JP2024033127A - Agent for imparting amine resistance to vinyl chloride resin - Google Patents

Abstract

To provide, e.g., an agent for imparting amine resistance to a vinyl chloride resin that can inhibit discoloration of the vinyl chloride resin due to amine and also can impart heat aging resistance.SOLUTION: An agent for imparting amine resistance to a vinyl chloride resin contains one or more sulfonyl imide compounds represented by the general formula (1) in the figure. In the formula, R1 and R2 are each independently F or a perfluoroalkyl group, and M1 is Li, Na, K, Mg, Ca, or the like.SELECTED DRAWING: None

Description

The present invention relates to an amine resistance imparting agent for vinyl chloride resins (hereinafter also referred to as "amine resistance imparting agent"), which can suppress discoloration of vinyl chloride resins due to amines and also impart heat aging resistance. Amine resistance imparting agent for vinyl chloride resin, stabilizer composition for vinyl chloride resin using the same, vinyl chloride resin composition, vinyl chloride resin molded article (hereinafter referred to as "stabilizer composition", respectively) The present invention relates to a method for suppressing discoloration of a resin composition, a laminate, an automobile interior material, and a vinyl chloride resin.

Vinyl chloride resin has excellent properties such as flame retardancy, chemical resistance, mechanical stability, heat resistance, and weather resistance, and is inexpensive, so it is widely used as a general-purpose resin material with high utility value. It is widely used as a skin material for automobile interior materials.

Various interior materials are used inside automobiles to improve riding comfort. Automotive interior materials usually consist of a skin layer that provides a soft feel (texture), a sense of luxury, and aesthetic design, and a base layer that maintains the structure. Furthermore, the skin layer is often lined with a foam layer made of urethane or the like to further enhance the soft feel.

For the skin layer, vinyl chloride resin, thermoplastic elastomer, polyolefin such as polyethylene, etc. are used. Among these, vinyl chloride resin is widely used because it can produce a variety of textures from semi-hard to soft depending on the amount of plasticizer added, is easy to mold, and has excellent design. There is.

Interior materials that use this vinyl chloride resin are made of polyvinyl chloride resin molded products lined with urethane resin, especially foamed polyurethane (also referred to as "polyurethane foam molded products") to give a soft feel. Laminated products with foamed polyurethane are often used.

However, when vinyl chloride resin is used as a laminate with foamed polyurethane, the amine compound used as a catalyst during the formation of the polyurethane foam molded product migrates to the vinyl chloride resin molded product, resulting in the molding of the vinyl chloride resin. There was a problem with the body becoming discolored.

On the other hand, for example, in Patent Documents 1 and 2, in order to prevent discoloration of vinyl chloride resin moldings caused by this amine compound, perchlorine such as sodium perchlorate, barium perchlorate, perchloric acid-treated hydrotalcite, etc. A method of blending an acid-based compound into a vinyl chloride-based resin composition has been proposed. Further, Patent Document 3 proposes a chlorine-containing resin composition to which an organic tin compound and a trifluoromethylsulfonyl compound are added.

Furthermore, when used as an interior material for automobiles, it may be exposed to relatively high temperatures.In particular, when exposed to the blazing sun in midsummer, the temperature can rise to nearly 100 degrees Celsius, causing discoloration. There was a problem in that it caused disadvantages (heat aging).

Japanese Patent Application Publication No. 5-17648 Japanese Unexamined Patent Publication No. 7-173354 Japanese Patent Application Publication No. 2006-152283

However, the method of blending a perchloric acid compound into a vinyl chloride resin composition as proposed in Patent Documents 1 and 2 cannot be said to have a sufficient discoloration suppressing effect. In addition, perchlorates, which are also used in gunpowder and explosives, are classified as Class 1 (oxidizing solids) dangerous substances under the Fire Service Act, and there is always a risk of explosion or fire caused by friction or impact. ing. Furthermore, water pollution from perchlorate has been reported in at least 20 states in the United States, and the California Department of Toxic Substances Control (DTSC) has established regulations regarding the handling of perchlorate. There are many safety and environmental concerns with the use of chlorate-based compounds. In view of the above, there has been a desire for a vinyl chloride-based resin composition suitable for automobile interior materials and the like, in which discoloration due to amines is suppressed without the use of perchloric acid-based compounds, and for automobile interior materials.

On the other hand, the invention proposed in Patent Document 3 is for improving the thermal stability and coloration during molding of a chlorine-containing resin added with an organic tin compound, and is aimed at improving the discoloration of vinyl chloride resin due to amines. This is clearly different from suppression, and the current situation is that no knowledge can be obtained on this point.

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide an amine resistance imparting agent for vinyl chloride resin that can suppress discoloration of vinyl chloride resin due to amines and also impart heat aging resistance. It is an object of the present invention to provide a stabilizer composition, a vinyl chloride resin composition, a vinyl chloride resin molded article, a laminate, an automobile interior material, and a method for suppressing discoloration of a vinyl chloride resin.

As a result of intensive studies to solve the above problems, the present inventors discovered that a certain sulfonylimide compound can suppress the discoloration of vinyl chloride resin caused by amines, and completed the present invention.

That is, the amine resistance imparting agent for vinyl chloride resins of the present invention is characterized by containing one or more sulfonylimide compounds represented by the following general formula (1).

In general formula (1), R ¹ and R ² each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Alternatively, R ¹ and R ² are linked to form a perfluoroalkylene group having 1 to 8 carbon atoms, and together with the sulfur atom to which they are bonded and the nitrogen atom to which the sulfur atom is bonded, they form a ring. m represents 1, 2 or 3; when m is 1, ^M1 represents a hydrogen atom, an alkali metal atom, Ag or _NH4 ; when m is 2, ^M1 represents a group 2 element, Zn, Mn or represents Cu, and when m is 3, M ¹ represents La or Ce.

The amine resistance imparting agent for vinyl chloride resins of the present invention can be suitably used in automobile interior materials. In particular, the amine resistance imparting agent for vinyl chloride resins of the present invention can be suitably used for automobile interior materials consisting of a laminate of a vinyl chloride resin molded article and a polyurethane foam molded article.

The stabilizer composition for vinyl chloride resins of the present invention is characterized by containing one or more stabilizers for vinyl chloride resins and the amine resistance imparting agent for vinyl chloride resins of the present invention. It is something.

The vinyl chloride resin composition of the present invention is characterized by containing a vinyl chloride resin and the amine resistance imparting agent for vinyl chloride resins of the present invention.

In the vinyl chloride resin composition of the present invention, the content of the amine resistance imparting agent for vinyl chloride resin is 0.005 to 3.0 parts by mass based on 100 parts by mass of the vinyl chloride resin. is preferred. The vinyl chloride resin composition of the present invention can be suitably used for powder molding.

The vinyl chloride resin molded article of the present invention is characterized in that it is obtained from the vinyl chloride resin composition of the present invention.

The laminate of the present invention is a laminate of a vinyl chloride resin molded article and a polyurethane foam molded article, and is characterized in that the vinyl chloride resin molded article is obtained from the vinyl chloride resin composition of the present invention. That is.

The automobile interior material of the present invention is characterized by containing the vinyl chloride resin molded article of the present invention.

Another automobile interior material of the present invention is characterized by containing the laminate of the present invention.

The method for suppressing discoloration of the present invention is a method for suppressing discoloration of an automobile interior material including a laminate of a vinyl chloride resin molded article and a polyurethane foam molded article, and the method comprises: It is characterized in that it is blended into the vinyl chloride resin that is the raw material resin for the vinyl chloride resin molded article.

