Polyvinyl chloride-based resin composition, and film produced therefrom

Abstract

Provided are: a polyvinyl chloride-based resin composition which has excellent process thermal stability and enables the suppression of discoloration in a film when the film is formed from the composition continuously; and a film which is formed from the composition and is suitable as a base material for wallpaper having a white-based design. The present invention is a polyvinyl chloride-based resin composition which comprises: 100 parts by mass of a resin mixture comprising 60-100% by mass of (A) a polyvinyl chloride-based resin and 40-0% by mass of (B) a core-shell rubber; 0.01-5 parts by mass of (C) a β-diketone compound; 0.01-10 parts by mass of (D) a phosphite compound; and 0-100 parts by mass of (E) a flame retardant. In the composition, the sum of the blending amount of the polyvinyl chloride-based resin (A) and the blending amount of the core-shell rubber (B) in the resin mixture is 100% by mass. The phosphite compound (D) may comprise one or more components selected from the group consisting of trialkyl phosphites, alkyl aryl phosphites and triaryl phosphites.

Description

Polyvinyl chloride resin composition and film thereof

[0001] The present invention relates to a polyvinyl chloride resin composition and a film thereof. More specifically, the present invention relates to a polyvinyl chloride resin composition that is inhibited from discoloring during continuous film production, and a film thereof.

[0002] Decorative and decorative adhesive films (so-called wallpapers) have been applied to the surfaces of walls of buildings made of wood-based materials such as wood, plywood, laminated wood, particle board, and hardboard; metal-based materials such as iron and aluminum; and inorganic materials such as gypsum. Also, decorative and decorative materials have been used for components of home appliances such as refrigerators, washing machines, air conditioners, mobile phones, and personal computers; furniture components such as display shelves, storage chests, cupboards, and desks; and building components such as floors, walls, and bathrooms. Decorative and decorative materials have been applied to substrates made of wood-based materials such as wood, plywood, laminated wood, particle board, and hardboard; substrates made of resin-based materials such as polystyrene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate, and polyester; or substrates made of metal-based materials such as iron and aluminum, with decorative sheets attached to the surface. Such wallpapers and decorative sheets often have designs based on white. Films made of polyvinyl chloride resin compositions are widely used as film substrates for wallpaper and decorative sheets. Polyvinyl chloride resin compositions allow for a wide range of flexibility adjustments depending on the amount of plasticizer used, and they offer excellent moldability, mechanical properties, flame retardancy, and other properties, while also being economical. However, polyvinyl chloride resin compositions often have insufficient process heat stability. Therefore, when films are continuously produced using polyvinyl chloride resin compositions, the film gradually becomes more yellowish, making it impossible to impart the desired design, particularly in designs based on white.

[0003] Furthermore, the Building Standards Act requires the use of fire-resistant materials for materials used in the interior of buildings. These fire-resistant materials are classified into "non-combustible materials," "semi-non-combustible materials," and "flame-retardant materials," and materials that pass tests prescribed by notices from the Ministry of Land, Infrastructure, Transport and Tourism are examined and certified for use. Therefore, wallpaper, as a decorative finishing material used in the interior of buildings, must be examined and certified by at least one of these standards. Therefore, it is desirable to use wallpaper film substrates containing flame retardants. However, polyvinyl chloride resin compositions containing flame retardants, particularly polyvinyl chloride resin compositions containing halogen-containing flame retardants, have insufficient process thermal stability and tend to gradually yellow during continuous film production.

[0004] JP 2017-105929 A JP 07-048493 A JP 2020-041033 A

[0005] An object of the present invention is to provide a polyvinyl chloride resin composition which has good process heat stability and is suppressed from discoloring when a film is continuously produced, and a film thereof.

[0006] As a result of extensive research, the present inventors have found that the above object can be achieved by using a specific polyvinyl chloride resin composition.

[0007] That is, the various aspects of the present invention are as follows. [1]. A polyvinyl chloride resin composition comprising, relative to 100 parts by mass of a resin mixture consisting of 60 to 100% by mass of (A) a polyvinyl chloride resin and 40 to 0% by mass of (B) a core-shell rubber, 0.01 to 5 parts by mass of (C) a β-diketone compound, 0.01 to 10 parts by mass of (D) a phosphite compound, and 0 to 100 parts by mass of (E) a flame retardant, wherein the sum of the amount of the (A) polyvinyl chloride resin and the amount of the (B) core-shell rubber in the resin mixture is 100% by mass. [2]. A polyvinyl chloride resin composition according to item [1], wherein the (D) phosphite compound comprises one or more compounds selected from the group consisting of trialkyl phosphites, alkylaryl phosphites, and triaryl phosphites. [3]. The polyvinyl chloride resin composition according to item [1], wherein the (D) phosphite compound comprises one or more compounds selected from the group consisting of trialkyl phosphites and alkylaryl phosphites. [4]. The polyvinyl chloride resin composition according to item [1], wherein the (D) phosphite compound comprises trialkyl phosphites and alkylaryl phosphites. [5]. The polyvinyl chloride resin composition according to any one of items [1] to [4], wherein the polyvinyl chloride resin composition does not comprise a hindered phenol compound. [6]. The polyvinyl chloride resin composition according to any one of items [1] to [5], further comprising 1 to 100 parts by mass of (E) a flame retardant per 100 parts by mass of the resin mixture consisting of (A) polyvinyl chloride resin and (B) core-shell rubber. [7]. The polyvinyl chloride resin composition according to any one of items [1] to [6], wherein the (E) flame retardant comprises a halogen-containing flame retardant. [8]. The polyvinyl chloride resin composition according to any one of items [1] to [7], wherein the (E) flame retardant comprises a brominated hydrocarbon flame retardant and an antimony flame retardant. [9] The polyvinyl chloride resin composition according to any one of items [1] to [8], further comprising: (F) 1 to 250 parts by mass of a plasticizer; (G) 0.01 to 10 parts by mass of a barium-zinc complex compound; (H) 0.01 to 3 parts by mass of hydrotalcite; and (J) 0.01 to 10 parts by mass of an ultraviolet absorber.

[10] A film formed from the polyvinyl chloride resin composition according to any one of items [1] to [9].

[11] Wallpaper or decorative sheet comprising the film according to item

[10] .

[0008] The polyvinyl chloride resin composition of the present invention has good process heat stability and can suppress discoloration when a film is continuously produced using the composition. A preferred polyvinyl chloride resin composition of the present invention has excellent process heat stability even when it contains a flame retardant and can suppress discoloration when a film is continuously produced using the composition. Therefore, a film formed from the polyvinyl chloride resin composition of the present invention can be suitably used as a film substrate for wallpaper or decorative sheets. Therefore, a preferred polyvinyl chloride resin composition of the present invention can be suitably used as a film substrate for wallpaper or decorative sheets having a white-based design and imparted flame retardancy.

[0009] FIG. 1 is a schematic cross-sectional view showing an example of wallpaper using the film of the present invention.

