JP5255191B2 - Surface protective film for interior and exterior building materials and method for producing the same - Google Patents
Surface protective film for interior and exterior building materials and method for producing the same Download PDFInfo
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- JP5255191B2 JP5255191B2 JP2006181972A JP2006181972A JP5255191B2 JP 5255191 B2 JP5255191 B2 JP 5255191B2 JP 2006181972 A JP2006181972 A JP 2006181972A JP 2006181972 A JP2006181972 A JP 2006181972A JP 5255191 B2 JP5255191 B2 JP 5255191B2
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- 239000004566 building material Substances 0.000 title claims description 28
- 230000001681 protective effect Effects 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000011347 resin Substances 0.000 claims description 39
- 229920005989 resin Polymers 0.000 claims description 39
- 239000004925 Acrylic resin Substances 0.000 claims description 37
- 229920000178 Acrylic resin Polymers 0.000 claims description 37
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 21
- -1 methacrylate ester Chemical class 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 19
- 238000004049 embossing Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 230000003746 surface roughness Effects 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 238000013461 design Methods 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 3
- 239000011342 resin composition Substances 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000002356 single layer Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 50
- 238000000034 method Methods 0.000 description 16
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000006224 matting agent Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000003475 lamination Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- FCKXGFANXSHGAW-DTXPUJKBSA-N (2s)-n,n'-bis[(2s)-1-(2-chloro-4-nitroanilino)-1-oxo-3-phenylpropan-2-yl]-2-hydroxybutanediamide Chemical compound C([C@H](NC(=O)C[C@H](O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(=O)NC=1C(=CC(=CC=1)[N+]([O-])=O)Cl)C(=O)NC=1C(=CC(=CC=1)[N+]([O-])=O)Cl)C1=CC=CC=C1 FCKXGFANXSHGAW-DTXPUJKBSA-N 0.000 description 2
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 230000004313 glare Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
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- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 229940116351 sebacate Drugs 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 2
- 239000010454 slate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009823 thermal lamination Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- UXWKVPJOPVIIRU-UHFFFAOYSA-N (6-methylsulfanylpyridin-3-yl)boronic acid Chemical compound CSC1=CC=C(B(O)O)C=N1 UXWKVPJOPVIIRU-UHFFFAOYSA-N 0.000 description 1
- JRJZZNAJSLMWGL-UHFFFAOYSA-N 1-(2-hydroxy-2-methylpropyl)-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC(C)(O)CN1C(C)(C)CC(O)CC1(C)C JRJZZNAJSLMWGL-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- VCYCUECVHJJFIQ-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 VCYCUECVHJJFIQ-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- CHDVXKLFZBWKEN-UHFFFAOYSA-N C=C.F.F.F.Cl Chemical compound C=C.F.F.F.Cl CHDVXKLFZBWKEN-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011049 pearl Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical group S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は内外装建材用表面保護フィルム及びその製造方法に関する。 The present invention relates to a surface protective film for interior and exterior building materials and a method for producing the same.
フッ素系樹脂製フィルムをプラスチック、金属、ゴム、合板、木板、ガラス、印刷紙、又はスレート等の基材表面に接着し、基材表面を保護して耐候性及び耐汚染性を付与すると同時に、基材に意匠性を付与する方法が知られている。 Adhering a fluororesin film to the surface of a substrate such as plastic, metal, rubber, plywood, wood board, glass, printing paper, or slate to protect the substrate surface and provide weather resistance and contamination resistance, A method for imparting design properties to a substrate is known.
プラスチック板や金属板を基材とする場合、フッ素系樹脂フィルムと基材を熱ラミネートする方法が広く用いられている。 When a plastic plate or a metal plate is used as a base material, a method of thermally laminating a fluororesin film and the base material is widely used.
表面保護フィルムの高級感や意匠性を高めるために艶消し調の低光沢表面を有するフィルムが使われている。表面を艶消し調にする加工方法として、例えば(1)フッ素系樹脂フィルムを押出成形する際に押出直後にエンボスロールを通過させ表面に凹凸を形成する方法(特許文献1参照)、(2)艶消し剤として無機物や有機物をフッ素系樹脂に添加する方法(3)フッ素系樹脂フィルム成型後フィルム表面にサンドブラストや研磨等の物理的な処理を施す方法、(4)フッ素系樹脂フィルム成型後フィルム表面に艶消し剤をコーティングする方法等が挙げられる。 In order to enhance the luxury and design of the surface protective film, a film having a matte and low gloss surface is used. As a processing method for making the surface matt, for example, (1) when extruding a fluororesin film, passing an embossing roll immediately after extrusion to form irregularities on the surface (see Patent Document 1), (2) A method of adding an inorganic or organic substance to the fluororesin as a matting agent (3) A method of subjecting the film surface to physical treatment such as sandblasting or polishing after molding of the fluororesin film, (4) A film after molding of the fluororesin film For example, a method of coating a matting agent on the surface.
