JP7786106B2 - Vinyl chloride resin composition, vinyl chloride resin molded article and laminate - Google Patents

Description

The present invention relates to a vinyl chloride resin composition, a vinyl chloride resin molded article, and a laminate.

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.

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

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 such as a polyester-based plasticizer, and additives such as a hydrotalcite-based stabilizer, a zeolite-based stabilizer, and β-diketones.

JP 2012-197394 A

Here, when a laminate is formed by lining (laminating) a polyvinyl chloride resin molded body with a polyurethane foam (hereinafter sometimes referred to as a "polyurethane foam molded body"), it is necessary to prevent the formation of relatively large voids (air gaps) in the polyurethane foam molded body.
On the other hand, vinyl chloride resin molded articles are required to have excellent abrasion resistance.
However, when the vinyl chloride resin composition of the above-mentioned prior art, which uses a polyester-based plasticizer as a plasticizer, is used, there is room for improvement in terms of improving the abrasion resistance of the vinyl chloride resin molded article while suppressing the generation of voids in the foamed polyurethane molded article laminated on the resulting vinyl chloride resin molded article.

Therefore, an object of the present invention is to provide a vinyl chloride resin composition capable of forming a vinyl chloride resin molded article that has excellent abrasion resistance and can suppress the generation of voids in the laminated polyurethane foam molded article.
Another object of the present invention is to provide a vinyl chloride resin molded article that has excellent abrasion resistance and can suppress the generation of voids in a laminated polyurethane foam molded article.
A further object of the present invention is to provide a laminate comprising the vinyl chloride resin molded article.

The present inventors conducted extensive research with the aim of solving the above-mentioned problems. They discovered that adding a cross-linked vinyl chloride resin and an ether-modified silicone oil having an HLB value equal to or greater than a predetermined value to a vinyl chloride resin composition containing a polyester-based plasticizer improves the abrasion resistance of a vinyl chloride resin molded article formed using the vinyl chloride resin composition, and also prevents the formation of voids in a foamed polyurethane molded article laminated onto the vinyl chloride resin molded article, leading to the completion of the present invention.

That is, the present invention has an object 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 cross-linked vinyl chloride resin, a polyester-based plasticizer, and an ether-modified silicone oil having an HLB value of 1.5 or more. Thus, a vinyl chloride resin composition comprising a vinyl chloride resin, a cross-linked vinyl chloride resin, a polyester-based plasticizer, and an ether-modified silicone oil having an HLB value of a predetermined value or more can form a vinyl chloride resin molded article that is excellent in abrasion resistance and can suppress the generation of voids in a laminated polyurethane foam molded article.
In the present invention, the term "HLB value" refers to the Hydrophile-Lipophile Balance, which is calculated according to the Griffin method using the following formula (1):
HLB value = 20 x
(Sum of formula weights of chain ethylene oxide structures/molecular weight) (1)
Here, in the present invention, the "chain ethylene oxide structure" refers to a chain ethylene oxide structure, which will be described in detail later, and does not include, for example, a cyclic ethylene oxide structure such as an epoxy group.

In the vinyl chloride resin composition of the present invention, the ether-modified silicone oil preferably has an HLB value of 10 or less. Using an ether-modified silicone oil with an HLB value of the above-mentioned specified value or less can improve the demoldability of vinyl chloride resin molded articles formed using the vinyl chloride resin composition.

In addition, in the vinyl chloride resin composition of the present invention, the ether-modified silicone oil preferably has ether groups having a chain-like ethylene oxide structure and a chain-like propylene oxide structure introduced into its side chain. Use of an ether-modified silicone oil having the above-described specific structure can further improve the abrasion resistance of vinyl chloride resin molded articles formed using the vinyl chloride resin composition and further suppress the occurrence of voids in the laminated foamed polyurethane molded article. Use of an ether-modified silicone oil having the above-described specific structure can also improve the demoldability of vinyl chloride resin molded articles formed using the vinyl chloride resin composition.

The vinyl chloride resin composition of the present invention preferably contains 0.01 to 2 parts by mass of the ether-modified silicone oil per 100 parts by mass of the vinyl chloride resin. When the content of the ether-modified silicone oil per 100 parts by mass of the vinyl chloride resin in the vinyl chloride resin composition is within the above-mentioned range, the abrasion resistance of vinyl chloride resin molded articles formed using the vinyl chloride resin composition can be further improved, and the occurrence of voids in laminated foamed polyurethane molded articles can be further suppressed. Furthermore, when the content of the ether-modified silicone oil per 100 parts by mass of the vinyl chloride resin in the vinyl chloride resin composition is within the above-mentioned range, the demoldability of vinyl chloride resin molded articles formed using the vinyl chloride resin composition can be improved, and contamination of the surface of a molding die or the like due to an excessive amount of ether-modified silicone oil can be suppressed, even when, for example, vinyl chloride resin molded articles are continuously molded using the vinyl chloride resin composition.

Furthermore, the vinyl chloride resin composition of the present invention preferably contains 0.1 to 20 parts by mass of the cross-linked vinyl chloride resin per 100 parts by mass of the vinyl chloride resin. When the content of the cross-linked vinyl chloride resin per 100 parts by mass of the vinyl chloride resin in the vinyl chloride resin composition is within the above-mentioned specified range, the abrasion resistance of a vinyl chloride resin molded article formed using the vinyl chloride resin composition can be further improved, and the demoldability of the vinyl chloride resin molded article can be improved.

Furthermore, in the vinyl chloride resin composition of the present invention, the polyester-based plasticizer preferably contains an adipic acid-based polyester. Using an adipic acid-based polyester as the polyester-based plasticizer can improve the heat shrinkage resistance of vinyl chloride resin molded articles formed using the vinyl chloride resin composition.

Furthermore, in the vinyl chloride resin composition of the present invention, the content of the polyester-based plasticizer is preferably 30 parts by mass or more and 200 parts by mass or less per 100 parts by mass of the vinyl chloride resin. When the content of the polyester-based plasticizer per 100 parts by mass of the vinyl chloride resin in the vinyl chloride resin composition is within the above-mentioned specified range, the tensile properties and heat shrinkage resistance of a vinyl chloride resin molded article formed using the vinyl chloride resin composition can be improved, while ensuring sufficiently high abrasion resistance and demoldability of the vinyl chloride resin molded article.

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, it is possible to easily obtain vinyl chloride resin molded articles that can be used favorably as automotive interior materials, such as the skin for automobile instrument panels.

