Vinyl chloride resin composition, vinyl chloride resin molded article and laminate

Abstract

To provide a polyvinyl chloride resin composition that is less prone to a change in color tone due to a difference in molding temperature.SOLUTION: A polyvinyl chloride resin composition contains a polyvinyl chloride resin, a plasticizer, a uracil compound, acetylacetone zinc, and acetylacetone calcium. The content of the acetylacetone calcium is at least 0.8 times the content of the acetylacetone zinc. Preferably the polyvinyl chloride resin composition is used in powder molding.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a vinyl chloride resin composition, a vinyl chloride resin molded article, and a laminate. [Background technology]

[0002] Vinyl chloride resins are generally used in a variety of applications due to their excellent properties such as cold resistance, heat resistance, and oil resistance. Specifically, for example, automobile interior parts such as automobile instrument panels and door trims are formed using automobile interior materials such as skins made of polyvinyl chloride resin molded products and laminates made by lining a skin made of polyvinyl chloride resin molded product with a foam such as polyurethane foam.

[0003] Vinyl chloride resin molded articles that form the skin of automobile interior parts such as automobile instrument panels are produced, for example, by molding a vinyl chloride resin composition containing vinyl chloride resin, a plasticizer, and an additive using a powder molding method such as powder slush molding (see, for example, Patent Document 1).

[0004] Specifically, for example, in Patent Document 1, a vinyl chloride resin molded article is produced by powder slush molding a vinyl chloride resin composition containing vinyl chloride resin particles, a plasticizer, and additives such as a hydrotalcite-based stabilizer, a zeolite-based stabilizer, and β-diketones. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 6-279640 Summary of the Invention [Problem to be solved by the invention]

[0006] Here, when a vinyl chloride resin composition is powder-molded, for example, if there is a temperature distribution in the mold used, the color tone of the vinyl chloride resin composition may vary depending on the molding temperature. Such color tone variation can lead to uneven color tone in the vinyl chloride resin molded article that is formed. Therefore, from the perspective of reducing uneven color tone in the vinyl chloride resin molded article, it is necessary to suppress the color tone variation due to the molding temperature difference in the vinyl chloride resin composition.

[0007] However, the vinyl chloride resin compositions of the above-mentioned prior art have room for improvement in terms of suppressing color tone variations due to differences in molding temperature.

[0008] Therefore, an object of the present invention is to provide a vinyl chloride resin composition in which color tone variation due to differences in molding temperature is suppressed. Another object of the present invention is to provide a vinyl chloride resin molded article formed using the vinyl chloride resin composition. A further object of the present invention is to provide a laminate comprising the vinyl chloride resin molded article. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above-mentioned problems, and have found that by adding a uracil compound, zinc acetylacetone, and calcium acetylacetone to a vinyl chloride resin composition and setting the ratio of the content of calcium acetylacetone to the content of zinc acetylacetone to a predetermined value or more, it is possible to suppress color tone fluctuations due to differences in molding temperature, and have completed the present invention.

[0010] That is, the present invention aims to advantageously solve the above-mentioned problems, and the vinyl chloride resin composition of the present invention is characterized by comprising a vinyl chloride resin, a plasticizer, a uracil compound, zinc acetylacetone, and calcium acetylacetone, and the content of calcium acetylacetone is 0.8 times or more the content of zinc acetylacetone. Thus, in a vinyl chloride resin composition comprising a vinyl chloride resin, a plasticizer, a uracil compound, zinc acetylacetone, and calcium acetylacetone, by setting the ratio of the content of calcium acetylacetone to the content of zinc acetylacetone to a predetermined value or more, it is possible to suppress variation in color tone due to differences in molding temperature of the vinyl chloride resin composition.

[0011] Here, in the vinyl chloride resin composition of the present invention, the uracil compound is represented by the following formula (I): [ka] [In formula (I), R1 and R2 each independently represent a hydrogen atom or an electron-donating group, R3 represents a hydrogen atom or an amino group.] When the uracil compound is a compound represented by the above-mentioned formula, variation in color tone due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed.

[0012] In the vinyl chloride resin composition of the present invention, the uracil compound preferably includes 6-amino-1,3-dimethyluracil. Use of 6-amino-1,3-dimethyluracil as the uracil compound can further suppress color tone variations due to differences in molding temperature of the vinyl chloride resin composition.

[0013] In the vinyl chloride resin composition of the present invention, the content of the uracil compound is preferably 0.1 parts by mass or more per 100 parts by mass of the vinyl chloride resin. When the content of the uracil compound in the vinyl chloride resin composition is equal to or more than the above-mentioned predetermined value, variation in color tone due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed.

[0014] Furthermore, in the vinyl chloride resin composition of the present invention, the content of the zinc acetylacetonate is preferably 0.06 parts by mass or more per 100 parts by mass of the vinyl chloride resin. When the content of the zinc acetylacetonate per 100 parts by mass of the vinyl chloride resin in the vinyl chloride resin composition is within the above-mentioned range, variation in color tone due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed.

[0015] Furthermore, in the vinyl chloride resin composition of the present invention, the content of calcium acetylacetonate per 100 parts by mass of vinyl chloride resin is preferably 0.05 parts by mass or more. When the content of calcium acetylacetonate per 100 parts by mass of vinyl chloride resin in the vinyl chloride resin composition is within the above-mentioned range, variation in color tone due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed.

[0016] Furthermore, the vinyl chloride resin composition of the present invention preferably further contains a fatty acid metal salt other than a fatty acid zinc salt. By using a fatty acid metal salt other than a fatty acid zinc salt, variation in color tone due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed.

[0017] In addition, in the vinyl chloride resin composition of the present invention, the fatty acid metal salt preferably contains a fatty acid calcium salt. If a fatty acid calcium salt is further used as a fatty acid metal salt other than a fatty acid zinc salt, variation in color tone due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed.

[0018] Furthermore, in the vinyl chloride resin composition of the present invention, the fatty acid metal salt preferably contains a metal salt of a fatty acid having a carbon number of 6 to 22. If a metal salt of a fatty acid having a carbon number within the above-mentioned specified range is used as the fatty acid metal salt other than the fatty acid zinc salt, variation in color tone due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed.

[0019] The vinyl chloride resin composition of the present invention is preferably used for powder molding. By using the vinyl chloride resin composition for powder molding, a vinyl chloride resin molded article that can be favorably used as an automobile interior material, such as a skin for an automobile instrument panel, can be easily obtained.

[0020] Furthermore, the vinyl chloride resin composition of the present invention is preferably used for powder slush molding. By using the vinyl chloride resin composition for powder slush molding, it is possible to more easily obtain a vinyl chloride resin molded article that can be favorably used as an automobile interior material, such as a skin for an automobile instrument panel.

[0021] The present invention has an object to advantageously solve the above-mentioned problems, and provides a vinyl chloride resin molded article of the present invention, characterized by being obtained by molding any of the vinyl chloride resin compositions described above. As described above, vinyl chloride resin molded articles obtained by molding the vinyl chloride resin compositions described above have reduced color unevenness and excellent appearance, and therefore can be suitably used as automotive interior materials.

[0022] The vinyl chloride resin molded article of the present invention is preferably used for the surface of an automobile instrument panel. By using the vinyl chloride resin molded article of the present invention for the surface of an automobile instrument panel, it is possible to produce an automobile instrument panel having a surface with reduced color unevenness and excellent appearance.

[0023] Furthermore, the present invention has an object to advantageously solve the above-mentioned problems, and provides a laminate comprising a polyurethane foam molded body and any of the vinyl chloride resin molded bodies described above. The laminate comprising the polyurethane foam molded body and the vinyl chloride resin molded body described above has a vinyl chloride resin molded body portion with reduced color unevenness and excellent appearance.

[0024] The laminate of the present invention is preferably used for an automobile instrument panel. In this way, by using the laminate of the present invention in an automobile instrument panel, uneven color tone in the surface of the manufactured automobile instrument panel can be reduced, and the appearance can be improved. [Effects of the Invention]

[0025] According to the present invention, it is possible to provide a vinyl chloride resin composition in which variation in color tone due to differences in molding temperature is suppressed. Furthermore, according to the present invention, it is possible to provide a vinyl chloride resin molded article formed using the vinyl chloride resin composition. Furthermore, according to the present invention, it is possible to provide a laminate comprising the vinyl chloride resin molded article. DETAILED DESCRIPTION OF THE INVENTION

[0026] Hereinafter, embodiments of the present invention will be described in detail. The vinyl chloride resin composition of the present invention can be used, for example, to form the vinyl chloride resin molded article of the present invention. The vinyl chloride resin molded article formed using the vinyl chloride resin composition of the present invention can be suitably used, for example, as an automobile interior material, such as the surface of automobile interior parts such as automobile instrument panels and door trims. The vinyl chloride resin molded article of the present invention can be used, for example, to form the laminate of the present invention. The laminate formed using the vinyl chloride resin molded article of the present invention can be suitably used, for example, as an automobile interior material used in producing automobile interior parts such as automobile instrument panels and door trims.

