WO2019073953A1 - Surface-modifying film for automobile interior/exterior components - Google Patents
Surface-modifying film for automobile interior/exterior components Download PDFInfo
- Publication number
- WO2019073953A1 WO2019073953A1 PCT/JP2018/037541 JP2018037541W WO2019073953A1 WO 2019073953 A1 WO2019073953 A1 WO 2019073953A1 JP 2018037541 W JP2018037541 W JP 2018037541W WO 2019073953 A1 WO2019073953 A1 WO 2019073953A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- parts
- weight
- photopolymerizable
- urethane acrylate
- automobile interior
- Prior art date
Links
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000203 mixture Substances 0.000 claims abstract description 60
- -1 acrylate compound Chemical class 0.000 claims abstract description 42
- 239000000945 filler Substances 0.000 claims abstract description 27
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 26
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 20
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 20
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 20
- 239000011737 fluorine Substances 0.000 claims abstract description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 239000011241 protective layer Substances 0.000 claims description 30
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 235000021189 garnishes Nutrition 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004407 fluoroaryl group Chemical group 0.000 claims description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000013461 design Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 230000000475 sunscreen effect Effects 0.000 description 17
- 239000000516 sunscreening agent Substances 0.000 description 17
- 239000002585 base Substances 0.000 description 15
- 239000006071 cream Substances 0.000 description 15
- 239000003921 oil Substances 0.000 description 14
- 238000000465 moulding Methods 0.000 description 12
- 230000003373 anti-fouling effect Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000007921 spray Substances 0.000 description 10
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 125000001153 fluoro group Chemical group F* 0.000 description 9
- 150000003527 tetrahydropyrans Chemical class 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 241000238631 Hexapoda Species 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005034 decoration Methods 0.000 description 6
- 208000035874 Excoriation Diseases 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000000077 insect repellent Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- PCTZLSCYMRXUGW-UHFFFAOYSA-N 1,1,1,2,2-pentafluorobutane Chemical group [CH2]CC(F)(F)C(F)(F)F PCTZLSCYMRXUGW-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- MMOXZBCLCQITDF-UHFFFAOYSA-N N,N-diethyl-m-toluamide Chemical compound CCN(CC)C(=O)C1=CC=CC(C)=C1 MMOXZBCLCQITDF-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000007850 degeneration Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- 239000012957 2-hydroxy-2-methyl-1-phenylpropanone Substances 0.000 description 1
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 1
- DOGMJCPBZJUYGB-UHFFFAOYSA-N 3-trichlorosilylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](Cl)(Cl)Cl DOGMJCPBZJUYGB-UHFFFAOYSA-N 0.000 description 1
- DSUGYJDTLAEJHG-GQPTWSKOSA-N CC(C(OCCC[Si+](O[Si](OC1(O2)[Si+](O[Si@](C)(O3)O[Si](C)(O4)O5)(O6)F)(O[Si]13F)F)(O[Si]24F)O[Si+]56F)=O)=C Chemical compound CC(C(OCCC[Si+](O[Si](OC1(O2)[Si+](O[Si@](C)(O3)O[Si](C)(O4)O5)(O6)F)(O[Si]13F)F)(O[Si]24F)O[Si+]56F)=O)=C DSUGYJDTLAEJHG-GQPTWSKOSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 206010040925 Skin striae Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229960001673 diethyltoluamide Drugs 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
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- 239000012153 distilled water Substances 0.000 description 1
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- HYIMSNHJOBLJNT-UHFFFAOYSA-N nifedipine Chemical compound COC(=O)C1=C(C)NC(C)=C(C(=O)OC)C1C1=CC=CC=C1[N+]([O-])=O HYIMSNHJOBLJNT-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 230000002940 repellent Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- 229940042596 viscoat Drugs 0.000 description 1
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
Definitions
- the present invention relates to a laminated film used as a molding material for automobile interior and exterior parts.
- the number of parts constituting one car is said to be about 30,000.
- engine parts are only about 10,000 of all parts, and about 20,000 other parts are in vehicles related to maintenance of vehicle structure, operation control, safety assurance, decoration, etc. It is an exterior part.
- engine parts are expected to be replaced with only a hundred batteries and motor parts, but there is no noticeable change in the number of automobile interior and exterior parts common to both gasoline and electric vehicles It is expected to be. Therefore, regardless of the spread of electric vehicles, the demand for development of interior and exterior parts of automobiles does not decline.
- Particularly visible automobile interior and exterior parts are, for example, instrument panels, seats, console boxes, sun visors, pillar trims, door trims, door trims, radiator grills, emblems, various garnishes, wheel caps, grille illuminations, covers inside and outside the vehicle .
- so-called "decorative parts” such as instrument panels, emblems, radiator grills and garnishes are the parts most easily recognized by the driver and passersby, so individual designs and particularly high quality are required for each vehicle type.
- Most automobile interior and exterior parts are mainly made of thin and bent plastic materials, and are manufactured by a method combining injection molding and injection molding and painting or laminate molding.
- a method (in-mold molding) in which a fluid plastic material is injected into the inside of an injection molding machine and molded into a thin, bent shape is one of the basic methods.
- a number of molding methods are known which are described in 2, 3 and 4.
- Patent Documents 5 and 6 describe sunscreen cream resistance as a recent required performance for automobile interior and exterior parts. Because skin care products such as hand creams and sunscreen creams are frequently attached to the hands of car occupants and persons approaching cars, such skin care products are delivered after the car product is delivered to the purchaser. Adheres to the surface of automobile interior and exterior products with high frequency. For this reason, skin care products have become unignorable as the causative agent of the quality deterioration of automobile interior and exterior parts. Thus, in recent years, in addition to natural stimuli such as wind and rain and insects, as a factor causing deterioration in the quality of automobile interior and exterior products, it is also considered that the soiling by the user's contact. From these facts, it can be understood that the market demand level for automobile interior and exterior parts tends to increase more and more.
- Patent Document 9 the present applicant has already proposed in Patent Document 9 to manufacture a surface-modified molded article by installing a previously molded antifouling film on the surface of the molded body by in-mold molding.
- Patent Document 9 also describes that such a stain resistant film can also be expected to have a decorative function of a molded product, and an automobile component is mentioned as a decorative molded product.
- Patent Document 9 has no specific proposal as to the material of the antifouling film suitable for surface modification / decoration of automobile parts, and any automobile component having surface modification / decoration fulfills market requirements There is also no description that verifies that it has a design. For this reason, the disclosure of Patent Document 9 only vaguely proposes a new means of surface modification and decoration of the interior and exterior parts of a car, and has not reached at all a technique for improving effective car parts.
- the present invention is as follows.
- (Invention 1) A surface modified film for automobile interior and exterior parts, wherein a surface protective layer is laminated on one side of an acrylic resin base film, The surface protective layer is a cured product of a photopolymerizable urethane acrylate composition
- the photopolymerizable urethane acrylate composition contains (A) a photopolymerizable urethane acrylate mixture and (C) a photopolymerization initiator, and optionally contains (B) a filler,
- the photopolymerizable urethane acrylate composition 60 parts by weight or more and 100 parts by weight of the (A) photopolymerizable urethane acrylate mixture is used per 100 parts by weight in total of the (A) photopolymerizable urethane acrylate mixture and the (B) filler.
- the following (B) filler is present in a proportion of 0 parts by weight or more and 40 parts by weight or less
- the (A) photopolymerizable urethane acrylate mixture is (a1) a photopolymerizable urethane acrylic polymer, (a2) a polyfunctional acrylate compound, (a3) a fluorine-containing photopolymerizable acrylic compound, (a4) Containing photopolymerizable acrylate oligomers having units derived from the fluorosilsesquioxane derivatives,
- the component (a1) is 20 parts by weight or more and 87.99 parts by weight or less
- the component (a2) is 1 part by weight or more and 25 parts by weight or less
- per 100 parts by weight of the (A) photopolymerizable urethane acrylate mixture a3) is present in an amount of 1 to 10 parts by weight
- the component (a4) is present in a proportion of 0.01 to 5 parts by weight.
- each of R f 1 to R f 7 independently represents a linear or branched C 1 -C 20 chain in which at least one methylene may be replaced by oxygen.
- a 1 is a group represented by the following formula (1-1) or the following formula (1-2).
- Y 3 represents an alkylene having 2 to 10 carbon atoms
- R 6 represents hydrogen, a linear or branched alkyl having 1 to 5 carbon atoms, or 6 to 10 carbon atoms It is aryl.
- Y 4 is a single bond or alkylene having 1 to 10 carbon atoms.
- the (A) photopolymerizable urethane acrylate mixture is 60 per 100 parts by weight in total of the (A) photopolymerizable urethane acrylate mixture and the (B) filler.
- (Invention 3) A photopolymerizable acrylate oligomer having a unit derived from ⁇ -methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane represented by the following formula (1-3): The surface-modified film for automobile interior and exterior parts according to Invention 1 or 2.
- Invention 4 A surface-modified film for automobile interior and exterior parts according to any one of Inventions 1 to 3, wherein the interior and exterior parts of the automobile are selected from an instrument panel, an emblem, a radiator grille and various garnishes.
- invention 5 An interior / exterior component of an automobile, wherein at least a part of the surface is covered with the surface modified film for the interior / exterior component according to any one of Inventions 1-4.
- modified film for automobile interior and exterior parts according to the present invention is oil-repellent, antifouling, water-repellent, sunscreen cream resistant, insect spray resistant, high surface hardness, transparency and transparency
- modified film has a balance between moldability and formability.
- the interior and exterior parts of an automobile having at least a part of the surface coated with the modified film of the present invention have oil repellency, stain resistance, water repellency, sunscreen cream resistance, insect spray resistance, high surface hardness, transparency, Transparency and formability are well balanced.
- Example 1 which performed the moldability test (Evaluation (9) mentioned later) is shown.
- the modified film of the comparative example 2 which performed the moldability test (Evaluation (9) mentioned later) is shown.
- the modified film of the present invention comprises (A) a photopolymerizable urethane acrylate mixture and (C) a photopolymerization initiator, and further, if necessary, a cured photopolymerizable urethane acrylate composition containing a (B) filler.
- the surface protection layer which consists of a thing is laminated
- the material used for the said surface protective layer is explained in full detail.
- the (A) photopolymerizable urethane acrylate composition used in the present invention is a main component of the above photopolymerizable urethane acrylate composition, and (a1) a photopolymerizable urethane acrylic polymer, (a2) a polyfunctional acrylate compound, (a3 And (4) a photopolymerizable acrylate oligomer having a unit derived from a fluorine-containing photopolymerizable acrylic compound and (a4) fluorosilsesquioxane derivative.
- the components (a1), (a2), (a3) and (a4) will be described in detail.
- the photopolymerizable urethane acrylic polymer is a reactive polymer which is widely used in industry.
- the molecule has a rigid acrylic oligomer chain and a flexible urethane oligomer chain as essential constitutional units, and has a weight average molecular weight of several thousands to several hundreds of thousands.
- a photopolymerizable urethane acrylic polymer is used for functionalization of a primer of a paint or the surface of a molded product, a solution-like photopolymerizable urethane acrylic polymer is applied to a target object, and then a coating film is exposed to ultraviolet light and the like. It is cured (photopolymerized) by light energy.
- the acryloyl group present at the molecular terminal of the photopolymerizable urethane acrylic polymer reacts with other acryloyl groups in the reaction system to extend the molecular chain, resulting in the strength derived from the acrylic oligomer chain and the urethane oligomer chain.
- a high molecular weight urethane acrylic polymer having flexibility derived from it adheres to the surface of the article to be coated. In general, the strength and flexibility of the coating film are controlled by selecting the molecular structure and molecular weight of the photopolymerizable urethane acrylic polymer.
- photopolymerizable urethane acrylic polymers as described above which can be used as a coating or coating agent as the (a1) photopolymerizable urethane acrylic polymer constituting the (A) photopolymerizable urethane acrylate mixture of the present invention Can be used without restriction.
- (a1) photopolymerizable urethane acrylic polymers for example, “Akrit 8 BR series” manufactured by Taisei Fine Chemical Co., Ltd., “UNIDIC” manufactured by DIC, “Hitaloid” manufactured by Hitachi Chemical Co., Ltd., “RUA series” manufactured by Subia Industrial Chemical Co., Ltd. It can be used.
- a polyfunctional acrylate compound is a monomer having a plurality of photopolymerizable groups in one molecule obtained by the condensation reaction of a polyhydric alcohol and various acrylic acid compounds, and is industrially one of the photopolymerizable polymer materials. Are often used.
- a photopolymerizable polymer such as a photopolymerizable urethane acrylate
- a crosslinked structure can be introduced into the urethane acrylate molecule simultaneously with the extension of the urethane acrylate molecular chain. Therefore, a polyfunctional acrylate compound is used to control the molecular weight and the strength of a cured product of a photopolymerizable polymer such as a photopolymerizable urethane acrylic polymer.
- the above-mentioned polyfunctional acrylate compounds can be used without restriction.
- examples of such (a2) polyfunctional acrylate compounds include photocurable acrylates manufactured by Shin-Nakamura Chemical Co., Ltd., “KAYARAD” manufactured by Nippon Kayaku Co., Ltd., “Alonix (registered trademark)” manufactured by Toagosei Co., Ltd. Acrylate, polyfunctional acrylate manufactured by Kyoeisha Chemical Co., Ltd., etc. can be used.
- the (A) photopolymerizable urethane acrylate composition used in the present invention further contains (a3) a fluorine-containing photopolymerizable acrylic compound in order to impart remarkable stain resistance and water repellency to the surface protective layer.
- a3 fluorine-containing photopolymerizable acrylic compound of the present invention a fluorine atom or a fluorine-containing group is added to a photopolymerizable acrylic oligomer or monomer such as a photopolymerizable urethane acrylic polymer or polyfunctional acrylate compound as described above.
- fluorine-containing acrylic polymers into which is introduced, can be used without limitation.
- (a3) fluorine-containing photopolymerizable acrylic compound for example, "LE-600” manufactured by Toho Chemical Co., Ltd., “Viscoat 8 FM” manufactured by Osaka Organic Chemical Industry Co., Ltd., “Megafuck RS” manufactured by DIC, Kanto Electrification Co., Ltd.
- a product such as "F-CLEAR (registered trademark)" can be used.
- the photopolymerizable acrylate oligomer having a unit derived from the (a4) fluorosilsesquioxane derivative used in the present invention is a photopolymerizable oligomer which contributes to the improvement of the antifouling property developed by the present applicant.
- the fluorosilsesquioxane derivative is a compound represented by the following formula (1).
- R f 1 to R f 7 each independently represent a linear or branched fluorocarbon having 1 to 20 carbon atoms in which at least one methylene may be replaced by oxygen.
- a 1 is a group represented by the following formula (1-1) or the following formula (1-2).
- R f 1 to R f 7 in the above formula (1) are each independently 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,3, 4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, heniko Subfluoro-1,1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl or ⁇ , ⁇ , ⁇ -trifluoromethylphenyl.
- R f 1 to R f 7 in the above formula (1) are each independently 3,3,3-trifluoropropyl or 3,3,4,4,5,5,6,6,6 6-nonafluorohexyl.
- Y 3 is alkylene having 2 to 10 carbon atoms, preferably alkylene having 2 to 6 carbon atoms
- R 6 is hydrogen, or a straight or branched chain having 1 to 5 carbon atoms
- Alkyl or aryl having 6 to 10 carbon atoms preferably hydrogen or alkyl having 1 to 3 carbon atoms.
- Y 4 is a single bond or alkylene having 1 to 10 carbon atoms.
- the above fluorosilsesquioxane derivative (1) is produced by the following method. First, the silicon compound (2) having a trifunctional hydrolyzable group represented by the following formula (2) is hydrolyzed and polycondensed in the presence of an alkali metal hydroxide in an oxygen-containing organic solvent, The compound (3) represented by following formula (3) is manufactured.
- M is an alkali metal in said Formula (3), it will not be specifically limited.
- alkali metal include lithium, sodium, potassium and cesium.
- R in the above formulas (2) and (3) independently corresponds to one group selected from R f 1 to R f 7 in the above formula (1), and at least one methylene is replaced by oxygen C 1-20 linear or branched fluoroalkyl; C 6-20 fluoroaryl in which at least one hydrogen is replaced by fluorine or trifluoromethyl; or at least in aryl It is a fluoroarylalkyl having 7 to 20 carbon atoms in which one hydrogen is replaced by fluorine or trifluoromethyl, and X is a hydrolyzable group.
- R in the above formulas (2) and (3) is each independently 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4, 4,5,5,6,6,6-Nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, helicosafluoro -1,1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl or ⁇ , ⁇ , It is ⁇ , ⁇ -trifluoromethylphenyl.
- each R in the above formula (2) is independently 3,3,3,4,3-trifluoropropyl or 3,3,4,4,5,5,6,6,6-nonafluorohexyl is there.
- the above fluorosilsesquioxane derivative (1) is obtained by reacting the above compound (3) with a compound (4) represented by the following formula (4).
- the group X in the above formula (4) is a group represented by the above formula (1-1) or the above formula (1-2).
- the fluorosilsesquioxane derivative (1) such as ⁇ -methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane is introduced into the coat layer, the antifouling function of the coat layer can be further improved .
- the fluorosilsesquioxane derivative (1) is contained in a photopolymerizable acrylic compound having no urethane unit and containing a fluorine atom, it does not have another urethane unit directly but contains a fluorine atom.
- the other urethane unit may be an oligomer prepared by previously crosslinking and / or polymerizing a photopolymerizable acrylic compound which does not have a urethane unit, or may be mixed with the photopolymerizable acrylic compound to be It may be mixed with photopolymerizable acrylic compounds containing no fluorine atom and containing a fluorine atom.
- the fluorosilsesquioxane derivative (1) is copolymerized with one or more acrylate copolymer components selected from the above monofunctional acrylates, the above bifunctional acrylates, and the above multifunctional acrylates to obtain fluorosilsesqui
- a polymer having an oxane derivative (1) unit is prepared in advance, and this polymer is used as part of a photopolymerizable acrylic compound having no urethane unit and containing a fluorine atom.
- the proportion of the polymer having the fluorosilsesquioxane derivative (1) unit is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the urethane acrylate. Mix to make
- compounds generally referred to as photocurable acrylic monomers, for example, monofunctional acrylates such as (meth) acrylic acid, (meth) acrylic acid ester and hydroxy group-containing (meth) acrylic acid ester (poly ( 2.)
- Difunctional acrylates such as alkylene glycol di (meth) acrylate, trifunctional or higher polyfunctional acrylates such as pentaerythritol triacrylate, etc.
- Such a copolymerization component may be an oligomer obtained by polymerizing a reactive compound containing the above photocurable acrylic monomer.
- the ratio by weight of the components (a1), (a2), (a3) and (a4) depends on the balance between the antifouling property, water repellency, durability, chemical resistance and sunscreen resistance of the surface protective layer. Adjusted as appropriate. Preferably, 20 parts by weight or more and 87.99 parts by weight or less of the component (a1) and 1 parts by weight or more and 25 parts by weight or less of the component (a2) per 100 parts by weight of the (A) photopolymerizable urethane acrylate mixture
- the component (a3) is present in an amount of 1 to 10 parts by weight, and the component (a4) is present in a proportion of 0.01 to 5 parts by weight.
- a (B) filler in addition to the (A) photopolymerizable urethane acrylate mixture, a (B) filler can be further blended in the photopolymerizable urethane acrylate composition of the present invention.
- an inorganic filler compounded for increasing, strengthening, glossing, imparting water repellency, imparting smoothness, imparting design property, etc. to plastic molding materials and paints can be used without limitation.
- (B) fillers for example, silica, zirconium oxide, barium titanate, titanium oxide, alumina and the like can be used. Among these, so-called fine grade fillers are preferred in that they do not impair the appearance of the surface protective layer.
- Filler "MHI” manufactured by Miku Miho Co., Ltd. and silica sol “MEK series” manufactured by Nissan Chemical Industries, Ltd. are preferable as the above-mentioned (B) filler in that the dispersibility in the photopolymerizable urethane acrylate composition is excellent.