According to the present invention, an amine resistance-imparting agent for vinyl chloride-based resins that can suppress discoloration of vinyl chloride-based resins due to amines and also impart heat aging resistance, and a stabilizer for vinyl chloride-based resins using the same. A composition, a vinyl chloride resin composition, a vinyl chloride resin molded article, a laminate, an automobile interior material, and a method for suppressing discoloration of a vinyl chloride resin can be provided.

The vinyl chloride resin molded article of the present invention has suppressed discoloration due to amines and is suitable as an automobile interior material.

Embodiments of the present invention will be described in detail below.
[Amine resistance imparting agent for vinyl chloride resin]
First, the amine resistance imparting agent for vinyl chloride resins of the present invention will be explained. The amine resistance imparting agent of the present invention has the function of imparting amine resistance to a vinyl chloride resin, which suppresses discoloration of the vinyl chloride resin due to an amine compound. The amine resistance imparting agent of the present invention contains one or more sulfonylimide compounds represented by the following general formula (1).

In general formula (1), R ¹ and R ² each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Alternatively, R ¹ and R ² are linked to form a perfluoroalkylene group having 1 to 8 carbon atoms, and together with the sulfur atom to which they are bonded and the nitrogen atom to which the sulfur atom is bonded, they form a ring. m represents 1, 2 or 3; when m is 1, ^M1 represents a hydrogen atom, an alkali metal atom, Ag or _NH4 ; when m is 2, ^M1 represents a group 2 element, Zn, Mn or represents Cu, and when m is 3, M ¹ represents La or Ce.

Examples of the perfluoroalkyl group having 1 to 4 carbon atoms for R ¹ and R ² in general formula (1) include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, and the like. It will be done.

Further, R ¹ and R ² in the general formula (1) are connected to form a perfluoroalkylene group having 1 to 8 carbon atoms, and together with the sulfur atom to which they are bonded and the nitrogen atom to which the sulfur atom is bonded, It may form a ring.

From the viewpoint of imparting amine resistance to the vinyl chloride resin, R ¹ and R ² are preferably a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, or a nonafluorobutyl group, and a trifluoromethyl group or a nonafluorobutyl group is preferable. is more preferred, and trifluoromethyl group is even more preferred.

Examples of the alkali metal atom for M ¹ in general formula (1) include lithium, sodium, potassium, rubidium, cesium, and francium.

Examples of the Group 2 element ^M1 in the general formula (1) include beryllium, magnesium, calcium, strontium, barium, and radium.

^M1 in general formula (1) is preferably an alkali metal atom, a Group 2 element, or Zn, and more preferably lithium, sodium, potassium, magnesium, calcium, or Zn, from the viewpoint of imparting amine resistance to the vinyl chloride resin. Preferably, lithium, sodium, potassium, magnesium, and calcium are even more preferred, lithium, sodium, and potassium are even more preferred, and lithium is most preferred.

Preferred specific examples of the sulfonylimide compound represented by the general formula (1) from the viewpoint of imparting amine resistance include the following compound No. 1~No. 13 are mentioned. Among these, from the viewpoint of imparting amine resistance, Compound No. 1.No. 2.No. 3.No. 4.No. 5, No. 6 is more preferable, and compound No. 6 is more preferable. 1.No. 2.No. 3.No. 4.No. 5 is even more preferred, and compound No. 5 is even more preferred. 1.No. 2.No. 3 is even more preferred, and compound No. 3 is even more preferred. 1 is most preferred.

[Stabilizer composition for vinyl chloride resin]
The amine resistance imparting agent of the present invention is also preferably used in combination with one or more stabilizers for vinyl chloride resins as a stabilizer composition for vinyl chloride resins. The stabilizer composition of the present invention is suitably used for automobile interior materials, and in particular, it can be used for automobile interior materials consisting of a laminate of a vinyl chloride resin molded article and a polyurethane foam molded article, which will be described later. More suitable.

As the stabilizer for vinyl chloride resins used in combination with the amine resistance imparting agent, zinc salts of organic acids are preferred from the viewpoints of amine resistance and heat aging resistance. Examples of such zinc salts of organic acids include zinc salts of organic carboxylic acids, phenols, organic phosphoric acids, and the like.

Examples of organic carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, neodecanoic acid, capric acid, undecanoic acid, isoundecylic acid, lauric acid, Isolauric acid, tridecanoic acid, myristic acid, isomyristic acid, palmitic acid, isopalmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, versatic acid, benzoic acid, monochlorobenzoic acid, 4- tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, toluic acid, dimethylbenzoic acid, 2, 4-dimethylbenzoic acid, 3,5-dimethylbenzoic acid, 2,4,6-trimethylbenzoic acid, ethylbenzoic acid, 2-ethylbenzoic acid, 3-ethylbenzoic acid, 4-ethylbenzoic acid, 2,4, 6-triethylbenzoic acid, 4-isopropylbenzoic acid, n-propylbenzoic acid, aminobenzoic acid, N,N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid, p-tertiary octylsalicylic acid, elaidic acid, oleic acid, Linoleic acid, linolenic acid, myristoleic acid, palmitoleic acid, eleostearic acid, eicosenoic acid, eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, arachidonic acid, docosapentaenoic acid, docosahexaenoic acid, ricinoleic acid, thio Monovalent carboxylic acids such as glycolic acid, mercaptopropionic acid, octylmercaptopropionic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid , terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, aconitic acid, thiodipropionic acid and other dihydric carboxylic acids, or their monoesters or monoamide compounds Di- or triester compounds of trivalent or tetravalent carboxylic acids such as butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid, merophanic acid, pyromellitic acid and the like can be mentioned.

Examples of phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, isooctylphenol, and 2-ethylhexylphenol. , tertiary nonylphenol, decylphenol, tertiary octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisohexylphenol, methyltertiary octylphenol, and the like.

Examples of organic phosphoric acids include mono- or dioctyl phosphoric acid, mono- or didodecyl phosphoric acid, mono- or dioctadecyl phosphoric acid, mono- or di-(nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, phosphonic acid stearyl ester, etc. It will be done.

The zinc salt of an organic acid may be an acidic salt, a neutral salt, a basic salt, or an overbased complex in which part or all of the base of the basic salt is neutralized with carbonic acid.

The zinc salt of an organic acid may be composed of two or more types of organic acids. For example, in the case of a zinc salt with a monovalent organic acid, the same organic acid may constitute the anion site and form a salt with the divalent zinc constituting the cation site; The species may constitute an anion site and form a salt with divalent zinc that constitutes a cation site.

From the viewpoint of amine resistance and heat aging resistance, zinc salts of organic acids include zinc benzoate, zinc toluate, zinc 4-tert-butylbenzoate, zinc stearate, zinc laurate, zinc versatate, and zinc octylate. , zinc oleate, zinc palmitate and zinc myristic are preferred. Only one type of zinc salt of an organic acid may be used, or two or more types may be used in combination.

When the stabilizer composition of the present invention contains a zinc salt of an organic acid, from the viewpoint of amine resistance and heat aging resistance, the content should be 5 to 20,000 parts by mass per 100 parts by mass of the amine resistance imparting agent. Parts by weight are preferable, 10 to 8000 parts by weight are more preferable, and 20 to 800 parts by weight are even more preferable.

Furthermore, in the stabilizer composition of the present invention, from the viewpoint of amine resistance and heat aging resistance, the stabilizer to be used in combination with the amine resistance imparting agent includes barium salts of organic acids and overbased barium carbonate salts. One or more types selected from are preferred.

First, the barium salt of an organic acid will be explained. Examples of barium salts of organic acids include barium salts of organic carboxylic acids, phenols, organic phosphoric acids, and the like.

Examples of the organic carboxylic acids, phenols, and organic phosphoric acids include those exemplified with zinc salts of organic acids.

