JP2016074876A - Vinyl chloride-based resin plasticizer composed of 1,4-cyclohexane dicarboxylic acid ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-phthalic acid ester-based vinyl chloride-based resin plasticizer in which the cold resistance and heat resistance is excellent, as well as the flexibility is good.SOLUTION: The vinyl chloride-based resin composition having an excellent cold resistance and heat resistance as well as a good flexibility can be produced by using, as a vinyl chloride-based resin plasticizer, a 1,4-cyclohexane dicarboxylic diester obtained by esterification reacting or transesterification reacting a particular saturated aliphatic alcohol and 1,4-cyclohexane dicarboxylic acid or dimethyl ester thereof.SELECTED DRAWING: None

Description

The present invention relates to a novel plasticizer for vinyl chloride resin and a vinyl chloride resin composition containing the same, and more specifically, a novel 1,4-cyclohexanedicarboxylic acid excellent in cold resistance, heat resistance and flexibility. The present invention relates to a plasticizer for vinyl chloride resin comprising an acid diester.

A vinyl chloride resin is added with a plasticizer for the purpose of imparting various performances including flexibility and lowering the processing temperature during molding processing such as extrusion and calendering and facilitating the molding processing. Often used as a vinyl chloride resin composition.

Functions required for the plasticizer used in such a vinyl chloride resin composition include various performances such as flexibility, cold resistance, heat resistance, and electrical characteristics when the composition is used as a raw material. It is in the place where it is added or exhibited. Examples of the plasticizer of such a vinyl chloride resin composition include phthalate ester plasticizers for vinyl chloride represented by di-2-ethylhexyl phthalate (DOP) and diisononyl phthalate (DINP). It is used for general purposes. However, due to the fact that toxicity has been observed when a large amount of DOP is administered to rodents in recent years with close-ups on chemical safety, the main protection for infants in Japan, Europe and the United States in accordance with the precautionary principle The use of phthalate-based compounds such as DOP is restricted as a target, and in the plasticizer field, non-phthalate ester-based plasticizers have been desired in the market. To date, non-phthalate plasticizers include tributyl acetyl citrate (hereinafter referred to as “ATBC”), di-2-ethylhexyl adipate (hereinafter referred to as “DOA”), tri-2 trimellitic acid. -Plasticizers for vinyl chloride such as ethylhexyl (hereinafter referred to as "TOTM") are known (Patent Documents 1 to 3), but the performance of these plasticizers is compared with phthalate ester plasticizers ATBC and DOA have insufficient heat resistance, and TOTM has excellent heat resistance, but there is a problem in that it is inferior in flexibility and cold resistance. In addition, 1,2-cyclohexanedicarboxylic acid diester plasticizer, 1,2-cyclohexanedicarboxylic acid diisononyl (hereinafter referred to as “DINCH”), has flexibility, heat resistance, and cold resistance similar to phthalate ester plasticizers. In recent years, it has been attracting attention as a well-balanced non-phthalate ester plasticizer (Patent Document 4).

However, in recent years, demands for cold resistance and heat resistance for non-phthalate ester plasticizers have become increasingly severe in wire coating applications and automotive member applications, and the above DINCH satisfies the requirements. In some cases, it is still necessary to rely on phthalate plasticizers for some applications, and the supply of alternative plasticizers is awaited.

JP 2000-226482 A JP 2002-194159 A JP2013-147520A JP-T-2001-526252

The object of the present invention is to provide a novel 1,4-cyclohexanedicarboxylic acid diester-based vinyl chloride system that satisfies the demands of more severe cold resistance and heat resistance, and that can solve the above problems, and has good flexibility. A plasticizer for resin and a vinyl chloride resin composition containing the plasticizer.

In view of the present situation, the present inventors have conducted extensive studies to solve the above problems, and as a result, esterified a specific saturated aliphatic alcohol and 1,4-cyclohexanedicarboxylic acid dimethyl or 1,4-cyclohexanedicarboxylic acid dimethyl ester. 1,4-cyclohexanedicarboxylic acid diester obtained by reaction or transesterification is a plasticizer having excellent cold resistance and heat resistance, good compatibility with vinyl chloride resin, and good flexibility. The headline and the present invention were completed.

That is, the present invention provides the following new plasticizers for vinyl chloride resins and vinyl chloride resin compositions containing the same.

[Item 1] 1,4 obtained by esterification or transesterification of 1,4-cyclohexanedicarboxylic acid or a dimethyl ester thereof and a saturated aliphatic alcohol mixture mainly containing a saturated aliphatic alcohol having 9 carbon atoms. -A plasticizer for vinyl chloride resin comprising a cyclohexanedicarboxylic acid diester, wherein the saturated aliphatic alcohol mixture is a straight chain of 9 carbon atoms having a content of 60 to 95% by weight in the saturated aliphatic alcohol mixture. A saturated fatty alcohol and 5 to 40% by weight of a branched saturated aliphatic alcohol having 9 carbon atoms are included, and the linear ratio of the saturated aliphatic alcohol mixture is 60 to 95%. Plasticizer for vinyl chloride resin.

[Item 2] The saturated fatty alcohol mixture is a linear saturated aliphatic alcohol having 9 to 9 carbon atoms and a carbon number of 9 to 10% by weight of 70 to 90% by weight in the saturated aliphatic alcohol mixture. The vinyl chloride resin plasticizer according to [Item 1], wherein the branched chain saturated aliphatic alcohol is included, and the linear chain ratio of the saturated aliphatic alcohol mixture is 70 to 90%.

[Item 3] 1,4 obtained by esterification or transesterification of 1,4-cyclohexanedicarboxylic acid or a dimethyl ester thereof and a saturated aliphatic alcohol mixture mainly containing a saturated aliphatic alcohol having 9 carbon atoms. -A plasticizer for a vinyl chloride resin comprising a cyclohexanedicarboxylic acid diester, wherein the saturated aliphatic alcohol mixture comprises (1) an aldehyde having 9 carbon atoms by hydroformylation reaction of 1-octene, carbon monoxide and hydrogen. And a saturated aliphatic alcohol having a straight chain structure and a branched chain structure produced by a production method comprising the step of producing and (2) a step of hydrogenating the aldehyde having 9 carbon atoms to reduce it to an alcohol. A plasticizer for vinyl chloride resin.