- the blending ratio of the (B) filler of the present invention is appropriately determined.
- 60 parts by weight or more and 100 parts by weight or less of the (A) photopolymerizable urethane acrylate mixture is contained per 100 parts by weight of the (A) photopolymerizable urethane acrylate mixture and the (B) filler in total;
- the filler is present in a proportion of 0 parts by weight or more and 40 parts by weight or less.
- the (A) photopolymerizable urethane acrylate mixture is used per 100 parts by weight of the (A) photopolymerizable urethane acrylate mixture and the (B) filler in total;
- the filler is present in a proportion of 10 parts by weight or more and 40 parts by weight or less.
- the photopolymerizable urethane acrylate composition of the present invention further comprises (C) a photopolymerization initiator.
- the kind and compounding quantity of said (C) photoinitiator are not restrict
- As the photopolymerization initiator (C) of the present invention various other commercial products manufactured by BASF "IRGACURE” (currently sold as “Omnirad” manufactured by IGM Resins) can be used.
- Examples of the (C) photopolymerization initiator include polymers of hydroxyketones such as oligo ⁇ 2-hydroxy-2-methyl-1-phenylpropanone ⁇ , 1-hydroxydicyclohexyl phenyl ketone, 2-hydroxy-2 -Methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- ⁇ 4 (2-hydroxyethoxy) phenyl ⁇ 2-hydroxy-2-methyl-1 -Propane 1-one, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis (2,4,6 trimethyl benzoyl) phenyl phosphine oxide, etc. can be used.
- hydroxyketones such as oligo ⁇ 2-hydroxy-2-methyl-1-phenylpropanone ⁇ , 1-hydroxydicyclohexyl phenyl ketone, 2-hydroxy-2 -Methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,
- additives In the photopolymerizable urethane acrylate composition, in addition to the components (A), (B) and (C), an antioxidant, a weathering stabilizer, a color-matching agent, and the like, which are generally compounded in paint and film materials Additives such as diluents can also be further formulated.
- the compounding amount is not limited as long as the function of the surface protective layer is not reduced.
- [Surface protection layer] Curing of a photopolymerizable urethane acrylate composition comprising the above-described (A) photopolymerizable urethane acrylate mixture, (B) filler, (C) photopolymerization initiator, and other additives which may be optionally blended
- An object forms the surface protection layer of the present invention.
- the surface protective layer of the present invention is laminated on one side of an acrylic resin base film.
- the acrylic resin base film used in the present invention is a single layer or multilayer film or sheet mainly composed of an acrylic resin.
- an acrylic resin which comprises the said acrylic resin base film the thing well-known as a material of an automobile interior and exterior part can be used without a restriction
- an acrylic resin base film for example, "Acriprene (registered trademark)” manufactured by Mitsubishi Chemical Co., Ltd., “Sunduren” manufactured by Kaneka Co., Ltd., “Parapure”” Komogurasu” manufactured by Kuraray Co., Ltd., etc. can be used.
- the thickness of the acrylic resin base film of the present invention is not particularly limited, but is usually 100 ⁇ m to 500 ⁇ m, preferably 200 ⁇ m to 400 ⁇ m.
- the solution-like photopolymerizable urethane acrylate composition is coated on one side of such an acrylic resin base film so that a coating thickness of usually 1 ⁇ m to 30 ⁇ m, preferably 1 ⁇ m to 20 ⁇ m can be obtained,
- a cured product of the photopolymerizable urethane acrylate composition in the form of a solution is generally formed on one surface of the acrylic resin base film as a surface protective layer of 1 ⁇ m to 30 ⁇ m, preferably 1 ⁇ m to 20 ⁇ m. Be done.
- the surface protective layer In the formation of the surface protective layer, first, a photopolymerizable urethane acrylate containing the above-mentioned (A) photopolymerizable urethane acrylate mixture and (C) a photopolymerization initiator and, if necessary, (B) a filler The resulting solution is prepared by diluting the composition with a solvent as needed. Next, this solution is applied to one surface of the above-mentioned acrylic resin base film, and after drying under appropriate conditions, the coated surface is irradiated with light energy rays such as ultraviolet rays to cure the above-mentioned photopolymerizable urethane acrylate composition. . Thus, the modified film of the present invention is obtained.
- the method of diluting the photopolymerizable urethane acrylate composition, the method of applying the photopolymerizable urethane acrylate composition in solution, the irradiation conditions of the light energy ray, the method of drying the cured product of the photopolymerizable urethane acrylate composition The conditions are appropriately selected from known conditions for handling the photopolymerizable paint.
- the modified film of the present invention On the surface protective layer side of the modified film of the present invention, all of antifouling property, water repellency, durability, chemical resistance and sunscreen cream resistance derived from the surface protective layer of the present invention appear in a well-balanced manner. Moreover, the modified film of the present invention is also suitable for relatively complicated shapes. Such a modified film of the present invention is effective for surface modification of automobile interior and exterior parts.
- the automobile interior and exterior parts of the present invention are automobile interior and exterior parts coated with at least a part of the surface with the modified film of the present invention.
- a method of manufacturing the interior and exterior parts of a car according to the present invention a method capable of adhering the material of the interior and exterior parts of a car mainly made of plastic to the above-mentioned modified film in a predetermined shape can be used without limitation.
- the modified film is placed in a mold, and film insert molding in which resin is filled by injection molding, laminate injection press molding, the reformed film is preformed, and then placed in the mold for injection
- film insert molding in which resin is filled by injection molding, laminate injection press molding, the reformed film is preformed, and then placed in the mold for injection
- methods include film-in-mold molding in which a resin is filled by molding, and methods in which these molding methods are combined with two-color molding, sandwich molding, and the like.
- the modified film of the present invention is effective for the entire interior and exterior parts of automobiles.
- various automotive vehicles such as instrument panels, seats, console boxes, sun visors, pillar trims, door trims, door trims, radiator grills, emblems, various garnishes, wheel caps, grille illumination, covers inside and outside the vehicle Interior and exterior parts can be manufactured.
- Particularly high value as such an automobile exterior part of the present invention is antifouling property, water repellency, durability, chemical resistance, sunscreen resistance since it is used under an environment where human beings frequently touch with fingers.
- Instrument panels, emblems, radiator grills, and various garnishes are required for all creaminess.
- the modified film of the present invention was produced by the following procedure. [Synthesis of ⁇ -methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane] Trifluoropropyltrimethoxysilane (100 g), THF (500 mL), deionized water (10.5 g) and sodium hydroxide (sodium hydroxide) in a 1 L four-necked flask fitted with a reflux condenser, thermometer and dropping funnel 7.9 g) was charged and heated with an oil bath from room temperature to a temperature at which THF was refluxed while stirring with a magnetic stirrer. Stirring was continued for 5 hours from the start of reflux to complete the reaction. Thereafter, the flask was taken out of the oil bath, allowed to stand at room temperature overnight, and then set in the oil bath again, and heated and concentrated under constant pressure until solids were precipitated.
- the precipitated product was filtered off using a pressure filter equipped with a membrane filter with a pore size of 0.5 ⁇ m. Next, the obtained solid was washed once with THF, and dried at 80 ° C. for 3 hours in a vacuum dryer to obtain 74 g of a colorless powdery solid.
- the mixture was concentrated by a rotary evaporator until a viscous solid was precipitated, 260 g of methanol was added, and the mixture was stirred until it became powdery.
- the powder was filtered using a pressure filter equipped with 5 ⁇ m filter paper and dried in a vacuum oven at 65 ° C. for 3 hours to obtain 41.5 g of a colorless powdery solid.
- the obtained solid was subjected to GPC and 1 H-NMR measurement to confirm the formation of ⁇ -methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane represented by the following formula (5).
- the polymer which it has was used.
- silica sol “MEK-ST-UP” manufactured by Nissan Chemical Industries, Ltd. was used.
- C "Omnirad 127" manufactured by IGM Resins, Inc. was used as a photopolymerization initiator.
- IPA isopropyl alcohol
- the above components (a1), (a2), (a3), (a4), (B) and (C) are selected as shown in Table 1, and the respective components are mixed in the amount ratio shown in Table 1
- a coating liquid containing the photopolymerizable urethane acrylate composition well dispersed at a concentration of 25% by weight was obtained.
- Oil Repellency The oil repellency of the surface protective layer of the obtained modified film with respect to a commercially available black oil-based ink was evaluated. The degree to which the black oil-based ink was repelled when a line was drawn on the surface of the surface protective layer of the resulting modified film with a Sharpie marker was determined according to the following criteria.
- the ink is repellent and the locus of the ink looks like a dot.
- a commercially available sunblock cream (Neutrogena ULTRA SHEER SUNSCREEN SPF 45) in an amount of 0.5 g / 100 cm 2 on the surface protection layer of a 50 mm ⁇ 50 mm test piece cut from the obtained modified film It applied to uniform thickness. Two sheets of white cloth and aluminum plate were stacked on the surface to which the sunscreen cream adhered, and a weight of 500 g was placed on the aluminum plate. In this state, the entire test article including the modified film was allowed to stand and heated in a thermostat at 55 ° C. for 4 hours. After heating, the weight, aluminum plate and white cloth were removed. The surface protective layer was rubbed with a non-woven cloth impregnated with a neutral detergent to remove the sunscreen attached to the surface protective layer. The condition of the surface protective layer from which the sunscreen cream was removed was determined according to the following criteria.
- Insect repellent spray resistance A commercially available insect repellent spray (OFF! Deep Woods (R) Sportsman with 25% DEET) on the surface protection layer of a 50 mm x 50 mm test piece cut from the obtained modified film. 0.05 g was evenly distributed. Two sheets of white cloth and an aluminum plate were stacked on the surface on which the insect spray was attached. In this state, the entire test product including the modified film was allowed to stand at room temperature (23 ° C.) for 24 hours. After this, the aluminum plate and the white cloth were removed. The state of the surface protective layer at this time was determined according to the following criteria.
- the hardness of the surface protective layer was measured by pencil hardness measurement in accordance with JIS K 5600.
- the haze (H 1 ) of a 120 mm ⁇ 70 mm test piece cut off from the obtained modified film was measured using a haze meter NDH-5000 type manufactured by Nippon Denshoku Kogyo Co., Ltd.
- the test piece for which the haze H 1 was measured was placed in an IMC-1557 abrasion resistance tester C manufactured by Imoto Machinery Co., Ltd., and the surface protective layer was subjected to abrasion treatment.
- the wear condition was # 0000 steel wool, load 400 g, 15 reciprocations.
- the haze (H 2 ) of the test piece after the abrasion treatment was measured by the same method as the measurement of the haze H 1 before the abrasion treatment.
- the degree of change in transparency ( ⁇ H) shown in the following equation was determined from the values of H 1 and H 2 . The smaller the ⁇ H, the higher the scratch resistance.
- the area of the modified film is 200% using a hemispherical mold having diamond-shaped filaments
- the modified film was vacuum and pressure formed into a dome-like thin shape under the conditions of The surface protective layer of the obtained dome-shaped modified film was visually observed, and the vacuum and pressure-forming property of the modified film was determined based on the following criteria.
- FIG. 1 shows the surface of a dome-shaped molded body obtained from the modified film of Example 1. Diamond-shaped filaments well fitted to the mold shape are reproduced on the surface of the molded body. The portion without striae forms a smooth curved surface.
- FIG. 2 shows the surface of a dome-shaped compact obtained from the modified film of Comparative Example 2. Irregularities, wrinkles and cracks occur on the entire surface.
- the modified films prepared in Example 1, Example 2, and Example 3 have oil repellency, stain resistance, water repellency, sunscreen cream resistance, insect spray resistance, high surface hardness. It has a good balance of transparency and moldability, and is suitable as a surface protection member for automobile interior and exterior parts.
- the modified films produced in Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4 in which the material of the surface protective layer is changed have oil repellency, stain resistance, water repellency, sunscreen cream resistance, Any one or more of the insect spray resistance, the surface hardness, the transparency, and the formability are greatly impaired, and the practicability as a surface protection member for automobile interior and exterior parts is lacking.
- the modified film of the present invention is well-balanced in oil repellency, stain resistance, water repellency, sunscreen cream resistance, insect spray resistance, high surface hardness, transparency / transparency, and moldability.
- Such a modified film of the present invention is useful as a surface protection member such as an instrument panel, an emblem, a radiator grill, various garnish, etc., as a molded article represented by automobile interior and exterior parts required to have high functionality and design. is there. It is expected that the present invention makes it possible to manufacture automobile interior and exterior parts that can withstand the recent and more sophisticated demands.
Abstract
[PROBLEM] To manufacture automobile interior/exterior components that exhibit superior functionality and design characteristics. [SOLUTION] Provided is a surface-modifying film for automobile interior/exterior components, said film obtained by layering a surface-protecting layer on one surface of an acrylic resin base film. The surface-protecting layer is the hardened product of a photopolymerisable urethane-acrylate composition. The photopolymerisable urethane-acrylate composition includes: (A) a photopolymerisable urethane-acrylate mixture; (C) a photopolymerisation initiator; and, as required, (B) a filler. Component (A) includes: (a1) a photopolymerisable urethane-acrylic polymer; (a2) a polyfunctional acrylate compound; (a3) a fluorine-containing photopolymerisable acrylic compound; and (a4) a photopolymerisable acrylate oligomer comprising a fluoro-silsesquioxane-derived unit.
Description
本発明は自動車内外装部品の成形材料として用いられる積層フィルムに関する。
The present invention relates to a laminated film used as a molding material for automobile interior and exterior parts.
自動車一台を構成する部品点数は約３万個と言われる。ガソリン車あるいはディーゼル車の場合、エンジン部品は全部品のうちの約１万点に過ぎず、そのほかの約２万点の部品は車体の構造維持、運転制御、安全確保、装飾などに関わる自動車内外装部品である。今後、電気自動車の普及によって、エンジン部品はわずか百個程度の電池及びモーター部品に置き換わると予想されるが、ガソリン車にも電気自動車にも共通な自動車内外装部品の点数に目立った変化はないと予想される。したがって、電気自動車の普及に関わらず自動車内外装部品の開発需要は衰えることがない。
The number of parts constituting one car is said to be about 30,000. In the case of gasoline or diesel vehicles, engine parts are only about 10,000 of all parts, and about 20,000 other parts are in vehicles related to maintenance of vehicle structure, operation control, safety assurance, decoration, etc. It is an exterior part. In the future, with the spread of electric vehicles, engine parts are expected to be replaced with only a hundred batteries and motor parts, but there is no noticeable change in the number of automobile interior and exterior parts common to both gasoline and electric vehicles It is expected to be. Therefore, regardless of the spread of electric vehicles, the demand for development of interior and exterior parts of automobiles does not decline.
しかも、自動車内外装部品は目に触れやすく乗員が高頻度で接触する部品であるため、どのような車種でも機能性とデザイン性が求められる部位である。今日、自動車メーカー間の開発競争が激しいハイブリッド車や電気自動車の価格はガソリン車に比べて比較的高く設定されるため、これらの車種の内外装部品に高級志向やブランド意識の高い購買層に見合った特に高い品質が求められることも多い。
Moreover, since the interior and exterior parts of a car are parts that are easily touched by the eye and frequently touched by an occupant, they are areas where functionality and design are required for any car type. Today, the prices of hybrid and electric cars, which are in intense competition for development among automakers, are set relatively high compared to gasoline cars, so the interior and exterior parts of these car models are commensurate with high-class and brand-conscious buyers In particular, high quality is often required.
このような事情から、これからの自動車製造において自動車内外装部品の高機能化と高デザイン化は一層大きな目標と言ってよい。
From such a situation, it can be said that high functionalization and high design of the interior and exterior parts of a car are further big targets in the future car manufacturing.
特に目に触れやすい自動車内外装部品は、例えば、インストルメントパネル、シート、コンソールボックス、サンバイザー、ピラートリム、ドアトリム、ラジエータグリル、エンブレム、各種ガーニッシュ、ホイールキャップ、グリルイルミネーション、車内外のカバー類である。中でもインストルメントパネル、エンブレム、ラジエータグリル、ガーニッシュなどのいわゆる「装飾部品」は運転者や通行人が最も認識しやすい部品であるため車種それぞれに個性的なデザインと特に高い品質が求められている。自動車内外装部品の多くは薄型で屈曲したプラスチック材料を主体に構成されており、射出成形や、射出成形と塗装あるいはラミネート成形とを組み合わせた方法で製造される。そのような方法の中で、射出成形機内部に流動性プラスチック材料を射出して薄型で屈曲した形状に成形する方法（インモールド成形）は基本的なものの一つであり、例えば特許文献１、２、３、４に記載された数多くの成形方法が知られている。
Particularly visible automobile interior and exterior parts are, for example, instrument panels, seats, console boxes, sun visors, pillar trims, door trims, door trims, radiator grills, emblems, various garnishes, wheel caps, grille illuminations, covers inside and outside the vehicle . Among them, so-called "decorative parts" such as instrument panels, emblems, radiator grills and garnishes are the parts most easily recognized by the driver and passersby, so individual designs and particularly high quality are required for each vehicle type. Most automobile interior and exterior parts are mainly made of thin and bent plastic materials, and are manufactured by a method combining injection molding and injection molding and painting or laminate molding. Among such methods, a method (in-mold molding) in which a fluid plastic material is injected into the inside of an injection molding machine and molded into a thin, bent shape (in-mold molding) is one of the basic methods. A number of molding methods are known which are described in 2, 3 and 4.
これら自動車装飾部品の品質向上のために成形材料自体の改良も数多く試みられている。自動車装飾部品の材料として代表的なポリカーボネート樹脂やアクリル樹脂の最適化例としては例えば特許文献５、６、７、８に記載されている。これらの最適化例では得られる成形品の耐擦傷性、透明性、耐衝撃性、耐熱性、耐薬品性、耐折り曲げ白化性の向上を目標としている。
Many attempts have been made to improve molding materials themselves in order to improve the quality of these automotive decorative parts. Examples of optimization of polycarbonate resins and acrylic resins representative of materials for automobile decorative parts are described in, for example, Patent Documents 5, 6, 7, and 8. In these optimization examples, it is aimed to improve the abrasion resistance, transparency, impact resistance, heat resistance, chemical resistance and whitening resistance of the resulting molded article.
特許文献５、６には、自動車内外装部品に対する近年の要求性能として日焼け止めクリーム耐性が記載されている。自動車の乗員や自動車に近づく人物の手には高い頻度でハンドクリームや日焼け止めクリームのようなスキンケア製品が付着しているため、自動車製品が購入者に引き渡された後は、このようなスキンケア製品が高い頻度で自動車内外装品表面に付着する。このため、自動車内外装部品の品質低下の原因物質としてスキンケア製品は無視できなくなっている。このように、近年は自動車内外装品の品質低下をもたらす要因として風雨や虫など自然界の刺激に加え、使用者の接触による汚れも検討するようになっている。こうしたことからも、自動車内外装部品に対する市場の要求レベルはますます高まる傾向にあることが理解できる。
Patent Documents 5 and 6 describe sunscreen cream resistance as a recent required performance for automobile interior and exterior parts. Because skin care products such as hand creams and sunscreen creams are frequently attached to the hands of car occupants and persons approaching cars, such skin care products are delivered after the car product is delivered to the purchaser. Adheres to the surface of automobile interior and exterior products with high frequency. For this reason, skin care products have become unignorable as the causative agent of the quality deterioration of automobile interior and exterior parts. Thus, in recent years, in addition to natural stimuli such as wind and rain and insects, as a factor causing deterioration in the quality of automobile interior and exterior products, it is also considered that the soiling by the user's contact. From these facts, it can be understood that the market demand level for automobile interior and exterior parts tends to increase more and more.