The barium salt of an organic acid may be composed of two or more types of organic acids. For example, in the case of a barium salt with a monovalent organic acid, the same organic acid may constitute an anion site and form a salt with divalent barium that constitutes a cation site; The species may constitute an anion site and form a salt with divalent barium that constitutes a cation site.

Only one type of barium salt of an organic acid may be used, or two or more types may be used in combination. Moreover, the barium salt of an organic acid may be an acidic salt, a neutral salt, or a basic salt.

Next, overbased barium carbonate salt will be explained. Overbased barium carbonate salts are liquid overbased carboxylate/carbonate complexes of barium. This complex differs from a simple mixture of barium carboxylic acid normal salt and barium carbonate; it is a complex formed by some interaction between these two, and while it has a high metal content, it is homogeneous in an organic solvent. It has the characteristic of exhibiting a liquid state. This complex is composed of barium carboxylic acid normal salt, barium carbonate, and a complex salt of barium carboxylic acid and carbonic acid. A complex salt of acid and carbonic acid exists around it, forming something like a micelle, so that it exhibits a uniform liquid state in an organic solvent.

These barium liquid overbased carboxylate/carbonate complexes can be produced, for example, by the production method disclosed in JP-A No. 2004-238364.

Further, as the liquid overbased barium carboxylate/carbonate complex, various commercially available complexes can be used as they are. Typical commercially available complexes include, for example, "Plastistab ^TM 2116" manufactured by AM STABILIZERS, USA (overbased barium oleate/carbonate complex: specific gravity 1.42-1.53, Ba = 33-36). %), "Plastistab ^TM 2513" (overbased barium oleate/carbonate complex: specific gravity 1.41 to 1.52, Ba = 33 to 36%), "Plastistab ^TM 2508" (overbased barium oleate/carbonate complex: specific gravity 1.39 to 1.51, Ba = 33 to 36%), etc.

These overbased barium carbonate salts may be used alone or in combination of two or more.

When the stabilizer composition of the present invention contains a barium salt of an organic acid or an overbased barium carbonate salt, from the viewpoint of amine resistance and heat aging resistance, the content thereof is determined based on 100 mass of the amine resistance imparting agent. parts, preferably 10 to 60,000 parts by weight, more preferably 30 to 10,000 parts by weight, and even more preferably 50 to 2,000 parts by weight.

Furthermore, in the stabilizer composition of the present invention, from the viewpoint of amine resistance and heat aging resistance, the stabilizer to be used in combination with the amine resistance imparting agent includes calcium salts of organic acids and overbased calcium carbonate salts. One or more types selected from are preferred. Examples of such calcium salts of organic acids include calcium salts of organic carboxylic acids, phenols, organic phosphoric acids, and the like.

Examples of the organic carboxylic acids, phenols, and organic phosphoric acids include those exemplified with zinc salts of organic acids.

The calcium salt of an organic acid may be composed of two or more types of organic acids. For example, in the case of a calcium salt with a monovalent organic acid, the same organic acid may form an anion site and form a salt with divalent calcium that forms a cation site, or a different monovalent organic acid may form a salt with divalent calcium that forms a cation site. The species may constitute an anion site and form a salt with divalent calcium that constitutes a cation site.

Only one type of calcium salt of an organic acid may be used, or two or more types may be used in combination. The calcium salt of an organic acid may be an acidic salt, a neutral salt, or a basic salt.

Next, overbased calcium carbonate salt will be explained. Overbased calcium carbonate salts are liquid overbased carboxylate/carbonate complexes of calcium. This complex is different from a simple mixture of calcium carboxylic acid normal salt and calcium carbonate; it is a complex formed by some interaction between these two, and while it has a high metal content, it is homogeneous in an organic solvent. It has the characteristic of exhibiting a liquid state. This complex is composed of calcium carboxylic acid normal salt, calcium carbonate, and a composite salt of calcium carboxylic acid and carbonic acid. A complex salt of acid and carbonic acid exists around it, forming something like a micelle, so that it exhibits a uniform liquid state in an organic solvent.

The liquid overbased carboxylate/carbonate complex of calcium can be prepared in a similar manner as the liquid overbased carboxylate/carbonate complex of barium. Moreover, various commercially available complexes can also be used as they are. A typical commercially available complex is, for example, "Plastistab ^TM 2265" (overbased calcium oleate/carbonate complex: specific gravity 1.04 to 1.09, Ca = 10%) manufactured by AM STABILIZERS, USA. ).

These overbased calcium carbonate salts may be used alone or in combination of two or more.

When the stabilizer composition of the present invention contains a calcium salt of an organic acid or an overbased calcium carbonate salt, from the viewpoint of amine resistance and heat aging resistance, the content thereof should be 100% by mass of the amine resistance imparting agent. parts, preferably 10 to 60,000 parts by weight, more preferably 30 to 10,000 parts by weight, and even more preferably 50 to 2,000 parts by weight.

Further, in the stabilizer composition of the present invention, as the stabilizer used in combination with the amine resistance imparting agent, a β-diketone compound is preferable from the viewpoint of amine resistance and heat aging resistance. Examples of such β-diketone compounds include acetylacetone, triacetylmethane, 2,4,6-heptatrione, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, distearoylmethane, Stearoyl acetylmethane, phenylacetylacetylmethane, dicyclohexylcarbonylmethane, benzoylformylmethane, benzoylacetylmethane, dibenzoylmethane, octylbenzoylmethane, bis(4-octylbenzoyl)methane, benzoyldiacetylmethane, 4-methoxybenzoylbenzoylmethane, bis (4-Carboxymethylbenzoyl)methane, 2-carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, ethyl acetoacetate, cyclohexane-1,3-dione, 3,6-dimethyl-2,4-dioxycyclohexane-1carboxylic acid Examples include methyl, 2-acetylcyclohexanone, dimedone, 2-benzoylcyclohexane, and metal salts thereof can also be used. Examples of metal salts include lithium, sodium, potassium, calcium, zinc, magnesium, and aluminum salts. Examples of preferred metal salts include acetylacetone calcium salt, acetylacetone zinc salt, and the like.

One type of β-diketone compound may be used, or two or more types may be used in combination. Among these β-diketone compounds, dibenzoylmethane, stearoylbenzoylmethane or acetylacetone zinc salt is preferred from the viewpoint of amine resistance and heat aging resistance.

When the stabilizer composition of the present invention contains a β-diketone compound, from the viewpoint of amine resistance and heat aging resistance, the content should be 10 to 60,000 parts by mass per 100 parts by mass of the amine resistance imparting agent. parts, more preferably 30 to 10,000 parts by weight, and even more preferably 50 to 2,000 parts by weight.

Further, in the stabilizer composition of the present invention, the stabilizer used in combination with the amine resistance imparting agent is preferably one or more phosphite compounds from the viewpoint of amine resistance and heat aging resistance. Such phosphite compounds include phosphite trialkyl ester, phosphite dialkyl ester, phosphite dialkyl monoallyl ester, phosphite alkyl allyl ester, phosphite monoalkyl diallyl ester, phosphite diallyl ester , phosphorous acid triallyl ester, and the like. In the stabilizer composition of the present invention, either triester or diester can be used, but it is preferable to use triester from the viewpoint of thermal stability. Also, thioesters can be used.