[Item 4] A vinyl chloride resin composition comprising a vinyl chloride resin and the plasticizer for vinyl chloride resin according to any one of [Item 1] to [Item 3].

[Claim 5] A vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition according to [Claim 4].

The plasticizer for vinyl chloride resin of the present invention has a good affinity with vinyl chloride resin, and can provide excellent cold resistance and heat resistance and good flexibility to vinyl chloride resin. As a plasticizer for resin, it can be used under various molding process conditions. In addition, by including the plasticizer for vinyl chloride resin, a vinyl chloride resin composition having excellent flexibility and excellent cold resistance and heat resistance that can be used under various molding conditions. Can be obtained.

<Plasticizer for vinyl chloride resin>
The plasticizer for vinyl chloride resin of the present invention is obtained by esterifying or transesterifying a specific saturated aliphatic alcohol (alcohol component) with 1,4-cyclohexanedicarboxylic acid or its dimethyl ester (acid component). It is characterized by being made of 1,4-cyclohexanedicarboxylic acid diester.

The 1,4-cyclohexanedicarboxylic acid diester (hereinafter referred to as “the present ester”) according to the present invention comprises a predetermined acid component and an alcohol component according to a conventional method, preferably in an inert gas atmosphere such as nitrogen. It can be easily obtained by esterification or transesterification in the absence of a catalyst or in the presence of a catalyst.

[Saturated fatty alcohol mixture]
The saturated aliphatic alcohol mixture used in the present invention is a mixture of saturated aliphatic alcohols mainly composed of a saturated aliphatic alcohol having 9 carbon atoms, and the ratio of the saturated aliphatic alcohol having 9 carbon atoms as the main component is In the saturated fatty alcohol mixture used in the invention, preferably 65% by weight or more (65 to 100%), more preferably 80% by weight or more (80 to 100%) is recommended.

In the saturated fatty alcohol mixture according to the present invention, the linearity of the mixture is recommended to be 60 to 95%, preferably 70 to 90%. Furthermore, it is recommended that the content of the linear saturated aliphatic alcohol having 9 carbon atoms is 60 to 95% by weight, preferably 70 to 90% by weight, in the saturated aliphatic alcohol mixture used in the present invention. In addition, it is recommended that the content of the branched saturated aliphatic alcohol having 9 carbon atoms (for example, 2-methyloctanol and the like) is 5 to 40% by weight, preferably 10 to 30% by weight.

As the details of the embodiment of the saturated aliphatic alcohol mixture used in the present invention, the saturated aliphatic alcohol mixture is mainly composed of a saturated aliphatic alcohol having 9 carbon atoms (preferably 65% by weight or more), and the saturated aliphatic alcohol. The mixture contains a linear saturated aliphatic alcohol having 9 to 9 carbon atoms and a branched saturated aliphatic alcohol having 9 to 9 carbon atoms and having a content in the mixture of 60 to 95% by weight. The linear chain ratio of the aliphatic alcohol mixture is 60 to 95%. In a more preferred embodiment, the saturated fatty alcohol mixture is composed mainly of a saturated aliphatic alcohol having 9 carbon atoms (preferably 80% by weight or more), and the content in the saturated aliphatic alcohol mixture is 70 to 90% by weight. A linear saturated aliphatic alcohol having 9 carbon atoms and a branched saturated aliphatic alcohol having 10 to 30% by weight of 9 carbon atoms, and the linear ratio of the saturated aliphatic alcohol mixture is 70 to An embodiment that is 90% is recommended.

  If the linear chain ratio of the saturated fatty alcohol mixture is 60% or more and the content of the linear saturated aliphatic alcohol having 9 carbon atoms is 60% by weight or more, the flexibility is sufficiently reduced. In addition, the heat resistance and cold resistance of the vinyl chloride resin, which is the object of the present invention, can be improved. On the other hand, when the linearity ratio is less than 60% or the content of the linear saturated aliphatic alcohol having 9 carbon atoms is less than 60% by weight, the improvement in cold resistance and heat resistance, which are the objects of the present invention, is not good. This is not preferable because it is sufficient and the flexibility tends to decrease.

In addition, when the saturated aliphatic alcohol mixture has a straight chain ratio of 95% or less and the content of the linear saturated alcohol having 9 carbon atoms is 95% by weight or less, the blending with the vinyl chloride resin is good. As a result, a decrease in tensile properties such as tensile elongation can be suppressed. On the other hand, when the linear ratio exceeds 95% or the content of the linear saturated aliphatic alcohol having 9 carbon atoms exceeds 95% by weight, the compatibility with the vinyl chloride resin deteriorates. As a result, the tensile properties such as tensile elongation tend to decrease, which is not preferable.

In the present specification and claims, the linear chain ratio of the saturated aliphatic alcohol mixture is the ratio (weight ratio) of the linear alcohol in the saturated aliphatic alcohol mixture, and from the viewpoint of the effects of the present invention. It can be said that the linear alcohol having 7 to 11 carbon atoms occupies substantially, and specifically, it can be obtained by a method of analysis by gas chromatography as described in the examples described later.

In addition, since there was no substantial difference in the reactivity of the saturated aliphatic alcohol mixture (substantially 7 to 11 carbon atoms) in the esterification reaction or transesterification reaction, the saturated aliphatic alcohol mixture (substantially The composition ratio (molar ratio) calculated from the composition ratio (weight ratio) of the alcohol component having 7 to 11 carbon atoms) and the composition ratio (molar ratio) of the alkyloxycarbonyl group portion of 1,4-cyclohexanedicarboxylic acid diester Is substantially the same ratio. The composition ratio of the alkyloxycarbonyl group portion of 1,4-cyclohexanedicarboxylic acid diester is, for example, hydrolyzing 1,4-cyclohexanedicarboxylic acid diester with a base, and extracting an alcohol component from the hydrolyzed crude product, The extract can be determined by analyzing it by a technique such as gas chromatography in the examples described later.