これらの加工方法のうち、(1)エンボスロールを使用する方法と、(2)艶消し剤を添加する方法では、フッ素系樹脂フィルムと基材を熱ラミネートした際に表面に艶が戻る場合や、艶消し剤の添加による分散性の悪化による外観不良(艶斑)が発生する場合や、機械強度低下が発生する場合があった。 Among these processing methods, (1) the method of using an embossing roll and (2) the method of adding a matting agent may be used when the gloss returns to the surface when the fluororesin film and the substrate are heat laminated. In some cases, appearance defects (matte spots) may occur due to deterioration of dispersibility due to the addition of a matting agent, or mechanical strength may decrease.
フッ素系樹脂フィルムに艶消し剤として架橋アクリル樹脂を添加する方法が知られている(特許文献2等参照)。 A method of adding a cross-linked acrylic resin as a matting agent to a fluororesin film is known (see Patent Document 2, etc.).
フッ素系樹脂フィルムの特徴である耐候性や耐汚染性を保持し、量産性に優れ、熱ラミネート時の艶戻りや艶斑を抑制するとともに、機械的強度が低下しにくく、艶消し調の表面を有する内外装建材用表面保護フィルムが求められていた。 Maintains the weather resistance and stain resistance, which are the characteristics of fluororesin films, is excellent in mass production, suppresses matting and mottling during thermal lamination, and is hard to decrease mechanical strength. There has been a demand for a surface protective film for interior / exterior building materials having the following.
内外装建材用表面保護フィルム及びその製造方法を提供する。 Provided are a surface protective film for interior and exterior building materials and a method for producing the same.
本発明はフッ化ビニリデン系樹脂90〜85質量部及びメタクリル酸エステル系樹脂10〜15質量部の合計100質量部に対して平均粒子径1〜10μmの架橋アクリル樹脂1〜10質量部を含有する樹脂組成物を用いた内外装建材用表面保護フィルム及びその製造方法である。 This invention contains 1-10 mass parts of crosslinked acrylic resins with an average particle diameter of 1-10 micrometers with respect to a total of 100 mass parts of 90-85 mass parts of vinylidene fluoride resin and 10-15 mass parts of methacrylic ester resin. It is the surface protection film for interior / exterior building materials using a resin composition, and its manufacturing method.
本発明の内外装建材用表面保護フィルムは、フッ素系樹脂フィルムの特徴である耐候性、耐汚染性を保持し、量産性に優れ、艶消し調の低光沢表面を有し、かつ熱ラミネート時の艶戻りや艶斑を抑制するとともに、機械的強度が低下しにくいなどの特徴を有する。 The surface protective film for interior / exterior building materials of the present invention retains the weather resistance and stain resistance characteristic of a fluororesin film, has excellent mass productivity, has a matte-like low gloss surface, and is thermally laminated. It has features such as preventing gloss return and gloss spots, and reducing mechanical strength.
本明細書における部及び%は、特に断りのない限り質量基準である。 In the present specification, “part” and “%” are based on mass unless otherwise specified.
本発明はフッ化ビニリデン系樹脂90〜85質量部及びメタクリル酸エステル系樹脂10〜15質量部の合計100質量部に対して平均粒子径1〜10μmの架橋アクリル樹脂1〜10質量部を含有する樹脂組成物を用いた内外装建材用表面保護フィルム及びその製造方法である。 This invention contains 1-10 mass parts of crosslinked acrylic resins with an average particle diameter of 1-10 micrometers with respect to a total of 100 mass parts of 90-85 mass parts of vinylidene fluoride resin and 10-15 mass parts of methacrylic ester resin. It is the surface protection film for interior / exterior building materials using a resin composition, and its manufacturing method.
(フッ化ビニリデン系樹脂)
フッ化ビニリデン系樹脂とは、フッ化ビニリデン単量体単位を有するビニル重合体であれば特に限定されず、フッ化ビニリデンのホモポリマであってもよく、フッ化ビニリデンと他のビニル化合物単量体の共重合体であってもよい。フッ化ビニリデンと併用可能なビニル化合物単量体としては例えばフッ化ビニル、四フッ化エチレン、三フッ化塩化エチレン、6フッ化プロピレン等のフッ素化されたビニル化合物や、スチレン、エチレン、ブタジエン、及びプロピレン等の公知のビニル単量体が挙げられる。
(Vinylidene fluoride resin)
The vinylidene fluoride resin is not particularly limited as long as it is a vinyl polymer having a vinylidene fluoride monomer unit, and may be a homopolymer of vinylidene fluoride. Vinylidene fluoride and other vinyl compound monomers The copolymer may be used. Examples of vinyl compound monomers that can be used in combination with vinylidene fluoride include fluorinated vinyl compounds such as vinyl fluoride, tetrafluoroethylene, ethylene trifluoride chloride, and hexafluoropropylene, styrene, ethylene, butadiene, And known vinyl monomers such as propylene.
