Fluororesin-cured coating layer-laminated polyvinyl chloride resin composition film, decorative film, and article

Abstract

To provide a laminated film having a fluororesin-cured coating layer formed on a surface of a polyvinyl chloride resin composition film, the laminated film being resistant to discoloration due to thermal aging.SOLUTION: A film composed of a polyvinyl chloride resin composition containing (A) a polyvinyl chloride resin, (B) a core-shell rubber, (C) a barium-zinc composite compound, and (D) a metal perchlorate is used as a base material. The polyvinyl chloride resin composition may preferably further contain (E) a β-diketone compound. A coating material for forming the fluororesin-cured coating layer preferably contains a fluororesin having a hydroxyl group and a compound having two or more isocyanate groups in one molecule.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a laminated film in which a cured fluororesin coating film is formed on the surface of a polyvinyl chloride resin composition film, a decorative film containing the laminated film, and an article decorated with the decorative film. [Background technology]

[0002] Adhering a decorative film to the surface of a structural component constituting an article, such as an automobile, building, furniture, or home appliance, has been proposed as a method for decorating or decorating the article (e.g., Patent Document 1). Such decorative films often have a cured coating formed on the surface of a film substrate to impart properties such as weather resistance, stain resistance, and corrosion resistance. The inventors considered that a cured coating formed using a paint containing a fluororesin, typically a fluororesin having a crosslinkable functional group and a curing agent reactive with the crosslinkable functional group, would be useful as the cured coating for such decorative films, because of its excellent properties such as weather resistance, water and oil repellency, and waterproof and moisture resistance (e.g., Patent Documents 2 to 4). Furthermore, films of polyvinyl chloride resin compositions are widely used as the film substrate for such decorative films. This is because polyvinyl chloride resin compositions allow for a wide range of flexibility adjustment by varying the amount of plasticizer, and have good moldability (when decoratively decorating the surface of a structural member using a decorative film) and mechanical properties, among other characteristics, and are also economically viable. Therefore, the inventors expected that a laminate film in which a cured fluororesin coating film is formed on the surface of a polyvinyl chloride resin composition film would be useful as a decorative film or decorative film component. However, it was discovered that a laminate film in which a cured fluororesin coating film is formed on the surface of a polyvinyl chloride resin composition film has a fatal drawback as a decorative film: it is prone to discoloration to red due to heat aging. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-119403 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-147841 [Patent Document 3] Japanese Patent Application Publication No. 2016-033181 [Patent Document 4] Japanese Patent Application Publication No. 2019-026807 [Patent Document 5] Japanese Patent Application Publication No. 06-262726 [Patent Document 6] Japanese Patent Application Publication No. 06-297624 [Patent Document 7] Japanese Patent Application Publication No. 07-233318 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a laminated film having a polyvinyl chloride resin composition film and a fluorine resin cured coating film formed on the surface thereof, which laminated film is inhibited from discoloring due to heat aging. [Means for solving the problem]

[0005] As a result of extensive research, the present inventors have found that the above object can be achieved by using a film made of a specific polyvinyl chloride resin composition.

[0006] That is, the various aspects of the present invention are as follows. [1]. A laminated film comprising an (α) polyvinyl chloride resin composition film having a (β) fluororesin cured coating film on at least one surface thereof, wherein the (α) polyvinyl chloride resin composition film contains 100 parts by mass of a resin mixture consisting of 60 to 100 mass% of (A) polyvinyl chloride resin and 40 to 0 mass% of (B) core-shell rubber, 0.01 to 10 parts by mass of (C) barium-zinc complex compound, and 0.01 to 5 parts by mass of (D) metal perchlorate, wherein the sum of the blending amount of the component (A) polyvinyl chloride resin and the blending amount of the component (B) core-shell rubber is 100 mass%. [2]. The laminated film according to item [1], wherein the polyvinyl chloride resin composition further contains 0.01 to 5 parts by mass of (E) a β-diketone compound. [3]. The laminated film according to item [1], wherein the (β) fluororesin cured coating film is made of a coating material containing a fluororesin having a hydroxyl group and a compound having two or more isocyanate groups in one molecule. [4]. The laminated film according to item [3], wherein the hydroxyl value of the hydroxyl-containing fluororesin is 1 to 200 mgKOH / g. [5]. The laminated film according to item [4], wherein the ratio (q / p) of the number (q) of isocyanates derived from the compound having two or more isocyanate groups per molecule in the coating material to the number (p) of hydroxyl groups derived from the fluororesin having hydroxyl groups is 0.1 to 2.0. [6]. A decorative film comprising the laminate film according to any one of items [1] to [5]. [7]. [6] An article comprising the decorative film described in item [6]. [Effects of the Invention]

[0007] The laminate film of the present invention is inhibited from discoloring due to thermal aging. The laminate film of the present invention has a surface formed by a cured fluororesin coating film, and is excellent in weather resistance, water and oil repellency, and waterproof and moisture-proof properties. The laminate film of the present invention has a polyvinyl chloride resin composition film as a film substrate, and its flexibility can be adjusted over a wide range by varying the amount of plasticizer contained in the polyvinyl chloride resin composition. It also has good moldability (the moldability when using the decorative film to decorate and decorate the surface of a structural member) and mechanical properties. Therefore, decorative films containing the laminate film of the present invention are suitable for use in decorating and decorating articles such as automobiles, buildings, furniture, and home appliances. DETAILED DESCRIPTION OF THE INVENTION

[0008] In this specification, the term "resin" is used to include a resin mixture containing two or more resins, and a resin composition containing components other than resin.

[0009] In this specification, the term "film" is used interchangeably or interchangeably with "sheet." In this specification, the terms "film" and "sheet" are used to refer to materials that can be industrially wound into rolls. The term "plate" is used to refer to materials that cannot be industrially wound into rolls. In addition, in this specification, laminating one layer and another layer in order includes both directly laminating the layers and laminating the layers with one or more additional layers, such as an anchor coat, interposed between them.

[0010] In this specification, the term "more than or equal to" in relation to a numerical range means a certain number or more than a certain number. For example, 20% or more means 20% or more than 20%. The term "less than or equal to" in relation to a numerical range means a certain number or less than a certain number. For example, 20% or less means 20% or less than 20%. Furthermore, the symbol "to" in relation to a numerical range means a certain number, more than a certain number and less than another certain number, or another certain number. Here, another certain number is a number greater than the certain number. For example, 10 to 90% means 10%, more than 10% and less than 90%, or 90%. Furthermore, the upper and lower limits of a numerical range can be arbitrarily combined, and embodiments incorporating such combinations can be interpreted. For example, from a statement regarding the numerical range of a certain characteristic such as "usually 10% or more, preferably 20% or more. On the other hand, it is usually 40% or less, preferably 30% or less," or "usually 10 to 40%, preferably 20 to 30%," it can be read that the numerical range of the certain characteristic is 10 to 40%, 20 to 30%, 10 to 30%, or 20 to 40% in one embodiment.

[0011] Other than in the examples, or where otherwise specified, all numerical values ​​used in the specification and claims should be understood to be modified by the term "about." Without attempting to limit the application of the doctrine of equivalents to the claims, each numerical value should be construed in light of the number of significant digits and by applying ordinary rounding techniques.

[0012] In this specification, terms specifying shapes or geometric conditions, such as parallel, orthogonal, and perpendicular, are intended to include not only the strict meanings but also substantially the same states.

[0013] In this specification, when it is explained that "comprises a certain substance," it is to be understood that, in one embodiment, it contains a certain substance, consists of a certain substance, or consists only of a certain substance. For example, from the explanation that "composition A comprises substances a1 and a2," it is to be understood that, in one embodiment, composition A comprises substances a1 and a2, composition A consists of substances a1 and a2, or composition A consists only of substances a1 and a2.

