Polyvinyl chloride resin composition and film

Abstract

Provided are: a polyvinyl chloride-based resin composition which has excellent process thermal stability and is capable of suppressing coloring during continuous production of a film; and a film which is composed of the composition and is suitable as a wallpaper base material having a white color-based design. The present invention pertains to a polyvinyl chloride resin composition containing 0.01-5 parts by mass of (C) a beta-diketone compound, 0.01-10 parts by mass of (D) a phosphite ester compound, and 0-100 parts by mass of (E) a flame retardant per 100 parts by mass of a resin mixture comprising (A) 60-100% by mass of a polyvinyl chloride resin and (B) 40-0% by mass of a core-shell rubber, wherein the sum of the blending amount of (A) the polyvinyl chloride resin and the blending amount of (B) the core-shell rubber in the resin mixture is 100 mass%. The phosphite ester compound (D) may contain one or more substances selected from among trialkyl phosphite esters, alkylaryl phosphite esters, and triaryl phosphite esters.

Description

TECHNICAL FIELD

[0001] The present application relates to a polyvinyl chloride-based resin composition and a film.

[0002] More specifically, the present application relates to a polyvinyl chloride-based resin composition and a film which can suppress discoloration when continuously producing a film. BACKGROUND

[0003] Conventionally, a decorative / adorned adhesive film (so-called wall paper) is attached to the surface of a wall of a building made of a wooden material such as wood, plywood, integrated wood, particle board, and hardboard; a metallic material such as iron and aluminum; and an inorganic material such as gypsum, to perform decoration / adornment. Further, a decorative sheet is attached to the surface of a member of a home appliance such as a refrigerator, a washing machine, an air conditioner, a mobile phone, and a personal computer; a member of furniture such as a decorative shelf, a storage cabinet, a dish cabinet, and a table; or a surface of a base material formed of a wooden material such as wood, plywood, integrated wood, particle board, and hardboard as a building material such as a floor, a wall, and a bathroom; a base material formed of a resin material such as polystyrene, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate, and polyester; or a base material formed of a metallic material such as iron and aluminum, to perform decoration / adornment. These wall papers and decorative sheets are often designed with white as a base tone. Further, a film base material of the wall paper and the decorative sheet is often formed of a polyvinyl chloride-based resin composition. This is because the polyvinyl chloride-based resin composition can adjust the softness in a wide range depending on the amount of a plasticizer, and has good molding processability, mechanical properties, flame retardancy, and other properties, and is also excellent in economy. However, many polyvinyl chloride-based resin compositions have insufficient process heat stability. Therefore, when a film is continuously produced using a polyvinyl chloride-based resin composition, there is a problem that a yellow tone gradually increases, resulting in inability to impart a desired design, particularly in a design with white as a base tone, inability to exhibit a desired white color.

[0004] Further, according to the Building Standards Act, a material used for interior finishing of a building must use a fireproof material. Such a fireproof material is classified as "non-combustible material", "quasi-non-combustible material", and "flame retardant material", and only a material that passes a test prescribed by the Ministry of Land, Infrastructure, Transport and Tourism can be certified and used. Therefore, a decorative surface material such as a wall paper used for interior finishing of a building needs to be certified at least in any one of them. For this reason, a material of a film base material of the wall paper needs to use a material mixed with a flame retardant. However, a polyvinyl chloride-based resin composition mixed with a flame retardant, particularly a polyvinyl chloride-based resin composition mixed with a halogen-containing flame retardant, has insufficient process heat stability, and there is a problem that a yellow tone easily gradually increases when a film is continuously produced.

[0005] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2017-105929 Patent Document 2: Japanese Patent Application Publication No. 07-048493 Patent Document 3: Japanese Patent Application Publication No. 2020-041033 Summary of the Invention The problem that the invention aims to solve The objective of this invention is to provide a polyvinyl chloride resin composition and film that have good process thermal stability and can suppress coloring during continuous film production.

[0006] Methods for solving problems Through in-depth research, the inventors discovered that the above-mentioned problems can be achieved through specific polyvinyl chloride resin compositions.

[0007] That is, the various embodiments of the present invention are described below. [1]. Polyvinyl chloride resin compositions, relative to those made from (A) Polyvinyl chloride resin 60-100% by mass (B) Core-shell rubber 40-0% by mass 100 parts by weight of the resin mixture comprising (C) 0.01–5 parts by weight of β-diketone compounds, (D) 0.01–10 parts by weight of phosphite compounds, and (E) 0-100 parts by weight of flame retardant; The sum of the mixing amount of (A) polyvinyl chloride resin and (B) core-shell rubber in the above resin mixture is 100 by mass. [2]. According to the polyvinyl chloride resin composition described in [1], (D) the phosphite compound comprises one or more selected from trialkyl phosphite, alkylaryl phosphite and triaryl phosphite. [3]. According to the polyvinyl chloride resin composition described in [1], (D) the phosphite compound comprises one or more selected from trialkyl phosphites and alkylaryl phosphites. [4]. According to the polyvinyl chloride resin composition described in [1], (D) the phosphite compound comprises a trialkyl phosphite and an alkylaryl phosphite. [5]. The polyvinyl chloride resin composition according to any one of [1] to [4] is free of hindered phenolic compounds. [6]. The polyvinyl chloride resin composition according to any one of [1] to [5] further comprises, relative to 100 parts by weight of the above resin mixture consisting of (A) polyvinyl chloride resin and (B) core-shell rubber, 1 to 100 parts by weight of (E) flame retardant. [7]. According to any one of [1] to [6], the polyvinyl chloride resin composition, (E) flame retardant comprises a halogenated flame retardant. [8]. According to any one of [1] to [7], the polyvinyl chloride resin composition (E) comprises a brominated hydrocarbon flame retardant and an antimony flame retardant. [9]. The polyvinyl chloride resin composition according to any one of [1] to [8] further comprises: (F) Plasticizer 1-250 parts by weight; (G) Barium-zinc complex, 0.01–10 parts by weight; (H) 0.01–3 parts by weight of hydrotalcite; and, (J) 0.01 to 10 parts by weight of ultraviolet absorber.

[10] The film is formed from a polyvinyl chloride resin composition as described in any one of [1] to [9].

[11] . Wallpaper or decorative sheet comprising the film described in

[10] .

[0019] Invention Effects The polyvinyl chloride (PVC) resin compositions of the present invention exhibit good process thermal stability, suppressing coloration during continuous film production. Preferred PVC resin compositions of the present invention maintain excellent process thermal stability even when containing flame retardants, suppressing coloration during continuous film production. Therefore, films formed from the PVC resin compositions of the present invention are suitable for use as film substrates for wallpaper and decorative sheets. Thus, the preferred PVC resin compositions of the present invention, as film substrates with a white base and flame-retardant properties, are suitable for use as wallpaper and decorative sheets. Attached Figure Description

[0020] Figure 1 This is a cross-sectional schematic diagram illustrating an example of wallpaper using the film of the present invention. Detailed Implementation

[0021] In this specification, the term "resin" is used as a term for a resin mixture comprising two or more resins, or a resin composition comprising components other than resins.

[0022] In this specification, the terms "film" and "sheet" are used interchangeably or interchangeably. In this specification, the terms "film" and "sheet" are used for materials that can be industrially wound into rolls. The term "plate" is used for materials that cannot be industrially wound into rolls. Furthermore, in this specification, "laminating one layer with other layers in sequence" includes both directly laminating these layers and laminating other layers, such as a primer, between these layers.

