JP2023081211A - Polyvinyl chloride resin composition, polyvinyl chloride resin molding and laminate - Google Patents

Abstract

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

Description

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

Vinyl chloride resins are generally used in various applications because of their excellent properties such as cold resistance, heat resistance, and oil resistance.
Specifically, for example, in the formation of automobile interior parts such as automobile instrument panels and door trims, the skin composed of a vinyl chloride resin molded body or the skin composed of a vinyl chloride resin molded body is lined with a foam such as foamed polyurethane. Automobile interior materials such as laminates formed by

Then, the vinyl chloride resin molded body that constitutes the skin of automobile interior parts such as automobile instrument panels is produced by, for example, powder slush molding a vinyl chloride resin composition containing vinyl chloride resin, a plasticizer, and an additive. is manufactured by molding using the method of powder molding (see, for example, Patent Document 1).

Specifically, for example, in Patent Document 1, a vinyl chloride resin composition containing vinyl chloride resin particles, a plasticizer, and additives such as a hydrotalcite-based stabilizer, a zeolite-based stabilizer, and β-diketones is prepared. We manufacture vinyl chloride resin moldings by powder slush molding.

JP-A-6-279640

Here, when the vinyl chloride resin composition is powder-molded, for example, if the mold used has a temperature distribution, the difference in molding temperature may cause variations in the color tone of the vinyl chloride resin composition. When such a change in color tone occurs, unevenness in color tone may occur in the vinyl chloride resin molded article to be formed. Therefore, from the viewpoint of reducing unevenness in color tone of a vinyl chloride resin molded article, it is required to suppress variation in color tone due to differences in molding temperatures in vinyl chloride resin compositions.

However, the vinyl chloride resin composition of the prior art described above has room for improvement in terms of suppressing variations in color tone due to differences in molding temperatures.

Accordingly, an object of the present invention is to provide a vinyl chloride resin composition in which variations in color tone due to differences in molding temperature are suppressed.
Another object of the present invention is to provide a vinyl chloride resin molded article formed using the vinyl chloride resin composition.
A further object of the present invention is to provide a laminate comprising the vinyl chloride resin molded article.

The inventor of the present invention has made intensive studies with the aim of solving the above problems. Then, the present inventor added a uracil compound, zinc acetylacetonate, and calcium acetylacetonate to a vinyl chloride resin composition, and found that if the ratio of the content of calcium acetylacetonate to the content of zinc acetylacetonate is a predetermined value or more, the molding temperature The inventors have found that it is possible to suppress variation in color tone due to the difference in the color tone, and completed the present invention.

That is, an object of the present invention is to advantageously solve the above problems, and a vinyl chloride resin composition of the present invention comprises a vinyl chloride resin, a plasticizer, a uracil compound, zinc acetylacetone, and acetylacetone. and calcium, wherein the content of calcium acetylacetonate is 0.8 times or more the content of zinc acetylacetonate. Thus, in the vinyl chloride resin composition containing the vinyl chloride resin, the plasticizer, the uracil compound, the zinc acetylacetonate, and the calcium acetone, the ratio of the content of the calcium acetylacetonate to the content of the zinc acetylacetonate is equal to or greater than a predetermined value. By doing so, it is possible to suppress variation in color tone due to differences in the molding temperature of the vinyl chloride resin composition.

〔式（Ｉ）中、Ｒ_１およびＲ_２は、それぞれ独立して、水素原子または電子供与基を表し、
Ｒ_３は水素原子またはアミノ基を表す。〕で示されることが好ましい。ウラシル化合物が上記所定の式で示される化合物であれば、塩化ビニル樹脂組成物の成形温度の差による色調の変動を更に抑制することができる。 Here, in the vinyl chloride resin composition of the present invention, the uracil compound is represented by the following formula (I):

[In formula (I), R ₁ and R ₂ each independently represent a hydrogen atom or an electron donating group,
_R3 represents a hydrogen atom or an amino group. ] is preferable. If the uracil compound is a compound represented by the given formula above, it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition.

Further, in the vinyl chloride resin composition of the present invention, the uracil compound preferably contains 6-amino-1,3-dimethyluracil. By using 6-amino-1,3-dimethyluracil as the uracil compound, it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition.

In the vinyl chloride resin composition of the present invention, the content of the uracil compound is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin. If the content of the uracil compound in the vinyl chloride resin composition is at least the predetermined value, it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition.

Furthermore, in the vinyl chloride resin composition of the present invention, the zinc acetylacetonate content is preferably 0.06 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin. If the content of zinc acetylacetonate in the vinyl chloride resin composition per 100 parts by mass of the vinyl chloride resin is within the predetermined range, it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition. .

Further, in the vinyl chloride resin composition of the present invention, the content of calcium acetylacetonate is preferably 0.05 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin. When the content of calcium acetylacetone in the vinyl chloride resin composition per 100 parts by mass of the vinyl chloride resin is within the above-described predetermined range, it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition. .

Furthermore, the vinyl chloride resin composition of the present invention preferably further contains a fatty acid metal salt other than fatty acid zinc. If a fatty acid metal salt other than fatty acid zinc is further used, it is possible to further suppress variation in color tone due to differences in the molding temperature of the vinyl chloride resin composition.

In the vinyl chloride resin composition of the present invention, the fatty acid metal salt preferably contains fatty acid calcium. If fatty acid calcium is further used as a fatty acid metal salt other than fatty acid zinc, it is possible to further suppress variations in color tone due to differences in molding temperature of the vinyl chloride resin composition.

Furthermore, in the vinyl chloride resin composition of the present invention, the fatty acid metal salt preferably contains a fatty acid metal salt having 6 or more and 22 or less carbon atoms. As the fatty acid metal salt other than the fatty acid zinc, if a metal salt of a fatty acid having a number of carbon atoms within the predetermined range is used, it is possible to further suppress variation in color tone due to differences in molding temperature of the vinyl chloride resin composition.

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

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

An object of the present invention is to advantageously solve the above problems, and the vinyl chloride resin molded article of the present invention is characterized by molding any of the vinyl chloride resin compositions described above. and As described above, the vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition described above has reduced unevenness in color tone and is excellent in appearance, so that it can be favorably used as an automobile interior material.

Further, the vinyl chloride resin molded article of the present invention is preferably used as an automobile instrument panel skin. By using the vinyl chloride resin molded product of the present invention for the skin of an automobile instrument panel, it is possible to produce an automobile instrument panel having a skin with reduced unevenness in color tone and excellent appearance.

Further, an object of the present invention is to advantageously solve the above problems, and a laminate of the present invention comprises a foamed polyurethane molded article and any one of the vinyl chloride resin molded articles described above. Characterized by A laminate comprising a foamed polyurethane molded article and the vinyl chloride resin molded article described above has a vinyl chloride resin molded article portion with reduced unevenness in color tone and excellent appearance.

And it is preferable that the laminated body of this invention is an object for a motor vehicle instrument panel. As described above, by using the laminate of the present invention for an automobile instrument panel, it is possible to reduce color unevenness in the outer skin of the produced automobile instrument panel and improve the appearance.

ADVANTAGE OF THE INVENTION According to this invention, the vinyl-chloride resin composition with which the fluctuation|variation of the color tone by the difference in molding temperature was suppressed can be provided.
Moreover, according to this invention, the vinyl-chloride resin molding formed using the said vinyl-chloride resin composition can be provided.
Furthermore, according to the present invention, it is possible to provide a laminate comprising the vinyl chloride resin molded article.