一方、本特許出願人は既に特許文献９によって、あらかじめ成形された防汚性フィルムをインモールド成形によって成形体表面に設置することによって表面改質された成形品を製造することを提案した。特許文献９にはこのような防汚性フィルムに成形品の加飾機能も期待できることも記載されており、加飾可能な成形品として自動車部品が挙げられている。
On the other hand, the present applicant has already proposed in Patent Document 9 to manufacture a surface-modified molded article by installing a previously molded antifouling film on the surface of the molded body by in-mold molding. Patent Document 9 also describes that such a stain resistant film can also be expected to have a decorative function of a molded product, and an automobile component is mentioned as a decorative molded product.
しかしながら、特許文献９に記載された加飾対象は可能性の列挙にすぎず、自動車部品は携帯電話端末、ノートＰＣ、デジタルカメラ、家電製品、化粧品容器などと並び、今日ある程度の機能性とデザイン性が要求される工業的に大量生産される成形製品の一つとして漠然と言及されたものに過ぎない。特許文献９には自動車部品の表面改質・加飾に適した防汚フィルムの材質について具体的な提案はなく、表面改質・加飾された何らかの自動車部品が市場の要求を満たす機能性とデザイン性を備えることを検証した記載もない。このため、特許文献９の開示は自動車内外装部品の表面改質・加飾の新たな手段を漠然と提案したにすぎず、実効性のある自動車部品の改良技術には全く到達していなかった。
However, the objects of decoration described in Patent Document 9 are only a list of possibilities, and automobile parts are lined with mobile phone terminals, notebook PCs, digital cameras, home appliances, cosmetic containers, etc. It is only vaguely mentioned as one of the industrially mass-produced molded products which require the property. Patent Document 9 has no specific proposal as to the material of the antifouling film suitable for surface modification / decoration of automobile parts, and any automobile component having surface modification / decoration fulfills market requirements There is also no description that verifies that it has a design. For this reason, the disclosure of Patent Document 9 only vaguely proposes a new means of surface modification and decoration of the interior and exterior parts of a car, and has not reached at all a technique for improving effective car parts.
そこで本特許出願人は、自ら提案した自動車部品成形体の表面改質と表面加飾の技術を実用可能な技術に飛躍させることを目標に、防汚フィルムの材質と構成の最適化を試みた。
Therefore, the present patent applicants tried to optimize the material and configuration of the antifouling film, with the goal of leaping the technology of surface modification and surface decoration of the automobile part molded body that he proposed to practical technology. .
その結果、防汚フィルムの材質と構成に関する膨大な選択肢の中から、市場の要求に耐える自動車内外装成形品に貢献できる最適な処方と組み合わせを導くことに成功した。すなわち本発明は以下のものである。
As a result, we have succeeded in deriving an optimal formulation and combination that can contribute to automobile interior and exterior molded articles that can withstand the market requirements, out of a huge selection of materials and configurations of antifouling films. That is, the present invention is as follows.
（発明１）アクリル樹脂製基材フィルムの片面に表面保護層が積層されている自動車内外装部品用表面改質フィルムであって、
上記表面保護層は光重合性ウレタンアクリレート組成物の硬化物であり、
上記光重合性ウレタンアクリレート組成物は、（Ａ）光重合性ウレタンアクリレート混合物と、（Ｃ）光重合開始剤とを含み、必要に応じて（Ｂ）フィラーを含み、
上記光重合性ウレタンアクリレート組成物において、上記（Ａ）光重合性ウレタンアクリレート混合物と上記（Ｂ）フィラーとの合計１００重量部あたり、上記（Ａ）光重合性ウレタンアクリレート混合物が６０重量部以上１００重量部以下、上記（Ｂ）フィラーが０重量部以上４０重量部以下の割合で存在し、
上記（Ａ）光重合性ウレタンアクリレート混合物が、（ａ１）光重合性ウレタンアクリルポリマー、（ａ２）多官能アクリレート化合物、（ａ３）フッ素含有光重合性アクリル化合物、（ａ４）下記式（１）で表されるフルオロシルセスキオキサン誘導体に由来する単位を有する光重合性アクリレートオリゴマーを含み、
上記（Ａ）光重合性ウレタンアクリレート混合物１００重量部あたり、上記成分（ａ１）が２０重量部以上８７．９９重量部以下、上記成分（ａ２）が１重量部以上２５重量部以下、上記成分（ａ３）が１重量部以上１０重量部以下、上記成分（ａ４）が０．０１重量部以上５重量部以下の割合で存在する、
自動車内外装部品用表面改質フィルム。 (Invention 1) A surface modified film for automobile interior and exterior parts, wherein a surface protective layer is laminated on one side of an acrylic resin base film,
The surface protective layer is a cured product of a photopolymerizable urethane acrylate composition,
The photopolymerizable urethane acrylate composition contains (A) a photopolymerizable urethane acrylate mixture and (C) a photopolymerization initiator, and optionally contains (B) a filler,
In the photopolymerizable urethane acrylate composition, 60 parts by weight or more and 100 parts by weight of the (A) photopolymerizable urethane acrylate mixture is used per 100 parts by weight in total of the (A) photopolymerizable urethane acrylate mixture and the (B) filler. The following (B) filler is present in a proportion of 0 parts by weight or more and 40 parts by weight or less,
The (A) photopolymerizable urethane acrylate mixture is (a1) a photopolymerizable urethane acrylic polymer, (a2) a polyfunctional acrylate compound, (a3) a fluorine-containing photopolymerizable acrylic compound, (a4) Containing photopolymerizable acrylate oligomers having units derived from the fluorosilsesquioxane derivatives,
The component (a1) is 20 parts by weight or more and 87.99 parts by weight or less, the component (a2) is 1 part by weight or more and 25 parts by weight or less, per 100 parts by weight of the (A) photopolymerizable urethane acrylate mixture a3) is present in an amount of 1 to 10 parts by weight, and the component (a4) is present in a proportion of 0.01 to 5 parts by weight.
Surface modified film for automobile interior and exterior parts.
上記表面保護層は光重合性ウレタンアクリレート組成物の硬化物であり、
上記光重合性ウレタンアクリレート組成物は、（Ａ）光重合性ウレタンアクリレート混合物と、（Ｃ）光重合開始剤とを含み、必要に応じて（Ｂ）フィラーを含み、
上記光重合性ウレタンアクリレート組成物において、上記（Ａ）光重合性ウレタンアクリレート混合物と上記（Ｂ）フィラーとの合計１００重量部あたり、上記（Ａ）光重合性ウレタンアクリレート混合物が６０重量部以上１００重量部以下、上記（Ｂ）フィラーが０重量部以上４０重量部以下の割合で存在し、
上記（Ａ）光重合性ウレタンアクリレート混合物が、（ａ１）光重合性ウレタンアクリルポリマー、（ａ２）多官能アクリレート化合物、（ａ３）フッ素含有光重合性アクリル化合物、（ａ４）下記式（１）で表されるフルオロシルセスキオキサン誘導体に由来する単位を有する光重合性アクリレートオリゴマーを含み、
上記（Ａ）光重合性ウレタンアクリレート混合物１００重量部あたり、上記成分（ａ１）が２０重量部以上８７．９９重量部以下、上記成分（ａ２）が１重量部以上２５重量部以下、上記成分（ａ３）が１重量部以上１０重量部以下、上記成分（ａ４）が０．０１重量部以上５重量部以下の割合で存在する、
自動車内外装部品用表面改質フィルム。 (Invention 1) A surface modified film for automobile interior and exterior parts, wherein a surface protective layer is laminated on one side of an acrylic resin base film,
The surface protective layer is a cured product of a photopolymerizable urethane acrylate composition,
The photopolymerizable urethane acrylate composition contains (A) a photopolymerizable urethane acrylate mixture and (C) a photopolymerization initiator, and optionally contains (B) a filler,
In the photopolymerizable urethane acrylate composition, 60 parts by weight or more and 100 parts by weight of the (A) photopolymerizable urethane acrylate mixture is used per 100 parts by weight in total of the (A) photopolymerizable urethane acrylate mixture and the (B) filler. The following (B) filler is present in a proportion of 0 parts by weight or more and 40 parts by weight or less,
The (A) photopolymerizable urethane acrylate mixture is (a1) a photopolymerizable urethane acrylic polymer, (a2) a polyfunctional acrylate compound, (a3) a fluorine-containing photopolymerizable acrylic compound, (a4) Containing photopolymerizable acrylate oligomers having units derived from the fluorosilsesquioxane derivatives,
The component (a1) is 20 parts by weight or more and 87.99 parts by weight or less, the component (a2) is 1 part by weight or more and 25 parts by weight or less, per 100 parts by weight of the (A) photopolymerizable urethane acrylate mixture a3) is present in an amount of 1 to 10 parts by weight, and the component (a4) is present in a proportion of 0.01 to 5 parts by weight.
Surface modified film for automobile interior and exterior parts.
（上記式（１）において、Ｒｆ
１～Ｒｆ
７はそれぞれ独立して、少なくとも１つのメチレンが酸素で置き換えられていてもよい、炭素数１～２０の、直鎖状もしくは分岐鎖状のフルオロアルキル；少なくとも１つの水素がフッ素もしくはトリフルオロメチルで置き換えられた、炭素数６～２０のフルオロアリール；またはアリール中の少なくとも１つの水素がフッ素もしくはトリフルオロメチルで置き換えられた、炭素数７～２０のフルオロアリールアルキルを示し、Ａ１は、下記式（１－１）または下記式（１－２）で表される基である。）
(In the above formula (1), each of R f 1 to R f 7 independently represents a linear or branched C 1 -C 20 chain in which at least one methylene may be replaced by oxygen. Fluoroalkyl; fluoroaryl having 6 to 20 carbon atoms in which at least one hydrogen is replaced by fluorine or trifluoromethyl; or at least one hydrogen in aryl is replaced by fluorine or trifluoromethyl, 20 is a fluoroarylalkyl, and A 1 is a group represented by the following formula (1-1) or the following formula (1-2).
（上記式（１－１）において、Ｙ３は炭素数２～１０のアルキレンを示し、Ｒ６は水素、または炭素数１～５の直鎖もしくは分岐鎖のアルキル、または炭素数６～１０のアリールである。）
(In the above formula (1-1), Y 3 represents an alkylene having 2 to 10 carbon atoms, R 6 represents hydrogen, a linear or branched alkyl having 1 to 5 carbon atoms, or 6 to 10 carbon atoms It is aryl.)
（上記式（１－２）において、Ｙ４は単結合または炭素数１～１０のアルキレンである。）
(In the above formula (1-2), Y 4 is a single bond or alkylene having 1 to 10 carbon atoms.)
（発明２）上記光重合性ウレタンアクリレート組成物において、上記（Ａ）光重合性ウレタンアクリレート混合物と上記（Ｂ）フィラーとの合計１００重量部あたり、上記（Ａ）光重合性ウレタンアクリレート混合物が６０重量部以上９０重量部以下、上記（Ｂ）フィラーが１０重量部以上４０重量部以下の割合で存在する、発明１に記載の自動車内外装部品用表面改質フィルム。
(Invention 2) In the photopolymerizable urethane acrylate composition, the (A) photopolymerizable urethane acrylate mixture is 60 per 100 parts by weight in total of the (A) photopolymerizable urethane acrylate mixture and the (B) filler. The surface-modified film for automobile interior and exterior parts according to Invention 1, wherein the filler (B) is present in a proportion of 10 parts by weight to 40 parts by weight based on parts by weight to 90 parts by weight.
（発明３）上記成分（ａ４）が下記式（１-３）で表されるγ－メタクリロキシプロピルヘプタ（トリフルオロプロピル）－Ｔ８－シルセスキオキサンに由来する単位を有する光重合性アクリレートオリゴマーである、発明１または２に記載の自動車内外装部品用表面改質フィルム。
(Invention 3) A photopolymerizable acrylate oligomer having a unit derived from γ-methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane represented by the following formula (1-3): The surface-modified film for automobile interior and exterior parts according to Invention 1 or 2.
（発明４）自動車内外装部品がインストルメントパネル、エンブレム、ラジエータグリル、各種ガーニッシュから選ばれる発明１～３のいずれかに記載の自動車内外装部品用表面改質フィルム。
(Invention 4) A surface-modified film for automobile interior and exterior parts according to any one of Inventions 1 to 3, wherein the interior and exterior parts of the automobile are selected from an instrument panel, an emblem, a radiator grille and various garnishes.
（発明５）発明１～４のいずれかに記載の自動車内外装部品用表面改質フィルムで表面の少なくとも一部が被覆された、自動車内外装部品。
(Invention 5) An interior / exterior component of an automobile, wherein at least a part of the surface is covered with the surface modified film for the interior / exterior component according to any one of Inventions 1-4.
本発明の自動車内外装部品用表面改質フィルム（以下「改質フィルム」）は撥油性、防汚性、撥水性、日焼け止めクリーム耐性、虫よけスプレー耐性、高い表面硬度、透明性・透明性、成形性をバランスよく備える。本発明の改質フィルムで表面の少なくとも一部が被覆された自動車内外装部品は、撥油性、防汚性、撥水性、日焼け止めクリーム耐性、虫よけスプレー耐性、高い表面硬度、透明性・透明性、成形性をバランスよく備える。
The surface modified film (hereinafter "modified film") for automobile interior and exterior parts according to the present invention is oil-repellent, antifouling, water-repellent, sunscreen cream resistant, insect spray resistant, high surface hardness, transparency and transparency Have a balance between moldability and formability. The interior and exterior parts of an automobile having at least a part of the surface coated with the modified film of the present invention have oil repellency, stain resistance, water repellency, sunscreen cream resistance, insect spray resistance, high surface hardness, transparency, Transparency and formability are well balanced.
本発明の改質フィルムは、（Ａ）光重合性ウレタンアクリレート混合物と、（Ｃ）光重合開始剤とを含み、さらに必要に応じて（Ｂ）フィラーを含む光重合性ウレタンアクリレート組成物の硬化物からなる表面保護層が、アクリル樹脂製基材フィルムの片面に積層されたものである。以下、上記表面保護層に用いる材料について詳述する。
The modified film of the present invention comprises (A) a photopolymerizable urethane acrylate mixture and (C) a photopolymerization initiator, and further, if necessary, a cured photopolymerizable urethane acrylate composition containing a (B) filler. The surface protection layer which consists of a thing is laminated | stacked on the single side | surface of the base film made from an acrylic resin. Hereinafter, the material used for the said surface protective layer is explained in full detail.
［（Ａ）光重合性ウレタンアクリレート混合物］
本発明で用いる（Ａ）光重合性ウレタンアクリレート組成物は上記光重合性ウレタンアクリレート組成物の主成分であって、（ａ１）光重合性ウレタンアクリルポリマー、（ａ２）多官能アクリレート化合物、（ａ３）フッ素含有光重合性アクリル化合物、（ａ４）フルオロシルセスキオキサン誘導体に由来する単位を有する光重合性アクリレートオリゴマーを含む。以下、上記成分（ａ１）、（ａ２）、（ａ３）、（ａ４）について詳述する。 [(A) photopolymerizable urethane acrylate mixture]
The (A) photopolymerizable urethane acrylate composition used in the present invention is a main component of the above photopolymerizable urethane acrylate composition, and (a1) a photopolymerizable urethane acrylic polymer, (a2) a polyfunctional acrylate compound, (a3 And (4) a photopolymerizable acrylate oligomer having a unit derived from a fluorine-containing photopolymerizable acrylic compound and (a4) fluorosilsesquioxane derivative. Hereinafter, the components (a1), (a2), (a3) and (a4) will be described in detail.
本発明で用いる（Ａ）光重合性ウレタンアクリレート組成物は上記光重合性ウレタンアクリレート組成物の主成分であって、（ａ１）光重合性ウレタンアクリルポリマー、（ａ２）多官能アクリレート化合物、（ａ３）フッ素含有光重合性アクリル化合物、（ａ４）フルオロシルセスキオキサン誘導体に由来する単位を有する光重合性アクリレートオリゴマーを含む。以下、上記成分（ａ１）、（ａ２）、（ａ３）、（ａ４）について詳述する。 [(A) photopolymerizable urethane acrylate mixture]
The (A) photopolymerizable urethane acrylate composition used in the present invention is a main component of the above photopolymerizable urethane acrylate composition, and (a1) a photopolymerizable urethane acrylic polymer, (a2) a polyfunctional acrylate compound, (a3 And (4) a photopolymerizable acrylate oligomer having a unit derived from a fluorine-containing photopolymerizable acrylic compound and (a4) fluorosilsesquioxane derivative. Hereinafter, the components (a1), (a2), (a3) and (a4) will be described in detail.
［（ａ１）光重合性ウレタンアクリルポリマー］
光重合性ウレタンアクリルポリマーは、工業的に多用されている反応性ポリマーである。その分子は剛直なアクリルオリゴマー鎖と柔軟なウレタンオリゴマー鎖を必須の構成単位とし、数千から数十万程度の重量平均分子量を有する。このような光重合性ウレタンアクリルポリマーを塗料のプライマーや成形品表面の機能化のために用いる場合、溶液状の光重合性ウレタンアクリルポリマーを目的物に塗布し、その後、塗膜を紫外線などの光エネルギーによって硬化（光重合）する。光重合の過程で光重合性ウレタンアクリルポリマーの分子末端に存在するアクリロイル基が反応系内の他のアクリロイル基と反応して分子鎖が延長し、アクリルオリゴマー鎖に由来する強度とウレタンオリゴマー鎖に由来する柔軟性を兼ね備える高分子量化されたウレタンアクリルポリマーが被塗布物表面に密着する。一般に、光重合性ウレタンアクリルポリマーの分子構造や分子量を選択することで、塗膜の強度や柔軟性が調節される。 [(A1) photopolymerizable urethane acrylic polymer]
The photopolymerizable urethane acrylic polymer is a reactive polymer which is widely used in industry. The molecule has a rigid acrylic oligomer chain and a flexible urethane oligomer chain as essential constitutional units, and has a weight average molecular weight of several thousands to several hundreds of thousands. When such a photopolymerizable urethane acrylic polymer is used for functionalization of a primer of a paint or the surface of a molded product, a solution-like photopolymerizable urethane acrylic polymer is applied to a target object, and then a coating film is exposed to ultraviolet light and the like. It is cured (photopolymerized) by light energy. In the process of photopolymerization, the acryloyl group present at the molecular terminal of the photopolymerizable urethane acrylic polymer reacts with other acryloyl groups in the reaction system to extend the molecular chain, resulting in the strength derived from the acrylic oligomer chain and the urethane oligomer chain. A high molecular weight urethane acrylic polymer having flexibility derived from it adheres to the surface of the article to be coated. In general, the strength and flexibility of the coating film are controlled by selecting the molecular structure and molecular weight of the photopolymerizable urethane acrylic polymer.
光重合性ウレタンアクリルポリマーは、工業的に多用されている反応性ポリマーである。その分子は剛直なアクリルオリゴマー鎖と柔軟なウレタンオリゴマー鎖を必須の構成単位とし、数千から数十万程度の重量平均分子量を有する。このような光重合性ウレタンアクリルポリマーを塗料のプライマーや成形品表面の機能化のために用いる場合、溶液状の光重合性ウレタンアクリルポリマーを目的物に塗布し、その後、塗膜を紫外線などの光エネルギーによって硬化（光重合）する。光重合の過程で光重合性ウレタンアクリルポリマーの分子末端に存在するアクリロイル基が反応系内の他のアクリロイル基と反応して分子鎖が延長し、アクリルオリゴマー鎖に由来する強度とウレタンオリゴマー鎖に由来する柔軟性を兼ね備える高分子量化されたウレタンアクリルポリマーが被塗布物表面に密着する。一般に、光重合性ウレタンアクリルポリマーの分子構造や分子量を選択することで、塗膜の強度や柔軟性が調節される。 [(A1) photopolymerizable urethane acrylic polymer]
The photopolymerizable urethane acrylic polymer is a reactive polymer which is widely used in industry. The molecule has a rigid acrylic oligomer chain and a flexible urethane oligomer chain as essential constitutional units, and has a weight average molecular weight of several thousands to several hundreds of thousands. When such a photopolymerizable urethane acrylic polymer is used for functionalization of a primer of a paint or the surface of a molded product, a solution-like photopolymerizable urethane acrylic polymer is applied to a target object, and then a coating film is exposed to ultraviolet light and the like. It is cured (photopolymerized) by light energy. In the process of photopolymerization, the acryloyl group present at the molecular terminal of the photopolymerizable urethane acrylic polymer reacts with other acryloyl groups in the reaction system to extend the molecular chain, resulting in the strength derived from the acrylic oligomer chain and the urethane oligomer chain. A high molecular weight urethane acrylic polymer having flexibility derived from it adheres to the surface of the article to be coated. In general, the strength and flexibility of the coating film are controlled by selecting the molecular structure and molecular weight of the photopolymerizable urethane acrylic polymer.