[0014] 1.Lamination film: The laminate film of the present invention has (β) a fluororesin cured coating film on at least one surface of (α) a polyvinyl chloride resin composition film. In one typical embodiment, the laminate film of the present invention has (β) the fluororesin cured coating film on the front surface of the (α) polyvinyl chloride resin composition film. Each layer will be described below.

[0015] (α) Polyvinyl chloride resin composition film: The (α) polyvinyl chloride resin composition film is a resin film that serves as the film substrate of the laminate film of the present invention. The (α) polyvinyl chloride resin composition film is made of a polyvinyl chloride resin composition containing (A) a polyvinyl chloride resin, (C) a barium-zinc complex compound, and (D) a metal perchlorate. In one embodiment, the (α) polyvinyl chloride resin composition film may be made of the polyvinyl chloride resin composition further containing (B) a core-shell rubber. Each component will be described below.

[0016] (A) Polyvinyl chloride resin: The polyvinyl chloride resin composition contains the component (A) polyvinyl chloride resin. The component (A) polyvinyl chloride resin is a polymer (including a copolymer) having primarily (usually 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and typically 90 to 100% by mass, assuming that the sum of all structural units is 100% by mass) structural units represented by (-CH2-CHCl-).

[0017] Examples of the polyvinyl chloride resin component (A) include polyvinyl chloride (vinyl chloride homopolymer); vinyl chloride-vinyl acetate copolymer, vinyl chloride-(meth)acrylic acid copolymer, vinyl chloride-methyl (meth)acrylate copolymer, vinyl chloride-ethyl (meth)acrylate copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride Examples include vinyl chloride copolymers of vinyl chloride with other monomers copolymerizable with vinyl chloride, such as vinyl-styrene-acrylonitrile terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylonitrile copolymer, and vinyl chloride-various vinyl ether copolymers; polyvinyl chloride such as post-chlorinated vinyl copolymers, or modified (chlorinated, etc.) vinyl chloride copolymers; and chlorinated polyolefins such as chlorinated polyethylene.

[0018] The average degree of polymerization of the polyvinyl chloride resin (component (A)) may be preferably 2500 or less, more preferably 2000 or less, even more preferably 1500 or less, and even more preferably 1200 or less, from the viewpoint of suppressing coloration during film formation. On the other hand, from the viewpoint of the mechanical properties of the film, it may be preferably 500 or more, more preferably 650 or more. Here, the average degree of polymerization of the polyvinyl chloride resin is calculated from the specific viscosity measured in accordance with the 4.1 specific viscosity of JIS K6720-2:1999 using formulas (1) and (2) of the JIS standard.

[0019] The component (A) polyvinyl chloride resin may preferably contain polyvinyl chloride (vinyl chloride homopolymer), and more preferably contain polyvinyl chloride (vinyl chloride homopolymer) having the above-mentioned average degree of polymerization.

[0020] As the component (A) polyvinyl chloride resin, one or more of these can be used.

[0021] (B) Core-shell rubber: In one embodiment, the polyvinyl chloride resin composition may further contain the component (B) core-shell rubber. By including the component (B) core-shell rubber, it is possible to improve the film-forming properties by calender rolling and the weather resistance.

[0022] The component (B) core-shell rubber is a rubber having a core-shell structure. Examples of the component (B) core-shell rubber include graft copolymers obtained by graft polymerizing an aromatic vinyl compound such as styrene, a methacrylic acid ester, an acrylic acid ester, acrylonitrile, or methacrylonitrile onto rubber particles, usually vulcanized rubber particles.

[0023] Examples of the rubber particles include conjugated diene rubbers such as butadiene rubber and styrene-butadiene rubber, acrylic rubbers such as (meth)acrylate rubber, and olefin rubbers such as ethylene-propylene rubber and ethylene-propylene-diene rubber. In this specification, "(meth)acrylate" refers to an acrylic ester or a methacrylic ester.

[0024] Examples of the methacrylic acid ester include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate.

[0025] Examples of the acrylic acid ester include alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate.

[0026] Examples of the core-shell rubber of component (B) include methacrylate ester / butadiene rubber graft copolymer, methacrylate ester-styrene / butadiene rubber graft copolymer, methacrylate ester / styrene-butadiene rubber graft copolymer, methacrylate ester-styrene / styrene-butadiene rubber graft copolymer, acrylonitrile-styrene / butadiene rubber graft copolymer, acrylonitrile-styrene / styrene-butadiene rubber graft copolymer, acrylonitrile-styrene / ethylene-propylene rubber graft copolymer, acrylonitrile-styrene / acrylate rubber graft copolymer, methacrylate ester / acrylate rubber graft copolymer, methacrylate ester-styrene / acrylate rubber graft copolymer, and methacrylate ester-acrylonitrile / acrylate rubber graft copolymer.

[0027] From the viewpoint of weather resistance, the component (B) core-shell rubber may preferably contain an acrylic core-shell rubber in which a (meth)acrylate rubber is graft-copolymerized with a (meth)acrylate ester, acrylonitrile, styrene, etc. Examples of the acrylic core-shell rubber include an acrylonitrile-styrene / acrylate rubber graft copolymer, a methacrylate / acrylate rubber graft copolymer, a methacrylate-styrene / acrylate rubber graft copolymer, and a methacrylate-acrylonitrile / acrylate rubber graft copolymer.

[0028] As the component (B) core-shell rubber, one or more of these can be used.

[0029] The amount of the component (B) core-shell rubber is an optional component and is not particularly limited as long as it does not detract from the objectives of the present invention. The amount of the component (B) core-shell rubber may typically be 0 to 40% by mass (100 to 60% by mass of the component (A)), where the sum of the amount of the component (A) polyvinyl chloride resin and the amount of the component (B) core-shell rubber is taken as 100% by mass. From the viewpoint of reliably obtaining an improved effect on film formability by calendar roll rolling and from the viewpoint of weather resistance, the amount of the component (B) core-shell rubber may preferably be 1% by mass or more (99% by mass or less of the component (A)), more preferably 3% by mass or more (97% by mass or less of the component (A)), and even more preferably 5% by mass or more (95% by mass or less of the component (A)). On the other hand, from the viewpoint of the mechanical properties of the film, it may be preferably 30% by mass or less (70% by mass or more of the component (A)), more preferably 20% by mass or less (80% by mass or more of the component (A)), and even more preferably 15% by mass or less (85% by mass or more of the component (A)). Furthermore, when a transparent film is desired as the (α) polyvinyl chloride resin composition film, from the viewpoint of transparency, it may be preferably 12% by mass or less (88% by mass or more of the component (A)), and more preferably 10% by mass or less (90% by mass or more of the component (A)).

[0030] (C) Barium-zinc complex compound: The polyvinyl chloride resin composition contains the barium-zinc complex compound (component (C)). The barium-zinc complex compound (component (C)) serves as a stabilizer for the polyvinyl chloride resin composition, typically functioning to scavenge free chlorine.

[0031] Examples of the above-mentioned component (C) barium-zinc complex compound include an organic acid barium-zinc complex salt containing barium, zinc, and an organic acid, and a mixture of a barium salt of an organic acid and a zinc salt of an organic acid.

[0032] Examples of the organic acid include saturated fatty acids, unsaturated fatty acids, and aromatic carboxylic acids.

[0033] Examples of the saturated fatty acids include linear saturated fatty acids such as caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and 12-hydroxystearic acid; branched saturated fatty acids such as 2-ethylhexanoic acid and 2-ethyloctanoic acid; and saturated fatty acids having an alicyclic ring such as cyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, and 4-ethylcyclohexanecarboxylic acid.

