Polyester-based plasticizer, vinyl chloride-based resin composition containing the same, and molded article thereof

Abstract

To provide a polyester-based plasticizer which can impart excellent weather resistance and salt water resistance to a resin composition, a vinyl chloride-based resin composition containing the same, and a molded body of the same.SOLUTION: A polyester-based plasticizer is obtained from a dibasic acid component (A), a glycol component (B), and a terminating component (C), wherein the dibasic acid component (A) is at least one of o-phthalic acid or isophthalic acid, the glycol component (B) is one or more selected from a group of neopentyl glycol, 3-methyl-1,5-pentanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, and 1,4-butanediol, and the terminating component (C) is one or more selected from a group of monohydric alcohols.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyester plasticizer, a vinyl chloride resin composition containing the same (hereinafter, also simply referred to as "resin composition"), and a molded body thereof. Specifically, the present invention relates to a polyester plasticizer capable of imparting excellent weather resistance and salt water resistance to the resin composition, a vinyl chloride resin composition containing the same, and a molded body thereof.

Background Art

[0002] Plasticizers are added to various synthetic resins such as vinyl chloride resins to lower their melt viscosity and facilitate molding processability, and to impart properties such as flexibility and elasticity to the synthetic resins, so as to adapt the synthetic resins to various uses, and are widely used.

[0003] As such plasticizers, monomeric plasticizers such as dioctyl phthalate and dioctyl adipate are generally used.

[0004] However, when vinyl chloride resins blended with these plasticizers are used outdoors, weather resistance against ultraviolet rays, rain, wind, temperature changes, etc. due to sunlight is required.

[0005] In addition, when vinyl chloride resins are used outdoors near the sea, seawater is blown by the wind and adheres, etc., and deterioration due to the salt content in seawater becomes a problem, and salt water resistance is required.

[0006] On the other hand, for example, in Patent Document 1, the use of phthalic acid plasticizers, trimellitic acid plasticizers, and polyester plasticizers is proposed, but their weather resistance performance is insufficient and not satisfactory. Regarding salt water resistance, there is no description at all, and no findings can be obtained.

[0007] Furthermore, while Patent Document 2 proposes the use of a polyester-based plasticizer with a specific structure, its weather resistance is insufficient and unsatisfactory, and there is no mention of saltwater resistance, making it impossible to gain any insights. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2003-73517 [Patent Document 2] Japanese Patent Application Publication No. 7-126466 [Overview of the project] [Problems that the invention aims to solve]

[0009] Thus, conventional plasticizers had the problem of insufficient performance in terms of weather resistance and saltwater resistance.

[0010] Therefore, an object of the present invention is to provide a polyester-based plasticizer that can impart excellent weather resistance and saltwater resistance to resin compositions. Furthermore, another object of the present invention is to provide a vinyl chloride-based resin composition containing the plasticizer of the present invention and a molded article thereof. [Means for solving the problem]

[0011] As a result of diligent research to resolve the above-mentioned problems, the inventors have found that a polyester-based plasticizer comprising a predetermined dibasic acid component, a predetermined glycol component, and a predetermined end-termination component can solve the above-mentioned problems, and have completed the present invention.

[0012] In other words, the polyester plasticizer of the present invention is a polyester plasticizer obtained from a dibasic acid component (A), a glycol component (B), and a terminal termination component (C), The dibasic acid component (A) is at least one of o-phthalic acid or isophthalic acid. The glycol component (B) is one or more selected from the group consisting of neopentyl glycol, 3-methyl-1,5-pentanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, and 1,4-butanediol. The end-stop component (C) is characterized by being one or more selected from the group consisting of monohydric alcohols.

[0013] In the polyester-based plasticizer of the present invention, the dibasic acid component (A) is preferably isophthalic acid.

[0014] Furthermore, in the polyester-based plasticizer of the present invention, it is preferable that the viscosity at 25°C is 50 to 5000 mPa·s.

[0015] The vinyl chloride resin composition of the present invention is characterized by containing the polyester plasticizer of the present invention.

