JP2018035304A - Vinyl chloride resin composition, vinyl chloride resin molding, and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride resin composition that can form a vinyl chloride resin molding that has the stickiness of its surface sufficiently suppressed and prevents voids from occurring in an adjacent polyurethane foam molding.SOLUTION: A vinyl chloride resin composition contains (a) a vinyl chloride resin, and (b) a silicone oil with a viscosity of 1×10cs or more, where the (b) silicone oil has the viscosity of more than 6×10cs, preferably. The (b) silicone oil is an unmodified silicone oil, preferably.SELECTED DRAWING: None

Description

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

  Since vinyl chloride resin is generally excellent in properties such as cold resistance, heat resistance and oil resistance, it is used in various applications. Specifically, vinyl chloride resin is used, for example, when forming the skin of an automobile instrument panel. Here, the automobile instrument panel has a laminated structure in which a layer of a polyurethane foam molded body is provided between a skin made of a molded body of a vinyl chloride resin and a base material. In recent years, for example, attempts have been made to improve a vinyl chloride resin molded article and a vinyl chloride resin composition used for forming a vinyl chloride resin molded article, which can be suitably used for the manufacture of automobile instrument panels.

  For example, Patent Document 1 discloses a vinyl chloride resin composition containing 100 parts by weight of a vinyl chloride resin, 20 to 200 parts by weight of a plasticizer, 0.01 to 5 parts of an antibacterial agent, and 0.05 to 5 parts of silicon oil. Has been. And according to patent document 1, this vinyl chloride resin composition is excellent in abrasion resistance, and has a smooth touch.

JP 2000-204212 A

  Here, when silicone oil is contained in the vinyl chloride resin composition, stickiness of the surface of the vinyl chloride resin molded body formed using the vinyl chloride resin composition is suppressed due to its function as a surface modifier. can do. On the other hand, as a result of repeated studies by the present inventor, when a laminate including a vinyl chloride resin molded body obtained from the vinyl chloride resin composition described in Patent Document 1 and a foamed polyurethane molded body is produced, a foamed polyurethane molded product is obtained. It has been clarified that fine bubbles in the body break up and a large void (hereinafter referred to as “void”) may be generated. When many such voids are generated, a problem occurs in the production of a laminate having a vinyl chloride resin molded body and a foamed polyurethane molded body. In addition, the cushioning property of the foamed polyurethane molded body in the void portion is impaired, and the void portion causes a problem of unevenness in the color tone and gloss of the surface of the vinyl chloride resin molded body laminated on the foamed polyurethane molded body. there is a possibility.

  Therefore, an object of the present invention is to provide a vinyl chloride resin molded body in which the stickiness of the surface is sufficiently suppressed and a void is hardly generated in the adjacent foamed polyurethane molded body. Another object of the present invention is to provide a vinyl chloride resin composition capable of forming the vinyl chloride resin molded body, and a laminate having the vinyl chloride resin molded body.

  The present inventor has intensively studied for the purpose of solving the above problems. Then, the inventor forms a vinyl chloride resin molded body using a vinyl chloride resin composition containing a vinyl chloride resin and a silicone oil having a viscosity equal to or higher than a predetermined value. The present inventors have found that the number of voids generated in a resin foam such as a foamed polyurethane molded product in contact with the vinyl chloride resin molded product can be reduced while suppressing stickiness.

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 and (b) a viscosity of 1 × 10 ⁴ cs. It contains the above silicone oil. As described above, when a vinyl chloride resin composition containing vinyl chloride resin particles and a silicone oil having a viscosity equal to or higher than the above-described value is used, the stickiness of the surface is sufficiently suppressed, and an adjacent foamed polyurethane molding is formed. It is possible to provide a vinyl chloride resin molded body in which voids are hardly generated in the body.
In the present invention, “viscosity” can be measured using an Ubbelohde viscometer at a temperature of 25 ° C. according to ASTM D 445-46T. When a mixture of two or more different silicone oils is used, the “viscosity” can be measured as a value of the entire mixture.

Here, in the vinyl chloride resin composition of the present invention, the viscosity of the (b) silicone oil is preferably more than 6 × 10 ⁴ cs. (B) If the viscosity of the silicone oil exceeds 6 × 10 ⁴ cs, the number of voids generated in the foamed polyurethane molded product adjacent to the obtained vinyl chloride resin molded product can be further reduced.