[0034] Examples of the unsaturated fatty acids include monounsaturated fatty acids such as crotonic acid, ricinoleic acid, oleic acid, behenic acid, and erucic acid; diunsaturated fatty acids such as linoleic acid; and triunsaturated fatty acids such as linolenic acid.

[0035] Examples of the aromatic carboxylic acid include benzoic acid, toluic acid, ethylbenzoic acid, isopropylbenzoic acid, 3-tert-butylbenzoic acid, 4-tert-butylbenzoic acid, 3,5-di-tert-butylbenzoic acid, salicylic acid, 5-tert-butylsalicylic acid, 3,5-di-tert-butylsalicylic acid, and naphthenic acid.

[0036] As the above-mentioned component (C) barium-zinc complex compound, an organic acid barium-zinc complex salt containing barium, zinc, and one or more of the above-mentioned organic acids, and a mixture of one or more barium salts of the above-mentioned organic acids and one or more zinc salts of the above-mentioned organic acids can be used.

[0037] The amount of the barium-zinc composite compound (C) may be typically 0.01 part by mass or more, preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and even more preferably 1 part by mass or more, per 100 parts by mass of the resin mixture consisting of the polyvinyl chloride resin (A) and the core-shell rubber (B) from the viewpoints of suppressing discoloration due to heat aging, thermal stability, and color stability over time. On the other hand, from the viewpoint of bloom resistance, the amount may be preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and even more preferably 5 parts by mass or less.

[0038] (D) Metal perchlorates: The polyvinyl chloride resin composition contains the component (D), a metal perchlorate. The component (D), a metal perchlorate, acts to strongly inhibit discoloration due to thermal aging. Without intending to be bound by theory, it is believed that the component (D), a metal perchlorate, strongly inhibits the generation of colored substances due to the antagonism between the components in the (α) polyvinyl chloride resin composition film and the components in the (β) fluorine-based resin cured coating film through a synergistic effect with the component (C), a barium-zinc complex compound.

[0039] Examples of the metal perchlorate salt of component (D) include sodium perchlorate, potassium perchlorate, calcium perchlorate, barium perchlorate, aluminum perchlorate, and zinc perchlorate. The metal perchlorate salt of component (D) may preferably include one or more selected from the group consisting of sodium perchlorate and barium perchlorate.

[0040] As the component (D), metal perchlorate, one or more of these can be used.

[0041] The blending amount of the component (D) metal perchlorate may be usually 0.01 part by mass or more, preferably 0.05 part by mass or more, more preferably 0.1 part by mass or more, per 100 parts by mass of the resin mixture consisting of the component (A) polyvinyl chloride resin and the component (B) core-shell rubber, from the viewpoints of suppressing discoloration due to heat aging, thermal stability, and color stability over time. On the other hand, from the viewpoint of bloom resistance, the blending amount may be preferably 5 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 1 part by mass or less, and even more preferably 0.6 parts by mass or less.

[0042] (E) β-diketone compounds: In one preferred embodiment, the polyvinyl chloride resin composition may further contain the component (E) β-diketone compound. The component (E) β-diketone compound is an organic compound having a structure (-CO-C-CO-) in which two ketones are bonded via one carbon atom. Without intending to be bound by theory, it is believed that the component (E) β-diketone compound assists and strengthens the synergistic action between the component (C) barium-zinc complex compound and the component (D) metal perchlorate, thereby further suppressing the generation of colored substances due to antagonism between the components in the (α) polyvinyl chloride resin composition film and the components in the (β) fluorine-based resin cured coating film.

[0043] Examples of the component (E) β-diketone compound include acetylacetone, triacetylmethane, 2,4,6-heptatrione, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, distearoylmethane, stearoylacetylmethane, phenylacetylacetylmethane, dicyclohexylcarbonylmethane, benzoylformylmethane, benzoylacetylmethane, dibenzoylmethane, octylbenzoylmethane, bis(4-octylbenzoyl)methane, benzo methylbenzoyldiacetylmethane, 4-methoxybenzoylbenzoylmethane, bis(4-carboxymethylbenzoyl)methane, 2-carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, ethyl acetoacetate, cyclohexane-1,3-dione, methyl 3,6-dimethyl-2,4-dioxycyclohexane-1-carboxylate, 2-acetylcyclohexanone, dimedone, and 2-benzoylcyclohexane, as well as metal salts thereof such as lithium salts, sodium salts, potassium salts, calcium salts, zinc salts, magnesium salts, and aluminum salts.

[0044] From the viewpoints of inhibiting discoloration due to thermal aging, thermal stability, and color stability over time, the component (E) β-diketone compound may preferably contain one or more compounds selected from the group consisting of dibenzoylmethane, stearoylbenzoylmethane, derivatives of dibenzoylmethane, and derivatives of stearoylbenzoylmethane.

[0045] As the component (E), the β-diketone compound, one or more of these can be used.

[0046] The amount of the β-diketone compound (E) is an optional component and is not particularly limited as long as it does not interfere with the object of the present invention. From the viewpoint of ensuring the desired effect of use, the amount of the β-diketone compound (E) is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and even more preferably 0.05 parts by mass or more, per 100 parts by mass of the resin mixture consisting of the polyvinyl chloride resin (A) and the core-shell rubber (B). On the other hand, from the viewpoint of weather resistance, the amount is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less.

[0047] (F) Plasticizer: In one embodiment, the polyvinyl chloride resin composition may further contain a plasticizer (F). The plasticizer (F) is not particularly limited as long as it is a plasticizer that is commonly used in polyvinyl chloride resin compositions.

[0048] Examples of the component (F) plasticizer include phthalate ester-based plasticizers, trimellitate ester-based plasticizers, pyromellitate ester-based plasticizers, adipate ester-based plasticizers, itaconate ester-based plasticizers, citrate ester-based plasticizers, cyclohexanedicarboxylate-based plasticizers, and epoxy-based plasticizers.

[0049] Examples of the component (F) plasticizer include polyester-based plasticizers obtained by using, as a polyhydric alcohol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol, etc., and as a polycarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, trimellitic acid, pimelic acid, suberic acid, maleic acid, azelaic acid, sebacic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, etc., and, if necessary, using a monohydric alcohol or a monocarboxylic acid as a stopper.

[0050] Examples of the phthalate ester plasticizer include dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate.

[0051] Examples of the trimellitic acid ester plasticizer include tri(2-ethylhexyl) trimellitate, tri(n-octyl) trimellitate, and tri(isononyl) trimellitate.

[0052] Examples of the adipate plasticizer include bis(2-ethylhexyl) adipate, di-n-octyl adipate, diisononyl adipate, and diisodecyl adipate.

[0053] Examples of the epoxy plasticizer include epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid octyl ester, and epoxidized fatty acid alkyl ester.

[0054] Other examples of the component (F) plasticizer include trimellitic acid-based plasticizers, tetrahydrophthalic acid diester-based plasticizers, glycerin ester-based plasticizers, epoxy hexahydrophthalic acid diester-based plasticizers, isosorbide diester-based plasticizers, phosphate-based plasticizers, azelaic acid-based plasticizers, sebacic acid-based plasticizers, stearic acid-based plasticizers, citric acid-based plasticizers, pyromellitic acid-based plasticizers, biphenyl tetracarboxylic acid ester-based plasticizers, and chlorine-based plasticizers.

[0055] As the component (F) plasticizer, one or more of these can be used.