[0027] (Vinyl chloride resin composition) The vinyl chloride resin composition of the present invention comprises (a) vinyl chloride resin, (b) plasticizer, (c) uracil compound, (d) zinc acetylacetonate, and (e) calcium acetylacetonate, and is characterized in that the ratio of the content of (e) calcium acetylacetonate to the content of (d) zinc acetylacetonate is equal to or greater than a predetermined value.

[0028] Furthermore, the vinyl chloride resin composition of the present invention may further contain, optionally, β-diketones other than zinc acetylacetonate and calcium acetylacetonate (hereinafter, sometimes referred to as "(f) other β-diketones"). Furthermore, the vinyl chloride resin composition of the present invention may optionally further contain (g) a zinc fatty acid. Furthermore, the vinyl chloride resin composition of the present invention may further contain, optionally, (h) a metal salt of a fatty acid other than a zinc fatty acid (hereinafter, sometimes referred to as "(h) other metal salt of a fatty acid"). The vinyl chloride resin composition of the present invention may further contain additives other than the above-mentioned (a) vinyl chloride resin, (b) plasticizer, (c) uracil compound, (d) zinc acetylacetone, (e) calcium acetylacetone, (f) other β-diketones, (g) fatty acid zinc salts, and (h) other fatty acid metal salts.

[0029] The vinyl chloride resin composition of the present invention contains at least the above-mentioned (a) vinyl chloride resin, (b) plasticizer, (c) uracil compound, (d) zinc acetylacetone, and (e) calcium acetylacetone, and the ratio of the content of (e) calcium acetylacetone to the content of (d) zinc acetylacetone is equal to or greater than a predetermined value, thereby making it possible to suppress variations in color tone due to differences in molding temperature.

[0030] Therefore, by using the vinyl chloride resin composition of the present invention, it is possible to obtain vinyl chloride resin molded articles that are suitable for use as automotive interior materials, such as automotive instrument panel skins and door trim skins, with reduced unevenness in color tone and excellent appearance. Furthermore, vinyl chloride resin molded articles formed using the vinyl chloride resin composition of the present invention can be inhibited from undergoing changes in color tone, such as yellowing, even when heated at high temperatures, for example, 270°C or higher.

[0031] From the viewpoint of easily obtaining a vinyl chloride resin molded article that can be favorably used as an automobile interior material, for example, using the vinyl chloride resin composition of the present invention, the vinyl chloride resin composition of the present invention is preferably used for powder molding, and more preferably used for powder slush molding.

[0032] <(a) Vinyl chloride resin> The (a) vinyl chloride resin is usually a particulate vinyl chloride resin. The (a) vinyl chloride resin may contain, for example, one or more types of vinyl chloride resin particles, and may optionally further contain one or more types of vinyl chloride resin microparticles. Among these, the (a) vinyl chloride resin preferably contains at least vinyl chloride resin particles, and more preferably contains vinyl chloride resin particles and vinyl chloride resin microparticles. The vinyl chloride resin (a) can be produced by any of the conventionally known production methods, such as suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization. In this specification, "resin particles" refers to particles having a particle diameter of 30 μm or more, and "resin fine particles" refers to particles having a particle diameter of less than 30 μm.

[0033] Examples of the (a) vinyl chloride resin include a homopolymer composed of vinyl chloride monomer units, as well as a vinyl chloride copolymer containing preferably 50% by mass or more, more preferably 70% by mass or more, of vinyl chloride monomer units. Specific examples of monomers (comonomers) copolymerizable with vinyl chloride monomers that can constitute vinyl chloride copolymers include those described in International Publication No. 2016 / 098344. These components may be used alone or in combination of two or more in any ratio.

[0034] <<Vinyl chloride resin particles>> In the vinyl chloride resin composition, the vinyl chloride resin particles usually function as a matrix resin (substrate). The vinyl chloride resin particles are preferably produced by a suspension polymerization method.

[0035] [Average degree of polymerization] The average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is preferably 800 or more, more preferably 1000 or more, and preferably 5000 or less, more preferably 3000 or less, and even more preferably 2800 or less. When the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is above the above-mentioned lower limit, the physical strength of a vinyl chloride resin molded article formed using the vinyl chloride resin composition can be sufficiently ensured, while, for example, improving tensile properties, particularly tensile elongation. Furthermore, a vinyl chloride resin molded article with good tensile elongation can be suitably used as an automotive interior material, such as the surface of an automobile instrument panel, which has excellent ductility and breaks as designed without scattering fragments when an airbag is inflated and deployed. On the other hand, when the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is below the above-mentioned upper limit, the meltability of the vinyl chloride resin composition can be improved. In the present invention, the "average degree of polymerization" can be measured in accordance with JIS K6720-2.

[0036] [Average particle size] The average particle size of the vinyl chloride resin particles is usually 30 μm or more, preferably 50 μm or more, more preferably 100 μm or more, and preferably 500 μm or less, more preferably 200 μm or less. When the average particle size of the vinyl chloride resin particles is equal to or greater than the above-mentioned lower limit, the powder flowability of the vinyl chloride resin composition can be improved. On the other hand, when the average particle size of the vinyl chloride resin particles is equal to or less than the above-mentioned upper limit, the meltability of the vinyl chloride resin composition can be improved, and the surface smoothness of a vinyl chloride resin molded article formed using the vinyl chloride resin composition can be improved. In the present invention, the "average particle size" can be measured as a volume average particle size by a laser diffraction method in accordance with JIS Z8825.

[0037] [Content ratio] The content of vinyl chloride resin particles in (a) vinyl chloride resin is preferably 70% by mass or more, more preferably 80% by mass or more, and can be 100% by mass, and is preferably 95% by mass or less, and more preferably 90% by mass or less. If the content of vinyl chloride resin particles in (a) vinyl chloride resin is equal to or greater than the above-mentioned lower limit, the tensile elongation of a vinyl chloride resin molded article formed using the vinyl chloride resin composition can be improved while ensuring sufficient physical strength. On the other hand, if the content of vinyl chloride resin particles in (a) vinyl chloride resin is equal to or less than the above-mentioned upper limit, the powder flowability of the vinyl chloride resin composition can be improved.

[0038] <<Vinyl chloride resin particles>> In the vinyl chloride resin composition, the vinyl chloride resin fine particles usually function as a dusting agent (powder flow improver). The vinyl chloride resin fine particles are preferably produced by emulsion polymerization.

[0039] [Average degree of polymerization] The average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin microparticles is preferably 500 or more, more preferably 700 or more, and preferably 2600 or less, more preferably 2400 or less. When the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin microparticles as a dusting agent is equal to or greater than the above-mentioned lower limit, the powder fluidity of the vinyl chloride resin composition can be improved and the tensile elongation of a vinyl chloride resin molded article formed using the vinyl chloride resin composition can be improved. When the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin microparticles is equal to or less than the above-mentioned upper limit, the meltability of the vinyl chloride resin composition can be improved, and the surface smoothness of a vinyl chloride resin molded article formed using the vinyl chloride resin composition can be improved.

[0040] [Average particle size] The average particle size of the vinyl chloride resin fine particles is usually less than 30 μm, preferably 10 μm or less, more preferably 5 μm or less, and preferably 0.1 μm or more, more preferably 1 μm or more. If the average particle size of the vinyl chloride resin fine particles is equal to or greater than the above-mentioned lower limit, the powder flowability of the vinyl chloride resin composition can be improved without excessively reducing the size of the fine particles used as a dusting agent. On the other hand, if the average particle size of the vinyl chloride resin fine particles is equal to or less than the above-mentioned upper limit, the meltability of the vinyl chloride resin composition can be improved, thereby improving the surface smoothness of a vinyl chloride resin molded article formed using the vinyl chloride resin composition.

[0041] [Content ratio] The content of vinyl chloride resin microparticles in (a) vinyl chloride resin may be 0% by mass, but is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 30% by mass or less, and more preferably 20% by mass or less. If the content of vinyl chloride resin microparticles in (a) vinyl chloride resin is equal to or greater than the above-mentioned lower limit, the powder fluidity of the vinyl chloride resin composition can be improved. On the other hand, if the content of vinyl chloride resin microparticles in (a) vinyl chloride resin is equal to or less than the above-mentioned upper limit, the physical strength of a vinyl chloride resin molded article formed using the vinyl chloride resin composition can be increased.

[0042] <(b) Plasticizer> The vinyl chloride resin composition of the present invention contains (b) a plasticizer. By containing (b) a plasticizer in the vinyl chloride resin composition, the vinyl chloride resin molded article formed can exhibit sufficient flexibility, making it suitable for use as, for example, an automobile interior material.