本発明の（Ａ）光重合性ウレタンアクリレート混合物を構成する（ａ１）光重合性ウレタンアクリルポリマーとしては、上述のような光重合性ウレタンアクリルポリマーの中で塗料用あるいはコート剤として使用可能なものを制限なく使用することができる。このような（ａ１）光重合性ウレタンアクリルポリマーとして例えば大成ファインケミカル社製「アクリット８ＢＲシリーズ」、ＤＩＣ社製「ＵＮＩＤＩＣ」、日立化成社製「ヒタロイド」、亜細亜工業化学社製「ＲＵＡシリーズ」などを使用することができる。
Among the photopolymerizable urethane acrylic polymers as described above which can be used as a coating or coating agent as the (a1) photopolymerizable urethane acrylic polymer constituting the (A) photopolymerizable urethane acrylate mixture of the present invention Can be used without restriction. As such (a1) photopolymerizable urethane acrylic polymers, for example, “Akrit 8 BR series” manufactured by Taisei Fine Chemical Co., Ltd., “UNIDIC” manufactured by DIC, “Hitaloid” manufactured by Hitachi Chemical Co., Ltd., “RUA series” manufactured by Subia Industrial Chemical Co., Ltd. It can be used.
［（ａ２）多官能アクリレート化合物］
多官能アクリレート化合物は、多価アルコールと各種アクリル酸系化合物との縮合反応で得られた１分子中に複数の光重合性基を有するモノマーであり、光重合性ポリマー材料の一つとして工業的に多用されている。光重合性ウレタンアクリレートなどの光重合性ポリマーを多官能アクリレート化合物の存在下に光硬化することによって、ウレタンアクリレートの分子鎖の延長と同時にウレタンアクリレート分子内に架橋構造を導入することができる。そのため、多官能アクリレート化合物は光重合性ウレタンアクリルポリマーなどの光重合性ポリマーの硬化物の分子量や強度の調節に用いられる。 [(A2) Multifunctional Acrylate Compound]
A polyfunctional acrylate compound is a monomer having a plurality of photopolymerizable groups in one molecule obtained by the condensation reaction of a polyhydric alcohol and various acrylic acid compounds, and is industrially one of the photopolymerizable polymer materials. Are often used. By photocuring a photopolymerizable polymer such as a photopolymerizable urethane acrylate in the presence of a polyfunctional acrylate compound, a crosslinked structure can be introduced into the urethane acrylate molecule simultaneously with the extension of the urethane acrylate molecular chain. Therefore, a polyfunctional acrylate compound is used to control the molecular weight and the strength of a cured product of a photopolymerizable polymer such as a photopolymerizable urethane acrylic polymer.
多官能アクリレート化合物は、多価アルコールと各種アクリル酸系化合物との縮合反応で得られた１分子中に複数の光重合性基を有するモノマーであり、光重合性ポリマー材料の一つとして工業的に多用されている。光重合性ウレタンアクリレートなどの光重合性ポリマーを多官能アクリレート化合物の存在下に光硬化することによって、ウレタンアクリレートの分子鎖の延長と同時にウレタンアクリレート分子内に架橋構造を導入することができる。そのため、多官能アクリレート化合物は光重合性ウレタンアクリルポリマーなどの光重合性ポリマーの硬化物の分子量や強度の調節に用いられる。 [(A2) Multifunctional Acrylate Compound]
A polyfunctional acrylate compound is a monomer having a plurality of photopolymerizable groups in one molecule obtained by the condensation reaction of a polyhydric alcohol and various acrylic acid compounds, and is industrially one of the photopolymerizable polymer materials. Are often used. By photocuring a photopolymerizable polymer such as a photopolymerizable urethane acrylate in the presence of a polyfunctional acrylate compound, a crosslinked structure can be introduced into the urethane acrylate molecule simultaneously with the extension of the urethane acrylate molecular chain. Therefore, a polyfunctional acrylate compound is used to control the molecular weight and the strength of a cured product of a photopolymerizable polymer such as a photopolymerizable urethane acrylic polymer.
本発明の（Ａ）光重合性ウレタンアクリレート混合物を構成する（ａ２）多官能アクリレート化合物としては、上述のような多官能アクリレート化合物を制限なく使用することができる。このような（ａ２）多官能アクリレート化合物として例えば新中村化学工業社製光硬化性アクリレート、日本化薬社製「ＫＡＹＡＲＡＤ」、東亞合成社製「アロニックス（登録商標）」、巴工業社製多官能アクリレート、共栄社化学社製多官能アクリレートなどを使用することができる。
As the (a2) polyfunctional acrylate compound which comprises the (A) photopolymerizable urethane acrylate mixture of this invention, the above-mentioned polyfunctional acrylate compounds can be used without restriction. Examples of such (a2) polyfunctional acrylate compounds include photocurable acrylates manufactured by Shin-Nakamura Chemical Co., Ltd., “KAYARAD” manufactured by Nippon Kayaku Co., Ltd., “Alonix (registered trademark)” manufactured by Toagosei Co., Ltd. Acrylate, polyfunctional acrylate manufactured by Kyoeisha Chemical Co., Ltd., etc. can be used.
［（ａ３）フッ素含有光重合性アクリル化合物］
本発明で用いる（Ａ）光重合性ウレタンアクリレート組成物は、上記表面保護層に顕著な防汚性と撥水性を付与するために、（ａ３）フッ素含有光重合性アクリル化合物をさらに含有する。本発明の（ａ３）フッ素含有光重合性アクリル化合物としては、上述のような光重合性ウレタンアクリルポリマーや多官能アクリレート化合物をはじめとする光重合性アクリル系オリゴマー・モノマーにフッ素原子あるいはフッ素含有基が導入されたいわゆるフッ素含有アクリルポリマーを制限なく使用することができる。このような（ａ３）フッ素含有光重合性アクリル化合物として例えば東振化学社製「ＬＥ-６００」、大阪有機化学工業社製「ビスコート８ＦＭ」、ＤＩＣ社製「メガファックＲＳ」、関東電化工業社製「エフクリア（登録商標）」などを使用することができる。 [(A3) Fluorine-Containing Photopolymerizable Acrylic Compound]
The (A) photopolymerizable urethane acrylate composition used in the present invention further contains (a3) a fluorine-containing photopolymerizable acrylic compound in order to impart remarkable stain resistance and water repellency to the surface protective layer. As the (a3) fluorine-containing photopolymerizable acrylic compound of the present invention, a fluorine atom or a fluorine-containing group is added to a photopolymerizable acrylic oligomer or monomer such as a photopolymerizable urethane acrylic polymer or polyfunctional acrylate compound as described above. So-called fluorine-containing acrylic polymers, into which is introduced, can be used without limitation. As such (a3) fluorine-containing photopolymerizable acrylic compound, for example, "LE-600" manufactured by Toho Chemical Co., Ltd., "Viscoat 8 FM" manufactured by Osaka Organic Chemical Industry Co., Ltd., "Megafuck RS" manufactured by DIC, Kanto Electrification Co., Ltd. A product such as "F-CLEAR (registered trademark)" can be used.
本発明で用いる（Ａ）光重合性ウレタンアクリレート組成物は、上記表面保護層に顕著な防汚性と撥水性を付与するために、（ａ３）フッ素含有光重合性アクリル化合物をさらに含有する。本発明の（ａ３）フッ素含有光重合性アクリル化合物としては、上述のような光重合性ウレタンアクリルポリマーや多官能アクリレート化合物をはじめとする光重合性アクリル系オリゴマー・モノマーにフッ素原子あるいはフッ素含有基が導入されたいわゆるフッ素含有アクリルポリマーを制限なく使用することができる。このような（ａ３）フッ素含有光重合性アクリル化合物として例えば東振化学社製「ＬＥ-６００」、大阪有機化学工業社製「ビスコート８ＦＭ」、ＤＩＣ社製「メガファックＲＳ」、関東電化工業社製「エフクリア（登録商標）」などを使用することができる。 [(A3) Fluorine-Containing Photopolymerizable Acrylic Compound]
The (A) photopolymerizable urethane acrylate composition used in the present invention further contains (a3) a fluorine-containing photopolymerizable acrylic compound in order to impart remarkable stain resistance and water repellency to the surface protective layer. As the (a3) fluorine-containing photopolymerizable acrylic compound of the present invention, a fluorine atom or a fluorine-containing group is added to a photopolymerizable acrylic oligomer or monomer such as a photopolymerizable urethane acrylic polymer or polyfunctional acrylate compound as described above. So-called fluorine-containing acrylic polymers, into which is introduced, can be used without limitation. As such (a3) fluorine-containing photopolymerizable acrylic compound, for example, "LE-600" manufactured by Toho Chemical Co., Ltd., "Viscoat 8 FM" manufactured by Osaka Organic Chemical Industry Co., Ltd., "Megafuck RS" manufactured by DIC, Kanto Electrification Co., Ltd. A product such as "F-CLEAR (registered trademark)" can be used.
［（ａ４）フルオロシルセスキオキサン誘導体に由来する単位を有する光重合性アクリレートオリゴマー］
本発明で用いる（ａ４）フルオロシルセスキオキサン誘導体に由来する単位を有する光重合性アクリレートオリゴマーは本出願人が開発に成功した防汚性の向上に寄与する光重合性オリゴマーである。上記フルオロシルセスキオキサン誘導体は下記式（１）で表される化合物である。 [(A4) Photopolymerizable Acrylate Oligomer Having a Unit Derived from a Fluorosilsesquioxane Derivative]
The photopolymerizable acrylate oligomer having a unit derived from the (a4) fluorosilsesquioxane derivative used in the present invention is a photopolymerizable oligomer which contributes to the improvement of the antifouling property developed by the present applicant. The fluorosilsesquioxane derivative is a compound represented by the following formula (1).
本発明で用いる（ａ４）フルオロシルセスキオキサン誘導体に由来する単位を有する光重合性アクリレートオリゴマーは本出願人が開発に成功した防汚性の向上に寄与する光重合性オリゴマーである。上記フルオロシルセスキオキサン誘導体は下記式（１）で表される化合物である。 [(A4) Photopolymerizable Acrylate Oligomer Having a Unit Derived from a Fluorosilsesquioxane Derivative]
The photopolymerizable acrylate oligomer having a unit derived from the (a4) fluorosilsesquioxane derivative used in the present invention is a photopolymerizable oligomer which contributes to the improvement of the antifouling property developed by the present applicant. The fluorosilsesquioxane derivative is a compound represented by the following formula (1).
上記式（１）において、Ｒｆ
１～Ｒｆ
７はそれぞれ独立して、少なくとも１つのメチレンが酸素で置き換えられていてもよい、炭素数１～２０の、直鎖状もしくは分岐鎖状のフルオロアルキル；少なくとも１つの水素がフッ素もしくはトリフルオロメチルで置き換えられた、炭素数６～２０のフルオロアリール；またはアリール中の少なくとも１つの水素がフッ素もしくはトリフルオロメチルで置き換えられた、炭素数７～２０のフルオロアリールアルキルであり、Ａ１は、下記式（１－１）または下記式（１－２）で表される基である。
In the above formula (1), R f 1 to R f 7 each independently represent a linear or branched fluorocarbon having 1 to 20 carbon atoms in which at least one methylene may be replaced by oxygen. Alkyl; fluoroaryl having 6 to 20 carbon atoms in which at least one hydrogen is replaced by fluorine or trifluoromethyl; or at least one hydrogen in aryl is substituted by fluorine or trifluoromethyl, 7 to 20 carbon atoms And A 1 is a group represented by the following formula (1-1) or the following formula (1-2).
好ましくは、上記式（１）におけるＲｆ
１～Ｒｆ
７はそれぞれ独立して、３，３，３－トリフルオロプロピル、３，３，４，４，４－ペンタフルオロブチル、３，３，４，４，５，５，６，６，６－ノナフルオロヘキシル、トリデカフルオロ－１，１，２，２－テトラヒドロオクチル、ヘプタデカフルオロ－１，１，２，２－テトラヒドロデシル、ヘンイコサフルオロ－１，１，２，２－テトラヒドロドデシル、ペンタコサフルオロ－１，１，２，２－テトラヒドロテトラデシル、（３－ヘプタフルオロイソプロポキシ）プロピル、ペンタフルオロフェニルプロピル、ペンタフルオロフェニル、またはα，α，α－トリフルオロメチルフェニルである。
Preferably, R f 1 to R f 7 in the above formula (1) are each independently 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,3, 4,4,5,5,6,6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, heniko Subfluoro-1,1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl or α, α, α-trifluoromethylphenyl.
より好ましくは、上記式（１）におけるＲｆ
１～Ｒｆ
７はそれぞれ独立して、３，３，３－トリフルオロプロピル、または３，３，４，４，５，５，６，６，６－ノナフルオロヘキシルである。
More preferably, R f 1 to R f 7 in the above formula (1) are each independently 3,3,3-trifluoropropyl or 3,3,4,4,5,5,6,6,6 6-nonafluorohexyl.
上記式（１－１）において、Ｙ３は炭素数２～１０のアルキレン、好ましくは炭素数２～６のアルキレンであり、Ｒ６は水素、または炭素数１～５の直鎖もしくは分岐鎖のアルキル、または炭素数６～１０のアリール、好ましくは水素または炭素数１～３のアルキルである。
In the above formula (1-1), Y 3 is alkylene having 2 to 10 carbon atoms, preferably alkylene having 2 to 6 carbon atoms, R 6 is hydrogen, or a straight or branched chain having 1 to 5 carbon atoms Alkyl or aryl having 6 to 10 carbon atoms, preferably hydrogen or alkyl having 1 to 3 carbon atoms.
上記式（１－２）において、Ｙ４は単結合または炭素数１～１０のアルキレンである。
In the above formula (1-2), Y 4 is a single bond or alkylene having 1 to 10 carbon atoms.
上記フルオロシルセスキオキサン誘導体（１）は、以下の方法により製造される。まず、下記式（２）で表される３官能の加水分解性基を有するケイ素化合物（２）をアルカリ金属水酸化物の存在下、含酸素有機溶剤中で加水分解し重縮合させることにより、下記式（３）で表される化合物（３）を製造する。
The above fluorosilsesquioxane derivative (1) is produced by the following method. First, the silicon compound (2) having a trifunctional hydrolyzable group represented by the following formula (2) is hydrolyzed and polycondensed in the presence of an alkali metal hydroxide in an oxygen-containing organic solvent, The compound (3) represented by following formula (3) is manufactured.
上記式（３）中、Ｍはアルカリ金属であれば特に限定されない。このようなアルカリ金属として、例えばリチウム、ナトリウム、カリウム、セシウム等が挙げられる。
If M is an alkali metal in said Formula (3), it will not be specifically limited. Examples of such an alkali metal include lithium, sodium, potassium and cesium.
上記式（２）、（３）におけるＲはそれぞれ独立して上記式（１）のＲｆ
１～Ｒｆ
７から選ばれる１つの基に一致し、少なくとも１つのメチレンが酸素で置き換えられていてもよい、炭素数１～２０の、直鎖状もしくは分岐鎖状のフルオロアルキル；少なくとも１つの水素がフッ素もしくはトリフルオロメチルで置き換えられた、炭素数６～２０のフルオロアリール；またはアリール中の少なくとも１つの水素がフッ素もしくはトリフルオロメチルで置き換えられた、炭素数７～２０のフルオロアリールアルキルであり、Ｘは、加水分解性基である。
R in the above formulas (2) and (3) independently corresponds to one group selected from R f 1 to R f 7 in the above formula (1), and at least one methylene is replaced by oxygen C 1-20 linear or branched fluoroalkyl; C 6-20 fluoroaryl in which at least one hydrogen is replaced by fluorine or trifluoromethyl; or at least in aryl It is a fluoroarylalkyl having 7 to 20 carbon atoms in which one hydrogen is replaced by fluorine or trifluoromethyl, and X is a hydrolyzable group.
好ましくは、上記式（２）、（３）におけるＲはそれぞれ独立して、３，３，３－トリフルオロプロピル、３，３，４，４，４－ペンタフルオロブチル、３，３，４，４，５，５，６，６，６－ノナフルオロヘキシル、トリデカフルオロ－１，１，２，２－テトラヒドロオクチル、ヘプタデカフルオロ－１，１，２，２－テトラヒドロデシル、ヘンイコサフルオロ－１，１，２，２－テトラヒドロドデシル、ペンタコサフルオロ－１，１，２，２－テトラヒドロテトラデシル、（３－ヘプタフルオロイソプロポキシ）プロピル、ペンタフルオロフェニルプロピル、ペンタフルオロフェニル、またはα，α，α－トリフルオロメチルフェニルである。
Preferably, R in the above formulas (2) and (3) is each independently 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4, 4,5,5,6,6,6-Nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, helicosafluoro -1,1,2,2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl or α, α, It is α, α-trifluoromethylphenyl.
より好ましくは、上記式（２）におけるＲはそれぞれ独立して、３，３，３－トリフルオロプロピル、または３，３，４，４，５，５，６，６，６－ノナフルオロヘキシルである。
More preferably, each R in the above formula (2) is independently 3,3,3,4,3-trifluoropropyl or 3,3,4,4,5,5,6,6,6-nonafluorohexyl is there.
次に、上記化合物（３）に下記式（４）で表される化合物（４）を反応させることによって、上記フルオロシルセスキオキサン誘導体（１）が得られる。
Next, the above fluorosilsesquioxane derivative (1) is obtained by reacting the above compound (3) with a compound (4) represented by the following formula (4).
上記式（４）における基Ｘは、上記式（１－１）または上記式（１－２）で表される基である。
The group X in the above formula (4) is a group represented by the above formula (1-1) or the above formula (1-2).
このようなフルオロシルセスキオキサン誘導体（１）の中で、下記式（５）で表されるγ－メタクリロキシプロピルヘプタ（トリフルオロプロピル）－Ｔ８－シルセスキオキサンが好ましい。
Among such fluorosilsesquioxane derivatives (1), γ-methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane represented by the following formula (5) is preferable.
γ－メタクリロキシプロピルヘプタ（トリフルオロプロピル）－Ｔ８－シルセスキオキサンなどのフルオロシルセスキオキサン誘導体（１）を、コート層に導入すると、コート層の防汚機能を一層向上することができる。フルオロシルセスキオキサン誘導体（１）を、ウレタン単位を有さずフッ素原子を含有する光重合性アクリル系化合物類に含有させる際は、これを直接他のウレタン単位を有さずフッ素原子を含有する光重合性アクリル系化合物類に混合してもよいし、これとウレタン単位を有さない光重合性アクリル系化合物類とをあらかじめ架橋及び／又は重合して製造したオリゴマーを、他のウレタン単位を有さずフッ素原子を含有する光重合性アクリル系化合物類に混合してもよい。
When the fluorosilsesquioxane derivative (1) such as γ-methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane is introduced into the coat layer, the antifouling function of the coat layer can be further improved . When the fluorosilsesquioxane derivative (1) is contained in a photopolymerizable acrylic compound having no urethane unit and containing a fluorine atom, it does not have another urethane unit directly but contains a fluorine atom. The other urethane unit may be an oligomer prepared by previously crosslinking and / or polymerizing a photopolymerizable acrylic compound which does not have a urethane unit, or may be mixed with the photopolymerizable acrylic compound to be It may be mixed with photopolymerizable acrylic compounds containing no fluorine atom and containing a fluorine atom.