The vinyl chloride resin composition of the present invention is preferably used in powder slush molding. By using the vinyl chloride resin composition in powder slush molding, it is possible to more easily obtain vinyl chloride resin molded articles that can be used effectively as automotive interior materials, such as the skin for automobile instrument panels.

Furthermore, the present invention aims to advantageously solve the above-mentioned problems, and the vinyl chloride resin molded article of the present invention is characterized by being formed by molding any of the vinyl chloride resin compositions described above. In this way, vinyl chloride resin molded articles formed by molding the vinyl chloride resin compositions described above have excellent abrasion resistance and can suppress the formation of voids in laminated polyurethane foam molded articles.

The vinyl chloride resin molded article of the present invention is preferably used for the skin of an automobile instrument panel. By using the vinyl chloride resin molded article of the present invention as the skin of an automobile instrument panel, it is possible to produce an automobile instrument panel having a skin that has excellent abrasion resistance and can suppress the formation of voids in the laminated polyurethane foam molded article.

Furthermore, the present invention aims to advantageously solve the above-mentioned problems, and the laminate of the present invention is characterized by having a polyurethane foam molded body and any of the vinyl chloride resin molded bodies described above. A laminate having a polyurethane foam molded body and any of the vinyl chloride resin molded bodies described above has a vinyl chloride resin molded body portion that is highly abrasion-resistant, and the occurrence of voids in the polyurethane foam molded body portion is reduced.

The laminate of the present invention is preferably used for automobile instrument panels. In this way, by using the laminate of the present invention in automobile instrument panels, it is possible to produce automobile instrument panels that have a surface with excellent abrasion resistance and that have reduced voids in the foamed polyurethane molded body portion.

According to the present invention, it is possible to provide a vinyl chloride resin composition capable of forming a vinyl chloride resin molded article that has excellent abrasion resistance and can suppress the generation of voids in the laminated polyurethane foam molded article.
Furthermore, according to the present invention, it is possible to provide a vinyl chloride resin molded article that has excellent abrasion resistance and can suppress the generation of voids in a laminated polyurethane foam molded article.
Furthermore, according to the present invention, it is possible to provide a laminate comprising the vinyl chloride resin molded article.

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.

(Vinyl chloride resin composition)
The vinyl chloride resin composition of the present invention is characterized by comprising (a) a vinyl chloride resin, (b) a cross-linked vinyl chloride resin, (c) a polyester-based plasticizer, and (c) an ether-modified silicone oil having an HLB value of a predetermined value or more.
The vinyl chloride resin composition of the present invention may optionally further contain (e) an amide compound.
Furthermore, the vinyl chloride resin composition of the present invention may optionally further contain a plasticizer other than the above-mentioned (c) polyester-based plasticizer (hereinafter, this may be referred to as "(f) other plasticizer").
Furthermore, the vinyl chloride resin composition of the present invention may optionally further contain additives other than the above-mentioned (a) vinyl chloride resin, (b) cross-linked vinyl chloride resin, (c) polyester-based plasticizer, (d) ether-modified silicone oil, (e) amide compound, and (f) other plasticizers.

Furthermore, vinyl chloride resin molded articles formed using the vinyl chloride resin composition of the present invention have excellent abrasion resistance, and when a laminate is formed by laminating a polyurethane foam molded article onto the vinyl chloride resin molded article, the occurrence of voids in the laminated polyurethane foam molded article can be suppressed.

Therefore, by using the vinyl chloride resin composition of the present invention, it is possible to prevent the formation of voids in a foamed polyurethane molded article when it is lined, and to obtain a vinyl chloride resin molded article that is suitable for use as an automotive interior material, such as the surface of an automotive instrument panel or door trim, and that also has excellent abrasion resistance.

Furthermore, vinyl chloride resin molded articles formed using the vinyl chloride resin composition of the present invention can be easily demolded from the mold used to mold the vinyl chloride resin composition. In other words, vinyl chloride resin molded articles formed using the vinyl chloride resin composition of the present invention have excellent demoldability.

In addition, from the viewpoint of easily obtaining vinyl chloride resin molded articles that can be used effectively, for example, as automotive interior materials, using the vinyl chloride resin composition of the present invention, the vinyl chloride resin composition of the present invention is preferably used in powder molding, and more preferably in powder slush molding.

<(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.

Examples of the vinyl chloride resin (a) include homopolymers composed of vinyl chloride monomer units, as well as vinyl chloride copolymers 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.
In the present invention, the (a) vinyl chloride resin is a non-crosslinked vinyl chloride resin, i.e., the (a) vinyl chloride resin does not include the (b) crosslinked vinyl chloride resin described below.

<<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.

[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. Furthermore, 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.

[Average particle diameter]
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. 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 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.

[Content ratio]
The content of vinyl chloride resin particles in the (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 98% by mass or less, and more preferably 95% by mass or less. If the content of vinyl chloride resin particles in the (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. Furthermore, if the content of vinyl chloride resin particles in the (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.

<<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.

[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. If the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin microparticles as a dusting agent is not less 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. Furthermore, if the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin microparticles is not more 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.

[Average particle diameter]
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, preferably 0.1 μm or more, and 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 particles used as a dusting agent. 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 the vinyl chloride resin molded article formed.

[Content ratio]
The content of vinyl chloride resin microparticles in (a) vinyl chloride resin may be 0% by mass, but is preferably 2% by mass or more, more preferably 5% 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 flowability of the vinyl chloride resin composition can be improved. Furthermore, 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 improved.

<(b) Cross-linked vinyl chloride resin>
The (b) cross-linked vinyl chloride resin is a component that can function as a dusting agent (powder flowability improver) in a vinyl chloride resin composition. The inclusion of the (b) cross-linked vinyl chloride resin in a vinyl chloride resin composition can improve the powder flowability of the vinyl chloride resin composition. Furthermore, the inclusion of the (b) cross-linked vinyl chloride resin in a vinyl chloride resin composition can improve the abrasion resistance and demoldability of the vinyl chloride resin molded article that is formed.

(b) Cross-linked vinyl chloride resin is a resin obtained by cross-linking vinyl chloride resin. (b) Cross-linked vinyl chloride resin can be prepared by cross-linking uncross-linked vinyl chloride resin. Examples of uncross-linked vinyl chloride resins that can be used as materials for preparing (b) cross-linked vinyl chloride resin include the homopolymers and vinyl chloride copolymers composed of vinyl chloride monomer units described above as specific examples of (a) vinyl chloride resin. The method for cross-linking vinyl chloride resin is not particularly limited; for example, it may be a chemical cross-linking method using a known cross-linking agent, or a cross-linking method using radiation such as an electron beam.

