JP2018062114A - Skin material for resin molded body, synthetic resin molded body, and method for producing synthetic resin molded body - Google Patents
Skin material for resin molded body, synthetic resin molded body, and method for producing synthetic resin molded body Download PDFInfo
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- JP2018062114A JP2018062114A JP2016201228A JP2016201228A JP2018062114A JP 2018062114 A JP2018062114 A JP 2018062114A JP 2016201228 A JP2016201228 A JP 2016201228A JP 2016201228 A JP2016201228 A JP 2016201228A JP 2018062114 A JP2018062114 A JP 2018062114A
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- 239000000463 material Substances 0.000 title claims abstract description 281
- 229920005989 resin Polymers 0.000 title claims abstract description 206
- 239000011347 resin Substances 0.000 title claims abstract description 206
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 109
- 239000000057 synthetic resin Substances 0.000 title claims abstract description 109
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000000049 pigment Substances 0.000 claims abstract description 106
- 239000003086 colorant Substances 0.000 claims abstract description 32
- 238000000465 moulding Methods 0.000 claims description 77
- 238000000034 method Methods 0.000 claims description 63
- 239000000203 mixture Substances 0.000 claims description 37
- 229920000178 Acrylic resin Polymers 0.000 claims description 21
- 239000004925 Acrylic resin Substances 0.000 claims description 21
- 239000000853 adhesive Substances 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 230000001070 adhesive effect Effects 0.000 claims description 13
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000003856 thermoforming Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 335
- 238000013461 design Methods 0.000 description 31
- 239000000758 substrate Substances 0.000 description 31
- 230000000694 effects Effects 0.000 description 26
- 239000012790 adhesive layer Substances 0.000 description 24
- 239000011342 resin composition Substances 0.000 description 19
- 239000000976 ink Substances 0.000 description 14
- -1 alkyl methacrylate Chemical compound 0.000 description 11
- 238000004049 embossing Methods 0.000 description 11
- 239000011254 layer-forming composition Substances 0.000 description 9
- 239000004814 polyurethane Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 229920002635 polyurethane Polymers 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000001771 impaired effect Effects 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 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 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
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- 230000037303 wrinkles Effects 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本開示は、樹脂成形体用表皮材、合成樹脂成形体、及び合成樹脂成形体の製造方法に関する。 The present disclosure relates to a skin material for a resin molded body, a synthetic resin molded body, and a method for producing a synthetic resin molded body.
インストルメントパネル、ドアトリム、座席、天井などの自動車内装部品、外装部品、トリム、座席、天井などの鉄道車輌内装部品、航空機内装部品、建具、家具、キッチン扉、収納扉等の建装用内外装部材などの用途に、表面に装飾を施した樹脂成形体が用いられている。
表面に意匠を施した樹脂成形体を製造する方法としては、樹脂を成形する際に、内面に凹凸による意匠を施した金型を用い、得られた樹脂成形体の表面に透明な塗料を塗布する方法、意匠形成用の表皮材を金型内に配置するか、或いは、被成形体である樹脂基材を表皮材で被覆した後、加熱及び加圧して成形する方法などが挙げられる。
Automotive interior parts such as instrument panels, door trims, seats, and ceilings, exterior parts, trims, seat interior parts such as railroad car interior parts, aircraft interior parts, fittings, furniture, kitchen doors, storage doors For such applications, resin molded bodies having a decorated surface are used.
As a method of manufacturing a resin molded body with a design on the surface, when molding the resin, use a mold with an uneven design on the inner surface, and apply a transparent paint to the surface of the resulting resin molded body And a method of arranging a skin material for forming a design in a mold, or a method of molding by heating and pressing after coating a resin base material which is a molded body with a skin material.
従来の加熱成形法による車両部品等の作製においては、深み感、立体感を付与する目的で、インナーエンボス加工を行うことがある。インナーエンボス加工は、例えば、透明樹脂シート層と片面に凹凸模様を施した樹脂シート層とを予め積層して表皮材を製造した後、得られた表皮材を樹脂成型体層に積層して成形体を製造する加工方法である。このため、得られた成形体表面の意匠性は表皮材に依存する。また、既述のインナーエンボス加工に用いられる表皮材における透明樹脂シートは、加熱成形性を備える必要があり、用いる材料、物性が限定され、耐傷性に改良の余地がある。 In the production of vehicle parts and the like by a conventional thermoforming method, inner embossing may be performed for the purpose of imparting a sense of depth and three-dimensionality. Inner embossing, for example, after preliminarily laminating a transparent resin sheet layer and a resin sheet layer with a concavo-convex pattern on one side to produce a skin material, the resulting skin material is laminated on a resin molding layer It is the processing method which manufactures a body. For this reason, the designability of the surface of the obtained molded body depends on the skin material. Moreover, the transparent resin sheet in the skin material used for the above-described inner embossing needs to have heat formability, the material and physical properties to be used are limited, and there is room for improvement in scratch resistance.
自動車のボディーや外装部品等の屋外用の成形物を製造する方法として、熱可塑性樹脂層、未硬化の紫外線硬化型ハードコート層、及び離型性フィルム層が積層した加飾フィルムを用い、射出成形用の金型の凸型に、加飾フィルムの熱可塑性樹脂層が射出成形樹脂に接するように配置し、凸型と加飾フィルムとの間の間隙に溶融樹脂を圧入して成形体とした後、紫外線を照射してハードコート層を硬化させ、次いで離型性フィルムを剥離することにより表面に加飾フィルム層が形成された成形物の製造方法が提案されている（例えば、特許文献１参照）。 As a method of manufacturing outdoor moldings such as automobile bodies and exterior parts, injection is performed using a decorative film in which a thermoplastic resin layer, an uncured UV-curable hard coat layer, and a release film layer are laminated. Placed in the convex mold of the mold for molding so that the thermoplastic resin layer of the decorative film is in contact with the injection molded resin, and the molten resin is press-fitted into the gap between the convex mold and the decorative film Then, a method for producing a molded article in which a decorative film layer is formed on the surface by irradiating ultraviolet rays to cure the hard coat layer and then peeling off the release film has been proposed (for example, Patent Documents). 1).
さらに、樹脂成形体表面に、輝度感と立体感とを有す意匠を形成する方法として、例えば、エンボス加工を行なった熱可塑性樹脂層の凸状部にメタリック調インクを付与し、色柄模様のインク塗布部を形成した熱可塑性ベースシートの片面にメタリック調粒子を含有する接着剤層を介して熱可塑性樹脂層と熱圧着させることで立体感のある意匠が形成された表層材が提案されている（例えば、特許文献２参照）。 Furthermore, as a method of forming a design having a sense of brightness and three-dimensionality on the surface of the resin molded body, for example, a metallic ink is applied to the convex portion of the embossed thermoplastic resin layer, and a color pattern A surface layer material is proposed in which a three-dimensional design is formed by thermocompression bonding with a thermoplastic resin layer via an adhesive layer containing metallic particles on one side of a thermoplastic base sheet on which an ink application part is formed. (For example, refer to Patent Document 2).
特許文献１に記載の方法では、未硬化のハードコート層を有する加飾フィルムを有する樹脂成形体を得た後、紫外線を照射して硬化させることが必要であり、工程が煩雑であり、また、成形体の最表面には、耐傷性の平滑な透明樹脂層が形成されるために、十分な立体感のある意匠を得ることが困難であった。
特許文献２に記載の方法では、意匠性に優れたエンボス加工を行った後、エンボス加工の凸状部のみメタリック調インクを付与する必要があり、製造方法の簡易性の点では、なお改良の余地がある。
In the method described in Patent Document 1, after obtaining a resin molded body having a decorative film having an uncured hard coat layer, it is necessary to cure by irradiating with ultraviolet rays, and the process is complicated. Since a scratch-resistant smooth transparent resin layer is formed on the outermost surface of the molded body, it has been difficult to obtain a design with a sufficient three-dimensional effect.
In the method described in Patent Document 2, after embossing with excellent design properties, it is necessary to apply metallic ink only to the convex portions of the embossing. There is room.
本発明の一実施形態の課題は、合成樹脂成形体表面に、立体感を有する外観を形成し得る樹脂成形体用表皮材、及び合成樹脂成形体を提供することである。
本発明の別の実施形態の課題は、立体感を有する外観を有し、耐傷性が良好な合成樹脂成形体の製造方法を提供することである。
An object of one embodiment of the present invention is to provide a skin material for a resin molded body that can form a three-dimensional appearance on the surface of the synthetic resin molded body, and a synthetic resin molded body.
The subject of another embodiment of this invention is providing the manufacturing method of the synthetic resin molding which has the external appearance which has a three-dimensional effect, and has favorable scratch resistance.
上記課題を解決するための手段は、以下の実施形態を含む。
＜１＞ 合成樹脂と、メタリック顔料と、メタリック顔料以外の着色剤と、を含む表皮基材層、及び前記表皮基材層の片方の面上に設けられ、合成樹脂を含み、前記表皮基材層と対向する側と反対側の面に凹凸を有する表皮層を備える樹脂成形体用表皮材。
＜２＞ 前記表皮基材層に含まれる合成樹脂が、塩化ビニル樹脂を含み、前記表皮層に含まれる合成樹脂が、アクリル樹脂及びフッ素樹脂から選ばれる少なくとも１種の樹脂を含む＜１＞に記載の樹脂成形体用表皮材。
＜３＞ 前記表皮基材層の厚みが、前記表皮層よりも厚い＜１＞又は＜２＞に記載の樹脂成形体用表皮材。
＜４＞ 樹脂成形基材の面上に、＜１＞〜＜３＞のいずれか１つに記載の樹脂成形体用表皮材と、透明樹脂層とを有する合成樹脂成形体。
Means for solving the above problems include the following embodiments.
<1> A skin base material layer including a synthetic resin, a metallic pigment, and a colorant other than the metallic pigment, and the skin base material layer provided on one surface of the skin base material layer, including the synthetic resin, A skin material for a resin molded body comprising a skin layer having irregularities on the surface opposite to the side facing the layer.
<2> The synthetic resin included in the skin base material layer includes a vinyl chloride resin, and the synthetic resin included in the skin layer includes at least one resin selected from an acrylic resin and a fluororesin. The skin material for resin moldings as described.
<3> The skin material for a resin molded body according to <1> or <2>, wherein the thickness of the skin base material layer is thicker than that of the skin layer.
<4> A synthetic resin molded body having the surface material for a resin molded body according to any one of <1> to <3> and a transparent resin layer on the surface of the resin molded substrate.
＜５＞ 合成樹脂を含み、表面に凹凸を有する表皮層を形成する工程、前記表皮層の凹凸を有する側とは反対側の面上に、合成樹脂と、メタリック顔料と、メタリック顔料以外の着色剤と、を含む表皮基材層を形成して、樹脂成形体用表皮材を得る工程、樹脂成形基材の表面に、前記樹脂成形体用表皮材を、前記樹脂成形基材と前記表皮基材層とが接するように配置し、加熱成形して予備成形体を得る工程、及び得られた予備成形体に配置された前記樹脂成形体用表皮材の表面に、透明樹脂を付与して透明樹脂層を形成する工程を有し、樹脂成形基材と、表皮基材層と、表皮層と、透明樹脂層と、をこの順に有する合成樹脂成形体を得る合成樹脂成形体の製造方法。
＜６＞ 前記樹脂成形基材と前記表皮基材層との間に接着剤層を形成する工程をさらに有する＜５＞に記載の合成樹脂成形体の製造方法。
＜７＞ 前記透明樹脂を付与して透明樹脂層を形成する工程が、前記樹脂成形体用表皮材の面上に透明樹脂層形成用組成物を塗布する工程を含む＜５＞又は＜６＞に記載の合成樹脂成形体の製造方法。
<5> Step of forming a skin layer having a synthetic resin and having irregularities on the surface, a color other than the synthetic resin, the metallic pigment, and the metallic pigment on the surface of the skin layer opposite to the side having the irregularities Forming a skin base material layer containing an agent, and obtaining a skin material for a resin molded body, the skin material for the resin molded body on the surface of the resin molded base material, the resin molded base material and the skin base Place the material layer in contact with it, heat-mold it to obtain a preform, and apply a transparent resin to the surface of the skin material for the resin molded body placed in the obtained preform to make it transparent The manufacturing method of the synthetic resin molding which has the process of forming a resin layer and obtains the synthetic resin molding which has a resin molding base material, an outer skin base material layer, an outer skin layer, and a transparent resin layer in this order.
<6> The method for producing a synthetic resin molded body according to <5>, further including a step of forming an adhesive layer between the resin molded substrate and the skin substrate layer.