[0056] The amount of the plasticizer (F) is an optional component and is not particularly limited as long as it does not detract from the objectives of the present invention. From the viewpoint of film-forming properties by calender roll rolling, the amount of the plasticizer (F) may be preferably 1 part by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, per 100 parts by mass of the resin mixture consisting of the polyvinyl chloride resin (A) and the core-shell rubber (B). On the other hand, from the viewpoints of suppressing problems due to plasticizer migration, printability, and blocking resistance, the amount may be usually 250 parts by mass or less, preferably 150 parts by mass or less, more preferably 100 parts by mass or less, even more preferably 60 parts by mass or less, still more preferably 45 parts by mass or less, and most preferably 35 parts by mass or less.

[0057] (G) UV absorber: In one embodiment, the polyvinyl chloride resin composition may further contain (G) an ultraviolet absorber. Here, the component (G) ultraviolet absorber does not include any of the compounds corresponding to any of the components (A) to (F) that have an ultraviolet absorbing function. In other words, any compound corresponding to any of the components (A) to (F) is excluded from the component (G) ultraviolet absorber.

[0058] Examples of the component (G) ultraviolet absorber include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, aromatic benzoate-based ultraviolet absorbers, and anilide oxalate-based ultraviolet absorbers.

[0059] Examples of the benzotriazole-based ultraviolet absorbers include 2-(5-chloro-2H-benzotriazole-2-yl)-4-methyl-6-tert-butylphenol, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], and 2-(2H-benzotriazole-2-yl)-p-cresol.

[0060] Examples of the triazine-based ultraviolet absorber include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

[0061] Examples of the benzophenone-based ultraviolet absorbers include [2-hydroxy-4-(octyloxy)phenyl](phenyl)methaneone, 2,2',4,4'-tetrahydroxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

[0062] Examples of the cyanoacrylate ultraviolet absorber include ethyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, and pentaerythritol tetrakis(3,3-diphenyl-2-cyanoacrylate).

[0063] Examples of the aromatic benzoate-based ultraviolet absorbers include 4-tert-butylphenyl salicylate, 4-octylphenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, and hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate.

[0064] Examples of the oxalic acid anilide ultraviolet absorbers include 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide.

[0065] As the component (G) ultraviolet absorber, one or more of these can be used.

[0066] The amount of the component (G) ultraviolet absorber is not particularly limited as long as it does not detract from the objectives of the present invention. From the viewpoints of color stability over time and weather resistance, the amount of the component (G) ultraviolet absorber may be preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, per 100 parts by mass of the resin mixture consisting of the component (A) polyvinyl chloride resin and the component (B) core-shell rubber. On the other hand, from the viewpoint of preventing problems such as bleeding out of the component (G) ultraviolet absorber onto the film surface, the amount may be preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and most preferably 1 part by mass or less.

[0067] The polyvinyl chloride resin composition may further contain optional components other than the components (A) to (G) as desired, provided that the objectives of the present invention are not adversely affected. Examples of such optional components include thermoplastic resins other than the component (A) polyvinyl chloride resin and the component (B) core-shell rubber; softeners other than the component (F) plasticizers commonly used in polyvinyl chloride resin compositions, such as paraffin oil; additives other than the component (C) barium-zinc complex compound, the component (D) metal perchlorate salt, the component (E) β-diketone compound, and the component (G) ultraviolet absorber; and colorants, fillers, and flame retardants.

[0068] Examples of the other thermoplastic resins include poly(meth)acrylic acid esters, styrene-(meth)acrylic acid ester copolymers, ethylene-vinyl acetate copolymers, ethylene-(meth)acrylic acid copolymers, ethylene-methyl (meth)acrylate copolymers, ethylene-ethyl (meth)acrylate copolymers, thermoplastic polyesters, thermoplastic polyamides, and thermoplastic polyurethanes.

[0069] Examples of the other additives include heat stabilizers such as calcium-zinc complex compounds and hydrotalcite; antioxidants such as hindered phenol antioxidants, phosphite antioxidants, thioether antioxidants, and amine antioxidants; weather resistance stabilizers such as antioxidants and light stabilizers; lubricants such as acid amides, fatty acids, fatty acid esters, fatty acid metal salts, waxes such as polyethylene wax, silicone oils, and modified silicone oils; nucleating agents such as aromatic phosphate metal salts and gelols; antistatic agents such as glycerin fatty acid esters; and mold release agents, processing aids, and antifouling agents.

[0070] Examples of the colorant include inorganic colorants such as titanium dioxide (titania), red iron oxide, ultramarine (ultramarine blue), and carbon black; and organic colorants such as aniline black, quinacridone red, isoindolinone yellow, and phthalocyanine blue.

[0071] Examples of the filler include inorganic fillers such as calcium carbonate, silica (silicon dioxide), talc, mica, clay, hydrotalcite, and zeolite; and organic fillers such as crosslinked acrylic resin particles.

[0072] Examples of the flame retardant include antimony-based flame retardants, halogen-based flame retardants, metal hydroxides, zinc-based flame retardants, organic phosphate ester-based flame retardants, and nitrogen-containing compound-based flame retardants.

[0073] As the other optional components, one or more of these can be used.

[0074] The amount of the other optional components is not particularly limited as long as it does not interfere with the object of the present invention. The amount of the other optional components may be typically 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, 0 to 1 part by mass, or about 0.01 to 50 parts by mass, relative to 100 parts by mass of the resin mixture consisting of the polyvinyl chloride resin (Component (A)) and the core-shell rubber (Component (B)).

[0075] In one embodiment, the polyvinyl chloride resin composition may not contain any one or more of the other optional components described above.

[0076] As used herein, "not containing a certain component" means that the component is not intentionally blended. In the technical field of polyvinyl chloride resin compositions, when a component is intentionally blended, it is typically blended in an amount of 0.01 part by mass or more. Therefore, "not containing a certain component" can also be rephrased as meaning that the content of the component is typically less than 0.01 part by mass, preferably 0.001 part by mass or less, and more preferably 0 to 0.0001 part by mass, per 100 parts by mass of a resin mixture consisting of the polyvinyl chloride resin (Component (A)) and the core-shell rubber (Component (B)).

[0077] From the viewpoint of conforming to environmental regulations such as the European REACH regulation, the polyvinyl chloride resin composition may not contain any lead-based heat stabilizer or cadmium-based heat stabilizer, and preferably may not contain any organotin compound-based stabilizer such as dibutyltin maleate.

[0078] Preparation of polyvinyl chloride resin composition: The polyvinyl chloride resin composition can be obtained by using any melt kneader to charge the components (A), (C), and (D), and any optional components used as desired, simultaneously or in any order into the melt kneader and melt kneading, preferably at a resin temperature of 120 to 200°C.

[0079] Examples of the melt kneader include batch kneaders such as pressure kneaders and mixers, extrusion kneaders such as single-screw extruders, co-rotating twin-screw extruders, and counter-rotating twin-screw extruders, and calendar roll kneaders. These may be used in any combination.

[0080] The resulting resin composition can be pelletized by any method and then formed into the polyvinyl chloride resin composition film (α) by any method, such as hot cutting, strand cutting, or underwater cutting.

[0081] In one embodiment, the polyvinyl chloride resin composition in the form of a block, rod, or strand discharged from the melt kneader may be sent directly to any film-forming device to form the polyvinyl chloride resin composition film (α).

[0082] (α) Formation of polyvinyl chloride resin composition film: The polyvinyl chloride resin composition film (α) can be obtained by forming the polyvinyl chloride resin composition using any film forming apparatus, such as a calender roll rolling film forming apparatus equipped with a calender roll processing machine and a winding device, or a T-die film forming apparatus equipped with an extruder, a T-die, and a winding device.