BEST MODE FOR CARRYING OUT THE INVENTION 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. Then, the vinyl chloride resin molded article formed using the vinyl chloride resin composition of the present invention can be suitably used as an automobile interior material, such as a skin provided for automobile interior parts such as automobile instrument panels and door trims. can be done.
Moreover, the vinyl chloride resin molded article of the present invention can be used, for example, when forming the laminate of the present invention. A laminate formed using the vinyl chloride resin molded article of the present invention can be suitably used as an automobile interior material for manufacturing automobile interior parts such as automobile instrument panels and door trims.

(Vinyl chloride resin composition)
The vinyl chloride resin composition of the present invention comprises (a) a vinyl chloride resin, (b) a plasticizer, (c) a uracil compound, (d) zinc acetylacetonate, and (e) calcium acetylacetonate, ( The ratio of the content of (e) calcium acetylacetonate to the content of d) zinc acetylacetonate is a predetermined value or more.

In addition, the vinyl chloride resin composition of the present invention optionally further contains β-diketones other than zinc acetylacetonate and calcium acetylacetonate (hereinafter sometimes referred to as “(f) other β-diketones”). obtain.
In addition, the vinyl chloride resin composition of the present invention may optionally further contain (g) fatty acid zinc.
Furthermore, the vinyl chloride resin composition of the present invention may optionally further contain (h) a fatty acid metal salt other than fatty acid zinc (hereinafter sometimes referred to as "(h) other fatty acid metal salt").
Further, the vinyl chloride resin composition of the present invention includes the above (a) vinyl chloride resin, (b) plasticizer, (c) uracil compound, (d) zinc acetylacetonate, (e) calcium acetylacetonate, (f) other β - diketones, (g) fatty acid zinc, and (h) other additives other than fatty acid metal salts.

And the vinyl chloride resin composition of the present invention contains at least the above (a) vinyl chloride resin, (b) plasticizer, (c) uracil compound, (d) zinc acetylacetonate, and (e) calcium acetylacetonate, Since the ratio of the content of (e) calcium acetylacetonate to the content of d) zinc acetylacetonate is equal to or greater than a predetermined value, variations in color tone due to differences in molding temperature can be suppressed.

Therefore, when the vinyl chloride resin composition of the present invention is used, unevenness in color tone is reduced, and vinyl chloride resin molding suitable as automotive interior materials such as automotive instrument panel skins and door trim skins with excellent appearance is obtained. you can get a body
In addition, the vinyl chloride resin molded article formed using the vinyl chloride resin composition of the present invention can suppress changes in color tone such as yellowing even when heated at a high temperature of 270° C. or higher. can be done.

For example, from the viewpoint of easily obtaining a vinyl chloride resin molded article that can be favorably used as an automobile interior material, the vinyl chloride resin composition of the present invention is a powder. It is preferably used for molding, more preferably for powder slush molding.

<(a) vinyl chloride resin>
(a) As the vinyl chloride resin, a particulate vinyl chloride resin is usually used. (a) The vinyl chloride resin may contain, for example, one or two or more types of vinyl chloride resin particles, and optionally one or two or more types of vinyl chloride resin fine particles. can be done. Above all, (a) the vinyl chloride resin preferably contains at least vinyl chloride resin particles, and more preferably contains vinyl chloride resin particles and vinyl chloride resin fine particles.
(a) The vinyl chloride resin can be produced by any conventionally known production method such as suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization.
In this 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.

In addition, the (a) vinyl chloride resin may be a homopolymer composed of vinyl chloride monomer units, or vinyl chloride containing vinyl chloride monomer units in an amount of preferably 50% by mass or more, more preferably 70% by mass or more. system copolymers. Specific examples of monomers (comonomers) that can be copolymerized with a vinyl chloride monomer that can constitute a vinyl chloride copolymer include, for example, those described in International Publication No. 2016/098344. things can be used. Moreover, these components may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

<<Vinyl chloride resin particles>>
In a vinyl chloride resin composition, 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 degree of polymerization]
The average polymerization degree of the vinyl chloride resin constituting the vinyl chloride resin particles is preferably 800 or more, more preferably 1000 or more, preferably 5000 or less, and more preferably 3000 or less. It is preferably 2800 or less, and more preferably 2800 or less. If the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is at least the above lower limit, the physical strength of the vinyl chloride resin molded article formed using the vinyl chloride resin composition is sufficiently ensured, for example, tensile Properties, especially tensile elongation, can be improved. Vinyl chloride resin moldings with good tensile elongation are used, for example, as skins of automotive instrument panels with excellent ductility that break as designed without scattering fragments when an airbag is inflated and deployed. It can be suitably used as an automobile interior material. On the other hand, when the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is equal to or less than the above upper limit, the meltability of the vinyl chloride resin composition can be improved.
The "average degree of polymerization" in the present invention can be measured according to JIS K6720-2.

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

[Content ratio]
(a) The content of the vinyl chloride resin particles in the vinyl chloride resin is preferably 70% by mass or more, more preferably 80% by mass or more, and can be 100% by mass. It is preferably 90% by mass or less, more preferably 90% by mass or less. (a) When the content of vinyl chloride resin particles in the vinyl chloride resin is at least the above lower limit, tensile elongation is achieved while sufficiently ensuring the physical strength of the vinyl chloride resin molding formed using the vinyl chloride resin composition. can be improved. On the other hand, (a) when the content of the vinyl chloride resin particles in the vinyl chloride resin is equal to or less than the above upper limit, the powder fluidity of the vinyl chloride resin composition can be improved.

<<Vinyl chloride resin particles>>
In a vinyl chloride resin composition, fine vinyl chloride resin particles usually function as a dusting agent (powder fluidity improver). In addition, it is preferable to manufacture vinyl chloride resin microparticles|fine-particles by the emulsion polymerization method.

[Average degree of polymerization]
The average polymerization degree of the vinyl chloride resin constituting the vinyl chloride resin fine particles is preferably 500 or more, more preferably 700 or more, preferably 2600 or less, and more preferably 2400 or less. If the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles as a dusting agent is at least the above lower limit, the powder flowability of the vinyl chloride resin composition is improved and the vinyl chloride resin composition is used. It is possible to improve the tensile elongation of the vinyl chloride resin molded article formed by. Further, if the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles is equal to or less than the above upper limit, the meltability of the vinyl chloride resin composition is improved, and the chloride formed using the vinyl chloride resin composition is The surface smoothness of the vinyl resin molding can be improved.

[Average particle size]
The average particle size of the vinyl chloride resin fine particles is usually less than 30 μm, preferably 10 μm or less, more preferably 5 μm or less, preferably 0.1 μm or more, and 1 μm or more. is more preferred. 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 improved, for example, without excessively reducing the size as a dusting agent. On the other hand, if the average particle size of the vinyl chloride resin fine particles is equal to or less than the above upper limit, the meltability of the vinyl chloride resin composition is improved, and the surface of the vinyl chloride resin molded article formed using the vinyl chloride resin composition is Smoothness can be improved.

[Content ratio]
(a) The content of vinyl chloride resin fine particles in the vinyl chloride resin may be 0% by mass, but is preferably 5% by mass or more, more preferably 10% by mass or more, It is preferably 30% by mass or less, more preferably 20% by mass or less. (a) If the content of vinyl chloride resin fine particles in the vinyl chloride resin is at least the above lower limit, the powder fluidity of the vinyl chloride resin composition can be improved. On the other hand, if (a) the content of vinyl chloride resin fine particles in the vinyl chloride resin is equal to or less than the above upper limit, the physical strength of the vinyl chloride resin molding formed using the vinyl chloride resin composition can be increased.