The saturated aliphatic alcohol mixture having 9 carbon atoms used in the present invention comprises (1) 1-octene, a step of producing a 9 carbon aldehyde by hydroformylation reaction of carbon monoxide and hydrogen, and (2) 9 carbon atoms. It can be produced by a production method comprising a step of hydrogenating an aldehyde to reduce it to an alcohol.

In the hydroformylation reaction in the step (1), for example, an aldehyde having 9 carbon atoms can be produced by reacting 1-octene, carbon monoxide and hydrogen in the presence of a cobalt catalyst or a rhodium catalyst.

The hydrogenation in the step (2) can be reduced to an alcohol by hydrogenating an aldehyde having 9 carbon atoms with hydrogen pressurization in the presence of a noble metal catalyst such as a nickel catalyst or a palladium catalyst.

As a specific example (commercially available product) of a saturated aliphatic alcohol mixture mainly composed of a saturated aliphatic alcohol having 9 carbon atoms obtained in the above step, about 70% by weight or more of linear nonanol and about 30% by weight Lineball 9 (trade name, Shell Chemicals Co., Ltd.), which is a mixture of the following branched nonanols, can be mentioned.

[Esterification reaction]
The esterification reaction according to the present invention means an esterification reaction between the alcohol component and 1,4-cyclohexanedicarboxylic acid, which is an acid component. In performing the esterification reaction, the alcohol component is, for example, 1 , 4-cyclohexanedicarboxylic acid is preferably used in an amount of preferably 2.00 to 5.00 mol, more preferably 2.01 to 3.00 mol, especially 2.02 to 2.50 mol. Is done.

When a catalyst is used for the esterification reaction, examples of the catalyst include mineral acids, organic acids, Lewis acids and the like. More specifically, examples of the mineral acid include sulfuric acid, hydrochloric acid, and phosphoric acid, examples of the organic acid include p-toluenesulfonic acid and methanesulfonic acid, and examples of the Lewis acid include aluminum derivatives, tin derivatives, and titanium. Derivatives, lead derivatives, and zinc derivatives are exemplified, and one or more of these can be used in combination.

Among them, p-toluenesulfonic acid, tetraalkyl titanate having 3 to 8 carbon atoms, titanium oxide, titanium hydroxide, fatty acid tin having 3 to 12 carbon atoms, tin oxide, tin hydroxide, zinc oxide, zinc hydroxide, Lead oxide, lead hydroxide, aluminum oxide and aluminum hydroxide are particularly preferred. The amount used is, for example, preferably from 0.01 to 5.0% by weight, more preferably from 0.02 to 4.0% by weight, particularly with respect to the total weight of the acid component and alcohol component which are the raw materials for ester synthesis. It is recommended to use 0.03-3.0% by weight.

As esterification temperature, 100-230 degreeC is illustrated, and esterification reaction is normally completed in 3 to 30 hours.

1,4-cyclohexanedicarboxylic acid, which is an acid component of the raw material of the ester, is not particularly limited, and those produced by a known method, commercially available products, reagents and the like can be used.

[Transesterification]
The transesterification according to the present invention means an ester exchange reaction between the above alcohol component and dimethyl 1,4-cyclohexanedicarboxylate, which is an acid component. In performing the transesterification, the alcohol component is, for example, Preferably, 2.00 mol to 5.00 mol, more preferably 2.01 mol to 3.00 mol, especially 2.02 mol to 2.50 mol per 1 mol of dimethyl 1,4-cyclohexanedicarboxylate. Recommended to use.

When a catalyst is used for the transesterification reaction, examples of the catalyst include Lewis acids or alkali metals. More specifically, examples of the Lewis acid include aluminum derivatives, tin derivatives, titanium derivatives, lead derivatives, and zinc derivatives. Examples of alkali metals include sodium alkoxide, potassium alkoxide, sodium hydroxide, and potassium hydroxide. It is possible to use one or more of these in combination.

Among them, tetraalkyl titanate having 3 to 8 carbon atoms, titanium oxide, titanium hydroxide, sodium alkoxide having 1 to 4 carbon atoms, sodium hydroxide, fatty acid tin having 3 to 12 carbon atoms, tin oxide, tin hydroxide, oxidation Zinc, zinc hydroxide, lead oxide, lead hydroxide, aluminum oxide and aluminum hydroxide are particularly preferred. The amount used is, for example, preferably from 0.01 to 5.0% by weight, more preferably from 0.02 to 4.0% by weight, particularly with respect to the total weight of the acid component and alcohol component which are the raw materials for ester synthesis. It is recommended to use 0.03-3.0% by weight.

Examples of the transesterification temperature include 100 to 230 ° C, and the reaction is usually completed in 3 to 30 hours.

The dimethyl 1,4-cyclohexanedicarboxylate, which is an acid component of the raw material of the ester, is not particularly limited, and those produced by known methods, commercially available products, reagents and the like can be used.

As the raw acid component of the transesterification reaction, dimethyl 1,4-cyclohexanedicarboxylate is preferable, but other lower alkyl esters of 1,4-cyclohexanedicarboxylic acid (for example, having 2 or 3 carbon atoms) should be used equally. Can do.

In the esterification reaction or transesterification reaction, it is possible to use an entrainer or an entraining agent such as benzene, toluene, xylene, and cyclohexane in order to promote the distillation of water or methanol produced by the reaction.

In addition, when oxygenated organic compounds such as oxides, peroxides, and carbonyl compounds are produced during the esterification reaction or transesterification reaction due to oxidative degradation of the raw material, the produced ester and the organic solvent (water entraining agent), heat resistance, weather resistance, etc. Adversely affects. In order to suppress the adverse effect and from the viewpoint of safety, it is desirable to carry out the reaction under atmospheric pressure or reduced pressure in an inert gas atmosphere such as nitrogen gas or in an inert gas stream. After completion of the esterification reaction or transesterification reaction, excess raw materials are usually distilled off under reduced pressure or normal pressure.

