JP5863589B2 - 加飾フィルム - Google Patents
加飾フィルム Download PDFInfo
- Publication number
- JP5863589B2 JP5863589B2 JP2012159951A JP2012159951A JP5863589B2 JP 5863589 B2 JP5863589 B2 JP 5863589B2 JP 2012159951 A JP2012159951 A JP 2012159951A JP 2012159951 A JP2012159951 A JP 2012159951A JP 5863589 B2 JP5863589 B2 JP 5863589B2
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- JP
- Japan
- Prior art keywords
- layer
- meth
- parts
- decorative
- acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000010410 layer Substances 0.000 claims description 130
- 239000000178 monomer Substances 0.000 claims description 89
- 239000003973 paint Substances 0.000 claims description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- 229920005989 resin Polymers 0.000 claims description 51
- 239000011347 resin Substances 0.000 claims description 51
- 239000000839 emulsion Substances 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 44
- 229920001169 thermoplastic Polymers 0.000 claims description 42
- 239000004416 thermosoftening plastic Substances 0.000 claims description 42
- 229920000178 Acrylic resin Polymers 0.000 claims description 39
- 239000004925 Acrylic resin Substances 0.000 claims description 39
- 239000012790 adhesive layer Substances 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 31
- 229920001577 copolymer Polymers 0.000 claims description 28
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 15
- 239000012798 spherical particle Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011258 core-shell material Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- -1 polypropylene Polymers 0.000 description 120
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 108
- 150000001875 compounds Chemical class 0.000 description 52
- 238000004519 manufacturing process Methods 0.000 description 41
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- 238000000576 coating method Methods 0.000 description 40
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 39
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- 239000002585 base Substances 0.000 description 33
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- 238000000034 method Methods 0.000 description 27
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 15
