポリカプロラクトンポリオール（ａ１）の数平均分子量は３００〜９００であり、好ましくは４００〜７００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２０５ＵＣ」、「プラクセルＬ２０５ＡＬ」、「プラクセル２０８」、「プラクセル３０３」、「プラクセル３０５」、「プラクセル３０５Ｔ」、「プラクセル３０８」などが挙げられる。
[Polycaprolactone polyol (a1)]
Polycaprolactone polyol (a1) is used to impart flexibility to the composition of the present invention and to provide good extensibility. Examples of the polycaprolactone polyol include polycaprolactone diol and polycaprolactone triol, which can be used alone or in combination of two or more. If the number average molecular weight of the polycaprolactone polyol is less than 300, the extensibility is not sufficient and the self-healing property is also impaired. On the other hand, when the number average molecular weight exceeds 900, the extensibility is sufficient, but the surface hardness decreases because it becomes too soft. Insufficient self-healing because it is vulnerable to scratches. From the above tendency, the number average molecular weight of the polycaprolactone polyol (a1) is 300 to 900, preferably 400 to 700. Available commercial products of polycaprolactone polyol include "Plaxel 205", "Plaxel 205H", "Plaxel 205U", "Plaxel 205UC", "Plaxel L205AL", "Plaxel 208", and "Plaxel" manufactured by Daicel Corporation. 303 ”,“ Praxel 305 ”,“ Praxel 305T ”,“ Praxel 308 ”and the like.
［数平均分子量５０〜３００のジオール（ａ２）］
数平均分子量５０〜３００のジオール（ａ２）は、本発明の組成物に強靭性を付与し、良好な伸張性と硬度を両立して発揮させるために用いる。数平均分子量５０〜３００のジオール（ａ２）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、１，２−プロピレングリコール、１，３−プロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ネオペンチルグリコールなどが挙げられる。これらは単独で用いても良く、２種以上を併用して用いることもできる。
[Diol (a2) having a number average molecular weight of 50 to 300]
The diol (a2) having a number average molecular weight of 50 to 300 is used to impart toughness to the composition of the present invention and to exhibit both good extensibility and hardness at the same time. Examples of the diol (a2) having a number average molecular weight of 50 to 300 include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, and 1,4-butanediol. , 1,5-Pentanediol, 1,6-Hexanediol, neopentyl glycol and the like. These may be used alone or in combination of two or more.
［脂肪族または脂環式ジイソシアネート（ａ３）］
本発明に用いるイソシアネートとしては、耐黄変性に優れることから、脂肪族ジイソシアネート、または脂環式ジイソシアネートを用いることが好ましい。具体的には、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、１，３−ビスイソシアナトメチルシクロヘキサン、１，４−ビスイソシアナトメチルシクロヘキサン、ノルボルナンジイソシアネート、ジシクロヘキシルメタン−４，４’−ジイソシアネートなどが挙げられる。これらの中でも、より強靭性に優れた硬化膜が得られることから、イソホロンジイソシアネート、ジシクロヘキシルメタン−４，４’−ジイソシアネートが好ましい。これらは単独で用いても良く、２種以上を併用して用いることもできる。
[Aliphatic or alicyclic diisocyanate (a3)]
As the isocyanate used in the present invention, it is preferable to use an aliphatic diisocyanate or an alicyclic diisocyanate because it is excellent in yellowing resistance. Specific examples thereof include hexamethylene diisocyanate, isophorone diisocyanate, 1,3-bisisocyanatomethylcyclohexane, 1,4-bisisocyanatomethylcyclohexane, norbornane diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate. Among these, isophorone diisocyanate and dicyclohexylmethane-4,4'-diisocyanate are preferable because a cured film having more excellent toughness can be obtained. These may be used alone or in combination of two or more.
［水酸基含有（メタ）アクリレート（ａ４）］
水酸基含有（メタ）アクリレート（ａ４）は、ウレタンプレポリマーの末端に重合性基を付加し、成分（Ａ）にラジカル反応性を付与する成分であり、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。具体的には、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）アクリレートなどの不飽和脂肪酸ヒドロキシアルキルエステル、２−ヒドロキシエチル（メタ）アクリレートなどの不飽和脂肪酸ヒドロキシアルキルエステルの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などが挙げられる。これら水酸基含有（メタ）アクリレートは、１種単独で用いてもよく、２種以上を組み合わせても良い。自己修復性、硬度、伸張性に優れる硬化物が得られるという観点から、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）が好ましく、特に伸張性に優れるという観点から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）がより好ましい。
[Hydroxy group-containing (meth) acrylate (a4)]
The hydroxyl group-containing (meth) acrylate (a4) is a component that adds a polymerizable group to the end of the urethane prepolymer to impart radical reactivity to the component (A), and contains at least one or more hydroxyl groups in one molecule. , A hydroxyl group-containing (meth) acrylate having one or more (meth) acryloyl groups. Specifically, unsaturated fatty acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and the like. Ε-Caprolactone adduct of unsaturated fatty acid hydroxyalkyl ester (average addition molars 1-10), polyethylene glycol (average addition molars 1-10) mono (meth) acrylate, polypropylene glycol (average addition molars 1-10) Examples thereof include mono (meth) acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate. These hydroxyl group-containing (meth) acrylates may be used alone or in combination of two or more. 2-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl from the viewpoint of obtaining a cured product having excellent self-healing property, hardness, and extensibility. The ε-caprolactone adduct of (meth) acrylate (average addition mole number 1 to 10) is preferable, and the ε-caprolactone adduct of 2-hydroxyethyl (meth) acrylate (average addition molar number 1) is particularly excellent from the viewpoint of excellent extensibility. 10) is more preferable.
本発明に用いるウレタン（メタ）アクリレート（Ａ）の重量平均分子量は２，０００〜３０，０００である。重量平均分子量が２，０００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硬度が不十分である。好ましくは３，０００〜２０，０００であり、より好ましくは４，０００〜１０，０００である。 The weight average molecular weight of the urethane (meth) acrylate (A) used in the present invention is 2,000 to 30,000. If the weight average molecular weight is less than 2,000, the self-healing property and extensibility are insufficient, and if it exceeds 30,000, the self-healing property and hardness are insufficient. It is preferably 3,000 to 20,000, more preferably 4,000 to 10,000.
