JP7580995B2 - Antistatic agent composition, vinyl chloride resin composition containing the same and molded article thereof - Google Patents

Description

The present invention relates to an antistatic agent composition, a vinyl chloride resin composition containing the same, and a molded article thereof. More specifically, the present invention relates to an antistatic agent composition that can impart an excellent antistatic effect to vinyl chloride resin and further has excellent bleeding resistance, a vinyl chloride resin composition containing the same, and a molded article thereof.

Vinyl chloride resins have excellent properties such as flame retardancy, chemical resistance, mechanical stability, heat resistance, and weather resistance, and are inexpensive, making them a highly useful general-purpose resin material. They are also widely used in various packaging films, containers, agricultural films, sheet flooring, wall materials, etc., as soft products with relatively large amounts of plasticizer added, or semi-rigid products with relatively small amounts of plasticizer added.

These vinyl chloride resins have good electrical insulation properties, which is a desirable property in fields where electrical insulation is required, but they have the problem of being easily charged by friction, etc.

Electrified polyvinyl chloride resin attracts surrounding dust and dirt, causing problems such as marring the appearance of resin molded products. Furthermore, in electronic products, for example in precision equipment such as computers, the circuits can become unable to function properly due to electrostatic charge. There is also the problem of electric shock. If an electric shock is generated by resin on the human body, not only will it cause discomfort to the person, but in places where flammable gases or dust are present, it could also lead to an explosion.

To solve these problems, antistatic treatments have been used. The most common antistatic treatment method is to add an antistatic agent to vinyl chloride resin. For example, Patent Document 1 proposes a quaternary ammonium salt of perchloric acid as an antistatic agent to be mixed with vinyl chloride resin. Patent Document 2 proposes a vinyl chloride resin composition that also uses an ester plasticizer.

Japanese Patent Application Publication No. 2-233744 Japanese Patent Application Publication No. 2-255852

However, as proposed in Patent Document 1, when a quaternary ammonium salt of perchloric acid is blended with a vinyl chloride resin as an antistatic agent, there is a problem that compatibility is poor and the antistatic agent bleeds onto the surface of the molded article. Even when an ester plasticizer is blended in combination with the resin, as proposed in Patent Document 2, the bleeding resistance is insufficient.

The object of the present invention is to provide an antistatic agent composition that can impart an excellent antistatic effect to vinyl chloride resins and also has excellent bleeding resistance, as well as a vinyl chloride resin composition containing the same and a molded article thereof.

As a result of intensive research into solving the above problems, the inventors discovered that the above problems could be solved by using a quaternary ammonium perchlorate salt having a specific structure in combination with a glycol diaryl ester compound having a specific structure, and thus completed the present invention.

で表される過塩素酸第四級アンモニウム塩であって、一般式（１）中、Ｒ^１、Ｒ^２、およびＲ^３のうち１つは炭素原子数が５～１８のアルキル基であり、他の２つは炭素原子数が１～４のアルキル基であり、Ｒ^４は炭素原子数が２～４のアルキレン基であり、ｎは１～５の整数を表し、
前記（Ｂ）成分が、一般式（２）、

で表されるグリコールジアリールエステル化合物であって、一般式（２）中、Ｒ^５は水素原子、または炭素原子数が１～４のアルキル基であり、Ａは、炭素原子数が４～９のグリコールの水酸基を除いた残基であることを特徴とするものである。 That is, the antistatic composition of the present invention is an antistatic composition containing 20 to 800 parts by mass of the component (B) per 100 parts by mass of the component (A),
The component (A) is represented by the general formula (1):

In the general formula (1), one of R ¹ , R ² , and R ³ is an alkyl group having 5 to 18 carbon atoms, the other two are alkyl groups having 1 to 4 carbon atoms, R ⁴ is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 to 5;
The component (B) is represented by the general formula (2):

In the general formula (2), ^R5 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and A is a residue obtained by removing a hydroxyl group from a glycol having 4 to 9 carbon atoms.

The vinyl chloride resin composition of the present invention is characterized by containing a vinyl chloride resin and the antistatic agent composition of the present invention.

In the vinyl chloride resin composition of the present invention, the content of the antistatic agent composition is preferably 0.1 to 10.0 parts by mass per 100 parts by mass of the vinyl chloride resin.

The molded article of the present invention is characterized by being obtained from the vinyl chloride resin composition of the present invention.

The present invention provides an antistatic agent composition that can impart an excellent antistatic effect to vinyl chloride resins and has excellent bleeding resistance, as well as a vinyl chloride resin composition containing the same and a molded article thereof.

Hereinafter, an embodiment of the present invention will be described in detail.
The antistatic agent composition of the present invention contains 20 to 800 parts by mass of the following component (B) relative to 100 parts by mass of the following component (A), where component (A) is a quaternary ammonium perchlorate represented by the following general formula (1), and component (B) is a glycol diaryl ester compound represented by the following general formula (2).

Component (A):

In general formula (1), one of R ¹ , R ² , and R ³ is an alkyl group having 5 to 18 carbon atoms, the other two are alkyl groups having 1 to 4 carbon atoms, R ⁴ is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 to 5.

Component (B):

In general formula (2), R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and A is a residue obtained by removing the hydroxyl group from a glycol having 4 to 9 carbon atoms.

First, the component (A) will be described.
In the antistatic agent composition of the present invention, the component (A) is a component that imparts antistatic properties to the vinyl chloride resin, and is a quaternary ammonium perchlorate represented by the following general formula (1).

In general formula (1), one of R ¹ , R ² , and R ³ is an alkyl group having 5 to 18 carbon atoms, the other two are alkyl groups having 1 to 4 carbon atoms, R ⁴ is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 to 5.