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- 239000000047 product Substances 0.000 description 13
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- 239000003795 chemical substances by application Substances 0.000 description 12
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 11
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
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- 239000006185 dispersion Substances 0.000 description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 229920000515 polycarbonate Polymers 0.000 description 9
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- 150000003254 radicals Chemical class 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
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- 239000012874 anionic emulsifier Substances 0.000 description 8
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 8
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- 238000000465 moulding Methods 0.000 description 8
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 7
- 125000005442 diisocyanate group Chemical group 0.000 description 7
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000010422 painting Methods 0.000 description 6
- 229920001225 polyester resin Polymers 0.000 description 6
- 239000004645 polyester resin Substances 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 5
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 239000004584 polyacrylic acid Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 4
- 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 4
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
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- 229910001507 metal halide Inorganic materials 0.000 description 4
- 150000005309 metal halides Chemical class 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
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- 238000010998 test method Methods 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
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- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
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- 239000004743 Polypropylene Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 3
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
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- ZKECVHXIVHRIIA-UHFFFAOYSA-N n-(2,2,6,6-tetramethylpiperidin-1-yl)prop-2-enamide Chemical compound CC1(C)CCCC(C)(C)N1NC(=O)C=C ZKECVHXIVHRIIA-UHFFFAOYSA-N 0.000 description 3
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
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- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
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- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
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- 238000011156 evaluation Methods 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
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- JZFHXRUVMKEOFG-UHFFFAOYSA-N tert-butyl dodecaneperoxoate Chemical compound CCCCCCCCCCCC(=O)OOC(C)(C)C JZFHXRUVMKEOFG-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
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Description
本発明に用いられる接着層は、本発明の加飾フィルムを物品に接着するための層である。上記接着層を形成するための接着剤としては、特に制限されず、公知の接着剤を適宜選択することができ、例えば、酢酸ビニル樹脂、塩化ビニル−酢酸ビニルコポリマー、熱可塑性ポリエステル樹脂、アクリル樹脂、ポリアミド樹脂、アイオノマー、塩素化ポリオレフィン樹脂、熱可塑ウレタン樹脂等の熱可塑性樹脂、及び硬化性ウレタン樹脂、エポキシ樹脂等の硬化性樹脂、並びにゴム系樹脂等を単独又は2種以上の混合物として含むものを挙げることができる。上記硬化性ウレタン樹脂としては、2液硬化型ウレタン樹脂、1液硬化型(湿気硬化型)ウレタン樹脂等が使用できる。
本発明に用いられる加飾層は、ベース塗料から形成され、該ベース塗料にはアクリル樹脂エマルション(A−1)を含む被膜形成性樹脂(A)、りん片状金属粉(B)及び球状粒子(C)を含有する水性メタリック塗料が用いられる。
上記熱可塑性フィルム層を形成する熱可塑性樹脂としては、例えば、ポリカーボネート、ポリスチレン、ポリエステル、ポリエチレンテレフタレート(以下、「PETフィルム」と称する場合がある)、ポリエチレンナフタレート、アクリル樹脂、ポリウレタン樹脂、エポキシ樹脂、メラミン樹脂、トリアセチルセルロース樹脂、ポリプロピレン、ABS樹脂、AS樹脂、塩化ビニル樹脂、ノルボルネン系、ポリフッ化ビニリデン系樹脂等が挙げられ、成形性の観点から、ポリカーボネート、ポリエチレンテレフタレート、アクリル樹脂、ポリウレタン樹脂、塩化ビニル樹脂、及びポリフッ化ビニリデン樹脂が好ましく、なかでも、耐候性の観点から、ポリカーボネート、アクリル樹脂、ポリウレタン樹脂、塩化ビニル樹脂が好ましい。
本発明の加飾フィルムにおける、所望によるクリヤ層は、特に制限されず、公知のクリヤ塗料を適宜選択して塗装することにより、又は塗装し、次いで硬化させることにより形成することができる。
本発明の加飾フィルムの層構造を、図面を参照しながら説明する。
温度計、サーモスタット、攪拌器、還流冷却器及び滴下装置を備えた反応容器に、脱イオン水65部、及び「Newcol562SF」(商品名、アニオン性乳化剤、固形分60%、日本乳化剤社製)0.5部を投入し、窒素気流下で、攪拌しながら混合し、85℃に昇温した。
温度計、サーモスタット、攪拌器、還流冷却器及び滴下装置を備えた反応容器に、脱イオン水65部、及び「Newcol562SF」(商品名、アニオン性乳化剤、不揮発分60%、日本乳化剤社製、)0.5部を投入し、窒素気流下で、攪拌しながら混合し、85℃に昇温した。
攪拌混合容器内において、アルミニウムペースト「GX−40A」(旭化成メタルズ社製、商品名、平均粒子径20μmのアルミニウムフレークの74%希釈ペースト)27部、2−エチル−1−ヘキサノール35部、リン酸基含有樹脂溶液(注1)12部、及び2−(ジメチルアミノ)エタノール0.2部を均一に混合して、アルミニウム顔料ペースト(B−1)を得た。