<7> The step of forming the transparent resin layer by applying the transparent resin includes a step of applying the transparent resin layer forming composition on the surface of the skin material for a resin molded body. <5> or <6> The manufacturing method of the synthetic resin molding as described in any one of.
本発明の一実施形態によれば、合成樹脂成形体表面に、立体感を有する外観を形成し得る樹脂成形体用表皮材、及び合成樹脂成形体を提供することができる。
本発明の別の実施形態によれば、立体感を有する外観を有し、耐傷性が良好な合成樹脂成形体の製造方法を提供することができる。
According to one embodiment of the present invention, it is possible to provide a skin material for a resin molded body that can form a three-dimensional appearance on the surface of the synthetic resin molded body, and a synthetic resin molded body.
According to another embodiment of the present invention, it is possible to provide a method for producing a synthetic resin molded article having a three-dimensional appearance and good scratch resistance.
本明細書において「〜」を用いて記載した数値範囲は、「〜」の前後の数値を下限値及び上限値として含む数値範囲を表す。
本明細書において「工程」との語は、独立した工程だけでなく、他の工程と明確に区別できない場合であっても工程の所期の目的が達成されれば、本用語に含まれる。
さらに、本明細書において組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
In the present specification, a numerical range described using “to” represents a numerical range including numerical values before and after “to” as a lower limit value and an upper limit value.
In this specification, the term “process” is not only an independent process, but is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
Further, in the present specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.
以下、本発明を詳細に説明する。
［樹脂成形体用表皮材］
本開示における樹脂成形体用表皮材（以下、単に「表皮材」と称することがある）は、合成樹脂と、メタリック顔料と、メタリック顔料以外の着色剤と、を含む表皮基材層、及び前記表皮基材層の片方の面上に設けられ、合成樹脂を含み、前記表皮基材層と対向する側と反対側の面に凹凸を有する表皮層を備える。即ち、表皮材は、樹脂成形基材に接する側から順に、表皮基材層と、表皮層とを少なくとも有する積層構造を有する表皮材である。
本開示の樹脂成形体用表皮材は、加熱を伴う合成樹脂成形体の製造、例えば、プレス成形（圧縮成型）、射出成形、真空成形などにより、立体感のある意匠を有する、外観に優れた合成樹脂成形体の製造に好適に用いられる。
Hereinafter, the present invention will be described in detail.
[Surface material for resin moldings]
A skin material for a resin molded body in the present disclosure (hereinafter sometimes simply referred to as “skin material”) includes a skin base material layer including a synthetic resin, a metallic pigment, and a colorant other than the metallic pigment, and A skin layer is provided on one surface of the skin base material layer, includes a synthetic resin, and has a skin layer having irregularities on a surface opposite to the side facing the skin base material layer. That is, the skin material is a skin material having a laminated structure having at least a skin base material layer and a skin layer in order from the side in contact with the resin molded base material.
The skin material for a resin molded body of the present disclosure has a design with a three-dimensional effect and excellent appearance by manufacturing a synthetic resin molded body with heating, for example, press molding (compression molding), injection molding, vacuum molding, etc. It is suitably used for the production of synthetic resin moldings.
本開示の表皮材を樹脂成形基材表面に配置して、加熱成形することで、樹脂成形基材表面に樹脂成形体用表皮材を有する予備成形体が得られる。得られた予備成形体の表面に、さらに透明樹脂層を形成することで、立体感のある意匠と、耐傷性の良好な表面物性を有する、後述する本開示における合成樹脂成形体を得ることができる。
本開示の表皮材を用いることで、従来の表皮材において、当初から最表面に透明樹脂層を有する表皮材を用いた場合における成形性の問題、成形後に透明樹脂層を形成した場合における立体感の低下の問題ななどの発生が抑制され、立体感を有し、耐傷性が良好な合成樹脂成形体を得ることができる。なお、合成樹脂成形体の製造方法については後述する。
以下、樹脂成形体用表皮材の各層について説明する。
By disposing the skin material of the present disclosure on the surface of the resin-molded base material and performing heat molding, a preform having the skin material for the resin-molded body on the surface of the resin-molded base material is obtained. By further forming a transparent resin layer on the surface of the obtained preform, it is possible to obtain a synthetic resin molded body according to the present disclosure, which will be described later, having a three-dimensional design and surface properties with good scratch resistance. it can.
By using the skin material of the present disclosure, in the conventional skin material, there is a problem of moldability when using a skin material having a transparent resin layer on the outermost surface from the beginning, and a three-dimensional effect when a transparent resin layer is formed after molding. It is possible to obtain a synthetic resin molded article in which the occurrence of a problem of deterioration of the resin is suppressed, a three-dimensional effect is provided, and scratch resistance is good. In addition, the manufacturing method of a synthetic resin molding is mentioned later.
Hereinafter, each layer of the skin material for a resin molded body will be described.
〔表皮基材層〕
表皮基材層は、樹脂層の基材となる合成樹脂と、立体感の付与に有用なメタリック顔料と、メタリック顔料以外の着色剤とを含む。
(Skin base material layer)
A skin base material layer contains the synthetic resin used as the base material of a resin layer, the metallic pigment useful for provision of a three-dimensional effect, and coloring agents other than a metallic pigment.
（合成樹脂）
表皮材に含まれる合成樹脂は、カレンダー法、溶融押出し法等の公知の成形方法によりフィルムやシートを成形し得る樹脂であれば特に制限はない。表皮基材層の形成に用い得る合成樹脂としては、例えば、塩化ビニル樹脂、アクリル樹脂、ポリウレタン、オレフィン樹脂等が挙げられる。
なかでも、加工容易性、及び得られる表皮材の柔軟性等の観点からは、塩化ビニル樹脂、アクリル樹脂、及びポリウレタンからなる群より選択される合成樹脂が好ましく、塩化ビニル樹脂がより好ましい。
(Synthetic resin)
The synthetic resin contained in the skin material is not particularly limited as long as it is a resin that can form a film or sheet by a known molding method such as a calender method or a melt extrusion method. Examples of the synthetic resin that can be used for forming the skin base material layer include vinyl chloride resin, acrylic resin, polyurethane, and olefin resin.
Among these, from the viewpoint of ease of processing and flexibility of the obtained skin material, a synthetic resin selected from the group consisting of vinyl chloride resin, acrylic resin, and polyurethane is preferable, and vinyl chloride resin is more preferable.
表皮基材層に用い得る塩化ビニル樹脂としては、従来、塩化ビニルレザーに使用されている樹脂であれば特に制限なく使用できる。具体的には、平均重合度８００〜２０００、好ましくは８００〜１５００程度のポリ塩化ビニルが挙げられる。また、塩化ビニルを主体とする、エチレン、酢酸ビニル、メタクリル酸エステル等との共重合樹脂、塩化ビニル単独重合体樹脂又は塩化ビニルを含む共重合体樹脂と、ポリエステル樹脂、エポキシ樹脂、アクリル樹脂、酢酸ビニル樹脂、ウレタン樹脂、アクリロニトリル、スチレン−ブタジエン共重合樹脂、部分ケン化ビニルアルコール等から選ばれる少なくとも１種の樹脂との混合樹脂等が挙げられる。 As the vinyl chloride resin that can be used for the skin base material layer, any resin conventionally used for vinyl chloride leather can be used without any particular limitation. Specifically, polyvinyl chloride having an average degree of polymerization of 800 to 2000, preferably about 800 to 1500 is mentioned. Further, a copolymer resin mainly composed of vinyl chloride, a copolymer resin with ethylene, vinyl acetate, methacrylate, etc., a vinyl chloride homopolymer resin or a copolymer resin containing vinyl chloride, a polyester resin, an epoxy resin, an acrylic resin, Examples thereof include a mixed resin with at least one resin selected from vinyl acetate resin, urethane resin, acrylonitrile, styrene-butadiene copolymer resin, partially saponified vinyl alcohol, and the like.
表皮基材層に用い得るアクリル樹脂としては、例えば、ポリメチルメタクリレート（ＰＭＭＡ）に代表されるメタクリル酸又はメタクリル酸エステルの重合体或いは共重合体、メタクリル酸アルキルとアクリル酸アルキルとスチレンの共重合体等が挙げられ、成形性の観点からは、メタクリル酸アルキルとアクリル酸アルキルとスチレンの共重合体及びメタクリル酸メチルとアクリル酸メチルの共重合体の混合物等が挙げられる。 Examples of the acrylic resin that can be used for the skin base material layer include a polymer or copolymer of methacrylic acid or a methacrylic ester represented by polymethyl methacrylate (PMMA), and a copolymer of alkyl methacrylate, alkyl acrylate, and styrene. From the viewpoint of moldability, a copolymer of alkyl methacrylate, alkyl acrylate and styrene, a mixture of a copolymer of methyl methacrylate and methyl acrylate, or the like can be given.
表皮基材層に用い得るポリウレタンとしては、ポリカーボネート系ポリウレタン、ポリエーテル系ポリウレタン、ポリエステル系ポリウレタン及びこれらの変性物が挙げられる。なかでも、自動車内装材等、長期耐久性が必要な場合には、ポリカーボネート系ポリウレタン等が好ましく挙げられる。 Examples of the polyurethane that can be used for the skin base material layer include polycarbonate-based polyurethane, polyether-based polyurethane, polyester-based polyurethane, and modified products thereof. Of these, polycarbonate-based polyurethane and the like are preferable when long-term durability is required, such as automobile interior materials.
表皮基材層に用い得るオレフィン樹脂としては、ポリエチレン、ポリプロピレン等、エチレン、プロピレン、炭素数が４から１０のα−オレフィン等から選ばれるオレフィンモノマー由来の構造単位を重合成分として含む樹脂が挙げられる。 Examples of the olefin resin that can be used for the skin base material layer include resins containing, as a polymerization component, a structural unit derived from an olefin monomer selected from polyethylene, polypropylene, and the like, ethylene, propylene, and α-olefin having 4 to 10 carbon atoms. .
表皮基材層には、合成樹脂を１種のみ含んでもよく、２種以上を含んでもよい。 The skin base material layer may contain only one type of synthetic resin or two or more types.
（メタリック顔料）
表皮基材層は、メタリック顔料を含む。表皮基材層中にメタリック顔料を含む態様としては、メタリック顔料を表皮基材層中に含む態様、及び、メタリック顔料を含まない樹脂層を形成し、前記樹脂層の表皮層と接する側にメタリック顔料含有層を設ける態様が挙げられる。表皮基材層中にメタリック顔料を含む場合、表皮基材層は単層構造であり、メタリック顔料を別層として設ける後者の場合、表皮基材層は、メタリック顔料を含まない樹脂層とメタリック顔料含有層の積層構造を有する。
なかでも、製造の容易性の観点からは、表皮基材層はメタリック顔料を含む単層構造であることが好ましい。
(Metallic pigment)
The skin base material layer contains a metallic pigment. As an aspect which contains a metallic pigment in an outer skin base material layer, the aspect which contains a metallic pigment in an outer skin base material layer, and the resin layer which does not contain a metallic pigment is formed, and a metallic side is contacted with the outer skin layer of the said resin layer The aspect which provides a pigment content layer is mentioned. In the case of including a metallic pigment in the skin base material layer, the skin base material layer has a single layer structure, and in the latter case in which the metallic pigment is provided as a separate layer, the skin base material layer includes a resin layer and a metallic pigment not containing the metallic pigment. It has a laminated structure of inclusion layers.
Especially, it is preferable that a skin base material layer is a single layer structure containing a metallic pigment from a viewpoint of the ease of manufacture.
表皮基材層に用い得るメタリック顔料としては、形成された樹脂層に光輝性、光沢等を付与し得る顔料であれば特に制限はない。メタリック顔料としては、例えば、光沢を有する金属顔料、パール顔料、雲母等が挙げられる。
光沢を有する金属顔料としては、アルミニウム顔料、シルバー顔料等が挙げられる。
パール顔料としては、酸化チタン被覆雲母（雲母チタン）、酸化チタン被覆ガラスフレーク、酸化チタン被覆タルク等が挙げられる。
なかでも、輝度感が良好で、耐久性がより良好であるという観点からは、本開示におけるメタリック顔料としては、アルミニウム顔料、シルバー顔料などの高輝度金属顔料が好ましい。
The metallic pigment that can be used for the skin base layer is not particularly limited as long as it is a pigment that can impart glitter, gloss, and the like to the formed resin layer. Examples of metallic pigments include glossy metal pigments, pearl pigments, mica, and the like.
Examples of the metallic pigment having gloss include an aluminum pigment and a silver pigment.