(メタクリル酸エステル系樹脂)
メタクリル酸エステル系樹脂は、メタクリル酸エステル単量体に基づくビニル重合体であれば特に限定されない。メタクリル酸エステル単量体としては、例えばメタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル、メタクリル酸ペンチル、メタクリル酸ヘキシル等が挙げられ、メタクリル酸メチルが好適に用いられる。メタクリル酸エステル単量体のプロピル基、ブチル基、ペンチル基、及びヘキシル基等のアルキル基は直鎖であってもよく、枝分かれしてもよい。
(Methacrylic ester resin)
The methacrylate ester resin is not particularly limited as long as it is a vinyl polymer based on a methacrylate ester monomer. Examples of the methacrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate and the like, and methyl methacrylate is preferably used. The alkyl group such as propyl group, butyl group, pentyl group, and hexyl group of the methacrylic acid ester monomer may be linear or branched.
メタクリル酸エステル系樹脂は、メタクリル酸エステル単量体の単量体や、複数のメタクリル酸エステル単量体の共重合体であってもよい。メタクリル酸エステル系樹脂には、メタクリル酸エステル以外の公知のビニル化合物であるスチレン、エチレン、ブタジエン、及びプロピレン等に由来する単量体単位を有してもよい。 The methacrylate ester resin may be a monomer of a methacrylate ester monomer or a copolymer of a plurality of methacrylate ester monomers. The methacrylic ester resin may have a monomer unit derived from styrene, ethylene, butadiene, propylene and the like which are known vinyl compounds other than the methacrylic ester.
(架橋アクリル樹脂)
架橋アクリル樹脂とは、メタクリル酸エステルと多官能性単量体の共重合体である。
(Crosslinked acrylic resin)
The cross-linked acrylic resin is a copolymer of a methacrylic acid ester and a polyfunctional monomer.
メタクリル酸エステルとしては、メタクリル酸メチル、メタクリル酸エチル、及びメタクリル酸ブチル等が挙げられる。 Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, and butyl methacrylate.
多官能性単量体とは、ビニル基以外で、化学反応で他の分子と結合を形成しうる官能基の数が2個以上有する物質で、ヒドロキシル基、カルボキシル基、エポキシ基、アミド基、アミノ基、メチロール基、スルホン酸基、スルファミン酸基、及び(亜)リン酸エステル基からなる官能基群より選ばれる官能基を2個以上有する官能基含有単量体である。 A polyfunctional monomer is a substance having two or more functional groups that can form a bond with another molecule by a chemical reaction other than a vinyl group, such as a hydroxyl group, a carboxyl group, an epoxy group, an amide group, A functional group-containing monomer having two or more functional groups selected from a functional group consisting of an amino group, a methylol group, a sulfonic acid group, a sulfamic acid group, and a (phosphite) ester group.
多官能性単量体は特に限定されないが、例えばエチレングリコールジメタクリレート、エチレングリコールビスメタクリレート、プロピレングリコールジアクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールテトラメタクリレート等が挙げられる。 The polyfunctional monomer is not particularly limited, and examples thereof include ethylene glycol dimethacrylate, ethylene glycol bismethacrylate, propylene glycol diacrylate, trimethylolpropane trimethacrylate, and pentaerythritol tetramethacrylate.
架橋アクリル樹脂は、エチレン、スチレン等の公知のビニル単量体に由来する単量体単位を有してもよい。架橋アクリル樹脂はフッ化ビニリデン系樹脂及びメタクリル酸エステル系樹脂と混合しても相溶しないで分散する材質を選択することが好ましい。 The cross-linked acrylic resin may have a monomer unit derived from a known vinyl monomer such as ethylene or styrene. For the crosslinked acrylic resin, it is preferable to select a material that is dispersed without being compatible with the vinylidene fluoride resin and the methacrylic ester resin.
架橋アクリル樹脂はJIS Z8819法によるレーザー散乱法(ミー散乱法)での平均粒子径(D50)が1〜10μmの粒状であり、平均粒子径が2〜8μmであることが好ましい。平均粒子径が小さいと表面光沢度が増して艶消し表面が得られない場合があり、平均粒子径が大きいと架橋アクリル樹脂の分散性が悪くなり、均一な艶消し表面が得られなくなるとともに、機械的強度が低下する場合がある。 The cross-linked acrylic resin is a granular material having an average particle diameter (D 50 ) of 1 to 10 μm in a laser scattering method (Mie scattering method) according to JIS Z8819 method, and preferably has an average particle diameter of 2 to 8 μm. If the average particle size is small, the glossiness of the surface may increase and the matte surface may not be obtained.If the average particle size is large, the dispersibility of the cross-linked acrylic resin will deteriorate, and a uniform matte surface cannot be obtained. Mechanical strength may decrease.