攪拌混合容器内において、アルミニウムペースト「GX−40A」(旭化成メタルズ社製、商品名、平均粒子径20μmのアルミニウムフレークの74%希釈ペースト)34部、2−エチル−1−ヘキサノール35部、リン酸基含有樹脂溶液(注1)15部、及び2−(ジメチルアミノ)エタノール0.2部を均一に混合して、アルミニウム顔料ペースト(B−2)を得た。
攪拌混合容器内において、アルミニウムペースト「GX−40A」(旭化成メタルズ社製、商品名、平均粒子径20μmのアルミニウムフレークの74%希釈ペースト)41部、2−エチル−1−ヘキサノール35部、リン酸基含有樹脂溶液(注1)18部、及び2−(ジメチルアミノ)エタノール0.2部を均一に混合して、アルミニウム顔料ペースト(B−3)を得た。
攪拌混合容器内において、アルミニウムペースト「7620NS」(東洋アルミニウム社製、商品名、平均粒子径19μmのアルミニウムフレークの70%希釈ペースト)36部、2−エチル−1−ヘキサノール35部、リン酸基含有樹脂溶液(注1)15部、及び2−(ジメチルアミノ)エタノール0.2部を均一に混合して、アルミニウム顔料ペースト(B−4)を得た。
攪拌器、温度調節器及び冷熱器を備えた反応容器に、メトキシプロパノール27.5部と、イソブタノール27.5部とを含む溶剤を入れ、110℃に加熱し、スチレン25部、n−ブチルメタクリレート27.5部、「イソステアリルアクリレート」(商品名、大阪有機化学工業社製、商品名、分岐高級アルキルアクリレート)20部、4−ヒドロキシブチルアクリレート7.5部、リン酸基含有重合性モノマー(注2)15部、2−メタクリロイルオキシエチルアシッドホスフェート12.5部、イソブタノール10部、及びt−ブチルパーオキシオクタノエート4部からなる混合物121.5部を、4時間かけて上記溶剤に添加し、t−ブチルパーオキシオクタノエート0.5部、及びイソプロパノール20部からなる混合物を1時間かけて滴下し、次いで、1時間、攪拌しながら熟成させることにより、固形分濃度50%のリン酸基含有樹脂溶液を得た。上記リン酸基含有樹脂溶液において、酸価は83mgKOH/gであり、水酸基価は29mgKOH/gであり、そして重量平均分子量は10,000であった。
攪拌器、温度調節器及び冷熱器を備えた反応容器に、モノブチルリン酸57.5部及びイソブタノール41部を入れ、90℃に昇温し、グリシジルメタクリレート42.5部を2時間かけて滴下し、1時間、攪拌しながら熟成させ、次いで、イソプロパノ−ル59部を加えることにより、固形分濃度50%のリン酸基含有重合性モノマー溶液を得た。得られたモノマーの酸価は285mgKOH/gであった。
「ACEMATT OK607」(商品名、デグサ社製、シリカ粉末、平均粒子径:4.5μm)50部を、脱イオン水450部に混合分散し、シリカの水分散液を得た。
「アートパールP800T」(商品名、根上工業社製、ウレタン粒子、平均粒子径:6μm)100部を、脱イオン水400部に混合分散し、ウレタン水粒子の分散液を得た。
製造例8においてウレタン粒子として「アートパールP800T」の代わりに「アートパールC400透明」(商品名、根上工業社製、ウレタン粒子、平均粒子径:15μm)を同量用いる以外は製造例8と同様にしてウレタン粒子の水分散液を得た。
温度計、サーモスタット、撹拌器、還流冷却器及び滴下装置を備えた反応容器にエチレングリコールモノブチルエーテル35部を仕込み、撹拌しながら100℃まで昇温した後、n−ブチルアクリレート30部、メチルメタクリレート17部、2−エチルヘキシルメタクリレート30部、スチレン5部、2−ヒドロキシエチルメタクリレート10部、メタクリル酸8部及びアゾビスイソブチロニトリル1部の混合物を、100℃に保ったまま、滴下ポンプを利用して4時間かけて一定速度で滴下した。滴下終了後100℃に1時間保ち、撹拌を続けた。その後、2,2´−アゾビス(2,4−ジメチルバレロニトリル)0.5部をエチレングリコールモノブチルエーテル10部に溶解させたものを1時間かけて一定速度で滴下し、さらに1時間115℃に保ちアクリル樹脂溶液を得た。反応終了後、2−(ジメチルアミノ)エタノールで当量中和し、さらに、エチレングリコールモノブチルエーテルを添加して固形分55%のアクリル樹脂溶液を得た。
製造例10で得られた55%アクリル樹脂溶液180部、脱イオン水360部、「サーフィノール104A」(商品名、エアープロダクツ社製消泡剤、固形分:50%)6部及び「SACHTLEBEN MICRO」(商品名、ウィルバーエリス社製、硫酸バリウム粉末、平均一次粒子径:0.7μm)250部を、ペイントコンディショナー中でガラスビーズ媒体を加えて、室温で1時間混合分散し、硫酸バリウムの水分散液を得た。
製造例11において硫酸バリウム粉末として「SACHTLEBEN MICRO」の代わりに「バリファインBF−1」(商品名、堺化学工業社製、硫酸バリウム粉末、平均一次粒子径:0.05μm)を同量用いる以外は製造例11と同様にして硫酸バリウムの分散液を得た。