[0083] Examples of the calender roll rolling machine include an upright three-roll machine, an upright four-roll machine, an L-shaped four-roll machine, an inverted L-shaped four-roll machine, and a Z-roll machine. Examples of the extruder include a single-screw extruder, a co-rotating twin-screw extruder, and a counter-rotating twin-screw extruder. Examples of the T-die include a manifold die, a fishtail die, and a coat hanger die.

[0084] The (α) polyvinyl chloride resin composition film can be obtained by using the polyvinyl chloride resin composition and preferably forming the film using a calendar roll rolling film forming apparatus, more preferably by forming the film using a calendar roll rolling film forming apparatus under conditions of a roll temperature of 160°C to 200°C.

[0085] The thickness of the (α) polyvinyl chloride resin composition film can be appropriately determined taking into consideration film-forming properties, the intended use and its required properties, and ease of handling. From the viewpoints of film-forming properties and ease of handling, the thickness of the (α) polyvinyl chloride resin composition film may be usually 20 μm or more, preferably 30 μm or more, more preferably 40 μm or more, and even more preferably 50 μm or more. On the other hand, from the viewpoint of meeting the demand for thinner articles containing the (α) polyvinyl chloride resin composition film, the thickness may be usually 1000 μm or less, preferably 500 μm or less, more preferably 200 μm or less, and even more preferably 150 μm or less.

[0086] The (α) polyvinyl chloride resin composition film may be transparent, opaque, colored and transparent, or colored and opaque or concealing.

[0087] When the (α) polyvinyl chloride resin composition film is transparent, the laminate film of the present invention can be suitably used as a material for constituting a decorative film having, from the surface, the (β) fluororesin cured coating film, a layer of the transparent (α) polyvinyl chloride resin composition film, a printed layer, and a concealing film substrate layer. When the (α) polyvinyl chloride resin composition film is colored and opaque or has concealing properties, the laminate film of the present invention can be suitably used as a decorative film having, from the surface, the (β) fluororesin cured coating film and a layer of the (α) polyvinyl chloride resin composition film colored in a desired color.

[0088] (β) Fluororesin cured coating: The laminate film of the present invention has the above-mentioned (β) fluororesin cured coating film on at least one surface of the above-mentioned (α) polyvinyl chloride resin composition film. In one typical embodiment, the above-mentioned (β) fluororesin cured coating film forms the surface of the decorative film including the laminate film of the present invention and functions to impart weather resistance, water and oil repellency, and waterproof and moisture proof properties.

[0089] The (β) fluororesin cured coating film can be formed using a coating material containing a fluororesin. In one typical embodiment, the (β) fluororesin cured coating film can be formed using a coating material containing a fluororesin having a crosslinkable functional group and a curing agent reactive with the crosslinkable functional group.

[0090] The fluororesin is a resin having a fluorine-carbon bond. Examples of the fluororesin used in the coating material for forming the (β) fluororesin cured coating film include polymers (including copolymers) of fluorine-containing monomers, and copolymers of fluorine-containing monomers with hydroxyl group-containing monomers and / or carboxyl group-containing monomers.

[0091] Examples of the fluorine-containing monomer include fluoroolefins and perfluoroalkyl vinyl ethers.

[0092] The fluoroolefin is a compound having a structure in which one or more hydrogen atoms of an α-olefin are substituted with fluorine atoms. Examples of the fluoroolefin include tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, hexafluoropropylene, pentafluoropropylene, tetrafluoropropylene, trifluoropropylene, and chlorotrifluoroethylene.

[0093] The perfluoroalkyl vinyl ether is a compound represented by the following general formula (1). CF2=CFOR (1) In the formula, R is a perfluoroalkyl group having 1 to 8 carbon atoms, or an ω-hydroperfluoroalkyl group, or a poly(perfluoroalkyleneoxy)fluoroalkyl group.

[0094] As the fluorine-containing monomer, one or more of these can be used.

[0095] The hydroxyl group-containing monomer is a monomer in which a hydroxyl group and an ethylenically unsaturated group are linked directly or via an ether bond or an ester bond. Examples of the hydroxyl group-containing monomer include (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl methacrylate, and 4-hydroxybutyl acrylate; hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, and 4-hydroxybutyl vinyl ether; and alkylene glycol monovinyl ethers such as diethylene glycol monovinyl ether.

[0096] The carboxyl group-containing monomer is a monomer in which a carboxyl group and an ethylenically unsaturated group are linked directly or via an ether bond or an ester bond. Examples of the carboxyl group-containing monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, and ethacrylic acid; and ether group-containing unsaturated monocarboxylic acids such as 3-allyloxypropionic acid.

[0097] As the hydroxyl group-containing monomer and / or the carboxy group-containing monomer, one or more of these can be used.

[0098] The polymer (including copolymer) of the fluorine-containing monomer and the copolymer of the fluorine-containing monomer with the hydroxyl group-containing monomer and / or the carboxy group-containing monomer may contain structural units derived from other monomers, if desired, to the extent that the object of the present invention is not violated.

[0099] Examples of the other monomers include α-olefins such as ethylene, propylene, and 1-butene; alkyl vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether; unsaturated monocarboxylic acid alkyl esters such as (meth)acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate; and vinyl acetate. As the other monomers, one or more of these can be used.

[0100] The fluororesin may preferably contain a fluororesin having a hydroxyl group, and the hydroxyl value of the fluororesin having a hydroxyl group may be preferably 1 to 200 mgKOH / g, more preferably 10 to 160 mgKOH / g.

[0101] The fluorine resin can be obtained by polymerizing (copolymerizing) the above-mentioned fluorine-containing monomer, or the above-mentioned fluorine-containing monomer and the above-mentioned hydroxyl group-containing monomer and / or the above-mentioned carboxyl group-containing monomer, and, if desired, further using the above-mentioned other monomers, by a known polymerization method such as solution polymerization, emulsion polymerization, or suspension polymerization.

[0102] As the fluororesin, one or more of these can be used.

[0103] The curing agent may be, for example, a compound having two or more crosslinkable functional groups per molecule, such as an isocyanate group, an epoxy group, a carbodiimide group, an oxazoline group, a hydroxyl group, a carboxyl group, a carbamoyl group, an amine group, an amide group, or a nitrile group.

[0104] When the fluororesin has a hydroxyl group, the curing agent may preferably contain a compound having two or more isocyanate groups per molecule. The hydroxyl group of the fluororesin reacts with the isocyanate group of the compound having two or more isocyanate groups per molecule to form a urethane bond, thereby imparting moldability to the cured coating film when decorating or decorating the surface of a structural member using a decorative film. This embodiment is particularly effective when the surface of the structural member has a three-dimensional shape, such as an uneven surface.

[0105] Examples of the compound having two or more isocyanate groups in one molecule include compounds having two isocyanate groups in one molecule, such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, methylenebis-4-cyclohexyl isocyanate, and diphenylmethane diisocyanate; and trimethylolpropane adducts of compounds having two isocyanate groups in one molecule, such as trimethylolpropane adducts of tolylene diisocyanate, trimethylolpropane adducts of hexamethylene diisocyanate, and trimethylolpropane adducts of isophorone diisocyanate. compounds having three isocyanate groups per molecule; isocyanurate forms of compounds having two isocyanate groups per molecule, such as isocyanurates of tolylene diisocyanate, isocyanurates of hexamethylene diisocyanate, and isocyanurates of isophorone diisocyanate, compounds having three isocyanate groups per molecule; biuret forms of compounds having two isocyanate groups per molecule, such as biuret forms of hexamethylene diisocyanate; and blocked polyisocyanates thereof.