In the component (A), the alkyl groups having 5 to 18 carbon atoms for R ¹ , R ² , and R ³ include n-pentyl, isopentyl, neopentyl, tert-pentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, 1,3-dimethylbutyl, 1-isopropylpropyl, 1,2-dimethylbutyl, n-heptyl, 2-heptyl, 1,4-dimethylpentyl, tert-heptyl, 2-methyl-1-isopropylpropyl, 1-ethyl-3-methylbutyl, n-octyl, tert-octyl, 2-ethylhexyl, 2-methyl-1-isopropylpropyl, 1-ethyl-3-methylbutyl, Examples of the alkyl group include propylhexyl, 2-propylhexyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, isoundecyl, n-dodecyl, isododecyl, n-tridecyl, isotridecyl, n-tetradecyl, isotetradecyl, n-pentadecyl, isopentadecyl, n-hexadecyl, isohexadecyl, n-heptadecyl, isoheptadecyl, n-octadecyl, isooctadecyl, cyclopentyl, cyclohexyl, cyclooctyl, and cyclododecyl groups. Among these, from the viewpoints of antistatic properties and bleed resistance, preferred are alkyl groups having 6 to 10 carbon atoms.

Examples of the remaining two alkyl groups having 1 to 4 carbon atoms among R ¹ , R ² , and R ³ of component (A) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group, and from the viewpoints of antistatic properties and bleed resistance, a methyl group is preferred.

^R4 in the quaternary ammonium perchlorate represented by general formula (1), component (A), is an alkylene group having 2 to 4 carbon atoms, such as an ethylene group, propylene group, isopropylene group, butylene group, or isobutylene group. From the viewpoints of antistatic properties and bleed resistance, an ethylene group is preferred.

In the quaternary ammonium perchlorate salt represented by general formula (1) of component (A), n is an integer from 1 to 5, and is preferably 1 from the viewpoints of antistatic properties and bleeding resistance.

From the standpoint of antistatic properties and bleeding resistance, the particularly preferred component (A) is compound A-1 below.

In the antistatic agent composition of the present invention, the quaternary ammonium perchlorate salt of component (A) may be used alone or in combination of two or more types.

Next, the component (B) will be described.
In the antistatic agent composition of the present invention, the component (B) is a component that imparts bleed resistance and is a glycol diaryl ester compound represented by the following general formula (2).

^R5 in the glycol diaryl ester compound of component (B) represented by general formula (2) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, etc. From the viewpoints of antistatic properties and bleeding resistance, a hydrogen atom is preferred.

In the glycol diaryl ester compound represented by general formula (2) of component (B), A is a residue of a glycol having 4 to 9 carbon atoms with the hydroxyl group removed. Examples of glycols having 4 to 9 carbon atoms include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol, with dipropylene glycol being preferred from the standpoint of antistatic properties and bleeding resistance. In other words, A is preferably a residue of dipropylene glycol with the hydroxyl group removed from the standpoint of antistatic properties and bleeding resistance.

As the glycol diaryl ester compound represented by the general formula (2) of the component (B), for example, diethylene glycol dibenzoate ester, triethylene glycol dibenzoate ester, tetraethylene glycol dibenzoate ester, dipropylene glycol dibenzoate ester, tripropylene glycol dibenzoate ester, diethylene glycol ditoluyl ester, triethylene glycol ditoluyl ester, tetraethylene glycol dibenzoate ester, dipropylene glycol ditoluyl ester, tripropylene glycol dibenzoate ester, etc. are listed as preferred compounds. Among these, from the viewpoint of antistatic properties and bleed resistance, diethylene glycol dibenzoate ester, triethylene glycol dibenzoate ester, tetraethylene glycol dibenzoate ester, dipropylene glycol dibenzoate ester, tripropylene glycol dibenzoate ester are more preferred, and dipropylene glycol dibenzoate ester is particularly preferred.

In the antistatic agent composition of the present invention, the glycol diaryl ester compound represented by general formula (2) of component (B) may be used alone or in combination of two or more types.

The glycol diaryl ester compound represented by general formula (2) of component (B) can be obtained by esterification reaction of a glycol having 4 to 12 carbon atoms with an aryl carboxylic acid such as benzoic acid. Of course, commercially available products may also be used.

The antistatic agent composition of the present invention contains 20 to 800 parts by mass of the glycol diaryl ester compound (B) per 100 parts by mass of the quaternary ammonium salt of perchlorate (A). From the viewpoints of antistatic properties and bleed resistance, the amount is preferably 50 to 350 parts by mass, more preferably 80 to 200 parts by mass, per 100 parts by mass of component (A). If the amount is less than 20 parts by mass, the bleed resistance is insufficient, and even if the amount exceeds 800 parts by mass, the improvement in effect is small and there is a possibility that other performance properties may be adversely affected.

The antistatic agent composition of the present invention is blended to impart antistatic properties to vinyl chloride resins, and is used as a vinyl chloride resin composition. In terms of antistatic properties and bleed resistance, the blending amount is preferably 0.1 to 10.0 parts by mass, more preferably 0.5 to 7.0 parts by mass, and even more preferably 1.0 to 4.0 parts by mass, per 100 parts by mass of vinyl chloride resin. If the amount is less than 0.1 part by mass, the antistatic properties may be insufficient, and even if the amount exceeds 10.0 parts by mass, the improvement in effect is small and there is a possibility that other performance properties may be adversely affected.