  In the vinyl chloride resin composition of the present invention, the (b) silicone oil preferably contains an unmodified silicone oil. (B) If an unmodified silicone oil is used as the silicone oil, the stickiness of the surface of the resulting vinyl chloride resin molded body is further suppressed, and voids formed in the foamed polyurethane molded body adjacent to the vinyl chloride resin molded body It is because the number of can be reduced easily.

  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 article used for an automobile instrument panel or the like. It is.

  And it is preferable that the vinyl chloride resin composition of this invention is used for powder slush molding. If the vinyl chloride resin composition is used for powder slush molding, for example, the vinyl chloride resin composition can be more suitably used for forming a vinyl chloride resin molded article used for an automobile instrument panel or the like. It is.

Further, the present invention aims to advantageously solve the above-mentioned problems, and the vinyl chloride resin molded article of the present invention is formed by molding any of the above-described vinyl chloride resin compositions. And If a vinyl chloride resin molded article is formed using the vinyl chloride resin composition containing the above (a) vinyl chloride resin and (b) silicone oil, stickiness of the surface of the resulting vinyl chloride resin molded article can be sufficiently suppressed. It is also possible to suppress the formation of voids in the foamed polyurethane molded product adjacent to the vinyl chloride resin molded product.
Note that the vinyl chloride resin molded body of the present invention has the surface stickiness sufficiently suppressed as described above, and does not generate a large amount of voids in the adjacent foamed polyurethane molded body. It can be suitably used for an instrument panel skin.

  Furthermore, this invention aims at solving the said subject advantageously, and the laminated body of this invention has a foaming polyurethane molding and one of the vinyl chloride resin moldings mentioned above. Features. The laminate including the foamed polyurethane molded body and the above-described vinyl chloride resin molded body has sufficiently suppressed stickiness on the surface of the vinyl chloride resin molded body, and the number of voids generated in the foamed polyurethane molded body is small. Therefore, the laminated body of this invention can be used suitably as a structural member of a vehicle instrument panel, for example.

ADVANTAGE OF THE INVENTION According to this invention, while the stickiness of the surface is fully suppressed, the vinyl chloride resin molded object which cannot produce a void easily in the adjacent foaming polyurethane molded object can be provided.
Moreover, according to this invention, the laminated body which has the vinyl chloride resin composition which can form the said vinyl chloride resin molded object, and the said vinyl chloride resin molded object can be provided.

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. Moreover, the vinyl chloride resin molded object formed using the vinyl chloride resin composition of this invention can be used for manufacture of the laminated body of this invention which has the said vinyl chloride resin molded object, for example. The vinyl chloride resin molded body of the present invention can be suitably used for automobile interior materials, for example, for the skin of automobile instrument panels.

(Vinyl chloride resin composition)
The vinyl chloride resin composition of the present invention comprises (a) a vinyl chloride resin and (b) a silicone oil having a viscosity of 1 × 10 ⁴ cs or more. In addition to the above components, the vinyl chloride resin composition of the present invention may optionally further contain an additive such as a plasticizer. And since the vinyl chloride resin composition of this invention contains the said predetermined | prescribed component, it can fully suppress the stickiness of the surface of the vinyl chloride resin molded object formed using the said composition. Moreover, it is also possible to suppress the formation of voids in the foamed polyurethane molded body adjacent to the vinyl chloride resin molded body formed using the composition.

In addition, although the reason which can suppress the void production | generation in a foaming polyurethane molding as mentioned above by mix | blending the silicone oil which has a high viscosity of 1 * 10 < ⁴ > cs or more is not certain, it is as follows. It is assumed that there is. That is, in general, silicone oil does not have a high affinity with the vinyl chloride resin in the vinyl chloride resin molded body, and is unevenly distributed near the surface of the vinyl chloride resin molded body, thereby reducing the dynamic friction coefficient of the surface of the molded body. The effect of reducing (that is, suppressing the stickiness of the surface) is exhibited. On the other hand, when a silicone oil having a relatively low viscosity is used, the silicone oil present in the vicinity of the surface of the vinyl chloride resin molded body becomes a layer made of a foamed polyurethane molded body produced adjacent to the vinyl chloride resin molded body. Migrate easily. Here, the low-viscosity silicone oil usually has a defoaming effect, and the diffusion of such low-viscosity silicone oil into the foamed polyurethane molded product generates voids in the foamed polyurethane molded product. This is considered to be a cause. Therefore, by using the above-described high-viscosity silicone oil, it is possible to suppress the silicone oil from moving to the foamed polyurethane molded body and diffusing in the molded body. As a result, voids in the foamed polyurethane molded body can be suppressed. It is inferred that generation can be suppressed.