内外装建材用表面保護フィルムを構成する樹脂の配合は、フッ化ビニリデン系樹脂90〜85重量%及びメタクリル酸エステル系樹脂10〜15重量%の合計100質量部に対し、平均粒子径1〜10μmの架橋アクリル樹脂1〜10質量部である。フッ化ビニリデン系樹脂の含有量が多いと、艶消し剤として配合する架橋アクリルを樹脂中に均一に分散することが困難になって、良好なフィルムの表面外観が得られない場合がある。フッ化ビニリデン系樹脂の含有量が少ないと、内外装建材用表面保護フィルムの耐候性及び耐汚染性が低下する場合がある。 The composition of the resin constituting the surface protective film for interior / exterior building materials is an average particle diameter of 1 to 10 μm with respect to a total of 100 parts by mass of 90 to 85% by weight of vinylidene fluoride resin and 10 to 15% by weight of methacrylate ester resin. 1 to 10 parts by mass of the crosslinked acrylic resin. If the content of the vinylidene fluoride resin is large, it may be difficult to uniformly disperse the cross-linked acrylic compounded as a matting agent in the resin, and a good film surface appearance may not be obtained. When the content of vinylidene fluoride resin is small, the weather resistance and stain resistance of the surface protective film for interior and exterior building materials may be lowered.
架橋アクリル樹脂の使用量は、フッ化ビニリデン系樹脂とメタクリル酸エステル系樹脂の合計量100重両部に対して1〜10質量部であり、2〜5質量部が好ましい。架橋アクリル樹脂の使用量が少ないと艶消し表面が得られず、過剰だと分散性が悪くなり均一な艶消し表面が得られなくなるとともに、機械的強度が低下する。 The amount of the crosslinked acrylic resin used is 1 to 10 parts by mass, preferably 2 to 5 parts by mass, based on 100 parts by weight of the total amount of vinylidene fluoride resin and methacrylic ester resin. If the amount of the cross-linked acrylic resin used is small, a matte surface cannot be obtained, and if it is excessive, dispersibility is deteriorated and a uniform matte surface cannot be obtained, and the mechanical strength is lowered.
架橋アクリル樹脂の粒子は表面凹凸が少ない形状であることが好ましく、例えば球状や楕円回転体等であることが好ましい。架橋アクリル樹脂の表面凹凸が多いと、フッ化ビニリデン系樹脂及びメタクリル酸エステル系樹脂に対する分散性が低下する場合がある。 The particles of the cross-linked acrylic resin preferably have a shape with few surface irregularities, and are preferably, for example, spherical or elliptical rotating bodies. If the surface roughness of the cross-linked acrylic resin is large, the dispersibility of the vinylidene fluoride resin and methacrylic ester resin may decrease.
紫外線吸収剤は特に限定されないが、使用する樹脂と相溶性があり、紫外線吸収剤の揮散を防ぐためには、高分子量のものが好ましい。紫外線吸収剤は、例えばベンゾトリアゾール系、オキザリックアシッド系、ベンゾフェノン系、ヒンダードアミン系等が使用できる。 Although a ultraviolet absorber is not specifically limited, In order to have compatibility with resin to be used and to prevent volatilization of a ultraviolet absorber, a high molecular weight thing is preferable. As the ultraviolet absorber, for example, benzotriazole, oxalic acid, benzophenone, hindered amine, and the like can be used.
ベンゾトリアゾール系の紫外線吸収剤としては、例えば2−[3,5−ジ−(アロフア−ジメチルベンジル−2−ヒドロキシフェニル]ベンゾトリアゾール、2−(3,5−ジ−t−ブチル−2−ヒドロキシフェニル)ベンゾトリアゾール、2−(3−t−ブチル−5−メチル−2−ヒドロキシフェニル)−5−クロロベンゾトリアゾール、2−(3,5−ジ−t−ブチル−2−ヒドロキシフェニル)−5−クロロベンゾトリアゾール、2−(3,5−ジ−t−アミル−2−ヒドロキシフェニル)ベンゾトリアゾール、2,2’−メチレンビス[4−(1,1,3,3−テトラメチルブチル)−6−[(2H−ベンゾトリアゾール−2−イル)フェノール]]、2−(2’−ヒドロキシ−5’−メタクリルオキシエチルフェニル)−2H−ベンゾトリアゾール、及び2−(4,6−ジフェニル−1,3,5−トリアジン−2−イル)−5−(ヘキシル)オキシフェノール等が挙げられる。 Examples of the benzotriazole-based ultraviolet absorber include 2- [3,5-di- (allopha-dimethylbenzyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxy]. Phenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5 -Chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 -[(2H-benzotriazol-2-yl) phenol]], 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole, and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol and the like.
オキザリックアシッド系の紫外線吸収剤としては、例えば2−エトキシ−2'−エチルオキザックアシッドビスアニリド、2−エトキシ−5−t−ブチル−2'−エチルオキザックアシッドビスアニリド等が挙げられる。 Examples of the oxalic acid UV absorber include 2-ethoxy-2′-ethyl oxac acid bisanilide, 2-ethoxy-5-t-butyl-2′-ethyl oxac acid bisanilide, and the like. .