製造例10で得られた55%アクリル樹脂溶液180部、脱イオン水360部、サーフィノール104A(商品名、エアープロダクツ社製消泡剤、固形分:50%)6部及び「MICROACE S−3」(商品名、日本タルク社製、タルク粉末、扁平状、平均一次粒子径:5μm)150部を、ペイントコンディショナー中でガラスビーズ媒体を加えて、室温で1時間混合分散し、タルクの水分散液を得た。
メチルエチルケトンを反応溶媒として、1,6−ヘキサンジオール系のポリカーボネート(数平均分子量1,000)52.0部、トリメチロールプロパン2.5部、1,4−ブタンジオール1.0部、ジメチロールプロピオン酸4.1部、及びイソホロンジイソシアネート33.9部を、ジブチルチンジラウレートを触媒として添加することにより反応させ、次いでトリエチルアミン0.8部添加して反応させることにより、ウレタンプレポリマーを合成した。上記ウレタンプレポリマーの遊離イソシアネート基の量は2.1%であった。次いで、トリエチルアミン3.1部を加えて中和し、ホモミキサーを用い、高速攪拌しながら蒸留水250部を添加し、系を乳化した。次いで、エバポレーターを用いて反応溶媒であるメチルエチルケトンを減圧回収することにより、固形分28%のウレタン樹脂エマルションを得た。
製造例15
攪拌混合容器に、製造例3で得られたアルミニウム顔料ペースト(B−1)74部(アルミニウムフレーク20部)を投入し、該アルミニウム顔料ペーストを攪拌しながら、製造例1で得られたアクリル系コアシェル型エマルション(A−1)200部(固形分70部)、製造例7で得られたシリカの水分散液50部(シリカ量5部)及び製造例14で得られたウレタン樹脂エマルション107部(固形分30部)を添加して混合した。得られた混合物に「プライマルASE−60」(商品名、ロームアンドハース社製、ポリアクリル酸系増粘剤)8.3部(固形分2.5部)を添加し、次いで、ジメチルエタノールアミン及び脱イオン水を添加することにより、pH8.0、固形分25%の水性メタリック塗料No.1を得た。
上記製造例15において、表1に示す配合組成に変更した以外は、製造例15と同様にして、水性メタリック塗料No.2〜No.18を得た。
「アクリプレンHBS010P」(三菱レイヨン社製、商品名、アクリル樹脂フィルム、厚み125μm)に、ナイフコーターを用いて、製造例15で得られた水性メタリック塗料No.1をベース塗料として使用して、乾燥膜厚が30μmになるように塗布し、80℃で30分乾燥させることにより、加飾層を形成した。次いで、接着層として東洋インキ製「EXT−57」を、上記加飾層の上にラミネート(温度:40℃,圧力:0.1MPa,速度:1m/min)し、加飾フィルムを得た。
表2に示す水性メタリック塗料をベース塗料として使用して加飾層を形成した以外は実施例1と同様にして、加飾フィルム及び加飾物品を作成した。
加飾フィルム及び加飾物品の表面のL値を、マルチアングル分光測色計「CM−512m3」(コニカミノルタ社製)を用いて、表面に垂直にある受光部を0°とした場合に、25°、45°、75°となる角度から光源を照射して測定されるL値を測定し、その測定値から延伸前後の外観変化(ΔL)を下記式から算出した。
加飾フィルム及び加飾物品の表面全体の外観変化を目視で下記基準で評価した。
◎:変化なし、
○:一部に若干変化が認められる、
△:全体に変化が認められる、
×:著しく変化が認められる。
JIS K 5600−5−6(1990)に準じて評価する。加飾物品に、カッターナイフで、素地(ABS製成形基材板)に到達するように切り込みを入れ、2mm×2mmのゴバン目100個を形成する。切込みを入れた面に、粘着テープを貼着し、次いで、急激に剥がし、加飾物品に残ったゴバン目の残存個数をカウントし、評価する。
○:残存個数が100個であるが、ゴバン目に一部縁欠けが認められる、
△:残存個数が、99個〜90個である、
×:残存個数が89個以下である。
40℃の温水に、168時間、加飾物品を浸漬し、浸漬後の加飾物品の外観及び上記の付着性(*3)を評価する。
〇:加飾フィルムの外観に異常がない。付着性に関しては、残存個数が100個であるが、ゴバン目に一部縁欠けが認められる。
△:加飾フィルムに、白化、ブリスター等の外観が観察される。付着性に関しては、残存個数が、99個〜90個である。
×:加飾フィルムに、白化、ブリスター等の外観が観察される。付着性に関しては、残存個数が89個以下である。
攪拌機、温度計、還流冷却器、及び滴下装置を備えた反応容器に、メトキシプロピルアセテート100部、「デスモジュールZ4470BA」(住化バイエルウレタン株式会社製、IPDIのイソシヌレート体)(NCO含量11.8wt%)100.0部、ジブチルスズジラウレート0.02部、及びハイドロキノンモノメチルエーテル0.2部の混合物を仕込んだ。上記混合物を攪拌しながら、50℃まで加熱した。続いて、上記混合物の温度が60℃を超えないようにしながら、1,6ヘキサンジオール1部を1時間かけて滴下し、固形分50%の化合物を得た。得られた化合物はNCO当量が380であった。
製造例34
