JP6728879B2 - Vinyl chloride resin composition and laminate - Google Patents

Description

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

Vinyl chloride resins are generally used for various purposes because of their excellent properties such as cold resistance, heat resistance, and oil resistance. Specifically, a vinyl chloride resin is used, for example, when forming a skin of an automobile instrument panel. Here, the automobile instrument panel has a laminated structure in which a foamed polyurethane layer is provided between a base material and the like made of a molded product of vinyl chloride resin and a base material. Further, various performances are required for the vinyl chloride resin molded body that constitutes the skin of the automobile instrument panel.

Therefore, in recent years, for example, attempts have been made to improve a vinyl chloride resin composition and a vinyl chloride resin molded product that can be suitably used for manufacturing an automobile instrument panel. In recent years, in order to reduce the weight of vehicles for the purpose of improving fuel efficiency, it has been required to reduce the weight of vinyl chloride resin moldings used as interior parts of vehicles. Here, although it is possible to reduce the weight of the vinyl chloride resin molded body by reducing the thickness of the vinyl chloride resin molded body, in that case, the vinyl chloride resin molded body is easily deformed, and the physical properties of the vinyl chloride resin molded body are also increased. The strength is also reduced.

Patent Document 1 proposes a vinyl chloride resin composition for powder molding in which 5 to 50 parts by weight of fine hollow glass spheres are blended per 100 parts by weight of the vinyl chloride resin in the vinyl chloride resin dry blended with a plasticizer. Has been done. According to Patent Document 1, the specific gravity of a molded product of a vinyl chloride resin composition can be reduced by blending the above-mentioned predetermined amount of fine hollow glass spheres.

JP, 11-152384, A

It is considered that the vinyl chloride resin composition described in Patent Document 1 is used to reduce the weight of the vinyl chloride resin molded product after molding the vinyl chloride resin. However, when the fine hollow glass spheres are used as in Patent Document 1, there is a possibility that the tensile strength of the vinyl chloride resin molded product may be reduced or defects may occur due to the expansion of the fine hollow glass spheres. Further, when the powder is molded, it may be deformed or melted by being exposed to a high temperature.

Therefore, it is an object of the present invention to provide a vinyl chloride resin composition that can reduce the weight of a vinyl chloride resin molded body while ensuring the tensile strength of the obtained vinyl chloride resin molded body. Another object of the present invention is to provide a laminate having a lightweight vinyl chloride resin molded product while ensuring tensile strength.

The present inventor has made earnest studies for the purpose of solving the above problems. Then, the present inventor uses a vinyl chloride resin composition in which an organic microballoon is blended with a vinyl chloride resin, to secure the tensile strength of the vinyl chloride resin molded article after molding, and to produce the vinyl chloride resin molded article. We have found that it can be made lighter. Then, the present inventor has completed the present invention based on the above findings.

That is, this invention aims at solving the above-mentioned subject advantageously, and the vinyl chloride resin composition of the present invention comprises (a) a vinyl chloride resin, (b) a plasticizer, and (c). And an organic microballoon. By using the vinyl chloride resin composition containing the organic microballoons, it is possible to reduce the weight of the vinyl chloride resin molded product while ensuring the tensile strength of the molded vinyl chloride resin molded product.

Further, in the vinyl chloride resin composition of the present invention, the content of the (c) organic microballoon is preferably 4 parts by mass or less based on 100 parts by mass of the (b) plasticizer. By setting the content of the organic microballoons within this range, the appearance of the vinyl chloride resin molded product after molding can be more reliably ensured.

Further, the vinyl chloride resin composition of the present invention preferably contains 1% by mass or more of the (c) organic microballoon. By including the above-mentioned predetermined amount of the organic microballoons, it is possible to more reliably reduce the weight of the molded vinyl chloride resin molded body.

Further, the vinyl chloride resin composition of the present invention is preferably used for powder molding. If the vinyl chloride resin composition is used for powder molding, for example, the vinyl chloride resin composition can be more suitably used for forming a vinyl chloride resin molded body used for automobile instrument panels and the like. Is.

The vinyl chloride resin composition of the present invention is preferably used for powder slush molding. When the vinyl chloride resin composition is used for powder slush molding, for example, the vinyl chloride resin composition can be more preferably used for forming a vinyl chloride resin molded body or the like used for an automobile instrument panel or the like. Is.

Further, a vinyl chloride resin molded body obtained by molding the vinyl chloride resin composition according to the present invention can be obtained. By forming a vinyl chloride resin molded product using the above vinyl chloride resin composition, surface stickiness can be suppressed.

Then, it is preferable to use the vinyl chloride resin molded product obtained by molding the vinyl chloride resin composition according to the present invention for the skin of an automobile instrument panel. When the vinyl chloride resin molded product of the present invention is used as the skin of an automobile instrument panel, the surface tackiness of the skin is suppressed, so that a good tactile sensation can be obtained.

Furthermore, the present invention has an object to advantageously solve the above problems, and a laminate of the present invention has a foamed polyurethane molded body and any one of the above-mentioned vinyl chloride resin molded bodies. Characterize. When the foamed polyurethane molded product and the above-mentioned vinyl chloride resin molded product are used to form a laminate, the laminate can be favorably used in an instrument panel for automobiles.

According to the present invention, it is possible to provide a vinyl chloride resin composition capable of reducing the weight of a vinyl chloride resin molded body while ensuring the tensile strength of the obtained vinyl chloride resin molded body. Further, according to the present invention, it is possible to provide a vinyl chloride resin molded product which is lightweight while ensuring tensile strength, and a laminate having the vinyl chloride resin molded product.

