JP2019052437A - Active energy ray-curable composition for floor material - Google Patents
Active energy ray-curable composition for floor material Download PDFInfo
- Publication number
- JP2019052437A JP2019052437A JP2017175709A JP2017175709A JP2019052437A JP 2019052437 A JP2019052437 A JP 2019052437A JP 2017175709 A JP2017175709 A JP 2017175709A JP 2017175709 A JP2017175709 A JP 2017175709A JP 2019052437 A JP2019052437 A JP 2019052437A
- Authority
- JP
- Japan
- Prior art keywords
- active energy
- energy ray
- parts
- flooring
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 97
- 239000000463 material Substances 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000010419 fine particle Substances 0.000 claims abstract description 23
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 238000009408 flooring Methods 0.000 claims description 57
- 239000011248 coating agent Substances 0.000 claims description 53
- 238000000576 coating method Methods 0.000 claims description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 34
- -1 polyethylene Polymers 0.000 claims description 27
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 21
- 239000011324 bead Substances 0.000 claims description 18
- 239000010434 nepheline Substances 0.000 claims description 16
- 229910052664 nepheline Inorganic materials 0.000 claims description 16
- 239000010435 syenite Substances 0.000 claims description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- 239000012965 benzophenone Substances 0.000 claims description 5
- 150000008062 acetophenones Chemical class 0.000 claims description 4
- 150000004056 anthraquinones Chemical class 0.000 claims description 4
- 150000008366 benzophenones Chemical class 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000006224 matting agent Substances 0.000 abstract description 5
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 20
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 20
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 18
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 18
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 11
- XRYLERSWWNDPDY-UHFFFAOYSA-N CCOC1=CC=CC=C1OC(=C)C(=O)O Chemical compound CCOC1=CC=CC=C1OC(=C)C(=O)O XRYLERSWWNDPDY-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 10
- 229910052753 mercury Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 8
- 238000011109 contamination Methods 0.000 description 8
- 125000004386 diacrylate group Chemical group 0.000 description 8
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 8
- 239000004566 building material Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- 229920000298 Cellophane Polymers 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- TVJCEUSYODDFLF-UHFFFAOYSA-N (2-ethoxyphenyl) prop-2-eneperoxoate Chemical compound C(C=C)(=O)OOC1=C(C=CC=C1)OCC TVJCEUSYODDFLF-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- 101000720524 Gordonia sp. (strain TY-5) Acetone monooxygenase (methyl acetate-forming) Proteins 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- UMLWXYJZDNNBTD-UHFFFAOYSA-N alpha-dimethylaminoacetophenone Natural products CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 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 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000011146 organic particle Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical class C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 2
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- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
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- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
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- QFUAZGOBONNJEI-UHFFFAOYSA-N 4-diphenylphosphorylphenol Chemical compound C1=CC(O)=CC=C1P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 QFUAZGOBONNJEI-UHFFFAOYSA-N 0.000 description 1
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- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- WYWZRNAHINYAEF-UHFFFAOYSA-N Padimate O Chemical compound CCCCC(CC)COC(=O)C1=CC=C(N(C)C)C=C1 WYWZRNAHINYAEF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- HXBPYFMVGFDZFT-UHFFFAOYSA-N allyl isocyanate Chemical compound C=CCN=C=O HXBPYFMVGFDZFT-UHFFFAOYSA-N 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 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
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011242 organic-inorganic particle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Floor Finish (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、主に階段や床などの建材用途に用いられる床材用活性エネルギー線硬化性組成物に関する。 The present invention relates to an active energy ray-curable composition for flooring mainly used for building materials such as stairs and floors.
活性エネルギー線硬化型組成物は従来のイソシアネートを硬化剤とする二液反応型ポリウレタン系組成物、アクリルポリオール系組成物、ポリエステル系組成物等に比べて、活性エネルギー線の照射により瞬時に硬化して塗膜性能も良好なことから、階段や床などの建材や家具や建具に使用される化粧シート用の塗料やコーティング剤として多く使用されている。
建材用途として求められる耐汚染性や耐摩耗性等の塗膜物性を向上させる目的とする光硬化性塗料組成物の硬化方法や製造方法の提案が成されている（例えば、特許文献１〜４）。また、耐汚染性や耐摩耗性等の塗膜物性の向上を目的とする活性エネルギー線硬化型組成物やそれを用いた化粧シートに関する提案も成されている（例えば、特許文献５、６）。
Active energy ray curable compositions are instantly cured by irradiation with active energy rays compared to conventional two-component reactive polyurethane-based compositions, acrylic polyol-based compositions, and polyester-based compositions that use isocyanate as a curing agent. Because of its good coating performance, it is often used as a paint or coating agent for decorative sheets used in building materials such as stairs and floors, furniture and fittings.
The proposal of the hardening method and manufacturing method of the photocurable coating composition aiming at improving the physical properties of a coating film, such as stain resistance and abrasion resistance, which are required as a building material application has been made (for example, Patent Documents 1 to 4). ). Moreover, the proposal regarding the active energy ray hardening-type composition aiming at the improvement of coating-film physical properties, such as pollution resistance and abrasion resistance, and a decorative sheet using the same is also made (for example, patent document 5, 6). .
活性エネルギー線硬化型組成物の良好な塗膜性能の一つとして、高光沢の塗膜が得られることがメリットとして挙げられるが、反対に低光沢の塗膜が得られ難いというデメリットがある。屋内建材の光沢は用途や意匠性により様々で、高光沢（グロス値で約６０以上）の仕上げは木目や印刷柄の透明感を強調するのに適しているが、昨今の床材を始めとする屋内建材は、照明器具の光が直接反射して質感が低下する事を抑制し、木質表面の適度な低光沢を持たせたマット調のものが好まれる傾向にある。
低光沢を実現して意匠性を向上させるために特定の艶消しシリカを用いた活性エネルギー線硬化型組成物が提案されてはいるが、その効果は決して十分であるとは言えない（例えば、特許文献７、８）。
また、低光沢化を目的とする艶消し剤を用いる事は有効であるが、配合できる量には限界があり、過度に艶消し剤を使用した場合は塗料の流動性や硬化塗膜の透明性が低下したり、塗膜表面がざらざらして手触りが悪くなるという問題が生じ易い。
One of the good coating performances of the active energy ray-curable composition is that a high-gloss coating can be obtained. On the other hand, there is a demerit that it is difficult to obtain a low-gloss coating. The gloss of indoor building materials varies depending on the application and design, and finishing with high gloss (gross value of about 60 or more) is suitable for emphasizing the transparency of wood grain and printed patterns. The indoor building materials that are used tend to be matte, which suppresses the deterioration of the texture due to direct reflection of the light from the luminaire, and has an appropriate low gloss on the wooden surface.
Although an active energy ray-curable composition using a specific matte silica has been proposed in order to achieve low gloss and improve design properties, its effect is never sufficient (for example, Patent Documents 7 and 8).
Also, it is effective to use a matting agent for the purpose of reducing gloss, but the amount that can be blended is limited, and if too much matting agent is used, the fluidity of the paint and the transparency of the cured coating film It is easy to cause the problem that the property is lowered or the surface of the coating film is rough and the touch becomes poor.
本発明の課題は、過度に艶消し剤を使用せずとも所望の低光沢化を図る事ができる床材用活性エネルギー線硬化性組成物を提供する事にある。 An object of the present invention is to provide an active energy ray-curable composition for flooring that can achieve a desired low gloss without using an excessive matting agent.
本発明者らは、活性エネルギー線重合性化合物（Ａ）、微粒子（Ｂ）、及び光重合開始剤（Ｃ）を含有する床材用活性エネルギー線硬化性組成物であって、（Ａ）である活性エネルギー線重合性基を１つ有する化合物（Ａ−１）と微粒子（Ｂ）が特定比率で含有する事で、微粒子（Ｂ）を過剰に使用することなく上記課題を解決するに至った。 The present inventors are an active energy ray-curable composition for a flooring material containing an active energy ray-polymerizable compound (A), fine particles (B), and a photopolymerization initiator (C), wherein (A) When the compound (A-1) having one active energy ray polymerizable group and the fine particles (B) are contained at a specific ratio, the above-described problems have been solved without excessive use of the fine particles (B). .
即ち本発明は、活性エネルギー線重合性化合物（Ａ）、微粒子（Ｂ）、及び光重合開始剤（Ｃ）を含有する床材用活性エネルギー線硬化性組成物であって、前記活性エネルギー線重合性化合物（Ａ）として活性エネルギー線重合性基を１つ有する化合物（Ａ−１）を前記組成物全量の２５〜４０質量％含有し、前記微粒子（Ｂ）を前記組成物全量の１０〜３５質量％含有し、且つ、式（１）で算出される値が２０〜５５であることを特徴とする床材用活性エネルギー線硬化性組成物を提供する。 That is, the present invention is an active energy ray-curable composition for flooring material comprising an active energy ray polymerizable compound (A), fine particles (B), and a photopolymerization initiator (C), wherein the active energy ray polymerization The compound (A-1) having one active energy ray polymerizable group as the active compound (A) is contained in an amount of 25 to 40% by mass of the total amount of the composition, and the fine particles (B) are contained in an amount of 10 to 35 of the total amount of the composition. Provided is an active energy ray-curable composition for flooring, which is contained by mass% and the value calculated by the formula (1) is 20 to 55.
（ａ−１）は前記組成物全量に対する活性エネルギー線重合性基を１つ有する化合物（Ａ−１）の質量％である。
(A-1) is the mass% of the compound (A-1) having one active energy ray polymerizable group with respect to the total amount of the composition.
また本発明は、活性エネルギー線重合性化合物（Ａ）として、（メタ）アクリロイル基を有するアクリル樹脂、ウレタン（メタ）アクリレート、エポキシ（メタ）アクリレート、ポリエステル（メタ）アクリレート、及び多官能（メタ）アクリレートからなる群から選ばれる活性エネルギー線重合性基を２つ以上有する化合物（Ａ−２）を含有する床材用活性エネルギー線硬化性組成物を提供する。 Further, the present invention provides an active energy ray polymerizable compound (A) as an acrylic resin having a (meth) acryloyl group, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyfunctional (meth). Provided is an active energy ray-curable composition for flooring, which contains a compound (A-2) having two or more active energy ray polymerizable groups selected from the group consisting of acrylates.
