JP2018048268A - Polyvinyl chloride resin composition, polyvinyl chloride resin molding and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyvinyl chloride resin composition that can form a polyvinyl chloride resin molding to resist changes in a surface color and glossiness even when used for a long time.SOLUTION: A polyvinyl chloride resin composition contains (a) a polyvinyl chloride resin, (b) a plasticizer, and (c) titanium dioxide particles. The content of (c) titanium dioxide particles is 0.5 pts.mass or more and 20 pts.mass or less relative to 100 pts.mass of (a) polyvinyl chloride resin. Each of (c) titanium dioxide particles preferably has a coating layer containing aluminum.SELECTED DRAWING: None

Description

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

  Conventionally, for the formation of automobile interior parts such as automobile instrument panels, a skin made of a vinyl chloride resin molded body, a laminate made of a foam made of foamed polyurethane or the like on a skin made of a vinyl chloride resin molded body, etc. Car interior materials are used.

  The vinyl chloride resin molded body used as the skin is formed by using a known molding method such as powder slush molding of a vinyl chloride resin composition containing a vinyl chloride resin, a plasticizer, and an additive such as a pigment. It is manufactured by molding (see, for example, Patent Document 1).

  Specifically, for example, in Patent Document 1, a vinyl chloride resin composition comprising vinyl chloride resin particles, trimellitic acid ester plasticizer, and an additive such as a pigment made of a mixture of phthalocyanine blue, titanium oxide and carbon. A skin made of a vinyl chloride resin molded body is manufactured by powder slush molding the product. In Patent Document 1, a total of 110 parts by mass of vinyl chloride resin particles (100 parts by mass of vinyl chloride resin particles having an average particle diameter of 110 μm and 10 parts by mass of vinyl chloride resin particles having an average particle diameter of 1 μm) is mixed. Two parts of a pigment made of the above-mentioned mixture whose ratio is unknown are blended.

JP-A-8-291243

  Here, a skin made of a vinyl chloride resin molded body used as an automobile interior material is required to have a small change in appearance even when used for a long period of time.

  However, in a skin made of a vinyl chloride resin molded body formed using the conventional vinyl chloride resin composition, the color change (color difference) over time of the surface of the skin is relatively long when used over a long period of time. In some cases, the glossiness is increased and the glossiness is increased.

Accordingly, an object of the present invention is to provide a vinyl chloride resin composition capable of forming a vinyl chloride resin molded article with little change in surface color and gloss even when used for a long period of time. And
It is another object of the present invention to provide a vinyl chloride resin molded article and a laminate with little change in surface color and gloss even when used over a long period of time.

  The present inventor has intensively studied for the purpose of solving the above problems. And if this inventor uses the vinyl chloride resin composition which contained the titanium dioxide particle by the predetermined | prescribed ratio, there will be little change of the color of a surface and a glossiness over time, for example, as an automobile interior material etc. The present inventors have found that a vinyl chloride resin molded article that can be suitably used is obtained, and completed the present invention.

  That is, this invention aims to solve the above-mentioned problem advantageously, and the vinyl chloride resin composition of the present invention comprises (a) a vinyl chloride resin, (b) a plasticizer, and (c). And (c) a content of the titanium dioxide particles is 0.5 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the (a) vinyl chloride resin. If the titanium dioxide particles are blended in the above proportion, a vinyl chloride resin molded body with little change in surface color and glossiness over time can be formed. Moreover, it can suppress that the tensile elongation of the obtained vinyl chloride resin molded object falls.

  Here, in the vinyl chloride resin composition of the present invention, the content of the (c) titanium dioxide particles is preferably 1 part by mass or more and 15 parts by mass or less per 100 parts by mass of the (b) plasticizer. If the content of titanium dioxide particles is within the above range, it is possible to further reduce the color change and glossiness change of the vinyl chloride resin molded article over time, and to sufficiently increase the tensile elongation of the vinyl chloride resin molded article. This is because it can be secured.

  In the vinyl chloride resin composition of the present invention, the (c) titanium dioxide particles preferably have a coating layer containing aluminum. This is because if the titanium dioxide particles having a coating layer containing aluminum are used, the color change and glossiness change of the vinyl chloride resin molded body over time can be further reduced.

  Furthermore, the vinyl chloride resin composition of the present invention is preferably used for powder molding. This is because, if the vinyl chloride resin composition is used for powder molding, for example, a vinyl chloride resin molded article that can be used favorably as an automobile interior material such as a skin for an automobile instrument panel is easily obtained.

  And it is preferable that the vinyl chloride resin composition of this invention is used for powder slush molding. This is because, if the vinyl chloride resin composition is used for powder slush molding, a vinyl chloride resin molded article that can be used favorably as an automobile interior material such as a skin for an automobile instrument panel is easily obtained.

  Moreover, this invention aims at solving the said subject advantageously, The vinyl chloride resin molded object of this invention shape | molds one of the vinyl chloride resin compositions mentioned above, It is characterized by the above-mentioned. And If a vinyl chloride resin molded article is formed using the vinyl chloride resin composition, a vinyl chloride resin molded article with little change in surface color and glossiness can be obtained even when used for a long period of time. .

  Here, the vinyl chloride resin molded article of the present invention is preferably for an automotive instrument panel skin. If the vinyl chloride resin molded article of the present invention is used as the skin of an automobile instrument panel, an excellent appearance can be maintained over a long period of time.

  Furthermore, the present invention aims to advantageously solve the above-mentioned problems, and the laminate of the present invention has a foamed polyurethane molded product and any of the above-described vinyl chloride resin molded products. And The laminate having the polyurethane foam molded article and the above-described vinyl chloride resin molded article can be favorably used as an automobile interior material used for forming an automobile interior part such as an automobile instrument panel.

ADVANTAGE OF THE INVENTION According to this invention, even if it is a case where it is used over a long period of time, the vinyl chloride resin composition which can form a vinyl chloride resin molding with little change of the color of a surface and a glossiness is obtained.
Moreover, according to this invention, even if it is a case where it is used over a long period of time, the vinyl chloride resin molded object and laminated body with little change of the color of a surface and a glossiness are obtained.

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, when forming the vinyl chloride resin molded article of the present invention. And the vinyl chloride resin molded object formed using the vinyl chloride resin composition of this invention can be used suitably as automotive interior materials, such as the skin | cover for automotive instrument panels, for example.
Moreover, the laminated body of this invention has the vinyl chloride resin molding of this invention, for example, can be used suitably as a vehicle interior material used for formation of vehicle interior components, such as a vehicle instrument panel.