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 product of the present invention. Further, the vinyl chloride resin molded body formed by using the vinyl chloride resin composition of the present invention can be used, for example, for producing a laminate of the present invention having the vinyl chloride resin molded body. Further, the vinyl chloride resin molded product of the present invention can be suitably used for an automobile interior material such as a skin of an automobile instrument panel.

(Vinyl chloride resin composition)
The vinyl chloride resin composition of the present invention is characterized by containing (a) a vinyl chloride resin, (b) a plasticizer, and (c) an organic microballoon. Moreover, the vinyl chloride resin composition of the present invention may optionally further contain additives in addition to the above components. Since the vinyl chloride resin composition of the present invention contains the above-mentioned predetermined components, it is possible to reduce the weight of the vinyl chloride resin molded product while ensuring the tensile strength of the obtained vinyl chloride resin molded product. As a result, for example, when the vinyl chloride resin molded body is used as a skin of an instrument panel of a car, the car can be lightened while ensuring the physical strength of the skin.

<(a) Vinyl chloride resin>
Here, the vinyl chloride resin (a) used in the vinyl chloride resin composition may contain, for example, one kind or two or more kinds of vinyl chloride resin particles, and optionally one kind or two or more kinds. Further, vinyl chloride resin fine particles may be contained. Among them, the vinyl chloride resin (a) preferably contains at least vinyl chloride resin particles, more preferably contains vinyl chloride resin particles and vinyl chloride resin fine particles, and one kind of vinyl chloride resin particles and two kinds of vinyl chloride resin particles. It is more preferable to contain fine particles of vinyl chloride resin.
In the present specification, "resin particles" refer to particles having a particle diameter of 30 µm or more, and "resin fine particles" refer to particles having a particle diameter of less than 30 µm.
The vinyl chloride resin (a) can be produced by any conventionally known production method such as a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, and a bulk polymerization method.

<< composition >>
(A) As the vinyl chloride resin, in addition to a homopolymer consisting of vinyl chloride monomer units, a vinyl chloride copolymer containing 50% by mass or more, and more preferably 70% by mass or more of vinyl chloride monomer units is used. Polymers may be mentioned. Specific examples of the monomer (comonomer) capable of forming a vinyl chloride-based copolymer and copolymerizable with a vinyl chloride monomer include olefins such as ethylene and propylene; allyl chloride, vinylidene chloride, Halogenated olefins such as vinyl fluoride and ethylene trifluoride chloride; 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 and maleic anhydride, Esters or acid anhydrides thereof; unsaturated nitriles such as acrylonitrile and methacrylonitrile; acrylamides such as acrylamide, N-methylolacrylamide, acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropyltrimethylammonium chloride; Allylamine benzoate, allylamine such as diallyldimethylammonium chloride and derivatives thereof; and the like. The above-exemplified monomers are only a part of the comonomer, and as the comonomer, “polyvinyl chloride” edited by Kinki Chemical Society, Vinyl Section, Nikkan Kogyo Shimbun (1988), No. 75- Various monomers exemplified on page 104 can be used. These comonomers may be used alone or in combination of two or more. The vinyl chloride resin (a) may be a resin such as ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, chlorinated polyethylene, or (1) chloride. Resins obtained by graft-polymerizing vinyl or (2) vinyl chloride and the above-mentioned comonomer are also included.
Here, in this specification, "(meth)acryl" means acryl and/or methacryl.

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

[Average degree of polymerization]
Here, the average degree of polymerization of the vinyl chloride resin particles is preferably 500 or more, more preferably 1000 or more, further preferably 1500 or more, preferably 5000 or less, more preferably 3000 or less, still more preferably 2500 or less. This is because if the average degree of polymerization of the vinyl chloride resin particles is at least the above lower limit, the physical strength of the vinyl chloride resin molded product formed using the vinyl chloride resin composition can be sufficiently secured. Further, if the average degree of polymerization of the vinyl chloride resin particles is not more than the above upper limit, it is possible to improve the meltability of the vinyl chloride resin molded product and improve the surface smoothness.
In addition, in this invention, "average degree of polymerization" can be measured based on JISK6720-2.

[Average particle size]
Further, the average particle size of the vinyl chloride resin particles is not particularly limited as long as it is 30 μm or more, preferably 50 μm or more, more preferably 100 μm or more, preferably 500 μm or less, more preferably 250 μm or less, and 200 μm or less. More preferable. This is because if the average particle size of the vinyl chloride resin particles is at least the above lower limit, the powder fluidity of the vinyl chloride resin composition will be further improved. Further, when 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 smoothness of the vinyl chloride resin molded product formed using the composition is further improved. This is because it can be improved.
In addition, in the present invention, the “average particle diameter” can be measured as a volume average particle diameter by a laser diffraction method according to JIS Z8825.

[Content ratio]
The content ratio of the vinyl chloride resin particles in the (a) vinyl chloride resin is usually 70% by mass or more, and preferably more than 70% by mass, based on 100% by mass of the (a) vinyl chloride resin. It is more preferably 75 mass% or more, further preferably 80 mass% or more, more preferably 100 mass%, less than 100 mass%, preferably 99 mass% or less, 95 mass% % Or less, more preferably 92% by mass or less.
(A) When the content ratio of the vinyl chloride resin particles in the vinyl chloride resin is at least the above lower limit, the physical strength of the vinyl chloride resin molded product formed by using the vinyl chloride resin composition can be sufficiently secured. Is. Further, if the content ratio of the vinyl chloride resin particles in the vinyl chloride resin (a) is not more than the above upper limit, the powder flowability of the vinyl chloride resin composition is further improved.