一般的には、フルオロシルセスキオキサン誘導体（１）と上記単官能アクリレート、上記二官能アクリレート、上記多官能アクリレートから選ばれる１種以上のアクリレート系共重合成分とを共重合してフルオロシルセスキオキサン誘導体（１）単位を有する重合体をあらかじめ製造し、この重合体を、ウレタン単位を有さずフッ素原子を含有する光重合性アクリル系化合物類の一部として用いる。この場合、フルオロシルセスキオキサン誘導体（１）単位を有する重合体が上記ウレタンアクリレート１００重量部に対して０．０１重量部～１０重量部、好ましくは０．０５重量部～５重量部の割合となるように配合する。
Generally, the fluorosilsesquioxane derivative (1) is copolymerized with one or more acrylate copolymer components selected from the above monofunctional acrylates, the above bifunctional acrylates, and the above multifunctional acrylates to obtain fluorosilsesqui A polymer having an oxane derivative (1) unit is prepared in advance, and this polymer is used as part of a photopolymerizable acrylic compound having no urethane unit and containing a fluorine atom. In this case, the proportion of the polymer having the fluorosilsesquioxane derivative (1) unit is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the urethane acrylate. Mix to make
上述の分子内にフッ素原子を有する光硬化性アクリルモノマー及び／又はオリゴマー、あるいは上述のフルオロシルセスキオキサン誘導体（１）と共に使用するウレタン単位を有さずフッ素原子を含有する光重合性アクリル系化合物類としては、一般に光硬化性アクリルモノマーと称される化合物、例えば、（メタ）アクリル酸、（メタ）アクリル酸エステルやヒドロキシ基含有（メタ）アクリル酸エステルのような単官能アクリレート、（ポリ）アルキレングリコールジ（メタ）アクリレートなどの二官能アクリレート、ペンタエリスリトールトリアクリレートのような３官能以上の多官能アクリレートなどを、使用することができる。このような共重合成分は、上記光硬化性アクリルモノマーを含む反応性化合物を重合して得られるオリゴマーであってもよい。
Photocurable acrylic monomers and / or oligomers having a fluorine atom in the molecule described above, or a photopolymerizable acrylic system containing a fluorine atom without having a urethane unit to be used together with the fluorosilsesquioxane derivative (1) described above As compounds, compounds generally referred to as photocurable acrylic monomers, for example, monofunctional acrylates such as (meth) acrylic acid, (meth) acrylic acid ester and hydroxy group-containing (meth) acrylic acid ester (poly ( 2.) Difunctional acrylates such as alkylene glycol di (meth) acrylate, trifunctional or higher polyfunctional acrylates such as pentaerythritol triacrylate, etc. can be used. Such a copolymerization component may be an oligomer obtained by polymerizing a reactive compound containing the above photocurable acrylic monomer.
［成分（ａ１）、（ａ２）、（ａ３）、（ａ４）の量比］
上記成分（ａ１）、（ａ２）、（ａ３）、（ａ４）の量比は上記表面保護層の防汚性、撥水性、耐久性、耐薬品性、耐日焼け止めクリーム性のバランスに応じて適宜調節される。好ましくは、上記（Ａ）光重合性ウレタンアクリレート混合物１００重量部あたり、上記成分（ａ１）が２０重量部以上８７．９９重量部以下、上記成分（ａ２）が１重量部以上２５重量部以下、上記成分（ａ３）が１重量部以上１０重量部以下、上記成分（ａ４）が０．０１重量部以上５重量部以下の割合で存在する。 [Quantity ratio of components (a1), (a2), (a3), (a4)]
The ratio by weight of the components (a1), (a2), (a3) and (a4) depends on the balance between the antifouling property, water repellency, durability, chemical resistance and sunscreen resistance of the surface protective layer. Adjusted as appropriate. Preferably, 20 parts by weight or more and 87.99 parts by weight or less of the component (a1) and 1 parts by weight or more and 25 parts by weight or less of the component (a2) per 100 parts by weight of the (A) photopolymerizable urethane acrylate mixture The component (a3) is present in an amount of 1 to 10 parts by weight, and the component (a4) is present in a proportion of 0.01 to 5 parts by weight.
上記成分（ａ１）、（ａ２）、（ａ３）、（ａ４）の量比は上記表面保護層の防汚性、撥水性、耐久性、耐薬品性、耐日焼け止めクリーム性のバランスに応じて適宜調節される。好ましくは、上記（Ａ）光重合性ウレタンアクリレート混合物１００重量部あたり、上記成分（ａ１）が２０重量部以上８７．９９重量部以下、上記成分（ａ２）が１重量部以上２５重量部以下、上記成分（ａ３）が１重量部以上１０重量部以下、上記成分（ａ４）が０．０１重量部以上５重量部以下の割合で存在する。 [Quantity ratio of components (a1), (a2), (a3), (a4)]
The ratio by weight of the components (a1), (a2), (a3) and (a4) depends on the balance between the antifouling property, water repellency, durability, chemical resistance and sunscreen resistance of the surface protective layer. Adjusted as appropriate. Preferably, 20 parts by weight or more and 87.99 parts by weight or less of the component (a1) and 1 parts by weight or more and 25 parts by weight or less of the component (a2) per 100 parts by weight of the (A) photopolymerizable urethane acrylate mixture The component (a3) is present in an amount of 1 to 10 parts by weight, and the component (a4) is present in a proportion of 0.01 to 5 parts by weight.
［（Ｂ）フィラー］
本発明の光重合性ウレタンアクリレート組成物には上記（Ａ）光重合性ウレタンアクリレート混合物に加えてさらに（Ｂ）フィラーを配合することができる。本発明の（Ｂ）フィラーとしてはプラスチック成形材料や塗料に増量、強化、艶出し、撥水性付与、平滑性付与、意匠性付与などのために配合される無機フィラーを制限なく使用することができる。このような（Ｂ）フィラーとして例えばシリカ、酸化ジルコニウム、チタン酸バリウム、酸化チタン、アルミナなどを使用することができる。これらの中でいわゆるファイングレードのフィラーは上記表面保護層の外観を損なわない点で好ましい。例えば御国色素社製フィラー「ＭＨＩ」、日産化学工業社製シリカゾル「ＭＥＫシリーズ」は光重合性ウレタンアクリレート組成物への分散性が優れる点で上記（Ｂ）フィラーとして好ましい。 [(B) filler]
In addition to the (A) photopolymerizable urethane acrylate mixture, a (B) filler can be further blended in the photopolymerizable urethane acrylate composition of the present invention. As the filler (B) of the present invention, an inorganic filler compounded for increasing, strengthening, glossing, imparting water repellency, imparting smoothness, imparting design property, etc. to plastic molding materials and paints can be used without limitation. . As such (B) fillers, for example, silica, zirconium oxide, barium titanate, titanium oxide, alumina and the like can be used. Among these, so-called fine grade fillers are preferred in that they do not impair the appearance of the surface protective layer. For example, Filler "MHI" manufactured by Miku Miho Co., Ltd. and silica sol "MEK series" manufactured by Nissan Chemical Industries, Ltd. are preferable as the above-mentioned (B) filler in that the dispersibility in the photopolymerizable urethane acrylate composition is excellent.
本発明の光重合性ウレタンアクリレート組成物には上記（Ａ）光重合性ウレタンアクリレート混合物に加えてさらに（Ｂ）フィラーを配合することができる。本発明の（Ｂ）フィラーとしてはプラスチック成形材料や塗料に増量、強化、艶出し、撥水性付与、平滑性付与、意匠性付与などのために配合される無機フィラーを制限なく使用することができる。このような（Ｂ）フィラーとして例えばシリカ、酸化ジルコニウム、チタン酸バリウム、酸化チタン、アルミナなどを使用することができる。これらの中でいわゆるファイングレードのフィラーは上記表面保護層の外観を損なわない点で好ましい。例えば御国色素社製フィラー「ＭＨＩ」、日産化学工業社製シリカゾル「ＭＥＫシリーズ」は光重合性ウレタンアクリレート組成物への分散性が優れる点で上記（Ｂ）フィラーとして好ましい。 [(B) filler]
In addition to the (A) photopolymerizable urethane acrylate mixture, a (B) filler can be further blended in the photopolymerizable urethane acrylate composition of the present invention. As the filler (B) of the present invention, an inorganic filler compounded for increasing, strengthening, glossing, imparting water repellency, imparting smoothness, imparting design property, etc. to plastic molding materials and paints can be used without limitation. . As such (B) fillers, for example, silica, zirconium oxide, barium titanate, titanium oxide, alumina and the like can be used. Among these, so-called fine grade fillers are preferred in that they do not impair the appearance of the surface protective layer. For example, Filler "MHI" manufactured by Miku Miho Co., Ltd. and silica sol "MEK series" manufactured by Nissan Chemical Industries, Ltd. are preferable as the above-mentioned (B) filler in that the dispersibility in the photopolymerizable urethane acrylate composition is excellent.
本発明において本発明の（Ｂ）フィラーの配合割合は適宜決定される。好ましくは、上記（Ａ）光重合性ウレタンアクリレート混合物と上記（Ｂ）フィラーとの合計１００重量部あたり、上記（Ａ）光重合性ウレタンアクリレート混合物が６０重量部以上１００重量部以下、上記（Ｂ）フィラーが０重量部以上４０重量部以下の割合で存在する。より好ましくは、（Ａ）光重合性ウレタンアクリレート混合物と上記（Ｂ）フィラーとの合計１００重量部あたり、上記（Ａ）光重合性ウレタンアクリレート混合物が６０重量部以上９０重量部以下、上記（Ｂ）フィラーが１０重量部以上４０重量部以下の割合で存在する。
In the present invention, the blending ratio of the (B) filler of the present invention is appropriately determined. Preferably, 60 parts by weight or more and 100 parts by weight or less of the (A) photopolymerizable urethane acrylate mixture is contained per 100 parts by weight of the (A) photopolymerizable urethane acrylate mixture and the (B) filler in total; The filler is present in a proportion of 0 parts by weight or more and 40 parts by weight or less. More preferably, 60 parts by weight or more and 90 parts by weight or less of the (A) photopolymerizable urethane acrylate mixture is used per 100 parts by weight of the (A) photopolymerizable urethane acrylate mixture and the (B) filler in total; The filler is present in a proportion of 10 parts by weight or more and 40 parts by weight or less.
［（Ｃ）光重合開始剤］
本発明の光重合性ウレタンアクリレート組成物にはさらに（Ｃ）光重合開始剤を含む。上記（Ｃ）光重合開始剤の種類と配合量は光重合性アクリル系ポリマーの光重合において慣用の手法に従い制限されない。本発明の（Ｃ）光重合開始剤としてはＢＡＳＦ社製「ＩＲＧＡＣＵＲＥ」（現在はＩＧＭ Ｒｅｓｉｎｓ社製「Ｏｍｎｉｒａｄ」として販売されている）他の各種市販品を使用することができる。上記（Ｃ）光重合開始剤としてとしては、例えば、オリゴ｛２－ヒドロキシ－２－メチル－１－フェニルプロパンオン｝等のヒドロキシケトンのポリマー体、１－ヒドロキシジシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、１－｛４（２－ヒドロキシエトキシ）フェニル｝２－ヒドロキシ－２－メチル－１－プロパン１－オン、２，４，６－トリメチルベンゾイルジフェニルフォスフインオキサイド、ビス（２，４，６トリメチルベンゾイル）フェニルフォスフインオキサイド等を使用することができる。 [(C) photopolymerization initiator]
The photopolymerizable urethane acrylate composition of the present invention further comprises (C) a photopolymerization initiator. The kind and compounding quantity of said (C) photoinitiator are not restrict | limited in the photopolymerization of a photopolymerizable acrylic polymer according to the conventional method. As the photopolymerization initiator (C) of the present invention, various other commercial products manufactured by BASF "IRGACURE" (currently sold as "Omnirad" manufactured by IGM Resins) can be used. Examples of the (C) photopolymerization initiator include polymers of hydroxyketones such as oligo {2-hydroxy-2-methyl-1-phenylpropanone}, 1-hydroxydicyclohexyl phenyl ketone, 2-hydroxy-2 -Methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- {4 (2-hydroxyethoxy) phenyl} 2-hydroxy-2-methyl-1 -Propane 1-one, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis (2,4,6 trimethyl benzoyl) phenyl phosphine oxide, etc. can be used.
本発明の光重合性ウレタンアクリレート組成物にはさらに（Ｃ）光重合開始剤を含む。上記（Ｃ）光重合開始剤の種類と配合量は光重合性アクリル系ポリマーの光重合において慣用の手法に従い制限されない。本発明の（Ｃ）光重合開始剤としてはＢＡＳＦ社製「ＩＲＧＡＣＵＲＥ」（現在はＩＧＭ Ｒｅｓｉｎｓ社製「Ｏｍｎｉｒａｄ」として販売されている）他の各種市販品を使用することができる。上記（Ｃ）光重合開始剤としてとしては、例えば、オリゴ｛２－ヒドロキシ－２－メチル－１－フェニルプロパンオン｝等のヒドロキシケトンのポリマー体、１－ヒドロキシジシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、１－｛４（２－ヒドロキシエトキシ）フェニル｝２－ヒドロキシ－２－メチル－１－プロパン１－オン、２，４，６－トリメチルベンゾイルジフェニルフォスフインオキサイド、ビス（２，４，６トリメチルベンゾイル）フェニルフォスフインオキサイド等を使用することができる。 [(C) photopolymerization initiator]
The photopolymerizable urethane acrylate composition of the present invention further comprises (C) a photopolymerization initiator. The kind and compounding quantity of said (C) photoinitiator are not restrict | limited in the photopolymerization of a photopolymerizable acrylic polymer according to the conventional method. As the photopolymerization initiator (C) of the present invention, various other commercial products manufactured by BASF "IRGACURE" (currently sold as "Omnirad" manufactured by IGM Resins) can be used. Examples of the (C) photopolymerization initiator include polymers of hydroxyketones such as oligo {2-hydroxy-2-methyl-1-phenylpropanone}, 1-hydroxydicyclohexyl phenyl ketone, 2-hydroxy-2 -Methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- {4 (2-hydroxyethoxy) phenyl} 2-hydroxy-2-methyl-1 -Propane 1-one, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis (2,4,6 trimethyl benzoyl) phenyl phosphine oxide, etc. can be used.
［その他の添加剤］
上記光重合性ウレタンアクリレート組成物には上記成分（Ａ），（Ｂ），（Ｃ）に加えて一般的に塗料やフィルムの材料に配合される酸化防止剤、耐候安定剤、調色剤、希釈剤などの添加剤もさらに配合することができる。その配合量は、上記表面保護層の機能を低下させない範囲であれば制限されない。 [Other additives]
In the photopolymerizable urethane acrylate composition, in addition to the components (A), (B) and (C), an antioxidant, a weathering stabilizer, a color-matching agent, and the like, which are generally compounded in paint and film materials Additives such as diluents can also be further formulated. The compounding amount is not limited as long as the function of the surface protective layer is not reduced.
上記光重合性ウレタンアクリレート組成物には上記成分（Ａ），（Ｂ），（Ｃ）に加えて一般的に塗料やフィルムの材料に配合される酸化防止剤、耐候安定剤、調色剤、希釈剤などの添加剤もさらに配合することができる。その配合量は、上記表面保護層の機能を低下させない範囲であれば制限されない。 [Other additives]
In the photopolymerizable urethane acrylate composition, in addition to the components (A), (B) and (C), an antioxidant, a weathering stabilizer, a color-matching agent, and the like, which are generally compounded in paint and film materials Additives such as diluents can also be further formulated. The compounding amount is not limited as long as the function of the surface protective layer is not reduced.
［表面保護層］
上述の（Ａ）光重合性ウレタンアクリレート混合物と、（Ｂ）フィラーと、（Ｃ）光重合開始剤と、必要に応じて配合され得るその他の添加剤からなる光重合性ウレタンアクリレート組成物の硬化物が本発明の表面保護層を形成する。本発明の表面保護層はアクリル樹脂製基材フィルムの片面に積層されている。 [Surface protection layer]
Curing of a photopolymerizable urethane acrylate composition comprising the above-described (A) photopolymerizable urethane acrylate mixture, (B) filler, (C) photopolymerization initiator, and other additives which may be optionally blended An object forms the surface protection layer of the present invention. The surface protective layer of the present invention is laminated on one side of an acrylic resin base film.
上述の（Ａ）光重合性ウレタンアクリレート混合物と、（Ｂ）フィラーと、（Ｃ）光重合開始剤と、必要に応じて配合され得るその他の添加剤からなる光重合性ウレタンアクリレート組成物の硬化物が本発明の表面保護層を形成する。本発明の表面保護層はアクリル樹脂製基材フィルムの片面に積層されている。 [Surface protection layer]
Curing of a photopolymerizable urethane acrylate composition comprising the above-described (A) photopolymerizable urethane acrylate mixture, (B) filler, (C) photopolymerization initiator, and other additives which may be optionally blended An object forms the surface protection layer of the present invention. The surface protective layer of the present invention is laminated on one side of an acrylic resin base film.
［アクリル樹脂製基材フィルム］
本発明で用いるアクリル樹脂製基材フィルムは、アクリル樹脂を主体とする単層あるいは多層のフィルムあるいはシートである。上記アクリル樹脂製基材フィルムを構成するアクリル樹脂としては自動車内外装部品の材料として公知のものを制限なく使用することができる。このようなアクリル樹脂製基材フィルムとして例えば三菱ケミカル社製「アクリプレン（登録商標）」、カネカ社製造「サンデュレン」、クラレ社製「パラピュア」「コモグラス」などを用いることができる。 [Base film made of acrylic resin]
The acrylic resin base film used in the present invention is a single layer or multilayer film or sheet mainly composed of an acrylic resin. As an acrylic resin which comprises the said acrylic resin base film, the thing well-known as a material of an automobile interior and exterior part can be used without a restriction | limiting. As such an acrylic resin base film, for example, "Acriprene (registered trademark)" manufactured by Mitsubishi Chemical Co., Ltd., "Sunduren" manufactured by Kaneka Co., Ltd., "Parapure""Komogurasu" manufactured by Kuraray Co., Ltd., etc. can be used.
本発明で用いるアクリル樹脂製基材フィルムは、アクリル樹脂を主体とする単層あるいは多層のフィルムあるいはシートである。上記アクリル樹脂製基材フィルムを構成するアクリル樹脂としては自動車内外装部品の材料として公知のものを制限なく使用することができる。このようなアクリル樹脂製基材フィルムとして例えば三菱ケミカル社製「アクリプレン（登録商標）」、カネカ社製造「サンデュレン」、クラレ社製「パラピュア」「コモグラス」などを用いることができる。 [Base film made of acrylic resin]
The acrylic resin base film used in the present invention is a single layer or multilayer film or sheet mainly composed of an acrylic resin. As an acrylic resin which comprises the said acrylic resin base film, the thing well-known as a material of an automobile interior and exterior part can be used without a restriction | limiting. As such an acrylic resin base film, for example, "Acriprene (registered trademark)" manufactured by Mitsubishi Chemical Co., Ltd., "Sunduren" manufactured by Kaneka Co., Ltd., "Parapure""Komogurasu" manufactured by Kuraray Co., Ltd., etc. can be used.