[0010] 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.

[0011] 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.

[0012] In this specification, the term "equivalent to or greater than" in relation to a numerical range means a certain numerical value or more than a certain numerical value. For example, 20% or greater means 20% or more than 20%. The term "equal to or less than" in relation to a numerical range means a certain numerical value or less than a certain numerical value. For example, 20% or less means 20% or less than 20%. Furthermore, a numerical range "x to y" including the symbol "to" is used to mean a certain numerical value x, greater than a certain numerical value x and less than another certain numerical value y, or another certain numerical value y. Here, the other certain numerical value y is a number greater than the certain numerical value x. For example, 10 to 90% means 10%, greater 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 are intended to be interpreted as including such combinations. 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.

[0013] 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.

[0014] 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.

[0015] 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 contains substances a1 and a2, composition A consists of substances a1 and a2, or composition A consists only of substances a1 and a2.

[0016] 1. Polyvinyl chloride resin composition The polyvinyl chloride resin composition of the present invention comprises (A) a polyvinyl chloride resin, (C) a β-diketone compound, and (D) a phosphite compound. In one embodiment, the polyvinyl chloride resin composition of the present invention comprises (A) a polyvinyl chloride resin, (B) a core-shell rubber, (C) a β-diketone compound, and (D) a phosphite compound. In one preferred embodiment, the polyvinyl chloride resin composition of the present invention further comprises (E) a flame retardant in addition to components (A), (C), and (D), or in addition to components (A), (B), (C), and (D). Each component will be described below.

[0017] (A) Polyvinyl chloride resin The polyvinyl chloride resin composition of the present invention contains (A) a polyvinyl chloride resin. (A) The polyvinyl chloride resin is a (—CH ２ The polymer (including copolymer) is a polymer (including copolymer) that mainly contains a structural unit represented by the formula -CHCl-) (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, where the sum of all structural units is 100% by mass).

[0018] Examples of (A) polyvinyl chloride resins 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-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, vinyl chloride-various vinyl ether copolymers, and vinyl chloride copolymers of other monomers copolymerizable with vinyl chloride; and modified (e.g., chlorinated) polyvinyl chloride or vinyl chloride copolymers such as post-chlorinated vinyl copolymers. Furthermore, in this specification, chlorinated polyolefins such as chlorinated polyethylene are also included in the category of (A) polyvinyl chloride resins.

[0019] The polyvinyl chloride resin (A) may preferably contain polyvinyl chloride (vinyl chloride homopolymer).

[0020] The average degree of polymerization of the (A) polyvinyl chloride resin may be preferably 2500 or less, more preferably 1500 or less, even more preferably 1300 or less, and most preferably 1000 or less, from the viewpoint of suppressing discoloration during continuous production of the film. On the other hand, the average degree of polymerization of the polyvinyl chloride resin may be preferably 300 or more, more preferably 500 or more, and even more preferably 650 or more, from the viewpoint of the mechanical properties of the film. In this specification, the average degree of polymerization of the polyvinyl chloride resin is calculated from the specific viscosity measured in accordance with 4.1 specific viscosity of JIS K6720-2:1999 using formulas (1) and (2) of the JIS standard.

[0021] As the polyvinyl chloride resin (A), one of these resins or a mixture of two or more thereof can be used.

[0022] (B) Core-shell rubber In one embodiment, the polyvinyl chloride resin composition of the present invention may further contain (B) a core-shell rubber. By including the core-shell rubber, it is possible to improve the film-forming properties by calender roll rolling and the weather resistance.

[0023] Examples of the (B) core-shell rubber include methacrylate ester-styrene / butadiene rubber graft copolymers, methacrylate ester-styrene / styrene-butadiene rubber graft copolymers, acrylonitrile-styrene / butadiene rubber graft copolymers, acrylonitrile-styrene / styrene-butadiene rubber graft copolymers, acrylonitrile-styrene / ethylene-propylene rubber graft copolymers, acrylonitrile-styrene / acrylate rubber graft copolymers, methacrylate ester / acrylate rubber graft copolymers, methacrylate ester-styrene / acrylate rubber graft copolymers, and methacrylate ester-acrylonitrile / acrylate rubber graft copolymers.

[0024] From the viewpoint of weather resistance, the (B) core-shell rubber may preferably contain an acrylic core-shell rubber in which a (meth)acrylic ester, acrylonitrile, styrene, or the like is graft-copolymerized onto a (meth)acrylic ester rubber. Examples of the acrylic core-shell rubber include an acrylonitrile-styrene / acrylic ester rubber graft copolymer, a methacrylic ester / acrylic ester rubber graft copolymer, a methacrylic ester-styrene / acrylic ester rubber graft copolymer, and a methacrylic ester-acrylonitrile / acrylic ester rubber graft copolymer. In this specification, "(meth)acrylic ester" means an acrylic ester or a methacrylic ester.

[0025] As the core-shell rubber (B), one of these or a mixture of two or more thereof can be used.

[0026] The amount of the (B) core-shell rubber is not particularly limited because it is an optional component. From the viewpoint of reliably obtaining an improved effect on the calender roll film formability and from the viewpoint of weather resistance, the amount of the (B) core-shell rubber may be usually 0% by mass or more (100% by mass or less of the above-mentioned component (A)), preferably 1% by mass or more (99% by mass or less of the above-mentioned component (A)), more preferably 3% by mass or more (97% by mass or less of the above-mentioned component (A)), and even more preferably 5% by mass or more (95% by mass or less of the above-mentioned component (A)), where the sum of the amount of the (A) polyvinyl chloride resin and the amount of the (B) core-shell rubber is taken as 100% by mass. On the other hand, the amount of the (B) core-shell rubber may be, from the viewpoint of the mechanical properties of the film, preferably 40% by mass or less (60% by mass or more of the above-mentioned component (A)), more preferably 30% by mass or less (70% by mass or more of the above-mentioned component (A)), even more preferably 20% by mass or less (80% by mass or more of the above-mentioned component (A)), and most preferably 15% by mass or less (85% by mass or more of the above-mentioned component (A)), where the sum of the amount of the (A) polyvinyl chloride resin and the amount of the (B) core-shell rubber is taken as 100% by mass. The amount of the (B) core-shell rubber may be typically 0% by mass or more and 40% by mass or less, preferably 0% by mass or more and 30% by mass or less, 0% by mass or more and 20% by mass or less, 0% by mass or more and 15% by mass or less, 1% by mass or more and 40% by mass or less, 1% by mass or more and 30% by mass or less, 1% by mass or more and 20% by mass or less, 1% by mass or more and 15% by mass or less, 3% by mass or more and 40% by mass or less, 3% by mass or more and 30% by mass or less, 3% by mass or more and 20% by mass or less, 3% by mass or more and 15% by mass or less, 5% by mass or more and 40% by mass or less, 5% by mass or more and 30% by mass or less, 5% by mass or more and 20% by mass or less, or 5% by mass or more and 15% by mass or less.