Examples of the pearl pigment include titanium oxide-coated mica (titanium mica), titanium oxide-coated glass flakes, and titanium oxide-coated talc.
Among these, from the viewpoint of good brightness and better durability, the metallic pigment in the present disclosure is preferably a high-brightness metal pigment such as an aluminum pigment or a silver pigment.
表皮基材層には、メタリック顔料を１種のみ含んでもよく、２種以上含んでもよい。
表皮基材層が、合成樹脂とメタリック顔料と他の着色剤を含む表皮基材層形成用組成物により形成される場合には、メタリック顔料の含有量は、表皮基材層形成用組成物の全固形分に対して、０．２５質量％以上、３０質量％以下であることが好ましく、１質量％以上２０質量％以下であることがより好ましい。
メタリック顔料の含有量が０．２５質量％以上であることで、表皮基材層の輝度が良好となり、凹凸を有する表皮層の面上に透明樹脂層を形成した後においても、立体感のある意匠性を維持し易い。メタリック顔料の含有量が３０質量％以下であることで、均一で十分な強度の表皮基材層を得易くなる。
The skin base material layer may contain only one type of metallic pigment or two or more types of metallic pigments.
When the skin base material layer is formed of a composition for forming a skin base material layer containing a synthetic resin, a metallic pigment, and another colorant, the content of the metallic pigment is the content of the composition for forming the skin base material layer. The total solid content is preferably 0.25% by mass or more and 30% by mass or less, and more preferably 1% by mass or more and 20% by mass or less.
When the content of the metallic pigment is 0.25% by mass or more, the brightness of the skin base material layer becomes good, and there is a three-dimensional effect even after the transparent resin layer is formed on the surface of the skin layer having irregularities. Easy to maintain design. When the content of the metallic pigment is 30% by mass or less, it is easy to obtain a skin base material layer having a uniform and sufficient strength.
また、メタリック顔料を含まない樹脂層とメタリック顔料含有層とを有する表皮基材層を形成する場合、メタリック顔料を含まない樹脂層を常法により形成した後、既述のメタリック顔料と被膜形成性を有する樹脂とを含むメタリック顔料含有層形成用組成物を調製して、メタリック顔料を含まない樹脂層の表皮層を形成する側に塗布する方法、或いは、樹脂層に公知のメタリック塗料、メタリックインク等を塗布する方法等の手段をとることができる。 In addition, when forming a skin base material layer having a resin layer not containing a metallic pigment and a metallic pigment-containing layer, after forming the resin layer not containing a metallic pigment by a conventional method, the above-described metallic pigment and film-forming property are formed. A method for preparing a metallic pigment-containing layer forming composition containing a resin having a metallic pigment and applying it to the side of forming a skin layer of a resin layer not containing a metallic pigment, or a known metallic paint or metallic ink for the resin layer A means such as a method of applying the above can be taken.
メタリック顔料含有層の形成に用い得る樹脂としては、公知の膜形成性樹脂、例えば、ポリウレタン、塩化ビニル樹脂、アクリル樹脂等が挙げられる。
メタリック顔料含有層の形成に用い得るメタリック塗料、メタリックインクとしては、効果の観点から、シルバーメタリックインクが好ましい。
メタリックインクは市販品を用いることができる。メタリック顔料含有層の形成に用い得る市販のメタリックインクとしては、例えば、大日精化工業（株）、メタリック印刷インキＬＲ輝シリーズ、女神インキ工業（株）、メタリックインキシリーズ、ＤＩＣ（株）、メタリックインク等が挙げられる。
Examples of the resin that can be used for forming the metallic pigment-containing layer include known film-forming resins such as polyurethane, vinyl chloride resin, and acrylic resin.
As the metallic paint and metallic ink that can be used for forming the metallic pigment-containing layer, silver metallic ink is preferable from the viewpoint of effects.
A commercially available product can be used as the metallic ink. Examples of commercially available metallic inks that can be used to form the metallic pigment-containing layer include, for example, Dainichi Seika Kogyo Co., Ltd., Metallic Printing Ink LR Kagaya Series, Megami Ink Industries Co., Ltd., Metallic Ink Series, DIC Corporation, and Metallic. And ink.
（メタリック顔料以外の着色剤）
表皮基材層は、既述のメタリック顔料以外の着色剤（以下、他の着色剤と称することがある）を含む。
表皮基材層が、メタリック顔料に加え、メタリック顔料以外の着色剤を含むことで、表皮材に任意の色相を与えることができるため、表皮材の意匠の自由度が向上する。
他の着色剤としては、メタリック顔料に起因する表皮基材層の輝度の低下が抑制され、且つ、表皮基材層が着色された状態にて明確に視認することができるという観点から、可視光を遮断し難い着色剤が好ましい。
表皮基材層が含み得る他の着色剤としては、例えば、染料、微細な粒径の顔料などを挙げることができる。
染料は可視光の透過を阻害し難い色相の染料が好ましく、顔料は、光の反射が生じ難い粒径、例えば、平均一次粒子径が０．７μｍ以下、より好ましくは０．４μｍ以下の平均粒子径の顔料が挙げられる。
顔料の平均一次粒子径は、走査型顕微鏡（ＳＥＭ）、又は透過型顕微鏡（ＴＥＭ）で観察し、粒子が凝集していない部分で粒子サイズを１００個計測し、平均値を算出することによって求めることができる。
(Coloring agents other than metallic pigments)
The skin base material layer contains a colorant other than the above-described metallic pigment (hereinafter sometimes referred to as other colorant).
Since the skin base material layer contains a colorant other than the metallic pigment in addition to the metallic pigment, an arbitrary hue can be imparted to the skin material, thereby improving the degree of freedom of the design of the skin material.
Other colorants include visible light from the viewpoint that the decrease in luminance of the skin base material layer due to the metallic pigment is suppressed and the skin base material layer can be clearly seen in a colored state. Colorants that are difficult to block are preferred.
Examples of other colorants that can be contained in the skin base material layer include dyes and pigments having a fine particle diameter.
The dye is preferably a dye having a hue that does not easily inhibit the transmission of visible light, and the pigment has a particle diameter that is difficult to cause light reflection, for example, an average primary particle diameter of 0.7 μm or less, more preferably 0.4 μm or less. Diameter pigments.
The average primary particle diameter of the pigment is obtained by observing with a scanning microscope (SEM) or a transmission microscope (TEM), measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value. be able to.
本発明の一実施形態である表皮材の効果がより良好に発現され、耐久性がより良好であるという観点からは、他の着色剤としては、メタリック顔料以外の顔料を用いることが好ましい。
他の着色剤の色相は任意であり、目的に応じて適宜選択された好適な色相の着色剤を用いればよい。
本発明に用い得る顔料は、有機顔料、無機顔料のいずれであってもよい。
以下に、他の着色剤として使用し得る顔料の例を挙げるが、以下に示す例に制限されない。
有機顔料としては、例えば、以下のものが挙げられる。
Ｃ．Ｉ．ピグメント イエロー １１，２４，１０８，１０９，１１０，１３８，１３９，１５０，１５１，１５４，１６７，１８０，１８５，
Ｃ．Ｉ．ピグメント オレンジ ３６，７１，
Ｃ．Ｉ．ピグメント レッド １２２，１５０，１７１，１７５，１７７，２０９，２２４，２４２，２５４，２５５，２６４，
Ｃ．Ｉ．ピグメント バイオレット １９，２３，３２，
Ｃ．Ｉ．ピグメント ブルー １５：１，１５：３，１５：６，１６，２２，６０，６６，
Ｃ．Ｉ．ピグメント ブラウン ２５，２８，
Ｃ．Ｉ．ピグメント グリーン ７，３６，３７，
Ｃ．Ｉ．ピグメントブラック １，
From the viewpoint that the effect of the skin material according to one embodiment of the present invention is expressed more favorably and the durability is better, it is preferable to use a pigment other than the metallic pigment as the other colorant.
The hues of the other colorants are arbitrary, and a colorant having a suitable hue appropriately selected according to the purpose may be used.
The pigment that can be used in the present invention may be either an organic pigment or an inorganic pigment.
Although the example of the pigment which can be used as another coloring agent is given to the following, it is not restrict | limited to the example shown below.
As an organic pigment, the following are mentioned, for example.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment orange 36, 71,
C. I. Pigment Red 122,150,171,175,177,209,224,242,254,255,264
C. I. Pigment violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Brown 25, 28,
C. I. Pigment Green 7, 36, 37,
C. I. Pigment Black 1,
無機顔料としては、カーボンブラック（Ｃ．Ｉ．ピグメントブラック ８）、チタンブラック、チタンホワイト、炭酸カルシウム、硫酸バリウム、水酸化アルミニウム等が挙げられる。 Examples of inorganic pigments include carbon black (CI pigment black 8), titanium black, titanium white, calcium carbonate, barium sulfate, and aluminum hydroxide.
他の着色剤として顔料を用いる場合には、用いる顔料及び分散媒である合成樹脂に適する公知の分散剤を用いることが好ましい。分散剤を用いることで、表皮基材層において、顔料の分散媒となる合成樹脂中における他の着色剤としての顔料及び既述のメタリック顔料の分散性をより良好にすることができる。例えば、メタリック顔料及び他の着色剤である顔料と分散剤と合成樹脂とを予め混合した混合物を用いて表皮基材層を形成することが顔料の均一分散性の観点から好ましい。 When a pigment is used as the other colorant, it is preferable to use a known dispersant suitable for the pigment used and the synthetic resin that is the dispersion medium. By using the dispersant, the dispersibility of the pigment as the other colorant in the synthetic resin serving as the pigment dispersion medium and the metallic pigment described above can be further improved in the skin base material layer. For example, it is preferable from the viewpoint of the uniform dispersibility of the pigment that the skin base material layer is formed using a mixture of a metallic pigment and another colorant, a dispersant, and a synthetic resin previously mixed.
表皮基材層には、他の着色剤を１種のみ含んでもよく、２種以上含んでもよい。
表皮基材層における他の着色剤の含有量は、表皮基材層形成用組成物の全固形分に対して、０質量％を超え、５０質量％以下であることが好ましく、１質量％以上４０質量％以下であることがより好ましい。
他の着色剤の含有量が０質量％を超えることで、表皮基材層において鮮明な色相が得易くなり、他の着色剤の含有量が５０質量％以下であることで、メタリック顔料を含有することによる効果が損なわれ難く、より立体感のある意匠を得ることができる。
The skin base material layer may contain only one kind of other colorant or two or more kinds.
The content of the other colorant in the skin base material layer is preferably more than 0% by weight and preferably 50% by weight or less, based on the total solid content of the composition for forming the skin base material layer. It is more preferable that it is 40 mass% or less.
When the content of the other colorant exceeds 0% by mass, a clear hue is easily obtained in the skin base material layer, and when the content of the other colorant is 50% by mass or less, a metallic pigment is contained. The effect by doing is hard to be impaired, and the design with a three-dimensional effect can be obtained.
表皮基材層は、合成樹脂、メタリック顔料及び他の着色剤に加え、本開示における効果を損なわない限り、目的に応じて公知の添加剤（以下、他の成分と称する）を含有することができる。
表皮基材層が含むことができる他の成分としては、可塑剤、滑剤、製膜助剤、発泡剤等が挙げられる。
The skin base material layer may contain known additives (hereinafter referred to as other components) depending on the purpose, in addition to the synthetic resin, metallic pigment and other colorants, as long as the effects of the present disclosure are not impaired. it can.
Examples of other components that can be contained in the skin base material layer include a plasticizer, a lubricant, a film forming aid, and a foaming agent.
表皮基材層は、合成樹脂、メタリック顔料、及びメタリック顔料以外の着色剤、さらに、所望により含有させる公知の添加剤を含む表皮基材層形成用組成物を調製し、得られた表皮基材層形成用組成物を、カレンダー法、キャスティング法等の公知の成形方法によりシート状に成形することで形成することができる。 The skin base material layer was prepared by preparing a composition for forming a skin base material layer containing a synthetic resin, a metallic pigment, a colorant other than the metallic pigment, and a known additive to be contained as required. The layer forming composition can be formed by forming into a sheet shape by a known forming method such as a calendar method or a casting method.
既述のように、表皮基材層が、メタリックインクを含まない樹脂層及びメタリック顔料含有層を有する場合には、メタリック顔料含有層を既述の方法でシート状に形成した後、形成したメタリック顔料含有層の面上にメタリックインクを含まない樹脂層を公知の塗布法を適用して形成することができる。 As described above, when the skin base material layer has a resin layer that does not contain a metallic ink and a metallic pigment-containing layer, the metallic pigment-containing layer is formed into a sheet by the method described above, and then the formed metallic material is formed. A resin layer not containing metallic ink can be formed on the surface of the pigment-containing layer by applying a known coating method.