<<Vinyl chloride resin 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 degree of polymerization]
Here, the average degree of polymerization of the vinyl chloride resin fine particles is preferably 500 or more, more preferably 700 or more, further preferably 900 or more, more preferably 5000 or less, more preferably 3000 or less, further preferably 2500 or less, and 1500 or less. More preferable. Then, for example, when two kinds of vinyl chloride resin fine particles having different average degrees of polymerization are used together as a dusting agent, one vinyl chloride resin fine particle has an average degree of polymerization of 500 or more and 1,000 or less; the other vinyl chloride resin fine particle. The average degree of polymerization of 1400 to 2200 can be selected as appropriate. This is because if the average degree of polymerization of the vinyl chloride resin fine particles as a dusting agent is at least the above lower limit, the flexibility and heat aging resistance (tensile property) of the molded product obtained using the composition will be better. ..

[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 more preferably 0.1 μm or more. This is because if the average particle diameter of the vinyl chloride resin fine particles is at least the above lower limit, the powder fluidity of the vinyl chloride resin composition can be more favorably exhibited without excessively reducing the size of the dusting agent. .. Further, when 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 smoothness of the formed vinyl chloride resin molded article can be further improved. is there.

[Content ratio]
The content ratio of the vinyl chloride resin fine particles in the (a) vinyl chloride resin is preferably 1% by mass or more, and more preferably 5% by mass or more, based on 100% by mass of the (a) vinyl chloride resin. It is preferably 30% by mass or less, more preferably 20% by mass or less, and may be 0% by mass. This is because when the content ratio of the vinyl chloride resin fine particles in the vinyl chloride resin (a) is at least the above lower limit, the powder flowability of the vinyl chloride resin composition is further improved. Further, when the content ratio of the vinyl chloride resin fine particles in the vinyl chloride resin (a) is not more than the above upper limit, the physical strength of the vinyl chloride resin molded product formed by using the vinyl chloride resin composition can be further increased. Because.

<(b) Plasticizer>
The vinyl chloride resin composition of the present invention is characterized by further containing (b) a plasticizer with respect to the content of the (a) vinyl chloride resin.

<<Contents>>
Here, the content of the (b) plasticizer is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and 100 parts by mass or more based on 100 parts by mass of the (a) vinyl chloride resin. Is more preferable, it is preferably 200 parts by mass or less, more preferably 180 parts by mass or less, and further preferably 150 parts by mass or less. When the content of the plasticizer (b) is within the above range, good tensile elongation of the vinyl chloride resin molded product formed by using the vinyl chloride resin composition can be secured.

<<Type>>
Here, specific examples of the plasticizer (b) include the following primary plasticizers and secondary plasticizers.
Examples of so-called primary plasticizers include trimethyl trimellitate, triethyl trimellitate, tri-n-propyl trimellitate, tri-n-butyl trimellitate, tri-n-pentyl trimellitate, and trim-n trimellitate. -Hexyl, tri-n-heptyl trimellitate, tri-n-octyl trimellitate, tri-n-nonyl trimellitate, tri-n-decyl trimellitate, tri-n-undecyl trimellitate, trimellitate Acid tri-n-dodecyl, trimellitic acid tri-n-tridecyl, trimellitic acid tri-n-tetradecyl, trimellitic acid tri-n-pentadecyl, trimellitic acid tri-n-hexadecyl, trimellitic acid trim-n- Heptadecyl, trimellitic acid tri-n-stearyl, trimellitic acid tri-n-alkyl ester (here, the number of carbon atoms of the alkyl group of the trimellitic acid tri-n-alkyl ester is different from each other in one molecule) , Etc., a straight-chain trimellitic acid ester in which the alkyl group constituting the ester is straight-chain [Note that these trimellitic acid esters are a mixture even if they are composed of a single compound. May be. ];
Tri-i-propyl trimellitate, tri-i-butyl trimellitate, tri-i-pentyl trimellitate, tri-i-hexyl trimellitate, tri-i-heptyl trimellitate, trimellitate 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 trimellitic acid -I-octadecyl, trimellitic acid trialkyl ester (wherein the alkyl group of trimellitic acid trialkyl ester may have different carbon numbers in one molecule), etc., an alkyl group constituting the ester. A branched trimellitic acid ester [wherein these trimellitic acid esters may be composed of a single compound or may be a mixture. ];
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, pyromellitic acid Tetra-n-heptyl, 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 pyromellitic acid tetra -N-stearyl, pyromellitic acid tetra-n-alkyl ester (wherein the carbon number of the alkyl group of pyromellitic acid tetra-n-alkyl ester may be different from each other in one molecule), and the like. A linear pyromellitic acid ester in which the alkyl group constituting the ester is linear [wherein, these pyromellitic acid esters may be composed of a single compound or may be a mixture. ];
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-pyromellitic acid tetra- i-octyl, 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 pyromellitic acid tetra -I-octadecyl, pyromellitic acid tetraalkyl ester (wherein, the carbon numbers of the alkyl groups of the pyromellitic acid tetraalkyl ester may be different from each other in one molecule), etc., and an alkyl group constituting the ester. Is a branched pyromellitic acid ester [Note that these pyromellitic acid esters may be composed of a single compound or may be a mixture. ];
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 and 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, diisooctyl azelate and di-n-hexyl azelate;
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 and 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 and di-(2-ethylhexyl) itaconate;
Oleic acid derivatives such as butyl oleate, glyceryl monooleate, diethylene glycol monooleate;
Ricinoleic acid derivatives such as methyl acetyl ricinoleate, butyl acetyl ricinoleate, glyceryl monoricinoleate and diethylene glycol monoricinoleate;
Stearic acid derivatives such as n-butyl stearate and diethylene glycol distearate (excluding 12-hydroxystearate ester);
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), dibutylmethylenebisthioglycolate, etc. A glycol derivative of
Glycerin derivatives such as glycerol monoacetate, glycerol triacetate, glycerol tributyrate;
Epoxy derivatives such as epoxy diisodecyl hexahydrophthalate, epoxy triglyceride, epoxidized octyl oleate, and epoxidized decyl oleate;
Polyester plasticizers such as adipic acid polyester, sebacic acid polyester, and phthalic acid polyester;
And so on.