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）成分と、分子量５０〜３００のジオール（ａ２）のモル比は、（ａ１）／（ａ２）で表したとき、０．２〜１０．０であり、好ましくは０．３〜８．０である。この範囲内であれば、（ａ１）成分および（ａ２）成分は十分量となり、本願特有の配合の効果が得られる。１０．０を超えると、すなわち（ａ１）成分が極端に多い場合、（ａ２）成分を配合したことによる効果がほとんど得られない。０．２未満、すなわち（ａ２）成分が極端に多い場合、伸張性が低下する上、生成するウレタン結合による増粘の影響が大きくなりすぎ、ウレタン（メタ）アクリレート（Ａ）の取扱いが困難になる。 In the production of urethane (meth) acrylate (A), the molar ratio of the polycaprolactone polyol (a1) component to the diol (a2) having a molecular weight of 50 to 300 is 0.2 when represented by (a1) / (a2). It is ~ 10.0, preferably 0.3 ~ 8.0. Within this range, the components (a1) and (a2) are in sufficient amounts, and the effect of the formulation peculiar to the present application can be obtained. If it exceeds 10.0, that is, when the component (a1) is extremely large, the effect of blending the component (a2) is hardly obtained. If it is less than 0.2, that is, if the component (a2) is extremely large, the extensibility is lowered and the effect of thickening due to the urethane bond formed becomes too large, making it difficult to handle the urethane (meth) acrylate (A). Become.
ウレタン（メタ）アクリレート（Ａ）の製造において、（ａ１）成分と（ａ２）成分の水酸基の合計と（ａ３）成分のイソシアネート基の当量比は、（（ａ１）＋（ａ２））／（ａ３）で表したとき、０．６５〜０．８５であり、好ましくは０．７５〜０．８５である。この範囲内であれば、ウレタン化反応における分子量が過大にならずウレタン（メタ）アクリレート（Ａ）の取扱いに問題が生じないし、自己修復性を十分に発揮することができ、硬度も十分となる。０．８５を超えると、すなわち（ａ１）成分と（ａ２）成分の合計が多い場合、ウレタン化反応において分子量が大きくなりすぎ、自己修復性が低下し、ウレタン（メタ）アクリレート（Ａ）の取扱いが困難になる。０．６５未満、すなわち（ａ３）成分の量が多い場合、ウレタン化反応において分子量が小さくなり、自己修復性を十分に発揮することが出来ず、硬度も不十分となる。 In the production of urethane (meth) acrylate (A), the total of the hydroxyl groups of the components (a1) and (a2) and the equivalent ratio of the isocyanate groups of the component (a3) are ((a1) + (a2)) / (a3). ), It is 0.65 to 0.85, preferably 0.75 to 0.85. Within this range, the molecular weight in the urethanization reaction does not become excessive, there is no problem in handling the urethane (meth) acrylate (A), self-healing property can be sufficiently exhibited, and the hardness becomes sufficient. .. If it exceeds 0.85, that is, when the total of the components (a1) and (a2) is large, the molecular weight becomes too large in the urethanization reaction, the self-healing property deteriorates, and the handling of urethane (meth) acrylate (A) Becomes difficult. If it is less than 0.65, that is, if the amount of the component (a3) is large, the molecular weight becomes small in the urethanization reaction, self-repairing property cannot be sufficiently exhibited, and the hardness becomes insufficient.
ウレタン（メタ）アクリレート（Ａ）の製造において、（ａ１）成分、（ａ２）成分および（ａ４）成分の水酸基の合計と（ａ３）成分のイソシアネート基の当量比は、（（ａ１）＋（ａ２）＋（ａ４））／（ａ３）で表したとき、好ましくは０．９〜１．１であり、より好ましくは０．９５〜１．０５である。この範囲内であれば、製造物の貯蔵安定性が高くなり、長期間安定的に保管することができる。 In the production of urethane (meth) acrylate (A), the total of the hydroxyl groups of the components (a1), (a2) and (a4) and the equivalent ratio of the isocyanate groups of the component (a3) are ((a1) + (a2). ) + (A4)) / (a3), it is preferably 0.9 to 1.1, and more preferably 0.95 to 1.05. Within this range, the storage stability of the product is high, and the product can be stably stored for a long period of time.
［ウレタン（メタ）アクリレート（Ａ）の製造］
上記の（ａ１）〜（ａ４）の成分を公知の常法によってウレタン化反応を行うことによって、本発明に用いるウレタン（メタ）アクリレート（Ａ）が得られる。例えば、反応容器中に成分（ａ１）〜（ａ４）を一括で投入し、ウレタン化触媒、重合禁止剤、黄変防止剤、有機溶剤を投入して反応させることができる。また、反応中の温度制御をし易くし、さらに得られるウレタン（メタ）アクリレート（Ａ）の分子量分布を制御しやすくなることから、まず成分（ａ１）〜（ａ３）、およびウレタン化触媒、重合禁止剤、黄変防止剤、有機溶剤を投入して、３０〜１００℃にて反応させたのち、さらに成分（ａ４）を投入して３０〜１００℃にて反応させる方法が好ましい。
[Manufacturing of urethane (meth) acrylate (A)]
The urethane (meth) acrylate (A) used in the present invention can be obtained by subjecting the above components (a1) to (a4) to a urethanization reaction by a known conventional method. For example, the components (a1) to (a4) can be put into the reaction vessel all at once, and the urethanization catalyst, the polymerization inhibitor, the yellowing inhibitor, and the organic solvent can be put into the reaction vessel to react. Further, since it is easy to control the temperature during the reaction and further to control the molecular weight distribution of the obtained urethane (meth) acrylate (A), first, the components (a1) to (a3), the urethanization catalyst, and the polymerization A method is preferable in which a banning agent, an anti-yellowing agent, and an organic solvent are added and reacted at 30 to 100 ° C., and then the component (a4) is further added and reacted at 30 to 100 ° C.
ウレタン化反応において、反応時間を短縮できることから、ウレタン化触媒を用いることが好ましい。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。 In the urethanization reaction, it is preferable to use a urethanization catalyst because the reaction time can be shortened. As the urethanization catalyst, an organotin compound such as dibutyltin dilaurate, an organic bismuth compound such as dibutylbismuth dilaurate, a tertiary amine such as triethylamine, and a quaternary ammonium such as tetraalkylammonium bromide 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 the reaction raw materials.