<(b) Plasticizer>
The vinyl chloride resin composition of the present invention contains (b) a plasticizer. By including (b) a plasticizer in the vinyl chloride resin composition, the vinyl chloride resin molded article formed can exhibit sufficient flexibility, so that it can be suitably used, for example, as an automobile interior material.

Here, the content of the (b) plasticizer in the vinyl chloride resin composition is preferably 50 parts by mass or more and 60 parts by mass or more with respect to 100 parts by mass of the (a) vinyl chloride resin. is more preferably 70 parts by mass or more, still more preferably 80 parts by mass or more, even more preferably 90 parts by mass or more, preferably 200 parts by mass or less, 180 parts by mass It is more preferably 160 parts by mass or less, even more preferably 140 parts by mass or less, and even more preferably 120 parts by mass or less. If the content of the (b) plasticizer in the vinyl chloride resin composition is at least the above lower limit with respect to 100 parts by mass of the (a) vinyl chloride resin, the flexibility of the vinyl chloride resin molded article to be formed can be increased. can. Furthermore, when the content of the (b) plasticizer in the vinyl chloride resin composition is at least the above lower limit, precipitation (blooming) of the compounded components on the surface of the vinyl chloride resin molded article to be formed can be suppressed. can. That is, the anti-blooming property of the vinyl chloride resin molding can be enhanced. On the other hand, if the content of the (b) plasticizer in the vinyl chloride resin composition is equal to or less than the above upper limit with respect to 100 parts by mass of the (a) vinyl chloride resin, the powder flowability of the vinyl chloride resin composition is improved. be able to.

The (b) plasticizer contained in the vinyl chloride resin composition of the present invention is not particularly limited, but for example, (b1) polyester and (b2) trimellitate ester are preferably used. As the (b) plasticizer, a plasticizer other than (b1) polyester and (b2) trimellitate ester (hereinafter sometimes referred to as "(b3) other plasticizer") may be used. good.

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

(b) The (b1) polyester that can be contained in the plasticizer is not particularly limited. It is possible to use polyesters such as containing polyesters (sebacic acid-based polyesters) and polyesters containing structural units derived from phthalic acid (phthalic acid-based polyesters). In addition, these polyesters may be used individually by 1 type, and may mix and use 2 or more types by arbitrary ratios.
Among them, from the viewpoint of further suppressing color tone fluctuation due to the difference in molding temperature of the vinyl chloride resin composition and further increasing the heat shrinkage resistance of the formed vinyl chloride resin molding, the (b1) polyester is derived from adipic acid. It is preferable to use a polyester containing a structural unit of, and it is particularly preferable to use a polyester containing a structural unit derived from adipic acid and a structural unit derived from 3-methyl-1,5-pentanediol.

Hereinafter, for convenience of explanation, the polyester containing structural units derived from adipic acid and structural units derived from 3-methyl-1,5-pentanediol will be referred to as "polyester A".
Here, the polyester A containing the predetermined structural unit may have a structural unit other than the structural unit derived from adipic acid and the structural unit derived from 3-methyl-1,5-pentanediol. The total amount of acid-derived structural units and 3-methyl-1,5-pentanediol-derived structural units is preferably 50% by mass or more, more preferably 80% by mass or more, of all structural units. Moreover, the polyester A containing the predetermined structural unit preferably has only structural units derived from adipic acid and structural units derived from 3-methyl-1,5-pentanediol as repeating units.

The polyester A containing the predetermined structural unit is not particularly limited and can be obtained by condensation polymerization of adipic acid and 3-methyl-1,5-pentanediol. The condensation polymerization described above can be carried out in the presence of a catalyst. Also, the condensation polymerization described above can be carried out using alcohols and/or monoacids as terminal terminating components. Furthermore, the condensation polymerization of adipic acid and 3-methyl-1,5-pentanediol, and the termination reaction of the obtained condensation polymer and the above-mentioned terminal terminating component may be carried out collectively or separately. It shall be permitted to do so. Further, the product obtained through condensation polymerization and termination reaction may be subjected to post-treatment such as distillation. Known conditions can be employed as reaction conditions for condensation polymerization, such as the amounts of the above-mentioned monomers, catalysts and terminal terminating components.
A commercial product may be used as the polyester A containing the predetermined structural unit.

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

Alcohols that can be used as terminal terminating components include, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, isohexanol, heptanol, isoheptanol, octanol, isooctanol, and 2-ethyl. Hexanol, nonanol, isononanol, decanol, isodecanol, undecanol, isoundecanol, dodecanol, tridecanol, isotridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, cellosolve, carbitol , phenol, nonylphenol, benzyl alcohol and mixtures thereof.
Furthermore, monobasic acids that can be used as end-terminating components include, for example, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, caproic acid, heptanoic acid, caprylic acid, 2-ethylhexylic acid, pelargonic acid, Capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, benzoic acid and mixtures thereof.
Among them, 2-ethylhexanol is preferable as the terminal terminating component.

The polyester A containing the predetermined structural unit preferably has a number average molecular weight of 1000 or more, more preferably 2000 or more, preferably 10000 or less, and more preferably 7000 or less. preferable.
The "number average molecular weight" can be measured by a VPO (vapor pressure osmotic pressure) method.
Moreover, the polyester A containing the predetermined structural unit preferably has an acid value of 1 or less.
Furthermore, it is preferable that the polyester A containing the predetermined structural unit has a hydroxyl value of 30 or less.

Furthermore, the polyester A containing the predetermined structural unit preferably has a viscosity of 500 mPa s or more, more preferably 1000 mPa s or more, and preferably 8000 mPa s or less, and preferably 5000 mPa s. The following are more preferable.
"Viscosity" can be measured at a temperature of 23°C in accordance with JIS Z8803.

(b) The content of (b1) polyester in the plasticizer is preferably 50% by mass or more, more preferably 55% by mass or more, further preferably 60% by mass or more, and 95% by mass. % or less, more preferably 90 mass % or less. If the content of (b1) polyester in the (b) plasticizer is at least the above lower limit, the heat shrinkage resistance of the resulting vinyl chloride resin molding can be further enhanced. On the other hand, when the content ratio of (b1) polyester in (b) plasticizer is equal to or less than the above upper limit, the resulting vinyl chloride resin molding can maintain good flexibility at low temperatures.

The content of the (b1) polyester in the vinyl chloride resin composition is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, relative to 100 parts by mass of the vinyl chloride resin (a). It is more preferably 50 parts by mass or more, still more preferably 60 parts by mass or more, preferably 120 parts by mass or less, and more preferably 110 parts by mass or less. When the content of (b1) polyester in the vinyl chloride resin composition is at least the above lower limit, the heat shrinkage resistance of the resulting vinyl chloride resin molding can be further enhanced. On the other hand, when the content of (b1) polyester in the vinyl chloride resin composition is equal to or less than the above upper limit, the powder fluidity of the vinyl chloride resin composition can be improved.

<<(b2) Trimellitate>>
(b) The plasticizer preferably contains (b2) a trimellitate. If the (b) plasticizer contains (b2) a trimellitate ester, the (b2) trimellitate ester is well absorbed by the (a) vinyl chloride resin, so that the powder flowability of the vinyl chloride resin composition can increase In addition, when the (b) plasticizer contains (b2) a trimellitate ester, the flexibility at low temperatures of the formed vinyl chloride resin molding can be enhanced.