[0027] (C) β-diketone compound The polyvinyl chloride resin composition of the present invention contains (C) a β-diketone compound. The (C) β-diketone compound is an organic compound having a structure (-CO-C-CO-) in which two ketones are bonded via one carbon atom. The (C) β-diketone compound also includes trione compounds having a β-diketone structure. The present inventors have found that the (C) β-diketone compound, through a synergistic effect with the (D) phosphite compound, can significantly suppress discoloration during continuous film production.

[0028] (C) Examples of the β-diketone compound include acetylacetone, triacetylmethane, 2,4,6-heptatrione, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylbenzoylmethane (1-phenyl-1,3-eicosanedione), palmitoylbenzoylmethane, distearoylmethane (stearoyl group = octadecanoyl group), stearoylacetylmethane, phenylacetylacetylmethane, dicyclohexylcarbonylmethane, benzoylformylmethane, benzoylacetylmethane, dibenzoylmethane, octylbenzoylmethane, bis(4-octylbenzoyl)methane, benzoylacetyl ... Examples of suitable benzoylbenzoates include benzoyldiacetylmethane, 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, 2-benzoylcyclohexane-1-one, and 2-benzoylcyclohexane-1,3-dione, as well as derivatives thereof such as metal salts thereof, such as lithium salts, sodium salts, potassium salts, calcium salts, zinc salts, magnesium salts, and aluminum salts.

[0029] From the viewpoint of suppressing coloration during continuous production of the film, the (C) β-diketone compound may preferably contain at least one selected from the group consisting of dibenzoylmethane, stearoylbenzoylmethane, derivatives of dibenzoylmethane, and derivatives of stearoylbenzoylmethane.

[0030] As the β-diketone compound (C), one of these compounds or a mixture of two or more of them can be used.

[0031] The amount of the (C) β-diketone compound may be usually 0.01 part by mass or more, preferably 0.03 part by mass or more, and more preferably 0.05 part by mass or more, relative to 100 parts by mass of the resin mixture consisting of the (A) polyvinyl chloride resin and the (B) core-shell rubber, from the viewpoint of suppressing discoloration during continuous production of the film. On the other hand, from the viewpoint of weather resistance, the amount may be usually 5 parts by mass or less, preferably 1 part by mass or less, more preferably 0.5 part by mass or less, even more preferably 0.3 part by mass or less, even more preferably 0.2 part by mass or less, and most preferably 0.1 part by mass or less. The blending amount of the (C) β-diketone compound is usually 0.01 parts by mass or more and 5 parts by mass or less, preferably 0.01 parts by mass or more and 1 part by mass or less, 0.01 parts by mass or more and 0.5 parts by mass or less, 0.01 parts by mass or more and 0.3 parts by mass or less, 0.01 parts by mass or more and 0.2 parts by mass or less, 0.01 parts by mass or more and 0.1 parts by mass or less, 0.03 parts by mass or less, based on 100 parts by mass of the resin mixture consisting of the (A) polyvinyl chloride resin and the (B) core-shell rubber. Parts by weight or more and 1 part by weight or less, 0.03 parts by weight or more and 0.5 parts by weight or less, 0.03 parts by weight or more and 0.3 parts by weight or less, 0.03 parts by weight or more and 0.2 parts by weight or less, 0.03 parts by weight or more and 0.1 parts by weight or less, 0.05 parts by weight The amount may be greater than or equal to 1 part by mass, less than or equal to 0.5 part by mass, greater than or equal to 0.05 part by mass and less than or equal to 0.3 part by mass, greater than or equal to 0.05 part by mass and less than or equal to 0.2 part by mass, or greater than or equal to 0.05 part by mass and less than or equal to 0.1 part by mass.

[0032] (D) Phosphite Compound The polyvinyl chloride resin composition of the present invention contains (D) a phosphite compound. The (D) phosphite compound is an organic compound having a phosphite structure. The phosphite compound also has the function of decomposing peroxides and reducing quinone structures to phenol structures, and acts as a so-called secondary antioxidant. The present inventors have found that the (D) phosphite compound, due to a synergistic effect with the (C) β-diketone compound, can act to significantly suppress discoloration during continuous film production.

[0033] Examples of the (D) phosphite compound include trialkyl phosphites such as trioleyl phosphite, trilauryl phosphite, triisodecyl phosphite, and tris(2-ethylhexyl)phosphite; alkylaryl phosphites such as 2-ethylhexyldiphenyl phosphite, isodecyldiphenyl phosphite, diphenyldecyl phosphite, and 2,2'-methylenebis(4,6-di-tert-butylphenyl)2-ethylhexyl phosphite; and compounds having one phosphite structure in one molecule, such as triaryl phosphites such as tris-(2,4-di-tert-butylphenyl)phosphite, trisnonylphenyl phosphite, tricresyl phosphite, and triphenyl phosphite; and Examples of such compounds include compounds having two or more phosphite structures in one molecule, such as tetraphenyldipropylene glycol diphosphite, 4,4'-butylidenebis(3-methyl-6-tert-butylphenylditridecylphosphite), bis(decyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra-dodecyl(propane-2,2-diylbis(4,1-phenylene))bis(phosphite), 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane.

[0034] From the viewpoint of suppressing the problem of bleeding out onto the film surface, the (D) phosphite compound may preferably contain a compound having one phosphite structure per molecule. From the viewpoint of suppressing the problem of bleeding out onto the film surface, the (D) phosphite compound may, in one embodiment, not contain a compound having two or more phosphite structures per molecule.

[0035] 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 certain component is intentionally blended, it is usually blended in an amount of 0.01 part by mass or more. Therefore, "not containing a certain component" in the polyvinyl chloride resin composition of the present invention can also be rephrased as meaning that the content of the component is usually less than 0.01 part by mass, preferably 0.001 part by mass or less, more preferably 0.0001 part by mass or less, and even more preferably substantially 0 part by mass, per 100 parts by mass of the resin mixture consisting of the component (A) polyvinyl chloride resin and the component (B) core-shell rubber.

[0036] From the viewpoint of suppressing discoloration during continuous production of the film, the (D) phosphite compound may preferably contain one or more compounds selected from the group consisting of trialkyl phosphites, alkylaryl phosphites, and triaryl phosphites, more preferably one or more compounds selected from the group consisting of trialkyl phosphites and alkylaryl phosphites, and even more preferably one containing trialkyl phosphites. In one preferred embodiment, the (D) phosphite compound may contain trialkyl phosphites and alkylaryl phosphites.

[0037] As the phosphite compound (D), one of these compounds or a mixture of two or more of them can be used.