また本発明は、前記微粒子（Ｂ）が、シリカ、タルク、ネフェリン閃長岩、マイカ、ベントナイト、珪藻土、炭酸カルシウム、アルミナ白、ポリエチレンワックス、ポリプロピレンワックス、アクリルビーズ顔料、又はウレタンビーズ顔料である床材用活性エネルギー線硬化性組成物を提供する。 The present invention also provides the flooring wherein the fine particles (B) are silica, talc, nepheline syenite, mica, bentonite, diatomaceous earth, calcium carbonate, alumina white, polyethylene wax, polypropylene wax, acrylic bead pigment, or urethane bead pigment. An active energy ray-curable composition for use is provided.
また本発明は、前期光重合開始剤（Ｃ）が、ベンゾフェノン類、アントラキノン類、チオキサントン類、アセトフェノン類、アシルフォスフィンオキサイド類、及びメチルフェニルグリオキシエステル類からなる群から選ばれる少なくとも１種以上である床材用活性エネルギー線硬化性組成物を提供する。 In the present invention, the photopolymerization initiator (C) is at least one selected from the group consisting of benzophenones, anthraquinones, thioxanthones, acetophenones, acylphosphine oxides, and methylphenylglyoxyesters. An active energy ray-curable composition for flooring is provided.
更に本発明は、床材用活性エネルギー線硬化性組成物を表面に被覆し硬化してなる床材をも提供する。 Furthermore, this invention also provides the flooring material which coat | covers and hardens | cures the active energy ray curable composition for flooring materials on the surface.
本発明の床材用活性エネルギー線硬化性組成物は、過度に艶消し剤を使用せずとも所望の低光沢化を図る事ができる。 The active energy ray-curable composition for flooring of the present invention can achieve a desired low gloss without using an excessive matting agent.
本発明の床材用活性エネルギー線硬化性組成物は、活性エネルギー線重合性化合物（Ａ）、微粒子（Ｂ）、及び光重合開始剤（Ｃ）を含有し、前記活性エネルギー線重合性化合物（Ａ）として活性エネルギー線重合性基を１つ有する化合物（Ａ−１）を前記組成物全量の２５〜４０質量％含有し、前記微粒子（Ｂ）を前記組成物全量の１０〜３５質量％含有し、且つ、式（１）で算出される値が２０〜５５であることを必須とする。 The active energy ray-curable composition for flooring of the present invention contains an active energy ray-polymerizable compound (A), fine particles (B), and a photopolymerization initiator (C), and the active energy ray-polymerizable compound ( The compound (A-1) having one active energy ray polymerizable group as A) is contained in 25 to 40% by mass of the total amount of the composition, and the fine particles (B) are contained in 10 to 35% by mass of the total amount of the composition. In addition, it is essential that the value calculated by the expression (1) is 20 to 55.
（ａ−１）は前記組成物全量に対する活性エネルギー線重合性基を１つ有する化合物（Ａ−１）の質量％である。
(A-1) is the mass% of the compound (A-1) having one active energy ray polymerizable group with respect to the total amount of the composition.
前記活性エネルギー線重合性基を１つ有する化合物（Ａ−１）としては、通常活性エネルギー線硬化性組成物に使用される公知の（メタ）アクリルモノマーや、アリルモノマー、ビニルエーテルモノマー等から任意に選んで用いることができる。なお本発明において「（メタ）アクリル」とはアクリルとメタクリルとを総称したものである。
例えばアクリル酸やメタクリル酸などの不飽和カルボン酸又はそのエステル、例えばアルキル（メタ）アクリレート、シクロアルキル（メタ）アクリレート、ハロゲン化アルキル（メタ）アクリレート、アルコキシアルキル（メタ）アクリレート、ヒドロキシアルキル（メタ）アクリレート、アミノアルキル（メタ）アクリレート、アリル（メタ）アクリレート、グリシジル（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−（メタ）アクリレート、アルキレングリコール、ポリオキシアルキレングリコール基等を有する単官能（メタ）アクリレート、（メタ）アクリルアミド又はその誘導体、例えばアルキル基やヒドロキシアルキル基でモノ置換又はジ置換された（メタ）アクリルアミド、ジアセトン（メタ）アクリルアミド、Ｎ，Ｎ’−アルキレンビス（メタ）アクリルアミドなど、アリル化合物、例えばアリルアルコール、アリルイソシアネート、ジアリルフタレート、トリアリルイソシアヌレートなどを挙げることができる。
The compound (A-1) having one active energy ray-polymerizable group is arbitrarily selected from known (meth) acrylic monomers, allyl monomers, vinyl ether monomers and the like that are usually used in active energy ray-curable compositions. You can choose and use it. In the present invention, “(meth) acryl” is a general term for acrylic and methacrylic.
For example, unsaturated carboxylic acids such as acrylic acid and methacrylic acid or esters thereof, such as alkyl (meth) acrylate, cycloalkyl (meth) acrylate, halogenated alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) Monofunctional (meth) having acrylate, aminoalkyl (meth) acrylate, allyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, phenoxy- (meth) acrylate, alkylene glycol, polyoxyalkylene glycol group, etc. Acrylate, (meth) acrylamide or derivatives thereof, for example, (meth) acrylamide, diacetone (meth) acrylic mono- or disubstituted with alkyl or hydroxyalkyl groups Bromide, N, N'-alkylenebis (meth) acrylamide, allyl compounds such as allyl alcohol, allyl isocyanate, diallyl phthalate, and the like triallyl isocyanurate.
（メタ）アクリルモノマーの他の例としては、エチレングリコール単位（以下（ＥＯ）と総称）を分子内にもつポリエチレングリコール（ｎはポリエチレングリコールの繰り返し単位数でｎが３以上であり、およそ１４以下）ジ（メタ）アクリレート、トリメチロールプロパンＥＯ変性（ｎは３以上であり、およそ１４以下）トリ（メタ）アクリレート、フェノールＥＯ変性（ｎは２以上であり、およそ１４以下）（メタ）アクリレートや、水酸基を分子内にもつ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、ペンタエリスリトールトリ（メタ）アクリレート、フタル酸モノヒドロキシエチル（メタ）アクリレートなどを挙げることができる。
例えばフェノールＥＯ変性アクリレート、ノニルフェノールＥＯ変性アクリレート、エトキシジエチレングリコールアクリレート、β−カルボキシエチルアクリレート、イソボルニルアクリレート、エトキシ化フェニルアクリレート、エトキシ化フェニルアクリレート、エポキシ樹脂ハーフアクリレート等が挙げられる。中でもフェノールＥＯ変性アクリレートが硬化性や床材用途としての物性が良好で低臭気であるといった点で好ましい。
これらの（メタ）アクリルモノマーは単独で用いてもよいし２種以上組み合わせて用いてもよい。
As another example of the (meth) acrylic monomer, polyethylene glycol having an ethylene glycol unit (hereinafter collectively referred to as (EO)) in the molecule (n is the number of repeating units of polyethylene glycol, n is 3 or more, and approximately 14 or less) ) Di (meth) acrylate, trimethylolpropane EO modified (n is 3 or more, approximately 14 or less) Tri (meth) acrylate, phenol EO modified (n is 2 or more, approximately 14 or less) (meth) acrylate or 2-hydroxyethyl (meth) acrylate having a hydroxyl group in the molecule, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, monohydroxyethyl phthalate (meth) An acrylate etc. can be mentioned.
Examples thereof include phenol EO-modified acrylate, nonylphenol EO-modified acrylate, ethoxydiethylene glycol acrylate, β-carboxyethyl acrylate, isobornyl acrylate, ethoxylated phenyl acrylate, ethoxylated phenyl acrylate, and epoxy resin half acrylate. Among them, phenol EO-modified acrylate is preferable in that it has good curability and physical properties as a flooring material and has low odor.
These (meth) acrylic monomers may be used alone or in combination of two or more.
本発明の床材用活性エネルギー線硬化性組成物に使用する活性エネルギー線重合性化合物（Ａ）として、前記活性エネルギー線重合性基を１つ有する化合物（Ａ−１）の他に、
活性エネルギー線重合性基を２つ以上有する化合物（Ａ−２）として、例えば（メタ）アクリロイル基を有するアクリル樹脂、ウレタン（メタ）アクリレート、エポキシ（メタ）アクリレート、ポリエステル（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート等の多官能（メタ）アクリレート、ジビニルベンゼン；エチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレートのごとき多価アルコールの（メタ）アクリル酸エステル；アリル（メタ）アクリレート、ジアリルフタレート、ジアリルマレエート、トリアリルシアヌレートなどのアリル化合物；ジオールジビニルエーテル類；ブタジエン、イソプレン等のジエン類など及びこれらのオリゴマー類を併用してもよい。
As the active energy ray-polymerizable compound (A) used in the active energy ray-curable composition for flooring of the present invention, in addition to the compound (A-1) having one active energy ray-polymerizable group,
As the compound (A-2) having two or more active energy ray polymerizable groups, for example, an acrylic resin having a (meth) acryloyl group, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, trimethylol Polyfunctional (meth) acrylates such as propane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate, divinylbenzene; (meth) of polyhydric alcohols such as ethylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate Acrylic esters; allyl compounds such as allyl (meth) acrylate, diallyl phthalate, diallyl maleate, triallyl cyanurate; diol divinyl ethers; dienes such as butadiene, isoprene, etc. Beauty may be used in combination with these oligomers.
本発明の床材用活性エネルギー線硬化性組成物に使用する微粒子（Ｂ）として、は有機粒子及び／又は無機粒子を添加することにより、その硬化塗膜は低光沢で、より耐擦り傷性に優れるものとすることができる。前記微粒子（Ｂ）の内、無機粒子としては、シリカ、タルク、ネフェリン閃長岩、マイカ、ベントナイト、珪藻土、炭酸カルシウム、アルミナ白等が好ましく、また有機粒子としてはポリエチレンワックス、ポリプロピレンワックス、アクリルビーズ顔料、又はウレタンビーズ顔料が好ましく、また無機・有機の分け隔てなく複数混合し用いてもよい。 As the fine particles (B) used in the active energy ray-curable composition for flooring of the present invention, by adding organic particles and / or inorganic particles, the cured coating film has a low gloss and more scratch resistance. It can be excellent. Of the fine particles (B), the inorganic particles are preferably silica, talc, nepheline syenite, mica, bentonite, diatomaceous earth, calcium carbonate, white alumina and the like, and the organic particles are polyethylene wax, polypropylene wax, acrylic bead pigment. Or, urethane bead pigments are preferable, and a plurality of them may be mixed and used without being separated from inorganic and organic.