(Vinyl chloride resin composition)
The vinyl chloride resin composition of the present invention comprises (a) a vinyl chloride resin, (b) a plasticizer, and (c) titanium dioxide particles, and (c) titanium dioxide relative to the content of the vinyl chloride resin. The content of the particles is in a predetermined range. In addition to the above components, the vinyl chloride resin composition of the present invention may optionally further contain additives and the like. And since the vinyl chloride resin composition of the present invention contains a predetermined amount of the above-mentioned predetermined components, it is possible to form a vinyl chloride resin molded body with little change in surface color and gloss over time. . Moreover, since the content of the said (c) titanium dioxide particle is below a predetermined value in the vinyl chloride resin composition of this invention, it can also suppress that the tensile elongation of the obtained vinyl chloride resin molded object falls. . Therefore, if the vinyl chloride resin composition of the present invention is used, even if it is used for a long period of time, there is little change in surface color and glossiness, and automobiles such as skins for automobile instrument panels. A vinyl chloride resin molded article particularly suitable as an interior material can be obtained.

<(A) Vinyl chloride resin>
Here, as the (a) vinyl chloride resin of the vinyl chloride resin composition, for example, one type or two or more types of vinyl chloride resin particles can be contained, and optionally one type or two or more types of vinyl chloride. Resin fine particles can be further contained. Among these, (a) the vinyl chloride resin preferably contains at least vinyl chloride resin particles, and more preferably contains vinyl chloride resin particles and vinyl chloride resin fine particles.
The (a) vinyl chloride resin can be produced by any conventionally known production method such as suspension polymerization method, emulsion polymerization method, solution polymerization method or bulk polymerization method.
In the present specification, “resin particles” refers to particles having a particle size of 30 μm or more, and “resin particles” refers to particles having a particle size of less than 30 μm.

The vinyl chloride resin (a) is preferably a vinyl chloride containing a vinyl chloride monomer unit in addition to a homopolymer composed of vinyl chloride monomer units, preferably 50% by mass or more, more preferably 70% by mass or more. Examples thereof include a system copolymer. Specific examples of a monomer (comonomer) copolymerizable with a vinyl chloride monomer that can constitute a vinyl chloride copolymer include olefins such as ethylene and propylene; allyl chloride, vinylidene chloride, Halogenated olefins such as vinyl fluoride and ethylene trifluorochloride; carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as isobutyl vinyl ether and cetyl vinyl ether; allyl-3-chloro-2-oxypropyl Allyl ethers such as ether and allyl glycidyl ether; unsaturated carboxylic acids such as acrylic acid, maleic acid, itaconic acid, 2-hydroxyethyl acrylate, methyl methacrylate, monomethyl maleate, diethyl maleate, maleic anhydride, Its esters or acid anhydrides; Unsaturated nitriles such as acrylonitrile and methacrylonitrile; acrylamides such as acrylamide, N-methylolacrylamide, acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidepropyltrimethylammonium chloride; allylamine benzoate, diallyldimethylammonium And allylamine such as chloride and derivatives thereof. The monomers exemplified above are only a part of the comonomer, and examples of the comonomer include “Polyvinyl Chloride” edited by Kinki Chemical Association Vinyl Division, Nikkan Kogyo Shimbun (1988), No. 75- Various monomers exemplified on page 104 can be used. These comonomer may use only 1 type and may use 2 or more types. The above (a) vinyl chloride resin includes ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, chlorinated polyethylene, and (1) chloride. A resin obtained by graft polymerization of vinyl or (2) vinyl chloride and the comonomer is also included.
Here, in this specification, “(meth) acryl” means acrylic and / or methacrylic.

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

[Average polymerization degree]
The average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is preferably 800 or more and 3000 or less, and more preferably 800 or more and 2000 or less. If the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is equal to or more than the above lower limit, the tensile elongation can be further increased while sufficiently securing the physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition. This is because it can be improved. Moreover, if the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is not more than the above upper limit, the meltability of the vinyl chloride resin composition can be improved and the surface smoothness of the vinyl chloride resin molded article can be improved. is there.
In the present invention, the “average polymerization degree” can be measured according to JIS K6720-2.

[Average particle size]
The average particle diameter of the vinyl chloride resin particles is usually 30 μm or more, preferably 50 μm or more, more preferably 100 μm or more, preferably 500 μm or less, and more preferably 200 μm or less. This is because if the average particle diameter of the vinyl chloride resin particles is equal to or greater than the above lower limit, the powder flowability of the vinyl chloride resin composition is further improved. Further, if the average particle diameter of the vinyl chloride resin particles is not more than the above upper limit, the meltability of the vinyl chloride resin composition is further improved, and the surface smoothness of the vinyl chloride resin molded body formed using the composition is improved. It is because it can improve more.
In the present invention, the “average particle diameter” can be measured as a volume average particle diameter by a laser diffraction method in accordance with JIS Z8825.

[Content ratio]
The content ratio of the vinyl chloride resin particles in the (a) vinyl chloride resin is preferably 70% by mass or more and 80% by mass or more with respect to 100% by mass of the (a) vinyl chloride resin. More preferably, it can be 100 mass%, it is preferable that it is 99 mass% or less, and it is more preferable that it is 95 mass% or less. (A) If the content ratio of the vinyl chloride resin particles in the vinyl chloride resin is not less than the above lower limit, the tensile elongation is ensured while sufficiently securing the physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition. It is because it can be made better. Moreover, it is because the powder fluidity | liquidity of a vinyl chloride resin composition will improve if the content rate of the vinyl chloride resin particle in (a) vinyl chloride resin is below the said upper limit.

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

[Average polymerization degree]
The average polymerization degree of the vinyl chloride resin constituting the vinyl chloride resin fine particles is preferably 500 or more, more preferably 700 or more, preferably 5000 or less, more preferably 3000 or less, and still more preferably 2500 or less. If the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles as a dusting agent is not less than the above lower limit, the powder flowability of the vinyl chloride resin composition becomes better, and the composition is used. This is because the tensile elongation of the obtained molded article becomes better. Further, if the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles is not more than the above upper limit, the meltability of the vinyl chloride resin composition is further improved, and a vinyl chloride resin molded article formed using the composition This is because the surface smoothness of the material is further improved.

[Average particle size]
The average particle diameter of the vinyl chloride resin fine particles is usually less than 30 μm, preferably 10 μm or less, and preferably 0.1 μm or more. This is because, if the average particle diameter of the vinyl chloride resin fine particles is not less than the above lower limit, for example, the powder fluidity of the vinyl chloride resin composition can be further improved without excessively reducing the size as a dusting agent. . Moreover, if the average particle diameter of the vinyl chloride resin fine particles is not more than the above upper limit, the meltability of the vinyl chloride resin composition is further increased, and the surface smoothness of the formed vinyl chloride resin molded product can be further improved. It is.