The reaction crude product of the present ester obtained by the above reaction is usually purified by subsequent post-treatment. For example, treatment methods employed in this technical field such as catalyst deactivation treatment (neutralization treatment, base treatment, acid treatment, etc.), water washing treatment, liquid-liquid extraction, distillation (decompression, dehydration treatment), adsorption treatment, etc. It can be purified alone or in appropriate combination.

The base used for the base treatment is not particularly limited as long as it is a basic compound, and examples thereof include sodium hydroxide and sodium carbonate.

Examples of the adsorbent used for the adsorption treatment include activated carbon, activated clay, activated alumina, hydrotalcite, silica gel, silica alumina, zeolite, magnesia, calcia, and diatomaceous earth. They can be used alone or in combination of two or more.

The purification treatment after the reaction may be performed at room temperature, but may be performed by heating to about 40 to 95 ° C.

This ester has stereoisomers at two alkyloxycarbonyl group sites with respect to the cyclohexane ring. The present ester may be in any form of a cis isomer alone, a trans isomer alone, or a mixture of a cis isomer and a trans isomer, and can be appropriately selected according to a desired function in the detailed use of the plasticizer. . The ratio of the cis- or trans-isomer of this ester mainly affects the ratio of 1,4-cyclohexanedicarboxylic acid or its dimethyl ester itself, the method of the subsequent esterification or transesterification, and the reaction conditions. Is done.

<Vinyl chloride resin composition>
The vinyl chloride resin composition of the present invention can be obtained by blending the above-described ester with a vinyl chloride resin as a plasticizer.

[Vinyl chloride resin]
The vinyl chloride resin used in the present invention is a homopolymer of vinyl chloride or vinylidene chloride and a copolymer of vinyl chloride or vinylidene chloride, and the production method thereof is carried out by a conventionally known polymerization method. In the case of a general-purpose vinyl chloride resin, a method of suspension polymerization in the presence of an oil-soluble polymerization catalyst can be used. For vinyl chloride paste resin, a method of emulsion polymerization in the presence of a water-soluble polymerization catalyst in an aqueous medium can be used. The degree of polymerization of these vinyl chloride resins is usually 300 to 5000, preferably 400 to 3500, and more preferably 700 to 3000. If the degree of polymerization is too low, heat resistance and the like are lowered, and if it is too high, moldability tends to be lowered.

In the case of a copolymer, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1- C2-C30 α-olefins such as tridecene, 1-tetradecene, acrylic acid and its esters, methacrylic acid and its esters, maleic acid and its esters, vinyl acetate, vinyl propionate, alkyl vinyl ether, etc. Copolymers of vinyl compounds, polyfunctional monomers such as diallyl phthalate, and mixtures thereof with vinyl chloride monomers, ethylene-acrylate copolymers such as ethylene-ethyl acrylate copolymers, ethylene-methacrylate esters Polymer, ethylene-vinyl acetate copolymer (EVA), chlorinated polyester Ren, butyl rubber, crosslinked acrylic rubber, polyurethane, butadiene-styrene-methyl methacrylate copolymer (MBS), butadiene-acrylonitrile- (α-methyl) styrene copolymer (ABS), styrene-butadiene copolymer, polyethylene, poly Examples thereof include a graft copolymer obtained by grafting vinyl chloride monomer onto methyl methacrylate and a mixture thereof.

[Vinyl chloride resin composition]
The content of the present ester in the vinyl chloride resin composition is appropriately selected according to its use, but is usually 1 to 100 parts by weight, preferably 5 to 100 parts by weight of the vinyl chloride resin. 50 parts by weight. If it is less than 1 part by weight, it is difficult to obtain a predetermined plasticizing effect, and if it exceeds 100 parts by weight, bleeding on the surface of the molded product is severe, which is not preferable in either case.
However, when adding a filler etc. with respect to said vinyl chloride resin composition, since the filler itself absorbs oil, the said plasticizer can be mix | blended exceeding said range. For example, when 100 parts by weight of calcium carbonate as a filler is blended with 100 parts by weight of a vinyl chloride resin, about 1 to 500 parts by weight of the plasticizer can be blended.

In the vinyl chloride resin composition, other known plasticizers can be used in combination with the ester. If necessary, flame retardants, stabilizers, stabilizing aids, colorants, processing aids, fillers, antioxidants (anti-aging agents), UV absorbers, light stabilizers such as hindered amines, lubricants or electrification Additives such as inhibitors can be blended.

Other plasticizers and additives other than the present ester may be used alone or in combination of two or more kinds together with the present ester.

As other plasticizers that can be used in combination with the present ester, known plasticizers conventionally used in this technical field can be used. For example, benzoic acid esters such as diethylene glycol dibenzoate, dibutyl phthalate (DBP) ), Di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), ditridecyl phthalate (DTDP), bis (2-ethylhexyl terephthalate) ( DOTP), phthalates such as bis (2-ethylhexyl) isophthalate (DOIP), di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-sebacate 2-ethylhexyl (DOS), Aliphatic dibasic acid esters such as diisononyl basinate (DINS), trimellitic acid esters such as trimellitic acid tri-2-ethylhexyl (TOTM), trimellitic acid triisononyl (TINTM), trimellitic acid triisodecyl (TIDTM) , Pyromellitic acid esters such as pyromellitic acid tetra-2-ethylhexyl (TOPM), phosphoric acid esters such as tri-2-ethylhexyl phosphate (TOP) and tricresyl phosphate (TCP), and polyvalent such as pentaerythritol Alkyl esters of alcohol, polyesters having a molecular weight of 800-4000 synthesized by polyesterification of dibasic acid such as adipic acid and glycol, epoxidized esters such as epoxidized soybean oil and epoxidized linseed oil, hexahydrophthalic acid Diisonononi Alicyclic dibasic acid esters such as esters (DINCH), fatty acid glycol esters such as dicapric acid-1,4-butanediol, tributyl acetyl citrate (ATBC), trihexyl acetyl citrate (ATHC) ), Citrate esters such as triethylhexyl acetyl citrate (ATEHC) and trihexyl butyryl citrate (BTHC), chlorinated paraffins chlorinated paraffin wax and n-paraffin, chlorinated fatty acid esters such as chlorinated stearates And higher fatty acid esters such as butyl oleate. When the other plasticizers that can be used in combination are blended, the blending amount is recommended to be about 1 to 100 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

Flame retardants include inorganic compounds such as aluminum hydroxide, antimony trioxide, magnesium hydroxide, zinc borate, cresyl diphenyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, trisdichloropropyl phosphate, etc. Illustrative are halogen compounds such as phosphorus compounds and chlorinated paraffins. Moreover, when mix | blending a flame retardant, about 0.1-20 weight part is recommended as the compounding quantity of the flame retardant with respect to 100 weight part of vinyl chloride resin.