ベンゾフェノン系としては、例えば2−ヒドロキシ−4−n−オクトオキシベンゾフェノン、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジニル)セバケート、ビス(2,2,6,6−テトラメチル−4−ピペリジニル)セバケート、ビス−(1−オクチルオキシ−2,2,6,6,−テトラメチル−4−ピペリジニル)セバケート、ジメチル−2−(4−ヒドロキシ−2,2,6,6−テトラメチル−1−ピペリジニル)エタノール、1−[2−3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)ポロピオニルオキシ]−2,2,6,6−T−テトラメチルピペリジン等がある。 Examples of the benzophenone series include 2-hydroxy-4-n-octoxybenzophenone, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, and bis (2,2,6,6-tetramethyl). -4-piperidinyl) sebacate, bis- (1-octyloxy-2,2,6,6, -tetramethyl-4-piperidinyl) sebacate, dimethyl-2- (4-hydroxy-2,2,6,6- Tetramethyl-1-piperidinyl) ethanol, 1- [2-3- (3,5-di-t-butyl-4-hydroxyphenyl) poropionyloxy] -2,2,6,6-T-tetramethyl There are piperidine and the like.
これらの紫外線吸収剤の中でも、ベンゾトリアゾール系を用いると少量で顕著な耐候性を示すため好ましい。紫外線吸収剤の使用量は特に限定されないが、フッ化ビニリデン系樹脂及びメタクリル酸エステル系樹脂の合計100質量部に対して紫外線吸収剤0.01〜5質量部とすると耐候性と機械強度のバランスが良く好ましい。 Among these ultraviolet absorbers, use of a benzotriazole type is preferable because it shows remarkable weather resistance in a small amount. Although the usage-amount of a ultraviolet absorber is not specifically limited, If it is 0.01-5 mass parts of ultraviolet absorbers with respect to a total of 100 mass parts of vinylidene fluoride resin and methacrylic ester resin, it is a balance of a weather resistance and mechanical strength. Is preferable.
内外装建材用表面保護フィルムには、酸化防止剤、分散剤、カップリング剤、熱安定剤、界面活性剤、帯電防止剤、防曇剤、及び着色剤として複合酸化物系無機顔料や無機系顔料、カーボンブラック、真珠顔料を使用してよい。 Surface protective films for interior and exterior building materials include antioxidants, dispersants, coupling agents, thermal stabilizers, surfactants, antistatic agents, antifogging agents, and colorants as complex oxide inorganic pigments and inorganic materials. Pigments, carbon black and pearl pigments may be used.
(内外装建材用表面保護フィルムの製造方法)
内外装建材用表面保護フィルムの製造方法は特に限定されないが、単軸押出機又は二軸押出機を使用し、Tダイス法等の溶融押出成形にて製造できる。
(Method for manufacturing surface protective film for interior and exterior building materials)
Although the manufacturing method of the surface protection film for interior / exterior building materials is not specifically limited, it can manufacture by melt extrusion molding, such as a T-die method, using a single screw extruder or a twin screw extruder.
フッ化ビニリデン系樹脂、メタクリル酸エステル系樹脂、架橋アクリル樹脂、その他の添加剤を混入する方法は特に限定されず、例えば粉末状又はペレット状の原料であるフッ化ビニリデン系樹脂、メタクリル酸エステル系樹脂、架橋アクリル樹脂樹脂と添加剤をあらかじめ混合しておき、単軸押出機を使用して溶融混練する方法が使用できる。 The method of mixing vinylidene fluoride resin, methacrylic ester resin, cross-linked acrylic resin, and other additives is not particularly limited. For example, vinylidene fluoride resin or methacrylic ester resin that is a raw material in powder or pellet form A method in which a resin, a cross-linked acrylic resin and an additive are mixed in advance and melt-kneaded using a single screw extruder can be used.
フッ化ビニリデン系樹脂、メタクリル酸エステル系樹脂、架橋アクリル樹脂を添加する際に、フッ化ビニリデン系樹脂又はメタクリル酸エステル系樹脂の一部又は全部と架橋アクリル樹脂をプレブレンドしてなるコンパウンドを製造し、コンパウンドと残りの成分を単軸押出機にて溶融混練してもよい。 Manufactures a compound made by pre-blending a part or all of vinylidene fluoride resin or methacrylate ester resin with crosslinked acrylic resin when adding vinylidene fluoride resin, methacrylate ester resin, or crosslinked acrylic resin Then, the compound and the remaining components may be melt kneaded with a single screw extruder.
内外装建材用表面保護フィルムの成形方法は特に限定されないが、押出成形時には表面を良好な艶消し調とするために片面又は両面をエンボスロールで艶消し、エンボス面とすることが好ましい。片面をエンボス面とする場合には、押出直後に艶消し表面がエンボスロール側に接触するようにエンボスロールと金属ロールに圧着され成形される。 The molding method of the surface protective film for interior / exterior building materials is not particularly limited, but it is preferable that one or both sides are matted with an embossing roll to form an embossed surface in order to make the surface have a good matte tone during extrusion molding. When one side is used as an embossed surface, it is pressure-bonded to an embossed roll and a metal roll so that the matte surface comes into contact with the embossed roll immediately after extrusion.