［改質フィルム］
本発明のアクリル樹脂製基材フィルムの厚みは特に限定されないが、通常は１００μｍ以上５００μｍ以下であり、好ましくは２００μｍ以上４００μｍ以下である。このようなアクリル樹脂製基材フィルムの片面に上記溶液状の上記光重合性ウレタンアクリレート組成物を通常は１μｍ以上３０μｍ以下、好ましくは１μｍ以上２０μｍ以下の塗膜厚が得られるように塗布し、最終的に上記溶液状の上記光重合性ウレタンアクリレート組成物の硬化物が一般的には１μｍ以上３０μｍ以下、好ましくは１μｍ以上２０μｍ以下の表面保護層として上記アクリル樹脂製基材フィルムの片面に形成される。 [Modified film]
The thickness of the acrylic resin base film of the present invention is not particularly limited, but is usually 100 μm to 500 μm, preferably 200 μm to 400 μm. The solution-like photopolymerizable urethane acrylate composition is coated on one side of such an acrylic resin base film so that a coating thickness of usually 1 μm to 30 μm, preferably 1 μm to 20 μm can be obtained, Finally, a cured product of the photopolymerizable urethane acrylate composition in the form of a solution is generally formed on one surface of the acrylic resin base film as a surface protective layer of 1 μm to 30 μm, preferably 1 μm to 20 μm. Be done.
本発明のアクリル樹脂製基材フィルムの厚みは特に限定されないが、通常は１００μｍ以上５００μｍ以下であり、好ましくは２００μｍ以上４００μｍ以下である。このようなアクリル樹脂製基材フィルムの片面に上記溶液状の上記光重合性ウレタンアクリレート組成物を通常は１μｍ以上３０μｍ以下、好ましくは１μｍ以上２０μｍ以下の塗膜厚が得られるように塗布し、最終的に上記溶液状の上記光重合性ウレタンアクリレート組成物の硬化物が一般的には１μｍ以上３０μｍ以下、好ましくは１μｍ以上２０μｍ以下の表面保護層として上記アクリル樹脂製基材フィルムの片面に形成される。 [Modified film]
The thickness of the acrylic resin base film of the present invention is not particularly limited, but is usually 100 μm to 500 μm, preferably 200 μm to 400 μm. The solution-like photopolymerizable urethane acrylate composition is coated on one side of such an acrylic resin base film so that a coating thickness of usually 1 μm to 30 μm, preferably 1 μm to 20 μm can be obtained, Finally, a cured product of the photopolymerizable urethane acrylate composition in the form of a solution is generally formed on one surface of the acrylic resin base film as a surface protective layer of 1 μm to 30 μm, preferably 1 μm to 20 μm. Be done.
上記表面保護層の形成において、はじめに、上述の（Ａ）光重合性ウレタンアクリレート混合物と、（Ｃ）光重合開始剤とを含み、さらに必要に応じて（Ｂ）フィラーを含む光重合性ウレタンアクリレート組成物を必要に応じて溶媒で希釈して得られる溶液が調整される。次にこの溶液を上記アクリル樹脂製基材フィルムの片面に塗布し、さらに適度な条件で乾燥後、塗布面に紫外線などの光エネルギー線を照射して上記光重合性ウレタンアクリレート組成物を硬化させる。こうして本発明の改質フィルムが得られる。
In the formation of the surface protective layer, first, a photopolymerizable urethane acrylate containing the above-mentioned (A) photopolymerizable urethane acrylate mixture and (C) a photopolymerization initiator and, if necessary, (B) a filler The resulting solution is prepared by diluting the composition with a solvent as needed. Next, this solution is applied to one surface of the above-mentioned acrylic resin base film, and after drying under appropriate conditions, the coated surface is irradiated with light energy rays such as ultraviolet rays to cure the above-mentioned photopolymerizable urethane acrylate composition. . Thus, the modified film of the present invention is obtained.
上記光重合性ウレタンアクリレート組成物の希釈方法、溶液状の上記光重合性ウレタンアクリレート組成物の塗布方法、上記光エネルギー線の照射条件、上記光重合性ウレタンアクリレート組成物の硬化物の乾燥方法は、光重合性塗料の取扱のための公知の条件から適宜選択される。
The method of diluting the photopolymerizable urethane acrylate composition, the method of applying the photopolymerizable urethane acrylate composition in solution, the irradiation conditions of the light energy ray, the method of drying the cured product of the photopolymerizable urethane acrylate composition The conditions are appropriately selected from known conditions for handling the photopolymerizable paint.
本発明の改質フィルムの表面保護層側では、本発明の表面保護層に由来する防汚性、撥水性、耐久性、耐薬品性、耐日焼け止めクリーム性の全てがバランスよく発現する。しかも本発明の改質フィルムは比較的複雑形状にも適している。このような本発明の改質フィルムは自動車内外装部品の表面改質に有効である。
On the surface protective layer side of the modified film of the present invention, all of antifouling property, water repellency, durability, chemical resistance and sunscreen cream resistance derived from the surface protective layer of the present invention appear in a well-balanced manner. Moreover, the modified film of the present invention is also suitable for relatively complicated shapes. Such a modified film of the present invention is effective for surface modification of automobile interior and exterior parts.
［自動車内外装部品の製造］
本発明の自動車内外装部品は、表面の少なくとも一部を本発明の改質フィルムで被覆された自動車内外装部品である。本発明の自動車内外装部品を製造する方法としては、上記改質フィルムにプラスチックを主体とする自動車内外装部品材料を所定の形状で密着することのできる方法を制限なく用いることができる。例えば、上記改質フィルムを金型内に配置しておき、射出成形にて樹脂を充填するフィルムインサート成形、ラミネートインジェクションプレス成形、上記改質フィルムを予備成形した後金型内に配置し、射出成形にて樹脂を充填するフィルムインモールド成形、これら成形方法に二色成形、サンドイッチ成形などを組み合わせた方法などがあげられる。 [Manufacture of automobile interior and exterior parts]
The automobile interior and exterior parts of the present invention are automobile interior and exterior parts coated with at least a part of the surface with the modified film of the present invention. As a method of manufacturing the interior and exterior parts of a car according to the present invention, a method capable of adhering the material of the interior and exterior parts of a car mainly made of plastic to the above-mentioned modified film in a predetermined shape can be used without limitation. For example, the modified film is placed in a mold, and film insert molding in which resin is filled by injection molding, laminate injection press molding, the reformed film is preformed, and then placed in the mold for injection Examples of such methods include film-in-mold molding in which a resin is filled by molding, and methods in which these molding methods are combined with two-color molding, sandwich molding, and the like.
本発明の自動車内外装部品は、表面の少なくとも一部を本発明の改質フィルムで被覆された自動車内外装部品である。本発明の自動車内外装部品を製造する方法としては、上記改質フィルムにプラスチックを主体とする自動車内外装部品材料を所定の形状で密着することのできる方法を制限なく用いることができる。例えば、上記改質フィルムを金型内に配置しておき、射出成形にて樹脂を充填するフィルムインサート成形、ラミネートインジェクションプレス成形、上記改質フィルムを予備成形した後金型内に配置し、射出成形にて樹脂を充填するフィルムインモールド成形、これら成形方法に二色成形、サンドイッチ成形などを組み合わせた方法などがあげられる。 [Manufacture of automobile interior and exterior parts]
The automobile interior and exterior parts of the present invention are automobile interior and exterior parts coated with at least a part of the surface with the modified film of the present invention. As a method of manufacturing the interior and exterior parts of a car according to the present invention, a method capable of adhering the material of the interior and exterior parts of a car mainly made of plastic to the above-mentioned modified film in a predetermined shape can be used without limitation. For example, the modified film is placed in a mold, and film insert molding in which resin is filled by injection molding, laminate injection press molding, the reformed film is preformed, and then placed in the mold for injection Examples of such methods include film-in-mold molding in which a resin is filled by molding, and methods in which these molding methods are combined with two-color molding, sandwich molding, and the like.
本発明の改質フィルムは自動車内外装部品の全般に有効である。本発明の改質フィルムを用いて、例えばインストルメントパネル、シート、コンソールボックス、サンバイザー、ピラートリム、ドアトリム、ラジエータグリル、エンブレム、各種ガーニッシュ、ホイールキャップ、グリルイルミネーション、車内外のカバー類などの各種自動車内外装部品を製造することができる。このような本発明の自動車外装部品として特に価値が高いものは、人が手指で触る頻度が高い環境下で使用されるために防汚性、撥水性、耐久性、耐薬品性、耐日焼け止めクリーム性の全てが求められる、インストルメントパネル、エンブレム、ラジエータグリル、各種ガーニッシュである。
The modified film of the present invention is effective for the entire interior and exterior parts of automobiles. Using the modified film of the present invention, various automotive vehicles such as instrument panels, seats, console boxes, sun visors, pillar trims, door trims, door trims, radiator grills, emblems, various garnishes, wheel caps, grille illumination, covers inside and outside the vehicle Interior and exterior parts can be manufactured. Particularly high value as such an automobile exterior part of the present invention is antifouling property, water repellency, durability, chemical resistance, sunscreen resistance since it is used under an environment where human beings frequently touch with fingers. Instrument panels, emblems, radiator grills, and various garnishes are required for all creaminess.
以下の手順で本発明の改質フィルムを製造した。
［γ－メタクリロキシプロピルヘプタ（トリフルオロプロピル）－Ｔ８－シルセスキオキサンの合成］
還流冷却器、温度計および滴下漏斗を取り付けた内容積１Ｌの４つ口フラスコに、トリフルオロプロピルトリメトキシシラン（１００ｇ）、ＴＨＦ（５００ｍＬ）、脱イオン水（１０．５ｇ）および水酸化ナトリウム（７．９ｇ）を仕込み、マグネチックスターラーで攪拌しながら、室温からＴＨＦが還流する温度までオイルバスにより加熱した。還流開始から５時間撹拌を継続して反応を完結させた。その後、フラスコをオイルバスから引き上げ、室温で１晩静置した後、再度オイルバスにセットし固体が析出するまで定圧下で加熱濃縮した。 The modified film of the present invention was produced by the following procedure.
[Synthesis of γ-methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane]
Trifluoropropyltrimethoxysilane (100 g), THF (500 mL), deionized water (10.5 g) and sodium hydroxide (sodium hydroxide) in a 1 L four-necked flask fitted with a reflux condenser, thermometer and dropping funnel 7.9 g) was charged and heated with an oil bath from room temperature to a temperature at which THF was refluxed while stirring with a magnetic stirrer. Stirring was continued for 5 hours from the start of reflux to complete the reaction. Thereafter, the flask was taken out of the oil bath, allowed to stand at room temperature overnight, and then set in the oil bath again, and heated and concentrated under constant pressure until solids were precipitated.
［γ－メタクリロキシプロピルヘプタ（トリフルオロプロピル）－Ｔ８－シルセスキオキサンの合成］
還流冷却器、温度計および滴下漏斗を取り付けた内容積１Ｌの４つ口フラスコに、トリフルオロプロピルトリメトキシシラン（１００ｇ）、ＴＨＦ（５００ｍＬ）、脱イオン水（１０．５ｇ）および水酸化ナトリウム（７．９ｇ）を仕込み、マグネチックスターラーで攪拌しながら、室温からＴＨＦが還流する温度までオイルバスにより加熱した。還流開始から５時間撹拌を継続して反応を完結させた。その後、フラスコをオイルバスから引き上げ、室温で１晩静置した後、再度オイルバスにセットし固体が析出するまで定圧下で加熱濃縮した。 The modified film of the present invention was produced by the following procedure.
[Synthesis of γ-methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane]
Trifluoropropyltrimethoxysilane (100 g), THF (500 mL), deionized water (10.5 g) and sodium hydroxide (sodium hydroxide) in a 1 L four-necked flask fitted with a reflux condenser, thermometer and dropping funnel 7.9 g) was charged and heated with an oil bath from room temperature to a temperature at which THF was refluxed while stirring with a magnetic stirrer. Stirring was continued for 5 hours from the start of reflux to complete the reaction. Thereafter, the flask was taken out of the oil bath, allowed to stand at room temperature overnight, and then set in the oil bath again, and heated and concentrated under constant pressure until solids were precipitated.
析出した生成物を、孔径０．５μｍのメンブランフィルターを備えた加圧濾過器を用いて濾取した。次いで、得られた固形物をＴＨＦで１回洗浄し、減圧乾燥機にて８０℃、３時間乾燥を行い、７４ｇの無色粉末状の固形物を得た。
The precipitated product was filtered off using a pressure filter equipped with a membrane filter with a pore size of 0.5 μm. Next, the obtained solid was washed once with THF, and dried at 80 ° C. for 3 hours in a vacuum dryer to obtain 74 g of a colorless powdery solid.
還流冷却器、温度計及び滴下漏斗を取り付けた内容積１Ｌの４つ口フラスコに、得られた固形物（６５ｇ）、ジクロロメタン（４９１ｇ）、トリエチルアミン（８．１ｇ）を仕込み、氷浴で３℃まで冷却した。次いでγ－メタクリロキシプロピルトリクロロシラン（２１．２ｇ）を添加し、発熱が収まったことを確認して氷浴から引き上げ、そのまま室温で一晩熟成した。イオン交換水で３回水洗した後、ジクロロメタン層を無水硫酸マグネシウムで脱水し、濾過により硫酸マグネシウムを除去した。ロータリーエバポレータで粘調な固体が析出するまで濃縮し、メタノール２６０ｇを加えて粉末状になるまで攪拌した。５μｍの濾紙を備えた加圧濾過器を用いて粉体を濾過し、減圧乾燥器にて６５℃、３時間乾燥を行い、４１．５ｇの無色粉末状固体を得た。得られた固体のＧＰＣ、１Ｈ－ＮＭＲ測定を行い、下記式（５）で表されるγ－メタクリロキシプロピルヘプタ（トリフルオロプロピル）－Ｔ８－シルセスキオキサンの生成を確認した。
The obtained solid (65 g), dichloromethane (491 g) and triethylamine (8.1 g) are charged into a 1-L four-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel, and heated to 3 ° C in an ice bath. It cooled down. Next, γ-methacryloxypropyltrichlorosilane (21.2 g) was added, and after confirming that the exotherm had subsided, it was pulled out from the ice bath and aged as it was overnight at room temperature. After washing with ion exchange water three times, the dichloromethane layer was dried over anhydrous magnesium sulfate, and the magnesium sulfate was removed by filtration. The mixture was concentrated by a rotary evaporator until a viscous solid was precipitated, 260 g of methanol was added, and the mixture was stirred until it became powdery. The powder was filtered using a pressure filter equipped with 5 μm filter paper and dried in a vacuum oven at 65 ° C. for 3 hours to obtain 41.5 g of a colorless powdery solid. The obtained solid was subjected to GPC and 1 H-NMR measurement to confirm the formation of γ-methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane represented by the following formula (5).
［（ａ４-１）γ－メタクリロキシプロピルヘプタ（トリフルオロプロピル）－Ｔ８－シルセスキオキサンに由来する単位を有する光重合性アクリレートオリゴマーの製造］
還流冷却器、温度計および滴下ロートを取り付けた内容積２００ｍＬの四つ口フラスコに、上述の方法で得られたγ－メタクリロキシプロピルヘプタ（トリフルオロプロピル）－Ｔ８－シルセスキオキサンを３６．６５ｇ、メチルメタクリレート（ＭＭＡ）を１８．３３ｇ、２－ヒドロキシエチルメタクリレート（ＨＥＭＡ）を２７．４９ｇ、片末端メタクリロキシ基変性ジメチルシリコーン（ＦＭ－０７２１、分子量約６，３００）を９．１６ｇ、２－ブタノン（ＭＥＫ）を１０６．４ｇ導入し、窒素シールした。９５℃に保ったオイルバスにセットして還流させ、１０分間脱酸素を行った。次いで０．７０ｇの２，２Ｔ
－アゾビスイソブチロニトリル（ＡＩＢＮ）と０．０８ｇのメルカプト酢酸（ＡｃＳＨ）を７．０ｇのＭＥＫに溶解させた溶液を導入し、還流温度に保ったまま重合を開始した。３時間重合した後、０．７０ｇのＡＩＢＮを７．０ｇのＭＥＫに溶解させた溶液を導入し、さらに５時間重合を継続した。重合終了後、重合液に変性アルコール（ソルミックスＡＰ－１、日本アルコール販売（株）製）を６５ｍＬ加えた後、１３００ｍＬのソルミックスＡＰ－１に注ぎ込んで重合体を析出させた。上澄みを除去し、減圧乾燥（４０℃、３時間、７０℃、３時間）して生成物を分離した。 [(A4-1) Preparation of Photopolymerizable Acrylate Oligomer Having a Unit Derived from γ-Methacryloxypropyl Hepta (Trifluoropropyl) -T8-Silsesquioxane]
The .gamma.-methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane obtained by the method described above was added to a 200 mL four-necked flask fitted with a reflux condenser, a thermometer and a dropping funnel. 65 g, 18.33 g of methyl methacrylate (MMA), 27.49 g of 2-hydroxyethyl methacrylate (HEMA), 9.16 g of one-end methacryloxy group-modified dimethyl silicone (FM-0721, molecular weight about 6,300), 2- 106.4 g of butanone (MEK) was introduced and sealed with nitrogen. It was set in an oil bath maintained at 95 ° C. to reflux and deoxygenated for 10 minutes. Then 0.70 g of 2, 2 T
A solution of azobisisobutyronitrile (AIBN) and 0.08 g of mercaptoacetic acid (AcSH) dissolved in 7.0 g of MEK was introduced, and polymerization was initiated while maintaining the reflux temperature. After polymerization for 3 hours, a solution of 0.70 g of AIBN dissolved in 7.0 g of MEK was introduced, and polymerization was continued for another 5 hours. After completion of the polymerization, 65 mL of a modified alcohol (Solmix AP-1, manufactured by Nippon Alcohol Sales Co., Ltd.) was added to the polymerization solution, and then poured into 1300 mL of Solmix AP-1 to precipitate a polymer. The supernatant was removed and dried under reduced pressure (40 ° C., 3 hours, 70 ° C., 3 hours) to separate the product.
還流冷却器、温度計および滴下ロートを取り付けた内容積２００ｍＬの四つ口フラスコに、上述の方法で得られたγ－メタクリロキシプロピルヘプタ（トリフルオロプロピル）－Ｔ８－シルセスキオキサンを３６．６５ｇ、メチルメタクリレート（ＭＭＡ）を１８．３３ｇ、２－ヒドロキシエチルメタクリレート（ＨＥＭＡ）を２７．４９ｇ、片末端メタクリロキシ基変性ジメチルシリコーン（ＦＭ－０７２１、分子量約６，３００）を９．１６ｇ、２－ブタノン（ＭＥＫ）を１０６．４ｇ導入し、窒素シールした。９５℃に保ったオイルバスにセットして還流させ、１０分間脱酸素を行った。次いで０．７０ｇの２，２Ｔ
－アゾビスイソブチロニトリル（ＡＩＢＮ）と０．０８ｇのメルカプト酢酸（ＡｃＳＨ）を７．０ｇのＭＥＫに溶解させた溶液を導入し、還流温度に保ったまま重合を開始した。３時間重合した後、０．７０ｇのＡＩＢＮを７．０ｇのＭＥＫに溶解させた溶液を導入し、さらに５時間重合を継続した。重合終了後、重合液に変性アルコール（ソルミックスＡＰ－１、日本アルコール販売（株）製）を６５ｍＬ加えた後、１３００ｍＬのソルミックスＡＰ－１に注ぎ込んで重合体を析出させた。上澄みを除去し、減圧乾燥（４０℃、３時間、７０℃、３時間）して生成物を分離した。 [(A4-1) Preparation of Photopolymerizable Acrylate Oligomer Having a Unit Derived from γ-Methacryloxypropyl Hepta (Trifluoropropyl) -T8-Silsesquioxane]
The .gamma.-methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane obtained by the method described above was added to a 200 mL four-necked flask fitted with a reflux condenser, a thermometer and a dropping funnel. 65 g, 18.33 g of methyl methacrylate (MMA), 27.49 g of 2-hydroxyethyl methacrylate (HEMA), 9.16 g of one-end methacryloxy group-modified dimethyl silicone (FM-0721, molecular weight about 6,300), 2- 106.4 g of butanone (MEK) was introduced and sealed with nitrogen. It was set in an oil bath maintained at 95 ° C. to reflux and deoxygenated for 10 minutes. Then 0.70 g of 2, 2 T
A solution of azobisisobutyronitrile (AIBN) and 0.08 g of mercaptoacetic acid (AcSH) dissolved in 7.0 g of MEK was introduced, and polymerization was initiated while maintaining the reflux temperature. After polymerization for 3 hours, a solution of 0.70 g of AIBN dissolved in 7.0 g of MEK was introduced, and polymerization was continued for another 5 hours. After completion of the polymerization, 65 mL of a modified alcohol (Solmix AP-1, manufactured by Nippon Alcohol Sales Co., Ltd.) was added to the polymerization solution, and then poured into 1300 mL of Solmix AP-1 to precipitate a polymer. The supernatant was removed and dried under reduced pressure (40 ° C., 3 hours, 70 ° C., 3 hours) to separate the product.