[0043] Here, the content of the (b) plasticizer in the vinyl chloride resin composition is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, even more preferably 70 parts by mass or more, even more preferably 80 parts by mass or more, even more preferably 90 parts by mass or more, and preferably 200 parts by mass or less, more preferably 180 parts by mass or less, even more preferably 160 parts by mass or less, even more preferably 140 parts by mass or less, and even more preferably 120 parts by mass or less, per 100 parts by mass of the (a) vinyl chloride resin. When the content of the (b) plasticizer in the vinyl chloride resin composition is equal to or greater than the above-mentioned lower limit, the flexibility of the vinyl chloride resin molded article formed can be improved. Furthermore, when the content of the (b) plasticizer in the vinyl chloride resin composition is equal to or greater than the above-mentioned lower limit, the precipitation (blooming) of the blended components on the surface of the vinyl chloride resin molded article formed can be suppressed. That is, the blooming resistance of the vinyl chloride resin molded article can be improved. On the other hand, when the content of (b) plasticizer in the vinyl chloride resin composition is not more than the above upper limit per 100 parts by mass of (a) vinyl chloride resin, the powder flowability of the vinyl chloride resin composition can be improved.

[0044] The (b) plasticizer contained in the vinyl chloride resin composition of the present invention is not particularly limited, but for example, (b1) polyester and (b2) trimellitic ester are preferably used. Note that, as the (b) plasticizer, plasticizers other than (b1) polyester and (b2) trimellitic ester (hereinafter, sometimes referred to as "(b3) other plasticizers") may also be used.

[0045] <<(b1) Polyester>> The (b) plasticizer preferably contains the (b1) polyester. If the (b) plasticizer contains the (b1) polyester, the heat shrinkage resistance of the vinyl chloride resin molded article formed can be improved.

[0046] The (b1) polyester that can be contained in the (b) plasticizer is not particularly limited, and examples thereof include polyesters containing structural units derived from adipic acid (adipic acid-based polyesters), polyesters containing structural units derived from sebacic acid (sebacic acid-based polyesters), and polyesters containing structural units derived from phthalic acid (phthalic acid-based polyesters). These polyesters may be used alone or in combination of two or more in any ratio. In particular, from the viewpoints of further suppressing color tone variations due to differences in molding temperature of the vinyl chloride resin composition and further increasing the heat shrinkage resistance of the vinyl chloride resin molded article to be formed, it is preferable to use a polyester containing structural units derived from adipic acid as the (b1) polyester, and it is particularly preferable to use a polyester containing structural units derived from adipic acid and structural units derived from 3-methyl-1,5-pentanediol.

[0047] For convenience of explanation, the polyester containing structural units derived from adipic acid and structural units derived from 3-methyl-1,5-pentanediol will be referred to as "polyester A" hereinafter. Here, the polyester A containing the above-mentioned predetermined structural units may have structural units other than the structural units derived from adipic acid and the structural units derived from 3-methyl-1,5-pentanediol, but the total of the structural units derived from adipic acid and the structural units derived from 3-methyl-1,5-pentanediol is preferably 50% by mass or more, more preferably 80% by mass or more, of the total structural units.Furthermore, the polyester A containing the above-mentioned predetermined structural units preferably has only the structural units derived from adipic acid and the structural units derived from 3-methyl-1,5-pentanediol as repeating units.

[0048] The polyester A containing the above-mentioned predetermined structural unit can be obtained by condensation polymerization of adipic acid and 3-methyl-1,5-pentanediol, without any particular limitation. The condensation polymerization can be carried out in the presence of a catalyst. The condensation polymerization can be carried out using an alcohol and / or a monobasic acid as a terminal-terminating component. The condensation polymerization of adipic acid and 3-methyl-1,5-pentanediol and the termination reaction of the resulting condensation polymer with the terminal-terminating component can be carried out simultaneously or separately. The product obtained through the condensation polymerization and termination reaction can be subjected to post-treatment such as distillation. The reaction conditions for the condensation polymerization, such as the amounts of the monomers, catalyst, and terminal-terminating component used, can be any known conditions. As the polyester A containing the above-mentioned predetermined structural unit, a commercially available product may be used.

[0049] The catalyst used in the condensation polymerization reaction is not particularly limited, and examples thereof include dibutyltin oxide and tetraalkyl titanate.

[0050] Examples of alcohols that can be used as end-stopping components include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, isohexanol, heptanol, isoheptanol, octanol, isooctanol, 2-ethylhexanol, nonanol, isononanol, decanol, isodecanol, undecanol, isoundecanol, dodecanol, tridecanol, isotridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, cellosolve, carbitol, phenol, nonylphenol, benzyl alcohol, and mixtures thereof. Additionally, monobasic acids that may be used as end-stoppers include, for example, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, caproic acid, heptanoic acid, caprylic acid, 2-ethylhexyl acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, benzoic acid, and mixtures thereof. Among these, 2-ethylhexanol is preferred as the end-stopping component.

[0051] The polyester A containing the above-mentioned predetermined structural units preferably has a number average molecular weight of 1,000 or more, more preferably 2,000 or more, and preferably 10,000 or less, more preferably 7,000 or less. The "number average molecular weight" can be measured by the VPO (vapor pressure osmosis) method. Moreover, the polyester A containing the above-mentioned predetermined structural unit preferably has an acid value of 1 or less. Furthermore, the polyester A containing the above-mentioned predetermined structural unit preferably has a hydroxyl value of 30 or less.

[0052] Furthermore, the polyester A containing the above-mentioned predetermined structural unit preferably has a viscosity of 500 mPa·s or more, more preferably 1000 mPa·s or more, and preferably 8000 mPa·s or less, more preferably 5000 mPa·s or less. The "viscosity" can be measured at a temperature of 23°C in accordance with JIS Z8803.

[0053] The content of (b1) polyester in the (b) plasticizer is preferably 50% by mass or more, more preferably 55% by mass or more, and even more preferably 60% by mass or more, and is preferably 95% by mass or less, and more preferably 90% by mass or less. If the content of (b1) polyester in the (b) plasticizer is equal to or greater than the above-mentioned lower limit, the heat shrinkage resistance of the vinyl chloride resin molded article formed can be further improved. On the other hand, if the content of (b1) polyester in the (b) plasticizer is equal to or less than the above-mentioned upper limit, the flexibility of the vinyl chloride resin molded article formed at low temperatures can be well maintained.

[0054] The content of the (b1) polyester in the vinyl chloride resin composition is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 50 parts by mass or more, and even more preferably 60 parts by mass or more, and is preferably 120 parts by mass or less, and more preferably 110 parts by mass or less, per 100 parts by mass of the (a) vinyl chloride resin. If the content of the (b1) polyester in the vinyl chloride resin composition is equal to or greater than the above-mentioned lower limit, the heat shrinkage resistance of the vinyl chloride resin molded article formed can be further improved. On the other hand, if the content of the (b1) polyester in the vinyl chloride resin composition is equal to or less than the above-mentioned upper limit, the powder flowability of the vinyl chloride resin composition can be improved.

[0055] <<(b2) Trimellitic acid esters>> The (b) plasticizer preferably contains (b2) a trimellitic ester. If the (b) plasticizer contains (b2) a trimellitic ester, the (b2) trimellitic ester is well absorbed by the (a) vinyl chloride resin, thereby improving the powder fluidity of the vinyl chloride resin composition. Furthermore, if the (b) plasticizer contains (b2) a trimellitic ester, the flexibility of the vinyl chloride resin molded article formed at low temperatures can be improved.

[0056] The trimellitic acid ester (b2) contained in the plasticizer (b) is preferably an ester compound of trimellitic acid and a monohydric alcohol.

[0057] Specific examples of the monohydric alcohol include, but are not limited to, aliphatic alcohols such as 1-hexanol, 1-heptanol, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, etc. Among these, the monohydric alcohol is preferably an aliphatic alcohol having 6 to 18 carbon atoms, and more preferably a linear aliphatic alcohol having 6 to 18 carbon atoms.

[0058] Among these, the trimellitic acid ester (b2) is preferably a triester product in which substantially all of the carboxy groups of trimellitic acid are esterified with the above-mentioned monohydric alcohol, and the alcohol residue portions in the triester product may be derived from the same alcohol or different alcohols. The trimellitic acid ester (b2) may consist of a single compound or may be a mixture of different compounds.