As the so-called secondary plasticizer, epoxidized vegetable oil such as epoxidized soybean oil and epoxidized linseed oil; fatty acid ester of glycol such as chlorinated paraffin and triethylene glycol dicaprylate, butyl epoxy stearate, phenyl oleate. , Methyl dihydroabietic acid, and the like.

These plasticizers may be used alone or in combination of two or more kinds such as primary plasticizer and secondary plasticizer. When a secondary plasticizer is used, it is preferable to use the secondary plasticizer in combination with a primary plasticizer having an equal mass or more.
Among the above-mentioned plasticizers, from the viewpoint of obtaining good tensile elongation, it is preferable to use trimellitic acid ester and/or pyromellitic acid ester, more preferable to use trimellitic acid ester, and straight chain. It is more preferable to use trimellitic acid ester, and it is more preferable to use linear trimellitic acid ester having two or more alkyl groups having different carbon numbers in the molecule. The alkyl group preferably has 8 to 10 carbon atoms, and more preferably the alkyl group is an n-octyl group or an n-decyl group. Then, it is preferable to further use epoxidized soybean oil together with the trimellitic acid ester.

Here, the form of the (b) plasticizer is not particularly limited, but from the viewpoint of (a) easy mixing with the vinyl chloride resin, blooming occurs on the surface of the formed vinyl chloride resin molded body (molded body surface Further, from the viewpoint of suppressing the phenomenon that the compounding components break out and the surface becomes white, it is preferably a liquid at room temperature.

<(c) Organic microballoon>
The vinyl chloride resin composition of the present invention is characterized by containing (c) an organic microballoon in addition to the above-mentioned (a) vinyl chloride resin and (b) plasticizer.

Here, the above-mentioned (c) organic microballoon refers to hollow particles having an outer shell made of an organic material. It is preferable that the hollow particles contain a hydrocarbon-based organic solvent from the viewpoint of preventing crushing. Further, the outer shell is preferably made of one containing an organic polymer, and more preferably one containing an organic polymer having excellent heat resistance. c) It is more preferable that the organic microballoons are made of an organic polymer that hardly thermally expands. This is because, when the organic solvent is contained in the hollow particles and the organic microballoons are heated, it is possible to prevent the organic solvent from being gasified and the pressure inside the organic microballoons rising to be collapsed.

<<Type>>
The organic microballoons are classified into an inflated type and an unexpanded type, and there is no particular limitation in use, and the organic microballoons may be an inflated type or an unexpanded type. Although it may be a mixture of these, it is preferable to use only organic microballoons that do not expand during thermoforming, and it is more preferable to use only already expanded organic microballoons.

The organic polymer constituting the outer shell of the organic microballoon is not intended to be limited, but a methacrylic acid ester copolymer, an acrylic acid ester copolymer, a methacrylic acid ester-acrylic acid ester copolymer, polyacrylonitrile, Polymethacrylonitrile, acrylonitrile-methacrylonitrile copolymer, acrylonitrile-methacrylic acid ester copolymer, acrylonitrile-acrylic acid ester copolymer, methacrylonitrile-methacrylic acid ester copolymer, methacrylonitrile-acrylic acid ester Copolymer, methacrylic acid ester-acrylic acid ester-acrylonitrile copolymer, methacrylic acid ester-acrylic acid ester-methacrylonitrile copolymer, acrylonitrile-methacrylonitrile-methacrylic acid ester copolymer, acrylonitrile-methacrylonitrile -Acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-acrylic acid ester copolymer, melamine resin; and the like. Among these, polyacrylonitrile, polymethacrylonitrile, acrylonitrile-methyl methacrylate copolymer, methacrylonitrile-methyl methacrylate copolymer, acrylonitrile-methacrylonitrile-methyl methacrylate copolymer and the like, glass transition temperature Is preferably an organic polymer having a temperature of 100° C. or higher. When the glass transition temperature is 100° C. or higher, the softening point of the organic polymer becomes high, and in powder slush molding of the vinyl chloride resin composition of the present invention, (c) expansion of the organic microballoon due to heating during molding. Can be suppressed.
Furthermore, from the viewpoint of (c) the crack resistance of the organic microballoon, acrylonitrile-methyl methacrylate copolymer, methacrylonitrile-methyl methacrylate copolymer, and acrylonitrile-methacrylonitrile-methyl methacrylate copolymer are more preferable. Acrylonitrile-methacrylonitrile-methyl methacrylate copolymer is more preferred. By copolymerizing acrylonitrile or methacrylonitrile with methyl methacrylate, (c) while suppressing expansion of the organic microballoons due to heating during molding, (c) further imparting crack resistance to the organic microballoons. You can
The organic solvent is not limited, but includes n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexanes, isopentanes, isooctanes, 2, 2-dimethylbutane and the like can be mentioned.
The organic microballoons may contain inorganic fillers such as magnesium hydroxide and limestone, and various additives such as antiaging agents.