前記活性エネルギー線重合性化合物（Ａ）として活性エネルギー線重合性基を１つ有する化合物（Ａ−１）を前記組成物全量の２５〜４０質量％含有し、前記微粒子（Ｂ）を前記組成物全量の１０〜３５質量％含有し、且つ、式（１）で算出される値が２０〜５５であることを必須とする。 The active energy ray-polymerizable compound (A) contains 25 to 40% by mass of the compound (A-1) having one active energy ray-polymerizable group in the total amount of the composition, and the fine particles (B) are contained in the composition. It is essential that the content is 10 to 35% by mass of the total amount and the value calculated by the formula (1) is 20 to 55.
（ａ−１）は前記組成物全量に対する活性エネルギー線重合性基を１つ有する化合物（Ａ−１）の質量％である。
（１）式で示す比率が、２０〜５５の範囲であれば該組成物が硬化してなる塗工皮膜は十分な硬化性を保ちつつ効率的に低光沢性を兼備する事ができる。（１）式で示す比率が２０を下回ると低光沢性が低下する傾向にあり、また５５を上回るとコーティング剤としての流動性、転移性が損なわれる傾向となり易い。
(A-1) is the mass% of the compound (A-1) having one active energy ray polymerizable group with respect to the total amount of the composition.
If the ratio shown by Formula (1) is in the range of 20 to 55, the coating film formed by curing the composition can efficiently have low gloss while maintaining sufficient curability. When the ratio represented by the formula (1) is less than 20, the low glossiness tends to decrease, and when it exceeds 55, the fluidity and transferability as a coating agent tend to be impaired.
前記微粒子（Ｂ）の平均粒子径は１〜１０μｍが好ましく、その添加量の総計は組成物全量の１５〜２５質量％の範囲が好ましい。平均粒子サイズが１μｍ以上であれば十分は艶消し効果を発現でき、平均粒子サイズが１０μｍ以下であれば、表面の凹凸に汚れが入り込むことによる汚染性の悪化や、粒子の脱落・埋没による艶変化・傷付が発生が抑制できる。
一方で、添加量が１５質量％以上であれば低光沢性の効果が保持できる傾向となり、また２５質量％以下であれば、コーティング剤としての流動性、転移性が損なわれることなく好ましい。
The average particle diameter of the fine particles (B) is preferably 1 to 10 μm, and the total addition amount is preferably in the range of 15 to 25% by mass of the total amount of the composition. If the average particle size is 1 μm or more, the matte effect can be fully expressed. If the average particle size is 10 μm or less, the contamination is deteriorated due to dirt entering the surface irregularities, and the gloss caused by dropping or embedding of the particles. Changes and scratches can be suppressed.
On the other hand, if the addition amount is 15% by mass or more, the effect of low gloss tends to be maintained, and if it is 25% by mass or less, the fluidity and transferability as a coating agent are preferred without being impaired.
本発明の床材用活性エネルギー線硬化性組成物は、基材に塗布後、活性エネルギー線を照射することで硬化皮膜とすることができる。この活性エネルギー線とは、紫外線、電子線、α線、β線、γ線等の電離放射線が挙げられる。これらのなかでも特に、硬化性および利便性の点から紫外線（ＵＶ）が好ましい。 The active energy ray-curable composition for flooring of the present invention can be formed into a cured film by irradiating active energy rays after being applied to a substrate. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Of these, ultraviolet (UV) is particularly preferred from the viewpoint of curability and convenience.
本発明の床材用活性エネルギー線硬化性組成物を硬化させる活性エネルギー線としては、上記の通り、紫外線、電子線、α線、β線、γ線のような電離放射線であるが、具体的なエネルギー源又は硬化装置としては、例えば、殺菌灯、紫外線用蛍光灯、紫外線発光ダイオード（ＵＶ−ＬＥＤ）、カーボンアーク、キセノンランプ、複写用高圧水銀灯、中圧又は高圧水銀灯、超高圧水銀灯、無電極ランプ、メタルハライドランプ、自然光等を光源とする紫外線、又は走査型、カーテン型電子線加速器による電子線等が挙げられる。 The active energy rays for curing the active energy ray-curable composition for flooring of the present invention are ionizing radiations such as ultraviolet rays, electron beams, α rays, β rays, and γ rays, as described above. Examples of suitable energy sources or curing devices include germicidal lamps, ultraviolet fluorescent lamps, ultraviolet light emitting diodes (UV-LEDs), carbon arcs, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, and nothing. Examples thereof include an electrode lamp, a metal halide lamp, an ultraviolet ray using natural light as a light source, or an electron beam by a scanning type or curtain type electron beam accelerator.
本発明の床材用活性エネルギー線硬化性組成物を硬化させる活性エネルギー線として紫外線を用いる場合には、硬化性組成物の硬化剤として公知公用の光重合開始剤（Ｃ）を利用することが可能であり、前記光重合開始剤（Ｃ）が、ベンゾフェノン類、アントラキノン類、チオキサントン類、アセトフェノン類、アシルフォスフィンオキサイド類、又はメチルフェニルグリオキシエステル類からなる群から選ばれる少なくとも１種以上である事が好ましい。 When ultraviolet rays are used as an active energy ray for curing the active energy ray-curable composition for flooring of the present invention, a publicly known photopolymerization initiator (C) may be used as a curing agent for the curable composition. The photoinitiator (C) is at least one selected from the group consisting of benzophenones, anthraquinones, thioxanthones, acetophenones, acylphosphine oxides, or methylphenylglyoxyesters. Something is preferable.
前記ベンゾフェノン類としては、ベンゾフェノン、メチルベンゾフェノン、４，４’−ジクロロベンゾフェノン、４，４’−ビス（ジエチルアミノ）ベンゾフェノン、ミヒラーズケトン、４−ベンゾイル−４’−メチルジフェニルサルファイド等が挙げられる。
前記アントラキノン類としては、２−メチルアントラキノン、２−エチルアントラキノン、２−ｔｅｒｔ−ブチルアントラキノン、１−クロロアントラキノン、２−アミルアントラキノン、２−アミノアントラキノン等が挙げられる。
前記チオキサントン類としては、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２−クロロチオキサントン、２，４−ジイソプロピルチオキサントン等が挙げられる。
前記アセトフェノン類としては、アセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、１，１−ジクロロアセトフェノン、１−ヒドロキシシクロヘキシルフェニルケトン、１−フェニル−２−ヒドロキシ−２−メチルプロパン−１−オン、１−（４−ｉ−プロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、４−（２−ヒドロキシエトキシ）フェニル−（２−ヒドロキシ−２−プロピル）ケトン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノ−１−プロパノン、Ｎ，Ｎ−ジメチルアミノアセトフェノン等が挙げられる。
前記アシルフォスフィンオキサイド類としては、アシルホスフィンオキサイド系光重合開始剤としては、例えば、（２，６−ジメトキシベンゾイル）−２，４，６−ペンチルホスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルホスフィンオキサイド、２，４，６−トリメチルベンゾイル−ジフェニルホスフィンオキサイド、エチル−２，４，６−トリメチルベンゾイルフェニルホスフィネイト、ビス(２，４，６−トリメチルベンゾイル)−フェニルホスフィンオキサイド、（２，５−ジヒドロキシフェニル）ジフェニルホスフィンオキサイド、（ｐ−ヒドロキシフェニル）ジフェニルホスフィンオキサイド、ビス（ｐ−ヒドロキシフェニル）フェニルホスフィンオキサイド、及びトリス（ｐ−ヒドロキシフェニル）ホスフィンオキサイド等が挙げられる。
前記２，４，６−トリメチルベンゾイル−ジフェニルホスフィンオキサイドは、３８５ｎｍや３９５ｎｍに発光波長を有するＵＶ−ＬＥＤの発光波長領域に合致するＵＶ吸収波長を有することで、好適な硬化性が得られ、且つ、硬化皮膜の黄変が少ない点でより好ましい。
前記メチルフェニルグリオキシエステル類としては、オキシフェニル酢酸、２−［２−オキソ−２−フェニルアセトキシエトキシ］エチルエステルとオキシフェニル酢酸、２−（２−ヒドロキシエトキシ）エチルエステルの混合物が市販品として入手できる。
中でも、活性エネルギー線硬化性化合物溶解時に溶解液の着色が無く、経時による黄変の少ない、アセトフェノン類である１−ヒドロキシシクロヘキシルフェニルケトンがより好ましい。
Examples of the benzophenones include benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bis (diethylamino) benzophenone, Michler's ketone, 4-benzoyl-4′-methyldiphenyl sulfide, and the like.
Examples of the anthraquinones include 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone and the like.
Examples of the thioxanthones include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.
Examples of the acetophenones include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1-phenyl-2- Hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy- 2-propyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, N, N-dimethylaminoacetophenone and the like.
Examples of the acylphosphine oxides include acylphosphine oxide photopolymerization initiators such as (2,6-dimethoxybenzoyl) -2,4,6-pentylphosphine oxide and bis (2,4,6-trimethyl). Benzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, ethyl-2,4,6-trimethylbenzoylphenylphosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide , (2,5-dihydroxyphenyl) diphenylphosphine oxide, (p-hydroxyphenyl) diphenylphosphine oxide, bis (p-hydroxyphenyl) phenylphosphine oxide, and tris (p-hydroxyphenyl) Phosphine oxide and the like.
The 2,4,6-trimethylbenzoyl-diphenylphosphine oxide has a UV absorption wavelength that matches the emission wavelength region of a UV-LED having an emission wavelength of 385 nm or 395 nm, thereby providing suitable curability, and The cured film is more preferable in terms of less yellowing.
As the methylphenylglyoxyesters, a mixture of oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester is commercially available. Available.
Among these, 1-hydroxycyclohexyl phenyl ketone, which is an acetophenone, is preferable because it does not cause coloring of the solution when dissolving the active energy ray-curable compound and causes little yellowing over time.
前記した光重合開始剤はそれぞれ単独で用いてもよいし、２種以上を組み合わせて用いてもよい。前記光重合開始剤の総計の含有率は、床材用活性エネルギー線硬化性組成物全量に対し０．１〜１０質量％の範囲にあることが好ましい。０．１質量％未満の添加量では良好な硬化性を得ることが困難であり、また１０質量％を超える添加量では、開始剤量が過剰となり、組成物塗工時の流動性を損ない加工性、作業性が低下することから好ましくない。 The above-described photopolymerization initiators may be used alone or in combination of two or more. The total content of the photopolymerization initiator is preferably in the range of 0.1 to 10% by mass with respect to the total amount of the active energy ray-curable composition for flooring. When the addition amount is less than 0.1% by mass, it is difficult to obtain good curability. When the addition amount exceeds 10% by mass, the initiator amount becomes excessive, and the fluidity during coating of the composition is impaired. This is not preferable because the workability and workability deteriorate.