表皮基材層の膜厚は、特に制限はなく、表皮基材層が単層である場合には、例えば、５０μｍ〜３００μｍの範囲とすることが好ましく、１００μｍ〜２００μｍの範囲とすることがより好ましく、１００μｍ〜１５０μｍの範囲であることがさらに好ましい。厚みが上記範囲であれば、表皮材を用いて合成樹脂成形体を形成する際に、メタリック顔料及び他の着色剤を含んだ表皮基材層に起因する立体感がより明確になり、意匠性がより良好となる。 The film thickness of the skin base material layer is not particularly limited. When the skin base material layer is a single layer, for example, it is preferably in the range of 50 μm to 300 μm, more preferably in the range of 100 μm to 200 μm. Preferably, it is in the range of 100 μm to 150 μm. If the thickness is within the above range, when forming a synthetic resin molding using a skin material, the three-dimensional effect due to the skin base material layer containing a metallic pigment and other colorants becomes clearer, and the design property Is better.
表皮基材層が、メタリック顔料を含まない樹脂層及びメタリック顔料含有層を有する場合において、メタリック顔料を含まない樹脂層の厚みは、１μｍ〜５００μｍの範囲が好ましく、５０μｍ〜３００μｍの範囲がより好ましい。
メタリック顔料含有層の厚みは、立体感をより得易いとの観点から、５０μｍ〜３００μｍの範囲が好ましく、１００μｍ〜１５０μｍの範囲がより好ましい。
In the case where the skin base material layer has a resin layer not containing a metallic pigment and a metallic pigment-containing layer, the thickness of the resin layer not containing the metallic pigment is preferably in the range of 1 μm to 500 μm, more preferably in the range of 50 μm to 300 μm. .
The thickness of the metallic pigment-containing layer is preferably in the range of 50 μm to 300 μm and more preferably in the range of 100 μm to 150 μm from the viewpoint that it is easier to obtain a three-dimensional effect.
〔表皮層〕
表皮材における前記表皮基材層の片方の面上に表皮層を有する。表皮層は、前記表皮基材層の片方の面上に設けられ、合成樹脂を含み、前記表皮基材層とは反対側の面に凹凸を有する。凹凸の形状、配置間隔などは、成形体表面における意匠により適宜選択される。凹凸は、例えば、格子模様、ストライプ等の連続模様であってもよく、ドット柄、迷彩柄などの不連続模様であってもよい。
(Skin layer)
A skin layer is provided on one surface of the skin base material layer in the skin material. The skin layer is provided on one surface of the skin base material layer, includes a synthetic resin, and has unevenness on the surface opposite to the skin base material layer. The shape of the unevenness, the arrangement interval, and the like are appropriately selected depending on the design on the surface of the molded body. The unevenness may be, for example, a continuous pattern such as a lattice pattern or a stripe pattern, or a discontinuous pattern such as a dot pattern or a camouflage pattern.
表皮層に含まれる合成樹脂としては、特に制限はないが、形成された凹凸の保持性、耐傷性が良好であるという観点からは、アクリル樹脂及びフッ素樹脂から選ばれる少なくとも１種の樹脂を含むことが好ましい。
表皮層がフッ素樹脂及びアクリル樹脂から選ばれる少なくとも１種の樹脂を含有する態様については、特に制限はなく、例えば、アクリル樹脂における水素原子の一部がフッ素原子に置き換わったフッ素原子含有アクリル樹脂を用いる態様、フッ素樹脂とアクリル樹脂との混合物を用いる態様、フッ素樹脂とフッ素原子含有アクリル樹脂との混合物を用いる態様、フッ素樹脂含有層とアクリル樹脂含有層との重層構造を有する態様などが挙げられる。
なかでも、得られた合成樹脂表皮材の光沢、耐傷性、及び耐汚れ性がより良好であるという観点からは、表皮層は、フッ素樹脂とアクリル樹脂とを含むことが好ましい。
Although there is no restriction | limiting in particular as a synthetic resin contained in a skin layer, From a viewpoint that the maintenance of the formed unevenness | corrugation and scratch resistance are favorable, at least 1 sort (s) of resin chosen from an acrylic resin and a fluororesin is included. It is preferable.
The embodiment in which the skin layer contains at least one resin selected from a fluororesin and an acrylic resin is not particularly limited. For example, a fluorine atom-containing acrylic resin in which a part of hydrogen atoms in the acrylic resin is replaced with a fluorine atom is used. Examples include a mode in which a mixture of a fluororesin and an acrylic resin is used, a mode in which a mixture of a fluororesin and a fluorine atom-containing acrylic resin is used, and a mode having a multilayer structure of a fluororesin-containing layer and an acrylic resin-containing layer. .
Especially, from a viewpoint that the glossiness, scratch resistance, and stain resistance of the obtained synthetic resin skin material are better, the skin layer preferably contains a fluororesin and an acrylic resin.
（アクリル樹脂）
表皮層に含まれ得るアクリル樹脂としては、例えば、ポリメチルメタクリレート（ＰＭＭＡ）に代表されるメタクリル酸又はメタクリル酸エステルの重合体或いは共重合体、メタクリル酸アルキルとアクリル酸アルキルとスチレンの共重合体等が挙げられ、成形性の観点からは、メタクリル酸アルキルとアクリル酸アルキルとスチレンの共重合体及びメタクリル酸メチルとアクリル酸メチルの共重合体の混合物等が挙げられる。
また、フッ素変成されたアクリル樹脂であってもよい。
(acrylic resin)
Examples of the acrylic resin that can be included in the skin layer include a polymer or copolymer of methacrylic acid or a methacrylic ester represented by polymethyl methacrylate (PMMA), and a copolymer of alkyl methacrylate, alkyl acrylate, and styrene. From the viewpoint of moldability, a copolymer of alkyl methacrylate, alkyl acrylate, and styrene, a mixture of a copolymer of methyl methacrylate and methyl acrylate, and the like can be given.
Alternatively, a fluorine-modified acrylic resin may be used.
（フッ素樹脂）
表皮層に含まれ得るフッ素樹脂は、分子内に１以上のフッ素原子を含有する樹脂を指し、例えば、オレフィン樹脂における水素原子がフッ素原子に置き換わった樹脂等が挙げられる。
フッ素樹脂としては、四フッ化エチレン樹脂、三フッ化塩化エチレン樹脂、六フッ化エチレンプロピレン樹脂、エチレン−四フッ化エチレン共重合体、フッ化ビニリデン樹脂等が挙げられる。
(Fluorine resin)
The fluororesin that can be contained in the skin layer refers to a resin containing one or more fluorine atoms in the molecule, and examples thereof include a resin in which a hydrogen atom in an olefin resin is replaced with a fluorine atom.
Examples of the fluororesin include tetrafluoroethylene resin, trifluorochloroethylene resin, hexafluoroethylenepropylene resin, ethylene-tetrafluoroethylene copolymer, and vinylidene fluoride resin.
表皮層の形成方法には特に制限はなく、公知の層形成方法を適用して形成すればよい。
表皮層の厚みは、１０μｍ〜１００μｍの範囲であることが好ましく、３０μｍ〜７０μｍの範囲であることがより好ましい。
表皮材における表皮基材層の厚みは、表皮層よりも厚いことが、得られる意匠の立体感がより良好になるという観点から好ましい。
表皮層は表皮基材層におけるメタリック顔料に起因する外観に反映させるため、透明であることが好ましい。ここで、透明とは可視域の波長の光の透過性が８０％以上であることを指し、９０％以上であることが好ましい。
表皮層における可視域の波長の光の透過性は、分光光度計を用いて測定した吸光度により確認することができる。
吸収特性及び透過率は、例えば、吸光度計（分光光度計とも称される。島津製作所社製、分光光度計ＵＶ−３１００）を用いて４００〜７００ｎｍの波長光の吸収スペクトル又は透過率スペクトルを測定することで求めることができる。
透過率は、吸光度から、以下の式により算出した値である。
透過率＝１００／（１０＾（吸光度））
There is no restriction | limiting in particular in the formation method of a skin layer, What is necessary is just to form by applying a well-known layer formation method.
The thickness of the skin layer is preferably in the range of 10 μm to 100 μm, and more preferably in the range of 30 μm to 70 μm.
The thickness of the skin base material layer in the skin material is preferably thicker than the skin layer, from the viewpoint that the three-dimensional effect of the resulting design becomes better.
The skin layer is preferably transparent in order to reflect the appearance due to the metallic pigment in the skin base material layer. Here, “transparent” means that the transmittance of light having a wavelength in the visible region is 80% or more, and preferably 90% or more.
The transmittance of light having a visible wavelength in the skin layer can be confirmed by the absorbance measured using a spectrophotometer.
Absorption characteristics and transmittance are measured, for example, by using an absorptiometer (also referred to as a spectrophotometer, manufactured by Shimadzu Corporation, spectrophotometer UV-3100) to measure an absorption spectrum or transmittance spectrum of light having a wavelength of 400 to 700 nm. You can ask for it.
The transmittance is a value calculated from the absorbance according to the following formula.
Transmittance = 100 / (10 ^ (absorbance))
表皮層の表皮基材層とは反対側の表面に凹凸を形成する方法は、公知の凹凸形成方法を任意に適用することができる。例えば、予め凹凸が形成された離型材表面に表皮層形成樹脂を塗布して表皮層表面に離型材の凹凸を転写する方法、表皮層に、凹凸が形成された絞（シボ）ロールを接触させ、加圧、加熱してラミネートエンボスし、絞ロールの凹凸を表皮層に転写する方法などが挙げられる。転写法を適用する際には、凹凸の形成と、接着とを同時に行ってもよい。
絞ロールに予め凹凸を形成し、絞ロールを用いてラミネートエンボスする転写法を適用することにより、表皮層と表皮基材層との貼り合わせと、表皮層へのシボ押し、即ち、凹凸模様の形成を一工程で行うことができる。
As a method for forming unevenness on the surface of the skin layer opposite to the skin base material layer, a known unevenness forming method can be arbitrarily applied. For example, a method in which a skin layer forming resin is applied to the surface of a release material on which unevenness has been formed in advance and the unevenness of the release material is transferred to the surface of the skin layer, and a squeeze roll with unevenness is brought into contact with the skin layer. For example, there may be mentioned a method of embossing by laminating under pressure and heating, and transferring the unevenness of the squeeze roll to the skin layer. When applying the transfer method, the formation of unevenness and adhesion may be performed simultaneously.
By applying a transfer method in which unevenness is formed in advance on the squeeze roll and laminating and embossing using the squeeze roll, bonding of the skin layer and the skin base material layer and embossing on the skin layer, that is, the concavo-convex pattern Formation can be done in one step.
表皮層の形成に際して、表皮層と表皮基材層との逐次形成法及び表皮層と表皮基材層との積層体を用いた一工程での形成法の何れにおいても、ラミネートエンボスにおける加熱温度は、１００℃〜１９０℃が好適である。
本開示における表皮材は、樹脂成形体表面の立体感を有する意匠の形成に有用であり、加熱による成形を経ても外観が損なわれず、成形性が良好であることから、加熱加圧を伴う合成樹脂成形体の形成に有用である。
In the formation of the skin layer, the heating temperature in the laminating embossing is any of the sequential formation method of the skin layer and the skin base material layer and the formation method in one step using the laminate of the skin layer and the skin base material layer. 100 ° C. to 190 ° C. is preferable.
The skin material in the present disclosure is useful for forming a design having a three-dimensional effect on the surface of a resin molded body, and the appearance is not impaired even after molding by heating, and the moldability is good. It is useful for forming a resin molded body.
表皮層には、既述の合成樹脂以外にも、目的に応じて公知の添加剤〔他の成分と称することがある）を含有してもよい。
表皮層が含み得る他の成分としては、つや消し剤、可塑剤、滑剤、製膜助剤等が挙げられる。
In addition to the above-described synthetic resin, the skin layer may contain a known additive (sometimes referred to as other component) depending on the purpose.
Examples of other components that can be contained in the skin layer include matting agents, plasticizers, lubricants, film-forming aids, and the like.