[0016] The molded article of the present invention is characterized by being composed of the vinyl chloride resin composition of the present invention. [Effects of the Invention]

[0017] According to the present invention, a polyester-based plasticizer can be provided that can impart excellent weather resistance and saltwater resistance to a resin composition. Furthermore, according to the present invention, a vinyl chloride-based resin composition with excellent weather resistance and saltwater resistance, and a molded article of a vinyl chloride-based resin with excellent weather resistance and saltwater resistance can be provided. [Modes for carrying out the invention]

[0018] Embodiments of the present invention will be described in detail below. First, the polyester plasticizer of the present invention will be described. The polyester plasticizer of the present invention is a polyester plasticizer obtained from a dibasic acid component (A), a glycol component (B), and a terminal blocking component (C), wherein the dibasic acid component (A) is at least one of o-phthalic acid or isophthalic acid, the glycol component (B) is one or more selected from the group consisting of neopentyl glycol, 3-methyl-1,5-pentanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, and 1,4-butanediol, and the terminal blocking component (C) is one or more selected from the group consisting of monohydric alcohols.

[0019] In the polyester plasticizer of the present invention, the dibasic acid component (A) is at least one of o-phthalic acid or isophthalic acid, and isophthalic acid is preferred from the viewpoints of weather resistance and salt water resistance.

[0020] Further, the dibasic acid component may be a derivative of a dibasic acid, and examples of the derivative include carboxylic acid anhydrides, carboxylic acid esters (e.g., alkyl carboxylic acid esters such as methyl carboxylic acid ester), carboxylic acid alkali metal salts (sodium carboxylic acid salt), carboxylic acid halides (e.g., carboxylic acid chloride), and the like.

[0021] In addition to the dibasic acid component (A), in the polyester plasticizer of the present invention, any dibasic acid can be used as long as the effects of the present invention are not impaired. Examples of the arbitrary dibasic acid include terephthalic acid, sebacic acid, azelaic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, undecanedioic acid, dodecanedioic acid, and the like.

[0022] In the polyester plasticizer of the present invention, the glycol component (B) is one or more selected from the group consisting of neopentyl glycol, 3-methyl-1,5-pentanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, and 1,4-butanediol.

[0023] In addition to the glycol component (B), the polyester plasticizer of the present invention may also use any glycol as long as it does not impair the effects of the present invention. Examples of any glycol include ethylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decanediol, 2-butyl-2-ethyl-1,5-propanediol, 1,12-octadecanediol, diethylene glycol, dipropylene glycol, and the like.

[0024] In the polyester-based plasticizer of the present invention, the end-termination component (C) is one or more selected from the group of monohydric alcohols. Examples of monohydric alcohols include 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-butanol, isobutanol, decantal butanol, tertiary butanol, 1-heptanol, isohexanol, isooctanool, 2-ethylhexanol, isononyl alcohol, 2-methyloctanol, isodecanol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecanol, hexadecanol, stearyl alcohol, and the like.

[0025] In addition to the monohydric alcohol as the terminal termination component (C) of the polyester plasticizer of the present invention, any monohydric fatty acid may be used as long as it does not impair the effects of the present invention. Examples of any monohydric fatty acid include octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, myristic acid, palmitic acid, stearic acid, oleic acid, and linoleic acid.

[0026] Furthermore, the polyester plasticizer of the present invention can use hydroxy acids such as 12-hydroxystearic acid, lactic acid, ricinoleic acid, and glycolic acid, glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, trimellitic acid, pyromellitic acid, etc. as optional components within the range that does not impair the effects of the present invention, and trivalent or higher polyhydric alcohols and polybasic acids.

[0027] In terms of weather resistance and salt water resistance, the component ratios of the dibasic acid component (A), glycol component (B), and terminal blocking component (C) of the polyester plasticizer of the present invention are preferably 30 to 60% by mass for the dibasic acid component (A), 1 to 30% by mass for the glycol component (B), and 20 to 70% by mass for the terminal blocking component (C), and more preferably 30 to 50% by mass for the dibasic acid component (A), 1 to 20% by mass for the glycol component (B), and 30 to 70% by mass for the terminal blocking component (C).

[0028] In terms of weather resistance and salt water resistance, the number average molecular weight of the polyester plasticizer of the present invention is preferably 500 to 1000, more preferably 500 to 900, and even more preferably 500 to 800. If it is less than 500, it is not preferable in terms of weather resistance and salt water resistance, and if it exceeds 1000, it is not preferable in terms of cold resistance.

[0029] The measurement method of the number average molecular weight is preferably the measurement method by GPC, and the measurement method is shown below.