＜単官能または二官能（メタ）アクリレート（Ｂ）＞
本発明に用いる単官能または二官能（メタ）アクリレート（Ｂ）は、脂環式構造、芳香族環、複素環構造の内少なくとも一つの構造を有する、単官能または二官能（メタ）アクリレートであり、樹脂組成物の基材に対する密着性を付与し、さらに硬化後の樹脂組成物の伸張性を高める目的で用いられる。
<Monofunctional or bifunctional (meth) acrylate (B)>
The monofunctional or bifunctional (meth) acrylate (B) used in the present invention is a monofunctional or bifunctional (meth) acrylate having at least one of an alicyclic structure, an aromatic ring, and a heterocyclic structure. , The resin composition is used for the purpose of imparting adhesion to the substrate and further enhancing the extensibility of the resin composition after curing.
前記（メタ）アクリレートとしては、シクロヘキシル（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、ジシクロペンタニル（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、ジシクロペンタニルオキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレートなどの脂環式構造を有する（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、ノニルフェノキシポリエチレングリコール（メタ）アクリレート、フタル酸モノヒドロキシエチルアクリレート、エトキシ化o-フェニルフェノール（メタ）アクリレート、エトキシ化ビスフェノールAジ（メタ）アクリレート、トリシクロデカノールジ（メタ）アクリレートなどの芳香族環を有する（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、アクリロイルモルホリン、イミド（メタ）アクリレートなどの複素環構造を有する（メタ）アクリレートを用いることができる。 Examples of the (meth) acrylate include cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentanyloxyethyl (meth). (Meta) acrylate having an alicyclic structure such as acrylate and isobornyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, Monohydroxyethyl phthalate acrylate, o-phenylphenol (meth) acrylate ethoxylated, bisphenol A di (meth) acrylate ethoxylated, tricyclodecanoldi (meth) acrylate and other (meth) acrylates having an aromatic ring, tetrahydro A (meth) acrylate having a heterocyclic structure such as furfuryl (meth) acrylate, acryloyl morpholine, and imide (meth) acrylate can be used.
これらの中でも、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、エトキシ化o-フェニルフェノール（メタ）アクリレート、フェノキシポリエチレングリコール（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、ジシクロペンタニルオキシエチル（メタ）アクリレート、エトキシ化ビスフェノールAジ（メタ）アクリレートは、本発明の硬化物が良好な硬度と自己修復性を示すことから好ましく、フェノキシエチル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレートは、より優れた自己修復性と硬度、および良好な伸張性を示すため、さらに好ましい。 Among these, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, Dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and ethoxylated bisphenol A di (meth) acrylate are preferable because the cured product of the present invention exhibits good hardness and self-repairing property. , Phenoxyethyl (meth) acrylates, tetrahydrofurfuryl (meth) acrylates are even more preferred as they exhibit better self-healing and hardness and good extensibility.
＜活性エネルギー線硬化型樹脂組成物＞
本発明の活性エネルギー線樹脂組成物は、ウレタン（メタ）アクリレート（Ａ）と単官能または二官能（メタ）アクリレート（Ｂ）の質量比が（Ａ）／（Ｂ）＝５０／５０〜９５／５であることを特徴とし、好ましくは６０／４０〜９０／１０である。５０／５０未満では硬化性、硬化物の硬度、伸張性が十分でなく、９５／５を超えると硬化物の密着性が不十分となる。
<Active energy ray-curable resin composition>
In the active energy ray resin composition of the present invention, the mass ratio of urethane (meth) acrylate (A) to monofunctional or bifunctional (meth) acrylate (B) is (A) / (B) = 50/50 to 95 /. It is characterized by being 5, preferably 60/40 to 90/10. If it is less than 50/50, the curability, hardness and extensibility of the cured product are not sufficient, and if it exceeds 95/5, the adhesion of the cured product is insufficient.
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。 A photopolymerization initiator may be added to the active energy ray-curable resin composition of the present invention. Examples of the photopolymerization initiator include benzoin or benzoin alkyl ether such as benzoin and benzoin methyl ether; aromatic ketones such as benzophenone and benzoylbenzoic acid; benzyl ketal such as benzyl dimethyl ketal and benzyl diethyl ketal; 1-hydroxycyclohexyl. Acetophenone such as phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propane-1-one; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) Examples thereof include acylphosphine oxides such as phenylphosphine oxide.
さらに、任意成分として、本発明の効果を損なわない範囲で（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、有機溶剤等を配合することができる。 Further, as an optional component, a (meth) acrylic polymer, a surface conditioner, a leveling agent, a filler, a pigment, a silane coupling agent, an antistatic agent, an antifoaming agent, and an antifouling agent, as long as the effects of the present invention are not impaired. , Antistatic agent, ultraviolet absorber, light stabilizer, organic solvent and the like can be blended.
本発明の活性エネルギー線硬化性樹脂組成物を基材上に塗布硬化することによって、本発明の塗布硬化層を表面に有する硬化物を得ることができる。本発明の活性エネルギー線硬化型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出来る。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出来る。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、１００〜２，５００ｍＪ／ｃｍ2が好ましく、２００〜２，０００ｍＪ／ｃｍ2がより好ましい。照射時の雰囲気は空気中でも良く、窒素やアルゴン等の不活性ガス中で硬化しても良い。 By applying and curing the active energy ray-curable resin composition of the present invention on a substrate, a cured product having the coating and curing layer of the present invention on the surface can be obtained. As a method for curing the active energy ray-curable resin composition of the present invention, it is possible to select a light beam selected from a group of active energy rays such as infrared rays, visible rays, ultraviolet rays, X-rays, γ-rays, and electron beams. You can. As the method of irradiating the active energy rays, a usual method of curing the curable resin composition can be used. When ultraviolet rays are used as the active energy ray irradiation device, electrodeless lamps such as H-valves manufactured by Fusion UV Systems Co., Ltd., low-pressure mercury lamps, high-pressure mercury lamps, and ultra-high-pressure mercury lamps that have a spectral distribution in the wavelength range of 200 to 450 nm. , Xenon lamps, gallium lamps, metal halide lamps and the like. The dose of the active energy rays are usually 10~3,000mJ / cm 2 as the accumulated light quantity is preferably 100~2,500mJ / cm 2, 200~2,000mJ / cm 2 is more preferable. The atmosphere at the time of irradiation may be in air, and 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として有用である。 The active energy ray-curable resin composition of the present invention is useful as various coating agents for display screens, housings for mobile devices, decorative films, and the like.