<<Contents>>
Here, in order to surely reduce the weight of the obtained vinyl chloride resin molded body, the vinyl chloride resin composition preferably contains (c) the organic microballoons in an amount of 0.1% by mass or more, and 0.4% by mass or more. It is more preferable that the content is 1.0 mass% or more, and it is further preferable that the content is 1.5 mass% or more.

The content of the (c) organic microballoon is preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and more preferably 4 parts by mass with respect to 100 parts by mass of the (b) plasticizer. The following is more preferable. According to the study by the present inventor, it has been found that when the blending amount of the organic microballoons is excessive with respect to the blending amount of the plasticizer, a hole-shaped pattern called “pinhole” is formed. Here, the “pinhole” is a hole-shaped pattern with a diameter of 50 μm or more observed with the naked eye, and is considered to occur when the organic microballoons are not sufficiently mixed with the plasticizer. If a large number of pinholes are generated, it will spoil the appearance. It was confirmed by the study of the present inventor that by setting the content of the organic microballoons to the above upper limit or less, the generation of pinholes can be more reliably suppressed.

<<Average particle size>>
The average particle diameter of the organic microballoon (c) is not particularly limited and may be, for example, 20 μm or more and 200 μm or less, and may be 30 μm or more and 60 μm or less, or may be 80 to 140 μm.
In addition, in the present invention, the “average particle diameter” can be measured as a volume average particle diameter by a laser diffraction method according to JIS Z8825.

<<True Specific Gravity>>
(C) The true specific gravity (true density) of the organic microballoon is not particularly limited and is, for example, 0.01 or more and 0.2 or less (0.01 g/cm ³ or more and 0.2 g/cm ³ or less). You can
In addition, in this invention, "true specific gravity" can be measured using a pycnometer method based on JISK0061 and JISZ8807.

<Additive>
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 stabilizers such as perchloric acid-treated hydrotalcite, zeolite, β-diketone, and fatty acid metal salt; release agents; dusting agents other than the above vinyl chloride resin fine particles; and Other additives; and the like.

<<Perchloric acid treated hydrotalcite>>
The perchloric acid-treated hydrotalcite that may be contained in the vinyl chloride resin composition is, for example, hydrotalcite is added to a dilute aqueous solution of perchloric acid and stirred, and then, if necessary, filtered, dehydrated or dried. By substituting at least a part of the carbonate anion (CO ₃ ^2- ) in the hydrotalcite with the perchlorate anion (ClO ₄ ^- ) (2 mol of the perchlorate anion is replaced per 1 mol of the carbonate anion). It can be easily produced as a partially introduced perchloric acid type hydrotalcite. The molar ratio of the hydrotalcite to the perchloric acid can be set arbitrarily, but in general, 0.1 mol or more and 2 mol or less of perchloric acid is preferable with respect to 1 mol of the hydrotalcite.

Here, the substitution rate of the carbonate anion to the perchlorate anion in the untreated (unsubstituted partially not introducing the perchlorate anion) hydropercite is preferably 50 mol% or more, more preferably 70 mol% or more. It is at least mol%, more preferably at least 85 mol%. Further, the substitution ratio of carbonate anion to unchlorinated (unsubstituted with partial introduction of perchlorate anion) hydrotalcite to perchlorate anion is preferably 95 mol% or less. When the substitution ratio of carbonate anion to perchlorate anion in untreated (unsubstituted with no perchlorate anion introduced) is within the above range, a vinyl chloride resin molded article is obtained. This is because it can be manufactured more easily.

Hydrotalcite is a nonstoichiometric 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. Substance having a layered crystal structure composed 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- Is. Here, in the above general formula, x is a number in the range of more than 0 and 0.33 or less. Natural hydrotalcite is Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O. As the synthesized hydrotalcite, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O is commercially available. A method for synthesizing synthetic hydrotalcite is described in, for example, Japanese Patent Publication No. 61-174270.

Here, the content of the perchloric acid-treated hydrotalcite is not particularly limited, and is preferably 0.5 part by mass or more, and 1 part by mass or more based on 100 parts by mass of the (a) vinyl chloride resin. It is more preferably 7 parts by mass or less, and even more preferably 6 parts by mass or less. When the content of the perchloric acid-treated hydrotalcite is within the above range, the vinyl chloride resin molded product obtained by molding the vinyl chloride resin composition can better maintain the tensile elongation of the molded product. is there.

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

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

<<β-diketone>>
The β-diketone is used to more effectively suppress the fluctuation of the initial color tone of the vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition. Specific examples of the β-diketone include dibenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane and the like. These β-diketones may be used alone or in combination of two or more.

The content of β-diketone is not particularly limited, and is preferably 0.01 part by mass or more and preferably 5 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin (a).