The content of the (b) cross-linked vinyl chloride resin in the vinyl chloride resin composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, even more preferably 4 parts by mass or more, even more preferably 5 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, even more preferably 12 parts by mass or less, even more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, per 100 parts by mass of the (a) vinyl chloride resin. When the content of the (b) cross-linked vinyl chloride resin in the vinyl chloride resin composition is equal to or greater than the above-mentioned lower limit per 100 parts by mass of the (a) vinyl chloride resin, the abrasion resistance and demoldability of the vinyl chloride resin molded article formed can be further improved. On the other hand, when the content of the (b) cross-linked vinyl chloride resin in the vinyl chloride resin composition is equal to or less than the above-mentioned upper limit per 100 parts by mass of the (a) vinyl chloride resin, the demoldability of the vinyl chloride resin molded article formed can be further improved.

In the vinyl chloride resin composition, the total content of the vinyl chloride resin microparticles and cross-linked vinyl chloride resin as dusting agents per 100 parts by mass of the vinyl chloride resin particles as the base material is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, even more preferably 8 parts by mass or more, even more preferably 10 parts by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 16 parts by mass or less. When the total content of the vinyl chloride resin microparticles and cross-linked vinyl chloride resin microparticles as dusting agents per 100 parts by mass of the vinyl chloride resin particles as the base material 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 improved. On the other hand, when the total content of the vinyl chloride resin microparticles and cross-linked vinyl chloride resin microparticles as dusting agents per 100 parts by mass of the vinyl chloride resin particles as the base material in the vinyl chloride resin composition is equal to or less than the above-mentioned upper limit, the physical strength of the vinyl chloride resin molded article formed can be improved.

Furthermore, the mass ratio of vinyl chloride resin microparticles to cross-linked vinyl chloride resin in the vinyl chloride resin composition (vinyl chloride resin microparticles/cross-linked vinyl chloride resin) is preferably 1/5 or more, more preferably 2/5 or more, and even more preferably 3/5 or more, and is preferably 5/1 or less, more preferably 5/2 or less, and even more preferably 5/3 or less. When the mass ratio of vinyl chloride resin microparticles to cross-linked vinyl chloride resin in the vinyl chloride resin composition (vinyl chloride resin microparticles/cross-linked vinyl chloride resin) is within the above-mentioned specified range, the demoldability of the resulting vinyl chloride resin molded article can be further improved.

Furthermore, the content of the (b) cross-linked vinyl chloride resin in the vinyl chloride resin composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, even more preferably 4 parts by mass or more, even more preferably 5 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, even more preferably 12 parts by mass or less, even more preferably 10 parts by mass or less, and even more preferably 7 parts by mass or less, per 100 parts by mass of the (c) polyester-based plasticizer, as described below. When the content of the (b) cross-linked vinyl chloride resin in the vinyl chloride resin composition is equal to or greater than the above-mentioned lower limit per 100 parts by mass of the (c) polyester-based plasticizer, the abrasion resistance and demoldability of the vinyl chloride resin molded article formed can be further improved. On the other hand, when the content of the (b) cross-linked vinyl chloride resin in the vinyl chloride resin composition is equal to or less than the above-mentioned upper limit per 100 parts by mass of the (c) polyester-based plasticizer, the demoldability of the vinyl chloride resin molded article formed can be further improved.

The (b) cross-linked vinyl chloride resin is typically a particulate cross-linked vinyl chloride resin. From the perspective of further improving the powder fluidity (particularly high-temperature powder fluidity) of the vinyl chloride resin composition, the (b) cross-linked vinyl chloride resin preferably contains cross-linked vinyl chloride resin microparticles, and more preferably consists solely of cross-linked vinyl chloride resin microparticles. The (b) cross-linked vinyl chloride resin can contain one or more types of cross-linked vinyl chloride resin microparticles.

The average particle diameter of the cross-linked vinyl chloride resin microparticles is typically 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 diameter of the cross-linked vinyl chloride resin microparticles is at least the above lower limit, the powder flowability of the vinyl chloride resin composition can be further improved, for example, without excessively reducing the size of the cross-linked vinyl chloride resin microparticles used as a dusting agent. Furthermore, if the average particle diameter of the cross-linked vinyl chloride resin microparticles is at most the above upper limit, the meltability of the vinyl chloride resin composition can be enhanced, and the surface smoothness of the resulting vinyl chloride resin molded article can be improved.

<(c) Polyester-based plasticizer>
The (c) polyester-based plasticizer is a component that can impart sufficient tensile properties (tensile strength and tensile elongation) to a vinyl chloride resin molded article formed using the vinyl chloride resin composition. Furthermore, by using the (c) polyester-based plasticizer as a plasticizer, when a laminate is formed by backing a foamed polyurethane molded article with a vinyl chloride resin molded article formed using the vinyl chloride resin composition, the (c) polyester-based plasticizer is unlikely to migrate from the vinyl chloride resin molded article to the foamed polyurethane molded article even at high temperatures, and therefore the heat shrinkage resistance of the vinyl chloride resin molded article can be improved.

The (c) polyester-based 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.
Among these, from the viewpoint of further improving the heat shrinkage resistance of the vinyl chloride resin molded article, it is preferable to use an adipic acid-based polyester (a polyester containing a structural unit derived from adipic acid) as the (c) polyester-based plasticizer.

The viscosity of the (c) polyester-based plasticizer is preferably 500 mPa·s or more, more preferably 1000 mPa·s or more, and is preferably 8000 mPa·s or less, more preferably 5000 mPa·s or less.
The "viscosity" can be measured at a temperature of 25°C in accordance with JIS Z8803.

The content of the (c) polyester-based plasticizer in the vinyl chloride resin composition is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 70 parts by mass or more, even more preferably 90 parts by mass or more, even more preferably 95 parts by mass or more, and preferably 200 parts by mass or less, more preferably 180 parts by mass or less, even more preferably 150 parts by mass or less, even more preferably 130 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 (c) polyester-based plasticizer in the vinyl chloride resin composition is equal to or greater than the above-mentioned lower limit per 100 parts by mass of the (a) vinyl chloride resin, the tensile properties and heat shrinkage resistance of the resulting vinyl chloride resin molded article can be improved. On the other hand, when the content of the (c) polyester-based plasticizer in the vinyl chloride resin composition is equal to or less than the above-mentioned upper limit per 100 parts by mass of the (a) vinyl chloride resin, the resulting vinyl chloride resin molded article can have sufficiently high abrasion resistance and demoldability.