[0106] From the viewpoint of molding processability when decorating and decorating the surface of a structural member using a decorative film, and weather resistance, the compound having two or more isocyanate groups in one molecule is preferably a trimethylolpropane adduct of a compound having two isocyanate groups in one molecule, which has three isocyanate groups in one molecule; an isocyanurate of a compound having two isocyanate groups in one molecule, which has three isocyanate groups in one molecule; and a biuret of a compound having two isocyanate groups in one molecule, which has three isocyanate groups in one molecule. The compound may contain one or more compounds selected from the group consisting of a trimethylolpropane adduct of hexamethylene diisocyanate having three isocyanate groups in one molecule, an isocyanurate of hexamethylene diisocyanate having three isocyanate groups in one molecule, and a biuret of hexamethylene diisocyanate having three isocyanate groups in one molecule.

[0107] Without intending to be bound by theory, it is believed that these films have a structural feature in which isocyanate groups are located at distant positions at the ends of hexamethylene chains, which results in an appropriate crosslink density and excellent moldability and weather resistance when using decorative films to decorate and decorate the surface of structural components. Therefore, it is believed that films that have a similar structural feature in which isocyanate groups are located at distant positions at the ends of alkyl chains can also be used preferably.

[0108] As the curing agent, one or more of these can be used.

[0109] When the curing agent is used, the amount of the curing agent to be added can be determined appropriately, taking into consideration the types of the fluororesin and the curing agent, from the viewpoint of ensuring that the crosslinkable functional groups of the curing agent are consumed in the curing reaction and do not remain unreacted in the coating film, and from the viewpoint of ensuring that the crosslinking reaction proceeds sufficiently.

[0110] An example will be described in which the fluororesin is a fluororesin having hydroxyl groups and the curing agent is a compound having two or more isocyanate groups per molecule. The ratio (q / p) of the number of isocyanates (q) derived from the compound having two or more isocyanate groups per molecule in the coating material to the number of hydroxyl groups (p) derived from the fluororesin having hydroxyl groups is preferably 2.0 or less, more preferably 1.6 or less, even more preferably 1.4 or less, and even more preferably 1.2 or less, from the viewpoint of preventing unreacted isocyanate groups from remaining in the coating film. On the other hand, from the viewpoint of sufficiently progressing the crosslinking reaction, it is preferably 0.1 or more, more preferably 0.3 or more, even more preferably 0.5 or more, and even more preferably 0.7 or more. For example, when the hydroxyl value of the fluororesin having hydroxyl groups is 5.6 mgKOH / g (the number of hydroxyl groups per unit amount is 0.10 mol / kg) and the number of isocyanate groups per unit amount of the compound having two or more isocyanate groups in one molecule is 1.0 mol / kg, the amount of the compound having isocyanate groups can be calculated to be preferably 1 to 20 parts by mass, more preferably 3 to 16 parts by mass, even more preferably 5 to 14 parts by mass, and still more preferably 7 to 12 parts by mass per 100 parts by mass of the fluororesin.

[0111] The (β) coating material for forming a cured fluorine resin coating film may contain an organometallic catalyst, which can accelerate the curing reaction. Examples of the organometallic catalyst include organotin compounds such as dibutyltin laurate, organoaluminum compounds such as aluminum trisacetylacetonate, organozirconium compounds such as tetra-n-propoxyzirconium, and organotitanium compounds such as tetra-i-propoxytitanium. One or more of these may be used as the organometallic catalyst.

[0112] The (β) coating material for forming a cured fluorine resin coating film may further contain a solvent from the viewpoint of productivity when forming a wet coating film. Examples of the solvent include water, methanol, ethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 2-ethylhexyl glycol, and 2-ethylhexyl diglycol. One or more of these solvents can be used as the solvent.

[0113] The (β) coating material for forming a fluorine resin cured coating film may further contain optional components other than the fluorine resin, the curing agent, and the organometallic catalyst, as desired, within the scope of the object of the present invention. Examples of the optional components include antifoaming agents, leveling agents, surfactants, thixotropy-imparting agents, antistatic agents, printability improvers, antioxidants, weather resistance stabilizers, light resistance stabilizers, ultraviolet absorbers, heat stabilizers, inorganic colorants, organic colorants, inorganic fillers such as silica (silicon dioxide), and organic fillers such as crosslinked acrylic resin particles.

[0114] As the optional component, one or more of these may be used.

[0115] The amount of the optional components is not particularly limited as long as it does not contradict the object of the present invention. In one embodiment, the amount of the optional components may be 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, 1 part by mass or less, 0.5 parts by mass or less, 0 to 0.5 parts by mass, or about 0.01 to 50 parts by mass, relative to 100 parts by mass of the fluororesin.

[0116] In one embodiment, the coating material for forming a cured fluororesin coating film (β) may not contain any one or more of the optional components described above.

[0117] In this specification, "not containing a certain component" means that the component is not intentionally blended. In the technical field of paints, when a component is intentionally blended, it is usually blended in an amount of 0.001 part by mass or more. Therefore, "not containing a certain component" can also be rephrased as meaning that the content of the component is usually less than 0.001 part by mass, preferably 0 to 0.0001 part by mass, per 100 parts by mass of the fluororesin.

[0118] The coating material (β) for forming a cured fluororesin coating film can be obtained by mixing and stirring these components.

[0119] The method for forming the (β) fluororesin cured coating film on the surface of the (α) polyvinyl chloride resin composition film using the (β) fluororesin cured coating film-forming coating material is not particularly limited, and any known web coating method can be used. Examples of the web coating method include rod coating, roll coating, gravure coating, reverse coating, kiss reverse coating, dip coating, spray coating, spin coating, air knife coating, and die coating. Among these methods, rod coating, roll coating, gravure coating, reverse coating, kiss reverse coating, and die coating are preferred from the viewpoint of applying the coating material productively by the roll-to-roll method.

[0120] The thickness of the (β) fluororesin cured coating film is not particularly limited as long as it does not contradict the object of the present invention. From the viewpoint of reliably achieving the purpose of forming the coating film, the thickness of the (β) fluororesin cured coating film may be preferably 0.5 μm or more, more preferably 1.0 μm or more, even more preferably 2.0 μm or more, and even more preferably 3.0 μm or more. On the other hand, from the viewpoint of productivity in forming the (β) fluororesin cured coating film, the thickness may be preferably 100 μm or less, more preferably 60 μm or less, even more preferably 30 μm or less, even more preferably 20 μm or less, and most preferably 15 μm or less.

[0121] 2.Decorative film: The decorative film of the present invention includes the laminate film of the present invention. The decorative film of the present invention usually has a surface formed by the (β) fluororesin cured coating film of the laminate film of the present invention. Here, the "surface" means the surface that is normally visible when the decorative film is used for the make-up and decoration of a structural member (hereinafter sometimes referred to as "actual use state").

[0122] In one embodiment, the decorative film of the present invention may have, from the surface, the above-mentioned (β) fluorine resin cured coating film, the above-mentioned (α) polyvinyl chloride resin composition film layer which is a transparent layer, a printed layer, and a concealing film substrate layer.

[0123] In another embodiment, the decorative film of the present invention may have, in order from the surface, the above-mentioned (β) fluorine resin cured coating film and the above-mentioned (α) polyvinyl chloride resin composition film layer, which is colored in a desired color and has hiding properties.

[0124] 1 is a cross-sectional conceptual diagram showing one embodiment of the decorative film of the present invention, which comprises, from the surface, a (β) fluorine resin cured coating film 1, a transparent (α) polyvinyl chloride resin composition film layer 2, a printed layer 3, a concealable film substrate layer 4, and an adhesive layer 5.

[0125] 3. Goods: The article of the present invention includes the decorative film of the present invention. In one preferred embodiment, the article of the present invention is an article such as an automobile, a building, furniture, or a home appliance (including parts of the article; the same applies hereinafter), in which the decorative film of the present invention is applied to the surface of a structural member constituting the article.