[0038] The blending amount of the (D) phosphite compound may be usually 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.3 parts by mass or more, and most preferably 0.5 parts by mass or more, relative to 100 parts by mass of the resin mixture consisting of the (A) polyvinyl chloride resin and the (B) core-shell rubber, from the viewpoint of suppressing discoloration during continuous production of the film. On the other hand, the blending amount of the (D) phosphite compound may be usually 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 2 parts by mass or less, and most preferably 1.5 parts by mass or less, relative to 100 parts by mass of the resin mixture consisting of the (A) polyvinyl chloride resin and the (B) core-shell rubber, from the viewpoint of suppressing problems due to hydrolysis of the phosphite compound. The blending amount of the (D) phosphite compound is usually 0.01 parts by mass or more and 10 parts by mass or less, preferably 0.01 parts by mass or more and 5 parts by mass or less, 0.01 parts by mass or more and 3 parts by mass or less, 0.01 parts by mass or more and 2 parts by mass or less, 0.01 parts by mass or more and 1.5 parts by mass or less, 0.05 parts by mass or more and 10 parts by mass or less, 0.05 parts by mass or more and 5 parts by mass or less, 0.05 parts by mass or more and 3 parts by mass or less, 0.05 parts by mass or more and 2 parts by mass or less, 0.05 parts by mass or more and 1.5 parts by mass or less, 0.1 Parts by mass or more and 10 parts by mass or less, 0.1 parts by mass or more and 5 parts by mass or less, 0.1 parts by mass or more and 3 parts by mass or less, 0.1 parts by mass or more and 2 parts by mass or less, 0.1 parts by mass or more and 1.5 parts by mass or less, 0.3 parts by mass or more and 10 parts by mass or less, 0.3 parts by mass or more and 3 parts by mass or less , 0.3 parts by mass to 2 parts by mass, 0.3 parts by mass to 1.5 parts by mass, 0.5 parts by mass to 10 parts by mass, 0.5 parts by mass to 5 parts by mass, 0.5 parts by mass to 3 parts by mass, 0.5 parts by mass to 2 parts by mass, or 0.5 parts by mass to 1.5 parts by mass.

[0039] (E) Flame Retardant In one preferred embodiment, the polyvinyl chloride resin composition of the present invention may further contain a (E) flame retardant. The (E) flame retardant is not particularly limited, as long as it is a flame retardant commonly used in polyvinyl chloride resin compositions. The (E) flame retardant is not particularly limited, as long as it is a flame retardant that does not exhibit coloration that would interfere with imparting the desired design, preferably for use as a film substrate for wallpaper or decorative sheets. Here, the (E) flame retardant does not include any of the compounds corresponding to any of the above components (A) to (D) that have the function of improving flame retardancy. In other words, any compound corresponding to any of the above components (A) to (D) is excluded from the (E) flame retardant.

[0040] (E) Examples of the flame retardant include antimony-based flame retardants, halogen-based flame retardants, metal hydroxides, zinc-based flame retardants, phosphorus-based flame retardants, and nitrogen-containing compound-based flame retardants.

[0041] Examples of the antimony-based flame retardant include diantimony trioxide, diantimony pentoxide, antimony trichloride, antimony borate, and antimony molybdate.

[0042] Examples of the halogen-based flame retardant include brominated hydrocarbon flame retardants such as 1,2-bis(pentabromophenyl)ethane, pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, bis(tetrabromophthalimide)ethane, poly(dibromopropyl ether), tetrabromobisphenol A carbonate oligomer, tetrabromobisphenol epoxy oligomer, tetrabromobisphenol A-bis(dibromopropyl ether), brominated polystyrene, and hexabromobenzene; and chlorinated hydrocarbon flame retardants such as chlorinated paraffin, chlorinated polyphenyl, and perchloropentacyclodecane.

[0043] Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide.

[0044] Examples of the zinc-based flame retardant include zinc stannate and zinc borate.

[0045] Examples of the phosphorus-based flame retardant include organic phosphate ester-based flame retardants such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, trineopentyl phosphate, tri(2-ethylhexyl)phosphate, tri(butylated phenyl)phosphate, tri(isopropylated phenyl)phosphate, triphenyl phosphate, trixylenyl phosphate, and t-butyldiphenyl phosphate; Examples of such flame retardants include condensed organic phosphate ester-based flame retardants whose main component is a compound in which three or more molecules are condensed; compounds in which one or more hydrogen atoms of an organic phosphate ester or a condensed organic phosphate ester are substituted with bromine atoms, for example, brominated organic phosphate ester-based flame retardants such as tris(tribromoneopentyl)phosphate; compounds in which one or more hydrogen atoms of an organic phosphate ester or a condensed organic phosphate ester are substituted with chlorine atoms, for example, chlorinated organic phosphate ester-based flame retardants such as tris(2,3-dichloropropyl)phosphate; and ammonium polyphosphate-based flame retardants.

[0046] Examples of the nitrogen-containing compound-based flame retardant include cyanurate-based flame retardants such as melamine cyanurate, tris(2-hydroxyethyl)isocyanurate, and tris(2,3-epoxypropyl)isocyanurate; triazine-based flame retardants; and guanidine-based flame retardants.

[0047] From the viewpoint of passing the fire-resistant material test established by the notification of the Ministry of Land, Infrastructure, Transport and Tourism with a smaller blending amount, the (E) flame retardant may preferably contain one or more selected from the group consisting of the above-mentioned brominated hydrocarbon flame retardants and the above-mentioned antimony-based flame retardants. In one preferred embodiment, the (E) flame retardant may contain the above-mentioned brominated hydrocarbon flame retardants and the above-mentioned antimony-based flame retardants.

[0048] In another embodiment, the (E) flame retardant may include a flame retardant containing a halogen element. Examples of the halogen-containing flame retardant include the halogen-based flame retardants such as the brominated hydrocarbon-based flame retardants, the brominated organic phosphate ester-based flame retardants, and the chlorinated organic phosphate ester-based flame retardants.

[0049] As the flame retardant (E), one of these may be used alone or in combination with two or more thereof.

[0050] The amount of the flame retardant (E) is not particularly limited, since it is an optional component. In one embodiment, the polyvinyl chloride resin composition of the present invention may not contain the flame retardant (E). From the viewpoint of passing the fire-resistant material test specified by the Ministry of Land, Infrastructure, Transport and Tourism Notification, the amount of the flame retardant (E) may be preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 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 suppressing discoloration during continuous film production, the amount of the flame retardant (E) may be preferably 100 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 35 parts by mass or less, even more preferably 20 parts by mass or less, and most preferably 15 parts by mass or less, per 100 parts by mass of the resin mixture consisting of the polyvinyl chloride resin (A) and the core-shell rubber (B). The blending amount of the (E) flame retardant, relative to 100 parts by mass of the resin mixture consisting of the (A) polyvinyl chloride resin and the (B) core-shell rubber, may be typically 0 parts by mass or more and 100 parts by mass or less, preferably 0 parts by mass or more and 60 parts by mass or less, 0 parts by mass or more and 35 parts by mass or less, 0 parts by mass or more and 20 parts by mass or less, 0 parts by mass or more and 15 parts by mass or less, 1 part by mass or more and 100 parts by mass or less, 1 part by mass or more and 60 parts by mass or less, 1 part by mass or more and 35 parts by mass or less, 1 part by mass or more and 20 parts by mass or less, 1 part by mass or more and 15 parts by mass or less, 3 parts by mass or more and 100 parts by mass or less, 3 parts by mass or more and 60 parts by mass or less, 3 parts by mass or more and 35 parts by mass or less, 3 parts by mass or more and 20 parts by mass or less, 3 parts by mass or more and 15 parts by mass or less, 5 parts by mass or more and 100 parts by mass or less, 5 parts by mass or more and 60 parts by mass or less, 5 parts by mass or more and 35 parts by mass or less, 5 parts by mass or more and 20 parts by mass or less, or 5 parts by mass or more and 15 parts by mass or less.