<(A) Vinyl chloride resin>
Here, as the (a) vinyl chloride resin used in 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 particles can be contained. Vinyl chloride resin fine particles can be further contained. Among them, (a) the vinyl chloride resin 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. More preferably, vinyl chloride resin fine particles are used in combination.
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.
Further, (a) the vinyl chloride resin can be produced by any conventionally known production method such as a suspension polymerization method, an emulsion polymerization method, a solution polymerization method or a bulk polymerization method.

<< Composition >>
(A) As the vinyl chloride resin, a vinyl chloride copolymer containing a vinyl chloride monomer unit in addition to a homopolymer composed of vinyl chloride monomer units is preferably 50% by mass or more, more preferably 70% by mass or more. A polymer is mentioned. 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]
Here, the average degree of polymerization of the vinyl chloride resin particles is preferably 800 or more, more preferably 1000 or more, further preferably 1500 or more, preferably 5000 or less, and more preferably 3000 or less. If the average degree of polymerization of the vinyl chloride resin particles is not less than the above lower limit, the tensile elongation at low temperature can be improved while ensuring the physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition. Because. Moreover, if the average degree of polymerization of the vinyl chloride resin particles is not more than the above upper limit, the meltability of the vinyl chloride resin molded body can be improved and the surface smoothness can be improved.
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, more preferably 250 μm or less, and further 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 improved. Moreover, 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 improved and the surface smoothness of the vinyl chloride resin molded body formed using the composition is improved. It is because it can be made.
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 more preferably 75% by mass or more with respect to 100% by mass of the (a) vinyl chloride resin. Preferably, it can be 100 mass%, it is preferable that it is 95 mass% or less, and it is more preferable that it is 90 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 physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition can be sufficiently secured, and at a low temperature This is because the tensile elongation at can be improved. 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]
Here, the average degree of polymerization of the vinyl chloride resin fine particles is preferably 600 or more, more preferably 900 or more, and 2000 or less as a whole of the vinyl chloride resin fine particles contained in the vinyl chloride resin (a). Is preferable, and it is more preferable that it is 1700 or less. For example, when two types of vinyl chloride resin fine particles having different average polymerization degrees are used as a dusting agent, the average polymerization degree of one vinyl chloride resin fine particle is set to 500 to 1000; the other vinyl chloride resin fine particles The average degree of polymerization is more than 1000 and 2500 or less. If the average degree of polymerization of the vinyl chloride resin fine particles as the dusting agent is not less than the above lower limit, the powder flowability of the vinyl chloride resin composition is improved and the vinyl chloride resin molding formed using the composition is used. This is because the tensile elongation of the body at a low temperature is improved. Moreover, if the average degree of polymerization of the vinyl chloride resin fine particles is not more than the above upper limit, the meltability of the vinyl chloride resin composition is improved, and the surface smoothness of the vinyl chloride resin molded body formed using the composition is improved. Because.
Here, from the viewpoint of further improving the meltability of the vinyl chloride resin composition, the average polymerization degree of the vinyl chloride resin fine particles as the dusting agent is smaller than the average polymerization degree of the vinyl chloride resin particles as the base material. Is preferred.

[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. . Further, 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 increased, and the surface smoothness of the formed vinyl chloride resin molded product can be improved. .

[Content ratio]
And the content ratio of the vinyl chloride resin fine particles in the (a) vinyl chloride resin is preferably 5% by mass or more, more preferably 10% by mass or more with respect to 100% by mass of the (a) vinyl chloride resin. Preferably, it is preferably 30% by mass or less, and more preferably 25% 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 improved. Further, (a) 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 tensile elongation at low temperature of the vinyl chloride resin molded body formed using the vinyl chloride resin composition can be improved. Because.