［合成樹脂成形体］
既述のようにして得た表皮材を樹脂成形基材表面に配置し、成形した後、透明樹脂層を形成することで、立体感を有する概観が形成された樹脂成形体を得ることができる。
本開示における合成樹脂成形体は、樹脂成形基材の面上に、既述の樹脂成形体用表皮材と、透明樹脂層とを有する。
図１は、本発明の一実施形態である合成樹脂成形体の層構成を示す部分概略断面図である。
図１に示す合成樹脂成形体１０は、樹脂成形基材１２の面上に、既述の樹脂成形体用表皮材１４と、透明樹脂層２４とを有する。図１では、樹脂成形基材１２の面上に、密着性向上を目的として、接着剤層１６及びとプライマー層１８が設けられ、樹脂成形基材１２は、接着剤層１６及びプライマー層１８を介して、表皮材１４における表皮基材層２０と密着している。表皮基材層２０の樹脂成形基材１２とは反対側の面に、凹凸を有する表皮層２２を有する。表皮層２２の表面には、好ましくは塗工により設けられた透明樹脂層２４を有する。
図１において、接着剤層１６及びプライマー層１８は、得られる合成樹脂成形体１０の耐久性向上の観点から備えられる任意の層である。
公知の表皮材では、表皮基材層と表皮層と透明樹脂層とを備えることが一般的であり、透明樹脂層に成形性を持たせるために透明樹脂層の処方の自由度が十分ではないという問題がある。本開示における表皮材は、透明樹脂層を有さないため、熱加工性が良好である。そして、後述するように、本開示における好ましい合成樹脂成形体の製造方法においては、樹脂成形基材と表皮材とを加熱成形して得られる予備成形体の形成後に透明樹脂層を形成するために、例えば、ハードコート層など、熱加工性には劣るが、耐傷性、耐久性等に優れる透明樹脂層等の、目的に応じた任意の組成の透明樹脂層を容易に備えることができる。
[Synthetic resin molding]
By placing the skin material obtained as described above on the surface of the resin-molded base material and molding it, by forming a transparent resin layer, it is possible to obtain a resin molded body having a three-dimensional appearance. .
The synthetic resin molding in the present disclosure has the above-described skin material for a resin molding and a transparent resin layer on the surface of the resin molding substrate.
FIG. 1 is a partial schematic cross-sectional view showing a layer structure of a synthetic resin molded body according to an embodiment of the present invention.
The synthetic resin molded body 10 shown in FIG. 1 has the above-described resin molded body skin material 14 and the transparent resin layer 24 on the surface of the resin molded substrate 12. In FIG. 1, an adhesive layer 16 and a primer layer 18 are provided on the surface of the resin molded substrate 12 for the purpose of improving adhesion, and the resin molded substrate 12 includes the adhesive layer 16 and the primer layer 18. The skin base material layer 20 in the skin material 14 is in close contact therewith. A surface layer 22 having irregularities is provided on the surface of the skin base material layer 20 opposite to the resin-molded base material 12. The surface of the skin layer 22 preferably has a transparent resin layer 24 provided by coating.
In FIG. 1, the adhesive layer 16 and the primer layer 18 are arbitrary layers provided from the viewpoint of improving the durability of the resulting synthetic resin molded body 10.
In a known skin material, it is common to have a skin base material layer, a skin layer, and a transparent resin layer, and the degree of freedom of formulation of the transparent resin layer is not sufficient to give the transparent resin layer formability. There is a problem. Since the skin material in the present disclosure does not have a transparent resin layer, the heat processability is good. And, as will be described later, in the preferred method for producing a synthetic resin molded body in the present disclosure, in order to form a transparent resin layer after forming a preformed body obtained by thermoforming a resin molded substrate and a skin material For example, a transparent resin layer having an arbitrary composition according to the purpose, such as a transparent resin layer which is inferior in thermal processability but excellent in scratch resistance, durability and the like, such as a hard coat layer, can be easily provided.
〔樹脂成形基材〕
合成樹脂成形体における樹脂成形基材１２は、目的とする合成樹脂成形体１０に応じた形状、大きさ、重さ等を有する成形基材であり、その表面に沿って表皮材１４が配置され、所望により配置される接着剤層１６及びプライマー層１８を介して表皮材１４と樹脂成形基材１２とが接着され、成形されて、立体感を有する意匠が形成された合成樹脂成形体１０を得る。
樹脂成形基材１２の材質、形状、大きさ等は、製造する成形体の用途、目的、デザイン、コスト等を考慮して選択すればよい。
[Resin molding substrate]
The resin molded substrate 12 in the synthetic resin molded body is a molded substrate having a shape, size, weight and the like corresponding to the target synthetic resin molded body 10, and the skin material 14 is disposed along the surface thereof. The synthetic resin molded body 10 in which the skin material 14 and the resin molded base material 12 are bonded and molded through an adhesive layer 16 and a primer layer 18 that are arranged as desired to form a three-dimensional design. obtain.
The material, shape, size, and the like of the resin molded substrate 12 may be selected in consideration of the application, purpose, design, cost, etc. of the molded body to be manufactured.
〔透明樹脂層〕
合成樹脂成形体における透明樹脂層は、表皮材の意匠性、立体感を損なわない範囲において形成される。
透明樹脂層の形成に用いられる樹脂は、形成される層の透明性が高く、耐傷性等の必要な物性を与えることができる樹脂であれば特に制限なく使用することができる。なお、樹脂層が透明であるとは、透明樹脂層の形成後に、透明樹脂層を介して、下層である表皮材の表面における凹凸模様が視認できることを意味する。
なかでも、耐傷性が良好なハードコート層を形成することができる紫外線硬化型樹脂組成物が好ましい。
[Transparent resin layer]
The transparent resin layer in the synthetic resin molded body is formed in a range that does not impair the design and the three-dimensional effect of the skin material.
The resin used for forming the transparent resin layer can be used without particular limitation as long as the formed layer has high transparency and can give necessary physical properties such as scratch resistance. In addition, that the resin layer is transparent means that after the formation of the transparent resin layer, the uneven pattern on the surface of the skin material as the lower layer can be visually recognized through the transparent resin layer.
Especially, the ultraviolet curable resin composition which can form a hard-coat layer with favorable scratch resistance is preferable.
透明樹脂層の形成に好適に用いられる紫外線硬化型樹脂組成物について説明する。紫外線硬化型樹脂組成物は、紫外線照射によって硬化し、耐傷性を有するハードコート層としての透明樹脂層を形成し得る材料から選択することができる。具体的には、例えば、ウレタンアクリレート、アクリルモノマー等の重合性モノマーの少なくとも１種と、ラジカル型光重合開始剤とを含む組成物が挙げられる。 The ultraviolet curable resin composition used suitably for formation of a transparent resin layer is demonstrated. The ultraviolet curable resin composition can be selected from materials that can be cured by ultraviolet irradiation to form a transparent resin layer as a hard coat layer having scratch resistance. Specifically, for example, a composition containing at least one polymerizable monomer such as urethane acrylate and acrylic monomer and a radical photopolymerization initiator can be mentioned.
紫外線硬化型樹脂組成物を表皮材の凹凸を有する側の面に付与する方法は特に限定されない。公知の塗布装置を用いることができる。なかでも、コーター法にて表皮材の凹凸を有する面に塗工する方法が好ましい。スプレーコート方などによる付与も可能ではあるが、紫外線硬化型樹脂組成物のロスの発生を抑制し、より効率よく均一に付与し得るという観点からは、コート法が好ましい。コート法により、表皮材の面上に紫外線硬化型樹脂組成物層を形成した後、乾燥することが好ましい。なかでも、層厚みの均一性、表面平滑性などの観点から、ダイレクトリバースコーター法が好ましい。乾燥は、塗工後、風を当てながら乾燥させる方法が好ましい。 The method for applying the ultraviolet curable resin composition to the surface of the skin material having unevenness is not particularly limited. A known coating apparatus can be used. Of these, a method of coating the surface of the skin material with irregularities by the coater method is preferable. Although application | coating by the spray coating method etc. is also possible, the coating method is preferable from a viewpoint that generation | occurrence | production of the loss of an ultraviolet curable resin composition can be suppressed and it can provide more efficiently and uniformly. It is preferable to dry after forming the ultraviolet curable resin composition layer on the surface of the skin material by a coating method. Of these, the direct reverse coater method is preferable from the viewpoint of uniformity of layer thickness, surface smoothness, and the like. The drying is preferably performed by applying air after coating.
透明樹脂層の厚さは、合成樹脂成形体の用途等により適宜決定される。なかでも、紫外線照射によって硬化させた後の透明樹脂層の耐傷性及び平滑性を確保する観点から、硬化後の厚さで例えば５μｍ〜５０μｍであることが好ましく、１０μｍ〜３０μｍであることがより好ましい。
形成された透明樹脂層は、硬化後の硬さで、サファイヤ針３０ｇでキズなしであるか、又は、ＪＩＳ Ｋ−５４００（１９９０年）鉛筆ひっかき試験による鉛筆硬度でＨ以上である耐傷性を有することが好ましい。
The thickness of the transparent resin layer is appropriately determined depending on the use of the synthetic resin molded body. Especially, from the viewpoint of ensuring scratch resistance and smoothness of the transparent resin layer after being cured by ultraviolet irradiation, the thickness after curing is preferably, for example, 5 μm to 50 μm, and more preferably 10 μm to 30 μm. preferable.
The formed transparent resin layer has hardness after curing, and is scratch-free with 30 g of sapphire needles, or has scratch resistance that is H or higher in pencil hardness according to JIS K-5400 (1990) pencil scratch test. It is preferable.
透明樹脂層を形成するための紫外線硬化型樹脂組成物層は、既述のように塗布法で形成してもよいが、未硬化の紫外線硬化型樹脂組成物層を表皮材における凹凸を有する面に密着させた場合に表皮材の凹凸に追従し得る物性を有すれば転写法により付与してもよい。転写法で表皮材の面上に紫外線硬化型樹脂組成物層を付与する場合には、紫外線透過性の仮支持体上に紫外線硬化型樹脂組成物層を形成し、表皮材に密着させた後、仮支持体を介して、又は仮支持体を剥離して、紫外線を照射することで、硬化した透明樹脂層を形成することができる。
紫外線透過性の仮支持体は、紫外線透過性、離型性等に加え、紫外線照射時、仮支持体剥離時の成形品の表面平滑性を確保する観点から鏡面性を有することが好ましい。
また、成形時の偏伸びによるシワなどの発生を防ぐ観点から伸長性を有するものが好ましい。
仮支持体として、具体的には、例えば、ポリエチレン（ＰＥ）フィルム、ポリプロピレン（ＰＰ）フィルム、ポリエチレンテレフタレート（ＰＥＴ）フィルム、などが挙げられる。なかでも、低温での成形性の観点から、ＰＥフィルム、ＰＰフィルムが好ましく、低密度ポリエチレン（ＬＤＰＥ）系クリアフィルムが特に好ましい。
仮支持体の厚みは、必要な強度を有すれば特に制限はない。例えば、１００μｍ〜２００μｍのフィルムが好ましい。
The ultraviolet curable resin composition layer for forming the transparent resin layer may be formed by the coating method as described above, but the uncured ultraviolet curable resin composition layer is a surface having irregularities in the skin material. If they have physical properties that can follow the unevenness of the skin material when they are closely attached to each other, they may be applied by a transfer method. When an ultraviolet curable resin composition layer is applied on the surface of the skin material by the transfer method, after the ultraviolet curable resin composition layer is formed on the ultraviolet transparent temporary support and adhered to the skin material The cured transparent resin layer can be formed by irradiating ultraviolet rays through the temporary support or by peeling the temporary support.
The UV-transparent temporary support preferably has specularity from the viewpoint of ensuring the surface smoothness of the molded product when irradiated with UV or when the temporary support is peeled, in addition to UV-permeability and releasability.
Moreover, what has extensibility is preferable from a viewpoint of preventing generation | occurrence | production of the wrinkles by the unbalanced elongation at the time of shaping | molding.
Specific examples of the temporary support include a polyethylene (PE) film, a polypropylene (PP) film, and a polyethylene terephthalate (PET) film. Among these, from the viewpoint of moldability at a low temperature, a PE film and a PP film are preferable, and a low density polyethylene (LDPE) clear film is particularly preferable.
The thickness of the temporary support is not particularly limited as long as it has a required strength. For example, a film of 100 μm to 200 μm is preferable.
〔合成樹脂成形体が有し得るその他の層〕
図１の部分概略断面図に示すように、本開示における合成樹脂成形体１０は、樹脂成形基材１２と、前記樹脂成形基材１２の面上に配置される、既述の樹脂成形体用表皮材１４と、透明樹脂層２４に加え、効果を損なわない限り、目的に応じてその他の層を有してもよい。その他の層としては、例えば、接着剤層、プライマー層などが挙げられる。
図１に示す一実施形態では、樹脂成形基材１２の面上に接着剤層１６を有し、さらに、接着剤層１６と表皮材１４との接着性向上の目的でプライマー層１８が設けられている。図１における接着剤層１６及びプライマー層１８は、目的に応じて備えられるその他の層である。
[Other layers that the synthetic resin molding may have]
As shown in the partial schematic cross-sectional view of FIG. 1, a synthetic resin molded body 10 according to the present disclosure is disposed on a surface of a resin molded base 12 and the resin molded base 12. In addition to the skin material 14 and the transparent resin layer 24, other layers may be provided depending on the purpose as long as the effects are not impaired. Examples of other layers include an adhesive layer and a primer layer.