還流冷却器、温度計およびセプタムキャップを取り付けた内容積２００ｍＬの四つ口フラスコに、生成物を１５．０ｇ、ＭＥＨＱを０．０１５ｇ、ＤＢＴＤＬを０．０２６３ｇ、酢酸エチルを１３０ｇ導入し、窒素シールした。４８℃に保ったオイルバスにセットし、昇温した。次いで液温が４５℃になったところで、アクリロイルオキシエチルイソシアネート（ＡＯＩ、昭和電工（株）製）１５．９ｇを導入し、反応を開始した。６時間反応した後、室温まで冷却してＭｅＯＨ１０．０ｇを導入して反応を終了した。反応終了後、反応液にソルミックスＡＰ－１を６５ｍＬ加えた後、１３００ｍＬのソルミックスＡＰ－１に注ぎ込んで反応物を析出させた。上澄みを除去し、減圧乾燥（４０℃、３時間、７０℃、３時間）させて１１．８ｇのγ－メタクリロキシプロピルヘプタ（トリフルオロプロピル）－Ｔ８－シルセスキオキサン単位を含み側鎖にアクリロイル基を有する重合体を得た。この重合体のＧＰＣ分析により求めた重量平均分子量は４５，０００、分子量分布は１．７であった。
1.5.0 g of product, 0.015 g of MEHQ, 0.0263 g of DBTDL, and 130 g of ethyl acetate are introduced into a four-necked flask with an internal volume of 200 mL fitted with a reflux condenser, a thermometer and a septum cap, and sealed with nitrogen did. It was set in an oil bath maintained at 48 ° C. and heated. Next, when the liquid temperature reached 45 ° C., 15.9 g of acryloyloxyethyl isocyanate (AOI, manufactured by Showa Denko KK) was introduced to initiate a reaction. After reacting for 6 hours, the reaction solution was cooled to room temperature and 10.0 g of MeOH was introduced to complete the reaction. After completion of the reaction, 65 mL of Solmix AP-1 was added to the reaction solution, and then poured into 1300 mL of Solmix AP-1 to precipitate a reaction product. The supernatant is removed and dried under reduced pressure (40 ° C., 3 hours, 70 ° C., 3 hours) to contain 11.8 g of γ-methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane units in the side chain A polymer having an acryloyl group was obtained. The weight average molecular weight of the polymer determined by GPC analysis was 45,000, and the molecular weight distribution was 1.7.
［光重合性ウレタンアクリレート組成物の調整］
紫外線硬化型ウレタンアクリルポリマー（ａ１）として大成ファインケミカル社製紫外線硬化型ウレタンアクリルポリマー「８ＢＲ－６００」を用いた。多官能アクリレート化合物（ａ２）として日本化薬社製６官能アクリレート化合物「ＫＡＹＡＲＡＤ ＤＰＣＡ-１２０」を用いた。フッ素含有光重合性アクリル化合物（ａ３）としてＤＩＣ社製「メガファックＲＳ７５」を用いた。フルオロシルセスキオキサン誘導体に由来する単位を有する光重合性アクリレートオリゴマー（ａ４）として上述のγ－メタクリロキシプロピルヘプタ（トリフルオロプロピル）－Ｔ８－シルセスキオキサン単位を含み側鎖にアクリロイル基を有する重合体を用いた。フィラー（Ｂ）として日産化学工業社製シリカゾル「ＭＥＫ－ＳＴ－ＵＰ」を用いた。（Ｃ）光重合開始剤としてＩＧＭ Ｒｅｓｉｎｓ社製「Ｏｍｎｉｒａｄ１２７」を使用した。さらに希釈剤としてイソプロピルアルコール（ＩＰＡ）を用いた。上記成分（ａ１）、（ａ２）、（ａ３）、（ａ４）、（Ｂ）、（Ｃ）を表１に示すように選択して各成分を表１に示す量比で混合し、これら成分が良好に分散した光重合性ウレタンアクリレート組成物を２５重量％の濃度で含む塗工液を得た。 [Preparation of photopolymerizable urethane acrylate composition]
An ultraviolet-curable urethane acrylic polymer "8BR-600" manufactured by Taisei Fine Chemical Co., Ltd. was used as the ultraviolet-curable urethane acrylic polymer (a1). A 6-functional acrylate compound "KAYARAD DPCA-120" manufactured by Nippon Kayaku Co., Ltd. was used as the polyfunctional acrylate compound (a2). As the fluorine-containing photopolymerizable acrylic compound (a3), “Megafuck RS75” manufactured by DIC Corporation was used. A photopolymerizable acrylate oligomer (a4) having a unit derived from a fluorosilsesquioxane derivative, which contains the above-mentioned γ-methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane unit, and an acryloyl group in the side chain The polymer which it has was used. As the filler (B), silica sol “MEK-ST-UP” manufactured by Nissan Chemical Industries, Ltd. was used. (C) "Omnirad 127" manufactured by IGM Resins, Inc. was used as a photopolymerization initiator. Furthermore, isopropyl alcohol (IPA) was used as a diluent. The above components (a1), (a2), (a3), (a4), (B) and (C) are selected as shown in Table 1, and the respective components are mixed in the amount ratio shown in Table 1 A coating liquid containing the photopolymerizable urethane acrylate composition well dispersed at a concentration of 25% by weight was obtained.
紫外線硬化型ウレタンアクリルポリマー（ａ１）として大成ファインケミカル社製紫外線硬化型ウレタンアクリルポリマー「８ＢＲ－６００」を用いた。多官能アクリレート化合物（ａ２）として日本化薬社製６官能アクリレート化合物「ＫＡＹＡＲＡＤ ＤＰＣＡ-１２０」を用いた。フッ素含有光重合性アクリル化合物（ａ３）としてＤＩＣ社製「メガファックＲＳ７５」を用いた。フルオロシルセスキオキサン誘導体に由来する単位を有する光重合性アクリレートオリゴマー（ａ４）として上述のγ－メタクリロキシプロピルヘプタ（トリフルオロプロピル）－Ｔ８－シルセスキオキサン単位を含み側鎖にアクリロイル基を有する重合体を用いた。フィラー（Ｂ）として日産化学工業社製シリカゾル「ＭＥＫ－ＳＴ－ＵＰ」を用いた。（Ｃ）光重合開始剤としてＩＧＭ Ｒｅｓｉｎｓ社製「Ｏｍｎｉｒａｄ１２７」を使用した。さらに希釈剤としてイソプロピルアルコール（ＩＰＡ）を用いた。上記成分（ａ１）、（ａ２）、（ａ３）、（ａ４）、（Ｂ）、（Ｃ）を表１に示すように選択して各成分を表１に示す量比で混合し、これら成分が良好に分散した光重合性ウレタンアクリレート組成物を２５重量％の濃度で含む塗工液を得た。 [Preparation of photopolymerizable urethane acrylate composition]
An ultraviolet-curable urethane acrylic polymer "8BR-600" manufactured by Taisei Fine Chemical Co., Ltd. was used as the ultraviolet-curable urethane acrylic polymer (a1). A 6-functional acrylate compound "KAYARAD DPCA-120" manufactured by Nippon Kayaku Co., Ltd. was used as the polyfunctional acrylate compound (a2). As the fluorine-containing photopolymerizable acrylic compound (a3), “Megafuck RS75” manufactured by DIC Corporation was used. A photopolymerizable acrylate oligomer (a4) having a unit derived from a fluorosilsesquioxane derivative, which contains the above-mentioned γ-methacryloxypropyl hepta (trifluoropropyl) -T8-silsesquioxane unit, and an acryloyl group in the side chain The polymer which it has was used. As the filler (B), silica sol “MEK-ST-UP” manufactured by Nissan Chemical Industries, Ltd. was used. (C) "Omnirad 127" manufactured by IGM Resins, Inc. was used as a photopolymerization initiator. Furthermore, isopropyl alcohol (IPA) was used as a diluent. The above components (a1), (a2), (a3), (a4), (B) and (C) are selected as shown in Table 1, and the respective components are mixed in the amount ratio shown in Table 1 A coating liquid containing the photopolymerizable urethane acrylate composition well dispersed at a concentration of 25% by weight was obtained.
［改質フィルムの製造］
３００μｍ厚みのアクリル樹脂製基材フィルム（クラレ社製アクリル樹脂シート「コモグラス」）の片面に、上述のそれぞれの塗工液をＲ．Ｄ．Ｓ．Ｗｅｂｓｔｅｒ社製ワイヤーバーコーターＮｏ．３０を用いて塗布し、８０℃で１分間乾燥した。その後、アイグラフィックス株式会社製 ８ｋＷ×１灯用 紫外線硬化用コンベア装置 ＥＳＣ－８０１Ｇ１型を用いて、積算光量：１０００ｍＪ／ｃｍ２で光重合性コーティング液を硬化させた。こうしてアクリル樹脂製基材フィルムの片面上に厚み１１μｍの光重合性ウレタンアクリレート組成物の硬化物からなる表面保護層が形成された７種類の改質フィルムが得られた。 [Production of modified film]
Each of the above-mentioned coating liquids was applied to one side of a 300 μm thick acrylic resin base film (Kuraray acrylic resin sheet “Comoglass”) by R. D. S. Webster Wire Bar Coater No. 30 and applied and dried at 80 ° C. for 1 minute. Thereafter, a photopolymerizable coating solution was cured at an integrated light quantity of 1000 mJ / cm 2 using a conveyor device for curing ultraviolet light of 8 kW × 1 lamp manufactured by Eye Graphics Co., Ltd., type ESC-801G1. Thus, seven types of modified films were obtained in which a surface protective layer consisting of a cured product of a photopolymerizable urethane acrylate composition having a thickness of 11 μm was formed on one surface of an acrylic resin base film.
３００μｍ厚みのアクリル樹脂製基材フィルム（クラレ社製アクリル樹脂シート「コモグラス」）の片面に、上述のそれぞれの塗工液をＲ．Ｄ．Ｓ．Ｗｅｂｓｔｅｒ社製ワイヤーバーコーターＮｏ．３０を用いて塗布し、８０℃で１分間乾燥した。その後、アイグラフィックス株式会社製 ８ｋＷ×１灯用 紫外線硬化用コンベア装置 ＥＳＣ－８０１Ｇ１型を用いて、積算光量：１０００ｍＪ／ｃｍ２で光重合性コーティング液を硬化させた。こうしてアクリル樹脂製基材フィルムの片面上に厚み１１μｍの光重合性ウレタンアクリレート組成物の硬化物からなる表面保護層が形成された７種類の改質フィルムが得られた。 [Production of modified film]
Each of the above-mentioned coating liquids was applied to one side of a 300 μm thick acrylic resin base film (Kuraray acrylic resin sheet “Comoglass”) by R. D. S. Webster Wire Bar Coater No. 30 and applied and dried at 80 ° C. for 1 minute. Thereafter, a photopolymerizable coating solution was cured at an integrated light quantity of 1000 mJ / cm 2 using a conveyor device for curing ultraviolet light of 8 kW × 1 lamp manufactured by Eye Graphics Co., Ltd., type ESC-801G1. Thus, seven types of modified films were obtained in which a surface protective layer consisting of a cured product of a photopolymerizable urethane acrylate composition having a thickness of 11 μm was formed on one surface of an acrylic resin base film.
［改質フィルムの評価］
上記７種類の改質フィルムを以下の観点・方法で評価した結果を表１に示す。 [Evaluation of modified film]
The results of evaluating the seven types of modified films according to the following viewpoints and methods are shown in Table 1.
上記７種類の改質フィルムを以下の観点・方法で評価した結果を表１に示す。 [Evaluation of modified film]
The results of evaluating the seven types of modified films according to the following viewpoints and methods are shown in Table 1.
（１）撥油性
得られた改質フィルムの表面保護層の市販の黒色油性インキに対する撥油性を評価した。得られた改質フィルムの表面保護層の表面にＳｈａｒｐｉｅ製マジックペンで線を描いた時の黒色油性インキの撥かれる程度を以下の基準で判定した。 (1) Oil Repellency The oil repellency of the surface protective layer of the obtained modified film with respect to a commercially available black oil-based ink was evaluated. The degree to which the black oil-based ink was repelled when a line was drawn on the surface of the surface protective layer of the resulting modified film with a Sharpie marker was determined according to the following criteria.
得られた改質フィルムの表面保護層の市販の黒色油性インキに対する撥油性を評価した。得られた改質フィルムの表面保護層の表面にＳｈａｒｐｉｅ製マジックペンで線を描いた時の黒色油性インキの撥かれる程度を以下の基準で判定した。 (1) Oil Repellency The oil repellency of the surface protective layer of the obtained modified film with respect to a commercially available black oil-based ink was evaluated. The degree to which the black oil-based ink was repelled when a line was drawn on the surface of the surface protective layer of the resulting modified film with a Sharpie marker was determined according to the following criteria.
＋：インキが撥かれインキの軌跡が点状に見える。
+: The ink is repellent and the locus of the ink looks like a dot.
－：インキが撥かれずインキの軌跡が線状に見える。
（２）防汚性
上記（１）撥油性テストで表面保護層に付着したインキの軌跡を不織布（小津産業社製ダスパーＫ－３）で１往復擦った時のインキの除去容易性を以下の基準で判定した。 -: The ink is not repelled and the trace of the ink looks linear.
(2) Antifouling property The locus of the ink attached to the surface protective layer in the above-mentioned (1) oil repellency test is rubbed once with a non-woven fabric (Dasper K-3 manufactured by Ozu Sangyo Co., Ltd.). It judged on the basis.
（２）防汚性
上記（１）撥油性テストで表面保護層に付着したインキの軌跡を不織布（小津産業社製ダスパーＫ－３）で１往復擦った時のインキの除去容易性を以下の基準で判定した。 -: The ink is not repelled and the trace of the ink looks linear.
(2) Antifouling property The locus of the ink attached to the surface protective layer in the above-mentioned (1) oil repellency test is rubbed once with a non-woven fabric (Dasper K-3 manufactured by Ozu Sangyo Co., Ltd.). It judged on the basis.
＋：インキが完全に拭き取れインキ跡が残らなかった。
+: The ink was completely wiped off and no ink mark remained.
－：インキが完全に拭き取れずインキ跡が残った。
-: Ink was not completely wiped off and ink marks remained.
（３）撥水性
得られた改質フィルムから切り取った２０ｍｍ×９０ｍｍのテスト片を、２５ｍｍ×１００ｍｍのステンレス板にアクリル樹脂製基材フィルム側が密着するように貼り付けた。この状態で改質フィルムの上面（表面保護層表面）の水接触角を、窒素・りん測定用蒸留水（関東化学社製）をプローブ水として自動接触角計ＤＭｓ-４００（協和界面科学社製）で測定した。水接触角が９５°以上が好ましく、より大きな水接触角はより高い撥水性を示す。 (3) Water Repellency A test piece of 20 mm × 90 mm cut from the obtained modified film was attached to a 25 mm × 100 mm stainless steel plate so that the acrylic resin base film side was in close contact. In this state, the contact angle of water on the upper surface (surface protective layer surface) of the modified film is measured using an automatic contact angle meter DMs-400 (Kyowa Interface Science Co., Ltd.) with probe water for distilled water for nitrogen and phosphorus measurement (manufactured by Kanto Chemical Co., Ltd.). It measured by). The water contact angle is preferably 95 ° or more, and a larger water contact angle indicates higher water repellency.
得られた改質フィルムから切り取った２０ｍｍ×９０ｍｍのテスト片を、２５ｍｍ×１００ｍｍのステンレス板にアクリル樹脂製基材フィルム側が密着するように貼り付けた。この状態で改質フィルムの上面（表面保護層表面）の水接触角を、窒素・りん測定用蒸留水（関東化学社製）をプローブ水として自動接触角計ＤＭｓ-４００（協和界面科学社製）で測定した。水接触角が９５°以上が好ましく、より大きな水接触角はより高い撥水性を示す。 (3) Water Repellency A test piece of 20 mm × 90 mm cut from the obtained modified film was attached to a 25 mm × 100 mm stainless steel plate so that the acrylic resin base film side was in close contact. In this state, the contact angle of water on the upper surface (surface protective layer surface) of the modified film is measured using an automatic contact angle meter DMs-400 (Kyowa Interface Science Co., Ltd.) with probe water for distilled water for nitrogen and phosphorus measurement (manufactured by Kanto Chemical Co., Ltd.). It measured by). The water contact angle is preferably 95 ° or more, and a larger water contact angle indicates higher water repellency.
（４）日焼け止めクリーム耐性
得られた改質フィルムから切り取った５０ｍｍ×５０ｍｍのテスト片の表面保護層上に市販の日焼け止めクリーム（Ｎｅｕｔｒｏｇｅｎａ ＵＬＴＲＡ ＳＨＥＥＲ ＳＵＮＳＣＲＥＥＮ ＳＰＦ４５）を０．５ｇ／１００ｃｍ２の量で均一厚みに塗布した。日焼け止めクリームが付着した面に白布を２枚、さらにアルミ板を重ね、アルミ板の上から５００ｇの重りを置いた。この状態で改質フィルムを含むテスト物全体を５５℃の恒温槽中で４時間静置加熱した。加熱後、重り、アルミニウム板、白布を取り除いた。中性洗剤を染み込ませた不織布で表面保護層をこすって表面保護層に付着した日焼け止めを除去した。 日焼け止めクリームが除去された表面保護層の状態を以下の基準で判定した。 (4) Sunscreen cream resistance A commercially available sunblock cream (Neutrogena ULTRA SHEER SUNSCREEN SPF 45) in an amount of 0.5 g / 100 cm 2 on the surface protection layer of a 50 mm × 50 mm test piece cut from the obtained modified film It applied to uniform thickness. Two sheets of white cloth and aluminum plate were stacked on the surface to which the sunscreen cream adhered, and a weight of 500 g was placed on the aluminum plate. In this state, the entire test article including the modified film was allowed to stand and heated in a thermostat at 55 ° C. for 4 hours. After heating, the weight, aluminum plate and white cloth were removed. The surface protective layer was rubbed with a non-woven cloth impregnated with a neutral detergent to remove the sunscreen attached to the surface protective layer. The condition of the surface protective layer from which the sunscreen cream was removed was determined according to the following criteria.
得られた改質フィルムから切り取った５０ｍｍ×５０ｍｍのテスト片の表面保護層上に市販の日焼け止めクリーム（Ｎｅｕｔｒｏｇｅｎａ ＵＬＴＲＡ ＳＨＥＥＲ ＳＵＮＳＣＲＥＥＮ ＳＰＦ４５）を０．５ｇ／１００ｃｍ２の量で均一厚みに塗布した。日焼け止めクリームが付着した面に白布を２枚、さらにアルミ板を重ね、アルミ板の上から５００ｇの重りを置いた。この状態で改質フィルムを含むテスト物全体を５５℃の恒温槽中で４時間静置加熱した。加熱後、重り、アルミニウム板、白布を取り除いた。中性洗剤を染み込ませた不織布で表面保護層をこすって表面保護層に付着した日焼け止めを除去した。 日焼け止めクリームが除去された表面保護層の状態を以下の基準で判定した。 (4) Sunscreen cream resistance A commercially available sunblock cream (Neutrogena ULTRA SHEER SUNSCREEN SPF 45) in an amount of 0.5 g / 100 cm 2 on the surface protection layer of a 50 mm × 50 mm test piece cut from the obtained modified film It applied to uniform thickness. Two sheets of white cloth and aluminum plate were stacked on the surface to which the sunscreen cream adhered, and a weight of 500 g was placed on the aluminum plate. In this state, the entire test article including the modified film was allowed to stand and heated in a thermostat at 55 ° C. for 4 hours. After heating, the weight, aluminum plate and white cloth were removed. The surface protective layer was rubbed with a non-woven cloth impregnated with a neutral detergent to remove the sunscreen attached to the surface protective layer. The condition of the surface protective layer from which the sunscreen cream was removed was determined according to the following criteria.