Stabilizers include lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc octylate, zinc laurate, zinc ricinoleate, stearic acid Metal soap compounds such as zinc, barium stearate-zinc, barium zinc laurate, barium zinc ricinoleate, barium zinc octylate, calcium stearate-zinc, calcium laurate zinc, calcium ricinoleate zinc, calcium octylate -Metal soap compounds such as organic acid compounds containing composite metals such as zinc, dimethyltin bis-2-ethylhexyl thioglycolate, dibutyltin maleate, dibutyltin bisbutyl maleate , Organotin compounds such as dibutyltin dilaurate, antimony mercaptan Tide compounds and the like. Moreover, when mix | blending a stabilizer, about 0.1-20 weight part is recommended as the compounding quantity of the stabilizer with respect to 100 weight part of vinyl chloride-type resin.

Stabilization aids include phosphite compounds such as triphenyl phosphite, monooctyl diphenyl phosphite, tridecyl phosphite, beta diketone compounds such as acetylacetone and benzoylacetone, glycerin, sorbitol, pentaerythritol, polyethylene glycol, etc. Examples include polyol compounds, perchlorate compounds such as barium perchlorate and sodium perchlorate, hydrotalcite compounds, and zeolites. Moreover, when mix | blending a stabilization adjuvant, about 0.1-20 weight part is recommended as the compounding quantity of the stabilization adjuvant with respect to 100 weight part of vinyl chloride-type resin.

Examples of the colorant include carbon black, lead sulfide, white carbon, titanium white, lithopone, benigara, antimony sulfide, chrome yellow, chrome green, cobalt blue, and molybdenum orange. Moreover, when mix | blending a coloring agent, about 1-100 weight part is recommended as the compounding quantity of the coloring agent with respect to 100 weight part of vinyl chloride resin.

Examples of the processing aid include liquid paraffin, polyethylene wax, stearic acid, stearic acid amide, ethylene bis stearic acid amide, butyl stearate, calcium stearate and the like. Moreover, when mix | blending a processing aid, about 0.1-20 weight part is recommended as the compounding quantity of the processing aid with respect to 100 weight part of vinyl chloride-type resin.

Fillers include metal oxides such as calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, ferrite, fibers and powders such as glass, carbon, metal, glass spheres, graphite, aluminum hydroxide, barium sulfate, oxidation Examples include magnesium, magnesium carbonate, magnesium silicate, calcium silicate, and the like. Moreover, when mix | blending a filler, about 1-100 weight part is recommended as the compounding quantity of the filler with respect to 100 weight part of vinyl chloride resin.

Antioxidants include 2,6-di-tert-butylphenol, tetrakis [methylene-3- (3,5-tert-butyl-4-hydroxyphenol) propionate] methane, 2-hydroxy-4-methoxybenzophenone, and the like. Sulfur compounds such as phenolic compounds, alkyl disulfides, thiodipropionic esters, benzothiazoles, trisnonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, tris (2,4-di-tert-butylphenyl) ) Phosphinic compounds such as phosphites, organometallic compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate. Moreover, when mix | blending antioxidant, about 0.2-20 weight part of the compounding quantity of antioxidant with respect to 100 weight part of vinyl chloride resin is recommended.

Examples of ultraviolet absorbers include salicylate compounds such as phenyl salicylate and p-tert-butylphenyl salicylate, benzophenone compounds such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-n-methoxybenzophenone, In addition to benzotriazole compounds such as 5-methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, cyanoacrylate compounds are exemplified. Moreover, when mix | blending a ultraviolet absorber, about 0.1-10 weight part is recommended as the compounding quantity of the ultraviolet absorber with respect to 100 weight part of vinyl chloride-type resin.

Examples of hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1 , 2,2,6,6-pentamethyl-4-piperidyl sebacate (mixture), bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1- Dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) ester and 1,1-dimethylethyl Reaction product of hydroperoxide and octane, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidino And higher fatty acid ester mixtures, 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, polycondensate of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 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}}, dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6) -Tetramethyl- Polycondensate of 4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, N, N ′, N ″, N ′ ″ − Tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1 , 10-diamine, etc. In addition, when a light stabilizer is blended, the blending amount of the light stabilizer with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 0.1 to 10 parts by weight.

Examples of the lubricant include silicone, liquid paraffin, baraffin wax, fatty acid metal salts such as metal stearate and metal laurate, fatty acid amides, fatty acid wax, and higher fatty acid wax. When a lubricant is blended, the blending amount of the lubricant with respect to 100 parts by weight of the vinyl chloride resin is recommended to be about 0.1 to 10 parts by weight.

Antistatic agents include alkyl sulfonate type, alkyl ether carboxylic acid type or dialkyl sulfosuccinate type anionic antistatic agents, non-ionic antistatic agents such as polyethylene glycol derivatives, sorbitan derivatives, diethanolamine derivatives, alkylamidoamine type, alkyl Examples include quaternary ammonium salts such as dimethylbenzyl type, cationic antistatic agents such as alkylpyridinium type organic acid salts or hydrochlorides, amphoteric antistatic agents such as alkylbetaine type and alkylimidazoline type. Moreover, when mix | blending an antistatic agent, about 0.1-10 weight part of the compounding quantity of the antistatic agent with respect to 100 weight part of vinyl chloride-type resin is recommended.