[0023] In this specification, the term "above" in relation to a numerical range is used to indicate a value or greater than a certain value. For example, "above 20%" means 20% or greater than 20%. The term "below" in relation to a numerical range is used to indicate a value or less than a certain value. For example, "below 20%" means 20% or less than 20%. Furthermore, the numerical range "x~y" containing the symbol "~" is used to indicate a value x, a value greater than x and less than another value y, or another value y. Here, the other value y is a value greater than a value x. For example, 10~90% means 10%, greater than 10% and less than 90%, or 90%. Further, the upper and lower limits of the numerical range can be arbitrarily combined and should be interpreted as any combination of implementation methods. For example, if the description of the numerical range of a certain characteristic states "usually 10% or more, preferably 20% or more. On the other hand, usually 40% or less, preferably 30% or less," or "usually 10 to 40%, preferably 20 to 30%," it should be interpreted as the numerical range of that characteristic being 10 to 40%, 20 to 30%, 10 to 30%, or 20 to 40% in one embodiment.

[0024] Except in the embodiments, or unless otherwise stated, all numerical values ​​used in this specification and the 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 interpreted according to significant figures and using conventional rounding methods.

[0025] In this specification, terms used to define shape and geometric conditions, such as parallel, orthogonal, and perpendicular, include not only their strict meanings but also substantially the same state.

[0026] In this specification, when it is stated that "comprising a substance", it should be interpreted as meaning that in one embodiment, the composition contains a substance, is composed of a substance, or is composed of only a substance. For example, according to the description "composition A comprises substance a1 and substance a2", it should be interpreted as meaning that in one embodiment, composition A contains substance a1 and substance a2, composition A is composed of substance a1 and substance a2, or composition A is composed of only substance a1 and substance a2.

[0027] 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, in addition to components (A), (C), and (D), or in addition to components (A), (B), (C), and (D), further comprises (E) a flame retardant. The components are described below.

[0028] (A) Polyvinyl chloride resins The polyvinyl chloride resin composition of the present invention comprises (A) a polyvinyl chloride resin. (A) The polyvinyl chloride resin is a polymer (including copolymers) that mainly comprises structural units represented by (-CH2-CHCl-) (with the sum of all structural units being 100% by mass, typically 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).

[0029] 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-(meth)acrylate copolymer, vinyl chloride-(meth)acrylate methyl ester copolymer, vinyl chloride-(meth)acrylate ethyl ester 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-chloropropylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymers, etc., in which vinyl chloride is copolymerized with other monomers that can be copolymerized with vinyl chloride; and substances obtained by modifying polyvinyl chloride and vinyl chloride copolymers by means of post-chlorination vinyl copolymers, etc. Furthermore, in this specification, chlorinated polyolefins such as chlorinated polyethylene are also included in the scope of (A) polyvinyl chloride resins.

[0030] (A) Polyvinyl chloride resins may preferably contain polyvinyl chloride (vinyl chloride homopolymer).

[0031] (A) From the viewpoint of suppressing coloration during continuous film production, the average degree of polymerization of the polyvinyl chloride resin is preferably 2500 or less, more preferably 1500 or less, even more preferably 1300 or less, and most preferably 1000 or less. On the other hand, from the viewpoint of the mechanical properties of the film, the average degree of polymerization of the polyvinyl chloride resin is preferably 300 or more, more preferably 500 or more, and even more preferably 650 or more.

[0032] In this specification, the average degree of polymerization of polyvinyl chloride resins is determined according to the specific viscosity in section 4.1 of JIS K6720-2:1999, and the specific viscosity is calculated according to the formulas (1) and (2) of the JIS standard.

[0033] As (A) polyvinyl chloride resin, one or a mixture of two or more of them can be used.

[0034] (B) Core-shell rubber In one embodiment, the polyvinyl chloride resin composition of the present invention may further comprise (B) a core-shell rubber. The inclusion of a core-shell rubber improves the calender roll calendering film-forming properties and weather resistance.

[0035] Examples of (B) core-shell rubbers include: methacrylate-styrene / butadiene rubber graft copolymers, methacrylate-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 / acrylate rubber graft copolymers, methacrylate-styrene / acrylate rubber graft copolymers, and methacrylate-acrylonitrile / acrylate rubber graft copolymers, etc.

[0036] From a weather resistance perspective, (B) the core-shell rubber preferably comprises an acrylic core-shell rubber that is a graft copolymer of (meth)acrylate rubber with (meth)acrylate, acrylonitrile, styrene, etc. Examples of such acrylic core-shell rubbers include, for instance, acrylonitrile-styrene / acrylate rubber graft copolymers, methacrylate / acrylate rubber graft copolymers, methacrylate-styrene / acrylate rubber graft copolymers, and methacrylate-acrylonitrile / acrylate rubber graft copolymers. In this specification, "(meth)acrylate" refers to acrylate or methacrylate.

[0037] As (B) core-shell rubber, one or a mixture of two or more of them can be used.

[0038] Since the core-shell rubber (B) is an optional component, there is no particular limitation on its mixing amount. From the viewpoint of reliably obtaining improved film-forming properties of calender rolls and good weather resistance, with the sum of the mixing amount of the polyvinyl chloride resin (A) and the mixing amount of the core-shell rubber (B) being 100% by mass, the mixing amount of the core-shell rubber (B) is generally 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)). On the other hand, from the viewpoint of the mechanical properties of the film, with the sum of the blending amount of (A) polyvinyl chloride resin and the blending amount of (B) core-shell rubber being 100% by mass, the blending amount of (B) core-shell rubber is preferably 40% by mass or less (the above-mentioned component (A) is 60% by mass or more), more preferably 30% by mass or less (the above-mentioned component (A) is 70% by mass or more), further preferably 20% by mass or less (the above-mentioned component (A) is 80% by mass or more), and most preferably 15% by mass or less (the above-mentioned component (A) is 85% by mass or more).

[0039] With the sum of the blending amount of (A) polyvinyl chloride resin and the blending amount of (B) core-shell rubber being 100% by mass, the blending amount of (B) core-shell rubber can generally be 0% or more and 40% or less by mass, preferably 0% or more and 30% or less by mass, 0% or more and 20% or less by mass, 0% or more and 15% or less by mass, 1% or more and 40% or less by mass, 1% or more and 30% or less by mass, 1% or more and 20% or less by mass, 1% or more and 15% or less by mass, 3% or more and 40% or less by mass, 3% or more and 30% or less by mass, 3% or more and 20% or less by mass, 3% or more and 15% or less by mass, 5% or more and 40% or less by mass, 5% or more and 30% or less by mass, 5% or more and 20% or less by mass, or 5% or more and 15% or less by mass.

[0040] (C) β-Diketone compounds The polyvinyl chloride resin compositions of the present invention comprise (C)β-diketone compounds. (C)β-diketone compounds are organic compounds having a structure in which two ketone groups are linked by a single carbon atom (-CO-C-CO-). (C)β-diketone compounds also include triketone compounds having a β-diketone structure. The inventors have discovered that (C)β-diketone compounds, through synergistic effects with (D) phosphite compounds, can significantly suppress coloration during continuous film production.

[0041] Examples of (C)β-diketone compounds include: acetylacetone, triacetylmethane, 2,4,6-heptanedione, butyrylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylbenzoylmethane (1-phenyl-1,3-eicosanodione), palmitoylbenzoylmethane, distearatemethane (stearoyl=octadecanoyl), stearoylacetylmethane, benzylacetone, dicyclohexylcarbonylmethane, benzoylcarboxylmethane, benzoylacetylmethane, dibenzoylmethane, octylbenzoylmethane, bis(4-octylbenzoyl) Methane, benzoyldiacetylmethane, 4-methoxybenzoylbenzoylmethane, bis(4-carboxymethylbenzoyl)methane, 2-carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, ethyl acetoacetate, cyclohexane-1,3-dione, methyl 3,6-dimethyl-2,4-dioxocyclohexane-1-carboxylate, 2-acetylcyclohexanone, dimethionine, 2-benzoylcyclohexane-1-one, and 2-benzoylcyclohexane-1,3-dione, as well as their derivatives, such as lithium, sodium, potassium, calcium, zinc, magnesium, and aluminum salts.