[0030] <Measurement Method of Number Average Molecular Weight by GPC> A sample obtained by dissolving 50 mg of the sample in 10 mL of THF is analyzed by splitting the peak with a differential refractive index detector using a semi-micro GPC column (SHODEX KF-402.5 manufactured by Showa Denko KK), and the average molecular weight is calculated in terms of polystyrene conversion.

[0031] The viscosity of the polyester plasticizer of the present invention is preferably 50 to 5000 mPa·s, more preferably 50 to 3000 mPa·s, and even more preferably 50 to 2000 mPa·s at 25°C from the viewpoints of weather resistance and salt water resistance. If it is less than 50 mPa·s, it is not preferable from the viewpoints of weather resistance and salt water resistance, and if it exceeds 5000 mPa·s, it is not preferable from the viewpoint of cold resistance. The method for measuring the viscosity is preferably the method using a B-type viscometer, and the measurement method is shown below.

[0032] <Method for Measuring Viscosity by B-Type Viscometer> After attaching a rotor and a measuring container according to the viscosity of the measurement sample to the B-type viscometer, immerse the measuring container in a constant temperature water bath set at 25°C. Leave it until the sample reaches a constant temperature, and select the rotation speed according to the viscosity. Perform the measurement for a specified time, and read the automatically calculated digital display measurement value.

[0033] The acid value of the polyester plasticizer of the present invention is preferably 0 to 10, more preferably 0 to 5, and even more preferably 0 to 3 from the viewpoints of weather resistance and salt water resistance. The acid value can be measured by the following measurement method.

[0034] <Acid Value Measurement Method> Precisely weigh the sample in the container in units of 10 mg, and dissolve it sufficiently with a neutral xylene / ethanol solution. Add a few drops of phenolphthalein indicator, and titrate with 0.1 N KOH aqueous solution.

[0035] The hydroxyl value of the polyester plasticizer of the present invention is preferably 0 to 30, more preferably 3 to 20 from the viewpoints of weather resistance and salt water resistance. The hydroxyl value can be measured by the following measurement method.

[0036] <Hydroxyl Value Measurement Method> Precisely weigh the sample in the container in units of 10 mg, and dissolve it sufficiently with 10 mL of TEP (triethyl phosphate). After adding 15 mL of Reagent A and stirring well, add 20 mL of Reagent D, and let it stand for 5 minutes. Add 50 mL of neutral isopropyl alcohol, add a few drops of phenolphthalein indicator, and titrate with 1.0 N KOH aqueous solution.

[0037] In the polyester-based plasticizer of the present invention, the method of production is not particularly limited, and known methods for producing polyester can be used. That is, components (A) to (C), and any optional components as needed, can be subjected to an esterification reaction. A catalyst may be used in the esterification reaction. During the reaction, pressure or vacuum may be applied, and the reaction temperature during the esterification reaction is preferably 150 to 250°C, more preferably 180 to 230°C.

[0038] Furthermore, after the esterification reaction is complete, operations to remove low molecular weight components can be performed as needed. Methods for removing low molecular weight components include thin-film distillation, column chromatography, and membrane separation, with thin-film distillation being preferred.

[0039] Examples of esterification catalysts include acidic catalysts such as sulfuric acid, phosphoric acid, zinc chloride, benzenesulfonic acid, p-toluenesulfonic acid, and 4-chlorobenzenesulfonic acid; alkoxytitanium compounds such as tetramethoxytitanium, tetraethoxytitanium, and tetraisopropoxytitanium; titanium acylate compounds such as polyhydroxytitanium stearate and polyisopropoxytitanium stearate; titanium chelate compounds such as titanium acetyl acetate, triethanolamine titanate, titanium ammonium lactate, titanium ethyl lactate, and titanium octylene glycolate; tin compounds such as dibutyltin dilaurate, dibutyltin oxide, and dibutyltin diacetate; metal acetate salts such as magnesium acetate, calcium acetate, and zinc acetate; and metal oxides such as antimony oxide and zirconium oxide. These can be used individually or in combination.

[0040] The polyester-based plasticizer of the present invention is preferably compounded with a vinyl chloride resin and used as a vinyl chloride resin composition.

[0041] The amount of the polyester plasticizer of the present invention blended into the vinyl chloride resin is preferably 1 to 200 parts by mass, preferably 5 to 150 parts by mass, preferably 8 to 150 parts by mass, and more preferably 10 to 100 parts by mass, per 100 parts by mass of the vinyl chloride resin.