更に、脂肪族アミン誘導体及び／又は安息香酸アミン誘導体から選ばれる３級アミン化合物を増感剤として添加することによって、硬化速度を速めることもできる。３級アミン化合物は、反応性を高め、酸素による反応阻害を阻止することで知られている。好適な３級アミン化合物としては、例えば、トリエチルアミン、メチルジエタノールアミン、トリエタノールアミンなどの遊離アルキルアミン、２−エチルヘキシル−４−ジメチルアミノベンゾエート、エチル−４−ジメチルアミノベンゾエートなどの芳香族アミン、およびポリアリルアミンとその誘導体としての高分子アミンなどが挙げられる。エチレン２重結合性不飽和アミン（例えば、（メタ）アクリレート化アミン類）などの活性エネルギー線重合性化合物は、低臭気性、低揮発性、および硬化によってポリマーマトリックス中に組み込むことができる能力によって黄ばみが抑制される性質があることから、好ましいとされる。 Furthermore, the curing rate can be increased by adding a tertiary amine compound selected from an aliphatic amine derivative and / or a benzoic acid amine derivative as a sensitizer. Tertiary amine compounds are known to increase reactivity and prevent reaction inhibition by oxygen. Suitable tertiary amine compounds include, for example, free alkyl amines such as triethylamine, methyldiethanolamine, triethanolamine, aromatic amines such as 2-ethylhexyl-4-dimethylaminobenzoate, ethyl-4-dimethylaminobenzoate, and polyamines. Examples include allylamine and a polymer amine as a derivative thereof. Active energy ray polymerizable compounds such as ethylene double bond unsaturated amines (eg, (meth) acrylated amines) have low odor, low volatility, and ability to be incorporated into the polymer matrix by curing. It is preferable because it has the property of suppressing yellowing.
前記３級アミン化合物は、床材用活性エネルギー線硬化性組成物全量に対して、好ましくは、０．１〜１０質量％、より好ましくは、０．３〜３質量％の量で用いる事ができる。 The tertiary amine compound is preferably used in an amount of 0.1 to 10% by mass, more preferably 0.3 to 3% by mass, based on the total amount of the active energy ray-curable composition for flooring. it can.
更に任意の成分として、ワックス、可塑剤、レベリング剤、界面活性剤、分散剤、泡消剤等を含有させることが出来る。 Furthermore, a wax, a plasticizer, a leveling agent, a surfactant, a dispersant, a defoaming agent and the like can be added as optional components.
本発明の床材用活性エネルギー線硬化性組成物では、必用に応じて有機溶剤を使用してもよい。前記溶剤としては、トルエン、キシレン等の芳香族系炭化水素、ｎ−ヘキサン、シクロヘキサン等の脂肪族または脂環式炭化水素、酢酸エチル、酢酸プロピル等のエステル類、メタノール、エタノール、イソプロピルアルコール等のアルコール類、アセトン、メチルエチルケトン等のケトン類、エチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル等のアルキレングリコールモノアルキルエーテルを挙げることができる。 In the active energy ray-curable composition for flooring of the present invention, an organic solvent may be used as necessary. Examples of the solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane, esters such as ethyl acetate and propyl acetate, methanol, ethanol, and isopropyl alcohol. Mention may be made of alcohols, ketones such as acetone and methyl ethyl ketone, and alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether.
本発明の床材用活性エネルギー線硬化性組成物は、木質基材に塗工した際の光沢がグロス値で１０以上〜３０以下の低光沢に伴うマット効果により、高級感ある床材を再現できる組成物である。グロス値が３０超〜６０以下の中程度の光沢よりも、より高級感が得られる。
また、グロス値が１０未満の場合、建材用途としては光の反射が著しく低下し、塗装が施されていないかの様な質感となる上、耐汚染性が低下する傾向にあるからである。尚、前記グロス値の測定条件は、入射角６０°反射角６０°としたものである。
The active energy ray-curable composition for flooring of the present invention reproduces a flooring with a high-class feeling by the matte effect associated with low glossiness of 10 to 30 in terms of gloss when coated on a wooden substrate. Composition. A higher-grade feeling can be obtained than a medium gloss with a gloss value of more than 30 to 60 or less.
In addition, when the gloss value is less than 10, the reflection of light is remarkably reduced as a building material application, and the texture is as if it has not been painted, and the contamination resistance tends to decrease. The measurement condition of the gloss value is that the incident angle is 60 ° and the reflection angle is 60 °.
本発明の床材用活性エネルギー線硬化性組成物は、木質基材上に、予め、シーラー塗膜、下塗り塗膜、中塗り塗膜のいずれかが施されてから塗工してもよい。これらシーラー塗膜、下塗り塗膜および、中塗り塗膜のすべてを塗設する場合には、その積層順序が、「木質基材／シーラー塗膜／下塗り塗膜／中塗り塗膜／床材用活性エネルギー線硬化性組成物からなる塗膜」となるように積層すればよい。なお、何れかの塗膜例えば、下塗塗膜を除外・省略する場合には、この順序を保持しつつ、「木質基材／シーラー塗膜／中塗り塗膜／床材用活性エネルギー線硬化性組成物からなる塗膜」の順序で積層すればよい。 The active energy ray-curable composition for flooring of the present invention may be applied after a sealer coating, an undercoat coating, or an intermediate coating is applied on a wooden substrate in advance. When all of these sealer coating, undercoat coating and intermediate coating are applied, the stacking order is “woody substrate / sealer coating / undercoating coating / intermediate coating / for flooring. What is necessary is just to laminate | stack so that it may become "the coating film which consists of an active energy ray curable composition." In addition, when excluding or omitting any coating film, for example, undercoating film, while maintaining this order, “woody substrate / sealer coating / intermediate coating film / active energy ray curability for flooring” What is necessary is just to laminate | stack in the order of "the coating film consisting of a composition".
このように木質基材上に、予め、シーラー塗膜、下塗り塗膜、中塗り塗膜のいずれか１種以上が塗布される場合には、これら各塗膜の塗布後に前記の如く活性エネルギー線、好ましくは紫外線等の光照射を行うことができる。その光源としては、通常ＵＶ硬化性コーティング剤に使用する光源、例えばメタルハライドランプ、キセノンランプ、カーボンアーク灯、ケミカルランプ、低圧水銀ランプ、高圧水銀ランプ等であれば問題なく硬化させることができる。例えばＦｕｓｉｏｎ Ｓｙｓｔｅｍ社製のＨランプ、Ｄランプ、Ｖランプ等の市販されているものを用いて行うことができる。
そして、それらの塗膜の最後の塗膜（層）上、例えば、中塗り塗膜上に、表面層(最外層、上塗層などとも言う。)となる上記を床材用活性エネルギー線硬化性組成物を塗布し、上記のように高圧水銀灯、メタルハライドランプなどでのセミキュア（半硬化）工程を実施したのち、無電極ＵＶランプを照射し完全硬化させることが好ましい。
また、木質床材の形状により単板の継ぎ目に溝加工が施されていたり、表面に１ｍｍ以上の厚みがある単板を使用して角の形状が加工された床材は、表面層が塗布されずに、溝の部分や角の形状にシーラー塗膜、下塗り塗膜、中塗り塗膜のいずれかが表層となることがあり、この場合も上記床材用活性エネルギー線硬化性組成物を用いることができる。
As described above, when any one or more of a sealer coating, an undercoat coating, and an intermediate coating are applied on the wooden substrate in advance, the active energy rays are applied as described above after the coating of each coating. Preferably, light irradiation such as ultraviolet rays can be performed. As the light source, a light source usually used for a UV curable coating agent, for example, a metal halide lamp, a xenon lamp, a carbon arc lamp, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, etc. can be cured without problems. For example, a commercially available product such as an H lamp, D lamp, or V lamp manufactured by Fusion System can be used.
Then, on the final coating film (layer) of these coating films, for example, on the intermediate coating film, the above-mentioned which becomes the surface layer (also referred to as the outermost layer, the top coating layer, etc.) is active energy ray curing for flooring. It is preferable to apply the composition and perform a semi-cure (semi-curing) step using a high-pressure mercury lamp, a metal halide lamp or the like as described above, and then irradiate an electrodeless UV lamp to completely cure.
In addition, the surface layer is applied to flooring that has been grooved on the seam of the veneer depending on the shape of the wooden flooring, or that has been processed into a square shape using a veneer with a thickness of 1 mm or more on the surface. Otherwise, the sealer coating, the undercoat coating, or the intermediate coating may be a surface layer in the groove part or corner shape. In this case, the active energy ray-curable composition for flooring is also used. Can be used.
尚、本発明の床材用活性エネルギー線硬化性組成物の塗布・印刷方式の具体的な例としては、コーティング方法としては、たとえばロールコーター、グラビアコーター、フレキソコーター、エアドクターコーター、ブレードコーター、エアナイフコーター、スクイズコーター、含浸コーター、トランスファロールコーター、キスコーター、カーテンコーター、キャストコーター、スプレイコーター、ダイコーター、オフセット印刷機、スクリーン印刷機等を適宜採用することができる。 In addition, as a specific example of the coating / printing method of the active energy ray-curable composition for flooring of the present invention, as a coating method, for example, a roll coater, a gravure coater, a flexo coater, an air doctor coater, a blade coater, An air knife coater, a squeeze coater, an impregnation coater, a transfer roll coater, a kiss coater, a curtain coater, a cast coater, a spray coater, a die coater, an offset printing machine, a screen printing machine, and the like can be appropriately employed.
以下、実施例により、本発明をさらに詳しく説明する。尚、以下実施例中にある部とは、質量部を表す。
微粒子（Ｂ）の平均粒子径は日機装株式会社製ナノ粒子粒度分布測定器Ｎａｎｏｔｒａｃ ＵＰＡ ＥＸ−１５０を使って測定した。
Hereinafter, the present invention will be described in more detail by way of examples. In addition, the part in an Example below represents a mass part.
The average particle size of the fine particles (B) was measured using a nano particle size distribution analyzer Nanotrac UPA EX-150 manufactured by Nikkiso Co., Ltd.