<(d) Ether-modified silicone oil>
The (d) ether-modified silicone oil having an HLB value of a predetermined value or more is a component that can impart abrasion resistance and demoldability to a vinyl chloride resin molded article when a foamed polyurethane molded article is laminated on a vinyl chloride resin molded article formed using the vinyl chloride resin composition, while suppressing the occurrence of voids in the foamed polyurethane molded article. In particular, by using the (d) ether-modified silicone oil in combination with the above-mentioned (b) crosslinked vinyl chloride resin, the vinyl chloride resin molded article formed using the vinyl chloride resin composition can exhibit excellent abrasion resistance and demoldability.

<<Types>>
Here, (d) ether-modified silicone oil is usually obtained by introducing an ether group into at least one of a main chain consisting of a siloxane bond (-Si-O-Si-), a side chain of the main chain, and an end of the main chain. Here, when an ether group is introduced into the main chain, the ether group is block-bonded to the middle of the main chain. Furthermore, when an ether group is introduced into the end, it may be introduced into one end or both ends. Furthermore, (d) ether-modified silicone oil may further have a substituent other than an ether group introduced into the main chain, a side chain of the main chain, and/or an end of the main chain.
The ether-modified silicone oil (d) preferably has an ether group introduced at least into the side chain.

[Ether group]
Examples of the ether group include a substituent having one or more chain alkylene oxide structures. Specifically, examples of the ether group include a group represented by the following general formula (2):
[wherein x is a natural number of 1 or more], a substituent having only a chain ethylene oxide structure (when x is a natural number of 2 or more in formula (2), it is also referred to as a "polyethylene oxide group") represented by the following general formula (3):
[In formula (3), y is a natural number of 1 or more.] (When y is a natural number of 2 or more in formula (3), it is also referred to as a "polypropylene oxide group") in any proportion; a substituent which, in addition to the above chain ethylene oxide structure, further has any organic structure (hereinafter referred to as "R" and "R'") other than a chain alkylene oxide structure (for example, -R-(C ₂ H ₄ O) _x -R'); a substituent which, in addition to a chain alkylene oxide structure such as the above chain ethylene oxide structure and chain propylene oxide structure, further has any organic structure R, R' (for example, -R-(C ₂ H ₄ O) _x (C ₃ H ₆ O) _y -R'); and the like. Here, for example, only one of the optional organic structures R and R' in the above-mentioned -R-(C ₂ H ₄ O) _x -R' and -R-(C ₂ H ₄ O) _x (C ₃ H ₆ O) _y -R' may be present.

In particular, from the viewpoint of further improving the abrasion resistance and demoldability of the vinyl chloride resin molded article while further suppressing the formation of voids in the foamed polyurethane molded article adjacent to the vinyl chloride resin molded article, although the reason is not clear, it is preferable for the ether group to have at least a chain ethylene oxide structure, more preferably a chain ethylene oxide structure and a chain propylene oxide structure, and even more preferably a plurality of chain ethylene oxide structures and a plurality of chain propylene oxide structures. Furthermore, from the viewpoint of excellent heat aging resistance, it is even more preferable for the ether group to have no unsaturated bonds.

[Other Substituents]
(d) Other substituents that can be further introduced into the ether-modified silicone oil are not particularly limited, and examples thereof include alkyl groups (-C _a H _2a+1 ; where a is any natural number), aralkyl groups (e.g., -CH ₂ -CH(CH ₃ )-C ₆ H ₅ ; where C ₆ H ₅ is a phenyl group), etc.

<<HLB value>>
Furthermore, the HLB value of the (d) ether-modified silicone oil must be 1.5 or higher, preferably 1.6 or higher, more preferably 1.7 or higher, even more preferably 1.8 or higher, even more preferably 1.9 or higher, even more preferably 2.0 or higher, and can be 20 or lower, preferably 10 or lower, more preferably 8 or lower, even more preferably 6.5 or lower, even more preferably 5.5 or lower, and even more preferably 4 or lower. If the HLB value of the (d) ether-modified silicone oil is above the lower limit, the formation of voids in the foamed polyurethane molded article laminated on the vinyl chloride resin molded article formed can be suppressed, while the abrasion resistance and demoldability of the vinyl chloride resin molded article can be improved. On the other hand, if the HLB value of the (d) ether-modified silicone oil is below the upper limit, the demoldability of the vinyl chloride resin molded article formed can be further improved.

<<Viscosity>>
Furthermore, the kinematic viscosity of the (d) ether-modified silicone oil at a temperature of 25°C is preferably 65 cSt or more, more preferably 100 cSt or more, even more preferably 300 cSt or more, more preferably 4000 cSt or less, more preferably 3000 cSt or less, even more preferably 1000 cSt or less, and even more preferably 800 cSt or less. If the kinematic viscosity of the (d) ether-modified silicone oil is above the above-mentioned lower limit, the abrasion resistance and demoldability of the vinyl chloride resin molded article formed can be further improved, and the generation of voids in the foamed polyurethane molded article laminated on the vinyl chloride resin molded article can be further suppressed. On the other hand, if the kinematic viscosity of the (d) ether-modified silicone oil is below the above-mentioned upper limit, the ether-modified silicone oil has excellent handleability, and the demoldability of the vinyl chloride resin molded article formed can be further improved.
In the present invention, the "kinematic viscosity" can be measured in accordance with ASTM D 445-46T at a temperature of 25°C as described in the examples. When a mixture of two or more different ether-modified silicone oils is used, the "kinematic viscosity" can be measured as the value of the entire mixture.

＜＜Content＞＞
The content of the (d) ether-modified silicone oil in the vinyl chloride resin composition is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, even more preferably 0.2 parts by mass or more, even more preferably 0.3 parts by mass or more, particularly preferably 0.4 parts by mass or more, and is preferably 2 parts by mass or less, more preferably 1.8 parts by mass or less, even more preferably 1.6 parts by mass or less, even more preferably 1.4 parts by mass or less, even more preferably 1.2 parts by mass or less, and particularly preferably 1 part by mass or less, relative to 100 parts by mass of the (a) vinyl chloride resin. If the content of the (d) ether-modified silicone oil in the vinyl chloride resin composition is equal to or more than the above lower limit relative to 100 parts by mass of the (a) vinyl chloride resin, the formation of voids in a foamed polyurethane molding laminated on the resulting vinyl chloride resin molding can be further suppressed, while the abrasion resistance and demoldability of the vinyl chloride resin molding can be further improved. On the other hand, when the content of the (d) ether-modified silicone oil in the vinyl chloride resin composition is equal to or less than the above upper limit per 100 parts by mass of the (a) vinyl chloride resin, for example, even when a vinyl chloride resin molded article is continuously molded, contamination of the surface of a molding die or the like due to an excessive amount of ether-modified silicone oil can be suppressed.
The content of the (d) ether-modified silicone oil in the vinyl chloride resin composition may be 0.5 parts by mass or more, 0.5 parts by mass or less, 0.7 parts by mass or more, 0.7 parts by mass or less, 0.9 parts by mass or more, or 0.9 parts by mass or less, relative to 100 parts by mass of the (a) vinyl chloride resin.