[Content ratio]
And the content ratio of the vinyl chloride resin fine particles in the (a) vinyl chloride resin may be 0% by mass with respect to 100% by mass of the (a) vinyl chloride resin, but it may be 1% by mass or more. Preferably, it is more preferably 5% by mass or more, preferably 30% by mass or less, and more preferably 20% by mass or less. (A) If the content ratio of the vinyl chloride resin fine particles in the vinyl chloride resin is not less than the above lower limit, the powder flowability of the vinyl chloride resin composition is further improved. Moreover, if the content ratio of the vinyl chloride resin fine particles in the vinyl chloride resin is not more than the above upper limit, the physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition can be further increased. Because.

<(B) Plasticizer>
Moreover, a known plasticizer can be used as the plasticizer (b) of the vinyl chloride resin composition. Specifically, examples of the plasticizer include the following primary plasticizer and secondary plasticizer.

As so-called primary plasticizers, trimethyl trimellitic acid, triethyl trimellitic acid, tri-n-propyl trimellitic acid, tri-n-butyl trimellitic acid, tri-n-pentyl trimellitic acid, tri-n trimellitic acid -Hexyl, tri-n-heptyl trimellitic acid, tri-n-octyl trimellitic acid, tri-n-nonyl trimellitic acid, tri-n-decyl trimellitic acid, tri-n-undecyl trimellitic acid, trimellitic Tri-n-dodecyl acid, tri-n-tridecyl trimellitic acid, tri-n-tetradecyl trimellitic acid, tri-n-pentadecyl trimellitic acid, tri-n-hexadecyl trimellitic acid, tri-n-trimellitic acid Heptadecyl, trimellitic acid tri-n-stearyl, trimellitic acid tri-n-a An ester such as a kill ester (an ester having two or more kinds of linear alkyl groups having different carbon numbers [wherein the carbon number is preferably 6 to 12, more preferably 8 to 10] in the molecule). A linear trimellitic acid ester in which the alkyl group is linear;
Trimellitic acid tri-i-propyl, trimellitic acid tri-i-butyl, trimellitic acid tri-i-pentyl, trimellitic acid tri-i-hexyl, trimellitic acid tri-i-heptyl, trimellitic acid tri- i-octyl, trimellitic acid tri- (2-ethylhexyl), trimellitic acid tri-i-nonyl, trimellitic acid tri-i-decyl, trimellitic acid tri-i-undecyl, trimellitic acid tri-i-dodecyl , Trimellitic acid tri-i-tridecyl, trimellitic acid tri-i-tetradecyl, trimellitic acid tri-i-pentadecyl, trimellitic acid tri-i-hexadecyl, trimellitic acid tri-i-heptadecyl, trimellitic acid trimethyl -I-octadecyl, trimellitic acid trialkyl ester (branched alkyl having different carbon number) Branches in which the alkyl group constituting the ester is branched, such as a ru group (wherein the number of carbon atoms is preferably 6 to 12, more preferably 8 to 10). Trimellitic acid ester;
Pyromellitic acid tetramethyl, pyromellitic acid tetraethyl, pyromellitic acid tetra-n-propyl, pyromellitic acid tetra-n-butyl, pyromellitic acid tetra-n-pentyl, pyromellitic acid tetra-n-hexyl, pyromellitic acid Tetra-n-heptyl, pyromellitic acid tetra-n-octyl, pyromellitic acid tetra-n-nonyl, pyromellitic acid tetra-n-decyl, pyromellitic acid tetra-n-undecyl, pyromellitic acid tetra-n-dodecyl , Pyromellitic acid tetra-n-tridecyl, pyromellitic acid tetra-n-tetradecyl, pyromellitic acid tetra-n-pentadecyl, pyromellitic acid tetra-n-hexadecyl, pyromellitic acid tetra-n-heptadecyl, pyromellitic acid tetra -N-stearyl, pyromellitic acid tet -N-alkyl ester (an alkyl group constituting an ester, such as a linear alkyl group having a different carbon number [wherein the number of carbon atoms is preferably 6 to 12] in the molecule) A linear pyromellitic ester in which is linear;
Pyromellitic acid tetra-i-propyl, pyromellitic acid tetra-i-butyl, pyromellitic acid tetra-i-pentyl, pyromellitic acid tetra-i-hexyl, pyromellitic acid tetra-i-heptyl, pyromellitic acid tetra- i-octyl, pyromellitic acid tetra- (2-ethylhexyl), pyromellitic acid tetra-i-nonyl, pyromellitic acid tetra-i-decyl, pyromellitic acid tetra-i-undecyl, pyromellitic acid tetra-i-dodecyl , Pyromellitic acid tetra-i-tridecyl, pyromellitic acid tetra-i-tetradecyl, pyromellitic acid tetra-i-pentadecyl, pyromellitic acid tetra-i-hexadecyl, pyromellitic acid tetra-i-heptadecyl, pyromellitic acid tetra -I-octadecyl, pyromellitic acid tetraalkyl Alkyl groups constituting the ester such as esters (branched alkyl groups having different carbon numbers [wherein the carbon number is preferably 6 to 12] in the molecule) and the like are branched. Branched pyromellitic acid ester;
Dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di- (2-ethylhexyl) phthalate, di-n-octyl phthalate, diisobutyl phthalate, diheptyl phthalate, diphenyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dibenzyl phthalate, Phthalic acid derivatives such as butylbenzyl phthalate, dinonyl phthalate, dicyclohexyl phthalate;
Isophthalic acid derivatives such as dimethyl isophthalate, di- (2-ethylhexyl) isophthalate, diisooctyl isophthalate;
Tetrahydrophthalic acid derivatives such as di- (2-ethylhexyl) tetrahydrophthalate, di-n-octyltetrahydrophthalate, diisodecyltetrahydrophthalate;
Adipic acid derivatives such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate;
Azelaic acid derivatives such as di- (2-ethylhexyl) azelate, diisooctylazelate, di-n-hexylazelate;
Sebacic acid derivatives such as di-n-butyl sebacate, di- (2-ethylhexyl) sebacate, diisodecyl sebacate, di- (2-butyloctyl) sebacate;
Maleic acid derivatives such as di-n-butyl maleate, dimethyl maleate, diethyl maleate, di- (2-ethylhexyl) maleate;
Fumaric acid derivatives such as di-n-butyl fumarate, di- (2-ethylhexyl) fumarate;
Citric acid derivatives such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri- (2-ethylhexyl) citrate;
Itaconic acid derivatives such as monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, di- (2-ethylhexyl) itaconate;
Oleic acid derivatives such as butyl oleate, glyceryl monooleate, diethylene glycol monooleate;
Ricinoleic acid derivatives such as methylacetylricinoleate, butylacetylricinoleate, glycerylmonoricinoleate, diethylene glycol monoricinoleate;
stearic acid derivatives such as n-butyl stearate and diethylene glycol distearate (excluding 12-hydroxystearic acid and its esters);
Other fatty acid derivatives such as diethylene glycol monolaurate, diethylene glycol dipelargonate, pentaerythritol fatty acid ester;
Phosphoric acid derivatives such as triethyl phosphate, tributyl phosphate, tri- (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (chloroethyl) phosphate;
Diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di- (2-ethylbutyrate), triethylene glycol di- (2-ethylhexoate), dibutylmethylene bisthioglycolate, etc. A glycol derivative of
Glycerol derivatives such as glycerol monoacetate, glycerol triacetate, glycerol tributyrate;
Epoxy derivatives such as epoxy hexahydrophthalate diisodecyl, epoxy triglyceride, epoxidized octyl oleate, epoxidized decyl oleate;
Polyester plasticizers such as adipic acid polyester, sebacic acid polyester, phthalic acid polyester;
Etc.