[0059] Specific examples of suitable (b2) trimellitic acid esters include tri-n-hexyl trimellitate, tri-n-heptyl trimellitate, tri-n-octyl trimellitate, tri-(2-ethylhexyl) trimellitate, tri-n-nonyl trimellitate, tri-n-decyl trimellitate, triisodecyl trimellitate, tri-n-undecyl trimellitate, tri-n-dodecyl trimellitate, trimellitic acid trialkyl esters (esters having two or more alkyl groups with different carbon numbers [with the carbon number being 6 to 18] in the molecule), trimellitic acid tri-n-alkyl esters (esters having two or more alkyl groups with different carbon numbers [with the carbon number being 6 to 18] in the molecule), and mixtures thereof. More preferred specific examples of (b2) trimellitic acid esters include tri-n-octyl trimellitate, tri-(2-ethylhexyl) trimellitate, tri-n-nonyl trimellitate, tri-n-decyl trimellitate, tri-n-alkyl trimellitate (esters having two or more alkyl groups with different carbon numbers [however, the number of carbon atoms is 6 to 18] in the molecule), and mixtures thereof.

[0060] The content of (b2) trimellitic ester in (b) plasticizer is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less. If the content of (b2) trimellitic ester in (b) plasticizer is equal to or greater than the above-mentioned lower limit, the powder fluidity of the vinyl chloride resin composition can be further increased, and the flexibility of the vinyl chloride resin molded article at low temperatures can be further increased. On the other hand, if the content of (b2) trimellitic ester in (b) plasticizer is equal to or less than the above-mentioned upper limit, the heat shrinkage resistance of the vinyl chloride resin molded article can be improved.

[0061] The content of (b2) trimellitic acid ester in the vinyl chloride resin composition is preferably 5 parts by mass or more, preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less, per 100 parts by mass of the (a) vinyl chloride resin. When the content of (b2) trimellitic acid ester in the vinyl chloride resin composition is equal to or greater than the above-mentioned lower limit, the powder fluidity of the vinyl chloride resin composition can be further increased, and the flexibility of the vinyl chloride resin molded article at low temperatures can be further increased. On the other hand, when the content of (b2) trimellitic acid ester in the vinyl chloride resin composition is equal to or less than the above-mentioned upper limit, the heat shrinkage resistance of the vinyl chloride resin molded article can be increased.

[0062] <<(b3) Other plasticizers>> The (b) plasticizer contained in the vinyl chloride resin composition may optionally contain (b3) other plasticizers other than the above-mentioned (b1) polyester and (b2) trimellitic ester.

[0063] Specific examples of the (b3) other plasticizer include plasticizers other than the (b1) polyesters and (b2) trimellitic esters described above among the plasticizers described in International Publication No. 2016 / 098344. Among these, epoxidized soybean oil is preferably used from the viewpoint of further enhancing the flexibility of the resulting vinyl chloride resin molded article at low temperatures.

[0064] The content of the (b3) other plasticizer in the (b) plasticizer is not particularly limited, but is preferably from 0% to 15% by mass. If the content of the (b3) other plasticizer in the (b) plasticizer is within the above range, the flexibility of the resulting vinyl chloride resin molded article at low temperatures after heating can be improved.

[0065] Furthermore, the content of the (b3) other plasticizer in the vinyl chloride resin composition is not particularly limited, but can be set to 0 parts by mass or more and 15 parts by mass or less per 100 parts by mass of the (a) vinyl chloride resin. In order to further enhance the flexibility of the vinyl chloride resin molded article at low temperatures, it is preferable to use, as the (b3) other plasticizer, an epoxidized vegetable oil such as epoxidized soybean oil in an amount of 2 to 7 parts by mass per 100 parts by mass of the (a) vinyl chloride resin.

[0066] <(c) Uracil Compounds> The vinyl chloride resin composition of the present invention contains (c) a uracil compound. By containing (c) a uracil compound, the vinyl chloride resin composition of the present invention can suppress color tone variations due to differences in molding temperature.

[0067] The (c) uracil compound contained in the vinyl chloride resin composition of the present invention is a compound having a uracil skeleton. From the viewpoint of further suppressing the variation in color tone due to differences in molding temperature of the vinyl chloride resin composition, the uracil compound (c) is a compound represented by the following formula (I): [ka] [In formula (I), R1 and R2 each independently represent a hydrogen atom or an electron-donating group, R3 represents a hydrogen atom or an amino group. It is preferable that the formula be:

[0068] Here, from the viewpoint of further suppressing variation in color tone due to differences in molding temperature of the vinyl chloride resin composition, it is preferable that at least one of R1 and R2 in the above formula (I) is an electron-donating group, and it is more preferable that both R1 and R2 are electron-donating groups. In the above formula (I), when R1 and / or R2 are electron-donating groups, the electron-donating groups are not particularly limited, but examples thereof include alkyl groups, amino groups, dialkylamino groups, etc. Among these, from the viewpoint of further suppressing variations in color tone due to differences in molding temperatures of the vinyl chloride resin composition, the electron-donating groups are preferably alkyl groups, more preferably alkyl groups having 6 or less carbon atoms, and most preferably methyl groups. In the above formula (I), R1 and R2 may be the same or different.

[0069] Specific examples of the (c) uracil compound represented by the formula (I) include uracil, 6-amino-1,3-dimethyluracil, 6-amino-1,3-diethyluracil, 6-amino-1,3-di-n-propyluracil, 6-amino-1,3-di-n-butyluracil, 6-amino-1,3-di-n-pentyluracil, and 6-amino-1,3-di-n-hexyluracil. Among these, 6-amino-1,3-dimethyluracil is preferred as the (c) uracil compound, from the viewpoint of further suppressing color tone variations due to differences in molding temperature of the vinyl chloride resin composition. These (c) uracil compounds may be used singly or in combination of two or more in any ratio.

[0070] The content of the (c) uracil compound in the vinyl chloride resin composition is preferably 0.10 parts by mass or more, more preferably 0.15 parts by mass or more, even more preferably 0.20 parts by mass or more, even more preferably 0.25 parts by mass or more, and preferably 3.00 parts by mass or less, more preferably 2.00 parts by mass or less, even more preferably 1.60 parts by mass or less, even more preferably 0.80 parts by mass or less, and even more preferably 0.40 parts by mass or less, per 100 parts by mass of the (a) vinyl chloride resin. When the content of the (c) uracil compound in the vinyl chloride resin composition is equal to or greater than the above-mentioned lower limit, color variation due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed. On the other hand, when the content of the (c) uracil compound in the vinyl chloride resin composition is equal to or less than the above-mentioned upper limit, the tensile properties (particularly tensile elongation) and blooming resistance of the resulting vinyl chloride resin molded article can be ensured to be sufficiently high.

[0071] <(d) Zinc acetylacetonate> The vinyl chloride resin composition of the present invention contains (d) zinc acetylacetonate. By containing (d) zinc acetylacetonate, the vinyl chloride resin composition of the present invention can suppress variation in color tone due to differences in molding temperature. (d) Zinc acetylacetonate is a metal complex formed when the conjugate base of acetylacetone combines with a zinc ion.

[0072] The content of (d) zinc acetylacetonate in the vinyl chloride resin composition is preferably 0.06 parts by mass or more, more preferably 0.10 parts by mass or more, even more preferably 0.12 parts by mass or more, even more preferably 0.15 parts by mass or more, and preferably 2.0 parts by mass or less, more preferably 1.0 parts by mass or less, even more preferably 0.80 parts by mass or less, even more preferably 0.50 parts by mass or less, and even more preferably 0.30 parts by mass or less, relative to 100 parts by mass of the (a) vinyl chloride resin. When the content of (d) zinc acetylacetonate in the vinyl chloride resin composition is equal to or greater than the above-mentioned lower limit, color variations due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed. On the other hand, when the content of (d) zinc acetylacetonate in the vinyl chloride resin composition is equal to or less than the above-mentioned upper limit, brown spots on the surface of the vinyl chloride resin molded article formed due to the so-called zinc burning phenomenon can be suppressed, and the tensile properties (particularly tensile elongation) and blooming resistance of the vinyl chloride resin molded article can be ensured to be sufficiently high.

[0073] The content of (d) zinc acetylacetonate in the vinyl chloride resin composition is, on a mass basis, preferably at least 0.2 times the content of (above c) the uracil compound, more preferably at least 0.3 times, even more preferably at least 0.4 times, even more preferably at least 0.5 times, even more preferably at least 0.6 times, and preferably at most 3.0 times, more preferably at most 2.5 times, even more preferably at most 2.0 times, even more preferably at most 1.5 times, and even more preferably at most 1.0 times. When the ratio of the content of (d) zinc acetylacetonate to the content of (c) the uracil compound in the vinyl chloride resin composition is at least the above lower limit, variation in color tone due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed. On the other hand, when the ratio of the content of (d) zinc acetylacetonate to the content of (c) uracil compound in the vinyl chloride resin composition is equal to or less than the above upper limit, the occurrence of brown spots on the surface of the vinyl chloride resin molded article to be formed can be suppressed, and the tensile properties (particularly tensile elongation) and blooming resistance of the vinyl chloride resin molded article can be ensured to be sufficiently high.