[0042] From the viewpoint of suppressing coloration during continuous film production, (C) β-diketone compound preferably includes one or more β-diketone compounds selected from dibenzoylmethane, stearoyl benzoylmethane, dibenzoylmethane derivatives and stearoyl benzoylmethane derivatives.

[0043] As (C)β-diketone compounds, one or a mixture of two or more of them can be used.

[0044] From the viewpoint of suppressing coloration during continuous film production, the amount of (C) β-diketone compound mixed in relation to 100 parts by weight of the resin mixture consisting of (A) polyvinyl chloride resin and (B) core-shell rubber is typically 0.01 parts by weight or more, preferably 0.03 parts by weight or more, and more preferably 0.05 parts by weight or more. On the other hand, from the viewpoint of weather resistance, it is typically 5 parts by weight or less, preferably 1 part by weight or less, more preferably 0.5 parts by weight or less, further preferably 0.3 parts by weight or less, even more preferably 0.2 parts by weight or less, and most preferably 0.1 parts by weight or less.

[0045] Relative to 100 parts by weight of the resin mixture consisting of (A) polyvinyl chloride resin and (B) core-shell rubber, the amount of (C) β-diketone compound is typically 0.01 parts by weight or more and 5 parts by weight or less, preferably 0.01 parts by weight or more and 1 part by weight or less, 0.01 parts by weight or more and 0.5 parts by weight or less, 0.01 parts by weight or more and 0.3 parts by weight or less, 0.01 parts by weight or more and 0.2 parts by weight or less, 0.01 parts by weight or more and 0.1 parts by weight or more, or 0.03 parts by weight or more. And less than 1 part by weight, more than 0.03 parts by weight and less than 0.5 parts by weight, more than 0.03 parts by weight and less than 0.3 parts by weight, more than 0.03 parts by weight and less than 0.2 parts by weight, more than 0.03 parts by weight and less than 0.1 parts by weight, more than 0.05 parts by weight and less than 1 part by weight, more than 0.05 parts by weight and less than 0.5 parts by weight, more than 0.05 parts by weight and less than 0.3 parts by weight, more than 0.05 parts by weight and less than 0.2 parts by weight, or more than 0.05 parts by weight and less than 0.1 parts by weight.

[0046] (D) Phosphite compounds The polyvinyl chloride resin composition of the present invention comprises a (D) phosphite compound. The (D) phosphite compound is an organic compound having a phosphite structure. Furthermore, the phosphite compound is an organic compound that functions as a so-called secondary antioxidant, possessing the ability to decompose peroxides and reduce quinone structures to phenolic structures. The inventors have discovered that the (D) phosphite compound, through synergistic action with the (C) β-diketone compound, can significantly suppress coloration during continuous film production.

[0047] Examples of (D) phosphite compounds include: Trialkyl phosphites, such as trioleyl phosphite, trilauryl phosphite, triisodecyl phosphite, and tri(2-ethylhexyl) phosphite; alkylaryl phosphites, such as 2-ethylhexyl diphenyl phosphite, isodeyl diphenyl phosphite, decyl diphenyl phosphite, and 2,2'-methylenebis(4,6-di-tert-butylphenyl)2-ethylhexyl phosphite; and triaryl phosphites and other organic compounds containing a phosphite structure in one molecule, such as tris(2,4-di-tert-butylphenyl) phosphite, trinonylphenyl phosphite, trimethylyl phosphite, and triphenyl phosphite; and... Compounds containing two or more phosphite structures in one molecule include tetraphenyldipropylene glycol diphosphite, 4,4'-butylidene bis(3-methyl-6-tert-butylphenyl tridecyl) phosphite, bis(decyl) pentaerythritol diphosphite, di(tetrazyl) pentaerythritol diphosphite, distearate pentaerythritol diphosphite, tetra(dodecyl)(propane-2,2-diylbis(4,1-phenylene))bis(phosphite), 3,9-di(octadecoxy)-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane, and 3,9-di(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosspiro[5.5]undecane.

[0048] From the viewpoint of suppressing precipitation on the film surface, preferably, the (D) phosphite compound may include a compound having one phosphite structure in one molecule. In one embodiment, from the viewpoint of suppressing precipitation on the film surface, the (D) phosphite compound may not include a compound having two or more phosphite structures in one molecule.

[0049] In this specification, "not containing a certain component" means that the component has not been intentionally mixed in. In the technical field of polyvinyl chloride resin compositions, when a certain component is intentionally mixed in, it is usually mixed in at least 0.01 parts by weight in the composition. Therefore, it can be understood that "not containing a certain component" in the polyvinyl chloride resin composition of the present invention means that, relative to 100 parts by weight of the resin mixture composed of the above-described component (A) polyvinyl chloride resin and the above-described component (B) core-shell rubber, the content of the component is usually less than 0.01 parts by weight, preferably less than 0.001 parts by weight, more preferably less than 0.0001 parts by weight, and even more preferably substantially 0 parts by weight.

[0050] From the viewpoint of suppressing coloration during continuous film production, the (D) phosphite compound is preferably a compound comprising one or more compounds selected from trialkyl phosphites, alkylaryl phosphites, and triaryl phosphites; more preferably, it is a compound comprising one or more compounds selected from trialkyl phosphites and alkylaryl phosphites; and even more preferably, it is a compound comprising trialkyl phosphites. In one preferred embodiment, the (D) phosphite compound is a compound comprising trialkyl phosphites and alkylaryl phosphites.

[0051] As (D) phosphite compounds, one or a mixture of two or more of them may be used.

[0052] From the viewpoint of suppressing coloration during continuous film production, the amount of (D) phosphite compound mixed in relation to 100 parts by mass of the resin mixture composed of (A) polyvinyl chloride resin and (B) core-shell rubber is 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, further preferably 0.3 parts by mass or more, and most preferably 0.5 parts by mass or more. On the other hand, from the viewpoint of suppressing the hydrolysis of phosphite compound, the amount of (D) phosphite compound mixed in relation to 100 parts by mass of the resin mixture composed of (A) polyvinyl chloride resin and (B) core-shell rubber is typically 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, further preferably 2 parts by mass or less, and most preferably 1.5 parts by mass or less.

[0053] Relative to 100 parts by weight of the resin mixture consisting of (A) polyvinyl chloride resin and (B) core-shell rubber, the amount of (D) phosphite compound can typically be 0.01 parts by weight or more and 10 parts by weight or less, preferably 0.01 parts by weight or more and 5 parts by weight or less, 0.01 parts by weight or more and 3 parts by weight or less, 0.01 parts by weight or more and 2 parts by weight or less, 0.01 parts by weight or more and 1.5 parts by weight or less, 0.05 parts by weight or more and 10 parts by weight or less, 0.05 parts by weight or more and 5 parts by weight or less, 0.05 parts by weight or more and 3 parts by weight or less, 0.05 parts by weight or more and 2 parts by weight or less, 0.05 parts by weight or more and 1.5 parts by weight or less, or 0.1 parts by weight or more. And less than 10 parts by weight, more than 0.1 parts by weight and less than 5 parts by weight, more than 0.1 parts by weight and less than 3 parts by weight, more than 0.1 parts by weight and less than 2 parts by weight, more than 0.1 parts by weight and less than 1.5 parts by weight, more than 0.3 parts by weight and less than 10 parts by weight, more than 0.3 parts by weight and less than 5 parts by weight, more than 0.3 parts by weight and less than 3 parts by weight, more than 0.3 parts by weight and less than 2 parts by weight, more than 0.3 parts by weight and less than 1.5 parts by weight, more than 0.5 parts by weight and less than 10 parts by weight, more than 0.5 parts by weight and less than 5 parts by weight, more than 0.5 parts by weight and less than 3 parts by weight, more than 0.5 parts by weight and less than 2 parts by weight, or more than 0.5 parts by weight and less than 1.5 parts by weight.