[0051] (F) Plasticizer The polyvinyl chloride resin composition of the present invention can further contain a (F) plasticizer, if desired, to the extent that it does not interfere with the object of the present invention. The (F) plasticizer is not particularly limited, as long as it is a plasticizer commonly used in polyvinyl chloride resin compositions. Here, the (F) plasticizer does not include any compound that corresponds to any of the above components (B) to (E) but has the function of plasticizing the (A) polyvinyl chloride resin. In other words, any compound that corresponds to any of the above components (B) to (E) is excluded from the (F) plasticizer.

[0052] Examples of the (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.

[0053] Examples of the (F) plasticizer include polyester-based plasticizers obtained by using, as polyhydric alcohols, 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, and the like, and as polycarboxylic acids, 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, and the like, and, if necessary, using a monohydric alcohol or a monocarboxylic acid as a stopper.

[0054] Examples of the phthalate ester plasticizer include dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate.

[0055] Examples of the trimellitic acid ester plasticizer include tri(2-ethylhexyl) trimellitate, tri(n-octyl) trimellitate, and tri(isononyl) trimellitate.

[0056] Examples of the adipate plasticizer include bis(2-ethylhexyl) adipate, dioctyl adipate, diisononyl adipate, and diisodecyl adipate.

[0057] Examples of the epoxy plasticizer include epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid octyl ester, and epoxidized fatty acid alkyl ester.

[0058] Other examples of the (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.

[0059] As the plasticizer (F), one of these or a mixture of two or more thereof can be used.

[0060] The amount of the (F) plasticizer is not particularly limited, since it is an optional component. In one embodiment, the polyvinyl chloride resin composition of the present invention may not contain the (F) plasticizer. From the viewpoint of film-forming properties by calender roll rolling, the amount of the (F) plasticizer may be preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, and most preferably 15 parts by mass or more, per 100 parts by mass of the resin mixture consisting of the (A) polyvinyl chloride resin and the (B) core-shell rubber. On the other hand, from the viewpoints of suppressing problems due to plasticizer migration, printability, and blocking resistance, the amount of the (F) plasticizer may be typically 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, per 100 parts by mass of the resin mixture consisting of the (A) polyvinyl chloride resin and the (B) core-shell rubber. The blending amount of the (F) plasticizer relative to 100 parts by mass of the resin mixture consisting of the (A) polyvinyl chloride resin and the (B) core-shell rubber is usually 0 parts by mass or more and 250 parts by mass or less, preferably 0 parts by mass or more and 150 parts by mass or less, 0 parts by mass or more and 100 parts by mass or less, 0 parts by mass or more and 60 parts by mass or less, 0 parts by mass or more and 45 parts by mass or less, 0 parts by mass or more and 35 parts by mass or less, 1 part by mass or more and 250 parts by mass or less, 1 part by mass or more and 150 parts by mass or less, 1 part by mass or more and 100 parts by mass or less, 1 part by mass or more and 60 parts by mass or less, 1 part by mass or more and 45 parts by mass or less, 1 part by mass or more and 35 parts by mass or less, 5 parts by mass or more and 250 parts by mass or less, 5 parts by mass or more and 1 50 parts by mass or more, 5 parts by mass or more and 100 parts by mass or less, 5 parts by mass or more and 60 parts by mass or less, 5 parts by mass or more and 45 parts by mass or less, 5 parts by mass or more and 35 parts by mass or less, 10 parts by mass or more and 250 parts by mass or less, 10 parts by mass or more and 150 parts by mass or less, 10 parts by mass or more and 60 parts by mass or less, 10 parts by mass or more and 60 parts by mass or less It may be at least 10 parts by mass and at most 35 parts by mass, at least 15 parts by mass and at most 250 parts by mass, at least 15 parts by mass and at most 150 parts by mass, at least 15 parts by mass and at most 100 parts by mass, at least 15 parts by mass and at most 45 parts by mass, or at least 15 parts by mass and at most 35 parts by mass.

[0061] (G) Barium-Zinc Complex Compound In one preferred embodiment, the polyvinyl chloride resin composition of the present invention may further contain (G) a barium-zinc complex compound. The (G) barium-zinc complex compound serves as a stabilizer for the polyvinyl chloride resin composition and typically functions to capture free chlorine.

[0062] (G) Examples of the 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.

[0063] Examples of the organic acid include saturated fatty acids, unsaturated fatty acids, and aromatic carboxylic acids.

[0064] 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 moiety such as cyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, and 4-ethylcyclohexanecarboxylic acid.

[0065] 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.

[0066] Examples of the aromatic carboxylic acid include benzoic acid, toluic acid (o-toluic acid, m-toluic acid, p-toluic acid, particularly p-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.

[0067] (G) Examples of the barium-zinc complex compound that can be used include an organic acid barium-zinc complex salt containing barium, zinc, and one or more of the above organic acids, and a mixture of one or more barium salts of the above organic acids and one or more zinc salts of the above organic acids.

[0068] The (G) barium-zinc complex compound is an optional component and is not particularly limited. In one embodiment, the polyvinyl chloride resin composition of the present invention may not contain the (G) barium-zinc complex compound. From the viewpoints of thermal stability and color stability over time, the blending amount of the (G) barium-zinc complex compound may be preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, and most preferably 1 part by mass or more, per 100 parts by mass of the resin mixture consisting of the (A) polyvinyl chloride resin and the (B) core-shell rubber. On the other hand, from the viewpoint of bloom resistance, the blending amount of the (G) barium-zinc complex compound may be preferably 10 parts by mass or less, more preferably 7 parts by mass or less, even more preferably 5 parts by mass or less, and most preferably 4 parts by mass or less, per 100 parts by mass of the resin mixture consisting of the (A) polyvinyl chloride resin and the (B) core-shell rubber. The (G) barium-zinc complex compound is typically used in an amount of 0 to 10 parts by mass, preferably 0 to 7 parts by mass, 0 to 5 parts by mass, 0 to 4 parts by mass, 0.01 to 10 parts by mass, 0.01 to 7 parts by mass, 0.01 to 5 parts by mass, 0.01 to 4 parts by mass, 0.01 to 10 parts by mass, 0.01 to 7 parts by mass, 0.01 to 5 parts by mass, 0.01 to 4 parts by mass, or Bottom, 0.1 parts by mass to 10 parts by mass, 0.1 parts by mass to 7 parts by mass, 0.1 parts by mass to 5 parts by mass, 0.1 parts by mass to 4 parts by mass, 0.5 parts by mass to 10 parts by mass, 0.5 parts by mass to 7 parts by mass , 0.5 parts by mass to 5 parts by mass, 0.5 parts to 4 parts by mass, 1 part to 10 parts by mass, 1 part to 7 parts by mass, 1 part to 5 parts by mass, or 1 part to 4 parts by mass.