<(B) Silicone oil>
The vinyl chloride resin composition of the present invention needs to further contain (b) silicone oil in addition to the above-mentioned (a) vinyl chloride resin.

<< Viscosity >>
Viscosity here, (b) a silicone oil are required to be 1 × ¹⁰ 4 cs or more, preferably 6 × ¹⁰ 4 cs greater, more preferably at 10 × ¹⁰ 4 cs or 25 × 10 ⁴ cs or more, more preferably 50 × 10 ⁴ cs or more, more preferably 200 × 10 ⁴ cs or more, and 1000 × 10 ⁴ cs or less. Is preferred. (B) When the viscosity of the silicone oil is less than the above lower limit, the number of voids in the polyurethane foam molding adjacent to the vinyl chloride resin molding formed using the vinyl chloride resin composition increases. Moreover, if the viscosity of (b) silicone oil is below the said upper limit, it is because the handling property and easy dispersibility of (b) silicone oil can be ensured.

<<< Type >>>
(B) The silicone oil may be an unmodified silicone oil, a modified silicone oil, or a mixture thereof.
Examples of the unmodified silicone oil include, but are not limited to, polymers having a polysiloxane structure such as polydimethylsiloxane, polydiethylsiloxane, and poly (methylethyl) siloxane, and mixtures thereof.
Further, as the modified silicone oil, for example, polar groups such as carboxyl group, hydroxyl group (silanol modification), mercapto group, amino group, epoxy group, (meth) acryloyloxy group are introduced into a polymer having a polysiloxane structure. Polar group-modified silicone oil; nonpolar group-modified silicone oil in which nonpolar groups are introduced into a polymer having a polysiloxane structure. Among these, polar group-modified silicone oil is preferable, and silanol-modified silicone oil is more preferable.
In addition, the site | part into which the said polar group or nonpolar group is introduce | transduced is the terminal (one terminal, both terminals) and / or a side chain of the polymer which has a polysiloxane structure.
Further, the stickiness of the surface of the vinyl chloride resin molded body formed from the vinyl chloride resin composition is further suppressed, and the number of voids generated in the foamed polyurethane molded body adjacent to the vinyl chloride resin molded body is further reduced. From the viewpoint, the (b) silicone oil preferably contains unmodified silicone oil, more preferably contains polydimethylsiloxane, and more preferably consists only of polydimethylsiloxane.
In the present specification, “(meth) acryloyloxy” means acryloyloxy and / or methacryloyloxy.

<< Content >>
Here, the content of the (b) silicone oil in the vinyl chloride resin composition is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the (a) vinyl chloride resin, and 0.3 masses. The amount is more preferably at least 1 part by mass, more preferably at most 1 part by mass, and even more preferably at most 0.6 part by mass. (B) If the content of the silicone oil is not less than the above lower limit, while further reducing the number of voids generated in the foamed polyurethane molded product adjacent to the obtained vinyl chloride resin molded product, the surface of the vinyl chloride resin molded product This is because stickiness can be further suppressed. Moreover, it is because the number of voids produced | generated to the foaming polyurethane molded object adjacent to the vinyl chloride resin molded object obtained can be further reduced if content of (b) silicone oil is below the said upper limit.

  Here, when a plasticizer described later is blended in the vinyl chloride resin composition, the plasticizer oozes out on the surface of the resulting vinyl chloride resin molded article, and the stickiness of the surface of the molded article may deteriorate. And even when such a plasticizer oozes out, from the viewpoint of sufficiently suppressing the stickiness of the surface of the vinyl chloride resin molded article, when the vinyl chloride resin composition further contains a plasticizer, b) The content of the silicone oil is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and 100 parts by mass or less with respect to 100 parts by mass of the plasticizer. Preferably, it is 0.5 parts by mass or less, more preferably 0.4 parts by mass or less. (B) If content of silicone oil is more than the said minimum, it is because generation | occurrence | production of the surface stickiness by a plasticizer of a vinyl chloride resin molded object can fully be suppressed. Moreover, it is because the number of voids produced | generated to the foaming polyurethane molded object adjacent to the vinyl chloride resin molded object obtained can be further reduced if content of (b) silicone oil is below the said upper limit.