内外装建材用表面保護フィルムの架橋アクリル樹脂の平均粒子径とエンボスロールの表面粗さRzの間に下式(A)が成立するものを用いるとよい。
架橋アクリル樹脂の平均粒子径≦エンボスロールの表面粗さRz・・・・(数式A)
フィルムを熱ロール圧着や熱プレス圧着等で熱ラミネート加工を行う際、エンボスロールの表面粗さに対し架橋アクリル樹脂の平均粒子径が同等若しくはそれ以下である事が重要となる。
It is good to use what the following Formula (A) is materialized between the average particle diameter of the bridge | crosslinking acrylic resin of the surface protection film for interior / exterior building materials, and the surface roughness Rz of an embossing roll.
Average particle diameter of cross-linked acrylic resin ≦ surface roughness R z of embossing roll (Formula A)
When the film is heat laminated by hot roll pressing or hot press pressing, it is important that the average particle size of the crosslinked acrylic resin is equal to or less than the surface roughness of the embossing roll.
エンボスロールの表面粗さに対し架橋アクリル樹脂の平均粒子径が同等若しくはそれ以下であれば、熱ラミネート等の加工によっても艶戻りや艶斑が抑制される。その理由として、エンボスロールにより形成された表面凹凸の凸部分が主に熱ロールや熱プレス表面と優先的に接するため、その影響を受け凹凸が緩和されるものの、表面の凹部分には球状の架橋アクリル樹脂による凹凸が存在しているために、凸部分のクッション効果と相まって大きな影響を受けず、その凹凸が保持されるためと考えられる。 If the average particle diameter of the cross-linked acrylic resin is equal to or less than the surface roughness of the embossing roll, gloss return and luster are also suppressed by processing such as thermal lamination. The reason for this is that the convex portions of the surface irregularities formed by the embossing roll mainly contact with the surface of the hot roll or hot press preferentially. It is considered that the unevenness due to the cross-linked acrylic resin is present, so that the unevenness is maintained without being greatly influenced by the cushioning effect of the convex portion.
エンボスロールの表面粗さRzと架橋アクリル樹脂の平均粒子径D50の比であるD50/Rz値は特に限定されないが、D50/Rz値が1以下であることが好ましく、0.8以下であることがより好ましく、0.7〜0.2であることが最も好ましい。D50/Rz値が大きいと、熱ラミネート時にエンボスロールによる表面凹凸よりも架橋アクリル樹脂自身による凹凸部分が優先的にピンチ圧着等の影響を受け易くなり、艶戻りや艶斑の原因になる場合がある。D50/Rz値が小さいと、架橋アクリル樹脂自身による艶消し効果が小さくなり、良好な艶消し表面が得られないと共に、熱加工時の艶戻りの原因となる恐れがある。 The D 50 / R z value, which is the ratio between the surface roughness R z of the embossing roll and the average particle diameter D 50 of the crosslinked acrylic resin, is not particularly limited, but the D 50 / R z value is preferably 1 or less. Is more preferably 0.8 or less, and most preferably 0.7 to 0.2. When the D 50 / R z value is large, the uneven portion due to the crosslinked acrylic resin itself is preferentially affected by the pinch pressure bonding rather than the surface unevenness due to the embossing roll at the time of heat lamination, which causes gloss return and gloss spots. There is a case. When the D 50 / R z value is small, the matting effect by the crosslinked acrylic resin itself is small, and a good matte surface cannot be obtained, and there is a possibility that it may cause matting at the time of heat processing.
本発明の内外装建材用表面保護フィルムは、表面に図柄を印刷すると、意匠性に優れるため好ましい。 The surface protective film for interior / exterior building materials of the present invention is preferable when a pattern is printed on the surface because it is excellent in design.
内外装建材用表面保護フィルムの膜厚は、種々の用途に合わせて決定されるが、150μm以下、好ましくは、10〜100μmの範囲である。 Although the film thickness of the surface protection film for interior / exterior building materials is determined according to various uses, it is 150 micrometers or less, Preferably, it is the range of 10-100 micrometers.
内外装建材用表面保護フィルムは各種基材に積層して積層体とすることもできる。基材としては例えばプラスチック、ゴム、塗料面、金属、ガラス、木、スレート等が挙げられる。基材と内外装建材用表面保護フィルムを積層して積層体とするにはフィルムを基材に接着剤を用いて接着する方法や、加熱接着する方法が挙げられる。 The surface protective film for interior / exterior building materials can be laminated on various substrates to form a laminate. Examples of the substrate include plastic, rubber, paint surface, metal, glass, wood, slate and the like. In order to laminate the base material and the surface protective film for interior / exterior building materials to form a laminate, there are a method of adhering the film to the base material using an adhesive and a method of heat-bonding.
使用される接着剤としては、エポキシ樹脂系、アクリル樹脂系、ウレタン樹脂系等の一般的接着剤を使用できるし、天然ゴム、アクリル樹脂系等を使用した感圧性接着剤をあらかじめ内外装建材用表面保護フィルムの接着面に塗布しておいて使用できる。感圧接着剤に離型紙をつけて、使用時に離型紙を剥がして基材に貼り合わせる事もできる。 As the adhesive used, general adhesives such as epoxy resin, acrylic resin, urethane resin, etc. can be used, and pressure sensitive adhesives using natural rubber, acrylic resin, etc. are used for interior and exterior building materials in advance. It can be used by being applied to the adhesive surface of the surface protective film. It is also possible to attach release paper to the pressure-sensitive adhesive, peel off the release paper at the time of use, and bond it to the substrate.