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

Specific examples of the monohydric alcohol include, but are not limited to, 1-hexanol, 1-heptanol, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, and the like. of fatty alcohols. Among these monohydric alcohols, aliphatic alcohols having 6 to 18 carbon atoms are preferable, and linear aliphatic alcohols having 6 to 18 carbon atoms are more preferable.

Among them, the trimellitic acid ester (b2) is preferably a triesterified product obtained by esterifying substantially all the carboxy groups of trimellitic acid with the above-mentioned monohydric alcohol. The alcohol residue moieties in the triester product may be derived from the same alcohol, or may be derived from different alcohols.
The trimellitate (b2) may consist of a single compound or a mixture of different compounds.

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

(b) The content of trimellitate (b2) in the plasticizer is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or less, It is more preferably 45% by mass or less, and even more preferably 40% by mass or less. If the content of (b2) the trimellitate ester in the (b) plasticizer is at least the above lower limit, the powder flowability of the vinyl chloride resin composition is further enhanced, and the low temperature of the vinyl chloride resin molded body to be formed is improved. flexibility can be further enhanced. On the other hand, if the content ratio of (b2) trimellitate ester in (b) plasticizer is equal to or less than the above upper limit, heat shrinkage resistance of the vinyl chloride resin molded article to be formed can be enhanced.

The content of the (b2) trimellitate ester in the vinyl chloride resin composition is preferably 5 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin (a). It is preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less. If the content of (b2) the trimellitate ester in the vinyl chloride resin composition is at least the above lower limit, the powder flowability of the vinyl chloride resin composition is further enhanced, and the low temperature of the formed vinyl chloride resin molding is maintained. flexibility can be further enhanced. On the other hand, if the content of (b2) the trimellitate ester in the vinyl chloride resin composition is equal to or less than the above upper limit, the heat shrinkage resistance of the vinyl chloride resin molded article to be formed can be enhanced.

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

Specific examples of (b3) other plasticizers include, among the plasticizers described in WO 2016/098344, plasticizers other than the above-mentioned (b1) polyester and (b2) trimellitate. be done. Among them, it is preferable to use epoxidized soybean oil from the viewpoint of further increasing the flexibility of the vinyl chloride resin molded article to be formed at low temperatures.

The content of (b3) other plasticizer in (b) plasticizer is not particularly limited, but is preferably 0% by mass or more and 15% by mass or less. If the content ratio of (b3) other plasticizer in (b) plasticizer is within the above range, the flexibility at low temperature after heating of the formed vinyl chloride resin molding can be enhanced.

In addition, the content of the (b3) other plasticizer in the vinyl chloride resin composition is not particularly limited, but is 0 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin (a). can do.
From the viewpoint of further increasing the flexibility of the vinyl chloride resin molded body to be formed at low temperatures, epoxidized vegetable oils such as epoxidized soybean oil are used as (b3) other plasticizers. It is preferable to use 2 parts by mass or more and 7 parts by mass or less based on the mass parts.

<(c) Uracil compound>
The vinyl chloride resin composition of the present invention contains (c) a uracil compound. Since the vinyl chloride resin composition of the present invention contains (c) a uracil compound, it is possible to suppress variations in color tone due to differences in molding temperature.

〔式（Ｉ）中、Ｒ_１およびＲ_２は、それぞれ独立して、水素原子または電子供与基を表し、
Ｒ_３は水素原子またはアミノ基を表す。〕
で示されることが好ましい。 The (c) uracil compound contained in the vinyl chloride resin composition of the present invention is a compound having a uracil skeleton.
From the viewpoint of further suppressing variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition, (c) the uracil compound has the following formula (I):

[In formula (I), R ₁ and R ₂ each independently represent a hydrogen atom or an electron donating group,
_R3 represents a hydrogen atom or an amino group. ]
is preferably represented by

Here, from the viewpoint of further suppressing variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition, in the above formula (I), at least one of R ₁ and R ₂ is preferably an electron donating group, and R More preferably both ₁ and R ₂ are electron donating groups.
In formula (I) above, when R ₁ and/or R ₂ is an electron donating group, the electron donating group is not particularly limited, and examples thereof include an alkyl group, an amino group, and a dialkylamino group. . Among them, the electron donating group is preferably an alkyl group, more preferably an alkyl group having 6 or less carbon atoms, and a methyl group, from the viewpoint of further suppressing variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition. Most preferred.
In formula (I) above, R ₁ and R ₂ may be the same or different.

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

The content of the (c) uracil compound in the vinyl chloride resin composition is preferably 0.10 parts by mass or more, more preferably 0.15 parts by mass, with respect to 100 parts by mass of the (a) vinyl chloride resin. It is more preferably 0.20 parts by mass or more, still more preferably 0.25 parts by mass or more, preferably 3.00 parts by mass or less, and 2.00 parts by mass. parts by mass or less, more preferably 1.60 parts by mass or less, even more preferably 0.80 parts by mass or less, and even more preferably 0.40 parts by mass or less. When the content of the (c) uracil compound in the vinyl chloride resin composition is at least the above lower limit, it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition. On the other hand, if the content of (c) the uracil compound in the vinyl chloride resin composition is equal to or less than the above upper limit, sufficiently high tensile properties (especially tensile elongation) and blooming resistance of the formed vinyl chloride resin molding are ensured. can do.

<(d) zinc acetylacetone>
The vinyl chloride resin composition of the present invention contains (d) zinc acetylacetonate. By containing (d) zinc acetylacetonate, the vinyl chloride resin composition of the present invention can suppress variation in color tone due to a difference in molding temperature.
Note that (d) zinc acetylacetonate is a metal complex formed by binding a conjugate base of acetylacetone to a zinc ion.

The content of (d) zinc acetylacetonate in the vinyl chloride resin composition is preferably 0.06 parts by mass or more, and is preferably 0.10 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin (a). more preferably 0.12 parts by mass or more, still more preferably 0.15 parts by mass or more, preferably 2.0 parts by mass or less, and 1.0 parts by mass or less is more preferably 0.80 parts by mass or less, even more preferably 0.50 parts by mass or less, and even more preferably 0.30 parts by mass or less. If the content of (d) zinc acetylacetonate in the vinyl chloride resin composition is at least the above lower limit, it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition. On the other hand, if the content of (d) zinc acetylacetonate in the vinyl chloride resin composition is equal to or less than the above upper limit, the surface of the formed vinyl chloride resin molding will have brown spots due to the so-called zinc burning phenomenon. It is possible to suppress the occurrence of this, and to ensure sufficiently high tensile properties (especially tensile elongation) and blooming resistance of the vinyl chloride resin molded product.

The content of (d) zinc acetylacetonate in the vinyl chloride resin composition is preferably 0.2 times or more, and preferably 0.3 times or more, the content of (c) the uracil compound on a mass basis. is more preferably 0.4 times or more, more preferably 0.5 times or more, even more preferably 0.6 times or more, and 3.0 times or less It is preferably 2.5 times or less, more preferably 2.0 times or less, even more preferably 1.5 times or less, and 1.0 times or less. Even more preferable. If the ratio of the content of (d) zinc acetylacetonate to the content of (c) uracil compound in the vinyl chloride resin composition is equal to or higher than the above lower limit, the variation in color tone due to the difference in molding temperature of the vinyl chloride resin composition is further reduced. can be suppressed. On the other hand, if the ratio of the content of (d) zinc acetylacetonate to the content of (c) uracil compound in the vinyl chloride resin composition is equal to or less than the above upper limit, brown spots appear on the surface of the vinyl chloride resin molded article to be formed. In addition, the tensile properties (especially tensile elongation) and blooming resistance of the vinyl chloride resin molding can be sufficiently high.