〔床材用活性エネルギー線硬化性組成物の調整〕
〔実施例１〕
ＤＩＣ社製ウレタンアクリレート「ユニディックＶ−４２６０」３０部、ＭＩＷＯＮ社製トリメチロールプロパンＥＯ変性トリアクリレート「ＭＩＲＡＭＥＲ Ｍ３１３０」１０部、ＭＩＷＯＮ社製１，６−ヘキサンジオールＥＯ変性ジアクリレート「ＭＩＲＡＭＥＲ Ｍ２０２」５部、ＭＩＷＯＮ社製２−エトキシフェノキシアクリレート「ＭＩＲＡＭＥＲ Ｍ１４２」４０部、ＢＡＳＦ社製１−ヒドロキシ-シクロヘキシル-フェニル-ケトン「ＩＲＧＡＣＵＲＥ １８４」５部、富士シリシア化学社製シリカ「サイリシア−３５０（平均粒子径１．８μｍ）」５部、根上工業社製アクリルビーズ「アートパール Ｊ−４Ｐ（平均粒子径２．２μｍ）」５部を添加し、攪拌機で１０分間撹拌混合して組成物１を作製した。
[Adjustment of active energy ray-curable composition for flooring]
[Example 1]
DIC urethane acrylate "Unidic V-4260" 30 parts, MIWON trimethylolpropane EO modified triacrylate "MIRAMER M3130" 10 parts, MIWON 1,6-hexanediol EO modified diacrylate "MIRAMER M202" 5 40 parts of 2-ethoxyphenoxyacrylate "MIRAMER M142" manufactured by MIWON, 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone "IRGACURE 184" manufactured by BASF, silica "Silicia-350 (average particle diameter) manufactured by Fuji Silysia Chemical Ltd. 1.8 parts by weight), 5 parts of acrylic beads “Art Pearl J-4P (average particle diameter: 2.2 μm)” manufactured by Negami Kogyo Co., Ltd. were added, and the mixture was stirred and mixed with a stirrer for 10 minutes to prepare Composition 1.
〔実施例２〕
ＤＩＣ社製ウレタンアクリレート「ユニディックＶ−４２６０」３０部、ＭＩＷＯＮ社製トリメチロールプロパンＥＯ変性トリアクリレート「ＭＩＲＡＭＥＲ Ｍ３１３０」１０部、ＭＩＷＯＮ社製１，６−ヘキサンジオールＥＯ変性ジアクリレート「ＭＩＲＡＭＥＲ Ｍ２０２」１０部、ＭＩＷＯＮ社製２−エトキシフェノキシアクリレート「ＭＩＲＡＭＥＲ Ｍ１４２」２５部、ＢＡＳＦ社製１−ヒドロキシ-シクロヘキシル-フェニル-ケトン「ＩＲＧＡＣＵＲＥ １８４」５部、東ソー・シリカ社製シリカ「ニップジェルＡＹ−４６０（平均粒子径３．０μｍ）」５部、根上工業社製アクリルビーズ「アートパール Ｊ−４Ｐ」５部、ＵＮＩＭＩＮ社製ネフェリン閃長岩「ＭＩＮＥＸ１０（平均粒子径２．１μｍ）」１０部を添加し、攪拌機で１０分間撹拌混合して組成物２を作製した。
[Example 2]
DIC urethane acrylate “Unidic V-4260” 30 parts, MIWON trimethylolpropane EO modified triacrylate “MIRAMER M3130” 10 parts, MIWON 1,6-hexanediol EO modified diacrylate “MIRAMER M202” 10 25 parts of 2-ethoxyphenoxyacrylate “MIRAMER M142” manufactured by MIWON, 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone “IRGACURE 184” manufactured by BASF, silica “Nipgel AY-460 (average particle) manufactured by Tosoh Silica 5 parts), 5 parts acrylic beads “Art Pearl J-4P” manufactured by Negami Kogyo Co., Ltd., and 10 parts nepheline syenite “MINEX10 (average particle diameter 2.1 μm)” manufactured by UNIMIN Co., Ltd. were added with a stirrer. 1 To prepare a composition for 2 minutes stirring mixture.
〔実施例３〕
ＤＩＣ社製ウレタンアクリレート「ユニディックＶ−４２６０」２５部、ＭＩＷＯＮ社製トリメチロールプロパンＥＯ変性トリアクリレート「ＭＩＲＡＭＥＲ Ｍ３１３０」５部、ＭＩＷＯＮ社製１，６−ヘキサンジオールＥＯ変性ジアクリレート「ＭＩＲＡＭＥＲ Ｍ２０２」５部、ＭＩＷＯＮ社製２−エトキシフェノキシアクリレート「ＭＩＲＡＭＥＲ Ｍ１４２」４０部、ＢＡＳＦ社製１−ヒドロキシ-シクロヘキシル-フェニル-ケトン「ＩＲＧＡＣＵＲＥ １８４」５部、東ソー・シリカ社製シリカ「ニップジェルＡＹ−４６０」５部、根上工業社製アクリルビーズ「アートパール Ｊ−４Ｐ」５部、ＵＮＩＭＩＮ社製ネフェリン閃長岩「ＭＩＮＥＸ１０」１０部を添加し、攪拌機で１０分間撹拌混合して組成物３を作製した。
Example 3
DIC urethane acrylate “Unidic V-4260” 25 parts, MIWON trimethylolpropane EO modified triacrylate “MIRAMER M3130” 5 parts, MIWON 1,6-hexanediol EO modified diacrylate “MIRAMER M202” 5 40 parts of 2-ethoxyphenoxyacrylate “MIRAMER M142” manufactured by MIWON, 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone “IRGACURE 184” manufactured by BASF, and 5 parts of silica “Nipgel AY-460” manufactured by Tosoh Silica Then, 5 parts of acrylic beads “Art Pearl J-4P” manufactured by Negami Kogyo Co., Ltd. and 10 parts of nepheline syenite “MINEX10” manufactured by UNIMIN were added and mixed with stirring for 10 minutes to prepare Composition 3.
〔実施例４〕
ＤＩＣ社製ウレタンアクリレート「ユニディックＶ−４２６０」３０部、ＭＩＷＯＮ社製トリメチロールプロパンＥＯ変性トリアクリレート「ＭＩＲＡＭＥＲ Ｍ３１３０」１０部、ＭＩＷＯＮ社製１，６−ヘキサンジオールＥＯ変性ジアクリレート「ＭＩＲＡＭＥＲ Ｍ２０２」１０部、興人社製アクリロイルモルフォリン「ＡＣＭＯ」２５部、ＢＡＳＦ社製１−ヒドロキシ-シクロヘキシル-フェニル-ケトン「ＩＲＧＡＣＵＲＥ １８４」５部、東ソー・シリカ社製シリカ「ニップジェルＡＹ−４６０」５部、根上工業社製アクリルビーズ「アートパール Ｊ−４Ｐ」５部、ＵＮＩＭＩＮ社製ネフェリン閃長岩「ＭＩＮＥＸ１０」１０部を添加し、攪拌機で１０分間撹拌混合して組成物４を作製した。
Example 4
DIC urethane acrylate “Unidic V-4260” 30 parts, MIWON trimethylolpropane EO modified triacrylate “MIRAMER M3130” 10 parts, MIWON 1,6-hexanediol EO modified diacrylate “MIRAMER M202” 10 Part, 25 parts of acryloylmorpholine “ACMO” manufactured by Kojin Co., Ltd., 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone “IRGACURE 184” manufactured by BASF, 5 parts of silica “Nipgel AY-460” manufactured by Tosoh Silica 5 parts of acrylic beads “Art Pearl J-4P” manufactured by Kogyo Co., Ltd. and 10 parts of nepheline syenite “MINEX 10” manufactured by UNIMIN were added and mixed with stirring for 10 minutes to prepare Composition 4.
〔実施例５〕
ＤＩＣ社製ウレタンアクリレート「ユニディックＶ−４２６０」２５部、ＭＩＷＯＮ社製トリメチロールプロパンＥＯ変性トリアクリレート「ＭＩＲＡＭＥＲ Ｍ３１３０」５部、ＭＩＷＯＮ社製１，６−ヘキサンジオールＥＯ変性ジアクリレート「ＭＩＲＡＭＥＲ Ｍ２０２」５部、興人社製アクリロイルモルフォリン「ＡＣＭＯ」４０部、ＢＡＳＦ社製１−ヒドロキシ-シクロヘキシル-フェニル-ケトン「ＩＲＧＡＣＵＲＥ １８４」５部、東ソー・シリカ社製シリカ「ニップジェルＡＹ−４６０」５部、根上工業社製アクリルビーズ「アートパール Ｊ−４Ｐ」５部、ＵＮＩＭＩＮ社製ネフェリン閃長岩「ＭＩＮＥＸ１０」１０部を添加し、攪拌機で１０分間撹拌混合して組成物５を作製した。
Example 5
DIC urethane acrylate “Unidic V-4260” 25 parts, MIWON trimethylolpropane EO modified triacrylate “MIRAMER M3130” 5 parts, MIWON 1,6-hexanediol EO modified diacrylate “MIRAMER M202” 5 , 40 parts of acryloylmorpholine “ACMO” manufactured by Kojin Co., Ltd., 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone “IRGACURE 184” manufactured by BASF, 5 parts of silica “Nipgel AY-460” manufactured by Tosoh Silica 5 parts of acrylic beads “Art Pearl J-4P” manufactured by Kogyo Co., Ltd. and 10 parts of nepheline syenite “MINEX10” manufactured by UNIMIN were added and mixed with stirring for 10 minutes to prepare Composition 5.
〔実施例６〕
ＤＩＣ社製ウレタンアクリレート「ユニディックＶ−４２６０」３０部、ＭＩＷＯＮ社製トリメチロールプロパンＥＯ変性トリアクリレート「ＭＩＲＡＭＥＲ Ｍ３１３０」１０部、ＭＩＷＯＮ社製トリプロピレングリコールジアクリレート「ＭＩＲＡＭＥＲ Ｍ２２０」１０部、ＭＩＷＯＮ社製１，６−ヘキサンジオールＥＯ変性ジアクリレート「ＭＩＲＡＭＥＲ Ｍ２０２」５部、東亜合成社製「２−エチルヘキシルアクリレート」２５部、ＢＡＳＦ社製１−ヒドロキシ-シクロヘキシル-フェニル-ケトン「ＩＲＧＡＣＵＲＥ １８４」５部、東ソー・シリカ社製シリカ「ニップジェルＡＹ−４６０」５部、根上工業社製アクリルビーズ「アートパール Ｊ−４Ｐ」５部、ＵＮＩＭＩＮ社製ネフェリン閃長岩「ＭＩＮＥＸ１０」５部を添加し、攪拌機で１０分間撹拌混合して組成物６を作製した。
Example 6
DIC urethane acrylate "Unidic V-4260" 30 parts, MIWON trimethylolpropane EO modified triacrylate "MIRAMER M3130" 10 parts, MIWON tripropylene glycol diacrylate "MIRAMER M220" 10 parts, MIWON 5 parts of 1,6-hexanediol EO-modified diacrylate “MIRAMER M202”, 25 parts of “2-ethylhexyl acrylate” manufactured by Toa Gosei Co., Ltd., 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone “IRGACURE 184” manufactured by BASF, Tosoh・ Add 5 parts of silica “Nipgel AY-460” manufactured by Silica, 5 parts of acrylic beads “Art Pearl J-4P” manufactured by Negami Kogyo Co., Ltd. and 5 parts of nepheline syenite “MINEX10” manufactured by UNIMIN. To prepare a composition 6 was stirred and mixed for 10 minutes in the machine.