(内外装建材用表面保護フィルム)
建築物の内外装用部材に使用されるプラスチック板や金属板、その他の各種基材は耐久性の向上や装飾を目的として、その表面を塗装したり、耐久性フィルム特にフッ素系樹脂の表面保護フィルムをラミネートしたりして使用されている。その用途は、例えば壁紙や車輌、エレベーター等の内外装材用のほか、マーキングフィルム、家具、家電製品、トレー、窓ガラス用等多岐にわたる。
(Surface protection film for interior and exterior building materials)
For the purpose of improving durability and decoration, plastic plates, metal plates, and other various base materials used for interior and exterior parts of buildings have their surfaces painted, and surface protection films of durable films, especially fluororesins It is used by laminating. The use is wide, for example, for interior and exterior materials such as wallpaper, vehicles, and elevators, as well as for marking films, furniture, home appliances, trays and window glass.
(実施例1〜4、比較例1〜5)表1及び表2に示す配合割合にて各樹脂をタンブラーにてブレンドし、φ45mm2軸押出機によって混練しコンパウンドを得た。次にφ50mm単軸押出機を用い、表1に示す膜厚比率の薄膜フィルムを製膜した。この際、表1に示す表面粗さのエンボスロールを使用した。次に表1及び表2の中でフィルム外観の良好なフィルムについて、表中に示す基材を使用し、アクリル樹脂系接着剤をフィルム表面に塗布後、加熱ラミネートを行った。加熱ラミネートはロールラミネーターを用い、加熱温度150℃の条件で熱接着し積層シートを得た。 (Examples 1 to 4, Comparative Examples 1 to 5) Each resin was blended with a tumbler at the blending ratios shown in Tables 1 and 2, and kneaded with a φ45 mm twin screw extruder to obtain a compound. Next, using a φ50 mm single screw extruder, a thin film having a film thickness ratio shown in Table 1 was formed. At this time, an embossing roll having a surface roughness shown in Table 1 was used. Next, for the films having good film appearance in Tables 1 and 2, the base materials shown in the tables were used, and after applying an acrylic resin adhesive on the film surface, heating lamination was performed. The heating laminate used a roll laminator and was thermally bonded under the condition of a heating temperature of 150 ° C. to obtain a laminated sheet.
(使用材料)
フッ化ビニリデン系樹脂:カイナーK720及びカイナーK740、アルケマ社製、市販品。
メタクリル酸エステル系樹脂:ハイペットHBS000、三菱レイヨン社製、市販品。
架橋アクリル樹脂A:アクリル酸及びエチレングリコールジメタクリレートの共重合体、平均粒子径(D50)が8μm、積水化成品工業社製、市販品。
架橋アクリル樹脂B:アクリル酸及びエチレングリコールビスメタクリレートの共重合体、平均粒子径(D50)が8μm、綜研化学社製。
架橋アクリル樹脂C:アクリル酸及びペンタエリスリトールテトラメタクリレートの重合体、平均粒子径(D50)が1μm、綜研化学社製。
架橋アクリル樹脂D:アクリル酸及びプロピレングリコールジアクリレートの重合体、平均粒子径9μm、綜研化学社製。
(Materials used)
Vinylidene fluoride resins: Kyner K720 and Kyner K740, commercially available from Arkema.
Methacrylate ester resin: Hi-pet HBS000, manufactured by Mitsubishi Rayon Co., Ltd.
Cross-linked acrylic resin A: a copolymer of acrylic acid and ethylene glycol dimethacrylate, an average particle size (D 50 ) of 8 μm, manufactured by Sekisui Plastics Co., Ltd., a commercial product.
Cross-linked acrylic resin B: copolymer of acrylic acid and ethylene glycol bismethacrylate, average particle size (D 50 ) is 8 μm, manufactured by Soken Chemical Co., Ltd.
Cross-linked acrylic resin C: polymer of acrylic acid and pentaerythritol tetramethacrylate, average particle size (D 50 ) is 1 μm, manufactured by Soken Chemical Co., Ltd.
Cross-linked acrylic resin D: polymer of acrylic acid and propylene glycol diacrylate, average particle size 9 μm, manufactured by Soken Chemical Co., Ltd.
(評価)
実施例、比較例にて得られた薄膜フィルム及び熱接着した積層シートについて以下の様な項目について評価を行った。結果を表1及び表2に示す。
1)外観
得られた薄膜フィルムの外観性を目視にて評価した。実施例1〜4及び比較例2,5の薄膜フィルムは艶消剤の分散不良もなく良好な低光沢表面を有すフィルムであった。比較例1,3,4の薄膜フィルムは艶消し剤の分散不良により外観が悪化した。
(Evaluation)
The following items were evaluated for the thin film obtained in Examples and Comparative Examples and the heat-bonded laminated sheets. The results are shown in Tables 1 and 2.