The vinyl chloride resin composition of the present invention is prepared by, for example, handling and mixing the ester, vinyl chloride resin and various additives as necessary, using a mortar mixer, Henschel mixer, Banbury mixer, ribbon blender, or the like. Stirring and mixing can be performed to obtain a mixed powder of the vinyl chloride resin composition.

Further, the present ester, vinyl chloride resin and, if necessary, other plasticizers and various additives other than the present ester, for example, a conical twin screw extruder, a parallel twin screw extruder, a single screw extruder, a kneader type kneader A pellet-like vinyl chloride resin composition can also be obtained by melt mixing with a kneader such as a roll kneader.

In addition, the present ester, vinyl chloride paste resin and optionally other plasticizers and various additives other than the present ester, such as pony mixer, butterfly mixer, planetary mixer, ribbon blender, kneader, dissolver, twin screw mixer, It can also mix uniformly with mixers, such as a Henschel mixer and a three roll mill, and if necessary, defoaming can be performed under reduced pressure to obtain a pasty vinyl chloride resin composition.

[Vinyl chloride resin molding]
Conventionally known methods such as vacuum molding, compression molding, extrusion molding, injection molding, calendar molding, press molding, blow molding, powder molding, etc., for the vinyl chloride resin composition (mixed powder or pellets) according to the present invention Can be molded into a desired shape.

On the other hand, the above-mentioned paste-like vinyl chloride resin composition is molded using a conventionally known molding method such as spread molding, dipping molding, gravure molding, slush molding, rotational molding, casting, screen processing, etc. It can be formed into a desired shape.

The shape of the molded body is not particularly limited, but, for example, rod-shaped, sheet-shaped, film-shaped, plate-shaped, cylindrical, circular, elliptical, etc., or special shapes such as toys, ornaments, such as stars, A polygonal shape is illustrated.

The molded body thus obtained includes pipes such as water pipes, joints for pipes, raindrops, etc., window frame siding, flat plate, corrugated sheet, automobile underbody coat, instrument panel, console, door seat. Automotive parts such as under carpets, trunk seats, door trims, various leathers, decorative sheets, agricultural films, food packaging films, electric wire coatings, various foam products, hoses, medical tubes, food tubes, refrigerators Gaskets, packing, wallpaper, flooring, boots, curtains, shoe soles, gloves, waterproofing boards, toys, decorative boards, blood bags, infusion bags, tarpaulins, mats, waterproof sheets, civil engineering sheets, roofing, tarpaulins It is useful for insulating sheets, industrial tapes, glass films, erasers, sealing materials and the like.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, the symbol of the compound in an Example and a comparative example, and the measurement of each characteristic are as follows.

(1) Linearity of saturated aliphatic alcohol mixture The linearity of the saturated aliphatic alcohol mixture (raw alcohol) used in Examples and Comparative Examples of the present invention was measured by gas chromatography (hereinafter abbreviated as GC). The measuring method of raw material alcohol by GC is as follows.
<< GC measurement conditions >>
Model: Gas chromatograph GC-17A (manufactured by Shimadzu Corporation)
Detector: FID
Column: Capillary column DB-1 30m
Column temperature: raised from 60 ° C to 290 ° C. Temperature increase rate = 13 ° C./min Carrier gas: helium Sample: 50% acetone solution Injection volume: 1 μl
Quantification method: Quantification was performed using 1-hexanol as an internal standard substance.
In selecting an internal standard substance, it was confirmed in advance that 1-hexanol in the raw material alcohol was below the detection limit by GC.

(2) Evaluation of physical properties of 1,4-cyclohexanedicarboxylic acid diester Esters obtained in the following production examples were analyzed by the following method.
Ester value: Measured according to JIS K-0070 (1992).
Acid value: measured in accordance with JIS K-0070 (1992).
Hue: The Hazen unit color number was determined according to the color number test method (Hazen) of JIS K-0071 (1998). The hue was evaluated based on the number of colors.

(3) Preparation of vinyl chloride resin composition and preparation of roll sheet and press sheet Stable in 100 parts by weight of vinyl chloride resin (straight, degree of polymerization 1050, trade name “Zest1000Z”, manufactured by Shin Daiichi PVC Co., Ltd.) After compounding 0.3 parts by weight and 0.2 parts by weight of calcium stearate (manufactured by Nacalai Tesque) and zinc stearate (manufactured by Nacalai Tesque) as agents, stirring and mixing with a mortar mixer, 50 parts by weight of a plasticizer was added and handled and mixed until uniform to obtain a vinyl chloride resin composition. This resin composition was melt-kneaded at 160 to 166 ° C. for 4 minutes using a 5 × 12 inch double roll to prepare a roll sheet. Subsequently, press molding was performed at 162 to 168 ° C. for 10 minutes to produce a press sheet having a thickness of about 1 mm.

[Evaluation of the physical properties]
(4) Tensile properties: Based on JIS K-6723 (1995), 100% modulus, breaking strength and breaking elongation of the press sheet were measured. The smaller the value of 100% modulus, the better the flexibility, and the breaking strength and breaking elongation are measures of the practical strength of the material. Generally, the larger the value, the more practical the strength. It can be said that it is excellent.

(5) Cold resistance: The flexible temperature (° C.) was measured according to JIS K-6773 (1999) using a Crushberg tester. The lower the softening temperature, the better the cold resistance. The flexible temperature here refers to a temperature at a low temperature limit indicating a predetermined torsional rigidity (3.17 × 10 ³ kg / cm ² ) in the measurement.