Vinyl chloride resins may be produced by any of a variety of polymerization methods, including bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and examples of such resins include polyvinyl chloride, chlorinated polyvinyl 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, vinyl chloride-chlorinated propylene copolymer, and the like. Examples of vinyl chloride resins include vinyl chloride-vinylidene chloride-vinyl acetate terpolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-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 copolymers, ethylene-vinyl acetate copolymers, ethylene-ethyl (meth)acrylate copolymers, blends with polyesters, block copolymers, graft copolymers, etc. These vinyl chloride resins may be a mixture of two or more types, or may be a mixture with other synthetic resins. The vinyl chloride resin used is preferably polyvinyl chloride in terms of antistatic properties and bleeding resistance.

Next, the vinyl chloride resin composition of the present invention will be described in further detail.
The vinyl chloride resin composition of the present invention contains a vinyl chloride resin and the antistatic agent composition of the present invention, and the vinyl chloride resin may be any of those described above. In the vinyl chloride resin composition of the present invention, it is preferable to contain a zinc salt of an organic acid from the viewpoint of thermal stability. Examples of the zinc salt of an organic acid include zinc salts of organic carboxylic acids, phenols, or organic phosphoric acids.

Examples of organic carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexyl acid, neodecanoic acid, capric acid, undecanoic acid, isoundecyl 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, and 4-tert-butylbenzoic acid. 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 Monovalent carboxylic acids such as aromatic acid, salicylic acid, p-tert-octyl salicylic 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, thioglycolic acid, mercaptopropionic acid, and octylmercaptopropionic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, and suberin. Examples of such divalent carboxylic acids include phthalic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, and thiodipropionic acid, as well as their monoesters and monoamide compounds; and di- or triester compounds of trivalent or tetravalent carboxylic acids, such as butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid, mellophanic acid, and pyromellitic acid.

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

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, nonylphenyl phosphonate, and stearyl phosphonate.

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 organic acids. For example, in the case of a zinc salt of a monovalent organic acid, the same organic acid may form an anionic site and form a salt with divalent zinc that forms a cationic site, or two different monovalent organic acids may form an anionic site and form a salt with divalent zinc that forms a cationic site.

From the viewpoint of thermal stability, zinc salts such as zinc benzoate, zinc toluate, zinc 4-tert-butylbenzoate, zinc stearate, zinc laurate, zinc versatate, zinc octylate, zinc oleate, zinc palmitate, and zinc myristate 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.

These organic acid zinc salts may be incorporated into the antistatic agent composition of the present invention and then incorporated into the vinyl chloride resin as an antistatic agent composition, or may be incorporated directly into the vinyl chloride resin.

From the viewpoint of thermal stability, it is preferable that the vinyl chloride resin composition of the present invention contains one or more selected from the group consisting of barium salts of organic acids and overbased barium carbonate salts.

First, we will explain barium salts of organic acids. Examples of barium salts of organic acids include barium salts of organic carboxylic acids, phenols, and organic phosphoric acids.

Examples of organic carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexyl acid, neodecanoic acid, capric acid, undecanoic acid, isoundecyl 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, and 4-tert-butylbenzoic acid. 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 Monovalent carboxylic acids such as aromatic acid, salicylic acid, p-tert-octyl salicylic 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, thioglycolic acid, mercaptopropionic acid, and octylmercaptopropionic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, and suberin. Examples of such divalent carboxylic acids include phthalic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, and thiodipropionic acid, as well as their monoesters and monoamide compounds; and di- or triester compounds of trivalent or tetravalent carboxylic acids, such as butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid, mellophanic acid, and pyromellitic acid.

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

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, nonylphenyl phosphonate, and stearyl phosphonate.

The barium salt of an organic acid may be composed of two or more organic acids. For example, in the case of a barium salt of a monovalent organic acid, the same organic acid may form an anionic site and form a salt with divalent barium that forms a cationic site, or two different monovalent organic acids may form an anionic site and form a salt with divalent barium that forms a cationic site.

A single type of barium salt of an organic acid may be used, or two or more types may be used in combination. The barium salt of an organic acid may be an acidic salt, a neutral salt, or a basic salt.

Next, we will explain about overbased barium carbonate. Overbased barium carbonate is a liquid overbased carboxylate/carbonate complex of barium. This complex is different from a simple mixture of barium carboxylate and barium carbonate, but is a complex formed by some kind of interaction between the two, and has the characteristic of being a uniform liquid in an organic solvent while having a high metal content. This complex is composed of barium carboxylate, barium carbonate, and a complex salt of barium carboxylate and carbonate, and is composed of barium carbonate at the center, barium carboxylate and barium complex salt of carboxylate and carbonate around it, forming something like a micelle, which causes it to be a uniform liquid in an organic solvent.

These liquid overbased carboxylate/carbonate complexes of barium can be produced, for example, by the method shown in JP-A-2004-238364.

In addition, various commercially available complexes can be used as the liquid overbased barium carboxylate/carbonate complex. Representative commercially available complexes include, for example, "Plastistab™ 2116" (overbased barium oleate/carbonate complex: specific gravity 1.42-1.53, Ba = 33-36%), "Plastistab™ 2513" (overbased barium oleate/carbonate complex: specific gravity 1.41-1.52, Ba = 33-36%), and "Plastistab™ 2508" (overbased barium oleate/carbonate complex: specific gravity 1.39-1.51, Ba = 33-36%) manufactured by AM STABILZERS, USA.

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

One or more selected from the group consisting of barium salts of organic acids and overbased barium carbonate salts may be blended into the antistatic agent composition of the present invention and then blended with vinyl chloride resin as an antistatic agent composition, or may be blended directly with vinyl chloride resin.