[0054] (E) Flame retardant In one preferred embodiment, the polyvinyl chloride resin composition of the present invention may further include (E) a flame retardant. There are no particular limitations on the (E) flame retardant, as long as it is a flame retardant commonly used in polyvinyl chloride resin compositions. Since the above-mentioned component (E) flame retardant is preferably used as a film substrate for wallpaper or decorative sheets, there are no particular limitations on the (E) flame retardant, as long as it does not cause coloring that hinders the desired design. Here, the (E) flame retardant does not include compounds belonging to any of components (A) to (D) above that have flame-retardant properties. That is, compounds belonging to any of components (A) to (D) above are excluded from the (E) flame retardant.

[0055] Examples of flame retardants (E) include antimony flame retardants, halogen flame retardants, metal hydroxides, zinc flame retardants, phosphorus flame retardants, and nitrogen-containing compound flame retardants.

[0056] Examples of antimony-based flame retardants include antimony trioxide, antimony pentoxide, antimony trichloride, antimony borate, and antimony molybdate.

[0057] Examples of halogenated flame retardants include: 1,2-bis(pentabromophenyl)ethane, pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, bis(tetrabromophthalimide)ethane, poly(dibromopropyl ether), tetrabromobisphenol A carbonate oligomers, tetrabromobisphenol A epoxy oligomers, tetrabromobisphenol A-bis(dibromopropyl ether), brominated polystyrene, and hexabromobenzene, etc.; as well as chlorinated hydrocarbon flame retardants such as chlorinated paraffin, chlorinated polyphenylene, and perchloropentacyclodecane, etc.

[0058] Examples of the aforementioned metal hydroxides include aluminum hydroxide and magnesium hydroxide.

[0059] Examples of zinc-based flame retardants include zinc stannate and zinc borate.

[0060] The aforementioned phosphorus-based flame retardants include, for example, organophosphate flame retardants such as: trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, tripentyl phosphate, tripentyl phosphate, tri(2-ethylhexyl) phosphate, tri(butylated phenyl) phosphate, tri(isopropylated phenyl) phosphate, triphenyl phosphate, tris(dimethyl) phosphate, and tert-butyl diphenyl phosphate, etc.; condensed from two or more molecules of one or more organophosphates. Flame retardants consisting mainly of condensed organophosphates; compounds in which one or more hydrogen atoms of an organophosphate or condensed organophosphate are replaced by bromine atoms, such as brominated organophosphates like tris(tribromoneopentyl)phosphate; compounds in which one or more hydrogen atoms of an organophosphate or condensed organophosphate are replaced by chlorine atoms, such as chlorinated organophosphates like tris(2,3-dichloropropyl) phosphate; and ammonium polyphosphate flame retardants, etc.

[0061] Examples of nitrogen-containing compound flame retardants include: cyanurate flame retardants such as melamine cyanurate, tris(2-hydroxyethyl) isocyanurate and tris(2,3-epoxypropyl) isocyanurate; triazine flame retardants; and guanidine flame retardants.

[0062] From the viewpoint that a relatively small amount of the mixture can pass the fire-retardant material test stipulated by the Ministry of Land, Infrastructure, Transport and Tourism, the flame retardant (E) preferably contains one or more of the brominated hydrocarbon flame retardants and the antimony flame retardants described above. In one preferred embodiment, the flame retardant (E) may contain both the brominated hydrocarbon flame retardants and the antimony flame retardants described above.

[0063] In one of the other embodiments, (E) the flame retardant may also include a halogenated flame retardant. Examples of such halogenated flame retardants include: the aforementioned brominated hydrocarbon flame retardants, the aforementioned brominated organophosphate flame retardants, and the aforementioned chlorinated organophosphate flame retardants.

[0064] As (E) flame retardants, one or a mixture of two or more of them may be used.

[0065] Since (E) flame retardant is an optional component, there are no particular restrictions on the amount to be mixed.

[0066] In one embodiment, the polyvinyl chloride resin composition of the present invention may be a composition that does not contain (E) flame retardant.

[0067] From the perspective of testing fire-retardant materials as stipulated in the Ministry of Land, Infrastructure, Transport and Tourism's announcement, the amount of flame retardant (E) mixed with 100 parts by weight of a resin mixture consisting of (A) polyvinyl chloride resin and (B) core-shell rubber is preferably 1 part by weight or more, more preferably 3 parts by weight or more, and even more preferably 5 parts by weight or more. On the other hand, from the perspective of suppressing coloration during continuous film production, the amount of flame retardant (E) mixed with 100 parts by weight of a resin mixture consisting of (A) polyvinyl chloride resin and (B) core-shell rubber is preferably 100 parts by weight or less, more preferably 60 parts by weight or less, even more preferably 35 parts by weight or less, even more preferably 20 parts by weight or less, and most preferably 15 parts by weight or less.

[0068] Relative to 100 parts by weight of the resin mixture consisting of (A) polyvinyl chloride resin and (B) core-shell rubber, the amount of flame retardant (E) can typically be 0 parts by weight or more and 100 parts by weight or less, preferably 0 parts by weight or more and 60 parts by weight or less, 0 parts by weight or more and 35 parts by weight or less, 0 parts by weight or more and 20 parts by weight or less, 0 parts by weight or more and 15 parts by weight or less, 1 part by weight or more and 100 parts by weight or less, 1 part by weight or more and 60 parts by weight or less, 1 part by weight or more and 35 parts by weight or less, 1 part by weight or more, 1 part ... more, 1 part by weight or less, 1 part by weight or more, 1 part by weight or more, 1 part by weight or more, 1 part by weight or more, 1 part by weight or more, 1 part by weight or more, 1 part by weight or more, 1 part by weight or more, 1 part by weight or more, 1 part by weight or more, 1 part by weight or more, 1 part by weight or more, 1 part by weight or more, 1 part by weight or more, 1 part by weight or more, 1 part by weight or more, 1 part by weight or more, 1 part by More than 20 parts by weight, more than 1 part by weight and less than 15 parts by weight, more than 3 parts by weight and less than 100 parts by weight, more than 3 parts by weight and less than 60 parts by weight, more than 3 parts by weight and less than 35 parts by weight, more than 3 parts by weight and less than 20 parts by weight, more than 3 parts by weight and less than 15 parts by weight, more than 5 parts by weight and less than 100 parts by weight, more than 5 parts by weight and less than 60 parts by weight, more than 5 parts by weight and less than 35 parts by weight, more than 5 parts by weight and less than 20 parts by weight, or more than 5 parts by weight and less than 15 parts by weight.

[0069] (F) Plasticizer In the polyvinyl chloride resin composition of the present invention, a plasticizer (F) may be further included as needed, without departing from the purpose of the present invention. There are no particular limitations on the plasticizer (F), as long as it is a plasticizer commonly used in polyvinyl chloride resin compositions. Here, the plasticizer (F) does not include compounds that belong to any of the components (B) to (E) above and have the function of plasticizing the polyvinyl chloride resin (A). That is, compounds belonging to any of the components (B) to (E) above are excluded from the plasticizer (F).