[0042] The vinyl chloride resin in the present invention is not particularly limited by its polymerization method, such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., and includes, for example, 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-chloride Examples of vinyl chloride resins include polypropylene copolymers, vinyl chloride-vinylidene chloride-vinyl acetate ternary copolymers, 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, polyesters, etc. Blends, block copolymers, graft copolymers, etc. These vinyl chloride resins may be mixtures of two or more types, or mixtures with other synthetic resins. Polyvinyl chloride is preferred as the vinyl chloride resin used from the viewpoint of cold resistance, non-migration, oil extraction resistance, volatility, and transparency of the molded product.

[0043] The vinyl chloride-based resin composition of the present invention will be further described. The vinyl chloride resin composition of the present invention contains the polyester plasticizer of the present invention. It is preferable to incorporate an ultraviolet absorber into the vinyl chloride resin composition of the present invention from the viewpoint of weather resistance and saltwater resistance.

[0044] UV absorbers can be used without particular limitations as long as they are known compounds. Specific examples of UV absorbers include 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-benzotriazolylphenol), 2,2'-methylenebis(4-ethylhydroxy-6-benzotriazolylphenol), 2,2'-Methylenebis(4-methyl-6-benzotriazolylphenol), polyethylene glycol ester of 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole, 2-[2-hydroxy-3-(2-acryloyloxyethyl)-5-methylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-octylphenyl 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-amyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-t 2-(2-hydroxyphenyl)benzotriazoles such as ert-butyl-5-(3-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-4-(2-methacryloyloxymethyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methacryloyloxy-2-hydroxypropyl)phenyl]benzotriazole, and 2-[2-hydroxy-4-(3-methacryloyloxypropyl)phenyl]benzotriazole; 2-(4,6-diphenyl-1,3,5-triazine) -2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(octyloxy)phenol, 2-(4,6-bis(4-butoxy-2-methylphenyl)-1,3,5-triazine-2-yl)-3,5-dibutoxyphenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)phenol, 2-(4,6-di([1,1'-biphenyl]-4-yl)-1,3,Phenol-containing triazines such as 5-triazin-2-yl)-5-hexyloxyphenol and 2-methylhexyl-2-(4,(4,6-di([1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl)-3-hydroxyphenoxy)propanoate; 2-hydroxybenzophenones such as 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,4-dihydroxybenzophenone, 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone), and 1,4-bis(4-benzoyl-3-hydroxyphenoxy)-butane; resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl(3,5-di-te Benzoates such as rt-butyl-4-hydroxy)benzoate, dodecyl(3,5-di-tert-butyl-4-hydroxy)benzoate, tetradecyl(3,5-di-tert-butyl-4-hydroxy)benzoate, hexadecyl(3,5-di-tert-butyl-4-hydroxy)benzoate, octadecyl(3,5-di-tert-butyl-4-hydroxy)benzoate, behenyl(3,5-di-tert-butyl-4-hydroxy)benzoate, etc.; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide, etc.; ethyl-2-cyano-3,3-diphenylacrylate, 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-α-cyano-β,β-diphenyl acrylate, methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate, 4-(2-cyano-3-(4-ethylphenoxy)-3-oxopropenyl)phenyl-4-propylcyclohexane-1-carboxylate, 4-(2-cyano-3-(4-ethylphenoxy)-3-oxopropenyl)phenyl-4-propylbenzoate, 4-butylphenyl-4-(2-cyano-3-oxo-3-(4-propylphenoxy)propenyl)benzoate, 4-(2-cyano-3 -(4-cyanophenoxy)-3-oxopropenyl)phenyl-4-pentylbenzoate, 4-(2-cyano-3-(4-fluorophenoxy)-3-oxopropenyl)phenyl-4-methylcyclohexane-1-carboxylate, 4-(2-cyano-3-(4-methoxyphenoxy)-3-oxopropenyl)phenyl-4-hexylcyclohexane-1-carboxylate, 4-(2-cyano-3-(4-ethoxyphenoxy)-3-oxopropenyl)phenyl-4-octylcyclohexane-1-carboxylate Luboxylate, 4-(2-cyano-3-oxo-3-(4-propoxyphenoxy)propenyl)phenyl-4-propylcyclohexane-1-carboxylate, 4-(2-cyano-3-oxo-3-(4-pentylphenoxy)propenyl)phenyl-4-propylcyclohexane-1-carboxylate, 4-(2-cyano-3-(4-octylphenoxy)-3-oxopropenyl)-4-propylcyclohexane-1-carboxylate, 1,3-bis-[(2'-cyano-3',3'-diphenylacrylate] Examples include cyanoacrylates such as liloyl)oxy]-2,2-bis-[[(2'-cyano-3',3'-diphenylacryloyl)oxy]methyl]propane; salicylic acids such as 4-tert-butylphenyl salicylate, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropanolphenyl salicylate; various metal salts or metal chelates, especially nickel and chromium salts or chelates.