It is preferable that the vinyl chloride resin composition of the present invention contains a plasticizer. Examples of plasticizers include phthalate-based plasticizers such as dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate; adipate-based plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, and di(butyldiglycol) adipate; phosphate-based plasticizers such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri(isopropylphenyl)phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri(butoxyethyl)phosphate, and octyldiphenyl phosphate; ethylene glycol, diethylene Polyester-based plasticizers using polyhydric alcohols such as glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, and neopentyl glycol, and dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid, and using monohydric alcohols and monocarboxylic acids as stoppers as necessary; other examples include tetrahydrophthalic acid-based plasticizers, azelaic acid-based plasticizers, sebacic acid-based plasticizers, stearic acid-based plasticizers, citric acid-based plasticizers, trimellitic acid-based plasticizers, pyromellitic acid-based plasticizers, and biphenylene polycarboxylic acid-based plasticizers. Only one of these plasticizers may be used, or two or more may be used in combination.

These plasticizers may be blended into the antistatic agent composition of the present invention and then blended with the vinyl chloride resin as an antistatic agent composition, or may be blended directly with the vinyl chloride resin.

The vinyl chloride resin composition of the present invention may contain one or more selected from the group consisting of calcium salts of organic acids and overbased calcium carbonate salts in terms of thermal stability.

Examples of calcium salts of such organic acids include calcium salts of organic carboxylic acids, phenols, or organic phosphoric acids.

Examples of organic carboxylic acids include those exemplified as barium salts described above. Examples of phenols include those exemplified as barium salts described above. Examples of organic phosphoric acids include those exemplified as barium salts described above.

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

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

Next, we will explain about overbased calcium carbonate. Overbased calcium carbonate is a liquid overbased carboxylate/carbonate complex of calcium. This complex is different from a simple mixture of calcium carboxylate and calcium carbonate, as they are formed by some kind of interaction. It has a high metal content and is characterized by being a uniform liquid in organic solvents. This complex is composed of calcium carboxylate, calcium carbonate, and a complex salt of calcium carboxylate and carbonate, with calcium carbonate at the center, calcium carboxylate and complex salt of calcium carboxylate and carbonate around it, forming something like a micelle, so to speak, which causes it to be a uniform liquid in organic solvents.

The liquid overbased carboxylate/carbonate complex of calcium can be produced in the same manner as the liquid overbased carboxylate/carbonate complex of barium described above. Various commercially available complexes can also be used as they are. A representative example of a commercially available complex is "PlastistabTM 2265" (overbased calcium oleate/carbonate complex: specific gravity 1.04-1.09, Ca=10%) manufactured by AM STABILZERS, USA.

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

One or more selected from the group consisting of calcium salts of organic acids and overbased calcium carbonate salts may be blended into the antistatic agent composition of the present invention and then blended with the vinyl chloride resin as an antistatic agent composition, or may be blended directly with the vinyl chloride resin.

The vinyl chloride resin composition of the present invention can also contain a β-diketone compound from the viewpoint of thermal stability.

Examples of β-diketone compounds include acetylacetone, triacetylmethane, 2,4,6-heptatrione, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, distearoylmethane, stearoylacetylmethane, 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, methyl 3,6-dimethyl-2,4-dioxycyclohexane-1 carboxylate, 2-acetylcyclohexanone, dimedone, 2-benzoylcyclohexane, and the like, and metal salts of these can also be used. Examples of metal salts include lithium salts, sodium salts, potassium salts, calcium salts, zinc salts, magnesium salts, and aluminum salts. Examples of preferred metal salts include calcium acetylacetone salt, zinc acetylacetone salt, and the like.

A single 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, and zinc acetylacetone are preferred from the standpoint of thermal stability.

These β-diketone compounds may be incorporated into the antistatic agent composition of the present invention and then incorporated into the vinyl chloride resin as an antistatic agent composition, or may be incorporated directly into the vinyl chloride resin.

The vinyl chloride resin composition of the present invention may contain one or more phosphite compounds from the viewpoint of thermal stability.

Examples of phosphite compounds include trialkyl phosphite, dialkyl phosphite, dialkyl monoallyl phosphite, alkyl allyl phosphite, monoalkyl diallyl phosphite, diallyl phosphite, triallyl phosphite, and the like. In the vinyl chloride resin composition of the present invention, either triesters or diesters can be used, but from the viewpoint of thermal stability, triesters are preferably used. Thioesters can also 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)octyl fluorophosphite, 2,2'-methylenebis(4,6-tert-butylphenyl)-2-ethylhexyl phosphite, 2,2'-methylenebis(4,6-tert-butylphenyl)-octadecyl phosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, octyldiphenyl phosphite, diphenyldecyl phosphite, diphenyl(2-ethylhexyl) phosphite, di(decyl)monophenyl phosphite, diphenyl t Lidecyl phosphite, diphenyl (C12-C15 mixed alkyl) phosphite, phenyl diisodecyl phosphite, phenyl bis (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 trithio phosphite, 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 Pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, di(tridecyl)pentaerythritol diphosphite, phenyl-4,4'-isopropylidenediphenol pentaerythritol diphosphite, tetra(C12-15 mixed alkyl)-4,4'-isopropylidenediphenyl diphosphite Phosphite, hydrogenated 4,4'-isopropylidenediphenol 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-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) 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-tri-tert-butylphenol monophosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5- methylphenyl) phosphite, tetra(tridecyl)isopropylidenediphenol 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-tri-tert-butylphenol, etc.

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

These phosphite ester compounds may be incorporated into the antistatic agent composition of the present invention and then incorporated into the vinyl chloride resin as an antistatic agent composition, or may be incorporated directly into the vinyl chloride resin.