[0070] Examples of plasticizers (F) include: phthalate plasticizers, trimellitate plasticizers, pyromellitic ester plasticizers, adipate plasticizers, itaconic acid ester plasticizers, citrate plasticizers, cyclohexane dicarboxylate plasticizers, and epoxy plasticizers.

[0071] As (F) plasticizers, examples include: polyester plasticizers obtained by using polyols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol, etc.; polycarboxylic acids such as oxaloyl, malonic acid, succinic acid, glutaric acid, adipic acid, trimellitic acid, pimelic acid, octanoic acid, maleic acid, azelaic acid, sebacic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, etc., and monohydric alcohols and monocarboxylic acids as end-capping agents as needed.

[0072] Examples of phthalate plasticizers include: dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, di-n-undecyl phthalate, di(tetrazyl) phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate.

[0073] Examples of trimellitic ester plasticizers include tri(2-ethylhexyl) trimellitate, tri(n-octyl) trimellitate, and tri(isononyl) trimellitate.

[0074] Examples of adipate ester plasticizers include di(2-ethylhexyl) adipate, dioctyl adipate, diisononyl adipate, and diisodecyl adipate.

[0075] Examples of epoxy plasticizers include epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid octyl esters, and epoxidized fatty acid alkyl esters.

[0076] Other plasticizers that can be listed as (F) include: trimellitic acid plasticizers, tetrahydrophthalic acid diester plasticizers, glyceryl ester plasticizers, epoxy hexahydrophthalic acid diester plasticizers, isosorbide diester plasticizers, phosphate ester plasticizers, azelaic acid plasticizers, sebacic acid plasticizers, stearic acid plasticizers, citric acid plasticizers, pyromellitic acid plasticizers, biphenyl tetracarboxylic acid ester plasticizers, and chlorine plasticizers, etc.

[0077] As (F) plasticizers, one or a mixture of two or more of them may be used.

[0078] Since (F) plasticizer is an optional component, there are no particular restrictions on the amount to be mixed.

[0079] In one embodiment, the polyvinyl chloride resin composition of the present invention may be a composition that does not contain (F) plasticizer.

[0080] From the viewpoint of calendering film formation, the amount of plasticizer (F) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, and most preferably 15 parts by mass or more, relative to 100 parts by mass of the resin mixture composed of (A) polyvinyl chloride resin and (B) core-shell rubber. On the other hand, from the viewpoint of suppressing problems caused by plasticizer migration, printability, and anti-blocking properties, the amount of plasticizer (F) is generally 250 parts by mass or less, preferably 150 parts by mass or less, more preferably 100 parts by mass or less, further preferably 60 parts by mass or less, even more preferably 45 parts by mass or less, and most preferably 35 parts by mass or less, relative to 100 parts by mass of the resin mixture composed of (A) polyvinyl chloride resin and (B) core-shell rubber.

[0081] Relative to 100 parts by weight of the resin mixture consisting of (A) polyvinyl chloride resin and (B) core-shell rubber, the amount of (F) plasticizer can typically be 0 to 250 parts by weight or less, preferably 0 to 150 parts by weight, 0 to 100 parts by weight, 0 to 60 parts by weight, 0 to 45 parts by weight, 0 to 35 parts by weight, 1 to 250 parts by weight, 1 to 150 parts by weight, 1 to 100 parts by weight, 1 to 60 parts by weight, 1 to 45 parts by weight, 1 to 35 parts by weight, 5 to 250 parts by weight, or 5 to 150 parts by weight. Less than 0 parts by weight, 5 to 100 parts by weight, 5 to 60 parts by weight, 5 to 45 parts by weight, 5 to 35 parts by weight, 10 to 250 parts by weight, 10 to 150 parts by weight, 10 to 100 parts by weight, 10 to 60 parts by weight, 10 to 45 parts by weight, 10 to 35 parts by weight, 15 to 250 parts by weight, 15 to 150 parts by weight, 15 to 100 parts by weight, 15 to 60 parts by weight, 15 to 45 parts by weight, or 15 to 35 parts by weight.

[0082] (G) Barium-Zinc Complex In one preferred embodiment, the polyvinyl chloride resin composition of the present invention may further comprise a (G) barium-zinc composite compound. The (G) barium-zinc composite compound, as a stabilizer in the polyvinyl chloride resin composition, typically functions to capture free chlorine.

[0083] Examples of (G) barium-zinc complexes include, for example, barium-zinc complex salts of organic acids containing barium, zinc and organic acids, and mixtures of barium salts of organic acids and zinc salts of organic acids.

[0084] Examples of organic acids mentioned above include saturated fatty acids, unsaturated fatty acids, and aromatic carboxylic acids.

[0085] Examples of the aforementioned saturated fatty acids include: straight-chain saturated fatty acids such as hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and 12-hydroxystearic acid; branched-chain saturated fatty acids such as 2-ethylhexanoic acid and 2-ethyloctanoic acid; and saturated fatty acids with alicyclic moieties such as cyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, and 4-ethylcyclohexanecarboxylic acid.

[0086] Examples of unsaturated fatty acids mentioned above 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.

[0087] Examples of the aforementioned aromatic carboxylic acids include: benzoic acid, toluene (o-toluene, m-toluene, p-toluene, especially p-toluene), 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 cycloalkanoic acids, etc.

[0088] As (G) barium-zinc complex compounds, the following can be used: barium-zinc complex salts of organic acids containing barium, zinc and one or more of the above-mentioned organic acids, and mixtures of barium salts of one or more of the above-mentioned organic acids and zinc salts of one or more of the above-mentioned organic acids.

[0089] Since the (G) barium-zinc complex is an optional component, there are no particular restrictions.

[0090] In one embodiment, the polyvinyl chloride resin composition of the present invention may be free of (G) barium-zinc composite compound.

[0091] From the viewpoint of thermal stability and color stability over time, the amount of barium-zinc composite compound (G) is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 0.5 parts by mass or more, and most preferably 1 part by mass or more, relative to 100 parts by mass of the resin mixture composed of (A) polyvinyl chloride resin and (B) core-shell rubber. On the other hand, from the viewpoint of anti-blooming properties, the amount of barium-zinc composite compound (G) is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, further preferably 5 parts by mass or less, and most preferably 4 parts by mass or less, relative to 100 parts by mass of the resin mixture composed of (A) polyvinyl chloride resin and (B) core-shell rubber.

[0092] Relative to 100 parts by weight of the resin mixture consisting of (A) polyvinyl chloride resin and (B) core-shell rubber, the (G) barium-zinc composite compound can typically be 0 parts by weight or more and 10 parts by weight or less, preferably 0 parts by weight or more and 7 parts by weight or less, 0 parts by weight or more and 5 parts by weight or less, 0 parts by weight or more and 4 parts by weight or less, 0.01 parts by weight or more and 10 parts by weight or less, 0.01 parts by weight or more and 7 parts by weight or less, 0.01 parts by weight or more and 5 parts by weight or less, 0.01 parts by weight or more and 4 parts by weight or less, 0.1 More than 10 parts by weight, more than 0.1 parts by weight and less than 7 parts by weight, more than 0.1 parts by weight and less than 5 parts by weight, more than 0.1 parts by weight and less than 4 parts by weight, more than 0.5 parts by weight and less than 10 parts by weight, more than 0.5 parts by weight and less than 7 parts by weight, more than 0.5 parts by weight and less than 5 parts by weight, more than 0.5 parts by weight and less than 4 parts by weight, more than 1 part by weight and less than 10 parts by weight, more than 1 part by weight and less than 7 parts by weight, more than 1 part by weight and less than 5 parts by weight, or more than 1 part by weight and less than 4 parts by weight.