以下に実施例を示す。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＞
撹拌装置、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８９．７ｇ、ジエチレングリコール（（株）日本触媒製）を１２．０ｇ、イソホロンジイソシアネート（住化コベストロウレタン（株）製デスモジュールＩ）を８３．５ｇ、酢酸ブチルを５０．０ｇ、ジブチルスズジラウレートを０．０３７ｇ投入し、空気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３．５０％以下であることを確認した。次に、ポリカプロラクトン変性ヒドロキシエチルアクリレート（（株）ダイセル製プラクセルＦＡ２Ｄ）を６４．７ｇ、メトキシハイドロキノンを０．０５ｇ投入した。空気を吹き込みながら内温を７５℃に保持して５時間反応させた後、イソシアネート基含有量が０．２％以下であることを確認し、重量平均分子量４，２４０のウレタンアクリレート（ＵＡ−１）を２９３．７ｇ得た。
An example is shown below. Unless otherwise specified, "parts" means parts by mass and "%" means% by mass.
<Synthesis Example 1: Production of Urethane (Meta) Acrylate (UA-1)>
89.7 g of polycaprolactone diol (Plaxel 205U manufactured by Daicel Corporation) and diethylene glycol (manufactured by Nippon Catalyst Co., Ltd.) having a number average molecular weight of 530 were placed in a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer. 12.0 g, isophorone diisocyanate (Death Module I manufactured by Sumika Cobestrolurethane Co., Ltd.) 83.5 g, butyl acetate 50.0 g, dibutyltin dilaurate 0.037 g were added, and the internal temperature was raised to 60 ° C while blowing air. After reacting with the mixture for 4 hours, it was confirmed by the method of JIS K 7301 that the isocyanate group content was 3.50% or less. Next, 64.7 g of polycaprolactone-modified hydroxyethyl acrylate (Plaxel FA2D manufactured by Daicel Corporation) and 0.05 g of methoxyhydroquinone were added. After keeping the internal temperature at 75 ° C. and reacting for 5 hours while blowing air, it was confirmed that the isocyanate group content was 0.2% or less, and a urethane acrylate (UA-1) having a weight average molecular weight of 4,240 was confirmed. ) Was obtained in an amount of 293.7 g.
＜合成例２：ウレタン（メタ）アクリレート（ＵＡ−２）の製造＞
撹拌装置、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３４．０ｇ、ジエチレングリコール（（株）日本触媒製）を２０．４ｇ、イソホロンジイソシアネート（住化コベストロウレタン（株）製デスモジュールＩ）を７１．３ｇ、酢酸ブチルを８５．７ｇ、ジブチルスズジラウレートを０．０３２ｇ投入し、空気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２．６６％以下であることを確認した。次に、ポリカプロラクトン変性ヒドロキシエチルアクリレート（（株）ダイセル製プラクセルＦＡ５）を８８．５ｇ、メトキシハイドロキノンを０．０４３ｇ投入した。空気を吹き込みながら内温を７５℃に保持して５時間反応させた後、イソシアネート基含有量が０．２％以下であることを確認し、重量平均分子量４，４９０のウレタンアクリレート（ＵＡ−２）を２９５．５ｇ得た。
<Synthesis Example 2: Production of Urethane (Meta) Acrylate (UA-2)>
34.0 g of polycaprolactone diol (Plaxel 205U manufactured by Daicel Corporation) and diethylene glycol (manufactured by Nippon Catalyst Co., Ltd.) having a number average molecular weight of 530 were placed in a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer. 20.4 g, isophorone diisocyanate (Death Module I manufactured by Sumika Cobestrolurethane Co., Ltd.) was added 71.3 g, butyl acetate 85.7 g, and dibutyltin dilaurate 0.032 g were added, and the internal temperature was raised to 60 ° C while blowing air. After reacting for 4 hours, it was confirmed that the isocyanate group content was 2.66% or less by the method of JIS K 7301. Next, 88.5 g of polycaprolactone-modified hydroxyethyl acrylate (Plaxel FA5 manufactured by Daicel Corporation) and 0.043 g of methoxyhydroquinone were added. After keeping the internal temperature at 75 ° C. and reacting for 5 hours while blowing air, it was confirmed that the isocyanate group content was 0.2% or less, and urethane acrylate (UA-2) having a weight average molecular weight of 4,490 was confirmed. ) Was obtained in an amount of 295.5 g.
＜合成例３：ウレタン（メタ）アクリレート（ＵＡ−３）の製造＞
撹拌装置、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５５．５ｇ、ジエチレングリコール（（株）日本触媒製）を１６．７ｇ、イソホロンジイソシアネート（住化コベストロウレタン（株）製デスモジュールＩ）を６９．８ｇ、酢酸ブチルを８５．７ｇ、ジブチルスズジラウレートを０．０３２ｇ投入し、空気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２．０２％以下であることを確認した。次に、ポリカプロラクトン変性ヒドロキシエチルアクリレート（（株）ダイセル製プラクセルＦＡ５）を７２．２ｇ、メトキシハイドロキノンを０．０４３ｇ投入した。空気を吹き込みながら内温を７５℃に保持して５時間反応させた後、イソシアネート基含有量が０．２％以下であることを確認し、重量平均分子量６，５４０のウレタンアクリレート（ＵＡ−３）を２９４．３ｇ得た。
<Synthesis Example 3: Production of Urethane (Meta) Acrylate (UA-3)>
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, 55.5 g of polycaprolactone diol (Plaxel 205U manufactured by Daicel Corporation) and diethylene glycol (manufactured by Nippon Catalyst Co., Ltd.) having a number average molecular weight of 530 was placed. 16.7 g, isophorone diisocyanate (Death Module I manufactured by Sumika Cobestrolurethane Co., Ltd.) 69.8 g, butyl acetate 85.7 g, dibutyltin dilaurate 0.032 g were added, and the internal temperature was raised to 60 ° C while blowing air. After reacting for 4 hours, it was confirmed that the isocyanate group content was 2.02% or less by the method of JIS K 7301. Next, 72.2 g of polycaprolactone-modified hydroxyethyl acrylate (Plaxel FA5 manufactured by Daicel Corporation) and 0.043 g of methoxyhydroquinone were added. After keeping the internal temperature at 75 ° C. and reacting for 5 hours while blowing air, it was confirmed that the isocyanate group content was 0.2% or less, and a urethane acrylate (UA-3) having a weight average molecular weight of 6,540 was confirmed. ) Was obtained in an amount of 294.3 g.