The vinyl chloride resin composition of the present invention may contain one or more phenolic antioxidants in terms of thermal stability.

Examples of phenol-based antioxidants include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, 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-hexamethylene bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], diphenyl)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'-butylidenebis(6-tert-butyl-m-cresol), 2,2'-ethylidenebis(4,6-ditert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2-methyl bis[2-tert-butyl-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)propionyloxy] diethyl] 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-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], etc.

The phenol-based antioxidant may be used alone or in combination of two or more kinds. These phenol-based antioxidants may be blended into the antistatic agent composition of the present invention and then blended with the vinyl chloride resin as the antistatic agent composition, or may be blended directly with the vinyl chloride resin.

The vinyl chloride resin composition of the present invention may contain one or more hindered amine light stabilizers from the viewpoint of thermal stability.

Examples of 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-piperidyl benzoate, 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(1, ... Bis(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 acrylate, 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}], ,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-tert-octylamino-s-triazine polycondensate condensation product, 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]undeca , 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, etc.

The hindered amine light stabilizer may be used alone or in combination of two or more kinds. In addition, these hindered amine light stabilizers may be blended into the antistatic agent composition of the present invention and then blended with the vinyl chloride resin as the antistatic agent composition, or may be blended directly with the vinyl chloride resin.

The vinyl chloride resin composition of the present invention may contain lead-based stabilizers, cadmium-based stabilizers, and tin-based stabilizers, but it is preferable not to add them due to their toxicity and adverse effects on the environment.

The vinyl chloride resin composition of the present invention may also contain a hydrotalcite compound.

Hydrotalcite compounds include compounds represented by the following general formula (3):

In general formula (3), x1, x2, and y1 each represent a number that satisfies the conditions represented by the following formulas: 0≦x2/x1<10, 2≦x1+x2<20, 0≦y1≦2, and m represents 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. It may also be one in which the water of crystallization has been dehydrated. It may also be one that has been treated with perchloric acid. Such hydrotalcite compounds may be natural products or synthetic products. There are no limitations on the crystal structure, crystal particle size, etc., of the hydrotalcite compound.

Hydrotalcite compounds whose surfaces are coated with higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleates, organic sulfonic acid metal salts such as alkali metal dodecylbenzenesulfonates, higher fatty acid amides, higher fatty acid esters, waxes, etc. can also be used.

Only one type of hydrotalcite compound may be used, or two or more types may be used in combination. In addition, these hydrotalcite compounds may be blended into the antistatic agent composition of the present invention and then blended with the vinyl chloride resin as an antistatic agent composition, or may be blended directly with the vinyl chloride resin.

The vinyl chloride resin composition of the present invention may also contain a polyhydric alcohol compound. Examples of polyhydric alcohol compounds include pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, neopentyl glycol, trimethylolpropane, ditrimethylolpropane, 1,3,5-tris(2-hydroxyethyl)isocyanurate, polyethylene glycol, glycerin, diglycerin, mannitol, maltitol, lactitol, sorbitol, erythritol, xylitol, xylose, sucrose, trehalose, inositol, fructose, maltose, lactose, etc.

Only one type of polyhydric alcohol compound may be used, or two or more types may be used in combination. In addition, these polyhydric alcohol compounds may be blended into the antistatic agent composition of the present invention and then blended with the vinyl chloride resin as the antistatic agent composition, or may be blended directly with the vinyl chloride resin.

The vinyl chloride resin composition of the present invention may contain a filler. 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 alumina silicate, hydrocalumite, aluminum silicate, magnesium silicate, calcium silicate, zeolite, activated clay, talc, clay, red iron oxide, asbestos, antimony trioxide, silica, glass beads, mica, sericite, glass flakes, asbestos, wollastonite, potassium titanate, PMF, gypsum fiber, zonolite, MOS, phosphate fiber, glass fiber, carbon fiber, aramid fiber, etc.

These fillers may be used alone or in combination of two or more. These fillers may be blended into the antistatic agent composition of the present invention and then blended with the vinyl chloride resin as an antistatic agent composition, or may be blended directly with the vinyl chloride resin.

The vinyl chloride resin composition of the present invention may contain a lubricant from the viewpoint of processability. Examples of lubricants include hydrocarbon-based lubricants such as low molecular weight wax, paraffin wax, polyethylene wax, chlorinated hydrocarbons, and fluorocarbons; natural wax-based lubricants such as carnauba wax and candelilla wax; fatty acid-based lubricants such as higher fatty acids such as lauric acid, stearic acid, and behenic acid, or oxyfatty acids such as hydroxystearic acid; fatty acid-based lubricants such as aliphatic amide compounds such as stearylamide, laurylamide, and oleylamide, or alkylene bisfatty amides such as methylene bisstearylamide and ethylene bisstearylamide; fatty acid monohydric alcohol ester compounds such as stearyl stearate, butyl stearate, and distearyl phthalate. Alternatively, examples include fatty acid polyhydric alcohol ester compounds such as glycerin tristearate, sorbitan tristearate, pentaerythritol tetrastearate, dipentaerythritol hexastearate, polyglycerin polyricinoleate, and hydrogenated castor oil, and fatty acid alcohol ester lubricants such as complex ester compounds of monovalent fatty acids and polybasic organic acids and polyhydric alcohols, such as dipentaerythritol adipic acid-stearic acid ester; fatty alcohol lubricants such as stearyl alcohol, lauryl alcohol, and palmityl alcohol; metal soaps; montanic acid lubricants such as partially saponified montanic acid ester; acrylic lubricants; and silicone oil.