Examples of phosphite compounds include triphenyl phosphite, tricresyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(mono- and di-mixed nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, diphenyl phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphite, 3-butylphenyl)octyl phosphite, 2,2'-methylenebis(4,6-tert-butylphenyl)-2-ethylhexylphosphite, 2,2'-methylenebis(4,6-tert-butylphenyl)-octadecylphosphite phyto, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, octyldiphenylphosphite, diphenyldecylphosphite, diphenyl(2-ethylhexyl)phosphite, di(decyl)monophenylphosphite Phosphite, diphenyltridecyl phosphite, diphenyl (C12-C15 mixed alkyl) phosphite, phenyldiisodecyl phosphite, phenylbis(isotridecyl) phosphite, triethyl phosphite, tributyl phosphite, tris(2-ethylhexyl) phosphite, tris (decyl) phosphite, trilauryl phosphite, tris(tridecyl) phosphite, trioleyl phosphite, tristearyl phosphite, diethyl phosphite, dibutyl phosphite, dilauryl phosphite, bis(2-ethylhexyl) phosphite, Dioleyl phosphite, trilauryl trithiophosphite, bis(neopentyl glycol)-1,4-cyclohexane dimethyl diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol Diphosphite, distearyl pentaerythritol diphosphite, di(nonylphenyl) pentaerythritol diphosphite, di(tridecyl) pentaerythritol diphosphite, phenyl-4,4'-isopropylidene diphenol pentaerythritol diphosphite , tetra(C12-15 mixed alkyl)-4,4'-isopropylidene diphenyl diphosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis(octylphenyl) bis[4,4' -n-butylidenebis(2-tert-butyl-5-methylphenol)] 1,6-hexanediol diphosphite, tetra(tridecyl)-4,4'-n-butylidenebis(2-tert-butyl-5-methyl phenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, hexa(tridecyl)-1,1,3-tris(2 -Methyl-5-tert-butyl-4-hydroxyphenyl)butane triphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol・2,4,6-tritert-butylphenol monophosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite , tetra(tridecyl)isopropylidene diphenol diphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphite, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo) d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol etc.

One type of phosphite compound may be used, or two or more types may be used in combination. Among these phosphite compounds, from the viewpoint of thermal stability, it is preferable to use a phosphite compound having 12 to 80 carbon atoms, and a phosphite compound having 12 to 46 carbon atoms is preferably used. It is more preferable to use a phosphite compound having 12 to 36 carbon atoms, and it is particularly preferable to use a phosphite compound having 18 to 30 carbon atoms.

When the stabilizer composition of the present invention contains a phosphite compound, from the viewpoint of amine resistance and heat aging resistance, the content is 10 to 30,000 parts by mass per 100 parts by mass of the amine resistance imparting agent. It is preferably 20 to 4000 parts by weight, more preferably 30 to 2000 parts by weight.

Further, in the stabilizer composition of the present invention, the stabilizer used in combination with the amine resistance imparting agent is preferably one or more phenolic antioxidants from the viewpoint of amine resistance and heat aging resistance. Examples of such phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and stearyl (3,5-di-tert-butyl-4- hydroxyphenyl)-propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6 -Hexamethylenebis[(3,5-ditert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylenebis[(3,5-ditert-butyl-4-hydroxyphenyl)propionic acid amide] , 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6- tert-butylphenol), bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid] glycol ester, 4,4'-butylidene bis(6-tert-butyl-m-cresol), 2 , 2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2-methyl- 4-Hydroxy-5-tert-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3 , 5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris[(3,5-di-tert-butyl- 4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, 2-tert-butyl-4-methyl- 6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methyl) phenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], etc. can be mentioned.

One type of phenolic antioxidant may be used, or two or more types may be used in combination. Among these phenolic antioxidants, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] or octadecyl 3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate is preferred.

When the stabilizer composition of the present invention contains a phenolic antioxidant, from the viewpoint of amine resistance and heat aging resistance, the content should be 1 to 2000 parts by mass per 100 parts by mass of the amine resistance imparting agent. Parts by mass are preferred, 4 to 400 parts by mass are more preferred, and 8 to 200 parts by mass are even more preferred.

Further, in the stabilizer composition of the present invention, as the stabilizer used in combination with the amine resistance imparting agent, one or more hindered amine light stabilizers are preferred from the viewpoint of amine resistance and heat aging resistance. Examples of such hindered amine light stabilizers include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate , bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4- Butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl- 4-piperidyl) bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) bis(tridecyl)-1,2 , 3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl) Malonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4 -diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], 1,2,3 ,4-butanecarboxylic acid/2,2-bis(hydroxymethyl)-1,3-propanediol/3-hydroxy-2,2-dimethylpropanal/1,2,2,6,6-pentamethyl-4- Piperidinyl ester polycondensate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) decanedioate/methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate mixture , 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethyl succinate polycondensate, 1, 6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/dibromoethane polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino) Hexane/2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6 -Tertiary octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl) )-amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1, 2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,6,11-tris[2,4- Bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-ylamino]undecane, 1,6,11-tris[2,4-bis (N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-ylamino]undecane, 3,9-bis[1,1-dimethyl-2 -{tris(2,2,6,6-tetramethyl-4-piperidyloxycarbonyl)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9- Bis[1,1-dimethyl-2-{tris(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)butylcarbonyloxy}ethyl]-2,4,8,10-tetraoxaspiro[ 5.5] Undecane, bis(1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 2,2,6,6-tetramethyl-4-piperidylhexadecanoate , 2,2,6,6-tetramethyl-4-piperidyloctadecanoate and the like. Only one type of hindered amine light stabilizer may be used, or two or more types may be used in combination.

When the stabilizer composition of the present invention contains a hindered amine light stabilizer, the content is 5 to 15,000 parts by mass based on 100 parts by mass of the amine resistance imparting agent, from the viewpoint of amine resistance and heat aging resistance. Parts by weight are preferable, 10 to 2000 parts by weight are more preferable, and even more preferably 20 to 700 parts by weight.

Further, in the stabilizer composition of the present invention, the stabilizer used in combination with the amine resistance imparting agent is preferably at least one inorganic auxiliary agent from the viewpoint of amine resistance and heat aging resistance. Examples of such inorganic auxiliary agents include hydrotalcite compounds and zeolite compounds.

Examples of the hydrotalcite compound include compounds represented by the following general formula (2).
Mg _x1 Zn _x2 Al ₂ (OH) _2x1+2x2+4 (CO ₃ ) _1-y1/2 (ClO ₄ ) _y1 mH ₂ O...(2)
In general formula (2), x1, x2, and y1 represent numbers that satisfy the following conditions, respectively: 0≦x2/x1<10, 2≦x1+x2<20, 0≦y1≦2, and m is Indicates 0 or any integer.

As the hydrotalcite compound, a double salt compound consisting of magnesium and aluminum or zinc, magnesium and aluminum is preferably used. Alternatively, it may be obtained by dehydrating crystal water. Such a hydrotalcite compound may be a natural product or a synthetic product. There are no limitations on the crystal structure, crystal particle size, etc. of the hydrotalcite compound.

In addition, as a hydrotalcite compound, its surface can be treated with higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate, organic sulfonic acid metal salts such as alkali metal salts of dodecylbenzenesulfonate, higher fatty acid amides, higher Those coated with fatty acid ester or wax can also be used.

However, in the stabilizer composition of the present invention, among hydrotalcite compounds, it is possible to use those containing perchlorate anions or those treated with perchlorate, but considering the environment, Its use is not recommended.

One type of hydrotalcite compound may be used, or two or more types may be used in combination.

Zeolite compounds are alkali or alkaline earth metal aluminosilicates with a unique three-dimensional zeolite crystal structure, typical examples of which are A-type, X-type, Y-type and P-type zeolites, monodenite, analcite. , sodalite group aluminosilicate, clinobutyrolite, erionite, chabasite, and the like. These zeolite compounds may be either hydrated compounds containing water of crystallization (so-called zeolite water) or anhydrous compounds from which water of crystallization has been removed, and those having a particle size of 0.1 to 50 μm may be used. In particular, those with a diameter of 0.5 to 10 μm are preferred. One type of zeolite compound may be used, or two or more types may be used in combination.