<(e) calcium acetylacetone>
(e) Calcium acetylacetone is a metal complex formed by combining the conjugate base of acetylacetone with calcium ions.
The vinyl chloride resin composition of the present invention contains (e) calcium acetylacetonate in a content that is at least a predetermined multiple of the content of (d) zinc acetylacetonate. The vinyl chloride resin composition of the present invention contains (e) calcium acetylacetonate in a content equal to or greater than a predetermined multiple of the content of (d) zinc acetylacetonate, thereby suppressing variations in color tone due to differences in molding temperature. be able to.

Here, the content of (e) calcium acetylacetonate in the vinyl chloride resin composition must be at least 0.8 times the content of (d) zinc acetylacetonate on a mass basis. It is preferably 0 times or more, more preferably 1.2 times or more, still more preferably 1.5 times or more, even more preferably 1.8 times or more, and 2.0 times or more. More preferably, it is still more preferably 2.3 times or more, preferably 12.0 times or less, more preferably 8.0 times or less, and 6.0 times or less It is more preferably 4.0 times or less, and even more preferably 3.0 times or less. If the ratio of the content of (e) calcium acetylacetonate to the content of (d) zinc acetylacetonate in the vinyl chloride resin composition is at least the above lower limit, the variation in color tone due to the difference in the molding temperature of the vinyl chloride resin composition is sufficiently suppressed. can be suppressed to On the other hand, if the ratio of the content of (e) calcium acetylacetonate to the content of (d) zinc acetylacetonate in the vinyl chloride resin composition is equal to or less than the above upper limit, the tensile properties (especially tensile elongation) and blooming resistance can be sufficiently high.
From the viewpoint of further suppressing variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition, the content of (e) calcium acetylacetonate in the vinyl chloride resin composition should be the same as that of (d) zinc acetylacetonate on a mass basis. It may be 3.0 times or more or 4.0 times or more of the content.

In addition, the content of (e) calcium acetylacetone in the vinyl chloride resin composition is preferably 0.05 parts by mass or more, and 0.12 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (a). 4. more preferably 0.20 parts by mass or more, still more preferably 0.24 parts by mass or more, even more preferably 0.30 parts by mass or more; It is preferably 0 parts by mass or less, more preferably 2.0 parts by mass or less, even more preferably 1.00 parts by mass or less, and even more preferably 0.80 parts by mass or less. It is more preferably 0.55 parts by mass or less. When the content of (e) calcium acetylacetone in the vinyl chloride resin composition is at least the above lower limit, it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition. On the other hand, if the content of (e) calcium acetylacetone in the vinyl chloride resin composition is equal to or less than the above upper limit, the tensile properties (especially tensile elongation) and blooming resistance of the formed vinyl chloride resin molding are sufficiently ensured. be able to.
From the viewpoint of further suppressing variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition, the content of (e) calcium acetylacetone in the vinyl chloride resin composition is set to 100 parts by mass of the above (a) vinyl chloride resin. It may be 0.50 parts by mass or more, 0.60 parts by mass or more, or 0.70 parts by mass or more.

Furthermore, the content of (e) calcium acetylacetonate in the vinyl chloride resin composition is preferably at least 0.6 times, and at least 0.8 times, the content of the above (c) uracil compound on a mass basis. is more preferably 1.0 times or more, more preferably 1.2 times or more, even more preferably 1.5 times or more, and 8.0 times or less It is preferably 6.0 times or less, more preferably 4.0 times or less, even more preferably 3.0 times or less, and 2.0 times or less. Even more preferable. If the ratio of the content of (e) calcium acetylacetonate to the content of (c) uracil compound in the vinyl chloride resin composition is equal to or higher than the above lower limit, the variation in color tone due to the difference in molding temperature of the vinyl chloride resin composition is further reduced. can be suppressed. On the other hand, if the ratio of the content of (e) calcium acetylacetonate to the content of (c) uracil compound in the vinyl chloride resin composition is equal to or less than the above upper limit, the tensile properties (especially tensile elongation) and blooming resistance can be sufficiently high.
From the viewpoint of further suppressing variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition, the content of (e) calcium acetylacetonate in the vinyl chloride resin composition is adjusted to the content of (c) uracil compound on a mass basis. It may be 2.0 times or more or 3.0 times or more of the content.

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

(f) Other β-diketones include, for example, acetylacetone; metal salts of acetylacetone such as magnesium acetylacetone, lithium acetylacetone, aluminum acetylacetone, and nickel acetylacetone; and β-diketone compounds other than acetylacetone and metal salts thereof; mentioned. A metal salt of a β-diketone compound such as acetylacetone is a metal complex formed by binding a conjugate base of a β-diketone compound such as acetylacetone to a metal ion.

(f) Other β-diketones include benzoyl groups such as dibenzoylmethane, stearoylbenzoylmethane, and palmitoylbenzoylmethane, from the viewpoint of further suppressing variations in color tone due to differences in molding temperature of the vinyl chloride resin composition. and more preferably stearoylbenzoylmethane.

The content of (f) other β-diketones in the vinyl chloride resin composition is preferably 0.40 parts by mass or more, preferably 0.50 parts by mass, based on 100 parts by mass of the vinyl chloride resin (a). It is more preferably at least 0.60 parts by mass, preferably at most 2.00 parts by mass, and more preferably at most 1.50 parts by mass. It is more preferably 20 parts by mass or less. When the content of (f) other β-diketones in the vinyl chloride resin composition is at least the above lower limit, it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition. On the other hand, if the content of (f) other β-diketones in the vinyl chloride resin composition is equal to or less than the above upper limit, the tensile properties (especially tensile elongation) and blooming resistance of the vinyl chloride resin molded product to be formed are improved. can be sufficiently secured.

In addition, the content of (f) other β-diketones in the vinyl chloride resin composition is preferably 1.0 times or more the content of the above (c) uracil compound on a mass basis. 15. It is more preferably 5 times or more, still more preferably 2.0 times or more, still more preferably 2.5 times or more, and even more preferably 3.0 times or more. It is preferably 0 times or less, more preferably 10.0 times or less, still more preferably 8.0 times or less, even more preferably 6.0 times or less, and 5.0 times or less. is even more preferable. If the ratio of the content of (f) other β-diketones to the content of (c) uracil compound in the vinyl chloride resin composition is equal to or higher than the above lower limit, the color tone due to the difference in the molding temperature of the vinyl chloride resin composition. can be further suppressed. On the other hand, if the ratio of the content of (f) other β-diketones to the content of (c) uracil compound in the vinyl chloride resin composition is equal to or less than the above upper limit, the tensile strength of the vinyl chloride resin molded body to be formed Sufficiently high properties (especially tensile elongation) and blooming resistance can be ensured.

In addition, the content of (f) other β-diketones in the vinyl chloride resin composition is preferably 1.0 times or more of the content of (d) zinc acetylacetonate on a mass basis. 20.5 times or more is more preferable, 2.0 times or more is still more preferable, 3.0 times or more is still more preferable, and 4.0 times or more is even more preferable. It is preferably 0 times or less, more preferably 15.0 times or less, still more preferably 10.0 times or less, even more preferably 8.0 times or less, and 6.0 times or less. is even more preferable. If the ratio of the content of (f) other β-diketones to the content of (d) zinc acetylacetone in the vinyl chloride resin composition is equal to or higher than the above lower limit, color tone due to the difference in molding temperature of the vinyl chloride resin composition. can be further suppressed. On the other hand, if the ratio of the content of (f) other β-diketones to the content of (d) zinc acetylacetone in the vinyl chloride resin composition is equal to or less than the above upper limit, the tensile strength of the vinyl chloride resin molded body to be formed Sufficiently high properties (especially tensile elongation) and blooming resistance can be ensured.