＋：日焼け止めクリーム塗布前の状態と同じで変質や変形は観察されない。
+: The same as the state before applying sunscreen cream, no deterioration or deformation is observed.
－：日焼け止めクリームの跡や溶解斑などが観察され変質や変形が認められた。
-: The marks of the sunscreen cream and the dissolution spots were observed, and degeneration or deformation was observed.
（５）虫よけスプレー耐性
得られた改質フィルムから切り取った５０ｍｍ×５０ｍｍのテスト片の表面保護層上に市販の虫よけスプレー（ＯＦＦ！ Ｄｅｅｐ Ｗｏｏｄｓ（登録商標）Ｓｐｏｒｔｓｍａｎ ｗｉｔｈ ２５％ ＤＥＥＴ）０．０５ｇを均一に撒布した。虫よけスプレーが付着した面に白布を２枚、さらにアルミ板を重ねた。この状態で改質フィルムを含むテスト物全体を室温（２３℃）で２４時間静置した。この後、アルミニウム板と白布を取り除いた。この時の表面保護層の状態を以下の基準で判定した。 (5) Insect repellent spray resistance A commercially available insect repellent spray (OFF! Deep Woods (R) Sportsman with 25% DEET) on the surface protection layer of a 50 mm x 50 mm test piece cut from the obtained modified film. 0.05 g was evenly distributed. Two sheets of white cloth and an aluminum plate were stacked on the surface on which the insect spray was attached. In this state, the entire test product including the modified film was allowed to stand at room temperature (23 ° C.) for 24 hours. After this, the aluminum plate and the white cloth were removed. The state of the surface protective layer at this time was determined according to the following criteria.
得られた改質フィルムから切り取った５０ｍｍ×５０ｍｍのテスト片の表面保護層上に市販の虫よけスプレー（ＯＦＦ！ Ｄｅｅｐ Ｗｏｏｄｓ（登録商標）Ｓｐｏｒｔｓｍａｎ ｗｉｔｈ ２５％ ＤＥＥＴ）０．０５ｇを均一に撒布した。虫よけスプレーが付着した面に白布を２枚、さらにアルミ板を重ねた。この状態で改質フィルムを含むテスト物全体を室温（２３℃）で２４時間静置した。この後、アルミニウム板と白布を取り除いた。この時の表面保護層の状態を以下の基準で判定した。 (5) Insect repellent spray resistance A commercially available insect repellent spray (OFF! Deep Woods (R) Sportsman with 25% DEET) on the surface protection layer of a 50 mm x 50 mm test piece cut from the obtained modified film. 0.05 g was evenly distributed. Two sheets of white cloth and an aluminum plate were stacked on the surface on which the insect spray was attached. In this state, the entire test product including the modified film was allowed to stand at room temperature (23 ° C.) for 24 hours. After this, the aluminum plate and the white cloth were removed. The state of the surface protective layer at this time was determined according to the following criteria.
＋：虫よけスプレー接触前の状態と同じで変質や変形は観察されない。
+: Insect Repellent As in the state before contact with the spray, no alteration or deformation is observed.
－：虫よけスプレーの跡や溶解斑などが観察され変質や変形が認められた。
-: A trace of an insect repellent spray or a dissolution spot was observed, and degeneration or deformation was observed.
（６）表面硬度
ＪＩＳ Ｋ ５６００に準拠した鉛筆硬度測定により表面保護層の硬度を測定した。 (6) Surface Hardness The hardness of the surface protective layer was measured by pencil hardness measurement in accordance with JIS K 5600.
ＪＩＳ Ｋ ５６００に準拠した鉛筆硬度測定により表面保護層の硬度を測定した。 (6) Surface Hardness The hardness of the surface protective layer was measured by pencil hardness measurement in accordance with JIS K 5600.
（７）透明性
得られた改質フィルムの全光線透過率（％）を測定した。 (7) Transparency The total light transmittance (%) of the obtained modified film was measured.
得られた改質フィルムの全光線透過率（％）を測定した。 (7) Transparency The total light transmittance (%) of the obtained modified film was measured.
（８）耐擦傷性
得られた改質フィルムから切り取った１２０ｍｍ×７０ｍｍのテスト片のヘイズ（Ｈ１）を日本電色工業（株）製のヘーズメーターＮＤＨ－５０００型を用いて測定した。ヘイズＨ１を測定したテスト片を（株）井元製作所社製ＩＭＣ－１５５７型耐摩耗試験器Ｃに設置し、その表面保護層を磨耗処理した。摩耗条件は＃００００のスチールウール使用、荷重４００ｇ、１５往復とした。摩耗処理後のテスト片のヘイズ（Ｈ２）を摩耗処理前のヘイズＨ１の測定と同じ方法で測定した。Ｈ１とＨ２の値から下記式に示す透明性変化度（ΔＨ）を求めた。ΔＨが小さいほどより高い耐擦傷性を示す。 (8) Scratch Resistance The haze (H 1 ) of a 120 mm × 70 mm test piece cut off from the obtained modified film was measured using a haze meter NDH-5000 type manufactured by Nippon Denshoku Kogyo Co., Ltd. The test piece for which the haze H 1 was measured was placed in an IMC-1557 abrasion resistance tester C manufactured by Imoto Machinery Co., Ltd., and the surface protective layer was subjected to abrasion treatment. The wear condition was # 0000 steel wool, load 400 g, 15 reciprocations. The haze (H 2 ) of the test piece after the abrasion treatment was measured by the same method as the measurement of the haze H 1 before the abrasion treatment. The degree of change in transparency (ΔH) shown in the following equation was determined from the values of H 1 and H 2 . The smaller the ΔH, the higher the scratch resistance.
得られた改質フィルムから切り取った１２０ｍｍ×７０ｍｍのテスト片のヘイズ（Ｈ１）を日本電色工業（株）製のヘーズメーターＮＤＨ－５０００型を用いて測定した。ヘイズＨ１を測定したテスト片を（株）井元製作所社製ＩＭＣ－１５５７型耐摩耗試験器Ｃに設置し、その表面保護層を磨耗処理した。摩耗条件は＃００００のスチールウール使用、荷重４００ｇ、１５往復とした。摩耗処理後のテスト片のヘイズ（Ｈ２）を摩耗処理前のヘイズＨ１の測定と同じ方法で測定した。Ｈ１とＨ２の値から下記式に示す透明性変化度（ΔＨ）を求めた。ΔＨが小さいほどより高い耐擦傷性を示す。 (8) Scratch Resistance The haze (H 1 ) of a 120 mm × 70 mm test piece cut off from the obtained modified film was measured using a haze meter NDH-5000 type manufactured by Nippon Denshoku Kogyo Co., Ltd. The test piece for which the haze H 1 was measured was placed in an IMC-1557 abrasion resistance tester C manufactured by Imoto Machinery Co., Ltd., and the surface protective layer was subjected to abrasion treatment. The wear condition was # 0000 steel wool, load 400 g, 15 reciprocations. The haze (H 2 ) of the test piece after the abrasion treatment was measured by the same method as the measurement of the haze H 1 before the abrasion treatment. The degree of change in transparency (ΔH) shown in the following equation was determined from the values of H 1 and H 2 . The smaller the ΔH, the higher the scratch resistance.
ΔＨ＝｜Ｈ１－Ｈ２｜
ΔH = | H 1 -H 2 |
（９）成形性
改質フィルムを成形部材の一部に用いて自動車内外装部品を成形する工程を想定し、ひし形の線条を有する半球状の金型を用い改質フィルムの面積が２００％に拡張する条件で改質フィルムをドーム状薄型形状に真空・圧空成形した。得られたドーム状の改質フィルムの表面保護層を目視観察し、改質フィルムの真空・圧空成形性を以下の基準で判定した。 (9) Assuming the process of forming the interior and exterior parts of an automobile by using the formable modified film as a part of the forming member, the area of the modified film is 200% using a hemispherical mold having diamond-shaped filaments The modified film was vacuum and pressure formed into a dome-like thin shape under the conditions of The surface protective layer of the obtained dome-shaped modified film was visually observed, and the vacuum and pressure-forming property of the modified film was determined based on the following criteria.
改質フィルムを成形部材の一部に用いて自動車内外装部品を成形する工程を想定し、ひし形の線条を有する半球状の金型を用い改質フィルムの面積が２００％に拡張する条件で改質フィルムをドーム状薄型形状に真空・圧空成形した。得られたドーム状の改質フィルムの表面保護層を目視観察し、改質フィルムの真空・圧空成形性を以下の基準で判定した。 (9) Assuming the process of forming the interior and exterior parts of an automobile by using the formable modified film as a part of the forming member, the area of the modified film is 200% using a hemispherical mold having diamond-shaped filaments The modified film was vacuum and pressure formed into a dome-like thin shape under the conditions of The surface protective layer of the obtained dome-shaped modified film was visually observed, and the vacuum and pressure-forming property of the modified film was determined based on the following criteria.
＋：表面保護層が金型形状に合致する。
+: The surface protective layer conforms to the mold shape.
－：表面保護層に金型形状に合致しない異常形状が観察される。
-: An abnormal shape not conforming to the mold shape is observed in the surface protective layer.
図１は実施例１の改質フィルムから得られたドーム状成形体の表面を示す。金型形状によく合致したひし形の線条が成形体表面に再現されている。線条のない部分は滑らかな曲面を形成している。
FIG. 1 shows the surface of a dome-shaped molded body obtained from the modified film of Example 1. Diamond-shaped filaments well fitted to the mold shape are reproduced on the surface of the molded body. The portion without striae forms a smooth curved surface.
図２は比較例２の改質フィルムから得られたドーム状成形体の表面を示す。表面全体に凹凸やしわ、クラックが発生している。
FIG. 2 shows the surface of a dome-shaped compact obtained from the modified film of Comparative Example 2. Irregularities, wrinkles and cracks occur on the entire surface.
表１に示されるように、実施例１、実施例２、実施例３で製造した改質フィルムは撥油性、防汚性、撥水性、日焼け止めクリーム耐性、虫よけスプレー耐性、高い表面硬度、透明性、成形性をバランスよく備え、自動車内外装部品の表面保護部材として適している。
As shown in Table 1, the modified films prepared in Example 1, Example 2, and Example 3 have oil repellency, stain resistance, water repellency, sunscreen cream resistance, insect spray resistance, high surface hardness. It has a good balance of transparency and moldability, and is suitable as a surface protection member for automobile interior and exterior parts.
これに対して表面保護層の材料を変更した比較例１、比較例２、比較例３、比較例４で製造された改質フィルムは撥油性、防汚性、撥水性、日焼け止めクリーム耐性、虫よけスプレー耐性、表面硬度、透明性、成形性のいずれか１つ以上が大きく損なわれており、自動車内外装部品の表面保護部材としての実用性に欠ける。
On the other hand, the modified films produced in Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4 in which the material of the surface protective layer is changed have oil repellency, stain resistance, water repellency, sunscreen cream resistance, Any one or more of the insect spray resistance, the surface hardness, the transparency, and the formability are greatly impaired, and the practicability as a surface protection member for automobile interior and exterior parts is lacking.
このように本発明では厳選した原料から製造された表面保護層を適切な基材フィルム上に配置することによって初めて実用性の高い自動車内外装部品用表面改質フィルムを得ることができた。
As described above, according to the present invention, it is possible to obtain a highly practical surface modified film for automobile interior and exterior parts only by arranging a surface protective layer manufactured from carefully selected raw materials on an appropriate base film.
本発明の改質フィルムは撥油性、防汚性、撥水性、日焼け止めクリーム耐性、虫よけスプレー耐性、高い表面硬度、透明性・透明性、成形性をバランスよく備える。このような本発明の改質フィルムは高い機能性とデザイン性が求められる自動車内外装部品を代表とする成形品、例えばインストルメントパネル、エンブレム、ラジエータグリル、各種ガーニッシュなどの表面保護部材として有用である。本発明により近年のより高度化した要求に耐え得る自動車内外装部品を製造することができると期待される。
The modified film of the present invention is well-balanced in oil repellency, stain resistance, water repellency, sunscreen cream resistance, insect spray resistance, high surface hardness, transparency / transparency, and moldability. Such a modified film of the present invention is useful as a surface protection member such as an instrument panel, an emblem, a radiator grill, various garnish, etc., as a molded article represented by automobile interior and exterior parts required to have high functionality and design. is there. It is expected that the present invention makes it possible to manufacture automobile interior and exterior parts that can withstand the recent and more sophisticated demands.
Claims (5)
- アクリル樹脂製基材フィルムの片面に表面保護層が積層されている自動車内外装部品用表面改質フィルムであって、
上記表面保護層は光重合性ウレタンアクリレート組成物の硬化物であり、
上記光重合性ウレタンアクリレート組成物は（Ａ）光重合性ウレタンアクリレート混合物と、（Ｃ）光重合開始剤とを含み、さらに必要に応じて （Ｂ）フィラーを含み、
上記光重合性ウレタンアクリレート組成物において、上記（Ａ）光重合性ウレタンアクリレート混合物と上記（Ｂ）フィラーとの合計１００重量部あたり、上記（Ａ）光重合性ウレタンアクリレート混合物が６０重量部以上１００重量部以下、上記（Ｂ）フィラーが０重量部以上４０重量部以下の割合で存在し、
上記（Ａ）光重合性ウレタンアクリレート混合物が、（ａ１）光重合性ウレタンアクリルポリマー、（ａ２）多官能アクリレート化合物、（ａ３）フッ素含有光重合性アクリル化合物、（ａ４）下記式（１）で表されるフルオロシルセスキオキサン誘導体に由来する単位を有する光重合性アクリレートオリゴマーを含み、
上記（Ａ）光重合性ウレタンアクリレート混合物１００重量部あたり、上記成分（ａ１）が２０重量部以上８７．９９重量部以下、上記成分（ａ２）が１重量部以上２５重量部以下、上記成分（ａ３）が１重量部以上１０重量部以下、上記成分（ａ４）が０．０１重量部以上５重量部以下の割合で存在する、
自動車内外装部品用表面改質フィルム。
The surface protective layer is a cured product of a photopolymerizable urethane acrylate composition,
The photopolymerizable urethane acrylate composition contains (A) a photopolymerizable urethane acrylate mixture and (C) a photopolymerization initiator, and further contains (B) a filler, if necessary
In the photopolymerizable urethane acrylate composition, 60 parts by weight or more and 100 parts by weight of the (A) photopolymerizable urethane acrylate mixture is used per 100 parts by weight in total of the (A) photopolymerizable urethane acrylate mixture and the (B) filler. The following (B) filler is present in a proportion of 0 parts by weight or more and 40 parts by weight or less,
The (A) photopolymerizable urethane acrylate mixture is (a1) a photopolymerizable urethane acrylic polymer, (a2) a polyfunctional acrylate compound, (a3) a fluorine-containing photopolymerizable acrylic compound, (a4) Containing photopolymerizable acrylate oligomers having units derived from the fluorosilsesquioxane derivatives,
The component (a1) is 20 parts by weight or more and 87.99 parts by weight or less, the component (a2) is 1 part by weight or more and 25 parts by weight or less, per 100 parts by weight of the (A) photopolymerizable urethane acrylate mixture a3) is present in an amount of 1 to 10 parts by weight, and the component (a4) is present in a proportion of 0.01 to 5 parts by weight.
Surface modified film for automobile interior and exterior parts.
- 上記光重合性ウレタンアクリレート組成物において、上記（Ａ）光重合性ウレタンアクリレート混合物と上記（Ｂ）フィラーとの合計１００重量部あたり、上記（Ａ）光重合性ウレタンアクリレート混合物が６０重量部以上９０重量部以下、上記（Ｂ）フィラーが１０重量部以上４０重量部以下の割合で存在する、
請求項１に記載の自動車内外装部品用表面改質フィルム。 In the photopolymerizable urethane acrylate composition, 60 parts by weight or more of the (A) photopolymerizable urethane acrylate mixture is contained per 100 parts by weight in total of the (A) photopolymerizable urethane acrylate mixture and the (B) filler. The filler (B) is present in a proportion of 10 parts by weight or more and 40 parts by weight or less by weight or less.
A surface modified film for automobile interior and exterior parts according to claim 1. - 上記成分（ａ４）が下記式（１-３）で表されるγ－メタクリロキシプロピルヘプタ（トリフルオロプロピル）－Ｔ８－シルセスキオキサンに由来する単位を有する光重合性アクリレートオリゴマーである、
請求項１または２に記載の自動車内外装部品用表面改質フィルム。
The surface modified film for automobile interior and exterior parts according to claim 1 or 2.
- 自動車内外装部品がインストルメントパネル、エンブレム、ラジエータグリル、各種ガーニッシュから選ばれる請求項１～３のいずれか１項に記載の自動車内外装部品用表面改質フィルム。 The surface modified film for automobile interior and exterior parts according to any one of claims 1 to 3, wherein the automobile interior and exterior parts are selected from an instrument panel, an emblem, a radiator grille, and various garnishes.
- 請求項１～４のいずれか１項に記載の自動車内外装部品用表面改質フィルムで表面の少なくとも一部が被覆された、自動車内外装部品。 An automobile interior and exterior part, wherein at least a part of the surface is coated with the surface modified film for automobile interior and exterior parts according to any one of claims 1 to 4.
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| WO2022137768A1 (en) * | 2020-12-25 | 2022-06-30 | 株式会社カネカ | Laminate and use thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012176742A1 (en) * | 2011-06-20 | 2012-12-27 | Jnc株式会社 | Transfer film for in-mold molding and method for producing same |
| WO2014097876A1 (en) * | 2012-12-19 | 2014-06-26 | Jnc株式会社 | Transfer film for in-mold molding, method for producing in-mold molded body, and molded body |
| WO2015133517A1 (en) * | 2014-03-05 | 2015-09-11 | Jnc株式会社 | Coating agent, cured film, laminate, molded product |
| WO2015133535A1 (en) * | 2014-03-05 | 2015-09-11 | グンゼ株式会社 | Laminate body |
| WO2016159023A1 (en) * | 2015-03-31 | 2016-10-06 | Jnc株式会社 | Coating agent, coating film, laminate, and surface-protected article |
-
2018
- 2018-10-09 JP JP2019548188A patent/JPWO2019073953A1/en active Pending
- 2018-10-09 WO PCT/JP2018/037541 patent/WO2019073953A1/en active Application Filing
- 2018-10-11 TW TW107135696A patent/TW201922503A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012176742A1 (en) * | 2011-06-20 | 2012-12-27 | Jnc株式会社 | Transfer film for in-mold molding and method for producing same |
| WO2014097876A1 (en) * | 2012-12-19 | 2014-06-26 | Jnc株式会社 | Transfer film for in-mold molding, method for producing in-mold molded body, and molded body |
| WO2015133517A1 (en) * | 2014-03-05 | 2015-09-11 | Jnc株式会社 | Coating agent, cured film, laminate, molded product |
| WO2015133535A1 (en) * | 2014-03-05 | 2015-09-11 | グンゼ株式会社 | Laminate body |
| WO2016159023A1 (en) * | 2015-03-31 | 2016-10-06 | Jnc株式会社 | Coating agent, coating film, laminate, and surface-protected article |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022137768A1 (en) * | 2020-12-25 | 2022-06-30 | 株式会社カネカ | Laminate and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2019073953A1 (en) | 2020-11-05 |
| TW201922503A (en) | 2019-06-16 |
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