Furthermore, the content of the (d) ether-modified silicone oil in the vinyl chloride resin composition is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, even more preferably 0.2 parts by mass or more, even more preferably 0.3 parts by mass or more, particularly preferably 0.4 parts by mass or more, and is preferably 2 parts by mass or less, more preferably 1.8 parts by mass or less, even more preferably 1.6 parts by mass or less, even more preferably 1.4 parts by mass or less, even more preferably 1.2 parts by mass or less, and particularly preferably 1 part by mass or less, relative to 100 parts by mass of the (c) polyester-based plasticizer. If the content of the (d) ether-modified silicone oil in the vinyl chloride resin composition is equal to or greater than the above lower limit relative to 100 parts by mass of the (c) polyester-based plasticizer, the formation of voids in the foamed polyurethane molding laminated on the vinyl chloride resin molding formed can be further suppressed, while the abrasion resistance and demoldability of the vinyl chloride resin molding can be further improved. On the other hand, when the content of (d) ether-modified silicone oil in the vinyl chloride resin composition is equal to or less than the above upper limit per 100 parts by mass of (c) polyester-based plasticizer, even when a vinyl chloride resin molded article is continuously molded, contamination of the surface of a molding die or the like due to an excessive amount of ether-modified silicone oil can be suppressed.
The content of the (d) ether-modified silicone oil in the vinyl chloride resin composition may be 0.5 parts by mass or more, 0.5 parts by mass or less, 0.7 parts by mass or more, 0.7 parts by mass or less, 0.8 parts by mass or more, or 0.8 parts by mass or less, relative to 100 parts by mass of the (c) polyester-based plasticizer.

In the present invention, ether-modified silicone oils are typically fluid at room temperature. In the present invention, "room temperature" refers to 23°C.

<(e) Amide Compound>
The vinyl chloride resin composition of the present invention may optionally contain an amide compound (e). When the vinyl chloride resin composition further contains an amide compound (e), the demoldability of the resulting vinyl chloride resin molded article can be further improved.
(e) The amide compound is a compound having an amide group, and is, for example, a compound represented by the following formula (4):
R ¹ (NR ² COR ³ ) _n (4)
[In formula (1), n is an integer of 2 or more and 6 or less, ^R1 is an n-valent hydrocarbon group, ^R2 is a monovalent hydrocarbon group or hydrogen, ^R3 is a monovalent hydrocarbon group, the n ^R2s may be the same or different, and the n ^R3s may be the same or different.] That is, the amide compound (e) has a structure in which, for example, n hydrogen atoms of a hydrocarbon are substituted with amide groups represented by ^{—NR2COR3 .}

<<Structure>>
[n]
Here, n in the above formula (4) is, for example, an integer of 2 or more and 6 or less, and n may be an integer of 2 or more and 3 or less, or may be 2.

[R ¹ ]
Furthermore, R ¹ in the above formula (4) is an n-valent hydrocarbon group, which may be an n-valent aliphatic hydrocarbon group or an n-valent aromatic hydrocarbon group.
Furthermore, the number of carbon atoms contained in R ¹ may be, for example, 1 or more, 2 or more, 8 or less, or 6 or less.

Examples of ^R1 include a methylene group, a methylmethylene group, an ethylene group (dimethylene group), a dimethylmethylene group, an isopropylene group, a trimethylene group, an isobutylene group, a tetramethylene group, and a hexamethylene group.

[ ^R2 ]
Furthermore, ^R2 in the above formula (4) is a monovalent hydrocarbon group or hydrogen, and the n ^R2s may be the same or different. Here, the monovalent hydrocarbon group of ^R2 may be a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group. The monovalent aliphatic hydrocarbon group is, for example, a monovalent chain aliphatic hydrocarbon group. Furthermore, the monovalent aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.
The hydrocarbon group of ^R2 has, for example, 1 or more and 2 or less carbon atoms.
Examples of ^R2 include hydrogen, a methyl group, and an ethyl group.

As for ^R2 , at least one of n ^R2 may be hydrogen, or all of n ^R2 may be hydrogen.

[R ³ ]
In addition, ^R3 in the above formula (4) is a monovalent hydrocarbon group, and the n ^R3s may be the same or different from one another. In other words, in the (e) amide compound, a saturated hydrocarbon group of ^R3 and an unsaturated hydrocarbon group of ^R3 may be mixed in one molecule, or only an unsaturated hydrocarbon group of ^R3 may be present, or only a saturated hydrocarbon group of ^R3 may be present.

Here, the saturated hydrocarbon group of ^R3 is, for example, a monovalent chain saturated aliphatic hydrocarbon group.
The saturated hydrocarbon group of ^R3 may have 11 or more carbon atoms, 13 or more carbon atoms, 15 or more carbon atoms, 23 or less carbon atoms, 21 or less carbon atoms, 19 or less carbon atoms, or 17 carbon atoms.
Examples of saturated hydrocarbon groups for ^R3 include _CH3 ( _CH2 ) _10- , CH3( _CH2 ) _12- , _CH3 (CH2) _14- , _CH3 ( _{CH2 ) 16- ,} CH3( _CH2 ) _18- , _CH3 ( _CH2 ) _20- , _CH3 ( _CH2 ) _22- , _and the like.

The unsaturated hydrocarbon group of ^R3 is, for example, a monovalent chain unsaturated aliphatic hydrocarbon group.
The number of carbon atoms in the unsaturated hydrocarbon group of ^R3 may be 11 or more, 13 or more, 15 or more, 23 or less, 21 or less, 19 or less, or 17.