[0074] <(e) Calcium acetylacetone> (e) Calcium acetylacetonate is a metal complex formed when the conjugate base of acetylacetone combines with calcium ions. The vinyl chloride resin composition of the present invention contains (e) calcium acetylacetonate in a content that is at least a predetermined multiple of the content of the (d) zinc acetylacetonate. By containing (e) calcium acetylacetonate in a content that is at least a predetermined multiple of the content of the (d) zinc acetylacetonate, the vinyl chloride resin composition of the present invention can suppress color tone variations due to differences in molding temperature.

[0075] Here, the content of (e) calcium acetylacetonate in the vinyl chloride resin composition must be at least 0.8 times, preferably at least 1.0 times, more preferably at least 1.2 times, even more preferably at least 1.5 times, even more preferably at least 1.8 times, even more preferably at least 2.0 times, even more preferably at least 2.3 times, preferably at most 12.0 times, more preferably at most 8.0 times, even more preferably at most 6.0 times, even more preferably at most 4.0 times, and even more preferably at most 3.0 times. When the ratio of the content of (e) calcium acetylacetonate to the content of (d) zinc acetylacetonate in the vinyl chloride resin composition is at least the above lower limit, variation in color tone due to differences in molding temperature of the vinyl chloride resin composition can be sufficiently suppressed. On the other hand, when the ratio of the content of (e) calcium acetylacetonate to the content of (d) zinc acetylacetonate in the vinyl chloride resin composition is not more than the above upper limit, the tensile properties (particularly tensile elongation) and blooming resistance of the vinyl chloride resin molded article formed can be ensured to be sufficiently high. From the viewpoint of further suppressing the variation in color tone due to differences in molding temperature of the vinyl chloride resin composition, the content of (e) calcium acetylacetonate in the vinyl chloride resin composition may be 3.0 times or more, or 4.0 times or more, by mass, the content of (d) zinc acetylacetonate.

[0076] Furthermore, the content of (e) calcium acetylacetone in the vinyl chloride resin composition is preferably 0.05 parts by mass or more, more preferably 0.12 parts by mass or more, even more preferably 0.20 parts by mass or more, even more preferably 0.24 parts by mass or more, even more preferably 0.30 parts by mass or more, and preferably 4.0 parts by mass or less, more preferably 2.0 parts by mass or less, even more preferably 1.00 parts by mass or less, even more preferably 0.80 parts by mass or less, and even more preferably 0.55 parts by mass or less, per 100 parts by mass of the (a) vinyl chloride resin. If the content of (e) calcium acetylacetone in the vinyl chloride resin composition is equal to or greater than the above-mentioned lower limit, color variation due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed. On the other hand, if the content of (e) calcium acetylacetone in the vinyl chloride resin composition is equal to or less than the above-mentioned upper limit, the tensile properties (particularly tensile elongation) and blooming resistance of the vinyl chloride resin molded article formed can be sufficiently ensured. From the viewpoint of further suppressing the variation in color tone due to differences in molding temperature of the vinyl chloride resin composition, the content of (e) calcium acetylacetone in the vinyl chloride resin composition may be 0.50 parts by mass or more, 0.60 parts by mass or more, or 0.70 parts by mass or more per 100 parts by mass of the above-mentioned (a) vinyl chloride resin.

[0077] Furthermore, the content of (e) calcium acetylacetone in the vinyl chloride resin composition is, on a mass basis, preferably at least 0.6 times, more preferably at least 0.8 times, even more preferably at least 1.0 times, even more preferably at least 1.2 times, even more preferably at least 1.5 times, and preferably at most 8.0 times, more preferably at most 6.0 times, even more preferably at most 4.0 times, even more preferably at most 3.0 times, and even more preferably at most 2.0 times the content of the (c) uracil compound in the vinyl chloride resin composition. When the ratio of the content of (e) calcium acetylacetone to the content of the (c) uracil compound in the vinyl chloride resin composition is equal to or greater than the above-mentioned lower limit, color tone variations due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed. On the other hand, when the ratio of the content of (e) calcium acetylacetone to the content of the (c) uracil compound in the vinyl chloride resin composition is equal to or less than the above-mentioned upper limit, the tensile properties (particularly tensile elongation) and blooming resistance of the vinyl chloride resin molded article formed can be ensured to be sufficiently high. From the viewpoint of further suppressing the variation in color tone due to differences in molding temperature of the vinyl chloride resin composition, the content of (e) calcium acetylacetonate in the vinyl chloride resin composition may be 2.0 times or more, or 3.0 times or more, by mass, the content of (c) uracil compound.

[0078] <(f) Other β-diketones> The vinyl chloride resin composition of the present invention preferably further contains (f) other β-diketones other than the above-mentioned (d) zinc acetylacetonate and (e) calcium acetylacetonate. By further using (f) other β-diketones in addition to the above-mentioned (d) zinc acetylacetonate and (e) calcium acetylacetonate, it is possible to further suppress variation in color tone due to differences in molding temperature of the vinyl chloride resin composition.

[0079] (f) Examples of other β-diketones include acetylacetone; metal salts of acetylacetone such as magnesium acetylacetone, lithium acetylacetone, aluminum acetylacetone, and nickel acetylacetone; and β-diketone compounds other than acetylacetone and their metal salts. Note that metal salts of β-diketone compounds such as acetylacetone are metal complexes formed by bonding the conjugate base of a β-diketone compound such as acetylacetone with a metal ion.

[0080] As the (f) other β-diketones, from the viewpoint of further suppressing variations in color tone due to differences in molding temperature of the vinyl chloride resin composition, it is preferable to use a β-diketone compound having a benzoyl group, such as dibenzoylmethane, stearoylbenzoylmethane, or palmitoylbenzoylmethane, and it is more preferable to use stearoylbenzoylmethane.

[0081] The content of (f) other β-diketones in the vinyl chloride resin composition is preferably 0.40 parts by mass or more, more preferably 0.50 parts by mass or more, and even more preferably 0.60 parts by mass or more, and preferably 2.00 parts by mass or less, more preferably 1.50 parts by mass or less, and even more preferably 1.20 parts by mass or less, per 100 parts by mass of the (a) vinyl chloride resin. When the content of (f) other β-diketones in the vinyl chloride resin composition is equal to or greater than the above-mentioned lower limit, color variation due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed. On the other hand, when the content of (f) other β-diketones in the vinyl chloride resin composition is equal to or less than the above-mentioned upper limit, the tensile properties (particularly tensile elongation) and blooming resistance of the resulting vinyl chloride resin molded article can be sufficiently ensured.

[0082] Furthermore, the content of (f) other β-diketones in the vinyl chloride resin composition is, on a mass basis, preferably at least 1.0 times, more preferably at least 1.5 times, even more preferably at least 2.0 times, even more preferably at least 2.5 times, even more preferably at least 3.0 times, and preferably at most 15.0 times, more preferably at most 10.0 times, even more preferably at most 8.0 times, even more preferably at most 6.0 times, and even more preferably at most 5.0 times the content of the (c) uracil compound in the vinyl chloride resin composition. When the ratio of the content of (f) other β-diketones to the content of the (c) uracil compound in the vinyl chloride resin composition is at or above the lower limit, color variations due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed. On the other hand, when the ratio of the content of (f) other β-diketones to the content of the (c) uracil compound in the vinyl chloride resin composition is at or below the upper limit, the tensile properties (particularly tensile elongation) and blooming resistance of the resulting vinyl chloride resin molded article can be ensured to be sufficiently high.

[0083] Furthermore, the content of (f) other β-diketones in the vinyl chloride resin composition is preferably at least 1.0 times, more preferably at least 1.5 times, even more preferably at least 2.0 times, even more preferably at least 3.0 times, even more preferably at least 4.0 times, and preferably at most 20.0 times, more preferably at most 15.0 times, even more preferably at most 10.0 times, even more preferably at most 8.0 times, and even more preferably at most 6.0 times the content of (d) zinc acetylacetonate, on a mass basis. When the ratio of the content of (f) other β-diketones to the content of (d) zinc acetylacetonate in the vinyl chloride resin composition is at or above the lower limit, color variations due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed. On the other hand, when the ratio of the content of (f) other β-diketones to the content of (d) zinc acetylacetonate in the vinyl chloride resin composition is at or below the upper limit, the tensile properties (particularly tensile elongation) and blooming resistance of the resulting vinyl chloride resin molded article can be ensured to be sufficiently high.

[0084] <(g) Zinc Fatty Acids> The vinyl chloride resin composition of the present invention preferably further contains (g) a fatty acid zinc salt. When the vinyl chloride resin composition of the present invention further contains (g) a fatty acid zinc salt, color variations due to differences in molding temperature can be further suppressed.