The inorganic auxiliary agent may be used alone, or two or more types may be used in combination, and a hydrotalcite compound and a zeolite compound may be used in combination.

When the stabilizer composition of the present invention contains an inorganic auxiliary agent, the content thereof is 50 to 80,000 parts by mass per 100 parts by mass of the amine resistance imparting agent from the viewpoint of amine resistance and heat aging resistance. parts by weight, more preferably from 100 to 8,000 parts by weight, and even more preferably from 200 to 4,000 parts by weight.

[Vinyl chloride resin composition]
Next, the vinyl chloride resin composition of the present invention will be explained.
The vinyl chloride resin composition of the present invention is characterized in that the amine resistance imparting agent of the present invention is blended with the vinyl chloride resin.

In the vinyl chloride resin composition of the present invention, the vinyl chloride resin is not particularly limited to the polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., and examples thereof include polyvinyl chloride, chlorinated polyvinyl chloride, Vinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer Polymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-maleate ester copolymer, vinyl chloride-methacrylate ester copolymer, vinyl chloride- Vinyl chloride resins such as acrylonitrile copolymers, vinyl chloride-various vinyl ether copolymers, and blends thereof or other chlorine-free synthetic resins, such as acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene Examples include copolymers, ethylene-vinyl acetate copolymers, ethylene-ethyl (meth)acrylate copolymers, blends with polyesters, block copolymers, graft copolymers, and the like. These vinyl chloride resins may be a mixture of two or more types, or a mixture with other synthetic resins. The vinyl chloride resin used is preferably polyvinyl chloride from the viewpoint of amine resistance, and particularly preferably polyvinyl chloride used for powder molding.

In the vinyl chloride resin composition of the present invention, from the viewpoint of imparting amine resistance to the vinyl chloride resin, the amount of the amine resistance imparting agent of the present invention ranges from 0.005 to 100 parts by mass of the vinyl chloride resin. It is preferable to use 3.0 parts by weight, more preferably 0.01 to 2.0 parts by weight, even more preferably 0.05 to 1.0 parts by weight, even more preferably 0.1 to 0.3 parts by weight. preferable. If it is less than 0.005 parts by mass, amine resistance may be insufficient, and even if it exceeds 3.0 parts by mass, the improvement in effect is small and may rather have an adverse effect on other performances.

In the vinyl chloride resin composition of the present invention, the amine resistance imparting agent of the present invention may be blended with the vinyl chloride resin as the stabilizer composition, or as a stabilizer for the vinyl chloride resin. It may be blended into the vinyl chloride resin separately from other components to be blended.

The vinyl chloride resin composition of the present invention preferably contains a plasticizer. Examples of plasticizers include phthalate plasticizers such as dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate; dioctyl adipate, diisononyl adipate, and diisodecyl. Adipate plasticizers such as adipate, di(butyl diglycol) adipate; triphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, tri(isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri(butoxy) Phosphate plasticizers such as ethyl) phosphate and octyl diphenyl phosphate; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol , 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol, and other polyhydric alcohols, and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebatine. A polyester plasticizer using a dibasic acid such as acid, phthalic acid, isophthalic acid, or terephthalic acid, and if necessary using a monohydric alcohol or monocarboxylic acid as a stopper; other types include tetrahydrophthalic acid plasticizer and azelaic acid plasticizer. agent, sebacic acid plasticizer, stearic acid plasticizer, citric acid plasticizer, trimellitic acid plasticizer, pyromellitic acid plasticizer, biphenylene polycarboxylic acid plasticizer, and the like. These plasticizers may be used alone or in combination of two or more.

Among these plasticizers, at least one selected from the group consisting of a trimellitic acid plasticizer, which is a trimellitic acid ester compound, and a pyromellitic acid plasticizer, which is a pyromellitic acid ester compound, has good amine resistance. preferred.

As the trimellitic acid ester compound or the pyromellitic acid ester compound, a triester compound or a tetraester compound of trimellitic acid or pyromellitic acid and a monohydric alcohol is used, respectively.

Examples of monohydric alcohols used to produce trimellitic acid triester compounds or pyromellitic acid tetraester compounds include methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, sec-butyl alcohol, Tertiary butyl alcohol, pentyl alcohol, isopentyl alcohol, hexanol, isohexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, isononyl alcohol, decanol, isodecanol, undecanol, dodecanol, tridecanol, isotridecanol, tetradecanol Examples include straight chain or branched alcohols such as alcohol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, icosanol, heniicosanol, docosanol, and mixtures thereof.

In the vinyl chloride resin composition of the present invention, the content of the plasticizer is preferably 5 to 200 parts by weight, more preferably 10 to 150 parts by weight, based on 100 parts by weight of the vinyl chloride resin. preferable.

The vinyl chloride resin composition of the present invention preferably contains one or more stabilizers for vinyl chloride resins. The stabilizers may be blended as a stabilizer composition or may be blended individually.

In addition, other additives normally used in vinyl chloride resin compositions, such as epoxy compounds, polyhydric alcohol compounds, ultraviolet absorbers, fillers, etc., are also added to the vinyl chloride resin composition of the present invention. be able to.

Examples of the epoxy compound include bisphenol type and novolak type epoxy resins, epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, epoxidized safflower oil, Epoxidized tall oil octyl fatty acid, epoxidized linseed oil fatty acid butyl fatty acid, epoxymethyl stearate, -butyl, -2-ethylhexyl or -stearyl, tris(epoxypropyl) isocyanurate, 3-(2-xenoxy)-1,2- Epoxypropane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl-6-methylepoxycyclohexane carboxylate, bis( Examples include 3,4-epoxycyclohexyl) adipate. One type of epoxy compound may be used, or two or more types may be used in combination.

Examples of polyhydric alcohol compounds include pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, neopentyl glycol, trimethylolpropane, ditrimethylolpropane, 1,3,5-tris(2-hydroxyethyl) isocyanate. Nurate, polyethylene glycol, glycerin, diglycerin, mannitol, maltitol, lactitol, sorbitol, erythritol, xylitol, xylose, sucrose, trehalose, inositol, fructose, maltose, lactose and the like. Only one type of polyhydric alcohol compound may be used, or two or more types may be used in combination.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as; 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tertiary octylphenyl)benzotriazole, 2-(2-hydroxy-3,5 -di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5- dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-benzotriazolyl)phenol, 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole 2-(2-hydroxyphenyl)benzotriazoles such as polyethylene glycol ester; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2, Benzoates such as 4-di-tert-amylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxy Substituted oxanilides such as oxanilide, 2-ethoxy-4'-dodecyl oxanilide; ethyl-α-cyano-β,β-diphenylacrylate, methyl-2-cyano-3-methyl-3-(p-methoxy Cyanoacrylates such as phenyl)acrylate; 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy -4-methoxyphenyl)-4,6-diphenyl-s-triazine, 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl) Examples include triaryltriazines such as -s-triazine. These ultraviolet absorbers may be used alone or in combination of two or more.

Examples of fillers include calcium carbonate, calcium oxide, calcium hydroxide, zinc hydroxide, zinc carbonate, zinc sulfide, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, sodium aluminosilicate, hydrocarma aluminum silicate, magnesium silicate, calcium silicate, zeolite, activated clay, talc, clay, red iron, asbestos, antimony trioxide, silica, glass beads, mica, sericite, glass flakes, asbestos, wollastonite, Potassium titanate, PMF (processed mineral fiber), gypsum fiber, zonolite, MOS (magnesium hydroxide sulfate hydrate, fibrous magnesium compound), phosphate fiber, glass fiber, carbon fiber, aramid fiber, etc. These fillers may be used alone or in combination of two or more.