<<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 them, 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 further preferable. Specific examples of the fatty acid metal salt include lithium stearate, magnesium stearate, aluminum stearate, calcium stearate, strontium stearate, barium stearate, zinc stearate, calcium laurate, barium laurate, zinc laurate, and 2-ethyl. Examples thereof include barium hexanoate, zinc 2-ethylhexanoate, barium ricinoleate, and zinc ricinoleate. As the metal constituting the fatty acid metal salt, a metal capable of forming a polyvalent cation is preferable, a metal capable of forming a divalent cation is more preferable, 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 of the 4th 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 (a) vinyl chloride resin. It is preferably 5 parts by mass or less, more preferably 1 part by mass or less, still more preferably 0.5 part by mass or less. 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 product obtained by molding the vinyl chloride resin composition can be reduced.

<<Release agent>>
The release agent is not particularly limited, and examples thereof include 12-hydroxystearic acid-based lubricants such as 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 vinyl chloride resin (a).

<<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. , Polystyrene resin fine particles, polyethylene resin fine particles, polypropylene resin fine particles, polyester resin fine particles, polyamide resin fine particles, and other organic fine particles. Among them, inorganic fine particles having an average particle diameter of 10 nm or more and 100 nm or less are preferable.

Here, the content of the other dusting agent 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 the (a) vinyl chloride resin. The above can be done. The other dusting agents may be used alone or in combination of two or more, and may be used in combination with the above-mentioned vinyl chloride resin fine particles.

<<Other additives>>
Other additives that may be contained in the vinyl chloride resin composition are not particularly limited, and examples thereof include colorants (pigments), impact modifiers, perchloric acid compounds other than perchloric acid-treated hydrotalcite. (Sodium perchlorate, potassium perchlorate, etc.), antioxidants, fungicides, flame retardants, antistatic agents, fillers, light stabilizers, foaming agents and the like.

Specific examples of colorants (pigments) are quinacridone pigments, perylene pigments, polyazo condensation pigments, isoindolinone pigments, copper phthalocyanine pigments, titanium white, and carbon black. One or more pigments are used.
The quinacridone pigment is obtained by treating p-phenylenedianthranilic 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-based pigment is obtained by a condensation reaction of perylene-3,4,9,10-tetracarboxylic acid anhydride and an aromatic primary amine, and exhibits red to reddish purple and brown hues. Specific examples of the perylene pigments are perylene red, perylene orange, perylene maroon, perylene vermillion, and perylene bordeaux.
The polyazo condensation pigment is obtained by condensing an azo dye in a solvent to have a high molecular weight, and exhibits a hue of a yellow or red pigment. Specific examples of polyazo condensation pigments are polyazo red, polyazo yellow, chromophthal orange, chromophthal red and chromophthal scarlet.
The isoindolinone pigment is obtained by a condensation reaction of 4,5,6,7-tetrachloroisoindolinone and an aromatic primary diamine, and exhibits greenish yellow, red, and brown hues. A specific example of the isoindolinone-based pigment is isoindolinone yellow.
The copper phthalocyanine-based pigment is a pigment in which copper is coordinated to phthalocyanines and exhibits a yellowish green to a vivid blue hue. Specific examples of the copper phthalocyanine pigments are phthalocyanine green and phthalocyanine blue.
Titanium white is a white pigment made of titanium dioxide, which has a large hiding power and is classified into anatase type and rutile type.
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 resistance improver are 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 in the vinyl chloride resin composition as a non-uniform phase of fine elastic particles. In the vinyl chloride resin composition, the chains and polar groups graft-polymerized on the elastic particles are compatible with the vinyl chloride resin (a), and the impact resistance of the vinyl chloride resin composition is improved.

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

Specific examples of the antifungal agent include aliphatic ester antifungal agents, hydrocarbon antifungal agents, organic nitrogen antifungal agents, and organic nitrogen sulfur antifungal agents.

Specific examples of the flame retardant include halogen-based flame retardants such as chlorinated paraffins; phosphorus-based flame retardants such as phosphoric acid 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; and the like.

Specific examples of the filler are silica, talc, mica, calcium carbonate, 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 foaming 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 CFCs, carbon dioxide gas, water and pentane; and gas-based foaming agents such as microcapsules containing these.

<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, as a mixing method of the vinyl chloride resin (a), the plasticizer (b), the organic microballoon (c), and vinyl chloride resin fine particles and various additives which are further used in combination as necessary, The method is not particularly limited, and examples thereof include a method of mixing the components excluding the dusting agent containing the vinyl chloride resin fine particles by dry blending, and then adding and mixing the dusting agent. Here, it is preferable to use a Henschel mixer for the dry blending. The temperature during dry blending is not particularly limited and is preferably 50°C or higher, more preferably 70°C or higher, and preferably 200°C or lower. Further, the organic microballoon (c) is preferably added when the dried-up mixture is cooled to a temperature of 150° C. or lower, more preferably added when it is cooled to 130° C. or lower, 110 It is more preferable to add it when cooled to below 100°C, and more preferable to add it when cooled to below 100°C. Although it depends on the type of the organic microballoon, the change in the expanded state of the organic microballoon can be more reliably suppressed by adding it at the temperature or lower.
The dry-up means a state in which the plasticizer is absorbed by the vinyl chloride resin particles which are vinyl chloride resin, and the mixture is further dried.

<Use 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)
A vinyl chloride resin molding can be obtained by molding the above-mentioned vinyl chloride resin composition by an arbitrary method. Since this vinyl chloride resin molded product is formed using the vinyl chloride resin composition of the present invention, surface stickiness can be suppressed. Therefore, this vinyl chloride resin molded product is preferably used as a skin of automobile interior materials such as automobile instrument panels and door trims, and particularly preferably used as a skin of automobile instrument panels.