1) Appearance The appearance of the obtained thin film was visually evaluated. The thin film films of Examples 1 to 4 and Comparative Examples 2 and 5 were films having a good low-gloss surface without poor dispersion of the matting agent. The thin film films of Comparative Examples 1, 3, and 4 deteriorated in appearance due to poor dispersion of the matting agent.
2)表面光沢度
得られた薄膜フィルムの表面光沢度を光沢度計(日本電色工業製グロスメーターVGS−1D)を用い測定した。実施例1〜4及び比較例2,5については低光沢表面であることが確認された。比較例1,3,4については外観が悪かったため評価を中止した。
2) Surface glossiness The surface glossiness of the obtained thin film was measured using a gloss meter (Nippon Denshoku Co., Ltd. gloss meter VGS-1D). Examples 1 to 4 and Comparative Examples 2 and 5 were confirmed to have a low gloss surface. Since Comparative Example 1, 3 and 4 had a bad appearance, the evaluation was stopped.
3)熱加工性
加熱ラミネート後の積層シートの表面光沢度を光沢度計(日本電色工業製グロスメーターVGS−1D)を用い測定した。加熱ラミネート前との光沢度を比較した結果、実施例1〜4、比較例2については、加熱ラミネート後の光沢度変化は少なく熱加工性に優れることを確認した。比較例5については、艶戻りが生じ光沢度が上昇した。
3) Thermal processability The surface glossiness of the laminated sheet after heat lamination was measured using a gloss meter (Nippon Denshoku Co., Ltd. gloss meter VGS-1D). As a result of comparing the glossiness before heating lamination, it was confirmed that Examples 1 to 4 and Comparative Example 2 had little change in glossiness after heating lamination and excellent heat workability. As for Comparative Example 5, gloss return occurred and the glossiness increased.
4)耐候性
得られた積層シートの耐候性をJIS A1415に準拠し、サンシャインウエザーオメーターを用い測定した。ブラックパネル温度63℃、シャワーサイクル120分間隔で18分間とし、1000時間後の積層シートの外観評価を行った。実施例1〜4については、試験後も外観上の変化は見られないことを確認した。比較例2については、フィルムにヒビ割れが生じた。
4) Weather resistance The weather resistance of the obtained laminated sheet was measured according to JIS A1415 using a sunshine weatherometer. The appearance of the laminated sheet after 1000 hours was evaluated with a black panel temperature of 63 ° C. and a shower cycle of 18 minutes at intervals of 120 minutes. About Examples 1-4, it confirmed that the change on an external appearance was not seen after a test. In Comparative Example 2, the film was cracked.
本発明は内外装建材用表面保護フィルムは、フッ素系樹脂フィルムの特徴である耐候性、耐汚染性を保持し、量産性に優れ、艶消し調の低光沢表面を有し、かつ熱ラミネート時の艶戻りや艶斑を抑制するとともに、機械的強度が低下しにくいなどの特徴を有するため、壁紙、車輌内外装、エレベーター内外装等の内外装材用途のほか、マーキングフィルム、家具、家電製品、トレー、窓ガラス用等用途に適する。
In the present invention, the surface protective film for interior and exterior building materials retains the weather resistance and stain resistance characteristic of a fluororesin film, has an excellent mass productivity, has a matte-like low gloss surface, and is thermally laminated. It has features such as preventing glare and glare from being lost, and mechanical strength is unlikely to decrease, so it can be used for interior and exterior materials such as wallpaper, vehicle interior and exterior, elevator interior and exterior, as well as marking films, furniture, and home appliances. Suitable for applications such as trays and window glass.
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JP5790498B2 (en) | 2010-01-26 | 2015-10-07 | 三菱レイヨン株式会社 | Fluorine matte film, fluorine matte laminate film, fluorine matte decorative laminate film, laminate sheet, laminate molded product obtained by laminating these, and method for producing the same |
EP3722384A1 (en) * | 2012-06-29 | 2020-10-14 | Agc Inc. | Powder coating composition, process for producing cured film and coated article |
WO2014057933A1 (en) * | 2012-10-10 | 2014-04-17 | 電気化学工業株式会社 | Vinylidene fluoride resin composition, resin film, solar cell backsheet, and solar cell module |
CN107075220B (en) * | 2014-07-14 | 2020-05-15 | 三菱化学株式会社 | Thermoplastic resin composition for matting, fluorine-based matting film, and fluorine-based matting laminate film |
PL3251842T3 (en) * | 2015-01-27 | 2022-06-13 | Toppan Printing Co., Ltd. | Non-combustible decorative sheet, metal decorative member and method for producing metal decorative member |
CN107107593B (en) * | 2015-01-27 | 2019-11-19 | 凸版印刷株式会社 | The manufacturing method of noninflammability decoration sheet, metal finishing component and metal finishing component |
EP3278983B1 (en) * | 2015-03-31 | 2020-05-06 | Dai Nippon Printing Co., Ltd. | Decorative panel for exterior use, and method for manufacturing same |
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