Examples of the unsaturated hydrocarbon group for ^R3 include monounsaturated hydrocarbon groups such as _CH3 ( _CH2 ) _7CH =CH( _CH2 ) _7- and _CH3 (CH2) _7CH =CH _{( CH2} ) _11- ; diunsaturated hydrocarbon groups such as _CH3 ( _CH2 ) ₄ (CH= _CHCH2 ) ₂ ( _CH2 ) _6- ; triunsaturated hydrocarbon groups _such as _CH3CH2 (CH= _CHCH2 ) ₃ ( _CH2 ) _6- ; tetraunsaturated hydrocarbon groups; pentaunsaturated hydrocarbon groups; and hexaunsaturated hydrocarbon groups; and other unsaturated hydrocarbon groups having a carbon-carbon double bond.

Specific examples of (e) amide compounds include ethylene bisoleic acid amide (particularly dimethylene bisoleic acid amide), ethylene biserucic acid amide, hexamethylene bisoleic acid amide, ethylene bislauric acid amide, ethylene bisstearic acid amide (particularly dimethylene bisstearic acid amide), ethylene bispalmitic acid amide, and hexamethylene bisstearic acid amide.

<<Melting point>>
The melting point of the (e) amide compound may be 20°C or higher, 40°C or higher, or 119°C or lower, or 117°C or lower.
Furthermore, the melting point of the (e) amide compound may be 130°C or higher, 135°C or higher, or 140°C or higher, or 250°C or lower, 200°C or lower, or 160°C or lower.
In the present invention, the melting point refers to the melting point observed when the target product is heated for the second time in differential scanning calorimetry (DSC) at a heating rate of 10°C/min in air.

＜＜Content＞＞
The content of the (e) amide compound in the vinyl chloride resin composition may be 0 part by mass, 0.1 parts by mass or more, 0.25 parts by mass or more, 0.5 parts by mass or more, 1.5 parts by mass or less, 1.25 parts by mass or less, or 1 part by mass or less, relative to 100 parts by mass of the (a) vinyl chloride resin.

The content of the (e) amide compound in the vinyl chloride resin composition may be 0 parts by mass, 0.1 parts by mass or more, 0.25 parts by mass or more, 0.5 parts by mass or more, 1.5 parts by mass or less, 1.25 parts by mass or less, or 1 part by mass or less, per 100 parts by mass of the (c) polyester plasticizer.

It goes without saying that the vinyl chloride resin composition of the present invention does not necessarily need to contain (e) the amide compound.

<(f) Other Plasticizers>
The vinyl chloride resin composition of the present invention may optionally further contain (f) other plasticizers other than the above-mentioned (c) polyester-based plasticizers.

Specific examples of (f) other plasticizers include those plasticizers described in WO 2016/098344 other than the aforementioned (c) polyester-based plasticizer. Among these, from the viewpoint of further improving the tensile properties of the resulting vinyl chloride resin molded article, it is preferable to use epoxidized vegetable oil, and it is more preferable to use epoxidized soybean oil.

The content of the (f) 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.
When an epoxidized vegetable oil such as epoxidized soybean oil is used as the (f) other plasticizer, from the viewpoint of further improving the tensile properties of the vinyl chloride resin molded article to be formed, the content of the epoxidized vegetable oil as the (f) other plasticizer is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and even more preferably 4 parts by mass or more, and is preferably 10 parts by mass or less, and more preferably 7 parts by mass or less, per 100 parts by mass of the (a) vinyl chloride resin.

The content of the (f) 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 (c) polyester plasticizer.
Furthermore, when an epoxidized vegetable oil such as epoxidized soybean oil is used as the (f) other plasticizer, from the viewpoint of further improving the tensile properties of the vinyl chloride resin molded article formed, the content of the epoxidized vegetable oil as the (f) other plasticizer is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and even more preferably 4 parts by mass or more, and is preferably 10 parts by mass or less, and more preferably 7 parts by mass or less, per 100 parts by mass of the (c) polyester plasticizer.

<Additives>
The vinyl chloride resin composition of the present invention may further contain various additives in addition to the components described above. The additives are not particularly limited, and examples thereof include lubricants, stabilizers such as perchloric acid-treated hydrotalcite, zeolite, β-diketone, and fatty acid metal salts, 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 (e.g., sodium perchlorate and potassium perchlorate), antioxidants, mildew inhibitors, flame retardants, antistatic agents, fillers, light stabilizers, foaming agents, and pigments.

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.

<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.
Here, the method of mixing the (a) vinyl chloride resin, (b) cross-linked vinyl chloride resin, (c) polyester plasticizer, (d) ether-modified silicone oil, and optionally further blended (e) amide compound, (f) other plasticizers, and various additives is not particularly limited, and examples thereof include a method in which components other than the dusting agent (including vinyl chloride resin fine particles) are mixed by dry blending, and then the dusting agent is added and mixed. Here, the use of a Henschel mixer is preferred for dry blending. The temperature during dry blending is also not particularly limited, and is preferably 50°C or higher, more preferably 70°C or higher, and preferably 200°C or lower.

<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.

(Vinyl chloride resin molded body)
The vinyl chloride resin molded article of the present invention is characterized by being 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) a vinyl chloride resin, (b) a cross-linked vinyl chloride resin, (c) a polyester-based plasticizer, and (d) an ether-modified silicone oil. The vinyl chloride resin molded article of the present invention has excellent abrasion resistance, and when a laminate is formed by laminating a polyurethane foam molded article on the vinyl chloride resin molded article, the occurrence of voids in the laminated polyurethane foam molded article can be suppressed. Furthermore, the vinyl chloride resin molded article of the present invention also has excellent demoldability.
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.

<Method for forming vinyl chloride resin molded article>
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.

The method for producing a vinyl chloride resin molded article is not particularly limited, and the following method can be used, for example. That is, the vinyl chloride resin composition of the present invention is sprinkled onto a mold kept at the temperature range described above, and left for 5 to 30 seconds, after which the excess vinyl chloride resin composition is shaken off, and the mold is further left at a desired 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 removed from the mold. A sheet-like molded article conforming to the shape of the mold is then obtained.

(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 includes the vinyl chloride resin molded article of the present invention, which has excellent abrasion resistance. Furthermore, because the laminate of the present invention includes the vinyl chloride resin molded article of the present invention, the generation of voids in the foamed polyurethane molded article is suppressed.
Therefore, the laminate of the present invention is suitable for use as an automobile interior part, particularly as an automobile interior material forming an automobile instrument panel.

There are no particular limitations on the method for laminating the polyurethane foam molded body and the vinyl chloride resin molded body, 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, thermal bonding, 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 and polymerized on the vinyl chloride resin molded body, and the polyurethane is foamed using 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 simplicity 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.