In one embodiment shown in FIG. 1, an adhesive layer 16 is provided on the surface of the resin molded substrate 12, and a primer layer 18 is provided for the purpose of improving the adhesiveness between the adhesive layer 16 and the skin material 14. ing. The adhesive layer 16 and the primer layer 18 in FIG. 1 are other layers provided according to the purpose.
（接着剤層）
接着剤層１６は、表皮材１４を樹脂成形基材１２の表面に沿って配置し、成形する前の樹脂成形基材１２の表面に接着剤を付与して形成することができる。
(Adhesive layer)
The adhesive layer 16 can be formed by disposing the skin material 14 along the surface of the resin molded substrate 12 and applying an adhesive to the surface of the resin molded substrate 12 before being molded.
接着剤層の形成に用いる接着剤としては特に制限はなく、樹脂成形基材１２の種類等により適宜選択される。例えば（１）２液硬化型ポリエステル系接着剤、（２）２液硬化型ウレタン系接着剤、（３）２液硬化型アクリル系粘着剤などが好適に使用される。
接着剤層の形成に使用される接着剤は市販品としても入手可能であり、例えば、オリバインシリーズ〔東洋インキ（株）〕、ウェルダー用接着剤Ｎｏ．３６６０〔２液硬化型ポリウレタン系接着剤：ノーテープ工業（株）〕、ダイカラック７２５０ＮＴ〔２液硬化型ポリエステル系接着剤：大同化成工業（株）〕などが好適である。
接着剤層１６の厚さは、乾燥膜厚で２０μｍ〜５０μｍの範囲であることが好ましい。
There is no restriction | limiting in particular as an adhesive agent used for formation of an adhesive bond layer, According to the kind etc. of the resin molding base material 12, etc., it selects suitably. For example, (1) two-component curable polyester-based adhesive, (2) two-component curable urethane-based adhesive, and (3) two-component curable acrylic pressure-sensitive adhesive are preferably used.
The adhesive used for forming the adhesive layer is also available as a commercial product. For example, the Oliveline series [Toyo Ink Co., Ltd.], Welder Adhesive No. 3660 [two-component curable polyurethane adhesive: No Tape Industry Co., Ltd.], Daikarak 7250NT [two-component curable polyester adhesive: Daido Kasei Kogyo Co., Ltd.] and the like are suitable.
The thickness of the adhesive layer 16 is preferably in the range of 20 μm to 50 μm in terms of dry film thickness.
なお、接着剤層１６は、図１では、樹脂成形基材１２とプライマー層１８との間に設けられているが、これに限定されず、本開示における効果を損なわない限り、各層の密着性を向上させる目的で、任意の層間に設けてもよい。 In FIG. 1, the adhesive layer 16 is provided between the resin-molded substrate 12 and the primer layer 18. However, the adhesive layer 16 is not limited to this, and the adhesiveness of each layer is not limited unless the effects of the present disclosure are impaired. For the purpose of improving, it may be provided between arbitrary layers.
（プライマー層）
本開示における合成樹脂成形体１０は、プライマー層１８を有していてもよい。プライマー層１８は、樹脂成形基材１２と表皮材１４、或いは、任意の層である既述の接着剤層１６と表皮材１４との密着性を高めるために必要に応じて設けられる層である。
プライマー層１８は、樹脂成形基材１２の表面に所望により設ける既述の接着剤層１６の形成と同様に、表皮材１４と樹脂成形基材１２等との密着性を向上させる材料を、表皮材１４の表皮基材層２０側の面上に塗工してプライマー層１８を形成することができる。具体的には、例えば、表皮材１４の表皮基材層２０側の面上にウレタン系塗料を塗布、乾燥することで形成することができる。
(Primer layer)
The synthetic resin molded body 10 in the present disclosure may have a primer layer 18. The primer layer 18 is a layer provided as necessary in order to improve the adhesion between the resin-molded base 12 and the skin material 14 or the above-described adhesive layer 16 and the skin material 14 which are arbitrary layers. .
The primer layer 18 is made of a material that improves the adhesion between the skin material 14 and the resin molded substrate 12 and the like, similar to the formation of the adhesive layer 16 described above that is optionally provided on the surface of the resin molded substrate 12. The primer layer 18 can be formed by coating on the surface of the material 14 on the skin base material layer 20 side. Specifically, for example, it can be formed by applying and drying a urethane-based paint on the surface of the skin material 14 on the skin base material layer 20 side.
プライマー層１８には、既述の隣接する層との密着性を向上させる材料を１種のみ含んでもよく、２種以上含んでもよい。
プライマー層１８の厚みには特に限定はない。通常は１μｍ〜５μｍであり、好ましくは２μｍ〜３μｍである。
The primer layer 18 may contain only one type of material that improves the adhesion to the adjacent layer described above, or two or more types.
There is no particular limitation on the thickness of the primer layer 18. Usually, it is 1 micrometer-5 micrometers, Preferably it is 2 micrometers-3 micrometers.
（合成樹脂成形体について）
本開示における合成樹脂成形体１０は、樹脂成形基材１２の面上に、既述の如き構成の表皮材１４と透明樹脂層２４とを備えるため、表皮基材層２０と表皮層２２とを有する表皮材１４及び透明樹脂層２４の機能が相俟って、表面が平滑で耐傷性が良好であり、且つ、立体感を有する意匠が表面に形成され外観に優れた合成樹脂成形体１０となり、その応用範囲は広い。
(About synthetic resin moldings)
Since the synthetic resin molded body 10 in the present disclosure includes the skin material 14 and the transparent resin layer 24 having the structure described above on the surface of the resin molded base material 12, the skin base material layer 20 and the skin layer 22 are provided. Combined with the functions of the skin material 14 and the transparent resin layer 24, the synthetic resin molded body 10 has a smooth surface, good scratch resistance, and a three-dimensional design formed on the surface, which is excellent in appearance. The application range is wide.
［合成樹脂成形体の製造方法］
本開示における合成樹脂成形体は、合成樹脂を含み、表面に凹凸を有する表皮層を形成する工程〔工程（Ａ）〕、前記表皮層の凹凸を有する側とは反対側の面上に、合成樹脂と、メタリック顔料と、メタリック顔料以外の着色剤と、を含む表皮基材層を形成して、樹脂成形体用表皮材を得る工程〔工程（Ｂ）〕、樹脂成形基材表面に、前記樹脂成形体用表皮材を、前記樹脂成形基材と前記表皮基材層とが接するように配置し、加熱成形して予備成形体を得る工程〔工程（Ｃ）〕、及び得られた予備成形体に配置された前記表皮材の表面に、透明樹脂を付与して透明樹脂層を形成する工程〔工程（Ｄ）〕を有し、樹脂成形基材と、表皮基材層と、表皮層と、透明樹脂層と、をこの順に有する合成樹脂成形体を得る合成樹脂成形体の製造方法である。
[Method for producing synthetic resin molding]
The synthetic resin molded body in the present disclosure includes a synthetic resin and a step of forming a skin layer having unevenness on the surface [step (A)], on the surface opposite to the side having the unevenness of the skin layer, Forming a skin base material layer containing a resin, a metallic pigment, and a colorant other than the metallic pigment to obtain a skin material for a resin molding [step (B)], on the surface of the resin molding base, A step of placing the skin material for a resin molded body so that the resin molded base material and the skin base material layer are in contact with each other, and heat-molding to obtain a preform (step (C)), and the obtained preform A step of forming a transparent resin layer by applying a transparent resin to the surface of the skin material disposed on the body [step (D)], a resin-molded base material, a skin base material layer, and a skin layer; , A transparent resin layer, and a synthetic resin molded body for obtaining a synthetic resin molded body having this order. .
〔合成樹脂を含み、表面に凹凸を有する表皮層を形成する工程：工程（Ａ）〕
工程（Ａ）では、合成樹脂を含む表皮層を形成する。表皮層の片面には、意匠性を高めるための凹凸模様（以下、絞（シボ）と称することがある）が形成される。
表皮層は、合成樹脂を含む表皮層形成用組成物を製膜することで形成することができる。凹凸は、例えば、既述のように、予め凹凸が形成された離型材に表皮層形成用組成物を付与して、表皮層形成用組成物層を形成し、離型材を剥離することで片方の表面に凹凸を有する表皮層を形成することができる。
また、平滑な離型材に表皮層形成用組成物を塗布して凹凸を有しない表皮層形成用組成物層を形成し、その後、後述の工程（Ｂ）を行って、表皮層形成用組成物層の離型材とは反対側の面上に表皮基材層形成用組成物を付与して表皮基材層形成用組成物層を設け、表皮層形成用組成物層と表皮基材層形成用組成物層との積層体を絞ロールにてラミネートエンボスすることで、表皮層と表皮基材層とを密着させ、且つ、表皮層の表皮基材層を有する側とは反対側の面に凹凸を形成することもできる。
表皮層形成用組成物の詳細、好ましい膜厚などは既述の通りである。
[Step of forming a skin layer containing a synthetic resin and having irregularities on the surface: Step (A)]
In the step (A), a skin layer containing a synthetic resin is formed. On one side of the skin layer, a concavo-convex pattern (hereinafter sometimes referred to as a “squeeze”) for improving the design is formed.
The skin layer can be formed by forming a skin layer forming composition containing a synthetic resin. As described above, for example, as described above, the surface layer forming composition layer is applied to the release material on which the unevenness has been previously formed, the skin layer forming composition layer is formed, and the mold release material is peeled off on one side. A skin layer having irregularities on the surface can be formed.
Also, the composition for forming the skin layer is formed by applying the composition for forming the skin layer on a smooth release material to form a composition layer for forming the skin layer having no irregularities, and then performing the step (B) described later. The composition for forming the skin base material layer is provided on the surface opposite to the release material of the layer to provide the composition layer for forming the skin base material layer, and the composition layer for forming the skin base layer and the skin base material layer forming By laminating and embossing the laminate with the composition layer with a squeeze roll, the skin layer and the skin base material layer are brought into close contact with each other and the surface of the skin layer opposite to the side having the skin base material layer is uneven. Can also be formed.
Details of the composition for forming the skin layer, preferable film thickness, and the like are as described above.
〔表皮層の凹凸を有する側とは反対側の面上に、合成樹脂と、メタリック顔料と、メタリック顔料以外の着色剤と、を含む表皮基材層を形成して、樹脂成形体用表皮材を得る工程：工程（Ｂ）〕
工程（Ｂ）では、表皮層の凹凸を有しない（凹凸を形成しない）側の面上に、合成樹脂と、メタリック顔料と、メタリック顔料以外の着色剤と、を含む表皮基材層形成用組成物を付与して、表皮基材層形成用組成物層を形成し、その後、表皮基材層形成用組成物層を乾燥、硬化させて表皮基材層を形成する。
表皮基材層形成用組成物の詳細、好ましい膜厚などは既述の通りである。
[A skin material for a resin molded body is formed by forming a skin base material layer containing a synthetic resin, a metallic pigment, and a colorant other than the metallic pigment on the surface of the skin layer opposite to the uneven side. Step: (B)]
In the step (B), a composition for forming a skin base material layer comprising a synthetic resin, a metallic pigment, and a colorant other than the metallic pigment on the surface of the skin layer having no unevenness (not forming unevenness). An object is provided to form a composition layer for forming a skin base material layer, and then the composition layer for forming a skin base material layer is dried and cured to form a skin base material layer.
The details of the composition for forming the skin base material layer, the preferable film thickness, and the like are as described above.
前記工程（Ａ）及び前記工程（Ｂ）を実施することにより、本開示における表皮材を得る。表皮材の形成には、以下に示す方法が挙げられる。
例えば、工程（Ａ）と工程（Ｂ）とを、独立した工程として別々に行ない、その後、得られた表皮層と表皮基材層とを密着させて表皮材を得ることができる。
また、まず、工程（Ｂ）を実施して表皮基材層形成用組成物層を形成し、表皮基材層形成用組成物層の片面に、合成樹脂を含む表皮層形成用組成物層を形成し、得られた積層体を、絞ロールによりラミネートエンボスして、表皮層の表皮基材層と接する面とは反対側の面に凹凸を設け、且つ、表皮層と表皮基材層とを密着させて表皮材を得ることができる。
さらに、絞型が形成された離型材表面に表皮層形成用組成物層を形成し、形成された表皮層形成用組成物層の離型材とは反対の面に、表皮基材層形成用組成物層を形成し、硬化させ、離型材を剥離して、凹凸を有する表皮層と表皮基材層とを備える表皮材を得ることができる。
By carrying out the step (A) and the step (B), a skin material in the present disclosure is obtained. Examples of the method for forming the skin material include the following methods.