These lubricants may be used alone or in combination of two or more. These lubricants may be blended into the antistatic agent composition of the present invention and then blended with the vinyl chloride resin as the antistatic agent composition, or may be blended directly with the vinyl chloride resin.

The vinyl chloride resin composition of the present invention may contain a processing aid from the viewpoint of processability. 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 with alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate; copolymers of the above alkyl methacrylates with aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; and copolymers of the above alkyl methacrylates with vinyl cyanide compounds such as acrylonitrile and methacrylonitrile.

These processing aids may be used alone or in combination of two or more. These processing aids may be blended into the antistatic agent composition of the present invention and then blended with the vinyl chloride resin as an antistatic agent composition, or may be blended directly with the vinyl chloride resin.

The vinyl chloride resin composition of the present invention may further contain other additives that are typically used in vinyl chloride resins, such as sulfur-based antioxidants, epoxy compounds, ultraviolet absorbers, impact modifiers, reinforcing agents, zeolite compounds, perchlorates, magnesium salts of organic acids, overbased magnesium carbonates, flame retardants, flame retardant assistants, pigments, stabilizing assistants, etc. These additives may be incorporated into the antistatic agent composition of the present invention and then incorporated into the vinyl chloride resin as an antistatic agent composition, or may be incorporated directly into the vinyl chloride resin.

Examples of sulfur-based antioxidants include dialkyl thiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid, and β-alkyl mercaptopropionate esters of polyols such as pentaerythritol tetra(β-dodecyl mercaptopropionate). These sulfur-based antioxidants may be used alone or in combination of two or more types.

Examples of epoxy compounds include epoxidized animal and vegetable oils such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, and epoxidized safflower oil; epoxidized tall oil fatty acid esters such as epoxidized tall oil fatty acid octyl; epoxidized linseed oil fatty acid esters such as epoxidized linseed oil fatty acid butyl; epoxidized methyl stearate, epoxidized butyl stearate, epoxidized 2-ethylhexyl stearate, epoxidized stearyl stearate, epoxidized polybutadiene, tris(ethoxysilane), Examples of epoxy compounds include bis(3,4-epoxypropyl) isocyanurate, 3-(2-xenoxy)-1,2-epoxypropane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, bisphenol-type and novolac-type epoxy resins, vinylcyclohexene diepoxide, dicyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl-6-methyl epoxycyclohexane carboxylate, bis(3,4-epoxycyclohexyl) adipate, 3,4-epoxycyclohexylmethyl, epoxycyclohexane carboxylate, etc. These epoxy compounds may be used alone or in combination of two or more kinds.

Examples of ultraviolet absorbers include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-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, and polyethylene glycol esters of 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole; phenyl salicylate; benzoates such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β,β-diphenylacrylate, methyl- Examples of such ultraviolet absorbents include cyanoacrylates such as 2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate, and triaryltriazines such as 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, and 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine. These ultraviolet absorbents may be used alone or in combination of two or more.

Examples of impact improvers include polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer rubber, methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene 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 rubber, etc. Examples of dienes in the ethylene-propylene-diene copolymer rubber (EPDM) include 1,4-hexanediene, dicyclopentadiene, methylenenorbornene, ethylidenenorbornene, propenylnorbornene, etc. These impact modifiers may be used alone or in combination of two or more.

The reinforcing agent may be in the form of fiber, plate, granule, or powder, which is normally used to reinforce synthetic resins. Specifically, inorganic fibrous reinforcing materials such as glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, sepiolite, asbestos, slag fiber, zonolite, elestadite, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, and boron fiber, polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate fiber, kenaf, ramie, cotton, jute, hemp, rhinocerose, etc. may be used. Examples of the reinforcing agents include organic fibrous reinforcing agents such as sieve, flax, linen, silk, Manila hemp, sugar cane, wood pulp, waste paper, waste paper, and wool; and plate-shaped or granular reinforcing agents such as glass flakes, non-swelling mica, graphite, metal foil, ceramic beads, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, finely powdered silicic acid, feldspar powder, potassium titanate, silicic balloons, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dawsonite, and white clay. These reinforcing agents may be coated or bundled with a thermoplastic resin such as an ethylene/vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or may be treated with a coupling agent such as an aminosilane or an epoxysilane. These reinforcing agents may be used alone or in combination of two or more types.

Zeolite compounds are aluminosilicates of alkali or alkaline earth metals with a unique three-dimensional zeolite crystal structure. Representative examples include A-type, X-type, Y-type and P-type zeolites, monodenite, analcite, sodalite-group aluminosilicates, clinobutyrolite, erionite and chabazite. These zeolite compounds may be either hydrated containing water of crystallization (so-called zeolite water) or anhydrous from which the water of crystallization has been removed. In addition, those with a particle size of 0.1 to 50 μm may be used, with those with a particle size of 0.5 to 10 μm being particularly preferred. These zeolite compounds may be used alone or in combination of two or more types.

Examples of perchlorates include metal perchlorates 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. Metal perchlorates may be anhydrous or hydrated, or may be dissolved in alcohol-based or ester-based solvents such as butyl diglycol and butyl diglycol adipate, or may be dehydrated. These perchlorates may be used alone or in combination of two or more.

Examples of magnesium salts of organic acids include magnesium salts of organic carboxylic acids, phenols, or organic phosphoric acids.

The organic carboxylic acid may be, for example, one exemplified by a zinc salt of an organic acid. The phenol may be, for example, one exemplified by a zinc salt of an organic acid. The organic phosphoric acid may be, for example, one exemplified by a zinc salt of an organic acid. The magnesium salt of an organic acid may be composed of two or more organic acids. For example, in the case of a magnesium salt of a monovalent organic acid, the same organic acid may form an anion site and form a salt with a divalent magnesium that forms a cation site, or two different monovalent organic acids may form an anion site and form a salt with a divalent magnesium that forms 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. The magnesium salt of an organic acid may be an acidic salt, a neutral salt, or a basic salt.