  In addition, so-called secondary plasticizers include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; fatty acid esters of glycols such as chlorinated paraffin and triethylene glycol dicaprylate, butyl epoxy stearate, phenyl oleate And methyl dihydroabietate.

  In addition, these plasticizers may use only 1 type, for example, may use together 2 or more types, such as a primary plasticizer and a secondary plasticizer. Moreover, when using a secondary plasticizer, it is preferable to use together the said primary plasticizer and the primary plasticizer of equal mass or more.

  Among the plasticizers described above, trimellitic acid ester and / or pyromellitic acid ester are preferably used, and trimellitic acid ester is more preferably used from the viewpoint of obtaining good tensile elongation. And as a plasticizer, it is preferable to further use epoxidized soybean oil with the said trimellitic acid ester.

[Content]
Here, the content of the (b) plasticizer is preferably 1 part by mass or more, more preferably 60 parts by mass or more, and 80 parts by mass with respect to 100 parts by mass of the (a) vinyl chloride resin. More preferably, it is 180 parts by mass or less, more preferably 170 parts by mass or less, and still more preferably 160 parts by mass or less. (B) If content of a plasticizer is more than the said minimum, the tensile elongation of the vinyl chloride resin molded object formed using the vinyl chloride resin composition can fully be ensured. Moreover, if content of (b) plasticizer is below the said upper limit, it can suppress that the surface of the formed vinyl chloride resin molding is sticky resulting from bleed-out of a plasticizer.

<(C) Titanium dioxide particles>
Furthermore, the vinyl chloride resin composition contains (c) titanium dioxide particles in a predetermined ratio.

[Structural component]
Here, the titanium dioxide (TiO ₂ ) constituting the titanium dioxide particles may be anatase type or rutile type. Among these, from the viewpoint of further reducing the color change and the gloss change over time of the vinyl chloride resin molded article formed using the vinyl chloride resin composition, the titanium dioxide constituting the titanium dioxide particles is a rutile type. It is preferable.
Moreover, the ratio for which titanium dioxide accounts in a titanium dioxide particle is 80 mass% or more normally, and it is preferable that it is 90 mass% or more.

  Furthermore, the titanium dioxide particles may optionally have a coating layer made of a compound other than titanium dioxide.

[Coating layer]
Here, the coating layer is not particularly limited, and examples thereof include a coating layer containing at least one selected from the group consisting of aluminum, silicon, and an organic compound. Among these, as the coating layer, a coating layer containing at least aluminum is preferable.
The coating layer may have a single layer structure or a multilayer structure. And when the coating layer contains two or more selected from the group consisting of aluminum, silicon and organic compounds, the coating layer is two or more selected from the group consisting of aluminum, silicon and organic compounds May be a single layer structure covering layer, or may be a multilayer structure covering layer formed by laminating a plurality of layers having different compositions.

And it does not specifically limit as a coating layer containing aluminum, For example, the coating layer containing a hydrous alumina and the coating layer containing anhydrous alumina are mentioned.
In addition, the coating layer containing aluminum is, for example, neutralized after contacting a solution of an aluminum compound such as sodium aluminate with titanium dioxide particles prepared using a known method such as a sulfuric acid method or a chlorine method. It can be formed by aging, solid-liquid separation and drying, and optionally firing the dried product.

In addition, the coating layer containing silicon is not particularly limited, and examples thereof include a coating layer containing anhydrous silica and a coating layer containing hydrated silica. Especially, as a coating layer containing silicon, a coating layer containing anhydrous silica is preferable.
The silicon-containing coating layer is neutralized after bringing a solution of a silicon compound such as sodium silicate into contact with titanium dioxide particles prepared using a known method such as a sulfuric acid method or a chlorine method. It can be formed by aging, solid-liquid separation and drying, and optionally firing the dried product.

Furthermore, the coating layer containing an organic compound is not particularly limited, and polyols such as trimethylolpropane, trimethylolethane, ditrimethylolpropane, trimethylolpropane ethoxylate, pentaerythritol; monoethanolamine, monopropanol Alkanolamines such as amines, diethanolamine, dipropanolamine, triethanolamine, tripropanolamine; and derivatives of polyols and alkanolamines (eg acetate, oxalate, tartrate, formate, benzoate) And a coating layer containing at least one organic compound selected from the group consisting of organic acid salts).
The coating layer containing an organic compound is prepared by, for example, mixing titanium dioxide particles prepared using a known method such as a sulfuric acid method or a chlorine method with an organic compound, and depositing the organic compound on the surface of the particles. Can be formed.

  Among the coating layers described above, the coating layer includes a coating layer containing aluminum, such as a coating layer made of hydrous alumina, a coating layer made of anhydrous alumina; a layer made of hydrous alumina or anhydrous alumina, and a layer made of an organic compound in this order. A coating layer comprising aluminum and an organic compound, such as a coating layer comprising: a layer made of hydrous silica or anhydrous silica, a layer made of hydrous alumina or anhydrous alumina, and a layer made of an organic compound in this order Preferred is a coating layer comprising silicon, aluminum and an organic compound, such as a layer.

[Average particle size]
The average particle diameter of the titanium dioxide particles is not particularly limited, and is preferably, for example, from 0.1 μm to 0.4 μm, and more preferably from 0.1 μm to 0.3 μm.

[Content]
And content of (c) titanium dioxide particle needs to be 0.5 to 20 mass parts with respect to 100 mass parts of (a) vinyl chloride resin, and is 2 mass parts or more. It is preferably 4 parts by mass or more, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less. The reason is not clear, but if the content of (c) titanium dioxide particles is within the above range, the color change and gloss over time of the surface of the vinyl chloride resin molded body formed using the vinyl chloride resin composition The change in degree can be reduced. Moreover, if content of (c) titanium dioxide particle is below the said upper limit, it can suppress that the tensile elongation of the obtained vinyl chloride resin molded object falls.