[0069] (H) Hydrotalcite In one embodiment, the polyvinyl chloride resin composition of the present invention may further contain (H) hydrotalcite. (H) Hydrotalcite serves as a stabilizer for the polyvinyl chloride resin composition, typically functioning to scavenge free chlorine.

[0070] (H) Hydrotalcite is a layered inorganic compound consisting of a positively charged layer and a negatively charged layer, and is typically an inorganic compound represented by the following formula (1): [M ２＋ 1-Ｘ M ３＋ Ｘ (OH) ２ ] Ｘ＋ [A ｎ－ Ｘ／ｎ ・mH ２ O] Ｘ－ ...(1) (In the formula, M ２＋ is Mg ２＋ , Zn ２＋ Divalent metal ions such as M ３＋ is Al ３＋ , Fe ３＋ Trivalent metal ions such as A ｎ－ is CO ３ ２－ , Cl － , NO ３－ an n-valent anion such as the above, where X is a number satisfying 0<X≦0.33, typically 0.20≦X≦0.33, and m is a number satisfying 0≦m≦0.5.

[0071] From the viewpoints of thermal stability and color stability over time, the (H) hydrotalcite may preferably include carbonate ion-type hydrotalcite, more preferably carbonate ion magnesium aluminum-type hydrotalcite. The carbonate ion-type hydrotalcite is a hydrotalcite represented by the formula (1) in which the n-valent anion is a carbonate ion (CO ３ ２－ The carbonate ion magnesium aluminum type hydrotalcite is an inorganic compound represented by the formula (1) in which the n-valent anion is a carbonate ion (CO ３ ２－ ), and the divalent metal ion is magnesium ion (Mg ２＋), the trivalent metal ion is an aluminum ion (Al ３＋ As the carbonate ion magnesium aluminum type hydrotalcite, for example, a compound represented by the following formula (2) can be mentioned: Mg ６ Al ２ (OH) １６ CO ３ ・4H ２ O... (2)

[0072] As the (H) hydrotalcite, one of these or a mixture of two or more thereof can be used.

[0073] The amount of (H) hydrotalcite is not particularly limited, since it is an optional component. In one embodiment, the polyvinyl chloride resin composition of the present invention may not contain (H) hydrotalcite. From the viewpoints of thermal stability and color stability over time, the amount of (H) hydrotalcite may be typically 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.2 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 suppressing coloration during continuous film production, the amount of (H) hydrotalcite may be typically 3 parts by mass or less, preferably 2 parts by mass or less, and more preferably 1 part by mass or less, per 100 parts by mass of the resin mixture consisting of the polyvinyl chloride resin (A) and the core-shell rubber (B). The amount of the (H) hydrotalcite, relative to 100 parts by mass of the resin mixture consisting of the (A) polyvinyl chloride resin and the (B) core-shell rubber, may typically be 0 parts by mass or more and 3 parts by mass or less, preferably 0 parts by mass or more and 2 parts by mass or less, 0 parts by mass or more and 1 part by mass or less, 0.01 parts by mass or more and 3 parts by mass or less, 0.01 parts by mass or more and 2 parts by mass or less, 0.01 parts by mass or more and 1 part by mass or less, 0.05 parts by mass or more and 3 parts by mass or less, 0.05 parts by mass or more and 2 parts by mass or less, 0.05 parts by mass or more and 1 part by mass or less, 0.05 parts by mass or more and 1 part by mass or less, 0.1 parts by mass or more and 3 parts by mass or less, 0.1 parts by mass or more and 2 parts by mass or less, 0.1 parts by mass or more and 1 part by mass or less, 0.2 parts by mass or more and 3 parts by mass or less, 0.2 parts by mass or more and 2 parts by mass or less, or 0.2 parts by mass or more and 1 part by mass or less.

[0074] (J) Ultraviolet Absorber In one embodiment, the polyvinyl chloride resin composition of the present invention may further contain (J) an ultraviolet absorber. Here, the (J) ultraviolet absorber does not include a compound corresponding to any of the above components (A) to (H) that has an ultraviolet absorbing function. In other words, a compound corresponding to any of the above components (A) to (H) is excluded from the (J) ultraviolet absorber.

[0075] Examples of (J) ultraviolet absorbers 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.

[0076] Examples of the benzotriazole-based ultraviolet absorbers include 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], and 2-(2H-benzotriazol-2-yl)-p-cresol.

[0077] 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.

[0078] 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.

[0079] 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).

[0080] Examples of the aromatic benzoate ultraviolet absorber 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.

[0081] Examples of the oxalic acid anilide ultraviolet absorbers include 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide.

[0082] As the ultraviolet absorber (J), one of these may be used alone or in combination with two or more thereof.

[0083] The amount of the (J) ultraviolet absorber is not particularly limited, since it is an optional component. In one embodiment, the polyvinyl chloride resin composition of the present invention may not contain the (J) ultraviolet absorber. From the viewpoints of color stability over time and weather resistance, the amount of the (J) ultraviolet absorber may be preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, and most preferably 0.2 parts by mass or more, per 100 parts by mass of the resin mixture consisting of the (A) polyvinyl chloride resin and the (B) core-shell rubber. On the other hand, from the viewpoint of preventing the problem of the ultraviolet absorber bleeding out to the film surface, the amount of the (J) ultraviolet absorber 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, per 100 parts by mass of the resin mixture consisting of the (A) polyvinyl chloride resin and the (B) core-shell rubber. The blending amount of (J) ultraviolet absorber is usually 0 to 10 parts by mass, preferably 0 to 5 parts by mass, 0 to 3 parts by mass, 0 to 1 part by mass, 0.01 to 10 parts by mass, 0.01 to 5 parts by mass, 0.01 to 3 parts by mass, 0.01 to 10 parts by mass, 0.01 to 5 parts by mass, 0.01 to 3 parts by mass, 0.01 to 1 part by mass, 0.05 to 10 parts by mass, 0.05 to 10 parts by mass, 0.05 to 10 parts by mass, 0.05 to 10 parts by mass, 0.01 to 10 parts by mass, 0.01 to 1 part by mass, 0.01 to 1 part by mass, 0.05 to 10 parts ...1 to 1 part by mass, 0.05 to 10 parts by mass, 0.01 to 1 part by mass, Part by weight or more and 10 parts by weight or less, 0.05 part by weight or more and 5 parts by weight or less, 0.05 part by weight or more and 3 parts by weight or less, 0.05 part by weight or more and 1 part by weight or less, 0.1 part by weight or more and 10 parts by weight or less, 0.1 part by weight or more and 5 parts by weight or less, 0.1 part by weight The amount may be from 0.1 parts by weight to 1 parts by weight, from 0.2 parts by weight to 10 parts by weight, from 0.2 parts by weight to 5 parts by weight, from 0.2 parts by weight to 3 parts by weight, or from 0.2 parts by weight to 1 part by weight.