＜合成例４：ウレタン（メタ）アクリレート（ＵＡ−４）の製造＞
撹拌装置、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１２２．３ｇ、ジエチレングリコール（（株）日本触媒製）を３．５ｇ、イソホロンジイソシアネート（住化コベストロウレタン（株）製デスモジュールＩ）を７３．２ｇ、酢酸ブチルを８５．７ｇ、ジブチルスズジラウレートを０．０３２ｇ投入し、空気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２．０３％以下であることを確認した。次に、２−ヒドロキシエチルアクリレート（（株）日本触媒製ＨＥＡ）を１５．３ｇ、メトキシハイドロキノンを０．０４３ｇ投入した。空気を吹き込みながら内温を７５℃に保持して５時間反応させた後、イソシアネート基含有量が０．２％以下であることを確認し、重量平均分子量５，２００のウレタンアクリレート（ＵＡ−４）を２９４．６ｇ得た。
<Synthesis Example 4: Production of Urethane (Meta) Acrylate (UA-4)>
122.3 g of polycaprolactone diol (Plaxel 205U manufactured by Daicel Corporation) and diethylene glycol (manufactured by Nippon Catalyst Co., Ltd.) having a number average molecular weight of 530 were placed in a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer. Add 3.5 g, isophorone diisocyanate (Death Module I manufactured by Sumika Cobestrourethane Co., Ltd.) 73.2 g, butyl acetate 85.7 g, and dibutyltin dilaurate 0.032 g, and keep the internal temperature at 60 ° C while blowing air. After reacting for 4 hours, it was confirmed that the isocyanate group content was 2.03% or less by the method of JIS K 7301. Next, 15.3 g of 2-hydroxyethyl acrylate (HEA manufactured by Nippon Shokubai Co., Ltd.) and 0.043 g of methoxyhydroquinone were added. After keeping the internal temperature at 75 ° C. and reacting for 5 hours while blowing air, it was confirmed that the isocyanate group content was 0.2% or less, and a urethane acrylate (UA-4) having a weight average molecular weight of 5,200 was confirmed. ) Was obtained in an amount of 294.6 g.
＜合成例５：ウレタン（メタ）アクリレート（ＵＡ−５）の製造＞
撹拌装置、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８３０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２０８）を１３６．２ｇ、ジエチレングリコール（（株）日本触媒製）を１１．６ｇ、イソホロンジイソシアネート（住化コベストロウレタン（株）製デスモジュールＩ）を８１．０ｇ、酢酸ブチルを５０．０ｇ、ジブチルスズジラウレートを０．０３７ｇ投入し、空気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２．８７％以下であることを確認した。次に、２−ヒドロキシエチルアクリレート（（株）日本触媒製ＨＥＡ）を２１．２ｇ、メトキシハイドロキノンを０．０５ｇ投入した。空気を吹き込みながら内温を７５℃に保持して５時間反応させた後、イソシアネート基含有量が０．２％以下であることを確認し、重量平均分子量４，３８０のウレタンアクリレート（ＵＡ−５）を２９２．８ｇ得た。
<Synthesis Example 5: Production of Urethane (Meta) Acrylate (UA-5)>
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, 136.2 g of polycaprolactone diol (Plaxel 208 manufactured by Daicel Corporation) and diethylene glycol (manufactured by Nippon Catalyst Co., Ltd.) having a number average molecular weight of 830 was placed. 11.6 g, isophorone diisocyanate (Death Module I manufactured by Sumika Cobestrolurethane Co., Ltd.) was added at 81.0 g, butyl acetate at 50.0 g, and dibutyltin dilaurate at 0.037 g, and the internal temperature was raised to 60 ° C while blowing air. After reacting for 4 hours, it was confirmed that the isocyanate group content was 2.87% or less by the method of JIS K 7301. Next, 21.2 g of 2-hydroxyethyl acrylate (HEA manufactured by Nippon Shokubai Co., Ltd.) and 0.05 g of methoxyhydroquinone were added. After maintaining the internal temperature at 75 ° C. and reacting for 5 hours while blowing air, it was confirmed that the isocyanate group content was 0.2% or less, and a urethane acrylate (UA-5) having a weight average molecular weight of 4,380 was confirmed. ) Was obtained in an amount of 292.8 g.
＜比較合成例１：ウレタン（メタ）アクリレート（ＵＡ’−１）の製造＞
撹拌装置、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１２０．７ｇ、ジエチレングリコール（（株）日本触媒製）を１．６ｇ、イソホロンジイソシアネート（住化コベストロウレタン（株）製デスモジュールＩ）を７１．９ｇ、酢酸ブチルを５０．０ｇ、ジブチルスズジラウレートを０．０３７ｇ投入し、空気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２．８２％以下であることを確認した。次に、ポリカプロラクトン変性ヒドロキシエチルアクリレート（（株）ダイセル製プラクセルＦＡ２Ｄ）を５５．７ｇ、メトキシハイドロキノンを０．０５ｇ投入した。空気を吹き込みながら内温を７５℃に保持して５時間反応させた後、イソシアネート基含有量が０．２％以下であることを確認し、重量平均分子量５，０７０のウレタンアクリレート（ＵＡ’−１）を２９２．８ｇ得た。
<Comparative Synthesis Example 1: Production of Urethane (Meta) Acrylate (UA'-1)>
In a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer, 120.7 g of polycaprolactone diol (Plaxel 205U manufactured by Daicel Corporation) and diethylene glycol (manufactured by Nippon Catalyst Co., Ltd.) having a number average molecular weight of 530 was placed. 1.6 g, isophorone diisocyanate (Death Module I manufactured by Sumika Cobestrourethane Co., Ltd.) was added 71.9 g, butyl acetate 50.0 g, and dibutyltin dilaurate 0.037 g were added, and the internal temperature was raised to 60 ° C while blowing air. After reacting with the mixture for 4 hours, it was confirmed by the method of JIS K 7301 that the isocyanate group content was 2.82% or less. Next, 55.7 g of polycaprolactone-modified hydroxyethyl acrylate (Plaxel FA2D manufactured by Daicel Corporation) and 0.05 g of methoxyhydroquinone were added. After keeping the internal temperature at 75 ° C. and reacting for 5 hours while blowing air, it was confirmed that the isocyanate group content was 0.2% or less, and urethane acrylate (UA'-) having a weight average molecular weight of 5,070 was confirmed. 1) was obtained in an amount of 292.8 g.