  In addition, the content of (c) titanium dioxide particles is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and 15 parts by mass or less with respect to 100 parts by mass of (b) plasticizer. It is preferable that it is 10 parts by mass or less. The change in color and gloss of the surface of the vinyl chloride resin molding over time is presumed to be influenced by bleeding and / or decomposition of the plasticizer, but the content of (c) titanium dioxide particles is in the above range. If it is inside, the change of the color of the surface of the vinyl chloride resin molding formed using the vinyl chloride resin composition with time and the change of the glossiness can be further reduced. Moreover, if content of (c) titanium dioxide particle is below the said upper limit, it can fully suppress that the tensile elongation of the obtained vinyl chloride resin molded object falls.

<Additives>
The vinyl chloride resin composition may further contain various additives in addition to the components described above. Examples of additives include, but are not limited to, silicone oils; stabilizers such as perchloric acid-treated hydrotalcite, zeolite, β-diketone, and fatty acid metal salts; mold release agents; dusting other than the above vinyl chloride resin fine particles. And other additives; and the like.

<< Silicone oil >>
The silicone oil that can be contained in the vinyl chloride resin composition may be an unmodified silicone oil, a modified silicone oil, or a mixture thereof.
The unmodified silicone oil is not particularly limited, and examples thereof include polymers having a polysiloxane structure such as polydimethylsiloxane, polydiethylsiloxane, and poly (methylethyl) siloxane.
Examples of the modified silicone oil include a polar group-modified silicone oil in which polar groups such as a carboxyl group, a mercapto group, an amino group, an epoxy group, and a (meth) acryloyloxy group are introduced into a polymer having a polysiloxane structure; And nonpolar group-modified silicone oil in which a nonpolar group is introduced into a polymer having a polysiloxane structure.
In the present specification, “(meth) acryloyloxy” means acryloyloxy and / or methacryloyloxy.

  The content of the silicone oil is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more with respect to 100 parts by mass of (a) the vinyl chloride resin, and 5 parts by mass or less. Preferably, it is 3 parts by mass or less, and more preferably 0.8 part by mass or less. This is because if the content of the silicone oil is equal to or more than the above lower limit, the stickiness of the surface of the vinyl chloride resin molded body by the plasticizer can be sufficiently reduced. Further, if the silicone oil content is not more than the above upper limit, it is possible to further reduce the color change and glossiness change with time of the surface of the vinyl chloride resin molded body formed using the vinyl chloride resin composition. Because it can.

<< Perchloric acid-treated hydrotalcite >>
The perchloric acid-treated hydrotalcite that can be contained in the vinyl chloride resin composition is, for example, adding hydrotalcite to a dilute aqueous solution of perchloric acid, stirring, and then filtering, dehydrating or drying as necessary. By substituting at least a part of the carbonate anion (CO ₃ ²⁻ ) in the hydrotalcite with a perchlorate anion (ClO ₄ ⁻ ) (2 mol of the perchlorate anion is substituted for 1 mol of the carbonate anion), It can be easily produced as a perchloric acid-introduced hydrotalcite. The molar ratio of the hydrotalcite and the perchloric acid can be arbitrarily set, but generally 0.1 mol or more and 2 mol or less of perchloric acid is preferable with respect to 1 mol of hydrotalcite.

  Here, the substitution rate of the carbonate anion to the perchlorate anion in the untreated (unsubstituted without introducing the perchlorate anion) is preferably 50 mol% or more, more preferably 70 mol%. As mentioned above, More preferably, it is 85 mol% or more. Further, the substitution rate of the carbonate anion to the perchlorate anion in the untreated (unsubstituted without introducing a perchlorate anion) is preferably 95 mol% or less. The replacement rate of carbonate anion to perchlorate anion in untreated (unsubstituted without introduced perchlorate anion) is within the above range, making it easier to mold vinyl chloride resin This is because it can be manufactured.

Hydrotalcite is a non _- stoichiometric compound represented by the general formula: [Mg _1-x Al _x (OH) ₂ ] ^{x +} [(CO ₃ ) _{x / 2} · mH ₂ O] ^x- , and is positively charged. Inorganic material having a layered crystal structure consisting of a basic layer [Mg _1-x Al _x (OH) ₂ ] ^{x +} and a negatively charged intermediate layer [(CO ₃ ) _{x / 2} · mH ₂ O] ^x- It is. Here, in the above general formula, x is a number in the range of greater than 0 and less than or equal to 0.33. The natural hydrotalcite is Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O. The synthetic _{hydrotalcite, Mg 4.5 Al 2 (OH)} 13 CO 3 · 3.5H 2 O are commercially available. A method for synthesizing synthetic hydrotalcite is described in, for example, Japanese Patent Application Laid-Open No. 61-174270.

  Here, the content of the perchloric acid-treated hydrotalcite is not particularly limited, and is preferably 0.5 parts by mass or more and 1 part by mass or more with respect to 100 parts by mass of the above (a) vinyl chloride resin. More preferably, 7 parts by mass or less is preferable, and 6 parts by mass or less is more preferable. This is because, if the content of the perchloric acid-treated hydrotalcite is within the above range, the tensile elongation of the vinyl chloride resin molded article formed by molding the vinyl chloride resin composition can be maintained better.

<< Zeolite >>
The vinyl chloride resin composition may contain zeolite as a stabilizer. Zeolite is represented by the general formula: M _{x / n} · [(AlO ₂ ) _x · (SiO ₂ ) _y ] · zH ₂ O (wherein M is a metal ion having a valence of n, and x + y is four sides per single lattice. The number of bodies, z is the number of moles of water). Examples of M in the general formula include monovalent or divalent metals such as Na, Li, Ca, Mg, Zn, and mixed types thereof.

  Here, the content of zeolite is not particularly limited, and is preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of (a) vinyl chloride resin.

<< β-diketone >>
β-diketone is used in order to more effectively suppress fluctuations in the initial color tone of a vinyl chloride resin molded article obtained by molding a vinyl chloride resin composition. Specific examples of the β-diketone include dibenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, and the like. One of these β-diketones may be used alone, or two or more thereof may be used in combination.

  In addition, content of (beta) -diketone is not restrict | limited in particular, (a) 0.01 mass part or more and 5 mass parts or less are preferable with respect to 100 mass parts of vinyl chloride resin.