For example, the step (A) and the step (B) are separately performed as independent steps, and then the obtained skin layer and the skin base material layer are brought into close contact with each other to obtain a skin material.
First, the step (B) is carried out to form a skin base layer forming composition layer, and a skin layer forming composition layer containing a synthetic resin is formed on one side of the skin base layer forming composition layer. The laminated body obtained is laminated and embossed with a squeeze roll to provide irregularities on the surface of the skin layer opposite to the surface in contact with the skin base material layer, and the skin layer and the skin base material layer. A skin material can be obtained by closely adhering.
Further, a composition layer for forming the skin layer is formed on the surface of the release material on which the drawing mold is formed, and the composition for forming the skin base material layer is formed on the surface opposite to the release material of the formed composition layer for forming the skin layer. A material layer can be formed and cured, and a release material can be peeled off to obtain a skin material having an uneven skin layer and a skin base material layer.
〔樹脂成形基材表面に、樹脂成形体用表皮材を、樹脂成形基材と表皮基材層とが接するように配置し、加熱成形して予備成形体を得る工程：工程（Ｃ）〕
工程（Ｃ）では、樹脂成形基材の表面に、工程（Ａ）及び工程（Ｂ）により得られた表皮材の、表皮基材層側を接触させ、常法により、加熱成形して、表面に表皮材が固定化され、所望の形状に成形された予備成形体を得る。
樹脂成形基材は、目的とする合成樹脂成形体に応じた形状、大きさ、重さ等を有する成形基材であり、その表面に沿って既述の表皮材が配置され、成形されて、立体感を有する意匠が形成された合成樹脂成形体を得る。
樹脂成形基材１２の材質、形状、大きさ等は、製造する成形体の用途、目的、デザイン、コスト等を考慮して選択すればよい。
加熱成形は公知の成形方法を目的に応じて選択すればよい。加熱成形方法としては、例えば、プレス成形（圧縮成型）、射出成形、真空成形、メンブレン成形、ＴＯＭ成形などが挙げられる。
[Process for obtaining a preformed body by arranging a resin-molded skin material on the surface of the resin-molded base material so that the resin-molded base material and the skin base material layer are in contact with each other: Step (C)]
In the step (C), the surface of the skin material obtained in the step (A) and the step (B) is brought into contact with the surface of the resin-molded base material, and the surface is subjected to heat molding by a conventional method. An outer skin material is fixed to a preform to obtain a preform molded into a desired shape.
The resin-molded substrate is a molded substrate having a shape, size, weight, etc. according to the intended synthetic resin molded body, and the aforementioned skin material is arranged along the surface and molded, A synthetic resin molded body having a three-dimensional design is obtained.
The material, shape, size, and the like of the resin molded substrate 12 may be selected in consideration of the application, purpose, design, cost, etc. of the molded body to be manufactured.
For the heat molding, a known molding method may be selected according to the purpose. Examples of the heat molding method include press molding (compression molding), injection molding, vacuum molding, membrane molding, and TOM molding.
真空成形、メンブレン成形、ＴＯＭ成形などの気圧の圧力差を利用した成形方法を行うことで、比較的低温にて、表皮材の密着性が良好な合成樹脂成形体を得ることができる。
ＴＯＭ（Three dimension Overlay Method）成形は、樹脂等によって予め成形した樹脂成形基材と表皮材とを真空状態の環境下において空気を抜き、加熱、成形、加圧などの工程を通じて成形体を装飾させる方法である。ＴＯＭ成形によれば、高温での射出工程が不要であり、低温で目的の立体感が良好な意匠を有する剛性樹脂成形体を製造することができる。
予備成形体を得る場合、表皮材は、樹脂成形基材表面に配置してもよく、成形金型内に配置してもよい。
By performing a molding method using a pressure difference of atmospheric pressure, such as vacuum molding, membrane molding, and TOM molding, a synthetic resin molded article having good adhesion of the skin material can be obtained at a relatively low temperature.
In TOM (Three dimension Overlay Method) molding, the molded body is decorated through a process such as heating, molding, and pressurizing the resin-molded base material and skin material, which are pre-molded with resin, in a vacuum environment. Is the method. According to the TOM molding, an injection process at a high temperature is not required, and a rigid resin molded body having a design with a desired stereoscopic effect at a low temperature can be produced.
When obtaining a preformed body, the skin material may be disposed on the surface of the resin-molded base material or in a molding die.
〔得られた予備成形体に配置された表皮材の表面に、透明樹脂を付与して透明樹脂層を形成する工程〔工程（Ｄ）〕
工程（Ｃ）にて得られた予備成形体は、樹脂成形基材の表面に、メタリック顔料等を含む表皮基材層と最表面に凹凸を有する表皮層とを、樹脂成形基材側からこの順に有する表皮材を有する。工程（Ｄ）では、凹凸を有する表皮材の最表面に透明樹脂を付与して透明樹脂層を形成する。
透明樹脂を付与して透明樹脂層を形成する工程が、樹脂成形体用表皮材の面上に透明樹脂層形成用組成物を塗布する工程であることが、より立体感のある意匠を得られるという観点から好ましい。
[Step of forming a transparent resin layer by applying a transparent resin to the surface of the skin material disposed on the obtained preform [Step (D)]
The preformed body obtained in the step (C) has a surface of the resin-molded base material having a skin base material layer containing a metallic pigment or the like and a skin layer having irregularities on the outermost surface from the resin-molded base material side. It has the skin material which it has in order. In the step (D), a transparent resin layer is formed by applying a transparent resin to the outermost surface of the skin material having irregularities.
It is possible to obtain a more three-dimensional design that the step of forming the transparent resin layer by applying the transparent resin is a step of applying the composition for forming the transparent resin layer on the surface of the resin molded body skin material. It is preferable from the viewpoint.
例えば、透明樹脂層形成用組成物の好ましい一例である紫外線硬化型樹脂組成物を例に挙げて説明する。紫外線硬化型樹脂組成物を、表皮材の凹凸を有する側の面にコーター法により塗布し、表皮材の面上に透明樹脂層形成用組成物層である紫外線硬化型樹脂組成物層を形成した後、乾燥することで、層厚みが均一で、表面が平滑性な層が形成される。コーター法としては、塗膜の均一性の観点から、ダイレクトリバースコーター法が好ましい。
紫外線硬化型樹脂組成物層の乾燥は、風を当てながら非接触で行うことが好ましい。
紫外線硬化型樹脂組成物層に、紫外線照射によりエネルギーを付与して、硬化させることで、耐傷性に優れた透明樹脂層を得ることができる。
紫外線を照射する光源は、透明樹脂層を硬化させる波長域の紫外光を照射することができれば特に限定されず、ＬＥＤ（発光ダイオード）光源、高圧水銀ランプ、ブラックライトなどを採用することができる。
For example, the ultraviolet curable resin composition which is a preferable example of the composition for forming a transparent resin layer will be described as an example. The ultraviolet curable resin composition was applied to the surface of the skin material having the irregularities by a coater method, and an ultraviolet curable resin composition layer that was a transparent resin layer forming composition layer was formed on the surface of the skin material. Thereafter, a layer having a uniform layer thickness and a smooth surface is formed by drying. As the coater method, the direct reverse coater method is preferable from the viewpoint of the uniformity of the coating film.
It is preferable to dry the ultraviolet curable resin composition layer in a non-contact manner while applying air.
A transparent resin layer having excellent scratch resistance can be obtained by applying energy to the UV curable resin composition layer by UV irradiation and curing.
The light source for irradiating ultraviolet rays is not particularly limited as long as it can irradiate ultraviolet light in a wavelength region that cures the transparent resin layer, and an LED (light emitting diode) light source, a high-pressure mercury lamp, a black light, or the like can be adopted.
通常は、凹凸を有する表皮材１４の表面に透明樹脂層を設けると、表面が平滑になり、表皮材１４に設けられた凹凸による立体感の視認性が低下することがある。本発明の一実施形態の合成樹脂成形体１０では、凹凸を有する表皮層２２の下層にメタリック顔料等を有する表皮基材層２０を有する表皮材１４を備えることで、立体感のある意匠が損なわれず、且つ、予備成形体の形成後に透明樹脂層２４を設けたことによる表面の平滑性、鏡面性、耐傷性等と、立体感を有する意匠性の実現が高いレベルで両立したものと考えている。 Usually, when a transparent resin layer is provided on the surface of the skin material 14 having unevenness, the surface becomes smooth, and the visibility of the three-dimensional effect due to the unevenness provided on the skin material 14 may be reduced. In the synthetic resin molded body 10 of one embodiment of the present invention, the three-dimensional design is impaired by including the skin material 14 having the skin base material layer 20 having a metallic pigment or the like under the skin layer 22 having irregularities. The surface smoothness, specularity, scratch resistance, and the like due to the provision of the transparent resin layer 24 after the formation of the preform, and the realization of the design with a three-dimensional effect are compatible at a high level. Yes.
〔任意の工程〕
本開示における合成樹脂成形体の製造方法は、工程（Ａ）、工程（Ｂ）、工程（Ｃ）及び工程（Ｄ）に加え、さらに任意の工程を有してもよい。
例えば、樹脂成形基材表面に、接着剤層を形成する工程をさらに有することができる。樹脂成形基材表面に接着剤層を有することで、樹脂成形基材と表皮材との密着性が向上し、耐久性がより良好な合成樹脂成形体を製造することができる。
樹脂成形基材１２の表面に接着剤層１６を形成する方法は特に限定されず、スプレー、コーター等による塗布法、転写法など公知の方法を採用することができる。
接着剤層の形成方法は、接着剤の種類、樹脂成形基材に含まれる樹脂の種類、得られる成形体の形状等に応じて選択すればよい。
[Optional process]
In addition to the step (A), the step (B), the step (C) and the step (D), the method for producing a synthetic resin molded body in the present disclosure may further include an optional step.
For example, it can further have the process of forming an adhesive bond layer on the resin-molded substrate surface. By having an adhesive layer on the surface of the resin molded substrate, the adhesion between the resin molded substrate and the skin material is improved, and a synthetic resin molded body with better durability can be produced.
The method for forming the adhesive layer 16 on the surface of the resin molded substrate 12 is not particularly limited, and a known method such as a coating method using a spray, a coater, or the like, or a transfer method can be employed.
What is necessary is just to select the formation method of an adhesive bond layer according to the kind of adhesive agent, the kind of resin contained in a resin molding base material, the shape of the molded object obtained, etc.
また、接着剤層１６と表皮材１４における表皮基材層２０との間にプライマー層１８を設ける工程を有してもよい。
プライマー層は、樹脂成形基材の表皮材を付与する側の表面に、前記接着剤層と同時に、又は、逐次に、樹脂成形基材又は接着剤層と表皮材１４との密着性を向上させる材料を付与して形成することができる。具体的には、例えば、表皮材の樹脂成形基材を接着させる側の面に、密着性を向上させる材料であるウレタン系塗料をグラビヤ塗工し、熱風乾燥してプライマー層を形成する方法が挙げられる。
Moreover, you may have the process of providing the primer layer 18 between the adhesive bond layer 16 and the skin base material layer 20 in the skin material 14.
The primer layer improves the adhesion between the resin molding substrate or adhesive layer and the skin material 14 simultaneously or sequentially with the surface of the resin molding substrate on the side to which the skin material is applied. It can be formed by applying a material. Specifically, for example, a method of forming a primer layer by applying a gravure coating of a urethane-based paint, which is a material for improving adhesion, on the surface of the skin material to which the resin-molded base material is bonded, and drying with hot air Can be mentioned.
（合成樹脂成形体の製造方法について）
本開示における製造方法によれば、立体感を有する外観を有し、耐傷性が良好な合成樹脂成形体を簡易な工程にて製造することができる。
得られた合成樹脂成形体は、表面の耐擦傷性と立体感を有する意匠性とが求められる種々の製品の製造に適用することができ、例えば、自動車、鉄道車両、航空機の内装材および外装材、建具、家具、キッチン扉、収納扉など種々の分野に好適に使用し得る。
(About the manufacturing method of synthetic resin moldings)
According to the production method of the present disclosure, a synthetic resin molded article having a three-dimensional appearance and good scratch resistance can be produced by a simple process.