<(g) fatty acid zinc>
The vinyl chloride resin composition of the present invention preferably further contains (g) fatty acid zinc. When the vinyl chloride resin composition of the present invention further contains (g) fatty acid zinc, it is possible to further suppress variation in color tone due to differences in molding temperature.

The number of carbon atoms in the fatty acid of (g) fatty acid zinc is not particularly limited, but is preferably 6 or more, more preferably 8 or more, more preferably 10 or more, and preferably 22 or less. , 21 or less, and even more preferably 20 or less. If a zinc salt of a fatty acid having a number of carbon atoms within the predetermined range is used as (g) fatty acid zinc, it is possible to further suppress variations in color tone due to differences in molding temperature of the vinyl chloride resin composition.
From the viewpoint of further suppressing variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition, it is particularly preferable to use zinc stearate as (g) fatty acid zinc.
In addition, as (g) fatty acid zinc, one type may be used alone, or two or more types may be mixed and used at an arbitrary ratio.

Here, the content of (g) fatty acid zinc in the vinyl chloride resin composition is preferably 0.05 parts by mass or more, and preferably 0.10 parts by mass, relative to 100 parts by mass of the vinyl chloride resin (a). parts by mass or more, more preferably 0.15 parts by mass or more, preferably 4.0 parts by mass or less, more preferably 3.0 parts by mass or less, and 2.0 It is more preferably not more than 1.0 part by mass, and even more preferably not more than 1.0 part by mass. When the content of (g) fatty acid zinc in the vinyl chloride resin composition is at least the above lower limit, it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition. On the other hand, if the content of (g) fatty acid zinc in the vinyl chloride resin composition is equal to or less than the above upper limit, it is possible to suppress the occurrence of brown spots on the surface of the vinyl chloride resin molded article to be formed. The tensile properties (especially tensile elongation) and blooming resistance of the vinyl chloride resin molding can be sufficiently ensured.

In addition, the content of (g) fatty acid zinc in the vinyl chloride resin composition is preferably 0.2 times or more, and preferably 0.3 times or more, the content of (c) uracil compound on a mass basis. is more preferably 0.4 times or more, more preferably 0.5 times or more, even more preferably 0.6 times or more, and 3 times or less , more preferably 2 times or less, still more preferably 1.5 times or less, even more preferably 1.2 times or less, and even more preferably 1.0 times or less. If the ratio of the content of (g) fatty acid zinc to the content of (c) uracil compound in the vinyl chloride resin composition is at least the above lower limit, the variation in color tone due to the difference in molding temperature of the vinyl chloride resin composition is further suppressed. can be suppressed. On the other hand, if the ratio of the content of (g) fatty acid zinc to the content of (c) uracil compound in the vinyl chloride resin composition is equal to or less than the above upper limit, brown spots will appear on the surface of the vinyl chloride resin molded article to be formed. In addition, the tensile properties (especially tensile elongation) and blooming resistance of the vinyl chloride resin molding can be sufficiently high.

Furthermore, the content of (g) zinc fatty acid in the vinyl chloride resin composition is preferably 0.2 times or more, and preferably 0.3 times or more, the content of (d) zinc acetylacetonate on a mass basis. is more preferably 0.4 times or more, more preferably 0.6 times or more, even more preferably 0.8 times or more, and 4.0 times or less It is preferably 3.0 times or less, more preferably 2.0 times or less, even more preferably 1.5 times or less, and 1.2 times or less. Even more preferable. If the ratio of the content of (g) fatty acid zinc to the content of (d) zinc acetylacetone in the vinyl chloride resin composition is equal to or higher than the above lower limit, the variation in color tone due to the difference in molding temperature of the vinyl chloride resin composition is further suppressed. can be suppressed. On the other hand, if the ratio of the content of (g) fatty acid zinc to the content of (d) zinc acetylacetone in the vinyl chloride resin composition is equal to or less than the above upper limit, brown spots will appear on the surface of the vinyl chloride resin molded article to be formed. In addition, the tensile properties (especially tensile elongation) and blooming resistance of the vinyl chloride resin molding can be sufficiently high.

<(h) Other fatty acid metal salts>
The vinyl chloride resin composition of the present invention may further contain (h) a fatty acid metal salt other than (g) fatty acid zinc. (h) Other fatty acid metal salts can suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition, and suppress the formation of brown spots on the surface of the formed vinyl chloride resin molded product. It is a component that can

Therefore, from the viewpoint of further suppressing color tone fluctuations due to differences in the molding temperature of the vinyl chloride resin composition and suppressing the occurrence of brown spots on the surface of the vinyl chloride resin molded article to be formed, the present invention is effective. The vinyl chloride resin composition preferably contains (h) other fatty acid metal salt.

Here, the reason why (h) the other fatty acid metal salt can suppress the occurrence of brown spots on the surface of the vinyl chloride resin molding to be formed is not clear, but is presumed as follows. . During molding of the vinyl chloride resin composition, (a) hydrogen chloride generated by thermal decomposition of the vinyl chloride resin reacts with (d) zinc acetylacetonate to form zinc chloride. Zinc chloride can cause brown spots on the surface of the vinyl chloride resin molding to be formed due to the so-called zinc burning phenomenon. On the other hand, (h) the reaction of other fatty acid metal salts with zinc chloride is thought to be able to suppress the occurrence of brown spots due to the zinc burning phenomenon.

When the vinyl chloride resin composition of the present invention contains (h) other fatty acid metal salt, the content of (h) other fatty acid metal salt in the vinyl chloride resin composition is 100 mass of the above (a) vinyl chloride resin. It is preferably 0.05 parts by mass or more, more preferably 0.10 parts by mass or more, still more preferably 0.20 parts by mass or more, and 0.30 parts by mass or more. more preferably 0.40 parts by mass or more, preferably 4.0 parts by mass or less, more preferably 2.0 parts by mass or less, 1.00 parts by mass is more preferably 0.60 parts by mass or less. When the content of (h) other fatty acid metal salt in the vinyl chloride resin composition is at least the above lower limit, the variation in color tone due to the difference in the molding temperature of the vinyl chloride resin composition is further suppressed, and the chloride formed is suppressed. It is possible to further suppress the occurrence of brown spots on the surface of the vinyl resin molding. On the other hand, if the content of (h) other fatty acid metal salt in the vinyl chloride resin composition is equal to or less than the above upper limit, the tensile properties (especially tensile elongation) and blooming resistance of the formed vinyl chloride resin molding are sufficiently improved. can be secured at a high level.

From the viewpoint of ensuring a sufficiently high anti-blooming property of the vinyl chloride resin molded article to be formed, the vinyl chloride resin composition of the present invention preferably does not contain (h) other fatty acid metal salts.

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

(h) Other metals of the fatty acid metal salt are not particularly limited as long as they are other than zinc, and examples thereof include calcium and barium. From the viewpoint of further suppressing the variation in color tone due to the difference in the molding temperature of the vinyl chloride resin composition and further suppressing the occurrence of brown spots on the surface of the vinyl chloride resin molded article to be formed, (h ) As other fatty acid metal salts, fatty acid calcium is preferably used.