<< Fatty acid metal salt >>
The fatty acid metal salt that can be contained in the vinyl chloride resin composition is not particularly limited, and can be any fatty acid metal salt. Among these, monovalent fatty acid metal salts are preferable, monovalent fatty acid metal salts having 12 to 24 carbon atoms are more preferable, and monovalent fatty acid metal salts having 15 to 21 carbon atoms are still more preferable. Specific examples of fatty acid metal salts include lithium stearate, magnesium stearate, aluminum stearate, calcium stearate, strontium stearate, barium stearate, zinc stearate, calcium laurate, barium laurate, zinc laurate, 2-ethyl Examples thereof include barium hexanoate, zinc 2-ethylhexanoate, barium ricinoleate, and zinc ricinoleate. The metal constituting the fatty acid metal salt is preferably a metal capable of generating a polyvalent cation, more preferably a metal capable of generating a divalent cation, and a divalent cation of the third to sixth periods of the periodic table. Is more preferable, and a metal capable of generating a divalent cation in the fourth period of the periodic table is particularly preferable. The most preferred fatty acid metal salt is zinc stearate.

  Here, the content of the fatty acid metal salt is not particularly limited, and is preferably 0.01 parts by mass or more and more preferably 0.03 parts by mass or more with respect to 100 parts by mass of the above (a) vinyl chloride resin. 5 parts by mass or less is preferable, 1 part by mass or less is more preferable, and 0.5 part by mass or less is still more preferable. This is because, if the content of the fatty acid metal salt is within the above range, the value of the color difference of the vinyl chloride resin molded article formed by molding the vinyl chloride resin composition can be further reduced.

<< Releasing agent >>
The release agent is not particularly limited, and examples thereof include 12-hydroxystearic acid type lubricants such as 12-hydroxystearic acid, 12-hydroxystearic acid ester and 12-hydroxystearic acid oligomer. Here, the content of the release agent is not particularly limited, and can be 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the (a) vinyl chloride resin.

<< Other dusting agents >>
Other dusting agents other than the above vinyl chloride resin fine particles that can be contained in the vinyl chloride resin composition include inorganic fine particles such as calcium carbonate, talc and aluminum oxide; polyacrylonitrile resin fine particles, poly (meth) acrylate resin fine particles , Organic fine particles such as polystyrene resin fine particles, polyethylene resin fine particles, polypropylene resin fine particles, polyester resin fine particles, and polyamide resin fine particles. Among these, inorganic fine particles having an average particle size of 10 nm to 100 nm are preferable.

  Here, the content of other dusting agents is not particularly limited, and is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and more preferably 10 parts by mass with respect to 100 parts by mass of (a) vinyl chloride resin. Or more. Other dusting agents may be used alone or in combination of two or more. Other dusting agents may be used in combination with the vinyl chloride resin fine particles described above.

<< Other additives >>
Other additives that can be contained in the vinyl chloride resin composition are not particularly limited, for example, other than colorants (pigments) other than titanium dioxide particles, impact resistance improvers, perchloric acid-treated hydrotalcite Perchloric acid compounds (sodium perchlorate, potassium perchlorate, etc.), antioxidants, fungicides, flame retardants, antistatic agents, fillers, light stabilizers, foaming agents and the like.

Here, specific examples of colorants (pigments) other than titanium dioxide particles are quinacridone pigments, perylene pigments, polyazo condensation pigments, isoindolinone pigments, copper phthalocyanine pigments, and carbon black. One or more pigments are used.
The quinacridone pigment is obtained by treating p-phenylene dianthranilic acid with concentrated sulfuric acid, and exhibits a yellowish red to reddish purple hue. Specific examples of the quinacridone pigment are quinacridone red, quinacridone magenta, and quinacridone violet.
The perylene pigment is obtained by a condensation reaction of perylene-3,4,9,10-tetracarboxylic anhydride and an aromatic primary amine, and exhibits a hue from red to reddish purple and brown. Specific examples of the perylene pigment are perylene red, perylene orange, perylene maroon, perylene vermilion, and perylene bordeaux.
The polyazo condensation pigment is obtained by condensing an azo dye in a solvent to obtain a high molecular weight, and exhibits a hue of a yellow or red pigment. Specific examples of the polyazo condensation pigment are polyazo red, polyazo yellow, chromophthal orange, chromophthal red, and chromophthal scarlet.
The isoindolinone-based pigment is obtained by a condensation reaction of 4,5,6,7-tetrachloroisoindolinone and an aromatic primary diamine, and exhibits a hue from greenish yellow to red and brown. A specific example of the isoindolinone pigment is isoindolinone yellow.
The copper phthalocyanine pigment is a pigment in which copper is coordinated to phthalocyanines, and exhibits a hue of yellowish green to vivid blue. Specific examples of the copper phthalocyanine pigment are phthalocyanine green and phthalocyanine blue.
Carbon black is a black pigment containing carbon as a main component and containing oxygen, hydrogen, and nitrogen. Specific examples of carbon black are thermal black, acetylene black, channel black, furnace black, lamp black, and bone black.

  Specific examples of the impact modifier include acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, chlorinated polyethylene, ethylene-vinyl acetate copolymer, chlorosulfonated polyethylene and the like. In the vinyl chloride resin composition, one or more impact modifiers can be used. The impact resistance improver is dispersed as a heterogeneous phase of fine elastic particles in the vinyl chloride resin composition. In the vinyl chloride resin composition, the chain and the polar group graft polymerized to the elastic particles are compatible with the vinyl chloride resin (a), and the impact resistance of the vinyl chloride resin molded article formed using the vinyl chloride resin composition is high. improves.

  Specific examples of the antioxidant include phenolic antioxidants, sulfur antioxidants, phosphorus antioxidants such as phosphites, and the like.

  Specific examples of the fungicide include aliphatic ester fungicides, hydrocarbon fungicides, organic nitrogen fungicides, organic nitrogen sulfur fungicides and the like.

  Specific examples of the flame retardant include halogen-based flame retardants; phosphorus-based flame retardants such as phosphate esters; inorganic hydroxides such as magnesium hydroxide and aluminum hydroxide;

  Specific examples of the antistatic agent include anionic antistatic agents such as fatty acid salts, higher alcohol sulfates and sulfonates; cationic antistatic agents such as aliphatic amine salts and quaternary ammonium salts; polyoxyethylene alkyl Nonionic antistatic agents such as ethers and polyoxyethylene alkylphenol ethers;

  Specific examples of the filler are silica, mica, clay and the like.

  Specific examples of the light stabilizer include benzotriazole-based, benzophenone-based, nickel chelate-based ultraviolet absorbers, hindered amine-based light stabilizers, and the like.

  Specific examples of the blowing agent include azo compounds such as azodicarbonamide and azobisisobutyronitrile, nitroso compounds such as N, N′-dinitrosopentamethylenetetramine, p-toluenesulfonyl hydrazide, p, p-oxybis (benzene). Organic foaming agents such as sulfonyl hydrazide compounds such as sulfonyl hydrazide; volatile hydrocarbon compounds such as chlorofluorocarbon gas, carbon dioxide gas, water, pentane, and gas-based foaming agents such as microcapsules encapsulating these.