＜比較合成例２：ウレタン（メタ）アクリレート（ＵＡ’−２）の製造＞
撹拌装置、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２，０００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２２０）を１５８．３ｇ、ジエチレングリコール（（株）日本触媒製）を８．４ｇ、イソホロンジイソシアネート（住化コベストロウレタン（株）製デスモジュールＩ）を４６．９ｇ、酢酸ブチルを５０．０ｇ、ジブチルスズジラウレートを０．０３７ｇ投入し、空気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１．７５％以下であることを確認した。次に、ポリカプロラクトン変性ヒドロキシエチルアクリレート（（株）ダイセル製プラクセルＦＡ２Ｄ）を３６．３ｇ、メトキシハイドロキノンを０．０５ｇ投入した。空気を吹き込みながら内温を７５℃に保持して５時間反応させた後、イソシアネート基含有量が０．２％以下であることを確認し、重量平均分子量７，５８０のウレタンアクリレート（ＵＡ’−２）を２８８．９ｇ得た。
<Comparative Synthesis Example 2: Production of Urethane (Meta) Acrylate (UA'-2)>
158.3 g of polycaprolactone diol (Plaxel 220 manufactured by Daicel Corporation) having a number average molecular weight of 2,000 and diethylene glycol (manufactured by Nippon Catalyst Co., Ltd.) in a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer. ), 46.9 g of isophorone diisocyanate (Death Module I manufactured by Sumika Cobestrolurethane Co., Ltd.), 50.0 g of butyl acetate, and 0.037 g of dibutyltin dilaurate, and the internal temperature is adjusted while blowing air. After keeping the temperature at 60 ° C. and reacting for 4 hours, it was confirmed by the method of JIS K 7301 that the isocyanate group content was 1.75% or less. Next, 36.3 g of polycaprolactone-modified hydroxyethyl acrylate (Plaxel FA2D manufactured by Daicel Corporation) and 0.05 g of methoxyhydroquinone were added. After keeping the internal temperature at 75 ° C. and reacting for 5 hours while blowing air, it was confirmed that the isocyanate group content was 0.2% or less, and a urethane acrylate (UA'-) having a weight average molecular weight of 7,580 was confirmed. 2) was obtained in an amount of 288.9 g.
＜比較合成例３：ウレタン（メタ）アクリレート（ＵＡ’−３）の製造＞
撹拌装置、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８８．６ｇ、ジエチレングリコール（（株）日本触媒製）を１４．２ｇ、イソホロンジイソシアネート（住化コベストロウレタン（株）製デスモジュールＩ）を７４．２ｇ、酢酸ブチルを１００．０ｇ、ジブチルスズジラウレートを０．０３０ｇ投入し、空気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１．０６％以下であることを確認した。次に、ポリカプロラクトン変性ヒドロキシエチルアクリレート（（株）ダイセル製プラクセルＦＡ２Ｄ）を２３．０ｇ、メトキシハイドロキノンを０．０４ｇ投入した。空気を吹き込みながら内温を７５℃に保持して５時間反応させた後、イソシアネート基含有量が０．２％以下であることを確認し、重量平均分子量９，５７０のウレタンアクリレート（ＵＡ’−３）を２９５．５ｇ得た。
<Comparative Synthesis Example 3: Production of Urethane (Meta) Acrylate (UA'-3)>
88.6 g of polycaprolactone diol (Plaxel 205U manufactured by Daicel Corporation) and diethylene glycol (manufactured by Nippon Catalyst Co., Ltd.) having a number average molecular weight of 530 were placed in a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer. 14.2 g, isophorone diisocyanate (Death Module I manufactured by Sumika Cobestrolurethane Co., Ltd.) was added at 74.2 g, butyl acetate at 100.0 g, and dibutyltin dilaurate at 0.030 g, and the internal temperature was raised to 60 ° C while blowing air. After reacting with the mixture for 4 hours, it was confirmed by the method of JIS K 7301 that the isocyanate group content was 1.06% or less. Next, 23.0 g of polycaprolactone-modified hydroxyethyl acrylate (Plaxel FA2D manufactured by Daicel Corporation) and 0.04 g of methoxyhydroquinone were added. After keeping the internal temperature at 75 ° C. and reacting for 5 hours while blowing air, it was confirmed that the isocyanate group content was 0.2% or less, and the urethane acrylate (UA'-) having a weight average molecular weight of 9,570 was confirmed. 3) was obtained in an amount of 295.5 g.
＜比較合成例４：ウレタン（メタ）アクリレート（ＵＡ’−４）の製造＞
撹拌装置、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７００のポリプロピレングリコール（（株）日油製ユニオールＤ−７００）を９７．８ｇ、ジエチレングリコール（（株）日本触媒製）を９．９ｇ、イソホロンジイソシアネート（住化コベストロウレタン（株）製デスモジュールＩ）を６８．９ｇ、酢酸ブチルを５０．０ｇ、ジブチルスズジラウレートを０．０３７ｇ投入し、空気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３．００％以下であることを確認した。次に、ポリオキシプロピレンモノアクリレート（（株）日油製ブレンマーＡＰ−４００）を７３．３ｇ、メトキシハイドロキノンを０．０５ｇ投入した。空気を吹き込みながら内温を７５℃に保持して５時間反応させた後、イソシアネート基含有量が０．２％以下であることを確認し、重量平均分子量５，１５０のウレタンアクリレート（ＵＡ’−４）を２９２．５ｇ得た。
<Comparative Synthesis Example 4: Production of Urethane (Meta) Acrylate (UA'-4)>
97.8 g of polypropylene glycol (Uniol D-700 manufactured by Nichiyu Co., Ltd.) with a number average molecular weight of 700 and diethylene glycol (manufactured by Japanese Industrial Standards Co., Ltd.) in a four-necked flask equipped with a stirrer, an air introduction tube, and a thermometer. ), 68.9 g of isophorone diisocyanate (Death Module I manufactured by Sumika Cobestrolurethane Co., Ltd.), 50.0 g of butyl acetate, and 0.037 g of dibutyltin dilaurate, and the internal temperature is adjusted while blowing air. After holding at 60 ° C. and reacting for 4 hours, it was confirmed by the method of JIS K 7301 that the isocyanate group content was 3.00% or less. Next, 73.3 g of polyoxypropylene monoacrylate (Blemmer AP-400 manufactured by NOF CORPORATION) and 0.05 g of methoxyhydroquinone were added. After keeping the internal temperature at 75 ° C. and reacting for 5 hours while blowing air, it was confirmed that the isocyanate group content was 0.2% or less, and a urethane acrylate (UA'-) having a weight average molecular weight of 5,150 was confirmed. 4) was obtained in an amount of 292.5 g.