The vinyl chloride resin composition of the present invention may further contain additives normally used for vinyl chloride resins, such as crosslinking agents, foaming agents, antistatic agents, antifogging agents, and plate-out prevention agents, as necessary. additives, surface treatment agents, lubricants, flame retardants, fluorescent agents, antifungal agents, bactericidal agents, metal deactivators, mold release agents, pigments, processing aids, solvents, etc., to the extent that they do not impair the effects of the present invention. can do. These optional components may be used alone or in combination of two or more.

Examples of lubricants include hydrocarbon lubricants such as low-molecular waxes, paraffin wax, polyethylene wax, chlorinated hydrocarbons, and fluorocarbons; natural wax lubricants such as carnauba wax and candelilla wax; lauric acid, stearic acid, and behenin. Higher fatty acids such as acids, or fatty acid lubricants such as oxyfatty acids such as hydroxystearic acid; aliphatic amide compounds such as stearylamide, laurylamide, and oleylamide; or alkylenes such as methylene bis stearyl amide and ethylene bis stearyl amide. Aliphatic amide lubricants such as bis-aliphatic amide; fatty acid monohydric alcohol ester compounds such as stearyl stearate, butyl stearate, distearyl phthalate, or glycerin tristearate, sorbitan tristearate, pentaerythritol tetrastearate, Fatty acid polyhydric alcohol ester compounds such as dipentaerythritol hexastearate, polyglycerol polyricinolate, and hydrogenated castor oil, or monovalent fatty acids and polybasic organic acids such as adipic acid and stearic acid esters of dipentaerythritol. Fatty alcohol ester lubricants such as complex ester compounds of polyhydric alcohols; Aliphatic alcohol lubricants such as stearyl alcohol, lauryl alcohol, and palmityl alcohol; Metal soaps; Montanic acid lubricants such as partially saponified montanic acid esters; Acrylic Type lubricant; silicone oil, etc. may be mentioned. These lubricants may be used alone or in combination of two or more.

Examples of the pigment include white pigments such as titanium dioxide, and blue pigments such as ultramarine blue and phthalocyanine blue.

Examples of processing aids include homopolymers or copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; copolymers of the above alkyl methacrylates and alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate; Coalescing; Copolymers of the above alkyl methacrylates and aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; Copolymers of the above alkyl methacrylates and vinyl cyan compounds such as acrylonitrile and methacrylonitrile, etc. can be mentioned. These processing aids may be used alone or in combination of two or more.

The vinyl chloride resin composition of the present invention further includes other additives normally used in vinyl chloride resins, such as sulfur-based antioxidants, impact modifiers, reinforcing agents, perchlorates, Magnesium salts of organic acids, overbased magnesium carbonate salts, flame retardants, flame retardant aids, and the like can also be blended within a range that does not impair the effects of the present invention.

Examples of sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid, and polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). Examples include β-alkylmercaptopropionic acid esters. These sulfur-based antioxidants may be used alone or in combination of two or more.

Examples of impact modifiers include polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer rubber, methyl methacrylate-butadiene-styrene copolymer, and methyl methacrylate-butadiene-styrene copolymer. Graft copolymer, acrylonitrile-styrene-butadiene copolymer rubber, acrylonitrile-styrene-butadiene graft copolymer, styrene-butadiene-styrene block copolymer rubber, styrene-isoprene-styrene copolymer rubber, styrene- Ethylene-butylene-styrene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber (EPDM), silicone-containing acrylic rubber, silicone/acrylic composite rubber graft copolymer, silicone-based Rubber etc. can be mentioned. The diene of the above-mentioned ethylene-propylene-diene copolymer rubber (EPDM) includes 1,4-hexadiene, dicyclopentadiene, methylenenorbornene, ethylidenenorbornene, propenylnorbornene, and the like. These impact resistance modifiers may be used alone or in combination of two or more.

As the reinforcing agent, those in the form of fibers, plates, particles, or powders that are normally used for reinforcing synthetic resins can be used. Specific examples of reinforcing agents include glass fibers, asbestos fibers, carbon fibers, graphite fibers, metal fibers, potassium titanate whiskers, aluminum borate whiskers, magnesium whiskers, silicon whiskers, wollastenite, sepiolite, and asbestos. , slag fibers, zonolite, elestadite, gypsum fibers, silica fibers, silica/alumina fibers, zirconia fibers, boron nitride fibers, inorganic fibrous reinforcement materials such as silicon nitride fibers and boron fibers, polyester fibers, nylon fibers, acrylic fibers, recycled Cellulose fibers, acetate fibers, kenaf, ramie, cotton, jute, hemp, sisal, flax, linen, silk, manila hemp, sugar cane, wood pulp, waste paper, waste paper, wool and other organic fibrous reinforcements, glass flakes, non-swellable Mica, graphite, metal foil, ceramic beads, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, finely divided silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide , aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dawsonite, clay, and other plate-shaped or granular reinforcing agents. These reinforcing agents may be coated or bundled with a thermoplastic resin such as ethylene/vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, and may be coated with a coupling agent such as aminosilane or epoxysilane. It may be processed. These reinforcing agents may be used alone or in combination of two or more.

Examples of perchlorates include metal perchlorates, ammonium perchlorate, and silicates treated with perchloric acid. Examples of metals constituting these metal salts include lithium, sodium, potassium, calcium, magnesium, strontium, barium, zinc, cadmium, lead, and aluminum. The perchlorate metal salt may be an anhydride or a hydrated salt, or may be dissolved in an alcohol-based or ester-based solvent such as butyl diglycol or butyl diglycol adipate, or a dehydrated product thereof. These perchlorates may be used alone or in combination of two or more. However, in the resin composition of the present invention, it is not preferable to use perchlorates from safety and environmental considerations.

Magnesium salts of organic acids will be explained. Examples of the magnesium salt of an organic acid include magnesium salts of organic carboxylic acids, phenols, or organic phosphoric acids.

Examples of the organic carboxylic acids, phenols, and organic phosphoric acids include those exemplified with zinc salts of organic acids.

The magnesium salt of an organic acid may be composed of two or more types of organic acids. For example, in the case of a magnesium salt with a monovalent organic acid, the same organic acid may constitute an anion site and form a salt with divalent magnesium constituting a cation site; The species may constitute an anion site and form a salt with divalent magnesium that constitutes a cation site.

Only one type of magnesium salt of an organic acid may be used, or two or more types may be used in combination. Moreover, the magnesium salt of an organic acid may be an acidic salt, a neutral salt, or a basic salt.

The overbased magnesium carbonate salt will be explained. Overbased magnesium carbonate salts are liquid overbased carboxylate/carbonate complexes of magnesium. This complex is different from a simple mixture of magnesium, carboxylic acid normal salt, and magnesium carbonate; it is a complex formed by some kind of interaction between these two, and while it has a high metal content, it is homogeneous in an organic solvent. It has the characteristic of exhibiting a liquid state. This complex is composed of magnesium carboxylic acid normal salt, magnesium carbonate, and a composite salt of magnesium carboxylic acid and carbonic acid. A complex salt of acid and carbonic acid exists around it, forming something like a micelle, so that it exhibits a uniform liquid state in an organic solvent.

The liquid overbased carboxylate/carbonate complex of magnesium can be prepared in a similar manner to the liquid overbased carboxylate/carbonate complex of barium. Moreover, commercially available complexes can also be used as they are.

These overbased magnesium carbonate salts may be used alone or in combination of two or more.