<Method for Preparing Vinyl Chloride Resin Composition>
The vinyl chloride resin composition of the present invention can be prepared by mixing the components described above.
Here, the mixing method of the (a) vinyl chloride resin, (b) plasticizer, (c) titanium dioxide particles, and various additives further blended as necessary is particularly limited. For example, the method of mixing the component except the dusting agent containing the said vinyl chloride resin microparticles | fine-particles by dry blending, and then adding and mixing a dusting agent is mentioned. Here, it is preferable to use a Henschel mixer for the dry blending. Moreover, the temperature at the time of dry blending is not specifically limited, 50 degreeC or more is preferable, 70 degreeC or more is more preferable, and 200 degreeC or less is preferable.

<Uses of vinyl chloride resin composition>
And the obtained vinyl chloride resin composition can be used suitably for powder molding, and can be used suitably by powder slush molding.

(Vinyl chloride resin molding)
The vinyl chloride resin molded article of the present invention is obtained by molding the above-described vinyl chloride resin composition by an arbitrary method. And since the vinyl chloride resin molded article of the present invention is formed using the vinyl chloride resin composition of the present invention, even if it is used over a long period of time, the surface color change and the glossiness change And has excellent properties such as tensile elongation. Therefore, the vinyl chloride resin molded article of the present invention is suitably used as an automobile interior material for forming automobile interior parts such as an automobile instrument panel and a door trim. Specifically, the vinyl chloride resin molded article of the present invention can be suitably used as the skin of automobile instrument panels and door trims, particularly as the skin of automobile instrument panels.

<< Method of molding vinyl chloride resin molding >>
Here, in the case of forming a vinyl chloride resin molded body by powder slush molding, the mold temperature at the time of powder slush molding is not particularly limited and is preferably 200 ° C. or higher, and preferably 220 ° C. or higher. More preferably, it is preferably 300 ° C. or less, and more preferably 280 ° C. or less.

  And when manufacturing a vinyl chloride resin molding, it is not specifically limited, For example, the following methods can be used. That is, the vinyl chloride resin composition of the present invention is sprinkled on a mold in the above temperature range and left for 5 seconds to 30 seconds, and then the excess vinyl chloride resin composition is shaken off, and further, at an arbitrary temperature. Leave for 30 seconds to 3 minutes. Thereafter, the mold is cooled to 10 ° C. or more and 60 ° C. or less, and the obtained vinyl chloride resin molded article of the present invention is removed from the mold. And the sheet-like molded object which modeled the shape of the metal mold | die is obtained.

(Laminate)
The laminate of the present invention has a foamed polyurethane molded product and the vinyl chloride resin molded product described above. The vinyl chloride resin molded body usually constitutes one surface of the laminate.
And since the laminated body of this invention has the vinyl chloride resin molded object formed using the vinyl chloride resin composition of this invention, even when it is a case where it is used over a long period of time, a vinyl chloride resin molding There are few changes in the color and glossiness of the body-side surface, and excellent properties such as tensile elongation. Therefore, the laminated body of the present invention is suitably used as an automobile interior material for forming automobile interior parts such as an automobile instrument panel and a door trim, and is particularly suitably used for an automobile instrument panel.

  Here, the lamination | stacking method of a foaming polyurethane molded object and a vinyl chloride resin molded object is not specifically limited, For example, the following methods can be used. That is, (1) A method in which a foamed polyurethane molded product and a vinyl chloride resin molded product are separately prepared and then bonded together by heat fusion, thermal bonding, or using a known adhesive; (2) Vinyl chloride Polymerization is performed by reacting isocyanates, which are raw materials of the polyurethane foam molded body, and polyols on the resin molded body, and polyurethane is foamed by a known method to form polyurethane foam on the vinyl chloride resin molded body. And a method of directly forming a molded body. Among these, the latter method (2) is preferable because the process is simple and the vinyl chloride resin molded body and the polyurethane foam molded body can be firmly bonded to each other even in the case of obtaining laminated bodies having various shapes. It is.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the following description, “%” and “part” representing amounts are based on mass unless otherwise specified.
And the initial tensile elongation in the normal temperature and low temperature of a vinyl chloride resin molded object and the change of the external appearance of a vinyl chloride resin molded object were measured and evaluated by the following method.

<Tensile elongation>
The obtained vinyl chloride resin molded sheet was punched with a No. 1 dumbbell described in JIS K6251, and in accordance with JIS K7113, at a pulling rate of 200 mm / min, at 23 ° C. (under normal temperature) and −35 ° C. (under low temperature). The tensile elongation at break (%) was measured. The larger the tensile elongation at break, the better the initial tensile elongation of the vinyl chloride resin molded article and the better the flexibility.
<Change in appearance>
A laminate having a foamed polyurethane molded product lined on a skin made of a vinyl chloride resin molded sheet was cut into a size of 7 cm × 14 cm to obtain a test piece.
Using a sunshine weather meter (product name “S80” manufactured by Suga Test Instruments Co., Ltd.), leaving the test piece for 200 hours under the condition of a black panel temperature of 83 ° C., the amount of change in skin color difference (ΔE) and gloss before and after being left. (Δ gloss) was determined. And the change of the external appearance was evaluated.
The color difference (ΔE) of the skin is measured with a CIE color system (L ^* , a ^* , b ^* ) using a color difference meter (product name “CR-400” manufactured by Konica Minolta Sensing Co., Ltd.) : ΔE = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2 . The smaller ΔE, the better the color tone stability and the less the change in appearance over time.
Further, the amount of change in glossiness (Δ gloss) of the skin is determined by measuring the glossiness (incident angle 60 °) on the skin side of the test piece with a gloss meter (product name “Glossmeter GP-60” manufactured by Tokyo Denshoku Co., Ltd.). Measurement was made to obtain Δ gloss (gloss after leaving-gloss before leaving), which is the difference between the gloss before leaving and the gloss after leaving. The closer the Δ gloss is to zero, the better the stability of the glossiness, and the less the change in appearance over time.