<Additives>
The vinyl chloride resin composition of the present invention may further contain various additives in addition to the components described above. Additives are not particularly limited, plasticizers; stabilizers such as perchloric acid-treated hydrotalcite, zeolite, β-diketone, fatty acid metal salt; mold release agent; dusting other than the above vinyl chloride resin fine particles And other additives; and the like.

<< Plasticizer >>
Examples of the plasticizer include the following primary plasticizers and secondary plasticizers.
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 The alkyl group constituting the ester, such as a kill ester (wherein the carbon number of the alkyl group of the trimellitic acid tri-n-alkyl ester may be different in one molecule) is linear. Linear trimellitic acid ester [Note that these trimellitic acid esters may be composed of a single compound or a mixture thereof. ];
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 (where trimellitic acid Branched trimellitic acid esters in which the alkyl group constituting the ester is branched, such as the number of carbon atoms of the alkyl group in the alkyl ester may be different from each other in one molecule. The ester may be a single compound or a mixture. ];
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 The alkyl group constituting the ester is linear, such as -n-alkyl ester (wherein the carbon number of the alkyl group of the pyromellitic acid tetra-n-alkyl ester may be different from each other in one molecule). Linear pyromellitic acid ester [These pyromellitic acid esters may be composed of a single compound or a mixture. ];
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 Branched pyromellitic acid in which the alkyl group constituting the ester is branched, such as an ester (wherein the carbon number of the alkyl group of the pyromellitic acid tetraalkyl ester may be different from each other in one molecule) Esters [These pyromellitic acid esters may be composed of a single compound or a mixture thereof. ];
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 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), 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, from the viewpoint of obtaining good tensile elongation at low temperatures, it is preferable to use trimellitic acid ester and / or pyromellitic acid ester, more preferably trimellitic acid ester, It is more preferable to use a linear trimellitic acid ester, and it is more preferable to use a linear trimellitic acid ester having two or more alkyl groups having different carbon numbers in the molecule. Moreover, it is preferable that carbon number of the said alkyl group is 8-10, and it is more preferable that the said alkyl group is n-octyl group and n-decyl group. And it is preferable to further use an epoxidized soybean oil together with the trimellitic acid ester.

  Here, the form of the plasticizer is not particularly limited, but (a) from the viewpoint of easy mixing with the vinyl chloride resin, it is preferably liquid at room temperature.

  The content of the plasticizer is preferably 80 parts by mass or more, more preferably 85 parts by mass or more, and preferably 200 parts by mass or less with respect to 100 parts by mass of (a) the vinyl chloride resin. 150 parts by mass or less, more preferably 120 parts by mass or less. If content of a plasticizer is more than the said minimum, favorable tensile elongation in low temperature of the vinyl chloride resin molded object formed using the vinyl chloride resin composition can be ensured. In addition, when the content of the plasticizer is blended above the lower limit, the above-described problem of stickiness on the surface of the vinyl chloride resin molded article may occur. However, in the present invention, the vinyl chloride resin composition is a predetermined one. Since (b) silicone oil having a viscosity of is contained, stickiness of the surface of the molded product can be suppressed. Moreover, if content of a plasticizer is below the said upper limit, the stickiness of the formed vinyl chloride resin molded object surface can be suppressed further.

<< Perchloric acid-treated hydrotalcite >>
The perchloric acid-treated hydrotalcite that can be contained in the vinyl chloride resin composition is, for example, added to a dilute aqueous solution of perchloric acid and stirred, and then filtered, dehydrated or dried 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 partial introduction type 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 with no perchlorate anion introduced) is preferably 50 mol% or more, more preferably 70. It is at least mol%, more preferably at least 85 mol%. Moreover, the substitution rate of the carbonate anion to the perchlorate anion in the untreated (unsubstituted with no perchlorate anion partially introduced) hydrotalcite is preferably 95 mol% or less. The substitution rate of carbonate anion to perchlorate anion in untreated (unsubstituted with no perchlorate anion introduced) hydrotalcite is in the above range, It is because it can be manufactured easily.

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, 1.5 parts by mass or more is further preferable, 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, a vinyl chloride resin molded article in which tensile elongation at low temperatures is ensured can be easily produced.

<< 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, and Zn, and mixed types thereof.

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

<< β-diketone >>
β-diketone is used to 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 especially, 0.1 mass part or more is preferable with respect to 100 mass parts of (a) vinyl chloride resin, and 5 mass parts or less are preferable.