＜実施例１〜１１、比較例１〜７＞
合成例１〜５、および比較合成例１〜４で得られたウレタンアクリレート、表２記載のアクリレートモノマーおよび表３または表４に記載の添加剤、溶剤を表３または表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。
<Examples 1 to 11 and Comparative Examples 1 to 7>
The urethane acrylates obtained in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 4, the acrylate monomers shown in Table 2, and the additives and solvents shown in Table 3 or Table 4 are 50 mL by weight shown in Table 3 or Table 4. Weighed in a brown screw tube and mixed with a vortex mixer for 1 minute to obtain an active energy ray-curable resin composition.
指触り性、自己修復性、硬度、耐カール性の評価を行う試験片を、以下の方法で作製した。得られた活性エネルギー線硬化型樹脂組成物を、１００μｍＰＥＴ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℃の恒温槽内に５分間静置し、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を得た。 Test pieces for evaluating touchability, self-healing property, hardness, and curl resistance were prepared by the following methods. The obtained active energy ray-curable resin composition is coated on a 100 μm PET film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) so that the dry film thickness is 25 μm, and is allowed to stand in a constant temperature bath at 80 ° C. for 5 minutes. It was placed and the organic solvent was evaporated. Subsequently, a cured product was obtained by irradiating an energy amount of an integrated light amount of 1,000 mJ / cm 2 using an 80 W / cm electrodeless UV lamp (H bulb).
伸張性の評価を行う試験片を、以下の方法で作製した。得られた活性エネルギー線硬化型樹脂組成物を、脱脂処理を行ったガラス基板上に乾燥膜厚が１００μｍとなるよう塗工し、８０℃の恒温槽内に５分間静置し、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を得た。得られた硬化物を静かにガラス基板から剥離したのち、型抜き器を用いてダンベル型試験片を作製した。 A test piece for evaluating extensibility was prepared by the following method. The obtained active energy ray-curable resin composition is coated on a degreased glass substrate so that the dry film thickness is 100 μm, and allowed to stand in a constant temperature bath at 80 ° C. for 5 minutes to apply an organic solvent. Evaporated. Subsequently, a cured product was obtained by irradiating an energy amount of an integrated light amount of 1,000 mJ / cm 2 using an 80 W / cm electrodeless UV lamp (H bulb). The obtained cured product was gently peeled from the glass substrate, and then a dumbbell-shaped test piece was prepared using a die-cutting device.
密着性の評価を行う試験片を、以下の方法で作製した。得られた活性エネルギー線硬化型樹脂組成物を、２ｍｍＡＢＳ樹脂上に乾燥膜厚が２５μｍとなるよう塗工し、８０℃の恒温槽内に５分間静置し、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を得た。 A test piece for evaluating the adhesion was prepared by the following method. The obtained active energy ray-curable resin composition was coated on a 2 mm ABS resin so as to have a dry film thickness of 25 μm, and allowed to stand in a constant temperature bath at 80 ° C. for 5 minutes to evaporate the organic solvent. Subsequently, a cured product was obtained by irradiating an energy amount of an integrated light amount of 1,000 mJ / cm 2 using an 80 W / cm electrodeless UV lamp (H bulb).
＜指触り性＞
得られた硬化物の表面を指でなぞり、タック感の有無で判定した。
○： タック感なし
×： タック感あり
＜自己修復性＞
<Finger touch>
The surface of the obtained cured product was traced with a finger, and the presence or absence of a tack feeling was determined.
○: No tack feeling ×: Tack feeling <Self-healing>
温度２５℃、相対湿度６０ＲＨ％の雰囲気下、真鍮ブラシを用いて硬化物表面を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５秒未満で復元する
○： 傷が５秒以上１０秒未満で復元する
△： 傷が１０秒以上５分未満で復元する
×： ５分経過後も傷が復元しない
In an atmosphere of a temperature of 25 ° C. and a relative humidity of 60 RH%, the surface of the cured product is rubbed 10 times with a load of 1 kg using a brass brush to determine whether or not the scratches on the surface of the cured product are restored, or the time until the scratches are restored. Was measured and judged according to the following criteria.
◎: Scratch is restored in less than 5 seconds ○: Scratch is restored in 5 seconds or more and less than 10 seconds △: Scratch is restored in 10 seconds or more and less than 5 minutes ×: Scratch is not restored even after 5 minutes have passed
＜硬度＞
ＪＩＳ Ｋ ５６００に準拠して、荷重７５０ｇの条件で引掻き硬度（鉛筆法）を測定し、傷がつかない中で最も硬い鉛筆硬度を結果とし、下記の基準で評価した。
◎： 鉛筆硬度がＨ以上
○： 鉛筆硬度がＨＢ〜Ｆ
△： 鉛筆硬度がＢ
×： 鉛筆硬度が２Ｂ以下
<Hardness>
In accordance with JIS K 5600, the scratch hardness (pencil method) was measured under the condition of a load of 750 g, and the hardest pencil hardness without being scratched was obtained as a result and evaluated according to the following criteria.
◎: Pencil hardness is H or higher ○: Pencil hardness is HB to F
Δ: Pencil hardness is B
×: Pencil hardness is 2B or less
＜伸張性＞
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
○： 破断伸度が１５０％以上２００％未満
△： 破断伸度が１００％以上１５０％未満
×： 破断伸度が１００％未満
<Extensibility>
A tensile test was conducted under the conditions of a tensile 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 ○: Breaking elongation is 150% or more and less than 200% Δ: Breaking elongation is 100% or more and less than 150% ×: Breaking elongation is less than 100%
＜密着性＞
ＪＩＳ Ｋ ５６００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。
◎： 残存面積が１００％
○： 残存面積が８０％以上１００％未満
×： 残存面積が８０％未満
<Adhesion>
A grid peeling test was conducted in accordance with JIS K 5600 and evaluated according to the following criteria.