[0093] (H) Hydrotalcite In one embodiment, the polyvinyl chloride resin composition of the present invention may further comprise (H) hydrotalcite. (H) hydrotalcite, as a stabilizer in the polyvinyl chloride resin composition, typically functions to capture free chlorine.

[0094] (H) Hydrotalcite is a layered inorganic compound consisting of positively charged and negatively charged layers, typically represented by the following formula (1).

[0095] [M 2+ 1-x M 3+ X [(OH)2] X+ [A n- x / n mH2O] X- (1) (where M) 2+ Indicates Mg 2+ Zn 2+ Divalent metal ions; M 3+ Indicates Al 3+ Fe 3+ Trivalent metal ions; A n- CO3 2- Cl - NO3 - (equal n-valent anions; X is 0 < X ​​≤ 0.33, typically 0.20 ≤ X ≤ 0.33; m is 0 ≤ m ≤ 0.5.) From the viewpoint of thermal stability and color stability over time, (H) hydrotalcite is preferably a carbonate-containing hydrotalcite, and more preferably a magnesium-aluminum carbonate-containing hydrotalcite. The carbonate-containing hydrotalcite described above is defined in formula (1) above, where the n-valent anion is a carbonate ion (CO3). 2- Inorganic compounds of the above-mentioned magnesium aluminum carbonate type hydrotalcite are those in formula (1) where the n-valent anion is carbonate ion (CO3). 2- And the divalent metal ion is magnesium ion (Mg). 2+ The trivalent metal ion is aluminum ion (Al). 3+ Inorganic compounds of the carbonate ion magnesium aluminum type hydrotalcite. For example, compounds represented by the following formula (2) can be listed as the above-mentioned magnesium aluminum carbonate hydrotalcite.

[0096] Mg6Al2(OH) 16 CO3 4H2O (2) As (H) hydrotalcite, one or a mixture of two or more of them can be used.

[0097] Since (H) hydrotalcite is an optional component, there are no particular restrictions on the amount to be mixed.

[0098] In one embodiment, the polyvinyl chloride resin composition of the present invention may be free of (H) hydrotalcite.

[0099] From the viewpoint of thermal stability and color stability over time, the amount of hydrotalcite (H) mixed in is 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, relative to 100 parts by mass of the resin mixture composed of (A) polyvinyl chloride resin and (B) core-shell rubber. On the other hand, from the viewpoint of suppressing coloration during continuous film production, the amount of hydrotalcite (H) mixed in is typically 3 parts by mass or less, preferably 2 parts by mass or less, and more preferably 1 part by mass or less, relative to 100 parts by mass of the resin mixture composed of (A) polyvinyl chloride resin and (B) core-shell rubber.

[0100] Relative to 100 parts by weight of the resin mixture consisting of (A) polyvinyl chloride resin and (B) core-shell rubber, the amount of (H) hydrotalcite can typically be 0 parts by weight or more and 3 parts by weight or less, preferably 0 parts by weight or more and 2 parts by weight or less, 0 parts by weight or more and 1 part by weight or less, 0.01 parts by weight or more and 3 parts by weight or less, 0.01 parts by weight or more and 2 parts by weight or less, 0.01 parts by weight or more and 1 part by weight or less, 0.05 parts by weight or more and 3 parts by weight or less, 0.05 parts by weight or more and 2 parts by weight or less, 0.05 parts by weight or more and 1 part by weight or less, 0.1 parts by weight or more and 3 parts by weight or less, 0.1 parts by weight or more and 2 parts by weight or less, 0.1 parts by weight or more and 1 part by weight or less, 0.2 parts by weight or more and 3 parts by weight or less, 0.2 parts by weight or more and 2 parts by weight or less, or 0.2 parts by weight or more and 1 part by weight or less.

[0101] (J) Ultraviolet absorbers In one embodiment, the polyvinyl chloride resin composition of the present invention may further include (J) an ultraviolet absorber. Here, the (J) ultraviolet absorber does not include compounds belonging to any of the components (A) to (H) above and having ultraviolet absorption function. That is, substances belonging to any of the compounds in components (A) to (H) above are excluded from the (J) ultraviolet absorber.

[0102] (J) Examples of ultraviolet absorbers include: benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, benzophenone ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, aromatic benzoate ultraviolet absorbers, and oxaloylaniline ultraviolet absorbers.

[0103] Examples of 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.

[0104] Examples of triazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol and 2,4,6-tris(2-hydroxy-4-hexoxy-3-methylphenyl)-1,3,5-triazine.

[0105] Examples of benzophenone-based ultraviolet absorbers include: [2-hydroxy-4-(octoxy)phenyl](phenyl) benzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.

[0106] Examples of cyanoacrylate-based ultraviolet absorbers include: ethyl 2-cyano-3,3-diphenylacrylate, 2-cyano-3,3-diphenylacrylate-2-ethylhexyl ester, pentaerythritol tetra(3,3-diphenyl-2-cyanoacrylate), etc.

[0107] Examples of aromatic benzoic acid esters that can be used as ultraviolet absorbers include: 4-tert-butylphenyl salicylate, 4-octylphenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate.

[0108] Examples of oxaloylaniline-based ultraviolet absorbers include 2-ethyl-2'-ethoxyoxaloylaniline and 2-ethoxy-4'-dodecyloxyoxaloylaniline.

[0109] As (J) ultraviolet absorbers, one or a mixture of two or more of them may be used.

[0110] Since the (J) ultraviolet absorber is an optional component, there are no particular restrictions on the amount mixed.

[0111] In one embodiment, the polyvinyl chloride resin composition of the present invention may not contain (J) ultraviolet absorber.

[0112] From the viewpoint of color stability over time and weather resistance, the amount of UV absorber (J) mixed in relation to 100 parts by weight of the resin mixture composed of (A) polyvinyl chloride resin and (B) core-shell rubber is preferably 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, further preferably 0.1 parts by weight or more, and most preferably 0.2 parts by weight or more. On the other hand, from the viewpoint of suppressing the precipitation of UV absorber on the film surface, the amount of UV absorber (J) mixed in relation to 100 parts by weight of the resin mixture composed of (A) polyvinyl chloride resin and (B) core-shell rubber is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, further preferably 3 parts by weight or less, and most preferably 1 part by weight or less.

[0113] Relative to 100 parts by weight of the resin mixture consisting of (A) polyvinyl chloride resin and (B) core-shell rubber, the amount of (J) ultraviolet absorber can typically be 0 parts by weight or more and 10 parts by weight or less, preferably 0 parts by weight or more and 5 parts by weight or less, 0 parts by weight or more and 3 parts by weight or less, 0 parts by weight or more and 1 part by weight or less, 0.01 parts by weight or more and 10 parts by weight or less, 0.01 parts by weight or more and 5 parts by weight or less, 0.01 parts by weight or more and 3 parts by weight or less, 0.01 parts by weight or more and 1 part by weight or less, or 0.05 parts by weight or less. More than 10 parts by weight, more than 0.05 parts by weight and less than 5 parts by weight, more than 0.05 parts by weight and less than 3 parts by weight, more than 0.05 parts by weight and less than 1 part by weight, more than 0.1 parts by weight and less than 10 parts by weight, more than 0.1 parts by weight and less than 5 parts by weight, more than 0.1 parts by weight and less than 3 parts by weight, more than 0.1 parts by weight and less than 1 part by weight, more than 0.2 parts by weight and less than 10 parts by weight, more than 0.2 parts by weight and less than 5 parts by weight, more than 0.2 parts by weight and less than 3 parts by weight, or more than 0.2 parts by weight and less than 1 part by weight.