[0126] Examples of methods for applying the decorative film of the present invention to the surface of the structural member include flat lamination molding, wrapping molding, vacuum molding, pressure molding, vacuum pressure molding, membrane press molding, in-mold molding, insert molding, and overlay vacuum molding. The method for applying the decorative film of the present invention to the surface of the structural member can be appropriately selected taking into consideration the surface shape of the structural member (whether it is smooth or has a three-dimensional shape such as unevenness) and the type of product.

[0127] This section describes an example of applying a decorative film to the surface of a structural member having a three-dimensional shape, such as an uneven surface, by vacuum forming. Figure 2 is a conceptual diagram showing an example of a vacuum forming device. First, as shown in Figure 2(a), the decorative film 11 is heated and softened using a heating device 12, such as an infrared heater. Next, the decorative film 11 is removed from the heating device 12 and quickly placed over the structural member 13 (Figure 2(b)). At this time, the surface of the decorative film 11 opposite the (β) fluorine resin cured coating film is to be attached to the structural member 13. The structural member 13 may also be preheated. Next, the space 14 between the decorative film 11 and the structural member 13 is depressurized, and the decorative film 11 is brought into close contact with the structural member 13, resulting in an article 15 in which the decorative film 11 is attached to the structural member 13 (Figure 2(c)).

[0128] The pressure in the space 14 may be preferably 10 KPa or less, more preferably 1 KPa or less, from the viewpoint of ensuring sufficient adhesion without leaving any air between the decorative film 11 and the structural member 13. The adhesion force increases as the pressure in the space 14 decreases, but considering the mechanical strength of the decorative film 11 and the structural member 13 and the fact that reducing the pressure increases costs exponentially, the lower limit of the pressure in the space 14 is practically 10 -5 It may be about KPa. [Example]

[0129] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0130] Measurement method (a) Color difference (discoloration resistance): (A-1) Measurement of L*a*b* coordinates of laminated film before processing: The L*a*b* coordinates of the film before processing were calculated in accordance with JIS Z8722:2009 using a spectrophotometer "CM600d (product name)" manufactured by Konita Minolta Japan Co., Ltd., by placing the laminate film on the surface of a white plate identical to the white calibration plate included in the spectrophotometer, with the surface of the laminate film having the (β) fluororesin cured coating film facing the incident side of the colorimetry light, and measuring the XYZ coordinates under geometric condition c, conditions including components that cause specular reflection, and then converting these to calculate the L*a*b* coordinates. For information on measuring L*a*b* coordinates, please refer to the Konita Minolta Japan Co., Ltd. website (address below). http: / / www.konicaminolta.jp / instruments / knowledge / color / part1 / 07.html

[0131] (A-2) Processing of laminated film: The laminated film was treated in a Geer oven (humidity was not controlled) at a temperature of 80° C. for 500 hours.

[0132] (A-3) Calculation of color difference (ΔE) before and after processing: The L*a*b* coordinates of the laminated film after the treatment were determined in the same manner as in (a-1) above for the measurement of the L*a*b* coordinates of the laminated film before treatment. Next, the color difference (ΔE) was calculated as an index of color fastness from the L*a*b* coordinates of the laminated film before treatment and the L*a*b* coordinates of the laminated film after treatment using the calculation method (ΔE*ab (CIE 1976)) built into the spectrophotometer.

[0133] (b) Cross-cut test (paint adhesion): According to JIS K5600-5-6:1999, 100 grids (1 grid = 1 mm x 1 mm) were cut into the laminated film on the (β) fluororesin cured coating side, and adhesion test tape was attached to the grids, rubbed with a finger, and then peeled off. The evaluation criteria were in accordance with Table 1 of the above JIS standard. Category 0: The edges of the cut are completely smooth and there are no peeling marks on any of the grids. Category 1: Small peeling of the coating at the intersection of the cuts. The cross-cut area affected does not appreciably exceed 5%. Category 2: The coating is peeling along the edges of the cuts and / or at the intersections. The cross-cut area is clearly more than 5% but not more than 15% affected. Category 3: The coating has partially or completely peeled off significantly along the edges of the cuts and / or partially or completely peeled off in various areas of the mesh. The cross-cut area is clearly more than 15% affected but not more than 35%. Category 4: The coating has partially or completely peeled off significantly along the edges of the cuts and / or partially or completely peeled off in several sections. The cross-cut area is clearly more than 35% affected but not more than 65%. Category 5: When the degree of peeling exceeds Category 4.

[0134] Raw materials used (A) Polyvinyl chloride resin: (A-1) Polyvinyl chloride homopolymer with a degree of polymerization of 800.

[0135] (B) Core-shell rubber: (B-1) Mitsubishi Chemical Corporation's core-shell rubber (methyl methacrylate-styrene / ethyl acrylate rubber graft copolymer) "Metablen W-300A (product name)."

[0136] (C) Barium-zinc complex compound: (C-1) A 2:1:1 (mass ratio) mixture of barium caprate, zinc bis-4-t-butylbenzoate, and zinc bis-p-toluate.

[0137] (D) Metal perchlorates: (D-1) ADEKA Corporation's stabilizer "CPL-37 (trade name)" containing 30% by mass of barium perchlorate. (D-2) ADEKA Corporation's stabilizer "CPL-46 (trade name)" containing 40% by mass of sodium perchlorate.

[0138] (E) β-diketone compounds: (E-1) Dibenzoylmethane. CAS number 120-46-7. (E-2) Stearoylbenzoylmethane. CAS number 58446-52-9

[0139] (F) Plasticizer: (F-1) Diisononyl phthalate "DINP (trade name)" from J-Plus Corporation. (F-2) ADEKA Corporation's epoxidized soybean oil "O-130S (product name)".

[0140] (G) UV absorber: (G-1) Benzotriazole-based UV absorber "Tinuvin 326 (trade name)" from BASF Japan Ltd.

[0141] (H) Other optional ingredients: (H-1) Mitsubishi Chemical Corporation's acrylic processing aid "P-530A (product name)."

[0142] (P) Fluororesin: (P-1) AGC Inc.'s hydroxyl group-containing fluororesin emulsion "Lumiflon FE4400 (trade name)", solid content (content of the fluororesin in the emulsion) 50 mass%, hydroxyl value (value as emulsion) 24.5 mg KOH / g. (P-2) Aqueous dispersion of perfluoroalkyl group-containing fluororesin "Asahiguard AG-E060 (trade name)", solid content (content of the fluororesin in the aqueous dispersion) 20 mass%.

[0143] (Q) Hardener: (Q-1) "No. 21 Curing Agent (trade name)," a biuret compound of hexamethylene diisocyanate from Natoco Corporation, which has three isocyanate groups per molecule, with the number of isocyanate groups per unit amount being 3.24 mol / kg.

[0144] (β) Fluororesin cured coating coating: (β-1) 200 parts by mass of the above component (P-1) (100 parts by mass in terms of solid content), 2.5 parts by mass of the above component (P-2) (0.5 parts by mass in terms of solid content), 25 parts by mass of the above component (Q-1), 8 parts by mass of 2-ethylhexyl diglycol, 8 parts by mass of 2-ethylhexyl glycol, and 280 parts by mass of water were mixed and stirred to prepare a coating material (β-1) for forming a cured fluorine resin coating film.