[0084] The polyvinyl chloride resin composition of the present invention may further contain optional components other than the above components (A) to (J), as desired, to the extent that the addition does not contradict the object of the present invention. Examples of the optional components include thermoplastic resins other than (A) polyvinyl chloride resin and (B) core-shell rubber, as well as additives other than (C) β-diketone compounds, (D) phosphite compounds, (G) barium-zinc composite compounds, (H) hydrotalcite, and (J) ultraviolet absorbers.

[0085] 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, and ethylene-ethyl(meth)acrylate copolymers.

[0086] Examples of the other additives include heat stabilizers such as calcium-zinc complex compounds, antioxidants such as hindered phenol compounds, weather resistance stabilizers, light resistance stabilizers, lubricants such as oleic acid amide, waxes such as polyethylene wax, antistatic agents such as glycerin fatty acid esters, mold release agents, processing aids, antifouling agents, nucleating agents, inorganic particles, organic particles, inorganic colorants, and organic colorants.

[0087] As the other optional components, one of these or a mixture of two or more thereof can be used.

[0088] 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, and 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 component (A) polyvinyl chloride resin and the component (B) core-shell rubber.

[0089] In one embodiment, the polyvinyl chloride resin composition of the present invention may not contain any one or more of the other optional components described above.

[0090] In one embodiment, the polyvinyl chloride resin composition of the present invention may be free of a hindered phenol compound. Without intending to be bound by theory, a hindered phenol compound is an organic compound that has a radical-scavenging function and acts as a so-called primary antioxidant, and is effective in terminating oxidative degradation reactions. On the other hand, after functioning as an antioxidant, a hindered phenol compound becomes a compound having a quinone structure, which often develops a color such as yellow.

[0091] 2. Method for Producing Polyvinyl Chloride Resin Composition The polyvinyl chloride resin composition of the present invention can be obtained by using any melt kneader to charge the above-mentioned components (A) to (D) (or the above-mentioned components (A), (C) and (D) when the above-mentioned component (B) is not included) 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.

[0092] 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.

[0093] The resulting resin composition can be pelletized by any method and then molded into any article by any method, such as hot cutting, strand cutting, or underwater cutting.

[0094] In one embodiment, the polyvinyl chloride resin composition in the form of blocks, rods, or strands discharged from the melt kneader may be sent directly to any molding machine to be molded into an article.

[0095] 3. Film The film of the present invention is a film formed from the polyvinyl chloride resin composition of the present invention. The film of the present invention can be suitably used as a film substrate for wallpaper or decorative sheets.

[0096] The film of the present invention can be obtained by forming the polyvinyl chloride resin composition of the present invention using any film-forming apparatus, such as a calender roll-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.

[0097] 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.

[0098] The film of the present invention can be obtained by forming the polyvinyl chloride resin composition of the present invention preferably using a calender roll film-forming apparatus, more preferably using a calender roll film-forming apparatus at a roll temperature of 160°C to 200°C.

[0099] The thickness of the film of the present invention can be appropriately determined taking into consideration film-forming properties, applications and required properties, and handling properties. From the viewpoints of film-forming properties and handling properties, the thickness of the film of the present invention may be usually 20 μm or more, preferably 50 μm or more. On the other hand, from the viewpoint of meeting the demand for thinner articles containing the film of the present invention, the thickness of the film may be usually 1000 μm or less, preferably 500 μm or less, more preferably 200 μm or less.

[0100] The film of the present invention may be transparent, opaque, colored and transparent, or colored and opaque.

[0101] In one embodiment, the transparent film of the present invention can be suitably used as a film substrate for a decorative sheet to be attached to glass, such as a glass decorative film, etc. In one embodiment, the opaque or concealing film of the present invention can be suitably used as a film substrate for a decorative sheet to be used for decorating and decorating home appliances, furniture, and building components, and for wallpaper to be used for decorating and decorating the walls of buildings.

[0102] FIG. 1 is a conceptual cross-sectional view showing an example of wallpaper using the film of the present invention. This wallpaper comprises, from the surface side, a coating film 1 formed using a two-component curing urethane paint, a transparent thermoplastic resin film layer 2, a printed layer 3, a white-colored, concealing film layer 4 of the present invention, and a pressure-sensitive adhesive layer 5. In this specification, the "surface side" refers to the side that is normally visible in actual use. In the case of wallpaper, for example, the "actual use state" refers to the state in which the wallpaper is used to decorate and decorate the walls of a building.

[0103] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0104] Measurement Method (i) Heat Press Resistance Test (Process Thermal Stability) A polyvinyl chloride resin composition was used, and the composition was preheated at 180°C for 2 minutes, followed by heat pressing for 2 minutes, and immediately thereafter, by cold pressing at 20°C for 2 minutes to obtain Sample 1 having a thickness of 1 mm. Next, the L*a*b* coordinates of Sample 1 were determined by the measurement method described below. Next, Sample 1 was preheated at 190°C for 2 minutes, followed by heat pressing for 30 minutes, and immediately thereafter, by cold pressing at 20°C for 2 minutes to obtain Sample 2. Next, the L*a*b* coordinates of Sample 2 were determined by the measurement method described below. Here, the L*a*b* coordinates were measured in accordance with JIS Z8722:2009 using a spectrophotometer "CM600d" (product name) manufactured by Konita Minolta Japan Co., Ltd., by placing a sample on the surface of a white plate identical to the white calibration plate attached to the spectrophotometer, and measuring the XYZ coordinates under geometric condition c, a condition including a component that results in specular reflection, and then converting the measured values.２ *) and b* (b １ *) and the difference between these (b ２ *-b １ *) and calculated Δb*. Furthermore, the color difference (ΔE) was calculated from the L*a*b* coordinates of Sample 1 and the L*a*b* coordinates of Sample 2 using the calculation method (ΔE*ab (CIE1976)) built into the spectrophotometer. For information on measuring L*a*b* coordinates, etc., please refer to the website of Konita Minolta Japan Co., Ltd. (address below). http: / / www.konicaminolta.jp / instruments / knowledge / color / part1 / 07.html

[0105] Raw materials used: (A) Polyvinyl chloride resin (A-1) Polyvinyl chloride homopolymer with an average degree of polymerization of 800.

[0106] (B) Core-shell rubber (B-1) Mitsubishi Chemical Corporation's core-shell rubber (methyl methacrylate-styrene / ethyl acrylate rubber graft copolymer) "Metablen W-300A" (trade name).