<< 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 0.05 parts by mass or more and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the above (a) vinyl chloride resin. 5 mass parts or less are preferable, 1 mass part or less are more preferable, and 0.5 mass part or less are still more preferable. If the content of the fatty acid metal salt is within the above range, the color difference value of the vinyl chloride resin molded article formed by molding the vinyl chloride resin composition can be reduced, and fiber residue adhesion to the molded article surface can be suppressed. is there.

<< Releasing agent >>
The release agent is not particularly limited, and examples thereof include 12-hydroxystearic acid type 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 0.1 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 (powder fluidity improvers) other than the above-mentioned vinyl chloride resin fine particles that can be contained in the vinyl chloride resin composition include inorganic fine particles such as calcium carbonate, talc, aluminum oxide; polyacrylonitrile resin fine particles And organic fine particles such as poly (meth) acrylate resin fine particles, 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 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 (a) vinyl chloride resin. This can be done. Other dusting agents may be used alone or in combination of two or more, or may be used in combination with the above-described 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 resistance improvers, and 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 the colorant (pigment) 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-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.
Titanium white is a white pigment made of titanium dioxide and has a large hiding power, and there are 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 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 resistance improvers 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 (a) the vinyl chloride resin, and the impact resistance of the vinyl chloride resin molded article formed using the vinyl chloride resin composition. Will improve.

  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 above-mentioned (a) vinyl chloride resin, (b) silicone oil, and various additives further used as needed is not particularly limited. The method of mixing the component except the dusting agent containing microparticles | fine-particles and other dusting agents 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 obtained using the vinyl chloride resin composition of the present invention, the stickiness of the surface is sufficiently suppressed, and the vinyl chloride resin molded article Generation of voids in the adjacent foamed polyurethane molded product can also be suppressed. Therefore, the vinyl chloride resin molded article of the present invention is suitably used as a skin of an automobile interior material, for example, an automobile instrument panel and a door trim, and particularly preferably as a skin of an automobile instrument panel.

<< Method of molding 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, and preferably 300 ° C. or lower, and 280 ° C. More preferably, it is as follows.

  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. The demolded vinyl chloride resin molded body is obtained, for example, as a sheet-shaped molded body shaped like a mold.

(Laminate)
The laminate of the present invention has a foamed polyurethane molded product and the vinyl chloride resin molded product described above. 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, the stickiness of the surface is fully suppressed, and foaming is also carried out. The number of voids generated in the polyurethane molded body is small. Therefore, the laminate of the present invention is suitably used as an automobile interior material such as an automobile instrument panel and a door trim, and is particularly suitably used for an automobile instrument panel.

  Here, the laminating method is not particularly limited, and for example, polymerization is performed by reacting isocyanates and polyols, which are raw materials of the foamed polyurethane molded body, on a vinyl chloride resin molded body, and a known method. For example, a method of directly forming a foamed polyurethane molded product on a vinyl chloride resin molded product by foaming polyurethane by the above method may be used.

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 viscosity of silicone oil, average degree of polymerization of vinyl chloride resin particles and vinyl chloride resin fine particles, average particle diameter; tensile elongation at low temperature of vinyl chloride resin molded body after initial and heating (thermal aging test), vinyl chloride The surface stickiness (dynamic friction coefficient) of the resin molded body; the void generation amount of the foamed polyurethane molded body; was measured and evaluated by the following methods.

<Viscosity>
The viscosity of the silicone oil was measured as a kinematic viscosity η ^{CS / 25} (unit: mm ² / s = cs) at a temperature of 25 ° C. using an Ubbelohde viscometer according to ASTM D 445-46T.

<Average polymerization degree>
The average polymerization degree 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 / analyzed using the apparatus shown below. It was calculated by measuring the particle size distribution.
・ Apparatus: Laser diffraction type particle size distribution measuring machine (manufactured by 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 elongation at low temperature>
<< Initial >>
The obtained vinyl chloride resin molded sheet was punched out with a No. 1 dumbbell described in JIS K6251, and the tensile elongation at break (%) at a low temperature of −35 ° C. was measured at a pulling rate of 200 mm / min according to JIS K7113. did. The larger the tensile elongation at break, the better the initial (unheated) vinyl chloride resin molded product at low temperature.
<< After heating (heat aging test) >>
A laminated body lined with a foamed polyurethane molding was used as a sample. The sample was placed in an oven and heated for 100 hours in an environment of 130 ° C. Next, the polyurethane foam molded body was peeled off from the heated laminate, and only a vinyl chloride resin molded sheet was prepared. Then, the tensile breaking elongation (%) of the vinyl chloride resin molded sheet after heating for 100 hours was measured under the same conditions as in the initial case. The higher the tensile elongation at break at a temperature of -35 ° C., the better the ductility at low temperatures of the vinyl chloride resin molded article after heating (thermal aging test).