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 demoldability and abrasion resistance of the vinyl chloride resin molded article, and the degree of void formation in the polyurethane foam molded article in the laminate were measured and evaluated by the following methods.

<Removability>
A vinyl chloride resin composition was sprinkled onto a flat mold heated to 220°C to 280°C, and the mixture was left for 5 to 30 seconds. The excess vinyl chloride resin composition was then shaken off, and the mixture was left at a given temperature for 30 seconds to 3 minutes. The mold was then cooled to 20°C to 25°C, and the resulting vinyl chloride resin molded article was peeled from the flat mold at a speed of 300 mm/min in a direction 90° relative to the flat mold. The peel stress during demolding was measured over time, and the value when the peel stress stabilized was taken as the measured value (N).
The same procedure as above was repeated five times for each Example and Comparative Example, and the average of the measured values was taken as the demolding force. The relative demolding force values of each Example and Comparative Example, with the demolding force value obtained in Comparative Example 1 taken as 1.00, were then calculated.
The lower the demolding force, the better the demoldability of the vinyl chloride resin molded article.

<Wear resistance>
The surface slipperiness of the vinyl chloride resin molded article was evaluated by measuring the dynamic friction coefficient as follows.
Specifically, a Gakushin Abrasion Tester (RT-200, manufactured by Daiei Scientific Instruments) was used to conduct an abrasion test at 3N x 300 times using cotton cloth as an abrader under a measurement environment of 23°C temperature and 50% relative humidity. The appearance of the vinyl chloride resin molded article was then visually inspected before and after the test and evaluated according to the following criteria. If there is no change in the surface gloss of the vinyl chloride resin molded article before and after the test, the vinyl chloride resin molded article has excellent abrasion resistance.
A: There is no change in the surface gloss of the vinyl chloride resin molded article before and after the test. B: The surface gloss of the vinyl chloride resin molded article becomes stronger after the test than before the test.

<Degree of void occurrence>
The degree of void generation in the foamed polyurethane molding was evaluated as follows.
Specifically, the vinyl chloride resin sheet was peeled off from the laminate to prepare a polyurethane foam molded body (200 mm × 300 mm × 9 mm) alone, which served as a sample. The sample was then cut in the transverse direction at 50 mm intervals (divided into six sections), and the state of the cross sections was visually inspected. Specifically, voids with a diameter of 3 mm or more were considered to be voids, and the total number of voids (N ₁ ) present in the six cross sections was counted.
On the other hand, a foamed polyurethane molded body was produced in the same procedure as in "Formation of Laminate" in Example 1 described below, except that a vinyl chloride resin molded sheet was not placed in the mold. The foamed polyurethane molded body was also divided into six sections in the same manner as above, and the total number of voids (N ₀ ) present in the six cross sections was counted. Note that N ₀ does not represent voids originating from the vinyl chloride resin molded body, but rather represents the count of voids originating from the operating procedures when forming the foamed polyurethane molded body.
Then, for each sample, the void generation rate (%) = _N1 / _N0 × 100 was calculated, with _N0 being the standard (100%), and the degree of void generation was evaluated according to the following criteria: The lower the void generation rate (closer to 100%), the more void generation is suppressed in the foamed polyurethane molded product laminated to the vinyl chloride resin molded product.
A: The rate of occurrence of voids is less than 120%. B: The rate of occurrence of voids is 120% or more but less than 150%. C: The rate of occurrence of voids is 150% or more. If the rate of occurrence of voids is less than 100%, it is considered a measurement error and is included in the above evaluation A.

Example 1
<Preparation of vinyl chloride resin composition>
Of the ingredients shown in Table 1, all but the plasticizers (polyester plasticizer and epoxidized soybean oil) and the vinyl chloride resin fine particles (dusting agent) were placed in a Henschel mixer and mixed. When the temperature of the mixture reached 80°C, all of the plasticizer was added, and the mixture was allowed to dry up (referring to the state in which the plasticizer was absorbed into the vinyl chloride resin particles, which are vinyl chloride resin, and the mixture became smooth). When the dried-up mixture was cooled to a temperature of 70°C or below, the vinyl chloride resin fine particles (dusting agent) were added, and a vinyl chloride resin composition was prepared.
The vinyl chloride resin composition thus obtained was used to evaluate the demoldability of vinyl chloride resin molded articles. The results are shown in Table 1.
<Formation of vinyl chloride resin molded article>
The obtained vinyl chloride resin composition was sprinkled onto a textured mold heated to a temperature of 250°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 145 mm x 175 mm x 1 mm was removed from the mold as a vinyl chloride resin molded product.
The resulting vinyl chloride resin composition was evaluated for abrasion resistance, and the results are shown in Table 1.
<Formation of Laminate>
The obtained vinyl chloride resin molded sheet was cut into a piece of 100 mm x 100 mm, and two of the cut vinyl chloride resin molded sheets were placed in a 200 mm x 300 mm x 10 mm mold so as not to overlap, with the grained side facing down.
Separately, a polyol mixture consisting of 50 parts by mass of a propylene oxide-ethylene oxide (PO-EO) block adduct of propylene glycol (hydroxyl value 28, terminal EO unit content=10%, internal EO unit content 4%), 50 parts by mass of a PO-EO block adduct of glycerin (hydroxyl value 21, terminal EO unit content=14%), 2.5 parts by mass of water, 0.2 parts by mass of an ethylene glycol solution of triethylenediamine (manufactured by Tosoh Corporation, trade name: "TEDA-L33"), 1.2 parts by mass of triethanolamine, 0.5 parts by mass of triethylamine, and 0.5 parts by mass of a foam stabilizer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: "F-122"), and polymethylene polyphenylene polyisocyanate (polymeric MDI) were mixed in a ratio such that the index was 98 to prepare a mixed liquid. The prepared mixture was then poured onto two vinyl chloride resin molded sheets placed in the mold as described above. The mold was then sealed by covering it with an aluminum plate measuring 348 mm x 255 mm x 10 mm. Five minutes after sealing, a laminate consisting of a 1 mm thick vinyl chloride resin molded sheet backed with a polyurethane foam was removed from the mold, and immediately thereafter, the degree of voids in the polyurethane foam in the laminate was measured using the method described above. The results are shown in Table 1.

(Examples 2 to 6, Comparative Examples 1 to 6)
Vinyl chloride resin compositions, vinyl chloride resin molded articles, and laminates were prepared in the same manner as in Example 1, except that the types and/or amounts of each component used in preparing the vinyl chloride resin compositions were changed as shown in Table 1. Various evaluations were then carried out using the resulting vinyl chloride resin molded articles and laminates. The results are shown in Table 1.