〔実施例７〕
ＤＩＣ社製ウレタンアクリレート「ユニディックＶ−４２６０」２０部、ＭＩＷＯＮ社製トリメチロールプロパンＥＯ変性トリアクリレート「ＭＩＲＡＭＥＲ Ｍ３１３０」１０部、ＭＩＷＯＮ社製トリプロピレングリコールジアクリレート「ＭＩＲＡＭＥＲ Ｍ２２０」５部、ＭＩＷＯＮ社製１，６−ヘキサンジオールＥＯ変性ジアクリレート「ＭＩＲＡＭＥＲ Ｍ２０２」５部、東亜合成社製「２−エチルヘキシルアクリレート」４０部、ＢＡＳＦ社製１−ヒドロキシ-シクロヘキシル-フェニル-ケトン「ＩＲＧＡＣＵＲＥ １８４」５部、東ソー・シリカ社製シリカ「ニップジェルＡＹ−４６０」５部、根上工業社製アクリルビーズ「アートパール Ｊ−４Ｐ」５部、ＵＮＩＭＩＮ社製ネフェリン閃長岩「ＭＩＮＥＸ１０」５部を添加し、攪拌機で１０分間撹拌混合して組成物７を作製した。
Example 7
DIC urethane acrylate "Unidic V-4260" 20 parts, MIWON trimethylolpropane EO modified triacrylate "MIRAMER M3130" 10 parts, MIWON tripropylene glycol diacrylate "MIRAMER M220" 5 parts, MIWON 1,6-hexanediol EO-modified diacrylate “MIRAMER M202” 5 parts, Toa Gosei “2-ethylhexyl acrylate” 40 parts, BASF 1-hydroxy-cyclohexyl-phenyl-ketone “IRGACURE 184” 5 parts, Tosoh・ Add 5 parts of silica “Nipgel AY-460” manufactured by Silica, 5 parts of acrylic beads “Art Pearl J-4P” manufactured by Negami Kogyo Co., Ltd. and 5 parts of nepheline syenite “MINEX10” manufactured by UNIMIN. To prepare a composition 7 in mixed by stirring for 10 minutes.
〔実施例８〕
ＤＩＣ社製ウレタンアクリレート「ユニディックＶ−４２６０」２５部、、ＭＩＷＯＮ社製トリプロピレングリコールジアクリレート「ＭＩＲＡＭＥＲ Ｍ２２０」１５部、ＭＩＷＯＮ社製１，６−ヘキサンジオールＥＯ変性ジアクリレート「ＭＩＲＡＭＥＲ Ｍ２０２」５部、ＭＩＷＯＮ社製２−エトキシフェノキシアクリレート「ＭＩＲＡＭＥＲ Ｍ１４２」２５部、ＢＡＳＦ社製１−ヒドロキシ-シクロヘキシル-フェニル-ケトン「ＩＲＧＡＣＵＲＥ １８４」５部、根上工業社製アクリルビーズ「アートパール Ｊ−４Ｐ」５部、ＵＮＩＭＩＮ社製ネフェリン閃長岩「ＭＩＮＥＸ１０」２０部を添加し、攪拌機で１０分間撹拌混合して組成物８を作製した。
Example 8
DIC urethane acrylate "Unidic V-4260" 25 parts, MIWON tripropylene glycol diacrylate "MIRAMER M220" 15 parts, MIWON 1,6-hexanediol EO modified diacrylate "MIRAMER M202" 5 parts 25 parts of 2-ethoxyphenoxy acrylate “MIRAMER M142” manufactured by MIWON, 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone “IRGACURE 184” manufactured by BASF, 5 parts of acrylic beads “Art Pearl J-4P” manufactured by Negami Kogyo Co., Ltd. 20 parts of UNIFINE nepheline syenite “MINEX10” was added and mixed with stirring with a stirrer for 10 minutes to prepare composition 8.
〔実施例９〕
ＤＩＣ社製ウレタンアクリレート「ユニディックＶ−４２６０」２０部、ＭＩＷＯＮ社製トリプロピレングリコールジアクリレート「ＭＩＲＡＭＥＲ Ｍ２２０」５部、ＭＩＷＯＮ社製１，６−ヘキサンジオールＥＯ変性ジアクリレート「ＭＩＲＡＭＥＲ Ｍ２０２」５部、ＭＩＷＯＮ社製２−エトキシフェノキシアクリレート「ＭＩＲＡＭＥＲ Ｍ１４２」４０部、ＢＡＳＦ社製１−ヒドロキシ-シクロヘキシル-フェニル-ケトン「ＩＲＧＡＣＵＲＥ １８４」５部、根上工業社製アクリルビーズ「アートパール Ｊ−４Ｐ」５部、ＵＮＩＭＩＮ社製ネフェリン閃長岩「ＭＩＮＥＸ１０」２０部を添加し、攪拌機で１０分間撹拌混合して組成物９を作製した。
Example 9
DIC urethane acrylate “Unidic V-4260” 20 parts, MIWON tripropylene glycol diacrylate “MIRAMER M220” 5 parts, MIWON 1,6-hexanediol EO-modified diacrylate “MIRAMER M202” 5 parts, 40 parts of 2-ethoxyphenoxyacrylate “MIRAMER M142” manufactured by MIWON, 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone “IRGACURE 184” manufactured by BASF, 5 parts of acrylic beads “Art Pearl J-4P” manufactured by Negami Kogyo Co., Ltd. 20 parts of UNIFINE nepheline syenite “MINEX10” was added and stirred for 10 minutes with a stirrer to prepare composition 9.
〔実施例１０〕
ＤＩＣ社製ウレタンアクリレート「ユニディックＶ−４２６０」２０部、ＭＩＷＯＮ社製トリメチロールプロパンＥＯ変性トリアクリレート「ＭＩＲＡＭＥＲ Ｍ３１３０」１０部、ＭＩＷＯＮ社製２−エトキシフェノキシアクリレート「ＭＩＲＡＭＥＲ Ｍ１４２」３０部、ＢＡＳＦ社製１−ヒドロキシ-シクロヘキシル-フェニル-ケトン「ＩＲＧＡＣＵＲＥ １８４」５部、ＵＮＩＭＩＮ社製ネフェリン閃長岩「ＭＩＮＥＸ１０」３５部を添加し、攪拌機で１０分間撹拌混合して組成物１０を作製した。
Example 10
DIC urethane acrylate "Unidic V-4260" 20 parts, MIWON trimethylolpropane EO modified triacrylate "MIRAMER M3130" 10 parts, MIWON 2-ethoxyphenoxy acrylate "MIRAMER M142" 30 parts, BASF 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone “IRGACURE 184” and 35 parts of nepheline syenite “MINEX10” manufactured by UNIMIN were added and mixed with stirring for 10 minutes to prepare Composition 10.
〔比較例１〕
ＤＩＣ社製ウレタンアクリレート「ユニディックＶ−４２６０」３０部、ＭＩＷＯＮ社製トリメチロールプロパンＥＯ変性トリアクリレート「ＭＩＲＡＭＥＲ Ｍ３１３０」１０部、ＭＩＷＯＮ社製トリプロピレングリコールジアクリレート「ＭＩＲＡＭＥＲ Ｍ２２０」２０部、ＭＩＷＯＮ社製１，６−ヘキサンジオールＥＯ変性ジアクリレート「ＭＩＲＡＭＥＲ Ｍ２０２」１０部、ＭＩＷＯＮ社製２−エトキシフェノキシアクリレート「ＭＩＲＡＭＥＲ Ｍ１４２」２５部、ＢＡＳＦ社製１−ヒドロキシ-シクロヘキシル-フェニル-ケトン「ＩＲＧＡＣＵＲＥ １８４」５部を添加し、攪拌機で１０分間撹拌混合して組成物１１を作製した。
[Comparative Example 1]
DIC urethane acrylate "Unidic V-4260" 30 parts, MIWON trimethylolpropane EO modified triacrylate "MIRAMER M3130" 10 parts, MIWON tripropylene glycol diacrylate "MIRAMER M220" 20 parts, MIWON 10 parts of 1,6-hexanediol EO-modified diacrylate “MIRAMER M202”, 25 parts of 2-ethoxyphenoxyacrylate “MIRAMER M142” manufactured by MIWON, 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone “IRGACURE 184” manufactured by BASF Was added and stirred for 10 minutes with a stirrer to prepare composition 11.
〔比較例２〕
ＤＩＣ社製ウレタンアクリレート「ユニディックＶ−４２６０」３０部、ＭＩＷＯＮ社製トリメチロールプロパンＥＯ変性トリアクリレート「ＭＩＲＡＭＥＲ Ｍ３１３０」１５部、ＭＩＷＯＮ社製トリプロピレングリコールジアクリレート「ＭＩＲＡＭＥＲ Ｍ２２０」１０部、ＭＩＷＯＮ社製２−エトキシフェノキシアクリレート「ＭＩＲＡＭＥＲ Ｍ１４２」４０部、ＢＡＳＦ社製１−ヒドロキシ-シクロヘキシル-フェニル-ケトン「ＩＲＧＡＣＵＲＥ １８４」５部を添加し、攪拌機で１０分間撹拌混合して組成物１２を作製した。
[Comparative Example 2]
30 parts of urethane acrylate “Unidic V-4260” manufactured by DIC, 15 parts of trimethylolpropane EO-modified triacrylate “MIRAMER M3130” manufactured by MIWON, 10 parts of tripropylene glycol diacrylate “MIRAMER M220” manufactured by MIWON, manufactured by MIWON 40 parts of 2-ethoxyphenoxy acrylate “MIRAMER M142” and 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone “IRGACURE 184” manufactured by BASF were added and mixed with stirring for 10 minutes to prepare Composition 12.