[0114] In the polyvinyl chloride resin composition of the present invention, other optional components other than those listed in components (A) to (J) may be further included as needed, without departing from the purpose of the present invention. Examples of such other optional components include: (A) polyvinyl chloride resin and (B) other thermoplastic resins other than core-shell rubber; and (C) β-diketone compounds, (D) phosphite compounds, (G) barium-zinc composite compounds, (H) hydrotalcite, and (J) other additives other than ultraviolet absorbers.

[0115] Other thermoplastic resins mentioned above include, for example, poly(meth)acrylate, styrene-(meth)acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylate copolymer, ethylene-(meth)acrylate copolymer, ethylene-(meth)acrylate methyl acrylate copolymer, and ethylene-(meth)acrylate ethyl acrylate copolymer.

[0116] Other additives mentioned above include, for example: heat stabilizers such as calcium-zinc complexes, antioxidants such as hindered phenolic compounds, weather stabilizers, light stabilizers, lubricants such as oleamides, waxes such as polyethylene waxes, antistatic agents such as glycerol fatty acid esters, mold release agents, processing aids, antifouling agents, nucleating agents, inorganic particles, organic particles, inorganic colorants, and organic colorants.

[0117] As other optional ingredients mentioned above, one or a mixture of two or more of them may be used.

[0118] Since the other optional components mentioned above are optional, there are no particular restrictions on their mixing amounts, and they are not particularly limited to the extent that they do not depart from the purpose of this invention. Relative to 100 parts by weight of the resin mixture consisting of (A) polyvinyl chloride resin and (B) core-shell rubber, the mixing amounts of the other optional components mentioned above are typically 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 0 to 1 part by weight, or approximately 0.01 to 50 parts by weight.

[0119] 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.

[0120] In one embodiment, the polyvinyl chloride resin composition of the present invention may be free of hindered phenolic compounds. While not intended to be theoretically rigid, hindered phenolic compounds possess the function of scavenging free radicals and are organic compounds that function as so-called primary antioxidants, thus being effective from the viewpoint of halting oxidative degradation reactions. On the other hand, this is because hindered phenolic compounds, after functioning as antioxidants, often exhibit a quinone structure and thus display a yellow or other coloring.

[0121] 2. Method for manufacturing polyvinyl chloride resin compositions The polyvinyl chloride resin composition of the present invention can be obtained by using any melt blender, by simultaneously or in any order adding the above components (A) to (D) (or components (A), (C) and (D) if component (B) is not present) and optional components as needed into the melt blender, preferably by melt blending at a resin temperature of 120 to 200°C.

[0122] The aforementioned melt mixing machines can be categorized as follows: intermittent mixing machines such as pressure kneaders and mixers; extrusion mixing machines such as single-screw extruders, co-rotating twin-screw extruders, and counter-rotating twin-screw extruders; and calender roll mixers, etc. These can be used in any combination.

[0123] The resulting resin composition can be granulated by any method and then molded into any product using any means. The granulation can be carried out by methods such as hot cutting, strip cutting, and underwater pelletizing.

[0124] In addition, in one embodiment, the block, rod, or wire-shaped polyvinyl chloride resin composition discharged from the melt mixer can be directly fed into any molding machine to be molded into an article.

[0125] 3. Film The film of the present invention is formed from the polyvinyl chloride resin composition of the present invention. The film of the present invention is suitable as a film substrate for wallpaper and decorative sheets.

[0126] The film of the present invention can be obtained by using the polyvinyl chloride resin composition of the present invention and employing any film-forming apparatus. Examples of such film-forming apparatus include: a calendering roll forming apparatus equipped with a calendering roll calendering machine and a winding device; and a T-die forming apparatus equipped with an extruder, a T-die, and a winding device.

[0127] Examples of calendering machines that can be categorized as calendering rolls include: vertical three-roll, vertical four-roll, L-type four-roll, inverted L-type four-roll, and Z-type rolls. Examples of extruders that can be categorized as extruders include: single-screw extruders, co-rotating twin-screw extruders, and counter-rotating twin-screw extruders. Examples of T-type dies that can be categorized as T-die heads include: manifold die heads, fishtail die heads, and coat hanger die heads.

[0128] The film of the present invention can be obtained by using the polyvinyl chloride resin composition of the present invention, preferably by using a calendering roll calendering film forming device, and more preferably by using a calendering roll calendering film forming device and a roll temperature of 160°C to 200°C.

[0129] The thickness of the film of the present invention can be appropriately determined according to the film-forming properties, application, required performance, and operability. From the viewpoint of film-forming properties and operability, the thickness of the film of the present invention is generally 20 μm or more, preferably 50 μm or more. On the other hand, from the viewpoint of meeting the requirements for thinning articles containing the film of the present invention, the thickness of the film is generally 1000 μm or less, preferably 500 μm or less, and more preferably 200 μm or less.

[0130] The film of the present invention can be transparent or opaque, and can be colored transparent or colored opaque.

[0131] In one embodiment, the transparent film of the present invention can be suitable as a film substrate for decorative sheets that are attached to glass, such as glass decorative films. In another embodiment, the opaque or privacy-enhancing film of the present invention can be suitable as a film substrate for decorative sheets used for beautifying / decorating household appliances, furniture, and building components, as well as for wallpaper used for beautifying / decorating building walls.

[0132] Figure 1 This is a cross-sectional schematic diagram illustrating an example of wallpaper employing the film of the present invention. The wallpaper, from the surface side, sequentially comprises: a coating film 1 formed using a two-component curable polyurethane coating, a transparent thermoplastic resin film layer 2, a printing layer 3, a white-colored film layer 4 providing privacy, and an adhesive layer 5. Furthermore, in this specification, "surface side" refers to the side of the surface typically observed in actual use. "Actual use" refers to, for example, in the case of wallpaper, the state in which the wallpaper is used for beautifying / decorating the walls of a building.

[0133] Example The present invention will be described below through embodiments, but the present invention is not limited to these embodiments.

[0134] Determination methods (i) Heat pressure test (process thermal stability) Using a polyvinyl chloride resin composition, sample 1 with a thickness of 1 mm was obtained by preheating at 180°C for 2 minutes, followed by hot pressing for 2 minutes, and then immediately cooling and pressurizing at 20°C for 2 minutes. The L*a*b* coordinates of sample 1 were then determined using the measurement method described later. Next, sample 1 was preheated at 190°C for 2 minutes, followed by hot pressing for 30 minutes, and then immediately cooling and pressurizing at 20°C for 2 minutes to obtain sample 2. The L*a*b* coordinates of sample 2 were then determined using the measurement method described later.

[0135] Here, in accordance with JIS Z8722:2009, using the Konica Minolta Japan CM600d spectrophotometer (trade name), a sample was placed on a white plate identical to the white calibration plate provided with the spectrophotometer. Under geometric condition c, which includes specular reflection, the XYZ coordinates were measured, and the L*a*b* coordinates were measured through conversion. The difference (b2* - b1*) between b*(b2*) of sample 2 and b*(b1*) of sample 1 was calculated as Δb*. Furthermore, based on the L*a*b* coordinates of sample 1 and sample 2, the color difference (ΔE) was calculated using the built-in calculation method of the spectrophotometer (ΔE*ab (CIE1976)). It should be noted that for information on the measurement of L*a*b* coordinates, please refer to the official website of Konica Minolta Japan (address below).