Overbased magnesium carbonate is a liquid overbased carboxylate/carbonate complex of magnesium. This complex is different from a simple mixture of magnesium, a monobasic carboxylate, and magnesium carbonate; it is a complex formed by some kind of interaction between these, and has the characteristic of being a uniform liquid in an organic solvent while having a high metal content. This complex is composed of monobasic magnesium carboxylate, magnesium carbonate, and a complex salt of magnesium carboxylic acid and carbonate, and magnesium carbonate is at the center with monobasic magnesium carboxylate and complex salt of magnesium carboxylic acid and carbonate present around it, forming something like a micelle, so to speak, which causes it to be a uniform liquid in an organic solvent.

The liquid overbased carboxylate/carbonate complex of magnesium can be produced in the same manner as the liquid overbased carboxylate/carbonate complex of barium described above. Alternatively, commercially available complexes can be used as they are. These overbased magnesium carbonate salts can be used alone or in combination of two or more types.

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

Examples of triazine ring-containing compounds include melamine, ammeline, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylenediguanamine, norbornenediguanamine, methylenediguanamine, ethylenedimelamine, trimethylenedimelamine, tetramethylenedimelamine, hexamethylenedimelamine, and 1,3-hexylenedimelamine.

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

Examples of phosphate ester flame retardants include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trixylenyl 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 ester flame retardants include 1,3-phenylene bis(diphenyl phosphate), 1,3-phenylene bis(dixylenyl phosphate), bisphenol A bis(diphenyl phosphate), etc., and intumescent flame retardants include ammonium salts and amine salts of (poly)phosphoric acids, such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, ammonium pyrophosphate, melamine pyrophosphate, and piperazine pyrophosphate.

Other inorganic flame retardant assistants include, for example, inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, talc, and surface-treated products thereof. For example, various commercially available products such as TIPAQUE R-680 (titanium oxide: manufactured by Ishihara Sangyo Kaisha Ltd.) and Kyowamag 150 (magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.) can be used. These flame retardants and flame retardant assistants may be used alone or in combination of two or more kinds.

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

Examples of stabilizing agents that can be used include diphenylthiourea, anilinodithiotriazine, melamine, benzoic acid, cinnamic acid, and p-tert-butylbenzoic acid.

If necessary, the vinyl chloride resin composition of the present invention may further contain additives that are normally used in vinyl chloride resins, such as crosslinking agents, antistatic agents other than component (A), antifogging agents, plate-out inhibitors, surface treatment agents, fluorescent agents, antifungal agents, bactericides, metal deactivators, and release agents, to the extent that the effects of the present invention are not impaired. These optional components may be used alone or in combination of two or more. These additives may be incorporated into the antistatic agent composition of the present invention and then incorporated into the vinyl chloride resin as an antistatic agent composition, or may be incorporated directly into the vinyl chloride resin.

The vinyl chloride resin composition of the present invention can be prepared by mixing the antistatic agent composition of the present invention, a vinyl chloride resin, and, if necessary, other components, by stirring and mixing with a stirrer such as a mortar mixer, a Henschel mixer, a Banbury mixer, or a ribbon blender to obtain a mixed powder of the vinyl chloride resin composition.

It is also possible to obtain a pellet-shaped vinyl chloride resin composition by melt molding the antistatic agent composition of the present invention, a vinyl chloride resin, and other components as necessary, using a kneader such as a conical twin-screw extruder, a parallel twin-screw extruder, a single-screw extruder, a co-kneader type kneader, or a roll kneader.

The antistatic agent composition of the present invention, the vinyl chloride paste resin, and other components as required can also be mixed uniformly using a mixer such as a pony mixer, butterfly mixer, planetary mixer, ribbon blender, kneader, dissolver, twin-shaft mixer, Henschel mixer, or triple roll mill, and degassed under reduced pressure as required to obtain a vinyl chloride resin composition in the form of a paste.

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

On the other hand, the vinyl chloride resin composition in paste form can be molded into the desired shape by molding using conventional methods such as spread molding, dipping molding, gravure molding, slush molding, and screen processing.

The shape of the molded body is not particularly limited, but examples include rod-like, sheet-like, film-like, plate-like, cylindrical, circular, elliptical, star-like, polygonal, etc.

The vinyl chloride resin composition of the present invention and the molded articles obtained from it can be used in a wide range of industrial fields, including electricity, electronics, and communications, agriculture, forestry, and fisheries, mining, construction, food, textiles, clothing, medicine, coal, petroleum, rubber, leather, automobiles, precision instruments, wood, building materials, civil engineering, furniture, printing, and musical instruments.

More specifically, the vinyl chloride resin composition of the present invention and its molded articles are used in applications such as printers, personal computers, word processors, keyboards, PDAs (personal digital assistants), telephones, copying machines, facsimiles, ECRs (electronic cash registers), calculators, electronic organizers, cards, holders, stationery, and other office and office equipment; washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game consoles, irons, kotatsu, and other home appliances; TVs, VTRs, video cameras, radio cassette recorders, tape recorders, minidiscs, CD players, speakers, liquid crystal displays, and other AV equipment; connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulation materials, LED encapsulation materials, electric wires, cables, transformers, deflection yokes, distribution boards, and clocks, and other electric and electronic parts and communication devices; automotive interior and exterior materials; plate-making films, adhesive films, bottles, food containers, food packaging films, pharmaceutical and medical wrap films, product packaging films, agricultural films, agricultural sheets, and greenhouse films.