〔比較例３〕
ＤＩＣ社製ウレタンアクリレート「ユニディックＶ−４２６０」４０部、ＭＩＷＯＮ社製トリメチロールプロパンＥＯ変性トリアクリレート「ＭＩＲＡＭＥＲ Ｍ３１３０」１０部、ＭＩＷＯＮ社製１，６−ヘキサンジオールＥＯ変性ジアクリレート「ＭＩＲＡＭＥＲ Ｍ２０２」１５部、ＭＩＷＯＮ社製２−エトキシフェノキシアクリレート「ＭＩＲＡＭＥＲ Ｍ１４２」２５部、ＢＡＳＦ社製１−ヒドロキシ-シクロヘキシル-フェニル-ケトン「ＩＲＧＡＣＵＲＥ １８４」５部、東ソー・シリカ社製シリカ「ニップジェルＡＹ−４６０」２．５部、根上工業社製アクリルビーズ「アートパール Ｊ−４Ｐ」２．５部を添加し、攪拌機で１０分間撹拌混合して組成物１３を作製した。
[Comparative Example 3]
DIC urethane acrylate "Unidic V-4260" 40 parts, MIWON trimethylolpropane EO modified triacrylate "MIRAMER M3130" 10 parts, MIWON 1,6-hexanediol EO modified diacrylate "MIRAMER M202" 15 1. 25 parts of 2-ethoxyphenoxyacrylate “MIRAMER M142” manufactured by MIWON, 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone “IRGACURE 184” manufactured by BASF, silica “Nipgel AY-460” manufactured by Tosoh Silica 5 parts, 2.5 parts of acrylic beads “Art Pearl J-4P” manufactured by Negami Kogyo Co., Ltd. were added, and the mixture was stirred and mixed with a stirrer for 10 minutes to prepare Composition 13.
〔比較例４〕
ＤＩＣ社製ウレタンアクリレート「ユニディックＶ−４２６０」４０部、ＭＩＷＯＮ社製トリメチロールプロパンＥＯ変性トリアクリレート「ＭＩＲＡＭＥＲ Ｍ３１３０」５部、ＭＩＷＯＮ社製１，６−ヘキサンジオールＥＯ変性ジアクリレート「ＭＩＲＡＭＥＲ Ｍ２０２」５部、ＭＩＷＯＮ社製２−エトキシフェノキシアクリレート「ＭＩＲＡＭＥＲ Ｍ１４２」４０部、ＢＡＳＦ社製１−ヒドロキシ-シクロヘキシル-フェニル-ケトン「ＩＲＧＡＣＵＲＥ １８４」５部、東ソー・シリカ社製シリカ「ニップジェルＡＹ−４６０」２．５部、根上工業社製アクリルビーズ「アートパール Ｊ−４Ｐ」２．５部を添加し、攪拌機で１０分間撹拌混合して組成物１４を作製した。
[Comparative Example 4]
40 parts of urethane acrylate “Unidic V-4260” manufactured by DIC, 5 parts of trimethylolpropane EO modified triacrylate “MIRAMER M3130” manufactured by MIWON, 1,6-hexanediol EO modified diacrylate “MIRAMER M202” 5 manufactured by MIWON 1. 40 parts of 2-ethoxyphenoxyacrylate “MIRAMER M142” manufactured by MIWON, 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone “IRGACURE 184” manufactured by BASF, silica “Nipgel AY-460” manufactured by Tosoh Silica 5 parts, 2.5 parts of acrylic beads “Art Pearl J-4P” manufactured by Negami Kogyo Co., Ltd. were added, and the mixture was stirred and mixed with a stirrer for 10 minutes to prepare Composition 14.
〔比較例５〕
ＤＩＣ社製ウレタンアクリレート「ユニディックＶ−４２６０」３０部、ＭＩＷＯＮ社製トリメチロールプロパンＥＯ変性トリアクリレート「ＭＩＲＡＭＥＲ Ｍ３１３０」１０部、ＭＩＷＯＮ社製トリプロピレングリコールジアクリレート「ＭＩＲＡＭＥＲ Ｍ２２０」２０部、ＢＡＳＦ社製１−ヒドロキシ-シクロヘキシル-フェニル-ケトン「ＩＲＧＡＣＵＲＥ １８４」５部、ＵＮＩＭＩＮ社製ネフェリン閃長岩「ＭＩＮＥＸ１０」３５部を添加し、攪拌機で１０分間撹拌混合して組成物１５を作製した。
[Comparative Example 5]
DIC urethane acrylate "Unidic V-4260" 30 parts, MIWON trimethylolpropane EO modified triacrylate "MIRAMER M3130" 10 parts, MIWON tripropylene glycol diacrylate "MIRAMER M220" 20 parts, BASF 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone “IRGACURE 184” and 35 parts of nepheline syenite “MINEX10” manufactured by UNIMIN were added and stirred for 10 minutes with a stirrer to prepare composition 15.
〔比較例６〕
ＤＩＣ社製ウレタンアクリレート「ユニディックＶ−４２６０」１７部、ＭＩＷＯＮ社製２−エトキシフェノキシアクリレート「ＭＩＲＡＭＥＲ Ｍ１４２」４３部、ＢＡＳＦ社製１−ヒドロキシ-シクロヘキシル-フェニル-ケトン「ＩＲＧＡＣＵＲＥ １８４」５部、ＵＮＩＭＩＮ社製ネフェリン閃長岩「ＭＩＮＥＸ１０」３５部を添加し、攪拌機で１０分間撹拌混合して組成物１６を作製した。
[Comparative Example 6]
17 parts of urethane acrylate “Unidic V-4260” manufactured by DIC, 43 parts of 2-ethoxyphenoxyacrylate “MIRAMER M142” manufactured by MIWON, 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone “IRGACURE 184” manufactured by BASF, UNIMIN 35 parts of nepheline syenite “MINEX10” manufactured by the company was added and mixed by stirring for 10 minutes with a stirrer to prepare composition 16.
〔比較例７〕
ＤＩＣ社製ウレタンアクリレート「ユニディックＶ−４２６０」１７部、ＭＩＷＯＮ社製２−エトキシフェノキシアクリレート「ＭＩＲＡＭＥＲ Ｍ１４２」４０部、ＢＡＳＦ社製１−ヒドロキシ-シクロヘキシル-フェニル-ケトン「ＩＲＧＡＣＵＲＥ １８４」５部、ＵＮＩＭＩＮ社製ネフェリン閃長岩「ＭＩＮＥＸ１０」３８部を添加し、攪拌機で１０分間撹拌混合して組成物１７を作製した。
[Comparative Example 7]
17 parts of urethane acrylate “Unidic V-4260” manufactured by DIC, 40 parts of 2-ethoxyphenoxyacrylate “MIRAMER M142” manufactured by MIWON, 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone “IRGACURE 184” manufactured by BASF, UNIMIN 38 parts of nepheline syenite “MINEX10” manufactured by the company was added and mixed with stirring with a stirrer for 10 minutes to prepare composition 17.
〔比較例８〕
ＤＩＣ社製ウレタンアクリレート「ユニディックＶ−４２６０」３０部、ＭＩＷＯＮ社製トリメチロールプロパンＥＯ変性トリアクリレート「ＭＩＲＡＭＥＲ Ｍ３１３０」１０部、ＭＩＷＯＮ社製トリプロピレングリコールジアクリレート「ＭＩＲＡＭＥＲ Ｍ２２０」１５部、ＭＩＷＯＮ社製１，６−ヘキサンジオールＥＯ変性ジアクリレート「ＭＩＲＡＭＥＲ Ｍ２０２」１０部、ＭＩＷＯＮ社製２−エトキシフェノキシアクリレート「ＭＩＲＡＭＥＲ Ｍ１４２」１０部、ＢＡＳＦ社製１−ヒドロキシ-シクロヘキシル-フェニル-ケトン「ＩＲＧＡＣＵＲＥ １８４」５部、東ソー・シリカ社製シリカ「ニップジェルＡＹ−４６０」５部、根上工業社製アクリルビーズ「アートパール Ｊ−４Ｐ」５部、ＵＮＩＭＩＮ社製ネフェリン閃長岩「ＭＩＮＥＸ１０」１０部を添加し、攪拌機で１０分間撹拌混合して組成物１８を作製した。
[Comparative Example 8]
DIC urethane acrylate "Unidic V-4260" 30 parts, MIWON trimethylolpropane EO modified triacrylate "MIRAMER M3130" 10 parts, MIWON tripropylene glycol diacrylate "MIRAMER M220" 15 parts, MIWON 10 parts of 1,6-hexanediol EO-modified diacrylate “MIRAMER M202”, 10 parts of 2-ethoxyphenoxyacrylate “MIRAMER M142” manufactured by MIWON, 5 parts of 1-hydroxy-cyclohexyl-phenyl-ketone “IRGACURE 184” manufactured by BASF , 5 parts of silica “Nipgel AY-460” manufactured by Tosoh Silica Co., Ltd., 5 parts of acrylic beads “Art Pearl J-4P” manufactured by Negami Kogyo Co., Ltd. Nepheline syenite “M” manufactured by UNIMIN NEX10 "10 parts was added to prepare a composition 18 was mixed and stirred with a stirrer for 10 minutes.
〔床材の作製〕
厚さ１２ｍｍの突き板合板上に、シーラーとして「ポリメディックＳＫＳ−５４７ＬＶ」（ＤＩＣ（株）製、紫外線硬化性組成物）をロールコーターで塗布し高圧水銀灯で硬化させた。次に下塗りとして「ポリメディック ＳＫＳ−０１８」（ＤＩＣ（株）製、紫外線硬化性組成物）１００部に対して研磨剤ＷＡ−５００を３０部混合した組成物をロールコーターで塗布し高圧水銀灯で硬化させた。その後中塗りとして「ポリメディック ＳＫＳ−０１８」をロールコーターで塗布して高圧水銀灯で硬化させた。その塗装板を３２０番のサンドペーパーで研磨した後に、前記で調整した組成物をロールコーターで塗布して高圧水銀灯で積算光量５００ｍＪ／ｃｍ２の照射量で硬化させて床材評価用サンプルを作製した。
[Production of flooring]
On a veneer plywood having a thickness of 12 mm, “Polymedic SKS-547LV” (manufactured by DIC Corporation, UV curable composition) was applied as a sealer with a roll coater and cured with a high-pressure mercury lamp. Next, a composition obtained by mixing 30 parts of the abrasive WA-500 with 100 parts of “Polymedic SKS-018” (manufactured by DIC Corporation, UV curable composition) as an undercoat was applied with a roll coater, and a high pressure mercury lamp was used. Cured. Thereafter, “Polymedic SKS-018” was applied as an intermediate coating with a roll coater and cured with a high-pressure mercury lamp. After the coated plate is polished with No. 320 sandpaper, the composition prepared above is applied with a roll coater and cured with a high-pressure mercury lamp at an irradiation amount of an integrated light amount of 500 mJ / cm 2 to produce a sample for flooring evaluation. did.