<< Molding method of vinyl chloride resin molding >>
Here, the mold temperature at the time of powder slush molding is not particularly limited, and is preferably 200° C. or higher, more preferably 220° C. or higher, more preferably 300° C. or lower, and 280° C. The following is more preferable.

When the vinyl chloride resin molded body is manufactured, the following method can be used without any particular limitation. 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. Then, the mold is cooled to 10° C. or higher and 60° C. or lower, and the obtained vinyl chloride resin molded product of the present invention is released from the mold. Then, the demolded vinyl chloride resin molded body is obtained, for example, as a sheet-shaped molded body having a shape of a mold.

(Laminate)
The laminate of the present invention has a foamed polyurethane molded body and the above-mentioned vinyl chloride resin molded body. And since the laminated body of the present invention has the vinyl chloride resin molding formed using the vinyl chloride resin composition of the present invention, surface stickiness can be controlled. Therefore, the laminate of the present invention is preferably used as an automobile interior material such as an automobile instrument panel and a door trim, and particularly preferably used for an automobile instrument panel.

Here, the stacking method is not particularly limited, and for example, the following method can be used. That is, (1) a method in which a foamed polyurethane molded body and a vinyl chloride resin molded body are separately prepared and then bonded by heat fusion, thermal bonding, or using a known adhesive agent; (2) vinyl chloride resin On the molded article, isocyanates, which are the raw materials for the foamed polyurethane molded article, are reacted with polyols and the like to perform polymerization, and at the same time, polyurethane is foamed by a known method to form a foamed polyurethane molded article on the vinyl chloride resin molded article. A method of directly forming a body; and the like. Among them, the latter method (2) is preferable because the process is simple and the vinyl chloride resin molded product and the polyurethane foam molded product are easily bonded firmly even when a laminate having various shapes is obtained. Is preferred.

Hereinafter, the present invention will be specifically described 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.
And the average degree of polymerization of vinyl chloride resin particles and fine particles of vinyl chloride resin, average particle diameter; tensile strength of vinyl chloride resin molded body (maximum tensile stress); specific gravity and weight loss rate of vinyl chloride resin molded body; vinyl chloride resin The appearance evaluation of the molded article was measured and evaluated by the following method.

<Average degree of polymerization>
The average degree of polymerization of the vinyl chloride resin particles and the vinyl chloride resin fine particles was calculated by dissolving each of the vinyl chloride resin particles and the vinyl chloride resin fine particles in cyclohexanone and measuring the viscosity in accordance with JIS K6720-2. ..

<Average particle size>
The average particle diameter (volume average particle diameter (μm)) of the vinyl chloride resin particles and the vinyl chloride resin fine particles was measured according to JIS Z8825. Specifically, vinyl chloride resin particles and vinyl chloride resin fine particles are dispersed in a water tank, and the diffraction/scattering intensity distribution of light is measured and analyzed using the following apparatus, and the particle diameter and volume standard It was calculated by measuring the particle size distribution.
・Device: Laser diffraction type particle size distribution analyzer (Shimadzu Corporation, SALD-2300)
・Measurement method: Laser diffraction and scattering ・Measurement range: 0.017 μm to 2500 μm
・Light source: Semiconductor laser (wavelength 680 nm, output 3 mW)

<Tensile strength>
The obtained vinyl chloride resin molded sheet was punched with a No. 1 dumbbell described in JIS K6251 and, in accordance with JIS K7113, the maximum tensile stress (MPa) at -35°C was measured at a tensile speed of 200 mm/min, and chlorinated. The tensile strength of the vinyl resin molded sheet was measured.

<Specific gravity>
The specific gravity of the obtained vinyl chloride resin molded sheet was measured according to the method A (underwater substitution method) defined in JIS K7112. At the same time, the weight reduction rate of the specific gravity of each vinyl chloride resin molded sheet was calculated based on Example 1 described later.

<Appearance evaluation>
According to the following evaluation criteria, the number of pinholes in the obtained vinyl chloride resin molded sheet (150 mm×100 mm×1 mm) was visually observed and evaluated.
◯: The number of pinholes is 2 or less.
X: The number of pinholes is 3 or more.

(Example 1)
<Preparation of vinyl chloride resin composition>
Of the compounding components shown in Table 1, components other than microballoons, plasticizers (trimellitic acid ester plasticizers and epoxidized soybean oil), and emulsion-polymerized vinyl chloride resin fine particles that are dusting agents were placed in a Henschel mixer. Mixed. Then, when the temperature of the mixture rises to 80° C., all of the above-mentioned plasticizers are added, and the temperature is further raised to dry-up (as described above, the plasticizers become vinyl chloride resin particles that are vinyl chloride resin). It is said that the mixture has been absorbed and has become even more). Then, when the dried mixture was cooled to a temperature of 100° C. or lower, microballoons and 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 is sprinkled on a wrinkled mold heated to a temperature of 250° C., allowed to stand for an arbitrary time of about 10 seconds to 20 seconds to be melted, and then a surplus vinyl chloride resin composition. Shaken off. Thereafter, the embossed metal mold sprinkled with the vinyl chloride resin composition was allowed to stand still in an oven set to a temperature of 200° C., and 60 seconds after the stationary, the embossed metal mold was cooled with cooling water. .. When the mold temperature was cooled to 40° C., a 145 mm×175 mm×1 mm vinyl chloride resin molded sheet was released from the mold as a vinyl chloride resin molded body.
Then, with respect to the obtained vinyl chloride resin molded sheet, the specific gravity (and the weight reduction rate) and the tensile strength from the tensile stress at low temperature were measured and calculated according to the method described above. Further, according to the method described above, the appearance of the obtained vinyl chloride resin molded sheet was evaluated. The results are shown in Table 1.