(6) Heat resistance: Based on evaluation of volatile loss and sheet coloring.
a) Volatilization loss: The weight change of each roll sheet was measured after heating the roll sheet at 170 ° C. for 60 minutes and 120 minutes in a gear oven, and the weight reduction rate (% by weight) was calculated. This weight reduction rate is evaluated as volatile loss, and it can be said that the smaller the value, the higher the heat resistance.
Volatilization loss (% by weight) = ((weight before test−weight after test) / weight before test) × 100
b) Sheet coloring: The strength of each coloring degree after the roll sheet was heated at 170 ° C. for 30 minutes and 60 minutes in a gear oven was visually evaluated in 6 stages.
◎: No coloring, ○: Slightly colored, ○ △: Slightly colored,
Δ: Coloring, ×: Strong coloring, XX: Remarkable coloring

[Production Example 1]
In a 1 L four-necked flask equipped with a thermometer, decanter, stirring blade, and reflux condenser tube, 240 g (1.2 mol) of dimethyl 1,4-cyclohexanedicarboxylate (manufactured by SK Chemicals, trade name “SKY CHDM”), A saturated aliphatic alcohol mixture containing 85.1% by weight of a linear saturated aliphatic alcohol having 9 carbon atoms and 11.7% by weight of a branched saturated aliphatic alcohol having 9 carbon atoms as a raw material alcohol (Shell Chemicals) 416 g (2.9 mol) of trade name “Lineball 9”) and 0.5 g of tetraisopropyl titanate as a transesterification catalyst were added, and the transesterification reaction was carried out at a reaction temperature of 210 ° C. The reaction was carried out on the gas chromatography until the peaks of the raw material and the intermediate were below the detection limit while the raw material alcohol was refluxed under reduced pressure to remove the generated water from the system. After completion of the reaction, the unreacted alcohol was distilled out of the system under reduced pressure, and then neutralized (base treatment), washed with water and dehydrated according to a conventional method to obtain 1,4-cyclohexanedicarboxylic acid diester (hereinafter referred to as “ 450 g of ester 1 ”.
The obtained ester 1 had an ester value of 261 mgKOH / g, an acid value of 0.04 mgKOH / g, and a hue of 10.

[Production Example 2]
A saturated aliphatic alcohol mixture of 374 g (2.6 mol) of n-nonyl alcohol and 42 g (0.3 mol) of isononyl alcohol instead of 416 g of a saturated aliphatic alcohol mixture (manufactured by Shell Chemicals, trade name “Lineball 9”) Except having used the alcohol mixture, it implemented similarly to manufacture example 1 and obtained 1, 4- cyclohexane dicarboxylic acid diester (henceforth "ester 2") 381g.
The obtained ester 2 had an ester value of 259 mgKOH / g, an acid value of 0.03 mgKOH / g, and a hue of 10.

[Production Example 3]
A saturated aliphatic alcohol mixture of 291 g (2.0 mol) of n-nonyl alcohol and 124 g (0.9 mol) of isononyl alcohol instead of 416 g of a saturated aliphatic alcohol mixture (manufactured by Shell Chemicals, Inc .: trade name “LINEBOL 9”) Except having used the alcohol mixture, it implemented similarly to manufacture example 1, and obtained 372g of 1, 4- cyclohexane dicarboxylic acid diester (henceforth "ester 3").
The obtained ester 3 had an ester value of 260 mgKOH / g, an acid value of 0.02 mgKOH / g, and a hue of 10.

[Production Example 4]
The same procedure as in Production Example 1 was conducted, except that 374 g of 2-ethylhexanol was used instead of 416 g of a saturated aliphatic alcohol mixture (manufactured by Shell Chemicals: trade name “Lineball 9”). 435 g of 2-ethylhexyl (hereinafter referred to as “ester 4”) was obtained.
The obtained ester 4 had an ester value of 283 mgKOH / g, an acid value of 0.01 mgKOH / g, and a hue of 10.

[Production Example 5]
The same procedure as in Production Example 1 was carried out except that 416 g of isononyl alcohol was used instead of 416 g of a saturated aliphatic alcohol mixture (manufactured by Shell Chemicals: trade name “Rineball 9”), and diisononyl 1,4-cyclohexanedicarboxylate ( Hereinafter, the ester is referred to as “ester 3”.
The obtained ester 5 had an ester value of 265 mgKOH / g, an acid value of 0.01 mgKOH / g, and a hue of 15.

[Production Example 6]
Manufactured except that 208 g (1.4 mol) of n-nonyl alcohol and 208 g (1.4 mol) of isononyl alcohol were added in place of 416 g of the saturated fatty alcohol mixture (manufactured by Shell Chemicals: trade name “Lineball 9”). In the same manner as in Example 1, 451 g of 1,4-cyclohexanedicarboxylic acid diester (hereinafter referred to as “ester 6”) was obtained.
The obtained ester 6 had an ester value of 260 mgKOH / g, an acid value of 0.02 mgKOH / g, and a hue of 10.

[Production Example 7]
This was carried out in the same manner as in Production Example 1 except that 456 g (2.9 mol) of isodecyl alcohol was added instead of 416 g of a saturated aliphatic alcohol mixture (manufactured by Shell Chemicals: trade name “Lineball 9”). -461 g of diisodecyl cyclohexanedicarboxylate (hereinafter referred to as “ester 7”) was obtained.
The obtained ester 7 had an ester value of 246 mgKOH / g, an acid value of 0.02 mgKOH / g, and a hue of 10.

[Example 1]
Using the ester 1 obtained in Production Example 1, the vinyl chloride resin composition of the present invention was prepared by the above preparation method. Subsequently, using the obtained vinyl chloride resin composition, a roll sheet and a press sheet were produced by the production method described above, and a tensile test, a cold resistance test, and a heat resistance test were performed. The obtained results are shown in Table 1.

[Example 2]
The vinyl chloride resin composition of the present invention was prepared in the same manner as in Example 1 except that the ester 2 obtained in Production Example 2 was used instead of the ester 1, and a roll was prepared using the resin composition. Sheets and press sheets were prepared and subjected to a tensile test, a cold resistance test, and a heat resistance test. The results obtained are summarized in Table 1.

[Example 3]
A vinyl chloride resin composition of the present invention was prepared in the same manner as in Example 1 except that the ester 3 obtained in Production Example 3 was used instead of the ester 1, and a roll was prepared using the resin composition. Sheets and press sheets were prepared and subjected to a tensile test, a cold resistance test, and a heat resistance test. The results obtained are summarized in Table 1.