[0085] The number of carbon atoms in the fatty acid of the (g) fatty acid zinc salt is not particularly limited, but is preferably 6 or more, more preferably 8 or more, and more preferably 10 or more, and is preferably 22 or less, more preferably 21 or less, and even more preferably 20 or less. If a zinc salt of a fatty acid having a carbon number within the above-mentioned range is used as the (g) fatty acid zinc salt, variation in color tone due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed. From the viewpoint of further suppressing the variation in color tone due to differences in molding temperature of the vinyl chloride resin composition, it is particularly preferable to use zinc stearate as the (g) fatty acid zinc salt. As the (g) fatty acid zinc salt, one type may be used alone, or two or more types may be mixed in any ratio and used.

[0086] Here, the content of (g) fatty acid zinc in the vinyl chloride resin composition is preferably 0.05 parts by mass or more, more preferably 0.10 parts by mass or more, and even more preferably 0.15 parts by mass or more, and preferably 4.0 parts by mass or less, more preferably 3.0 parts by mass or less, even more preferably 2.0 parts by mass or less, and even more preferably 1.0 parts by mass or less, per 100 parts by mass of the (a) vinyl chloride resin. When the content of (g) fatty acid zinc in the vinyl chloride resin composition is equal to or greater than the above-mentioned lower limit, color variation due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed. On the other hand, when the content of (g) fatty acid zinc in the vinyl chloride resin composition is equal to or less than the above-mentioned upper limit, brown spots can be suppressed from appearing on the surface of the vinyl chloride resin molded article formed, and the tensile properties (particularly tensile elongation) and blooming resistance of the vinyl chloride resin molded article can be sufficiently ensured.

[0087] Furthermore, the content of (g) fatty acid zinc in the vinyl chloride resin composition is, on a mass basis, preferably at least 0.2 times, more preferably at least 0.3 times, even more preferably at least 0.4 times, even more preferably at least 0.5 times, even more preferably at least 0.6 times, and preferably at most 3 times, more preferably at most 2 times, even more preferably at most 1.5 times, even more preferably at most 1.2 times, and even more preferably at most 1.0 times the content of the (c) uracil compound in the vinyl chloride resin composition. When the ratio of the content of (g) fatty acid zinc to the content of the (c) uracil compound in the vinyl chloride resin composition is at least the above-mentioned lower limit, color tone variations due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed. On the other hand, when the ratio of the content of (g) fatty acid zinc to the content of the (c) uracil compound in the vinyl chloride resin composition is at most the above-mentioned upper limit, brown spots can be suppressed on the surface of the vinyl chloride resin molded article formed, and the tensile properties (particularly tensile elongation) and blooming resistance of the vinyl chloride resin molded article can be ensured to be sufficiently high.

[0088] Furthermore, the content of (g) fatty acid zinc in the vinyl chloride resin composition is, on a mass basis, preferably at least 0.2 times the content of (d) zinc acetylacetonate, more preferably at least 0.3 times, even more preferably at least 0.4 times, even more preferably at least 0.6 times, even more preferably at least 0.8 times, and preferably at most 4.0 times, more preferably at most 3.0 times, even more preferably at most 2.0 times, even more preferably at most 1.5 times, and even more preferably at most 1.2 times. When the ratio of the content of (g) fatty acid zinc to the content of (d) zinc acetylacetonate in the vinyl chloride resin composition is at least the above-mentioned lower limit, color variations due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed. On the other hand, when the ratio of the content of (g) fatty acid zinc to the content of (d) zinc acetylacetonate in the vinyl chloride resin composition is at most the above-mentioned upper limit, the occurrence of brown spots on the surface of the vinyl chloride resin molded article can be suppressed, and the tensile properties (particularly tensile elongation) and blooming resistance of the vinyl chloride resin molded article can be ensured to be sufficiently high.

[0089] <(h) Other fatty acid metal salts> The vinyl chloride resin composition of the present invention may further contain (h) other fatty acid metal salts other than the above-mentioned (g) fatty acid zinc salts. (h) other fatty acid metal salts are components that can suppress color tone variations due to differences in molding temperature of the vinyl chloride resin composition and can also suppress the occurrence of brown spots on the surface of the vinyl chloride resin molded article that is formed.

[0090] Therefore, from the viewpoints of further suppressing the variation in color tone due to differences in molding temperature of the vinyl chloride resin composition and suppressing the occurrence of brown spots on the surface of the vinyl chloride resin molded article to be formed, it is preferable that the vinyl chloride resin composition of the present invention contains (h) other fatty acid metal salt.

[0091] The reason why (h) other fatty acid metal salts can suppress the occurrence of brown spots on the surface of the vinyl chloride resin molded article is not clear, but is presumed to be as follows. It is believed that during molding of a vinyl chloride resin composition, hydrogen chloride generated by the thermal decomposition of (a) vinyl chloride resin reacts with (d) zinc acetylacetonate to produce zinc chloride. Zinc chloride can cause brown spots to appear on the surface of the vinyl chloride resin molded article due to the so-called zinc burning phenomenon. In contrast, it is believed that the reaction of (h) other fatty acid metal salts with zinc chloride can suppress the occurrence of brown spots due to the zinc burning phenomenon.

[0092] When the vinyl chloride resin composition of the present invention contains (h) other fatty acid metal salts, the content of (h) other fatty acid metal salts in the vinyl chloride resin composition is preferably 0.05 parts by mass or more, more preferably 0.10 parts by mass or more, even more preferably 0.20 parts by mass or more, even more preferably 0.30 parts by mass or more, even more preferably 0.40 parts by mass or more, and preferably 4.0 parts by mass or less, more preferably 2.0 parts by mass or less, even more preferably 1.00 parts by mass or less, and even more preferably 0.60 parts by mass or less, per 100 parts by mass of the above-mentioned (a) vinyl chloride resin. When the content of (h) other fatty acid metal salts in the vinyl chloride resin composition is at least the above lower limit, color variation due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed, and the occurrence of brown spots on the surface of the resulting vinyl chloride resin molded article can be further suppressed. On the other hand, when the content of (h) other fatty acid metal salts in the vinyl chloride resin composition is not more than the above upper limit, the tensile properties (particularly tensile elongation) and blooming resistance of the resulting vinyl chloride resin molded article can be ensured to be sufficiently high.

[0093] From the viewpoint of ensuring sufficiently high blooming resistance of the vinyl chloride resin molded article to be formed, it is preferable that the vinyl chloride resin composition of the present invention does not contain (h) other fatty acid metal salts.

[0094] The number of carbon atoms in the fatty acid of the (h) other fatty acid metal salt is not particularly limited, but is preferably 6 or more, more preferably 8 or more, and more preferably 10 or more, and is preferably 22 or less, more preferably 21 or less, and even more preferably 20 or less. If a metal salt of a fatty acid having a carbon number within the above-mentioned range is used as the (h) other fatty acid metal salt, variation in color tone due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed, and the occurrence of brown spots on the surface of the resulting vinyl chloride resin molded article can be further suppressed. From the viewpoint of further suppressing the occurrence of brown spots on the surface of the vinyl chloride resin molded article formed while further suppressing the variation in color tone due to differences in molding temperature of the vinyl chloride resin composition, it is particularly preferable that the fatty acid of the (h) other fatty acid metal salt is stearic acid.

[0095] The metal of the (h) other fatty acid metal salt is not particularly limited as long as it is other than zinc, and examples thereof include calcium, barium, etc. From the viewpoints of further suppressing color tone variations due to differences in molding temperature of the vinyl chloride resin composition and further suppressing the occurrence of brown spots on the surface of the vinyl chloride resin molded article formed, it is preferable to use fatty acid calcium as the (h) other fatty acid metal salt.

[0096] As the (h) other fatty acid metal salts, one kind may be used alone, or two or more kinds may be used by mixing in any ratio.

[0097] The content of (h) other fatty acid metal salts in the vinyl chloride resin composition is, on a mass basis, preferably at least 0.8 times the content of the (c) uracil compound, more preferably at least 1.0 times, even more preferably at least 1.2 times, even more preferably at least 1.4 times, even more preferably at least 1.6 times, and preferably at most 10.0 times, more preferably at most 8.0 times, even more preferably at most 6.0 times, even more preferably at most 4.0 times, and even more preferably at most 3.0 times. When the ratio of the content of (h) other fatty acid metal salts to the content of the (c) uracil compound in the vinyl chloride resin composition is at least the above lower limit, color variations due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed, and the occurrence of brown spots on the surface of the resulting vinyl chloride resin molded article can be further suppressed. On the other hand, when the ratio of the content of (h) other fatty acid metal salts to the content of (c) uracil compound in the vinyl chloride resin composition is not more than the above upper limit, the tensile properties (particularly tensile elongation) and blooming resistance of the resulting vinyl chloride resin molded article can be ensured to be sufficiently high.