[0045] The ultraviolet absorber may be a mixture of two or more types, or a masterbatch containing these.

[0046] From the viewpoint of weather resistance and saltwater resistance, the amount of ultraviolet absorber to be added is preferably 0.001 to 30 parts by mass, more preferably 0.01 to 20 parts by mass, even more preferably 0.03 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass, per 100 parts by mass of vinyl chloride resin.

[0047] The vinyl chloride resin composition of the present invention preferably contains a hindered amine-based light stabilizer from the viewpoint of weather resistance and saltwater resistance.

[0048] Hindered amine light stabilizers are not particularly limited and can be used as long as they are known compounds. Examples of hindered amine light stabilizers include compounds having the structure of 2,2,6,6-tetramethylpiperidyl, specifically, for example, 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(2,2,6,6-tetramethyl- 1-(octyloxy)piperidyl-4-yl) sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, butane-1,2,3,4-tetracarboxylic acid tetrakis(2,2,6,6-tetramethyl-4-piperidinyl), butane-1,2,3,4-tetracarboxylic acid tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl), bis(2,2,6,6-tetramethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2, 2,6,6-Pentamethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-diter-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-tri Adin polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tertiaryoctylamino-s-triazine polycondensate, 1-methyl-10-(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate polycondensate and bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate polycondensate, tetramethyl butanetetracarboxylic acid ester, spiroglycol and N-methylpiperidinol ester, butanetetracarboxylic acid, 3-hydroxy-2,Polycondensate of 2-dimethylpentanal and N-methylpiperidinol esters, 1,2,3,4-butanetetracarboxylic acid tetramethyl ester, 2,2,6,6-tetramethyl-4-piperidinol and β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol, 2,4-dichloro-6-(1,1,3,3-tetramethyl Butylamino)-1,3,5-triazine-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine polycondensate, 2,4-dichloro-6-(1,1,3,3-tetramethylbutylamino)-1,3,5-triazine, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-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-triazine-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-triazine-6-yl] Examples include aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine-6-yl]aminoundecane, bis{4-(1-octyloxy-2,2,6,6-tetramethyl)piperidyl}decandionate, and bis{4-(2,2,6,6-tetramethyl-1-undecyloxy)piperidyl)carbonate.

[0049] Hindered amine light stabilizers may be a mixture of two or more types, or a masterbatch containing them.

[0050] The amount of hindered amine-based light stabilizer added is preferably 0.001 to 30 parts by mass, more preferably 0.01 to 20 parts by mass, even more preferably 0.03 to 10 parts by mass, and even more preferably 0.05 to 5 parts by mass, per 100 parts by mass of vinyl chloride resin, from the viewpoint of weather resistance and saltwater resistance.

[0051] In addition to the polyester-based plasticizer of the present invention, known plasticizers may also be used in combination with the vinyl chloride-based resin composition of the present invention, as long as the effects of the present invention are not impaired.

[0052] Examples of plasticizers other than the polyester-based plasticizers of the present invention 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; and phosphates such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri(isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri(butoxyethyl) phosphate, and octyldiphenyl phosphate. Polyester plasticizers other than those of the present invention, using polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, and neopentyl glycol, and dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebatic acid, phthalic acid, isophthalic acid, and terephthalic acid; and other examples include tetrahydrophthalic acid plasticizers, azelaic acid plasticizers, sebatic acid plasticizers, stearic acid plasticizers, citric acid plasticizers, trimellitic acid plasticizers, pyromellitic acid plasticizers, and biphenylene polycarboxylic acid plasticizers.

[0053] The vinyl chloride resin composition of the present invention preferably contains a zinc salt of an organic acid from the viewpoint of thermal stability. Examples of such zinc salts of organic acids include zinc salts of organic carboxylic acids, phenols, or organic phosphoric acids.