[0136] http: / / www.konicaminolta.jp / instruments / knowledge / color / part1 / 07.html Raw materials used (A) Polyvinyl chloride resins (A-1) Polyvinyl chloride homopolymer with an average degree of polymerization of 800.

[0137] (B) Core-shell rubber (B-1) Core-shell rubber (methyl methacrylate-styrene / ethyl acrylate rubber graft copolymer) "METABLEN W-300A" (trade name) from Mitsubishi Chemical Corporation.

[0138] (C) β-Diketone compounds (C-1) Dibenzoylmethane. CAS No. 120-46-7.

[0139] (C-2) Stearoylbenzoylmethane (1-phenyl-1,3-eicosanodione). CAS No. 58446-52-9.

[0140] (D) Phosphite compounds (D-1) Alkyl aryl phosphite "ADEKA STAB 135A" (trade name) of ADEKA Co., Ltd. Isodecyl diphenyl phosphite. CAS number 26544-23-0.

[0141] (D-2) ADEKA STAB 3010 (trade name), a trialkyl phosphite from ADEKA Corporation. Triisodecyl phosphite. CAS No. 25448-25-3.

[0142] (D-3) ADECA STAB TPP (trade name), a triaryl phosphite from Adico Corporation. Triphenyl phosphite. CAS No. 101-02-0.

[0143] (E) Flame retardant (E-1) Albemarle Japan Co., Ltd.'s brominated hydrocarbon flame retardant (1,2-bis(pentabromophenyl)ethane) "SAYTEX 8010" (trade name).

[0144] (E-2) Antimony flame retardant (antimony trioxide) "MSA-S" (trade name) from Yamanaka Sangyo Co., Ltd.

[0145] (F) Plasticizer (F-1) Diisononyl phthalate "DINP" (trade name) from J-PLUS Co., Ltd.

[0146] (F-2) O-130S (trade name) of epoxidized soybean oil from Edico Co., Ltd.

[0147] (G) Barium-Zinc Complex A mixture of (G-1) barium decanoate, bis(4-tert-butylbenzoic acid) zinc and bis(p-methylbenzoic acid) zinc in a 2:1:1 (mass ratio).

[0148] (H) Hydrotalcite (H-1) FD-200 (trade name), a magnesium aluminum carbonate type hydrotalcite from Akishima Chemical Industry Co., Ltd.

[0149] (J) Ultraviolet absorbers (J-1) BASF Japan Co., Ltd.'s benzotriazole UV absorber "Tinuvin 326" (trade name).

[0150] (K) Other optional ingredients (K-1) P-530A (trade name), an acrylic processing aid from Mitsubishi Chemical Corporation.

[0151] (K-2) Titanium oxide (white pigment) "CR-90" (trade name) from Ishihara Sangyo Co., Ltd.

[0152] Example 1 By using a mixing mill and at a resin temperature of 140°C at discharge, 100 parts by mass of a resin mixture consisting of 90% by mass of component (A-1) and 10% by mass of component (B-1), 0.20 parts by mass of component (C-1), 0.50 parts by mass of component (D-1), 7.5 parts by mass of component (E-1), 2.5 parts by mass of component (E-2), 13 parts by mass of component (F-1), 4 parts by mass of component (F-2), 3.0 parts by mass of component (G-1), 0.30 parts by mass of component (H-1), 0.40 parts by mass of component (J-1), 1 part by mass of component (K-1), and 15 parts by mass of component (K-2) are melt-blended to obtain a polyvinyl chloride resin composition.

[0153] Examples 2 to 12 Except for the changes in proportions shown in Table 1, polyvinyl chloride resin compositions were obtained in the same manner as in Example 1. The above-described test (i) was performed. The results are shown in Table 1.

[0154] [Table 1]

[0155] It should be noted that in Example 10, because the sample 1 of the above test (i) had turned strongly yellow during the preparation stage, it was initially judged to have poor color and the test was stopped. The table records it as "poor initial coloring" (an abbreviation indicating poor coloring in the early stage of the test).

[0156] In addition, long-term continuous film production tests were conducted on Examples 1, 5-7, 9, and 12. Examples 9 and 12 were designated as comparative examples because they used polyvinyl chloride resin compositions that did not contain component (C). Using a mixing mill, the mixtures shown in Table 1 were melt-mixed at a resin temperature of 140°C at discharge to obtain polyvinyl chloride resin compositions. These compositions were then directly fed into a calendering and film-making apparatus equipped with an inverted L-shaped four-roll calender and a winding device. Long-term continuous production of films with a thickness of 80 μm was carried out under the conditions of 180°C for the first roll, 180°C for the second roll, 185°C for the third roll, 180°C for the fourth roll, and a winding speed of 60 m / min. For film 1 at the beginning of production and film 2 at the time point from the start of production to 5000 m of continuous production, 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.

[0157] It is known that the polyvinyl chloride resin composition of the present invention still exhibits excellent process thermal stability even when containing flame retardants, and can suppress coloration during continuous film production. Therefore, it is analyzed that the film formed from the polyvinyl chloride resin composition of the present invention is suitable as a film substrate for wallpaper and decorative sheets.

[0158] Symbol Explanation 1: Coating film formed using two-component curable polyurethane coatings 2: Transparent thermoplastic resin film layer 3: Printed layer 4: The thin film layer of the present invention is colored white and provides privacy. 5: Adhesive layer.

Claims

1. A polyvinyl chloride resin composition, relative to that made from... (A) Polyvinyl chloride resin 60-100% by mass (B) Core-shell rubber 40-0% by mass 100 parts by weight of the resin mixture comprising (C) 0.01–5 parts by weight of β-diketone compounds, (D) 0.01–10 parts by weight of phosphite compounds, and (E) 0-100 parts by weight of flame retardant; in, The sum of the mixing amount of (A) polyvinyl chloride resin and (B) core-shell rubber in the above resin mixture is 100 by mass.

2. The polyvinyl chloride resin composition according to claim 1, wherein (D) the phosphite compound comprises one or more selected from trialkyl phosphite, alkylaryl phosphite and triaryl phosphite.

3. The polyvinyl chloride resin composition according to claim 1, wherein (D) the phosphite compound comprises one or more selected from trialkyl phosphites and alkylaryl phosphites.

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

5. The polyvinyl chloride resin composition according to claim 1, wherein it does not contain hindered phenolic compounds.

6. The polyvinyl chloride resin composition according to claim 1, further comprising 1 to 100 parts by weight of (E) flame retardant relative to 100 parts by weight of the resin mixture consisting of (A) polyvinyl chloride resin and (B) core-shell rubber.

7. The polyvinyl chloride resin composition according to claim 6, wherein (E) the flame retardant comprises a halogenated flame retardant.

8. The polyvinyl chloride resin composition according to claim 6, wherein (E) the flame retardant comprises a brominated hydrocarbon flame retardant and an antimony flame retardant.

9. The polyvinyl chloride resin composition according to claim 1, further comprising, relative to 100 parts by weight of the resin mixture composed of (A) polyvinyl chloride resin and (B) core-shell rubber, a further comprising (F) Plasticizer 1-250 parts by weight; (G) Barium-zinc complex, 0.01–10 parts by weight; (H) 0.01–3 parts by weight of hydrotalcite; and, (J) 0.01 to 10 parts by weight of ultraviolet absorber.

10. A film formed from any one of the polyvinyl chloride resin compositions according to claims 1 to 9.

11. Wallpaper or decorative sheet comprising the film of claim 10.

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