[0098] The content of (h) other fatty acid metal salts in the vinyl chloride resin composition is, on a mass basis, preferably at least 0.8 times the content of (d) zinc acetylacetonate, more preferably at least 1.2 times, even more preferably at least 1.5 times, even more preferably at least 1.8 times, even more preferably at least 2.0 times, and preferably at most 12.0 times, more preferably at most 8.0 times, even more preferably at most 6.0 times, even more preferably at most 4.0 times, and even more preferably at most 3.0 times. When the ratio of the content of (h) other fatty acid metal salts to the content of (d) zinc acetylacetonate in the vinyl chloride resin composition is at least the above lower limit, color variations due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed, and the occurrence of brown spots on the surface of the resulting vinyl chloride resin molded article can be further suppressed. On the other hand, when the ratio of the content of (h) other fatty acid metal salts to the content of (d) zinc acetylacetonate in the vinyl chloride resin composition is not more than the above upper limit, the tensile properties (particularly tensile elongation) and blooming resistance of the vinyl chloride resin molded article formed can be ensured to be sufficiently high.

[0099] The mass ratio of the (h) other fatty acid metal salt to the (g) fatty acid zinc in the vinyl chloride resin composition ((h) other fatty acid metal salt / (g) fatty acid zinc) is preferably 1 / 1 or more, more preferably 3 / 2 or more, even more preferably 2 / 1 or more, and is preferably 20 / 1 or less, more preferably 15 / 1 or less, and even more preferably 10 / 1 or less. When the mass ratio of the (h) other fatty acid metal salt to the (g) fatty acid zinc in the vinyl chloride resin composition ((h) other fatty acid metal salt / (g) fatty acid zinc) is within the above-mentioned range, variation in color tone due to differences in molding temperature of the vinyl chloride resin composition can be further suppressed, and the occurrence of brown spots on the surface of the vinyl chloride resin molded article can be further suppressed.

[0100] <Additives> The vinyl chloride resin composition of the present invention may further contain various additives in addition to the above-mentioned components. The additives are not particularly limited, and examples thereof include lubricants, stabilizers such as perchloric acid-treated hydrotalcite and zeolite, mold release agents, dusting agents other than the above-mentioned vinyl chloride resin fine particles, impact modifiers, perchloric acid compounds other than perchloric acid-treated hydrotalcite (sodium perchlorate, potassium perchlorate, etc.), antioxidants, mildew inhibitors, flame retardants, antistatic agents, fillers, light stabilizers, foaming agents, pigments, etc.

[0101] The additives that may be contained in the vinyl chloride resin composition of the present invention include, for example, those described in WO 2016 / 098344, and the preferred content thereof may also be the same as that described in WO 2016 / 098344.

[0102] The vinyl chloride resin composition of the present invention may also contain silicone oil. Examples of silicone oils that may be contained in the vinyl chloride resin composition include the silicone oils described in JP 2018-35304 A. The content of silicone oil in the vinyl chloride resin composition is not particularly limited, but is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and is preferably 1 part by mass or less, more preferably 0.8 parts by mass or less, per 100 parts by mass of the (a) vinyl chloride resin.

[0103] <Method for preparing vinyl chloride resin composition> The vinyl chloride resin composition of the present invention can be prepared by mixing the above-mentioned components. The method for mixing the (a) vinyl chloride resin, (b) plasticizer, (c) uracil compound, (d) zinc acetylacetonate, (e) calcium acetylacetonate, and optionally further blended (f) other β-diketones, (g) zinc fatty acid, (h) other fatty acid metal salts, and various additives is not particularly limited. For example, the components excluding the dusting agent (including vinyl chloride resin microparticles) are mixed by dry blending, and then the dusting agent is added and mixed. A Henschel mixer is preferably used for dry blending. The temperature during dry blending is not particularly limited, but is preferably 50°C or higher, more preferably 70°C or higher, and preferably 200°C or lower.

[0104] <Uses of vinyl chloride resin compositions> The vinyl chloride resin composition thus obtained can be suitably used for powder molding, and more suitably used for powder slush molding.

[0105] (Vinyl chloride resin molded body) The vinyl chloride resin molded article of the present invention is characterized in that it is obtained by molding the above-mentioned vinyl chloride resin composition by any method. Since the vinyl chloride resin molded article of the present invention is formed using the above-mentioned vinyl chloride resin composition, it typically contains at least (a) vinyl chloride resin, (b) plasticizer, (c) uracil compound, (d) zinc acetylacetonate, and (e) calcium acetylacetonate, with the ratio of the content of (e) calcium acetylacetonate to the content of (d) zinc acetylacetonate being equal to or greater than a predetermined value. The vinyl chloride resin molded article of the present invention has reduced color unevenness and excellent appearance. Furthermore, the vinyl chloride resin molded article of the present invention can suppress changes in color tone, such as yellowing, even when heated at high temperatures, for example, 270°C or higher. Therefore, the vinyl chloride resin molded article of the present invention can be suitably used as an automobile interior material such as the surface of an automobile instrument panel.

[0106] <Method for forming vinyl chloride resin molded body> When a vinyl chloride resin molded article is formed by powder slush molding, the mold temperature during powder slush molding is not particularly limited, but is preferably 200°C or higher, more preferably 220°C or higher, and is preferably 300°C or lower, more preferably 280°C or lower. Furthermore, even if there is a temperature distribution in the mold during powder slush molding, for example, the vinyl chloride resin molded article of the present invention formed has reduced unevenness in color tone because the vinyl chloride resin composition of the present invention described above is used for molding.

[0107] The vinyl chloride resin molded article can be produced by any method, including, but not limited to, the following method. Specifically, the vinyl chloride resin composition of the present invention is sprinkled onto a mold at a temperature within the above range, and the mold is left standing for 5 to 30 seconds. The excess vinyl chloride resin composition is then shaken off, and the mold is then left standing at a given temperature for 30 seconds to 3 minutes. The mold is then cooled to 10 to 60°C, and the resulting vinyl chloride resin molded article of the present invention is then demolded from the mold. A sheet-like molded article conforming to the shape of the mold is then obtained.

[0108] (Laminate) The laminate of the present invention comprises a polyurethane foam molded article and the vinyl chloride resin molded article described above. The vinyl chloride resin molded article usually constitutes one surface of the laminate. The laminate of the present invention is formed, for example, using the vinyl chloride resin composition of the present invention, and has a vinyl chloride resin molded article with reduced color unevenness and excellent appearance, and is therefore suitably used as an automobile interior part, particularly as an automobile interior material for forming an automobile instrument panel. Furthermore, even when the laminate of the present invention is heated at a high temperature of, for example, 270° C. or higher, it is possible to suppress changes in color tone, such as yellowing, of the vinyl chloride resin molded body portion.

[0109] Here, the method for laminating a polyurethane foam molded body and a vinyl chloride resin molded body is not particularly limited, and the following methods can be used, for example: (1) a method in which a polyurethane foam molded body and a vinyl chloride resin molded body are separately prepared and then bonded together by heat fusion, heat adhesion, or using a known adhesive; (2) a method in which isocyanates and polyols, which are raw materials for the polyurethane foam molded body, are reacted on the vinyl chloride resin molded body to polymerize, and the polyurethane is foamed by a known method, thereby directly forming a polyurethane foam molded body on the vinyl chloride resin molded body; etc. Among these, the latter method (2) is preferred because of its simple process and the ease with which the vinyl chloride resin molded body and the polyurethane foam molded body can be firmly bonded together even when laminates of various shapes are obtained. [Example]

[0110] The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. In the following description, "%" and "parts" representing amounts are based on mass unless otherwise specified. The variation in color tone due to differences in molding temperature of the vinyl chloride resin composition was measured and evaluated by the following method.

[0111] <Color variation due to differences in molding temperature> The vinyl chloride resin composition obtained in each Example and Comparative Example was sprinkled onto a textured mold heated to a temperature of 230°C, left to melt for a desired period of time, and then the excess vinyl chloride resin composition was shaken off. The textured mold onto which the vinyl chloride resin composition had been sprinkled was then placed in an oven set to a temperature of 200°C, and 60 seconds after being placed thereon, the textured mold was cooled with cooling water. When the mold temperature had cooled to 40°C, a vinyl chloride resin molded sheet measuring 150 mm x 200 mm x 1 mm was removed from the mold as a vinyl chloride resin molded product. Further, molding was carried out in the same manner as above, except that the mold temperature (ie, molding temperature) was increased from 230°C to 270°C. Further, molding was carried out in the same manner as above, except that the mold temperature (ie, molding temperature) was increased from 230°C to 280°C. The color tone of the vinyl chloride resin molded sheets obtained by molding at each molding temperature of 230°C, 270°C, and 280°C was measured using a spectrophotometer (Konica Minolta "CM-700d"). For the vinyl chloride resin molded sheets obtained by molding at each molding temperature, the textured surface of the vinyl chloride resin molded sheet was divided into nine parts, and the color was measured at the center of each of the nine parts. * The average value of the values ​​was calculated. And b at a molding temperature of 270°C * From the average value of b at a molding temperature of 230°C * By subtracting the average value of Δb when the molding temperature difference is 230℃~270℃, * The value was calculated. Similarly, b at a molding temperature of 280°C * From the average value of b at a molding temperature of 230°C * By subtracting the average value of the values, Δb when the molding temperature difference is 230℃~280℃ * The value was calculated. In addition, Δb * The smaller the value of (a), the more the vinyl chloride resin composition is inhibited from varying in color tone due to differences in molding temperature.