〔評価方法〕
本発明の床材用活性エネルギー線硬化性組成物の実施例及び比較例の評価方法を示す。
〔Evaluation method〕
The evaluation method of the Example of an active energy ray curable composition for flooring of this invention and a comparative example is shown.
〔光沢〕
前記光沢評価用塗工紙サンプル、床材評価用サンプルの表面の光沢は株式会社堀場製作所社製グロスチェッカＩＧ−３２０を使用し、光沢の測定条件は入射角６０°反射角６０°とした。測定前に標準校正板（校正値９１）を用いて校正されていることを確認して測定したグロス値を光沢とし、１０以上〜３０以下を合格値とした。
[Glossy]
Gloss checker IG-320 manufactured by Horiba, Ltd. was used for the gloss of the coated paper sample for gloss evaluation and the sample for flooring evaluation, and the gloss measurement conditions were an incident angle of 60 ° and a reflection angle of 60 °. Before the measurement, the gloss value measured after confirming that it was calibrated using a standard calibration plate (calibration value 91) was defined as gloss, and 10 to 30 was defined as a pass value.
〔密着性〕
前記床材評価用サンプル表面の塗膜にカッターガイドに従い、縦横に２ｍｍ間隔で碁盤目状の切り傷を入れて１００個の升目を作る。そこにセロハンテープ（ニチバン エルパック ＬＰ−２４）を貼り付けでセロハンテープを密着させた後にセロハンテープを瞬間的に引っ張り、床材に残っている塗膜の升目を数えて評価した。全部残っている場合は１００／１００とした。
[Adhesion]
In accordance with a cutter guide, a grid pattern is cut at intervals of 2 mm in the vertical and horizontal directions on the coating film on the floor material evaluation sample surface to make 100 squares. The cellophane tape (Nichiban ELPACK LP-24) was attached to the cellophane tape, and the cellophane tape was brought into close contact with the cellophane tape, and the cellophane tape was instantaneously pulled to evaluate the coating film remaining on the flooring. When all remained, it was set to 100/100.
〔耐薬品性〕
前記床材評価用サンプル表面の耐薬品性についてＪＡＳ耐薬品性に従い、作製した床材サンプルを水平に置いた後、サンプルの表面に５％酢酸水溶液、１％炭酸ナトリウム水溶液、ＪＩＳラッカーシンナーを滴下して時計皿をかぶせて、６時間放置した後、溶剤を布に含ませてふき取る。その汚染痕を次の３段階で目視評価した。
○：塗膜に変化なし、塗膜の割れやふくれなどのわずかな変化が見られる。
△：塗膜のふくれや光沢に明らかな変化が見られる。
×：塗膜のふくれや光沢に著しい変化が見られる。
〔chemical resistance〕
About the chemical resistance of the sample surface for flooring evaluation According to JAS chemical resistance, the prepared flooring sample was placed horizontally, and 5% acetic acid aqueous solution, 1% sodium carbonate aqueous solution and JIS lacquer thinner were dropped on the surface of the sample. Then, cover the watch glass and let it stand for 6 hours, and then wipe the cloth with a solvent. The contamination mark was visually evaluated in the following three stages.
○: There is no change in the coating film, and slight changes such as cracking and blistering of the coating film are observed.
(Triangle | delta): A clear change is seen in the swelling and gloss of a coating film.
X: Significant changes are observed in the swelling and gloss of the coating film.
〔耐汚染性〕
前記床材評価用サンプル表面の耐汚染性についてＪＡＳ汚染性Ａに従い、作製した床材サンプルを水平に置いた後、サンプルの表面に一般市販品事務用青色インキ、黒色油性インキ及び赤色クレヨンで幅１０ｍｍの線を引き、６時間放置した後、溶剤を布に含ませてふき取る。その汚染痕を次の３段階で目視評価した。
○：塗膜に変化なし、またはわずかに汚れが残っている。
△：ほとんど汚れが残っている。
×：まったく汚れが落ちない。
[Contamination resistance]
Contamination resistance of the sample surface for flooring evaluation According to JAS contamination A, the prepared flooring sample was placed horizontally, and then the surface of the sample was widened with general commercial office blue ink, black oil ink and red crayon. A 10 mm line is drawn and allowed to stand for 6 hours, and then the cloth is wiped with a solvent. The contamination mark was visually evaluated in the following three stages.
○: No change in the coating film or slight dirt remains.
Δ: Dirt remains almost.
X: Dirt is not removed at all.
〔耐摩耗性〕
前記床材評価用サンプル表面の耐磨耗性について摩耗試験機でＪＡＳ摩耗Ａ試験に従い、作製した床材サンプルの耐摩耗性について評価した。
試験片の質量を測定した後、当該試験片を試験装置の回転盤に水平に固定し、研磨紙（ＪＩＳ Ｋ ６９０２（熱硬化性樹脂高圧化粧板試験方法）に定める検定に合格するものをいう。）を巻き付けたゴム製円板（ＪＩＳ Ｋ ６９０２（熱硬化性樹脂高圧化粧板試験方法）に定める検定に合格するものをいう。）２個を取り付けて試験片を１００回転させ、その後当該試験片の質量を測定し、摩耗量を算出する。この場合、試験片面上に加わる総質量は、ゴム製円板の質量を含め５００ｇとする。
○：化粧面の模様又は化粧材料の５０％以上が残っており、摩耗量が０．１ｇ未満。
△：化粧面の模様又は化粧材料の５０％未満が残っており、摩耗量が０．１ｇ以上。
×：化粧面の模様又は化粧材料が残っていない。
(Abrasion resistance)
About the abrasion resistance of the sample surface for flooring evaluation, the abrasion resistance of the produced flooring sample was evaluated according to the JAS abrasion A test with an abrasion tester.
After measuring the mass of the test piece, the test piece is horizontally fixed on the rotating disk of the test apparatus, and passes the test specified in the abrasive paper (JIS K 6902 (thermosetting resin high-pressure decorative board test method)). )) Wrapped around a rubber disc (meaning that passes the test specified in JIS K 6902 (Testing method for thermosetting resin high-pressure decorative board)). The mass of the piece is measured and the amount of wear is calculated. In this case, the total mass applied on the test piece surface is 500 g including the mass of the rubber disc.
◯: 50% or more of the decorative pattern or makeup material remains, and the wear amount is less than 0.1 g.
(Triangle | delta): Less than 50% of the pattern or cosmetic material of a makeup | decoration surface remains, and the abrasion loss is 0.1 g or more.
X: No decorative pattern or makeup material remains.
〔耐干割れ性〕
前記床材評価用サンプル表面の温度変化に対する耐候性についてＪＡＳ寒熱繰返しＡ試験に従って、作製した床材サンプルの温度変化に対する耐候性について評価した。
床材サンプルを８０℃±３℃の恒温器中に２時間放置した後、−２０℃±３℃の恒温器中に２時間放置する工程を２回繰り返し、室温に達するまで放置する。
○：塗膜に変化なし、塗膜の割れやふくれなどのわずかな変化が見られる。
△：塗膜のふくれや光沢に明らかな変化が見られる。
×：塗膜のふくれや光沢に著しい変化が見られる。
[Dry resistance]
About the weather resistance with respect to the temperature change of the sample surface for flooring evaluation According to the JAS cold heat repetition A test, the weather resistance with respect to the temperature change of the produced flooring sample was evaluated.
The flooring sample is left in an incubator at 80 ° C. ± 3 ° C. for 2 hours and then left in an incubator at −20 ° C. ± 3 ° C. for 2 hours.
○: There is no change in the coating film, and slight changes such as cracking and blistering of the coating film are observed.
(Triangle | delta): A clear change is seen in the swelling and gloss of a coating film.
X: Significant changes are observed in the swelling and gloss of the coating film.
床材用活性エネルギー線硬化性組成物の各配合、及びこれを用いた床材の評価結果を、実施例については表１、２に、比較例については表３、４に示す。 Each composition of the active energy ray-curable composition for flooring and the evaluation results of the flooring using the composition are shown in Tables 1 and 2 for Examples, and Tables 3 and 4 for Comparative Examples.
実施例に示す本発明の床材用活性エネルギー線硬化性組成物を用いた床材では、無機／有機の微粒子の含有量を過剰にすることなくモノマーとの配合の最適化により、突き板合板への密着性、耐薬品性、耐汚染性、耐摩耗性、及び耐千割れ性を兼備しつつ、効率的に低光沢化を図る事ができる。 In the flooring using the active energy ray-curable composition for flooring of the present invention shown in the examples, the veneer plywood is obtained by optimizing the blending with the monomer without excessive content of inorganic / organic fine particles. It is possible to efficiently reduce the gloss while combining adhesion to the surface, chemical resistance, contamination resistance, wear resistance, and cracking resistance.
Claims (5)
前記活性エネルギー線重合性化合物（Ａ）として活性エネルギー線重合性基を１つ有する化合物（Ａ−１）を前記組成物全量の２５〜４０質量％含有し、
前記微粒子（Ｂ）を前記組成物全量の１０〜３５質量％含有し、且つ、
式（１）で算出される値が２０〜５５であることを特徴とする床材用活性エネルギー線硬化性組成物。
（ａ−１）は前記組成物全量に対する活性エネルギー線重合性基を１つ有する化合物（Ａ−１）の質量％である。
An active energy ray-curable composition for a flooring material comprising an active energy ray-polymerizable compound (A), fine particles (B), and a photopolymerization initiator (C),
Containing 25 to 40% by mass of the total amount of the composition (A-1) having one active energy ray polymerizable group as the active energy ray polymerizable compound (A),
Containing the fine particles (B) in an amount of 10 to 35% by mass of the total amount of the composition; and
The active energy ray-curable composition for flooring, wherein the value calculated by the formula (1) is 20 to 55.
(A-1) is the mass% of the compound (A-1) having one active energy ray polymerizable group with respect to the total amount of the composition.
From the group consisting of an acrylic resin having a (meth) acryloyl group, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyfunctional (meth) acrylate as the active energy ray polymerizable compound (A). The active energy ray-curable composition for flooring according to claim 1, comprising a compound (A-2) having two or more active energy ray-polymerizable groups selected.
The fine particles (B) are silica, talc, nepheline syenite, mica, bentonite, diatomaceous earth, calcium carbonate, alumina white, polyethylene wax, polypropylene wax, acrylic bead pigment, or urethane bead pigment. Active energy ray-curable composition for flooring.
The photopolymerization initiator (C) is at least one selected from the group consisting of benzophenones, anthraquinones, thioxanthones, acetophenones, acylphosphine oxides, and methylphenylglyoxyesters. The active energy ray curable composition for flooring materials as described in any one of -3.
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