[0054] 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, isoundecylic acid, lauric acid, isolauric acid, tridecanoic acid, myristic acid, isomyristic acid, palmitic acid, isopalmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, versatic acid, benzoic acid, monochlorobenzoic acid, and 4-tert-butylbenzoic acid. Tolic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, o-tolic acid, m-tolic acid, p-tolic acid, tolic 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 Monocarboxylic acids such as fragrant acid, salicylic acid, p-teroctylsalicylic 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, octylmercaptopropionic acid, etc.; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, slipperidone Examples include divalent carboxylic acids such as chlorophthalic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, hydroxyphthalic acid, chlorphthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, and thiodipropionic acid, or their monoesters or monoamide compounds; and di or triester compounds of trivalent or tetravalent carboxylic acids such as butanetricarboxylic acid, butanetetracarboxylic acid, hemimeric acid, trimellitic acid, merophanic acid, and pyromellitic acid.

[0055] 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 methyltertiary octylphenol.

[0056] Examples of organophosphates include mono- or dioctyl phosphate, mono- or didodecyl phosphate, mono- or dioctadecyl phosphate, mono- or di-(nonylphenyl) phosphate, nonylphenyl phosphonate, stearyl phosphonate, and the like.

[0057] The zinc salt of the organic acid may be an acidic salt, a neutral salt, a basic salt, or an overbasic complex obtained by neutralizing some or all of the base of a basic salt with carbonic acid.

[0058] A 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 moiety and form a salt with divalent zinc which forms a cation moiety, or two different monovalent organic acids may form anionic moieties and form a salt with divalent zinc which forms a cation moiety.

[0059] From the viewpoint of thermal stability, zinc benzoate, zinc toluate, zinc 4-tert-butylbenzoate, zinc stearate, zinc laurate, zinc versatate, zinc octoate, zinc oleate, zinc palmitate, and zinc myristice are preferred as zinc salts. One type of zinc salt of organic acid may be used, or two or more types may be used in combination.

[0060] From the viewpoint of thermal stability, the vinyl chloride resin composition of the present invention preferably contains one or more selected from the group consisting of barium salts of organic acids and perbasic barium carbonate salts.

[0061] First, let's discuss barium salts of organic acids. Examples of such barium salts of organic acids include barium salts of organic carboxylic acids, phenols, or organic phosphoric acids.

[0062] 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, isoundecylic acid, lauric acid, isolauric acid, tridecanoic acid, myristic acid, isomyristic acid, palmitic acid, isopalmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, versatic acid, benzoic acid, monochlorobenzoic acid, and 4-tert-butylbenzoic acid. Tolic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, o-tolic acid, m-tolic acid, p-tolic acid, tolic 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 Monocarboxylic acids such as fragrant acid, salicylic acid, p-teroctylsalicylic 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, octylmercaptopropionic acid, etc.; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, slipperidone Examples include divalent carboxylic acids such as chlorophthalic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, hydroxyphthalic acid, chlorphthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, and thiodipropionic acid, or their monoesters or monoamide compounds; and di or triester compounds of trivalent or tetravalent carboxylic acids such as butanetricarboxylic acid, butanetetracarboxylic acid, hemimeric acid, trimellitic acid, merophanic acid, and pyromellitic acid.

[0063] 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 methyltertiary octylphenol.

[0064] Examples of organophosphates include mono- or dioctyl phosphate, mono- or didodecyl phosphate, mono- or dioctadecyl phosphate, mono- or di-(nonylphenyl) phosphate, nonylphenyl phosphonate, stearyl phosphonate, and the like.

[0065] Barium salts of organic acids 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 moiety and form a salt with divalent barium which forms a cation moiety, or two different monovalent organic acids may form anionic moieties and form a salt with divalent barium which forms a cation moiety.

[0066] You may use only one type of barium salt of an organic acid, or two or more types in combination.

[0067] Furthermore, the barium salt of the organic acid may be an acidic salt, a neutral salt, or a basic salt.

[0068] Next, we will explain overbasic barium carbonate salts. Overbasic barium carbonate salts are liquid overbasic carboxylate / carbonate complexes of barium. Unlike a simple mixture of barium carboxylate and barium carbonate, this complex is formed through some kind of interaction between the two, and it has the characteristic of exhibiting a uniform liquid state in organic solvents while having a high metal content. This complex is composed of barium carboxylate, barium carbonate, and a complex salt of barium carboxylic acid and carbonic acid as its constituent components. Barium carbonate is at the center, with barium carboxylate and the complex salt of barium carboxylic acid and carbonic acid surrounding it, forming something like micelles, which allows it to exhibit a uniform liquid state in organic solvents.