⊚: Remaining area is 100%
◯: Residual area is 80% or more and less than 100% ×: Residual area is less than 80%
＜耐カール性＞
ＰＥＴ基材ごと１０ｃｍ×１０ｃｍの試験片を切り出し、水平な台の上に静置したときの４辺の浮き上がり高さを測定し、その平均値を下記の基準で評価した。
◎： 浮き上がり高さが２ｍｍ未満
○： 浮き上がり高さが２ｍｍ以上１０ｍｍ未満
×： 浮き上がり高さが１０ｍｍ以上
<Curl resistance>
A 10 cm × 10 cm test piece was cut out together with the PET substrate, and the heights of the four sides raised when the test piece was allowed to stand on a horizontal table were measured, and the average value was evaluated according to the following criteria.
⊚: Lifting height is less than 2 mm ○: Lifting height is 2 mm or more and less than 10 mm ×: Lifting height is 10 mm or more
表３に示すように、実施例１〜１１は指触り性、自己修復性、硬度、伸張性、密着性、耐カール性がいずれも良好な樹脂組成物である。 As shown in Table 3, Examples 1 to 11 are resin compositions having good touchability, self-healing property, hardness, extensibility, adhesion, and curl resistance.
一方、表４に示すように、本発明の範囲外となる比較例１〜７のような場合には、いずれかの物性を十分に満足することが出来ない。 On the other hand, as shown in Table 4, in the cases of Comparative Examples 1 to 7 which are outside the scope of the present invention, any of the physical properties cannot be sufficiently satisfied.
比較例１は（ａ２）成分を用いていないために架橋密度が低下し、硬度が不十分である。比較例２は（ａ１）成分の分子量が範囲を超えて大きく、架橋密度が低下し、硬度が不十分である。比較例３は（（ａ１）＋（ａ２））／（ａ３）の比が範囲を超えて高く、自己修復速度が低下する。また、アクリロイル基濃度が低下するため、タックが生じる。比較例４はウレタン（メタ）アクリレート（Ａ）の原料にポリプロピレングリコールを用いているために指触り性、自己修復性、硬度が不十分であり、また強度が著しく低下することから伸張性も不十分となる。さらにＡＢＳとの密着性が低下する。 In Comparative Example 1, since the component (a2) is not used, the crosslink density is lowered and the hardness is insufficient. In Comparative Example 2, the molecular weight of the component (a1) is large beyond the range, the crosslink density is lowered, and the hardness is insufficient. In Comparative Example 3, the ratio of ((a1) + (a2)) / (a3) is higher than the range, and the self-healing speed is lowered. In addition, the concentration of acryloyl groups decreases, so that tack occurs. In Comparative Example 4, since polypropylene glycol is used as the raw material of urethane (meth) acrylate (A), the touch property, self-healing property, and hardness are insufficient, and the strength is significantly reduced, so that the extensibility is also poor. Will be enough. Further, the adhesion with ABS is lowered.
比較例５はアクリレートモノマー（Ｂ）の構造中に環状構造を保有していないことから、硬度が不十分となり、伸びに対しても脆くなるため伸張性が低下し、さらに密着性も低下する。比較例６はアクリレートモノマー（Ｂ）を使用していないために、密着性が不十分である。比較例７はアクリレートモノマー（Ｂ）の割合が範囲を超えて多いために硬化不良が起き、タックが残る。また硬度と伸張性が低下する。 In Comparative Example 5, since the structure of the acrylate monomer (B) does not have a cyclic structure, the hardness becomes insufficient and the acrylate monomer (B) becomes brittle with respect to elongation, so that the extensibility is lowered and the adhesion is also lowered. Since Comparative Example 6 does not use the acrylate monomer (B), the adhesion is insufficient. In Comparative Example 7, since the proportion of the acrylate monomer (B) is too large to exceed the range, curing failure occurs and tack remains. It also reduces hardness and extensibility.
Claims (2)
＜ウレタン（メタ）アクリレート（Ａ）＞
数平均分子量４００〜７００のポリカプロラクトンポリオール（ａ１）、数平均分子量５０〜３００のジオール（ａ２）、脂肪族または脂環式ジイソシアネート（ａ３）、および水酸基含有（メタ）アクリレート（ａ４）のウレタン化反応物であり、
前記ジオール（ａ２）に対する前記ポリカプロラクトンポリオール（ａ１）のモル比（ａ１）／（ａ２）が０．２〜１０．０であり、
前記ポリカプロラクトンポリオール（ａ１）と前記ジオール（ａ２）の水酸基の合計と、前記脂肪族または脂環式ジイソシアネート（ａ３）のイソシアネート基の当量比（（ａ１）＋（ａ２））／（ａ３）が０．６５〜０．８５であり、
重量平均分子量が２，０００〜３０，０００であるウレタン（メタ）アクリレート
＜単官能または二官能（メタ）アクリレート（Ｂ）＞
脂環式構造、芳香族環、複素環構造の内少なくとも一つの構造を有する、単官能または二官能（メタ）アクリレート It contains the following urethane (meth) acrylate (A) and the following monofunctional or bifunctional (meth) acrylate (B), and the urethane (meth) acrylate (A) and the monofunctional or bifunctional (meth). An active energy ray-curable resin composition having a mass ratio of acrylate (B) of (A) / (B) = 50/50 to 95/5.
<Urethane (meth) acrylate (A)>
Urethaneization of polycaprolactone polyols (a1) with a number average molecular weight of 400 to 700 , diols (a2) with a number average molecular weight of 50 to 300, aliphatic or alicyclic diisocyanates (a3), and hydroxyl group-containing (meth) acrylates (a4). It is a reactant and
The molar ratio (a1) / (a2) of the polycaprolactone polyol (a1) to the diol (a2) is 0.2 to 10.0.
The sum of the hydroxyl groups of the polycaprolactone polyol (a1) and the diol (a2) and the equivalent ratio of the isocyanate groups of the aliphatic or alicyclic diisocyanate (a3) ((a1) + (a2)) / (a3) It is 0.65 to 0.85,
Urethane (meth) acrylate having a weight average molecular weight of 2,000 to 30,000 <monofunctional or bifunctional (meth) acrylate (B)>
Alicyclic structure, aromatic ring, to have at least one structure of a heterocyclic structure, a monofunctional or difunctional (meth) acrylate
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