<Dynamic friction coefficient>
The surface stickiness of the vinyl chloride resin molding was evaluated by measuring the dynamic friction coefficient as follows.
Specifically, using a texture tester (manufactured by Trinity Labs, product name “TL201Ts”), in a measurement environment at a temperature of 23 ° C. and a relative humidity of 50%, load: 50 g, speed: 10 mm / second, test range: 50 mm, measurement range: 30 mm excluding 10 mm before and after the test range, by contacting the tactile contact with the vinyl chloride resin molded sheet before forming the laminate, the dynamic friction coefficient of the sheet surface It was measured. As the value of the dynamic friction coefficient is smaller, stickiness of the surface of the vinyl chloride resin molded body is suppressed.

<Void generation amount>
The vinyl chloride resin molded sheet was peeled from the laminate to prepare only a foamed polyurethane molded body (200 mm × 300 mm × 10 mm), which was used as a sample. The sample was cut (six divisions) in the short direction at intervals of 50 mm, and the state of the cross section was confirmed. Specifically, voids having a diameter of 3 mm or more were regarded as voids, and the number of voids (N ₁ ) present at five cut locations was counted.
On the other hand, except that the vinyl chloride resin molded sheet is not placed in the mold, a foamed polyurethane molded body is produced by the same procedure as that of “Formation of laminate” in Example 1, and the foamed polyurethane molded body is also described above. The number of voids (N ₀ ) existing at 5 cut locations was counted.
Then, in each sample, void generation amount (%) = N ₁ / N ₀ × 100 with N ₀ as a reference (100%) was calculated. As the value of void generation is smaller, voids are less likely to be generated in the foamed polyurethane molded product adjacent to the vinyl chloride resin molded product.

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 the temperature is further raised to dry up (the plasticizer is absorbed by the vinyl chloride resin particles, which are vinyl chloride resins, The mixture was 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.

<Manufacture of vinyl chloride resin molding>
The vinyl chloride resin composition obtained above is sprinkled on a grained mold heated to a temperature of 250 ° C. and allowed to melt for an arbitrary time of about 10 seconds to 20 seconds, and then an excess vinyl chloride resin composition. 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 vinyl chloride resin molded sheet of 200 mm × 300 mm × 1 mm was removed from the mold as a vinyl chloride resin molded body.
The obtained vinyl chloride resin molded sheet was evaluated for initial (unheated) low-temperature tensile elongation and surface stickiness (dynamic friction coefficient) according to the method described above. The results are shown in Table 1.

<Formation of laminate>
The obtained vinyl chloride resin molded sheet was allowed to stand in an oven set at 100 ° C. for 2 hours, and then laid down in a 200 mm × 300 mm × 10 mm mold with the surface with a textured side 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 vinyl chloride resin molded sheet laid in the metal mold | die as above-mentioned. 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 picked out from the metal mold | die, and according to the above-mentioned method, the tensile elongation in low temperature after a heating (thermal aging test) and the void production amount were evaluated. The results are shown in Table 1.

(Example 2)
In the preparation of the vinyl chloride resin composition, in the same manner as in Example 1, except that 0.2 part of silicone oil B was used instead of 0.4 part of silicone oil A, as shown in Table 1. A vinyl chloride resin composition, a vinyl chloride resin molded sheet, and a laminate were produced.
And it evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.