[0112] (Manufacturing example) The polyesters used in the examples and comparative examples were prepared as follows. <Polyester A> Adipic acid as a polycarboxylic acid, 3-methyl-1,5-pentanediol as a polyhydric alcohol, and 2-ethylhexanol as a stopper (terminal termination component) were charged into a reaction vessel, tetraisopropyl titanate as a catalyst was added, and a solvent was added as appropriate. The mixture was heated with stirring. The by-product water was removed under normal pressure and reduced pressure, and the temperature was finally raised to 220-230°C to complete the dehydration condensation reaction, yielding polyester A (viscosity: 3600 mPa·s, number average molecular weight: 5300, acid value: 0.32, hydroxyl value: 12.7) with 2-ethylhexoxy groups at the ends.

[0113] Example 1 <Preparation of vinyl chloride resin composition> Of the ingredients shown in Table 1, all but the plasticizer (trimellitic acid ester, polyester A, and epoxidized soybean oil) and the vinyl chloride resin fine particles serving as a dusting agent were placed in a Henschel mixer and mixed. When the temperature of the mixture rose to 80°C, all of the plasticizer was added, and the mixture was allowed to dry up (referring to the state in which the plasticizer is absorbed into the vinyl chloride resin particles serving as the vinyl chloride resin, and the mixture becomes smooth). When the dried-up mixture was cooled to a temperature of 70°C or below, the vinyl chloride resin fine particles serving as a dusting agent were added, and a vinyl chloride resin composition was prepared. The resulting vinyl chloride resin composition was used to evaluate the change in color tone due to differences in molding temperature. The results are shown in Table 1.

[0114] (Examples 2 to 8, Comparative Examples 1 to 6) Vinyl chloride resin compositions were prepared in the same manner as in Example 1, except that the blending composition was changed as shown in Table 1. The resulting vinyl chloride resin compositions were then used to evaluate the variation in color tone due to differences in molding temperature. The results are shown in Table 1.

[0115] [Table 1]

[0116] 1) Shin-Daiichi Vinyl Corporation, product name "ZEST (registered trademark) 1700ZI" (prepared by suspension polymerization method, average degree of polymerization: 1700, average particle size: 130 μm) 2) Shin-Daiichi Vinyl Corporation, product name "ZEST PQLTX" (prepared by emulsion polymerization method, average polymerization degree: 800, average particle size: 1.8 μm) 3) Kao Corporation, product name "Trimex N-08" 4) ADEKA Corporation, product name "ADEKA Cizer O-130S" 5) Kyowa Chemical Industry Co., Ltd., product name: Alkamiser (registered trademark) 5 6) Mizusawa Industrial Chemicals, product name "MIZUKALIZER DS" 7) Showa Denko Co., Ltd., product name "Karenz DK-1" 8) ADEKA Corporation, product name "ADEKA STAB LA-63P" 9) Sakai Chemical Industry Co., Ltd., product name "SAKAI SZ2000" 10) ADEKA Corporation, product name "ADEKA STAB LS-12" 11) Shin-Etsu Silicone Co., Ltd., product name "KF-96H-300,000cs" (unmodified silicone oil (polydimethylsiloxane), viscosity: 30 x 10 4 cs) 12) Dainichi Seika Color & Chemicals Co., Ltd., product name "DA P-1050 White" 13) Dainichi Seika Chemicals Co., Ltd., product name "DA PX 1720(A) Black" 14) Dainichi Seika Color & Chemicals Co., Ltd., product name "DA PX-1446 Yellow"

[0117] Table 1 shows that the vinyl chloride resin compositions of Examples 1 to 8, which contain a uracil compound, zinc acetylacetone, and calcium acetylacetone and in which the ratio of the calcium acetylacetone content to the zinc acetylacetone content is equal to or greater than a predetermined value, show sufficient suppression of color tone variations due to differences in molding temperature. On the other hand, it is clear that the vinyl chloride resin composition of Comparative Example 1, which does not contain any of a uracil compound, zinc acetylacetone, and calcium acetylacetone, is unable to sufficiently suppress color tone variations due to differences in molding temperature. It is also clear that the vinyl chloride resin composition of Comparative Example 2, which contains a uracil compound but neither zinc acetylacetone nor calcium acetylacetone, is unable to sufficiently suppress color tone variations due to differences in molding temperature. Furthermore, it is also evident that the vinyl chloride resin composition of Comparative Example 3, which contains a uracil compound and zinc acetylacetone but no calcium acetylacetone, is unable to sufficiently suppress color tone variations due to differences in molding temperature. It is also clear that the vinyl chloride resin composition of Comparative Example 4, which contains a uracil compound and calcium acetylacetone but no zinc acetylacetone, cannot sufficiently suppress color tone variations due to differences in molding temperature. Furthermore, it can be seen that the vinyl chloride resin composition of Comparative Example 5, which contains zinc acetylacetone and calcium acetylacetone, in which the ratio of the calcium acetylacetone content to the zinc acetylacetone content is equal to or greater than a predetermined value, but does not contain a uracil compound, also fails to sufficiently suppress color tone variations due to differences in molding temperature. Furthermore, it was also found that the vinyl chloride resin composition of Comparative Example 6, which contains a uracil compound, zinc acetylacetone, and calcium acetylacetone but in which the ratio of the calcium acetylacetone content to the zinc acetylacetone content is less than a predetermined value, was unable to sufficiently suppress color tone variations due to differences in molding temperature. [Industrial Applicability]

[0118] According to the present invention, it is possible to provide a vinyl chloride resin composition in which variation in color tone due to differences in molding temperature is suppressed. Furthermore, according to the present invention, it is possible to provide a vinyl chloride resin molded article formed using the vinyl chloride resin composition. Furthermore, according to the present invention, it is possible to provide a laminate comprising the vinyl chloride resin molded article.

Claims

1. vinyl chloride resin, A plasticizer, a uracil compound; Zinc acetylacetonate, Calcium acetylacetonate, zeolite, A vinyl chloride resin composition, wherein the content of calcium acetylacetonate is 0.8 times or more, by mass, the content of zinc acetylacetonate.

2. The uracil compound is represented by the following formula (I): 【Chemistry 1】 [In formula (I), R １ and R ２ each independently represents a hydrogen atom or an electron-donating group, R ３ represents a hydrogen atom or an amino group. The vinyl chloride resin composition according to claim 1, wherein

3. 3. The vinyl chloride resin composition according to claim 1, wherein the uracil compound comprises 6-amino-1,3-dimethyluracil.

4. 4. The vinyl chloride resin composition according to claim 1, wherein the content of the uracil compound is 0.1 parts by mass or more per 100 parts by mass of the vinyl chloride resin.

5. 5. The vinyl chloride resin composition according to claim 1, wherein the content of the zinc acetylacetonate is 0.06 parts by mass or more per 100 parts by mass of the vinyl chloride resin.

6. 6. The vinyl chloride resin composition according to claim 1, wherein the content of calcium acetylacetonate is 0.05 parts by mass or more per 100 parts by mass of the vinyl chloride resin.

7. The vinyl chloride resin composition according to any one of claims 1 to 6, further comprising a fatty acid metal salt other than a fatty acid zinc salt.

8. 8. The vinyl chloride resin composition according to claim 7, wherein the fatty acid metal salt contains fatty acid calcium.

9. 9. The vinyl chloride resin composition according to claim 7, wherein the fatty acid metal salt comprises a metal salt of a fatty acid having 6 to 22 carbon atoms.

10. The vinyl chloride resin composition according to any one of claims 1 to 9, which is used for powder molding.

11. The vinyl chloride resin composition according to any one of claims 1 to 10, which is used in powder slush molding.

12. A vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition according to any one of claims 1 to 11.

13. The vinyl chloride resin molded article according to claim 12, which is used for an automobile instrument panel skin.

14. A laminate comprising a polyurethane foam molded article and the vinyl chloride resin molded article according to claim 12 or 13.

15. The laminate of claim 14 for use in an automobile instrument panel.

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