[Comparative Example 1]
A vinyl chloride resin composition outside the present invention was prepared in the same manner as in Example 1 except that the ester 4 obtained in Production Example 4 was used instead of the ester 1, and the resin composition was used. A roll sheet and a press sheet were prepared and subjected to a tensile test, a cold resistance test, and a heat resistance test. The results obtained are summarized in Table 1.

[Comparative Example 2]
A vinyl chloride resin composition outside the present invention was prepared in the same manner as in Example 1 except that the ester 5 obtained in Production Example 5 was used instead of the ester 1, and the resin composition was used. A roll sheet and a press sheet were prepared and subjected to a tensile test, a cold resistance test, and a heat resistance test. The results obtained are summarized in Table 1.

[Comparative Example 3]
A vinyl chloride resin composition outside the present invention was prepared in the same manner as in Example 1 except that the ester 6 obtained in Production Example 6 was used instead of the ester 1, and the resin composition was used. A roll sheet and a press sheet were prepared and subjected to a tensile test, a cold resistance test, and a heat resistance test. The results obtained are summarized in Table 1.

[Comparative Example 4]
A vinyl chloride resin composition outside the present invention was prepared in the same manner as in Example 1 except that the ester 7 obtained in Production Example 7 was used instead of the ester 1, and the resin composition was used. A roll sheet and a press sheet were prepared and subjected to a tensile test, a cold resistance test, and a heat resistance test. The results obtained are summarized in Table 1.

[Comparative Example 5]
A vinyl chloride resin composition outside the present invention was prepared in the same manner as in Example 1 except that commercially available diisononyl 1,2-cyclohexanedicarboxylate (hexamol DINCH, manufactured by BASF) was used instead of ester 1. Then, a roll sheet and a press sheet were prepared using the resin composition, and a tensile test, a cold resistance test, and a heat resistance test were performed. The results obtained are summarized in Table 1.

[Comparative Example 6]
The vinyl chloride resin composition outside the present invention was carried out in the same manner as in Example 1 except that commercially available di-2-ethylhexyl phthalate (manufactured by Shin Nippon Rika Co., Ltd., Sunsocizer DOP) was used instead of ester 1. A roll sheet and a press sheet were prepared using the resin composition, and a tensile test, a cold resistance test, and a heat resistance test were performed. The results obtained are summarized in Table 1.

From the results of Table 1, it is clear that the 1,4-cyclohexanedicarboxylic acid diesters of the present invention (Examples 1 to 3) are DOPs of phthalate ester plasticizers used so far (not only Comparative Example 6), Compared to DINCH (Comparative Example 5), a non-phthalate plasticizer that is currently widely used, it can be seen that it has excellent flexibility and has greatly improved cold resistance and heat resistance. Even when compared with 1,4-cyclohexanedicarboxylic acid diesters having a chain length of 1 to 4 or a linearity ratio outside the scope of the present invention, it is clear that the balance between cold resistance, heat resistance and tensile properties is excellent. From the above results, it can be seen that the ester plasticizers within the scope of the present invention are extremely useful plasticizers that exhibit unprecedented high cold resistance and heat resistance and are excellent in balance with other physical properties.

The plasticizer for vinyl chloride resin essentially consisting of 1,4-cyclohexanedicarboxylic acid diester of the present invention has good compatibility with vinyl chloride resin and has excellent cold resistance and heat resistance with respect to vinyl chloride resin, As a plasticizer for a vinyl chloride resin that can impart good flexibility, it can be used under various molding conditions. Molded products obtained from the vinyl chloride resin composition containing the plasticizer are used for wire coating applications and automotive member applications that require high cold resistance, heat resistance and flexibility, general film sheets (laminates, Packaging, vehicles, miscellaneous goods, etc.), agricultural film applications, leather applications, compound applications, flooring applications, wallpaper applications, footwear applications, sealing materials applications, textile applications, hose applications, gasket applications, building materials applications, paint applications, It is very useful for adhesives, pastes, and medical applications.

Claims (5)

  1,4-cyclohexane obtained by esterification or transesterification of 1,4-cyclohexanedicarboxylic acid or dimethyl ester thereof and a mixture of saturated aliphatic alcohols mainly composed of saturated aliphatic alcohols having 9 carbon atoms A plasticizer for a vinyl chloride resin comprising a dicarboxylic acid diester, wherein the saturated aliphatic alcohol mixture is a linear saturated aliphatic hydrocarbon having a content of 60 to 95% by weight in a saturated aliphatic alcohol. A vinyl chloride comprising an alcohol and 5 to 40% by weight of a branched saturated aliphatic alcohol having 9 carbon atoms, and the linear ratio of the saturated aliphatic alcohol mixture is 60 to 95% Plasticizer for plastic resin.   The saturated fatty alcohol mixture has a saturated aliphatic alcohol content of 70 to 90% by weight of a linear saturated aliphatic alcohol having 9 to 9 carbon atoms and 10 to 30% by weight of a branched chain having 9 carbon atoms. 2. The plasticizer for vinyl chloride resin according to claim 1, comprising a saturated aliphatic alcohol and having a linear chain ratio of 70 to 90% in the saturated aliphatic alcohol mixture. 1,4-cyclohexanedicarboxylic acid obtained by esterification or transesterification of 1,4-cyclohexanedicarboxylic acid or its dimethyl ester and a saturated aliphatic alcohol mixture mainly composed of a saturated aliphatic alcohol having 9 carbon atoms A plasticizer for vinyl chloride resin comprising an acid diester,
The saturated aliphatic alcohol mixture comprises (1) a step of producing a 9-carbon aldehyde by hydroformylation reaction of 1-octene, carbon monoxide and hydrogen, and (2) an alcohol obtained by hydrogenating a 9-carbon aldehyde. A plasticizer for a vinyl chloride resin, comprising a saturated aliphatic alcohol having a straight chain structure and a branched chain structure, which is produced by a production process comprising a step of reducing to a vinyl chloride resin.   A vinyl chloride resin composition comprising a vinyl chloride resin and the plasticizer for vinyl chloride resin according to any one of claims 1 to 3.   A vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition according to claim 4.