The obtained synthetic resin molding can be applied to the production of various products that require surface scratch resistance and design with a three-dimensional effect, such as automobiles, railway vehicles, aircraft interior materials, and exteriors. It can be suitably used in various fields such as materials, joinery, furniture, kitchen doors and storage doors.
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらに制限されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited to these.
＜実施例１＞
〔合成樹脂成形体の製造〕
（表皮材の作製）
塩化ビニル樹脂〔Ｓ１００１Ｎ（商品名）（株）カネカ〕１００質量部に、メタリック顔料（６３２０ＮＳ：製品名、東洋アルミニウム（株）製）５質量部及びメタリック顔料以外の着色剤であるカーボンブラック ５質量部を投入し、２００℃に加熱しながら混合して表皮基材層形成用組成物を調製し、得られた表皮基材層形成用組成物をカレンダー法により、乾燥後の厚みが１５０μｍになるようにシート状に成形してメタリック顔料を含む表皮基材層を得た。
その後、フッ素樹脂含有層とアクリル樹脂含有層との積層体〔ＫＦＣフィルム ＦＴ−５０Ｙ（商品名）、呉羽化学工業（株）：厚み約５０μｍ〕を用いて、アクリル樹脂含有層側を前記で得た表皮基材層に接触させて、絞ロールを用いてラミネートエンボス加工（シート表面温度１７０℃、速度１０ｍ／分）を行い、表面に凹凸模様を形成した表皮層と、表皮基材層との積層体である実施例１の表皮材を得た。
その後、表皮材の表皮基材層側にウレタン系塗料であるレザロイド（登録商標）ＬＶ-５９７ＳＰグロス（商品名：大日精化工業（株）製）をグラビヤ塗工し、熱風乾燥して厚さ３μｍのプライマー層を形成した。
<Example 1>
[Production of synthetic resin moldings]
(Production of skin material)
Carbon black, which is a colorant other than metallic pigment (6320NS: product name, manufactured by Toyo Aluminum Co., Ltd.) and 100 parts by mass of vinyl chloride resin [S1001N (trade name) Kaneka Co., Ltd.] Part is added and heated and mixed at 200 ° C. to prepare a composition for forming the skin base material layer, and the resulting composition for forming the skin base material layer has a thickness after drying of 150 μm by a calendar method. Thus, it formed in the sheet form and obtained the skin base material layer containing a metallic pigment.
Thereafter, the acrylic resin-containing layer side was obtained using a laminate of a fluororesin-containing layer and an acrylic resin-containing layer [KFC film FT-50Y (trade name), Kureha Chemical Industry Co., Ltd .: thickness of about 50 μm]. The skin base material layer is subjected to lamination embossing (sheet surface temperature 170 ° C., speed 10 m / min) using a squeeze roll, and the skin base material layer having a concavo-convex pattern formed on the surface. The skin material of Example 1 which is a laminated body was obtained.
Thereafter, Rezaroid (registered trademark) LV-597SP gloss (trade name: manufactured by Dainichi Seika Kogyo Co., Ltd.), which is a urethane paint, is gravure-coated on the skin base material layer side of the skin material, dried with hot air, and then thickened. A 3 μm primer layer was formed.
（樹脂成形基材の作製）
アクリル樹脂（三菱レイヨン（株）製）１００質量部数と加工助剤（メタブレン：三菱レイヨン（株）製）５質量部を用い、カレンダー法にて厚さ３００μｍのアクリル系フィルムを製膜し、樹脂成形基材とした。
得られた樹脂成形基材表面に、ウレタン系接着剤であるＥ-２９５ＮＴ（製品名、大日精化工業（株）製）を塗工し、熱風乾燥して厚さ４０μｍの接着剤層を形成した。
(Production of resin-molded substrate)
Using 100 parts by weight of acrylic resin (Mitsubishi Rayon Co., Ltd.) and 5 parts by weight of processing aid (Metabrene: Mitsubishi Rayon Co., Ltd.), an acrylic film having a thickness of 300 μm is formed by the calender method, and the resin A molding substrate was obtained.
E-295NT (product name, manufactured by Dainichi Seika Kogyo Co., Ltd.), which is a urethane-based adhesive, is applied to the surface of the obtained resin molding substrate and dried with hot air to form an adhesive layer having a thickness of 40 μm. did.
樹脂成形基材の面上に形成された接着剤層と、前記で得た表皮材に形成されたプライマー層とを密着し、ＴＯＭ成形により、１５０℃で成形して予備成形体を得た。予備成形体の表面には、表皮材表面の凹凸による立体感を有し、ゴールドメタリックの色相を有する意匠が観察された。 The adhesive layer formed on the surface of the resin-molded substrate and the primer layer formed on the skin material obtained above were brought into close contact with each other and molded at 150 ° C. by TOM molding to obtain a preform. On the surface of the preform, a design having a three-dimensional effect due to unevenness on the surface of the skin material and having a gold metallic hue was observed.
（透明樹脂層の形成）
予備成形体の表皮材側の面上に、ウレタンアクリレート、アクリルモノマー及びラジカル型光重合開始剤を含む紫外線硬化型樹脂組成物（ＵＡ-１２２Ｐ：製品名、新中村化学工業（株）社製、溶媒としてメチルイソブチルケトンを含む固形分濃度７０質量％の溶液）をダイレクトリバースコーターにて塗工し、１００℃で１分間乾燥させ、紫外線硬化型樹脂組成物層を形成した。
メタルハライドランプにより、紫外線硬化型樹脂組成物層に紫外線を照射し（照射条件：８０Ｗ／ｃｍ，搬送速度２０ｍ／分）、紫外線硬化型樹脂組成物層を硬化させて、予備成形体表面に透明樹脂層を有する実施例１の合成樹脂成形体を得た。
(Formation of transparent resin layer)
An ultraviolet curable resin composition containing a urethane acrylate, an acrylic monomer, and a radical photopolymerization initiator (UA-122P: product name, manufactured by Shin-Nakamura Chemical Co., Ltd.) A solution having a solid content concentration of 70% by mass containing methyl isobutyl ketone as a solvent) was applied with a direct reverse coater and dried at 100 ° C. for 1 minute to form an ultraviolet curable resin composition layer.
With a metal halide lamp, the ultraviolet curable resin composition layer is irradiated with ultraviolet rays (irradiation conditions: 80 W / cm, transport speed 20 m / min), the ultraviolet curable resin composition layer is cured, and a transparent resin is formed on the surface of the preform. A synthetic resin molding of Example 1 having a layer was obtained.
〔合成樹脂成形体の評価〕
（外観の評価）
実施例１の合成樹脂成形体を目視したところ、表面は平滑で鏡面性であり、表皮材表面の凹凸による立体感を有し、ゴールドメタリックの色相を有する意匠が観察された。
（耐傷性の評価）
実施例１の合成樹脂成形体の表面を、ＪＩＳ Ｋ−５４００（１９９０年） 鉛筆ひっかき試験に準拠して硬度を測定したところ、鉛筆硬度でＨであり、十分な耐傷性を有することがわかる。
[Evaluation of synthetic resin moldings]
(Appearance evaluation)
When the synthetic resin molded body of Example 1 was visually observed, a design having a smooth and specular surface, a three-dimensional effect due to unevenness on the surface of the skin material, and a gold metallic hue was observed.
(Scratch resistance evaluation)
When the hardness of the surface of the synthetic resin molded body of Example 1 was measured according to a JIS K-5400 (1990) pencil scratch test, it was found that the pencil hardness was H, and the surface had sufficient scratch resistance.
＜比較例１＞
表皮基材層形成用組成物を調製する際に、メタリック顔料を添加しなかった以外は実施例１と同様にして比較例１の合成樹脂成形体を得た。
実施例１と同様にして外観を評価したところ、表面が平滑で鏡面性はあるが、表皮材の凹凸は視認できず、立体感のある意匠は得られなかった。
耐傷性を評価したところ、実施例１と同様に、鉛筆硬度でＨであり、表面の耐傷性は良好であった。
<Comparative Example 1>
A synthetic resin molded article of Comparative Example 1 was obtained in the same manner as Example 1 except that the metallic pigment was not added when preparing the composition for forming the skin base material layer.
When the appearance was evaluated in the same manner as in Example 1, the surface was smooth and had specularity, but the unevenness of the skin material was not visible, and a design with a three-dimensional effect was not obtained.
When scratch resistance was evaluated, as in Example 1, the pencil hardness was H, and the surface scratch resistance was good.
１０ 合成樹脂成形体
１２ 樹脂成形基材
１４ 樹脂成形体用表皮材（表皮材）
１６ 接着剤層
１８ プライマー層
２０ 表皮基材層
２２ 表皮層
２４ 透明樹脂層
DESCRIPTION OF SYMBOLS 10 Synthetic resin molding 12 Resin molding base material 14 Skin material for resin moldings (skin material)
16 Adhesive layer 18 Primer layer 20 Skin base material layer 22 Skin layer 24 Transparent resin layer
Claims (7)
前記表皮層の、前記凹凸を有する側とは反対側の面上に、合成樹脂と、メタリック顔料と、メタリック顔料以外の着色剤と、を含む表皮基材層を形成して、樹脂成形体用表皮材を得る工程と、
樹脂成形基材の表面に、前記樹脂成形体用表皮材を、前記樹脂成形基材と前記表皮基材層とが接するように配置し、加熱成形して予備成形体を得る工程、及び
得られた予備成形体に配置された前記樹脂成形体用表皮材の表面に、透明樹脂を付与して透明樹脂層を形成する工程を有し、
樹脂成形基材と、表皮基材層と、表皮層と、透明樹脂層と、をこの順に有する合成樹脂成形体を得る合成樹脂成形体の製造方法。 Including a synthetic resin, forming a skin layer having irregularities on the surface,
Forming a skin base material layer containing a synthetic resin, a metallic pigment, and a colorant other than the metallic pigment on the surface of the skin layer opposite to the side having the unevenness, for a resin molded body Obtaining a skin material;
Arranging the surface material for the resin molded body on the surface of the resin molded base material so that the resin molded base material and the skin base material layer are in contact with each other, and thermoforming to obtain a preform; and A step of forming a transparent resin layer by applying a transparent resin to the surface of the skin material for a resin molded body arranged in the preformed body,
The manufacturing method of the synthetic resin molding which obtains the synthetic resin molding which has a resin molding base material, an outer skin base material layer, an outer skin layer, and a transparent resin layer in this order.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019225386A1 (en) * | 2018-05-22 | 2019-11-28 | 共和レザー株式会社 | Decorative film, decorative film production method, decorative molded body and decorative molded body production method |
| JP2020029630A (en) * | 2018-08-21 | 2020-02-27 | アキレス株式会社 | Leather-like sheet for TOM molding |
| WO2020209003A1 (en) * | 2019-04-12 | 2020-10-15 | アルプスアルパイン株式会社 | Decorative sheet, processed decorative article, and manufacturing method |
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| JPH07125151A (en) * | 1993-10-29 | 1995-05-16 | Kyodo Printing Co Ltd | Mirror-finished decorative plate and manufacture thereof |
| JPH07125144A (en) * | 1993-11-08 | 1995-05-16 | Kyodo Printing Co Ltd | Mirror decorative plate with sheen and manufacture thereof |
| JP2016137612A (en) * | 2015-01-27 | 2016-08-04 | 共和レザー株式会社 | Synthetic resin skin material, method for producing synthetic resin skin material, molded body using synthetic resin skin material and method for producing molded body |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07125151A (en) * | 1993-10-29 | 1995-05-16 | Kyodo Printing Co Ltd | Mirror-finished decorative plate and manufacture thereof |
| JPH07125144A (en) * | 1993-11-08 | 1995-05-16 | Kyodo Printing Co Ltd | Mirror decorative plate with sheen and manufacture thereof |
| JP2016137612A (en) * | 2015-01-27 | 2016-08-04 | 共和レザー株式会社 | Synthetic resin skin material, method for producing synthetic resin skin material, molded body using synthetic resin skin material and method for producing molded body |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019225386A1 (en) * | 2018-05-22 | 2019-11-28 | 共和レザー株式会社 | Decorative film, decorative film production method, decorative molded body and decorative molded body production method |
| JP2020029630A (en) * | 2018-08-21 | 2020-02-27 | アキレス株式会社 | Leather-like sheet for TOM molding |
| WO2020209003A1 (en) * | 2019-04-12 | 2020-10-15 | アルプスアルパイン株式会社 | Decorative sheet, processed decorative article, and manufacturing method |
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