As the (h) other fatty acid metal salt, one kind may be used alone, or two or more kinds may be mixed and used at an arbitrary ratio.

The content of (h) other fatty acid metal salt in the vinyl chloride resin composition is, on a mass basis, preferably 0.8 times or more, and preferably 1.0 times, the content of (c) the uracil compound. more preferably 1.2 times or more, still more preferably 1.4 times or more, even more preferably 1.6 times or more, and 10.0 times or less is preferably 8.0 times or less, more preferably 6.0 times or less, even more preferably 4.0 times or less, and 3.0 times or less is even more preferred. If the ratio of the content of (h) the other fatty acid metal salt to the content of the (c) uracil compound in the vinyl chloride resin composition is equal to or higher than the above lower limit, the difference in color tone due to the difference in the molding temperature of the vinyl chloride resin composition will occur. It is possible to further suppress the variation and to further suppress the occurrence of brown spots on the surface of the vinyl chloride resin molding to be formed. On the other hand, if the ratio of the content of (h) other fatty acid metal salt to the content of (c) uracil compound in the vinyl chloride resin composition is equal to or less than the above upper limit, the tensile properties of the vinyl chloride resin molded body to be formed (especially tensile elongation) and blooming resistance can be sufficiently high.

The content of (h) other fatty acid metal salt in the vinyl chloride resin composition is preferably at least 0.8 times, and preferably 1.2 times, the content of (d) zinc acetylacetone on a mass basis. more preferably 1.5 times or more, still more preferably 1.8 times or more, even more preferably 2.0 times or more, and 12.0 times or less is preferably 8.0 times or less, more preferably 6.0 times or less, even more preferably 4.0 times or less, and 3.0 times or less is even more preferred. If the ratio of the content of (h) other fatty acid metal salt to the content of (d) zinc acetylacetonate in the vinyl chloride resin composition is equal to or higher than the above lower limit, the difference in color tone due to the difference in the molding temperature of the vinyl chloride resin composition will occur. It is possible to further suppress the variation and to further suppress the occurrence of brown spots on the surface of the vinyl chloride resin molding to be formed. On the other hand, if the ratio of the content of (h) other fatty acid metal salt to the content of (d) zinc acetylacetone in the vinyl chloride resin composition is equal to or less than the above upper limit, the tensile properties of the vinyl chloride resin molded body to be formed (especially tensile elongation) and blooming resistance can be sufficiently high.

The mass ratio of (h) other fatty acid metal salt to (g) fatty acid zinc ((h) other fatty acid metal salt/(g) fatty acid zinc) in the vinyl chloride resin composition is 1/1 or more. is preferably 3/2 or more, more preferably 2/1 or more, preferably 20/1 or less, more preferably 15/1 or less, 10/1 More preferably: If the mass ratio of (h) other fatty acid metal salt to (g) fatty acid zinc ((h) other fatty acid metal salt/(g) fatty acid zinc) in the vinyl chloride resin composition is within the predetermined range In addition, it is possible to further suppress variations in color tone due to differences in the molding temperature of the vinyl chloride resin composition, and to further suppress the occurrence of brown spots on the surface of the vinyl chloride resin molded article to be formed.

<Additive>
The vinyl chloride resin composition of the present invention may further contain various additives in addition to the components described above. Additives include, but are not limited to, lubricants; stabilizers such as perchloric acid-treated hydrotalcite and zeolite; release agents; dusting agents other than the vinyl chloride resin fine particles; perchloric acid compounds other than perchloric acid-treated hydrotalcite (sodium perchlorate, potassium perchlorate, etc.); antioxidants; fungicides; flame retardants; antistatic agents; fillers; agent; pigment; and the like.

As the above-mentioned additives that the vinyl chloride resin composition of the present invention may contain, for example, those described in International Publication No. 2016/098344 can be used, and the preferred content thereof is also International Publication No. 2016/ It can be the same as described in No. 098344.

Moreover, the vinyl chloride resin composition of the present invention may contain silicone oil.
Examples of the silicone oil that can be contained in the vinyl chloride resin composition include the silicone oil described in JP-A-2018-35304.
The content of the silicone oil in the vinyl chloride resin composition is not particularly limited, but is preferably 0.1 parts by mass or more, and 0.2 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (a). It is more preferably at least 1 part by mass, preferably at most 1 part by mass, and more preferably at most 0.8 part by mass.

<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 above (a) vinyl chloride resin, (b) plasticizer, (c) uracil compound, (d) zinc acetylacetonate, and (e) calcium acetylacetonate are further blended as necessary (f ) other β-diketones, (g) fatty acid zinc, (h) other fatty acid metal salts and various additives are not particularly limited. including) are mixed by dry blending, and then a dusting agent is added and mixed. Here, it is preferable to use a Henschel mixer for 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.

<Application of vinyl chloride resin composition>
The obtained vinyl chloride resin composition can be suitably used for powder molding, and can be suitably used for powder slush molding.

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

<Method for Forming Vinyl Chloride Resin Mold>
Here, when forming a vinyl chloride resin molded article by powder slush molding, the mold temperature during powder slush molding is not particularly limited, and is preferably 200° C. or higher, more preferably 220° C. or higher. It is more preferably 300° C. or lower, and more preferably 280° C. or lower.
For example, even if there is a temperature distribution in the mold during powder slush molding, since the vinyl chloride resin composition of the present invention is used for molding, the vinyl chloride resin molding of the present invention is formed. The unevenness of color tone is reduced on the body.

And when manufacturing a vinyl-chloride resin molded object, it can use the following method, for example, without being specifically limited. That is, the vinyl chloride resin composition of the present invention is sprinkled on a mold within the above temperature range, left to stand for 5 seconds or more and 30 seconds or less, and then the excess vinyl chloride resin composition is shaken off. , Leave for 30 seconds or more and 3 minutes or less. After that, the mold is cooled to 10° C. or higher and 60° C. or lower, and the obtained vinyl chloride resin molded article of the present invention is removed from the mold. Then, a sheet-like molded body having the shape of the mold is obtained.

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

Here, the method for laminating the foamed polyurethane molded article and the vinyl chloride resin molded article is not particularly limited, and for example, the following method can be used. That is, (1) a method in which a foamed polyurethane molded article and a vinyl chloride resin molded article are separately prepared and then bonded together by heat sealing, thermal adhesion, or using a known adhesive; (2) vinyl chloride; Isocyanates and polyols, which are the raw materials of the foamed polyurethane molded article, are reacted on the resin molded article to polymerize them, and at the same time, the polyurethane is foamed by a known method to obtain a foamed polyurethane on the vinyl chloride resin molded article. a method of directly forming a molded body; and the like. Among them, the latter method (2) is preferable in that the process is simple and that the vinyl chloride resin molded article and the foamed polyurethane molded article are easily adhered firmly even when laminates of various shapes are obtained. is.