[0107] (C) β-diketone compounds (C-1) Dibenzoylmethane. CAS No. 120-46-7. (C-2) Stearoylbenzoylmethane (1-phenyl-1,3-eicosanedione). CAS No. 58446-52-9.

[0108] (D) Phosphite Compounds (D-1) ADEKA Corporation's alkylaryl phosphite "ADEKA STAB 135A" (trade name). Isodecyl diphenyl phosphite. CAS number 26544-23-0. (D-2) ADEKA Corporation's trialkyl phosphite "ADEKA STAB 3010" (trade name). Triisodecyl phosphite. CAS number 25448-25-3. (D-3) ADEKA Corporation's triaryl phosphite "ADEKA STAB TPP" (trade name). Triphenyl phosphite. CAS number 101-02-0.

[0109] (E) Flame Retardants (E-1) Brominated hydrocarbon flame retardant (1,2-bis(pentabromophenyl)ethane) "SAYTEX8010" (trade name) from Albemarle Japan Co., Ltd. (E-2) Antimony flame retardant (antimony trioxide) "MSA-S" (trade name) from Yamanaka Sangyo Co., Ltd.

[0110] (F) Plasticizers (F-1) Diisononyl phthalate "DINP" (trade name) from J-Plus Corporation. (F-2) Epoxidized soybean oil "O-130S" (trade name) from ADEKA Corporation.

[0111] (G) Barium-Zinc Complex Compound (G-1) A 2:1:1 (mass ratio) mixture of barium caprate, zinc bis-4-t-butylbenzoate, and zinc bis-p-toluate.

[0112] (H) Hydrotalcite (H-1) Carbonate ion magnesium aluminum type hydrotalcite "FD-200" (trade name) manufactured by Akishima Chemical Industry Co., Ltd.

[0113] (J) Ultraviolet absorber (J-1) Benzotriazole-based ultraviolet absorber "Tinuvin 326" (trade name) from BASF Japan Ltd.

[0114] (K) Other optional components (K-1) Acrylic processing aid "P-530A" (trade name) from Mitsubishi Chemical Corporation. (K-2) Titanium oxide (white pigment) "CR-90" (trade name) from Ishihara Sangyo Kaisha, Ltd.

[0115] Example 1 A blend consisting of 100 parts by mass of a resin mixture consisting of 90% by mass of the component (A-1) and 10% by mass of the component (B-1), 0.20 parts by mass of the component (C-1), 0.50 parts by mass of the component (D-1), 7.5 parts by mass of the component (E-1), 2.5 parts by mass of the component (E-2), 13 parts by mass of the component (F-1), 4 parts by mass of the component (F-2), 3.0 parts by mass of the component (G-1), 0.30 parts by mass of the component (H-1), 0.40 parts by mass of the component (J-1), 1 part by mass of the component (K-1), and 15 parts by mass of the component (K-2) was melt-kneaded using a mixer kneader under the condition of a resin temperature of 140°C upon discharge, to obtain a polyvinyl chloride resin composition.

[0116] Examples 2 to 12 Polyvinyl chloride resin compositions were obtained in the same manner as in Example 1, except that the formulation was changed as shown in Table 1. The above test (i) was carried out. The results are shown in Table 1.

[0117]

[0118] In addition, since Example 10 had turned strongly yellow when Sample 1 was prepared in the above test (i), it was judged to have poor color tone from the beginning, and the test was discontinued. In the table, this is indicated as "poor initial adhesion" (an abbreviation indicating poor coloring at the beginning of the test).

[0119] Furthermore, long-run film production tests were conducted for Examples 1, 5-7, 9, and 12. Examples 9 and 12 were comparative examples because they used polyvinyl chloride resin compositions that did not contain component (C). The formulations shown in Table 1 were melt-kneaded using a mixer kneader at a discharge resin temperature of 140°C to obtain polyvinyl chloride resin compositions. The resulting compositions were then sent directly to a calendar roll film-forming apparatus equipped with an inverted L-shaped four-roll calendar roll mill and a winding device. Long-run production of 80 μm-thick films was carried out under the following conditions: first roll 180°C, second roll 180°C, third roll 185°C, fourth roll 180°C, and a winding speed of 60 m / min. For Film 1 immediately after the start of production and Film 2 after 5,000 m of continuous production had been completed, the L*a*b* coordinates were determined using the method described in Test (i) above, and the color difference (ΔE) and Δb* were calculated. The results are shown in Table 1.

[0120] It has been found that the polyvinyl chloride resin composition of the present invention, even if it contains a flame retardant, has excellent process heat stability and inhibits discoloration during continuous film production. Therefore, it is considered that a film made from the polyvinyl chloride resin composition of the present invention can be suitably used as a film substrate for wallpaper or decorative sheets.

[0121] 1: Coating film formed using a two-component curing urethane paint 2: Transparent thermoplastic resin film layer 3: Printed layer 4: White-colored film layer of the present invention having hiding properties 5: Pressure-sensitive adhesive layer

Claims

1. (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 the resin mixture consisting of (C) 0.01 to 5 parts by mass of a β-diketone compound, (D) 0.01 to 10 parts by mass of a phosphite compound, and (E) Flame retardant 1 to 100 parts by mass Including, Here, the sum of the blending amount of (A) polyvinyl chloride resin and the blending amount of (B) core-shell rubber in the resin mixture is 100% by mass. Polyvinyl chloride resin composition for films.

2. (E) A polyvinyl chloride resin composition for films as described in claim 1, wherein the flame retardant includes a flame retardant containing a halogen element.

3. (E) A polyvinyl chloride resin composition for films as described in claim 1, wherein the flame retardant includes a brominated hydrocarbon flame retardant and an antimony flame retardant.

4. 2. The polyvinyl chloride resin composition for films according to claim 1, wherein the phosphite compound (D) comprises at least one selected from the group consisting of trialkyl phosphites, alkylaryl phosphites, and triaryl phosphites.

5. 2. The polyvinyl chloride resin composition for films according to claim 1, wherein the phosphite compound (D) comprises at least one selected from the group consisting of trialkyl phosphites and alkylaryl phosphites.

6. 2. The polyvinyl chloride resin composition for films according to claim 1, wherein the phosphite compound (D) comprises a trialkyl phosphite and an alkylaryl phosphite.

7. 2. The polyvinyl chloride resin composition for films according to claim 1, which does not contain a hindered phenol compound.

8. Furthermore, for 100 parts by mass of the resin mixture consisting of (A) polyvinyl chloride resin and (B) core-shell rubber, (F) 1 to 250 parts by mass of a plasticizer; (G) 0.01 to 10 parts by mass of a barium-zinc complex compound; (H) 0.01 to 3 parts by mass of hydrotalcite; and (J) UV absorber 0.01 to 10 parts by mass The polyvinyl chloride resin composition for films according to claim 1, comprising:

9. A film formed from the polyvinyl chloride resin composition for film described in any one of claims 1 to 8.

10. Wallpaper or decorative sheet comprising the film described in claim 9.