(Example 3)
In the preparation of the vinyl chloride resin composition, the vinyl chloride resin was prepared in the same manner as in Example 2 except that the blending amount of the silicone oil B was changed from 0.2 part to 0.4 part as shown in Table 1. A composition, a vinyl chloride resin molded sheet, and a laminate were produced.
And it 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, as shown in Table 1, 0.4 parts of silicone oil C was used instead of 0.4 parts of silicone oil A, and the amount of vinyl chloride resin fine particles A was adjusted. The vinyl chloride resin composition, vinyl chloride was changed in the same manner as in Example 1 except that 10 parts of vinyl chloride resin fine particles C were used instead of 8 parts of vinyl chloride resin fine particles B. A resin molded sheet and a laminate were produced.
And it evaluated by the method similar to Example 1. FIG. The results are shown in Table 1.

1) Product name “ZEST (registered trademark) 1700ZI” (manufactured by Shin Daiichi PVC Co., Ltd.) (suspension polymerization method, average degree of polymerization: 1700, average particle size: 130 μm)
2) Product name “Trimex (registered trademark) N-08” manufactured by Kao Corporation
3) Product name “Adekasizer (registered trademark) O-130S” manufactured by ADEKA
4) Product name “Alkamizer (registered trademark) 5” manufactured by Kyowa Chemical Industry Co., Ltd.
5) Product name “MIZUKALIZER (registered trademark) DS” manufactured by Mizusawa Chemical Industry Co., Ltd.
6) Product name “Karenz (registered trademark) DK-1” manufactured by Showa Denko KK
7) Sakai Chemical Industry Co., Ltd., product name “SAKAISZ2000”
8) Product name “ADK STAB (registered trademark) LS-12” manufactured by ADEKA
9) Product name “KF-96H-300,000 cs” manufactured by Shin-Etsu Silicone Co., Ltd. (unmodified silicone oil (polydimethylsiloxane), viscosity: 30 × 10 ⁴ cs)
10) Product name “KF-96H-1 million cs” manufactured by Shin-Etsu Silicone Co., Ltd. (unmodified silicone oil (polydimethylsiloxane), viscosity: 100 × 10 ⁴ cs)
11) Product name “KF-96-5000cs” manufactured by Shin-Etsu Silicone Co., Ltd. (unmodified silicone oil, viscosity: 0.5 × 10 ⁴ cs)
12) Product name “ZEST (registered trademark) PQLTX” (Emulsion polymerization method, average degree of polymerization: 800, average particle size: 1.8 μm)
13) Product name “Luron Paste (registered trademark) 860” manufactured by Tosoh Corporation (emulsion polymerization method, average degree of polymerization: 1600, average particle size: 1.6 μm)
14) Product name “Lyuron Paste (registered trademark) 761” manufactured by Tosoh Corporation (emulsion polymerization method, average degree of polymerization: 2100, average particle size: 1.6 μm)
15) Product name “DA PX 1720 (A) Black” manufactured by Dainichi Seika Co., Ltd.

From Table 1, in Examples 1 to 3 using a silicone oil having a viscosity of 1 × 10 ⁴ cs or more, the stickiness of the surface of the vinyl chloride resin molded article is sufficiently suppressed, and in the foamed polyurethane molded article It can be seen that void generation is suppressed. On the other hand, in Comparative Example 1 using a silicone oil having a viscosity of less than 1 × 10 ⁴ cs, it can be seen that many voids are generated in the foamed polyurethane molded body.

ADVANTAGE OF THE INVENTION According to this invention, while the stickiness of the surface is fully suppressed, the vinyl chloride resin molded object which cannot produce a void easily in the adjacent foaming polyurethane molded object can be provided.
Moreover, according to this invention, the laminated body which has the vinyl chloride resin composition which can form the said vinyl chloride resin molded object, and the said vinyl chloride resin molded object can be provided.

Claims (8)

A vinyl chloride resin composition comprising (a) a vinyl chloride resin and (b) a silicone oil having a viscosity of 1 × 10 ⁴ cs or more. The vinyl chloride resin composition according to claim 1, wherein the viscosity of the (b) silicone oil is more than 6 × 10 ⁴ cs.   The vinyl chloride resin composition according to claim 1 or 2, wherein the (b) silicone oil contains an unmodified silicone oil.   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.   The vinyl chloride resin molded object formed by shape | molding the vinyl chloride resin composition as described in any one of Claims 1-5.   The vinyl chloride resin molded article according to claim 6, which is used for an automobile instrument panel skin. A foamed polyurethane molding,
A vinyl chloride resin molded article according to claim 6 or 7,
A laminate having