Example 1
<Preparation of vinyl chloride resin composition>
Among the blending components shown in Table 1, components other than the plasticizer (trimellitic acid ester and epoxidized soybean oil) and vinyl chloride resin fine particles as a dusting agent were placed in a Henschel mixer and mixed. Then, when the temperature of the mixture rises to 80 ° C., all of the plasticizer is added and dried up (the plasticizer is absorbed by the vinyl chloride resin particles, which are vinyl chloride resins, and the mixture is further improved) ). Thereafter, when the dried-up mixture was cooled to a temperature of 70 ° C. or less, vinyl chloride resin fine particles as a dusting agent were added to prepare a vinyl chloride resin composition.
<Formation of vinyl chloride resin molding>
The vinyl chloride resin composition obtained above was sprinkled on a mold with a texture heated to a temperature of 250 ° C., allowed to stand for an arbitrary time and melted, and then the excess vinyl chloride resin composition was shaken off. Thereafter, the embossed mold sprinkled with the vinyl chloride resin composition was allowed to stand in an oven set at a temperature of 200 ° C., and the embossed mold was cooled with cooling water when 60 seconds had elapsed after standing. . When the mold temperature was cooled to 40 ° C., a 145 mm × 175 mm × 1 mm vinyl chloride resin molded sheet as a vinyl chloride resin molded body was removed from the mold.
And the tensile elongation at normal temperature and low temperature was measured about the obtained vinyl chloride resin molded sheet according to the above-mentioned method.
<Formation of laminate>
Two obtained vinyl chloride resin molded sheets were laid in a 200 mm × 300 mm × 10 mm mold so that the two sheets do not overlap each other with the wrinkled surface down.
Separately, 50 parts of propylene glycol PO (propylene oxide) / EO (ethylene oxide) block adduct (hydroxyl value 28, content of terminal EO unit = 10%, content of internal EO unit 4%), PO of glycerin -50 parts of EO block adduct (hydroxyl value 21, content of terminal EO unit = 14%), 2.5 parts of water, ethylene glycol solution of triethylenediamine (trade name "TEDA-L33, manufactured by Tosoh Corporation") )), 0.2 parts of triethanolamine, 0.5 parts of triethylamine, and 0.5 parts of a foam stabilizer (trade name “F-122” manufactured by Shin-Etsu Chemical Co., Ltd.) A polyol mixture was obtained. Moreover, the liquid mixture which mixed the obtained polyol mixture and polymethylene polyphenylene polyisocyanate (polymeric MDI) in the ratio from which the index becomes 98 was prepared. And the prepared liquid mixture was poured on the two vinyl chloride resin molding sheets spread | laid in the metal mold | die. Thereafter, the mold was covered with an aluminum plate of 348 mm × 255 mm × 10 mm, and the mold was sealed. When the mold is sealed and left for 5 minutes, a foamed polyurethane molded product (thickness: 9 mm, density: 0.18 g / cm ³ ) is formed on the vinyl chloride resin molded sheet (thickness: 1 mm) as the skin. A lined laminate was formed in the mold.
And the formed laminated body was taken out from the metal mold | die, and the change of the external appearance was measured and evaluated according to the above-mentioned method. The results are shown in Table 1.

(Examples 2 to 6)
In the preparation of the vinyl chloride resin composition, a vinyl chloride resin composition and a vinyl chloride resin were obtained in the same manner as in Example 1 except that the blending components (amount and / or type of titanium dioxide particles) were changed as shown in Table 1. Molded sheets and laminates were produced.
And it measured and evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.

(Comparative Example 1)
In the preparation of the vinyl chloride resin composition, the titanium dioxide particles were not used, and the vinyl chloride resin composition, the vinyl chloride resin molded sheet and A laminate was produced.
And it measured and evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.

1) Product name “ZEST (registered trademark) 1000Z” (manufactured by Shin-Daiichi PVC Co., Ltd.) (prepared by suspension polymerization method, average degree of polymerization: 1000, average particle size: 140 μm)
2) Product name “ZEST PQLTX” (manufactured by Shin-Daiichi PVC Co., Ltd.) (prepared by emulsion polymerization method, average degree of polymerization: 800, average particle size: 1.8 μm)
3) Tri-2-ethylhexyl trimellitate manufactured by Mitsubishi Gas Chemical Co., Ltd., product name “TOTM”
4) Product name "Adekasizer O-130S" manufactured by ADEKA
5) Product name “Taipeke CR-60” manufactured by Ishihara Sangyo Co., Ltd. (TiO ₂ content ratio: 95%, coating layer: containing Al, average particle size: 0.21 μm)
6) Made by Ishihara Sangyo Co., Ltd., product name “Taipeku CR-60-2” (TiO ₂ content ratio: 95%, coating layer: Al, containing organic compound, average particle size: 0.21 μm)
7) manufactured by Ishihara Sangyo Co., Ltd., product name “Typaque PF-690” (TiO ₂ content ratio: 93%, coating layer: containing Si, Al, organic compound, average particle size: 0.21 μm)
8) Product name “Alkamizer 5” manufactured by Kyowa Chemical Industry Co., Ltd.
9) Product name “MIZUKALIZER DS” manufactured by Mizusawa Chemical Industry Co., Ltd.
10) Product name “Karenz DK-1” manufactured by Showa Denko KK
11) Sakai Chemical Industry Co., Ltd., product name “SAKAI SZ2000”
12) Product name “ADEKA STAB LA-63P” manufactured by ADEKA
13) Product name “ADEKA STAB LS-12” manufactured by ADEKA
14) Product name “KF-96-5000cs” manufactured by Shin-Etsu Silicone Co., Ltd. (viscosity: 5 × 10 ³ cs)
15) Product name “DA PX 1720 (A) Black” manufactured by Dainichi Seika Co., Ltd.

  From Table 1, in Examples 1 to 6 containing titanium dioxide particles at a predetermined ratio, appearance over time while suppressing a decrease in tensile elongation as compared with Comparative Example 1 in which no titanium dioxide particles were blended. It can be seen that the change in can be reduced.

ADVANTAGE OF THE INVENTION According to this invention, even if it is a case where it is used over a long period of time, the vinyl chloride resin composition which can form a vinyl chloride resin molding with little change of the color of a surface and a glossiness is obtained.
Moreover, according to this invention, even if it is a case where it is used over a long period of time, the vinyl chloride resin molded object and laminated body with little change of the color of a surface and a glossiness are obtained.

Claims (8)

(A) a vinyl chloride resin, (b) a plasticizer, and (c) titanium dioxide particles,
The vinyl chloride resin composition wherein the content of the (c) titanium dioxide particles is 0.5 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the (a) vinyl chloride resin.   The vinyl chloride resin composition according to claim 1, wherein the content of the (c) titanium dioxide particles is 1 part by mass or more and 15 parts by mass or less per 100 parts by mass of the (b) plasticizer.   The vinyl chloride resin composition according to claim 1 or 2, wherein the (c) titanium dioxide particles have a coating layer containing aluminum.   The vinyl chloride resin composition according to any one of claims 1 to 3, which is used for powder molding.   The vinyl chloride resin composition according to claim 4, which is used for 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 5.   The vinyl chloride resin molded article according to claim 6, which is used for an automobile instrument panel skin.   The laminated body which has a foaming polyurethane molded object and the vinyl chloride resin molded object of Claim 6.