製造例33で得られた(メタ)アクリロイルオキシ基含有ウレタン化合物(D−1)の溶液を163部(固形分81.5部)、「EBECRYL1290」(ダイセル・サイテック株式会社製、商品名、ウレタンアクリレート)18.5部、「ダロキュア1173」(メルクジャパン社製、商品名、光重合開始剤)3.0部、「TINUVIN400」(BASF製、商品名、紫外線吸収剤)1部、「TINUVIN123」(BASF製、商品名、系光安定剤)0.5部を混合し、酢酸エチルで固形分30%に希釈して、活性エネルギー線硬化型のクリヤ塗料No.1を製造した。
「アクリプレンHBS010P」(三菱レイヨン社製、商品名、アクリル樹脂フィルム、厚み125μm)上に、ナイフコーターを用いて、製造例15で得られた水性メタリック塗料No.1をベース塗料として使用し、乾燥膜厚が30μmとなるよう塗装し、80℃で30分間乾燥することにより、加飾層を形成した。上記加飾層の上に、ナイフコーターを用いて、製造例34で得られた活性エネルギー線硬化型のクリヤ塗料No.1を、乾燥膜厚が40μmとなるように塗装し、80℃で30分間乾燥することにより、クリヤ層を形成した。次に、「アクリプレンHBS010P」の、加飾層と反対側の面に接着剤層として「EXT−57」(東洋インキ製、接着剤、アクリル系)をラミネート(温度:40℃,圧力:0.1MPa,速度:1m/min)し、加飾フィルムを得た。
表3に示される水性メタリック塗料をベース塗料として用いた以外は実施例13と同様にして、加飾フィルム及び加飾物品を作成した。
厚さ250μmの「ノバクリアSG−10」(三菱化学製、無延伸PETフィルム)上に、ナイフコーターで、製造例34で得られた活性エネルギー線硬化型のクリヤ塗料No.1を、乾燥膜厚が40μmとなるように塗装し、そして80℃で30分間乾燥することにより、クリヤ層を形成した。上記クリヤ層の上に、ナイフコーターを用いて、製造例15で得られた水性メタリック塗料No.1をベース塗料として使用し、乾燥膜厚が30μmとなるように塗装し、そして80℃で30分間乾燥することにより、加飾層を形成した。次に、上記加飾層の上に、「EXT−57」(東洋インキ製、接着剤)をラミネート(温度:40℃,圧力:0.1MPa,速度:1m/min)し、加飾フィルムを得た。
表4に示される水性メタリック塗料をベース塗料として用いた以外は実施例25と同様にして、加飾フィルム及び加飾成形体を作成した。
「アクリプレンHBS010P」(三菱レイヨン社製、商品名、アクリル樹脂フィルム、厚み125μm)上に、ナイフコーターを用いて、製造例34で得られた活性エネルギー線硬化型のクリヤ塗料No.1を、乾燥膜厚が40μmとなるように塗装し、そして80℃で30分間乾燥することによりクリヤ層を形成した。
表5に示される水性メタリック塗料をベース塗料として用いた以外は実施例37と同様にして、加飾フィルム及び加飾成形体を作成した。
部品、外装部品、並びに家電製品に利用できる。
2 接着層
3 加飾層
4 熱可塑性フィルム層
5 クリヤ層
Claims (10)
- 接着層と、ベース塗料から形成された加飾層と、熱可塑性フィルム層とを含む加飾フィルムであって、
前記ベース塗料が、アクリル樹脂エマルション(A−1)を含む被膜形成性樹脂(A)
の固形分100質量部に対して、平均粒子径15〜50μmのりん片状金属粉(B)を12〜80質量部及び平均粒子径2〜20μmの球状粒子(C)を1〜25質量部含有し、且つりん片状金属粉(B)と球状粒子(C)の使用比が5:1〜3:1である水性メタリック塗料であることを特徴とする加飾フィルム。 - 球状粒子(C)がシリカである請求項1に記載の加飾フィルム。
- 球状粒子(C)がウレタン樹脂粒子である請求項1又は2に記載の加飾フィルム。
- アクリル樹脂エマルション(A−1)が、コポリマー(I)によるコア部と、コポリマー(II)によるシェル部とからなるコアシェル型エマルションであって、コポリマー(I)が1分子中に重合性不飽和基を2個以上有する重合性不飽和モノマー(a1)0.1〜20質量%と、重合性不飽和モノマー(a1)以外の重合性不飽和モノマー(a2)80〜99.9質量%とを共重合することにより得られ、コポリマー(II)が複数の重合性不飽和モノマー(a3)を共重合することにより得られ、且つコポリマー(I)/コポリマー(II)の固形分質量比が95/5〜5/95である、請求項1〜3のいずれか1項に記載の加飾フィルム。
- 前記接着層、前記加飾層、及び前記熱可塑性フィルム層の順に積層されている、請求項1〜4のいずれか1項に記載の加飾フィルム。
- クリヤ層をさらに含む、請求項1〜4のいずれか1項に記載の加飾フィルム。
- 前記接着層、前記熱可塑性フィルム層、前記加飾層、及び前記クリヤ層の順に積層されている、請求項6に記載の加飾フィルム。
- 前記接着層、前記加飾層、前記クリヤ層、及び前記熱可塑性フィルム層の順に積層されている、請求項6に記載の加飾フィルム。
- 前記接着層、前記加飾層、前記熱可塑性フィルム層、及び前記クリヤ層の順に積層されている、請求項6に記載の加飾フィルム。
- 請求項1〜9のいずれか1項に記載の加飾フィルムが接着されている加飾物品。
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