1) Shin-Dai-Ichi 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-Dai-Ichi Vinyl Corporation, product name "ZEST PQLTX" (prepared by emulsion polymerization, average degree of polymerization: 800, average particle size: 1.8 μm)
3) Tosoh Corporation, product name "Ryuron Paste AD50" (prepared by emulsion polymerization, average particle size: 1.7 μm)
4) ADEKA Corporation, product name "ADEKA Cizer HPN-3130" (adipic acid-based polyester, viscosity: 3,000 mPa s)
5) ADEKA Corporation, product name "ADEKA Cizer O-130S"
6) Kyowa Chemical Industry Co., Ltd., product name "Alcamizer (registered trademark) 5"
7) Mizusawa Industrial Chemicals, product name "MIZUKALIZER DS"
8) Sakai Chemical Industry Co., Ltd., product name "SAKAI SZ2000"
9) ADEKA Corporation, product name "ADEKA STAB LA-72"
10) ADEKA Corporation, product name "ADEKA STAB LS-12"
11) Shin-Etsu Chemical Co., Ltd., product name "F242TL" (ether-modified silicone oil [ether groups having a chain-like ethylene oxide structure and a chain-like propylene oxide structure introduced into the side chain], HLB value: 6, kinematic viscosity at 25°C: 1000 cSt)
12) Shin-Etsu Chemical Co., Ltd., product name "X-50-1039A" (ether-modified silicone oil [ether groups having a chain-like ethylene oxide structure and a chain-like propylene oxide structure introduced into the side chain], HLB value: 2, kinematic viscosity at 25°C: 500 cSt)
13) Shin-Etsu Chemical Co., Ltd., product name "X-22-2516" (ether-modified silicone oil [an ether group having a chain ethylene oxide structure, a chain propylene oxide structure, and an organic structure, a long-chain alkyl group, and an aralkyl group introduced into different side chains], HLB value: 1, kinematic viscosity at 25°C: 70 cSt)
14) Shin-Etsu Chemical Co., Ltd., product name "KF-9701" (silanol-modified silicone oil, HLB value: 0, kinematic viscosity at 25°C: 60 cSt)
15) Nippon Kasei Chemical Co., Ltd., product name: "Slipax (registered trademark) O"
16) Dainichiseika Color & Chemicals Co., Ltd., product name: "DA PX 1720 (A) Black"

Table 1 shows that by using a vinyl chloride resin composition containing a vinyl chloride resin, a cross-linked vinyl chloride resin, a polyester-based plasticizer, and an ether-modified silicone oil having an HLB value of a predetermined value or more, it is possible to form a vinyl chloride resin molded article that has excellent abrasion resistance and can suppress the generation of voids in the laminated foamed polyurethane molded article.
On the other hand, when the vinyl chloride resin composition of Comparative Example 5, which does not contain either cross-linked vinyl chloride resin or ether-modified silicone oil having an HLB value of a predetermined value or higher, is used, it is found that the vinyl chloride resin molded article formed has poor abrasion resistance.
It is also clear that when the vinyl chloride resin composition of Comparative Example 6, which contains an ether-modified silicone oil having an HLB value of a predetermined value or more but does not contain a cross-linked vinyl chloride resin, is used, the vinyl chloride resin molded article formed also has poor abrasion resistance.
Furthermore, it can be seen that when the vinyl chloride resin compositions of Comparative Examples 1 and 4, which contain cross-linked vinyl chloride resin but do not contain ether-modified silicone oil with an HLB value of a predetermined value or higher, are used, the vinyl chloride resin molded articles formed also have poor abrasion resistance.
Furthermore, when the vinyl chloride resin compositions of Comparative Examples 2 and 3, which contain a modified silicone oil having an HLB value less than a predetermined value instead of an ether-modified silicone oil having an HLB value equal to or greater than a predetermined value and further contain a cross-linked vinyl chloride resin, are used, it is found that the vinyl chloride compositions formed are unable to sufficiently suppress the generation of voids in the laminated foamed polyurethane molding.

According to the present invention, it is possible to provide a vinyl chloride resin composition capable of forming a vinyl chloride resin molded article that has excellent abrasion resistance and can suppress the generation of voids in the laminated polyurethane foam molded article.
Furthermore, according to the present invention, it is possible to provide a vinyl chloride resin molded article that has excellent abrasion resistance and can suppress the generation of voids in a laminated polyurethane foam molded article.
Furthermore, according to the present invention, it is possible to provide a laminate comprising the vinyl chloride resin molded article.

Claims (10)

vinyl chloride resin,
a cross-linked vinyl chloride resin;
A polyester plasticizer,
an ether-modified silicone oil having an HLB value of 1.5 or more;
Including,
the content of the cross-linked vinyl chloride resin is 0.1 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the vinyl chloride resin,
the content of the polyester plasticizer is 30 parts by mass or more and 200 parts by mass or less relative to 100 parts by mass of the vinyl chloride resin,
the content of the ether-modified silicone oil is 0.01 parts by mass or more and 2 parts by mass or less relative to 100 parts by mass of the vinyl chloride resin,
the vinyl chloride resin contains vinyl chloride resin fine particles,
a mass ratio of the vinyl chloride resin fine particles to the cross-linked vinyl chloride resin (vinyl chloride resin fine particles/cross-linked vinyl chloride resin) of 2/5 or more and 5/2 or less;
A vinyl chloride resin composition, wherein the cross-linked vinyl chloride resin is cross-linked vinyl chloride resin fine particles having a particle diameter of less than 30 μm. The vinyl chloride resin composition according to claim 1, wherein the HLB value of the ether-modified silicone oil is 10 or less. The vinyl chloride resin composition according to claim 1 or 2, wherein the ether-modified silicone oil has ether groups having a chain ethylene oxide structure and a chain propylene oxide structure introduced into its side chain. The vinyl chloride resin composition according to any one of claims 1 to 3, wherein the polyester plasticizer contains an adipic acid polyester. The vinyl chloride resin composition according to any one of claims 1 to 4, which is used for powder molding. The vinyl chloride resin composition according to any one of claims 1 to 5, which is used in powder slush molding. A vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition according to any one of claims 1 to 6. The vinyl chloride resin molded article according to claim 7, which is used for the surface of an automobile instrument panel. A laminate comprising a polyurethane foam molded body and the vinyl chloride resin molded body described in claim 7 or 8. The laminate according to claim 9, which is for use in an automobile instrument panel.