[0145] Example 1 (1) Formation of polyvinyl chloride resin composition film: A blend consisting of 93 parts by mass of the component (A-1), 7 parts by mass of the component (B-1), 3.50 parts by mass of the component (C-1), 0.50 parts by mass of the component (D-1) (0.15 parts by mass equivalent to barium perchlorate), 17 parts by mass of the component (F-1), 3 parts by mass of the component (F-2), 0.30 parts by mass of the component (G-1), and 2 parts by mass of the component (H-1) was melt-kneaded using a mixer kneader at a discharge resin temperature of 140°C to obtain a polyvinyl chloride resin composition. The resulting mixture was then sent directly to a calendar roll film-forming apparatus equipped with an inverted L-shaped four-roll calendar roll mill and a take-up device, and an 80 μm-thick polyvinyl chloride resin composition film was formed under conditions of a first roll temperature of 180°C, a second roll temperature of 180°C, a third roll temperature of 185°C, and a fourth roll temperature of 180°C, and a take-up speed of 10 m / min.

[0146] (2) Manufacturing of laminated film: On one side of the polyvinyl chloride resin composition film obtained in the above step (1), the above (β-1) fluororesin cured coating film-forming paint was used to form a wet coating film using a roll coating type coating device so that the thickness after curing would be 4.0 μm.The coating film was then passed through a drying oven set at an oven temperature of 100°C at a line speed such that the time required for passing from the entrance to the exit was 2 minutes, thereby drying and curing the coating film, and a laminated film was obtained.

[0147] (3) Evaluation of laminated film: The above tests (a) and (b) were carried out, and the results are shown in Table 1. The amount of the component (D-1) added is shown in the table as a value converted to barium perchlorate.

[0148] Examples 2 to 7 A laminated film was obtained in the same manner as in Example 1, except that the formulation of the polyvinyl chloride resin composition was changed as shown in Table 1. The above tests (a) and (b) were carried out. The results are shown in Table 1. The amount of the component (D-1) is shown in terms of barium perchlorate, and the amount of the component (D-2) is shown in terms of sodium perchlorate.

[0149] [Table 1]

[0150] The laminated film of the present invention is a laminated film in which a cured fluororesin coating film is formed on the surface of a polyvinyl chloride resin composition film, and it has been found that discoloration due to heat aging is suppressed.

[0151] The laminated film of Example 1 was further subjected to the following tests (c) and (e).

[0152] (c) Water contact angle (water repellency): The water contact angle (unit: degrees) of the (β) fluororesin cured coating surface of the laminated film was measured using an automatic contact angle meter "DSA20 (trade name)" manufactured by KRUSS Co., Ltd., according to a method of calculation from the width and height of the water droplet (see JIS R 3257:1999). The result was 93°.

[0153] (4) Dirt removal (oleic acid removal) Oleic acid (reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.) and carbon black "FW-200 (trade name)" manufactured by Orion Engineered Carbons, Inc. were blended in a mass ratio of 10:1 and thoroughly mixed and stirred to prepare a contaminant. Next, 1 mg of the contaminant obtained above was applied to the (β) fluororesin cured coating surface of the laminate film in a 20 mm diameter circle and then rinsed with tap water. Rinsing was performed by simply directing running water at a flow rate of 1 liter per 10 seconds onto the coated contaminant, positioned 10 cm below the tap, for 20 seconds. The coated contaminant was observed to lift and peel off from the (β) fluororesin cured coating surface. The coated contaminant was completely removed from the (β) fluororesin cured coating surface, leaving no trace of the application. Based on these findings, the stain removal ability was determined to be excellent.

[0154] (e) Vacuum formability: (1) Manufacturing of resin substrate: A thermoplastic resin structural component was obtained by injection molding using Techno Polymer Co., Ltd.'s ABS / PC alloy resin "Excelloy CK50 (trade name)" in a 100-ton injection molding machine under the following conditions: cylinder temperature 260°C, mold temperature 70°C, injection speed 250 mm / sec, and holding pressure 50 MPa. Figure 3 shows a photograph of the resulting structural component.

[0155] (2) Formation of adhesive layer: 100 parts by mass of the following component (S-1), 0.6 parts by mass of the following component (T-1), and 20 parts by mass of 1-methoxy-2-propanol were mixed and stirred to obtain a coating material for forming an adhesive layer. Next, the obtained coating material for forming an adhesive layer was applied to the surface of the laminated film opposite the (β) fluororesin cured coating film using a roll coater so that the dried thickness would be 45 μm, and the coating film was dried and cured by passing it through a drying oven set at an oven temperature of 80°C at a line speed such that the time required for passing from the entrance to the exit was 2 minutes, thereby forming an adhesive layer.

[0156] (S) Adhesive: (S-1) Adhesive "SK Dyne 1310 (product name)" from Soken Chemical & Engineering Co., Ltd.

[0157] (T) Hardener: (T-1) Tolylene diisocyanate, CAS number 26471-62-5.

[0158] (3) Manufacture of goods: Using the structural member obtained in (1) above and the laminated film having the adhesive layer obtained in (2) above, a vacuum forming method was used to adhere the adhesive layer of the laminated film having the adhesive layer obtained in (2) above to the surface of the structural member obtained in (1) above, thereby obtaining an article in which the laminated film was adhered to the surface of the structural member. At this time, the pressure in space (4) was 1.0 × 10 -3 The resulting article was conditioned for at least 24 hours at 23°C and 50% relative humidity.

[0159] (4) Evaluation of vacuum formability: The appearance of the article obtained in (3) above was visually observed, and no defects in appearance such as cracks, breaks, blistering, or unevenness were found, and the appearance was very good.

[0160] From these results, it was considered that the decorative film containing the laminated film of the present invention can be suitably used for the decoration and decoration of articles such as automobiles, buildings, furniture, and home appliances. [Brief explanation of the drawings]

[0161] [Figure 1] 1 is a conceptual cross-sectional view showing one embodiment of a decorative film of the present invention. [Figure 2] FIG. 1 is a conceptual diagram illustrating vacuum forming. [Figure 3] 1 is a photograph of a structural member used in evaluating vacuum formability. [Explanation of symbols]

[0162] 1:(β)Fluororesin cured coating film 2: Transparent (α) polyvinyl chloride resin composition film layer 3: Printing layer 4: Concealable film base layer 5: Adhesive layer 11:Decorative film 12:Heating device 13: Structural members 14: Space between the decorative film 11 and the structural member 13 15: Goods

Claims

1. (α) a polyvinyl chloride resin composition film having (β) a fluorine resin cured coating film on at least one surface thereof; The polyvinyl chloride resin composition film (α) is (A) 60 to 100% by mass of a polyvinyl chloride resin; (B) Core-shell rubber 40 to 0 mass% For 100 parts by mass of a resin mixture consisting of (C) 0.01 to 10 parts by mass of a barium-zinc complex compound, and (D) Metal perchlorate 0.01 to 5 parts by mass wherein the sum of the blending amount of the component (A) polyvinyl chloride resin and the blending amount of the component (B) core-shell rubber is 100 mass %. Laminated film.

2. The laminated film according to claim 1, wherein the polyvinyl chloride resin composition further comprises (E) 0.01 to 5 parts by mass of a β-diketone compound.

3. 2. The laminated film according to claim 1, wherein the (β) fluororesin cured coating film is made of a coating material containing a fluororesin having a hydroxyl group and a compound having two or more isocyanate groups in one molecule.

4. 4. The laminated film according to claim 3, wherein the hydroxyl value of the hydroxyl-containing fluororesin is 1 to 200 mgKOH / g.

5. 5. The laminate film according to claim 4, wherein the ratio (q / p) of the number (q) of isocyanates derived from the compound having two or more isocyanate groups per molecule in the coating material to the number (p) of hydroxyl groups derived from the fluororesin having hydroxyl groups is 0.1 to 2.

0.

6. A decorative film comprising the laminate film according to any one of claims 1 to 5.

7. An article comprising the decorative film of claim 6.

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