(Example 2)
A vinyl chloride resin composition and a vinyl chloride resin molded sheet were produced in the same manner as in Example 1 except that the compounding ingredients were changed as shown in Table 1 in the preparation of the vinyl chloride resin composition.
Then, measurement, calculation and evaluation were performed by the same method as in Example 1. The results are shown in Table 1.

(Example 3)
A vinyl chloride resin composition and a vinyl chloride resin molded sheet were produced in the same manner as in Example 1 except that the compounding ingredients were changed as shown in Table 1 in the preparation of the vinyl chloride resin composition.
Then, measurement, calculation and evaluation were performed by the same method as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
In the preparation of the vinyl chloride resin composition, a vinyl chloride resin composition and a vinyl chloride resin molded sheet were produced in the same manner as in Example 1 except that the organic microballoons were not used and the components were changed as shown in Table 1. did.
Then, measurement, calculation and evaluation were performed by the same method as in Example 1. The results are shown in Table 1.

1) New Dai-ichi Vinyl Co., Ltd., product name "ZEST (registered trademark) 2500Z" average degree of polymerization: 2500, average particle size: 155 μm)
2) ZEST (registered trademark) 1700Z (average degree of polymerization 1700, average particle size 130 μm), manufactured by Shin-Daiichi PVC Co., Ltd.
3) Product name "Trimex N-08" manufactured by Kao Corporation
4) Product name "ADEKA CIZER O-130S" manufactured by ADEKA
5) Product name "Alkamizer 5" manufactured by Kyowa Chemical Industry Co., Ltd.
6) Product name "MIZUKALIZER DS" manufactured by Mizusawa Chemical Industry Co., Ltd.
7) Showa Denko KK, product name "Karenzu DK-1"
8) Sakai Chemical Industry, product name "SAKAI SZ2000"
9) Product name "ADEKA STAB LS-12" manufactured by ADEKA
10) New Dai-ichi Vinyl Co., Ltd., product name "ZEST PQLTX" (average degree of polymerization: 800, average particle size: 1.8 μm)
11) Tosoh Corporation, product name “Luron Paste (registered trademark) 860” (average degree of polymerization: 1600, average particle size: 1.6 μm)
12) "Matsumoto Microsphere (registered trademark) F-80DE" manufactured by Matsumoto Yushi Co., Ltd. (expanded type, outer shell part: acrylonitrile copolymer, organic solvent: pentane, average particle size: 90 to 130 µm, true specific gravity; 0.020 ± 0.005)
13) Nippon Philite Co., Ltd. "EMC 40(B)" (expanded type, outer shell: acrylonitrile/methacrylonitrile/methyl methacrylate copolymer, organic solvent: isopentane, limestone, average particle size: 35 to 55 μm) , True specific gravity; 0.16±0.02)
14) Product name "DA PX 1720 (A) Black" manufactured by Dainichi Seika Co., Ltd.

From Table 1, vinyl chloride resin moldings obtained using the vinyl chloride resin compositions of Examples 1 to 3 blended with (a) vinyl chloride resin, (b) plasticizer, and (c) organic microballoons. It was found that each of the bodies had a smaller specific gravity than Comparative Example 1 and could be made lighter than Comparative Example 1.
On the other hand, from Examples 1 to 3 and Comparative Example 1, by adding the organic microballoons, although the tensile strength is slightly lowered, this is within the allowable range, and all of Examples 1 to 3 have tensile strengths. It was confirmed that they were sufficiently secured.
Further, from Examples 1 to 3, if the content of the organic microballoons was 4 parts by mass or less with respect to 100 parts by mass of the plasticizer, the number of pinholes was small, and the appearance of the vinyl chloride resin molded sheet was affected. I knew I wouldn't give it. On the other hand, as seen in Examples 2 and 3, when the content of the organic microballoons exceeds 4 parts by mass with respect to 100 parts by mass of the plasticizer, the amount can be further reduced as compared with Example 1, but the pinholes can be reduced. There was a case where the number of was relatively large.

According to the present invention, it is possible to provide a vinyl chloride resin composition capable of reducing the weight of a vinyl chloride resin molded body while ensuring the tensile strength of the obtained vinyl chloride resin molded body.
Further, according to the present invention, it is possible to provide a laminate having a vinyl chloride resin molded body that is lightweight while ensuring tensile strength.

Claims (6)

(A) a vinyl chloride resin, and (b) a plasticizer; and (c) the organic microballoons seen including,
The organic microballoon (c) has an outer shell part composed of an acrylonitrile-methacrylonitrile-methyl methacrylate copolymer,
The vinyl chloride resin composition , wherein the average particle size of the organic microballoon (c) is 30 μm or more and 60 μm or less . The vinyl chloride resin composition according to claim 1, wherein the content of the (c) organic microballoon is 4 parts by mass or less based on 100 parts by mass of the (b) plasticizer. The vinyl chloride resin composition according to claim 1 or 2, containing 1% by mass or more of the (c) organic microballoons. The vinyl chloride resin composition according to claim 1, which is used for powder molding. The vinyl chloride resin composition according to claim 4, which is used for powder slush molding. A foamed polyurethane molded body,
A vinyl chloride resin molded product obtained by molding the vinyl chloride resin composition according to claim 4 or 5.