Examples of flame retardants and flame retardant aids include triazine ring-containing compounds, metal hydroxides, other inorganic phosphorus, halogen flame retardants, silicone flame retardants, phosphate ester flame retardants, and condensed phosphate ester flame retardants. , intumescent flame retardants, antimony oxides such as antimony trioxide, other inorganic flame retardant aids, and organic flame retardant aids.

Examples of triazine ring-containing compounds include melamine, ammeline, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylene diguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, and trimethylene diguanamine. Examples include melamine, tetramethylene dimelamine, hexamethylene dimelamine, 1,3-hexylene dimelamine, and the like.

Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, Kismer 5A (magnesium hydroxide: manufactured by Kyowa Chemical Industry Co., Ltd.), and the like.

Examples of phosphoric acid ester flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, and trichloroethyl phosphate. Silenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, trisisopropylphenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis-(t-butylphenyl) phenyl phosphate, tris-(t-butylphenyl) ) phosphate, isopropylphenyl diphenyl phosphate, bis-(isopropylphenyl) diphenyl phosphate, tris-(isopropylphenyl) phosphate, and the like.

Examples of condensed phosphate flame retardants include 1,3-phenylene bis(diphenyl phosphate), 1,3-phenylene bis(dixylenyl phosphate), and bisphenol A bis(diphenyl phosphate). Intomescent flame retardants include ammonium salts and amine salts of (poly)phosphoric acid, such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, ammonium pyrophosphate, melamine pyrophosphate, and piperazine pyrophosphate.

Examples of other inorganic flame retardant aids include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, and talc, and surface-treated products thereof.For example, TIPAQUE R-680 (titanium oxide: Ishihara Sangyo Co., Ltd.) Various commercial products such as Kyowa Mag 150 (magnesium oxide manufactured by Kyowa Kagaku Kogyo Co., Ltd.) and the like can be used.

These flame retardants and flame retardant aids may be used alone or in combination of two or more.

Although it is possible for the vinyl chloride resin composition of the present invention to contain a lead-based stabilizer, a cadmium-based stabilizer, and a tin-based stabilizer, it is preferable not to contain them in terms of toxicity and adverse effects on the environment. preferable.

The vinyl chloride resin composition of the present invention may further contain a stabilizing aid that is normally used for vinyl chloride resins within a range that does not impair the effects of the present invention. Examples of such stabilizing aids include diphenylthiourea, anilinodithiotriazine, melamine, benzoic acid, cinnamic acid, and p-tert-butylbenzoic acid.

The vinyl chloride resin composition of the present invention contains the amine resistance imparting agent of the present invention, the vinyl chloride resin, and, if necessary, stabilizers, plasticizers, and various additives, such as mortar mixer, Henschel mixer, etc. It can be prepared by stirring and mixing with a stirrer such as a Banbury mixer or a ribbon blender, and thereby a mixed powder of the vinyl chloride resin composition can be obtained.

In addition, the amine resistance imparting agent of the present invention, the vinyl chloride resin, and, if necessary, stabilizers, plasticizers, and various additives can be processed using, for example, a conical twin screw extruder, a parallel twin screw extruder, or a single screw extruder. A vinyl chloride resin composition in the form of pellets can also be obtained by melt-molding with a kneader such as a kneader, a co-kneader type kneader, or a roll kneader.

In addition, the amine resistance imparting agent of the present invention, a paste-like vinyl chloride resin, and, if necessary, stabilizers, plasticizers, and various additives can be added to, for example, a pony mixer, butterfly mixer, planetary mixer, ribbon blender, etc. A paste-like vinyl chloride resin composition can be obtained by uniformly mixing with a mixer such as a kneader, dissolver, twin-screw mixer, Henschel mixer, or three-roll mill, and if necessary, defoaming under reduced pressure. can.

[Vinyl chloride resin molded body]
Next, the vinyl chloride resin molded article of the present invention will be explained.
The vinyl chloride resin molded article of the present invention can be produced by molding the vinyl chloride resin composition of the present invention (in the form of blended powder or pellets) by vacuum molding, compression molding, extrusion molding, injection molding, calendar molding, press molding, or blow molding. It can be molded into a desired shape by melt molding using a conventionally known method such as powder molding.

On the other hand, a paste-like vinyl chloride resin composition can be molded into a desired shape by using conventionally known methods such as spread molding, dipping molding, gravure molding, slush molding, and screen processing. can.

In the present invention, from the viewpoint of amine resistance, molded bodies obtained by powder molding such as powder slush molding, fluidized immersion molding, and powder rotary molding using the vinyl chloride resin composition of the present invention are preferred. Among these, molded bodies obtained by powder slush molding are particularly preferred. Therefore, the vinyl chloride resin composition of the present invention is suitable for powder molding.

The shape of the molded body is not particularly limited, and examples thereof include a rod shape, a sheet shape, a film shape, a plate shape, a cylindrical shape, a circle, an ellipse, a star shape, a polygon shape, and the like.

[Laminated body]
The vinyl chloride resin molded article of the present invention is useful when used as a laminate with a molded article using polyurethane, especially a polyurethane foam molded article, from the viewpoint of amine resistance.

A molded article using polyurethane, particularly a polyurethane foam molded article, may be any conventionally known one, and can be obtained, for example, as follows. That is, it is obtained by reacting raw materials for a polyurethane foam molded article containing polyols, polyisocyanates, a blowing agent, and a catalyst, and foaming and curing them.

As the polyols, polyether polyols or polyester polyols are used. As the polyether polyol, polypropylene glycol, polytetramethylene glycol, polyether polyol made of a polymer obtained by addition polymerizing propylene oxide and ethylene oxide to a polyhydric alcohol, modified products thereof, etc. are used. Examples of polyhydric alcohols include glycerin and dipropylene glycol. Examples of polyester polyols include condensed polyester polyols obtained by reacting polycarboxylic acids such as adipic acid and phthalic acid with polyols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin, as well as lactone-based polyester polyols and polycarbonate-based polyester polyols. Polyols are used.

Polyisocyanates are compounds having a plurality of isocyanate groups, and specifically include tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), and triphenyl diisocyanate. Methane triisocyanate, xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), modified products thereof, and the like are used.

The foaming agent is used to foam the polyurethane resin to form a polyurethane foam molded product, and for example, in addition to water, pentane, cyclopentane, hexane, cyclohexane, dichloromethane, carbon dioxide gas, etc. are used.

The catalyst is for promoting the urethanization reaction between polyols and polyisocyanates. As a catalyst, triethylenediamine, dimethylethanolamine, N,N',N'-trimethylaminoethylpiperazine, triphenylamine, triethylamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N-methylmorpholine, N-ethylmorpholine, N-acetylmorpholine, N-octylmorpholine, N-phenylmorpholine, N-hydroxylethylmorpholine, N-hydroxylmethylmorpholine, 4,4'-dithiodimorpholine, dimethylpiperazine, N , N,N',N'-tetramethylpropanediamine, trimethylaminoethylpiperazine, N,N-dimethylethanolamine, dimethylhexadecylamine, 1-(2-ethylhexenyl)piperazine, tri-n-octylamine, trimethylamine , N,N'-dimethylbenzylamine, triethanolamine, 1,2,4-trimethylpiperazine, N-methyldicyclohexylamine, methyldicyclohexylamine and the like are preferred.

The present invention is preferable because it is excellent in providing an effect of suppressing discoloration of vinyl chloride resin due to an amine catalyst that promotes this urethanization reaction.

The vinyl chloride resin molded article and the laminate of the vinyl chloride resin molded article and the polyurethane foam molded article of the present invention are useful and preferred as automobile interior materials from the viewpoint of amine resistance.