Furthermore, the vinyl chloride resin composition of the present invention and its molded article can be used in a wide variety of applications, including seats (padding, outer material, etc.), belts, ceiling coverings, convertible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, wheel covers, mattress covers, airbags, insulation materials, handrails, handrail straps, wire covering materials, electrical insulation materials, paints, coating materials, covering materials, flooring materials, corner walls, carpets, wallpaper, wall covering materials, exterior materials, interior materials, roofing materials, deck materials, wall materials, pillar materials, flooring boards, It can be used for a variety of purposes, including materials for fences, frameworks and moldings, window and door shapes, shingles, paneling, terraces, balconies, soundproofing boards, heat insulation boards, window materials, and other automobiles, vehicles, ships, aircraft, buildings, houses, and construction materials and civil engineering materials, clothing, curtains, sheets, nonwoven fabrics, plywood, synthetic fiber boards, carpets, entrance mats, partition curtains, sheets, buckets, hoses, powder transport hoses, containers, glasses, bags, cases, goggles, skis, rackets, tents, musical instruments, and other daily necessities and sporting goods.

The present invention will be specifically explained below with reference to examples. However, the present invention is not limited in any way by the following examples.

[Preparation of Antistatic Compositions: Antistatic Compositions 1 to 3, Comparative Antistatic Compositions 1 to 7]
Antistatic agent compositions 1 to 3 of the present invention and comparative antistatic agent compositions 1 to 7 were prepared by mixing various components according to the formulations shown in Tables 1 and 2. The following compound A-1 was used as component (A) of the antistatic agent composition of the present invention, and dipropylene glycol dibenzoate was used as component (B).

Component (A)

In addition, in comparative antistatic compositions 1 to 6, heptaethylene glycol dibenzoate and butyl diglycol adipate were used as comparative ester compounds in place of component (B). In comparative antistatic composition 7, only component (A) was blended.

[Production and Evaluation of Vinyl Chloride Resin Compositions: Examples 1 to 5, Comparative Examples 1 to 11]
Antistatic agent compositions 1 to 3 were blended in the amounts shown in Table 3 into 100 parts by mass of a vinyl chloride resin (TK-1300 (average degree of polymerization 1300) manufactured by Shin-Etsu Chemical Co., Ltd.). Furthermore, 2 parts by mass of a Ba/Zn-based stabilizer (AC-255 manufactured by ADEKA Corporation) and 50 parts by mass of diisononyl phthalate as a plasticizer were blended, and these were mixed to produce a vinyl chloride-based resin composition.

The obtained vinyl chloride resin composition was rolled at 170°C and 30 rpm, and then a test sheet 12 cm square and 1 mm thick was produced using an electric press. The obtained sheet was used to evaluate the antistatic properties and bleed resistance according to the following test methods. The evaluation results are shown in Table 3.

Furthermore, vinyl chloride resin compositions of Comparative Examples 1 to 11 were prepared in the same manner as in the Examples using Comparative Antistatic Agent Compositions 1 to 7 based on the blending amounts in Tables 4 and 5, and sheets were produced and evaluated in the same manner as in the Examples. The evaluation results are also shown in Tables 4 and 5.

<Surface resistivity (SR value) measurement method>
The obtained sheet was stored under conditions of a temperature of 25° C. and a humidity of 50% RH immediately after molding, and after storage for one day after molding, the surface resistivity (Ω/□) was measured in the same atmosphere using an R8340 resistance meter manufactured by Advantest Corp. under conditions of an applied voltage of 100 V and an application time of 1 minute. The measurement was performed at five points on five test pieces, and the average value was calculated.

<Volume resistivity (VR value) measurement method>
The obtained sheet was stored under conditions of a temperature of 25° C. and a humidity of 50% RH immediately after molding, and after storage for one day after molding, the volume resistivity (Ω cm) was measured under the same atmosphere using an R8340 resistance meter manufactured by Advantest Corp. under conditions of an applied voltage of 100 V and an application time of 1 minute. The measurement was performed at five points on five test pieces, and the average value was calculated.

<Bleeding resistance test>
The obtained sheet was left to stand for 30 days under conditions of a temperature of 40° C. and a humidity of 80% RH, and then the surface condition of the sheet was visually observed. The sheet was evaluated as ◯ when no bleeding phenomenon occurred and × when bleeding phenomenon occurred.

From the results shown in Tables 3 to 5, it is clear that the antistatic agent composition of the present invention can impart an excellent antistatic effect to vinyl chloride resins and further has excellent bleeding resistance.

Claims (4)

An antistatic agent composition comprising 50 to 350 parts by mass of component (B) per 100 parts by mass of component (A),
The component (A) is represented by the general formula (1):

In the general formula (1), one of R ¹ , R ² , and R ³ is an alkyl group having 5 to 18 carbon atoms, the other two are alkyl groups having 1 to 4 carbon atoms, R ⁴ is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 to 5;
The component (B) is represented by the general formula (2):

wherein in general formula (2), ^R5 is a hydrogen atom and A is a residue obtained by removing a hydroxyl group from a glycol having 4 to 9 carbon atoms, and the antistatic agent composition is for use in vinyl chloride resins . A vinyl chloride resin composition comprising a vinyl chloride resin and the antistatic agent composition according to claim 1. The vinyl chloride resin composition according to claim 2, wherein the content of the antistatic agent composition is 0.1 to 10.0 parts by mass per 100 parts by mass of the vinyl chloride resin. A molded article obtained from the vinyl chloride resin composition according to claim 2 or 3.