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

<Changes in color due to differences in molding temperature>
The vinyl chloride resin composition obtained in each example and comparative example was sprinkled on a textured mold heated to a temperature of 230° C., allowed to stand for an arbitrary time to melt, and then the excess vinyl chloride resin composition was shaken off. Dropped. After that, the textured mold sprinkled with the vinyl chloride resin composition was left to stand in an oven set to a temperature of 200 ° C., and when 60 seconds had passed since the standing, the textured mold was cooled with cooling water. . When the mold temperature was cooled to 40° C., the vinyl chloride resin molded sheet of 150 mm×200 mm×1 mm as the vinyl chloride resin molded product was removed from the mold.
Further, molding was performed in the same manner as above except that the temperature of the mold (that is, the molding temperature) was raised from 230°C to 270°C.
Furthermore, molding was performed in the same manner as above except that the temperature of the mold (that is, the molding temperature) was raised from 230°C to 280°C.
The color tone of the vinyl chloride resin molded sheets obtained by molding at respective molding temperatures of 230°C, 270°C and 280°C was measured with a spectrophotometer ("CM-700d" manufactured by Konica Minolta). In addition, for the vinyl chloride resin molded sheet obtained by molding at each molding temperature, a total of 9 points of color measurement was performed on the center points of each of the squares obtained by dividing the textured surface of the vinyl chloride resin molded sheet into 9, and b ^* The average value of the values of
Then, by subtracting the average b ^* value at a molding temperature of 230°C from the average b ^* value at a molding temperature of 270°C, the Δb ^* value when the molding temperature difference is 230°C to 270°C was calculated.
Similarly, by subtracting the average b ^* value at a molding temperature of 230°C from the average b ^* value at a molding temperature of 280°C, the Δb The value of ^* was calculated.
Incidentally, the smaller the value of Δb ^* , the more the vinyl chloride resin composition is inhibited from changing the color tone due to the difference in the molding temperature.

(Manufacturing example)
Polyesters used in Examples and Comparative Examples were prepared as follows.
<Polyester A>
Adipic acid as a polyhydric carboxylic acid, 3-methyl-1,5-pentanediol as a polyhydric alcohol, and 2-ethylhexanol as a stopper (terminal terminating component) were charged into a reaction vessel, and tetraisopropyl titanate was used as a catalyst. In addition, a solvent was added as appropriate, and the temperature was raised while stirring. The water produced as a by-product is removed under normal pressure and reduced pressure, and the temperature is finally raised to 220-230°C to complete the dehydration condensation reaction. Average molecular weight: 5300, acid value: 0.32, hydroxyl value: 12.7).

(Example 1)
<Preparation of vinyl chloride resin composition>
Of the ingredients shown in Table 1, the ingredients excluding the plasticizer (trimellitic acid ester, polyester A, and epoxidized soybean oil) and the vinyl chloride resin fine particles as a dusting agent were placed in a Henschel mixer and mixed. Then, when the temperature of the mixture rises to 80° C., all of the plasticizer is added and dried up (the plasticizer is absorbed by the vinyl chloride resin particles, and the mixture becomes smooth. ). Thereafter, when the dried 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.
Using the vinyl chloride resin composition thus obtained, variation in color tone due to differences in molding temperature was evaluated. Table 1 shows the results.

(Examples 2 to 8, Comparative Examples 1 to 6)
A vinyl chloride resin composition was produced in the same manner as in Example 1, except that the formulation was changed as shown in Table 1. Then, using the obtained vinyl chloride resin composition, variation in color tone due to difference in molding temperature was evaluated. Table 1 shows the results.

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

From Table 1, it can be seen that the vinyl chloride resin compositions of Examples 1 to 8 containing a uracil compound, zinc acetylacetonate, and calcium acetylacetonate, wherein the ratio of the content of calcium acetylacetonate to the content of zinc acetylacetonate is equal to or greater than a predetermined value, It can be seen that variations in color tone due to differences in molding temperature are sufficiently suppressed.
On the other hand, it can be seen that the vinyl chloride resin composition of Comparative Example 1, which does not contain any of the uracil compound, zinc acetylacetonate, and calcium acetylacetonate, cannot sufficiently suppress the variation in color tone due to the difference in molding temperature.
It is also found that the vinyl chloride resin composition of Comparative Example 2, which contains a uracil compound but does not contain zinc acetylacetonate or calcium acetylacetonate, cannot sufficiently suppress the variation in color tone due to the difference in molding temperature.
Furthermore, it can be seen that even in the vinyl chloride resin composition of Comparative Example 3 which contains a uracil compound and zinc acetylacetonate but does not contain calcium acetylacetonate, it is not possible to sufficiently suppress variations in color tone due to differences in molding temperature.
It is also found that the vinyl chloride resin composition of Comparative Example 4, which contains a uracil compound and calcium acetylacetonate but does not contain zinc acetylacetonate, cannot sufficiently suppress variations in color tone due to differences in molding temperature.
Furthermore, the vinyl chloride resin composition of Comparative Example 5, which contains zinc acetylacetonate and calcium acetylacetonate and has a ratio of the content of calcium acetylacetonate to the content of zinc acetylacetonate equal to or higher than a predetermined value, does not contain a uracil compound, and the molding temperature It can be seen that the variation in color tone due to the difference in the thickness cannot be sufficiently suppressed.
Also, in the vinyl chloride resin composition of Comparative Example 6, which contains a uracil compound, zinc acetylacetonate, and calcium acetylacetonate, but the ratio of the content of calcium acetylacetonate to the content of zinc acetylacetonate is less than a predetermined value, the molding temperature It can be seen that the variation in color tone due to the difference in the thickness cannot be sufficiently suppressed.

ADVANTAGE OF THE INVENTION According to this invention, the vinyl-chloride resin composition with which the fluctuation|variation of the color tone by the difference in molding temperature was suppressed can be provided.
Moreover, according to this invention, the vinyl-chloride resin molding formed using the said vinyl-chloride resin composition can be provided.
Furthermore, according to the present invention, it is possible to provide a laminate comprising the vinyl chloride resin molded article.

Claims (15)

vinyl chloride resin;
a plasticizer;
a uracil compound;
zinc acetylacetonate; and
calcium acetylacetonate; and
A vinyl chloride resin composition, wherein the content of calcium acetylacetonate is 0.8 times or more the content of zinc acetylacetonate. The uracil compound has the following formula (I):

[In formula (I), R ₁ and R ₂ each independently represent a hydrogen atom or an electron donating group,
_R3 represents a hydrogen atom or an amino group. ]
The vinyl chloride resin composition according to claim 1, represented by. 3. The vinyl chloride resin composition according to claim 1, wherein the uracil compound contains 6-amino-1,3-dimethyluracil. The vinyl chloride resin composition according to any one of claims 1 to 3, wherein the content of said uracil compound is 0.1 parts by mass or more with respect to 100 parts by mass of said vinyl chloride resin. The vinyl chloride resin composition according to any one of claims 1 to 4, wherein the zinc acetylacetone content is 0.06 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin. The vinyl chloride resin composition according to any one of claims 1 to 5, wherein the content of calcium acetylacetone is 0.05 parts by mass or more per 100 parts by mass of the vinyl chloride resin. The vinyl chloride resin composition according to any one of claims 1 to 6, further comprising a fatty acid metal salt other than fatty acid zinc. The vinyl chloride resin composition according to claim 7, wherein the fatty acid metal salt contains fatty acid calcium. The vinyl chloride resin composition according to claim 7 or 8, wherein the fatty acid metal salt contains a metal salt of a fatty acid having from 6 to 22 carbon atoms. The vinyl chloride resin composition according to any one of claims 1 to 9, which is used for powder molding. The vinyl chloride resin composition according to any one of claims 1 to 10, which is used for powder slush molding. A vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition according to any one of claims 1 to 11. 13. The vinyl chloride resin molding according to claim 12, which is used as an automobile instrument panel skin. A laminate comprising a foamed polyurethane molded article and the vinyl chloride resin molded article according to claim 12 or 13. 15. The laminate according to claim 14, which is for automotive instrument panels.