[Automotive interior materials]
The automobile interior material of the present invention may be any material as long as it contains the vinyl chloride resin molded article of the present invention or the laminate of the present invention. In particular, the automobile interior material of the present invention is preferably composed of a skin layer made of a laminate made of a vinyl chloride resin molded product and a polyurethane foam molded product, and a base material layer for maintaining the structure. As the base material layer, known materials such as polypropylene resin moldings and ABS resin (acrylonitrile-butadiene-styrene copolymer resin) moldings are used.

Examples of automotive interior materials include instrument panels, door trims, console boxes, glove boxes, pillar trims, dashboards, trunk trims, seats, ceiling materials, AT shifts, armrests, headrests, floor carpets, wire harnesses, various moldings, Examples include sashes, sealants, weather strips, gaskets, and undercoat materials. In particular, automobile interior materials using the laminate of the present invention are very useful and preferred as, for example, instrument panels, door trims, seat sheets, ceiling materials, and the like.

[Discoloration suppression method]
The method for suppressing discoloration of a vinyl chloride resin (hereinafter simply referred to as the discoloration suppressing method) of the present invention is a method for suppressing discoloration of an automobile interior material including a laminate of a vinyl chloride resin molded article and a polyurethane foam molded article. The amine resistance imparting agent of the invention is blended into a vinyl chloride resin that is a raw material resin for a vinyl chloride resin molded article. In the method for suppressing discoloration of the present invention, the amine resistance imparting agent of the present invention may be added alone to the vinyl chloride resin, or may be added as a stabilizer composition of the present invention.

Hereinafter, the present invention will be specifically explained using examples. However, the present invention is not limited in any way by the following examples.
[Examples 1 to 9, Comparative Examples 1 to 2]
100 parts by mass of vinyl chloride resin (manufactured by Shin-Etsu Chemical Co., Ltd., TK-1300 (average degree of polymerization 1300)), 70 parts by mass of ADEKASIZER C-8L (trimellitic acid plasticizer, manufactured by ADEKA Co., Ltd.), 5 parts by mass of epoxidized soybean oil (epoxy compound), 0.2 parts by mass of ADEKA STAB LS-12 (lubricant, manufactured by ADEKA Co., Ltd.), and 0.3 parts by mass of zinc stearate (stabilizer, zinc salt of organic acid) , 1.04 parts by mass of Mizukalyzer DS (inorganic auxiliary agent, zeolite, manufactured by Mizusawa Chemical Industry Co., Ltd.), 0.21 parts by mass of dibenzoylmethane (β-diketone compound), and further, an amine resistance imparting agent. As, the following compound No. 1.No. 2.No. 3. No. 4.No. 5, No. 6 was mixed in the amounts (parts by mass) listed in Table 1 to obtain vinyl chloride resin compositions of each example.

Next, a sheet was produced by powder slush molding. That is, the obtained vinyl chloride resin composition was heated to 110° C. using a Henschel mixer, then lowered to 50° C., and dried up. The obtained dry-up compound was sprinkled onto a textured mold heated to a surface temperature of 250° C. and allowed to stand for 15 seconds to melt. After shaking off the excess compound, the mold was placed in an oven set at 250°C and left standing for 45 seconds. The mold was taken out of the oven and cooled with water to obtain a 1 mm thick vinyl chloride resin sheet.

The obtained vinyl chloride resin sheet was backed with foamed polyurethane to a thickness of 10 mm to produce a laminate. The following <amine resistance test> was conducted using the obtained laminate. The results are shown in Tables 1 and 2. In addition, a sample containing no amine resistance imparting agent was used as Comparative Example 1, and evaluated in the same manner as in each Example. Furthermore, instead of adding an amine resistance imparting agent, 0.2 parts by mass of sodium perchlorate was added as Comparative Example 2, which was evaluated in the same manner as in each Example. The results are shown in Tables 1 and 2.

In addition, the following <heat aging test> was conducted using the obtained vinyl chloride resin sheet. The results are shown in Tables 1 and 2. In addition, a sample containing no amine resistance imparting agent was used as Comparative Example 1, and evaluated in the same manner as in each Example. Furthermore, instead of adding an amine resistance imparting agent, 0.2 parts by mass of sodium perchlorate was added as Comparative Example 2, which was evaluated in the same manner as in each Example. The results are shown in Tables 1 and 2.

<Amine resistance test>
The obtained laminate was placed in an oven and heated at 115° C. for 1000 hours, then the vinyl chloride resin sheet and foamed polyurethane were separated, and then the color difference (ΔE) of the vinyl chloride resin sheet before and after heating was measured. It can be said that the smaller the value, the better the amine resistance. The results are shown in Tables 1 and 2. In addition, in the table, it was described as amine resistance color difference (ΔE).

<Heat aging test>
The obtained vinyl chloride resin sheet was placed in an oven and heated at 115° C. for 1000 hours, and then the color difference (ΔE) of the vinyl chloride resin sheet before and after heating was measured. It can be said that the smaller the value, the better the heat aging resistance. The results are shown in Table 1. In addition, in the table, it was described as heat aging resistance color difference (ΔE).

Amine resistance imparting agent

From the results shown in Tables 1 and 2, it is clear that the amine resistance imparting agent of the present invention is excellent in suppressing discoloration of vinyl chloride resins due to amines and discoloration due to heat aging.

Claims (12)

An amine resistance imparting agent for vinyl chloride resins, characterized by containing one or more sulfonylimide compounds represented by the following general formula (1).

In general formula (1), R ¹ and R ² each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Alternatively, R ¹ and R ² are linked to form a perfluoroalkylene group having 1 to 8 carbon atoms, and together with the sulfur atom to which they are bonded and the nitrogen atom to which the sulfur atom is bonded, they form a ring. m represents 1, 2 or 3; when m is 1, ^M1 represents a hydrogen atom, an alkali metal atom, Ag or _NH4 ; when m is 2, ^M1 represents a group 2 element, Zn, Mn or represents Cu, and when m is 3, M ¹ represents La or Ce. The amine resistance imparting agent for vinyl chloride resin according to claim 1, which is used for automobile interior materials. The amine resistance imparting agent for vinyl chloride resin according to claim 2, wherein the automobile interior material is an automobile interior material comprising a laminate of a vinyl chloride resin molded product and a polyurethane foam molded product. A vinyl chloride resin containing one or more stabilizers for vinyl chloride resins and the amine resistance imparting agent for vinyl chloride resins according to any one of claims 1 to 3. stabilizer composition for use. A vinyl chloride resin composition comprising a vinyl chloride resin and the amine resistance imparting agent for vinyl chloride resins according to any one of claims 1 to 3. The vinyl chloride resin composition according to claim 5, wherein the content of the amine resistance imparting agent for vinyl chloride resin is 0.005 to 3.0 parts by mass based on 100 parts by mass of the vinyl chloride resin. The vinyl chloride resin composition according to claim 5, which is used for powder molding. A vinyl chloride resin molded article obtained from the vinyl chloride resin composition according to claim 5. A laminate of a vinyl chloride resin molded article and a polyurethane foam molded article, wherein the vinyl chloride resin molded article is obtained from the vinyl chloride resin composition according to claim 5. An automobile interior material comprising the vinyl chloride resin molded article according to claim 8. An automobile interior material comprising the laminate according to claim 9. A method for suppressing discoloration of an automobile interior material comprising a laminate of a vinyl chloride resin molded product and a polyurethane foam molded product, the amine resistance imparting agent for vinyl chloride resin according to any one of claims 1 to 3. A method for suppressing discoloration, which comprises blending the following into a vinyl chloride resin that is a raw material resin for a vinyl chloride resin molded article.