[0069] These liquid, overbasic barium carboxylate / carbonate complexes can be produced, for example, by the manufacturing method described in Japanese Patent Publication No. 2004-238364.

[0070] Furthermore, the above-mentioned liquid overbasic carboxylate / carbonate complex of barium can also be obtained by using various commercially available complexes as they are. A typical example of a commercially available complex is "Plastistab" manufactured by AM STABILIZERS, Inc. in the United States. TM 2116 (Hyperbasic barium oleate / carbonate complex: specific gravity 1.42~1.53, Ba=33~36%), "Plastistab TM 2513 (Hyperbasic barium oleate / carbonate complex: specific gravity 1.41~1.52, Ba=33~36%), "Plastistab TM Examples include "2508" (overbasic barium oleate / carbonate complex: specific gravity 1.39-1.51, Ba=33-36%).

[0071] These perbasic barium carbonate salts may be used individually or in combination of two or more types.

[0072] The vinyl chloride resin composition of the present invention may contain one or more substances selected from the group consisting of calcium salts of organic acids and perbasic calcium carbonates, from the viewpoint of thermal stability.

[0073] Examples of calcium salts of such organic acids include calcium salts of organic carboxylic acids, phenols, or organic phosphoric acids.

[0074] Examples of organic carboxylic acids include barium salts of organic acids. Examples of phenols include barium salts of organic acids. Furthermore, examples of organic phosphoric acids include barium salts of organic acids.

[0075] A 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 moiety and form a salt with divalent calcium which forms a cation moiety, or two different monovalent organic acids may form anionic moieties and form a salt with divalent calcium which forms a cation moiety.

[0076] You may use only one type of calcium salt of an organic acid, or two or more types in combination.

[0077] The calcium salt of the organic acid may be an acidic salt, a neutral salt, or a basic salt.

[0078] Next, we will explain overbasic calcium carbonate salts. Overbasic calcium carbonate salts are liquid overbasic carboxylate / carbonate complexes of calcium. Unlike a simple mixture of calcium carboxylic acid salt and calcium carbonate, this complex is formed through some kind of interaction between the two, and it has the characteristic of exhibiting a uniform liquid state in organic solvents while having a high metal content. This complex is composed of calcium carboxylic acid salt, calcium carbonate, and a complex salt of calcium carboxylic acid and carbonic acid as its constituent components. Calcium carbonate is at the center, with the calcium carboxylic acid salt and the complex salt surrounding it, forming something like micelles, which allows it to exhibit a uniform liquid state in organic solvents.

[0079] Liquid overbasic carboxylate / carbonate complexes of calcium can be prepared in the same manner as the liquid overbasic carboxylate / carbonate complexes of barium described above. Alternatively, various commercially available complexes can be used as is. A representative example of a commercially available complex is "Plastistab" from AM STABILIZERS, Inc., USA. TM One example is "2265" (a hyperbasic calcium oleate / carbonate complex: specific gravity 1.04-1.09, Ca=10%).

[0080] These perbasic calcium carbonate salts may be used individually or in combination of two or more types.

[0081] The vinyl chloride resin composition of the present invention may also contain a β-diketone compound from the viewpoint of thermal stability.

[0082] 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, and bis Examples of metal salts include (4-octylbenzoyl)methane, benzoyldiacetylmethane, 4-methoxybenzoylbenzoylmethane, bis(4-carboxymethylbenzoyl)methane, 2-carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, ethyl acetoethyl, cyclohexane-1,3-dione, methyl 3,6-dimethyl-2,4-dioxycyclohexane-1carboxylate, 2-acetylcyclohexanone, dimedone, 2-benzoylcyclohexane, etc., and their metal salts can be used in the same way. 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 acetylacetone calcium salt and acetylacetone zinc salt.

[0083] One type of β-diketone compound may be used, or two or more types may be used in combination. Among these β-diketone compounds, dibenzoylmethane, stearoylbenzoylmethane, and zinc acetylacetone are preferred from the viewpoint of thermal stability.

[0084] The vinyl chloride resin composition of the present invention may also contain one or more phosphite ester compounds from the viewpoint of thermal stability.

[0085] Examples of phosphite ester compounds include trialkyl phosphite, dialkyl phosphite, dialkyl monoallyl phosphite, alkylallyl phosphite, monoalkyldiallyl phosphite, diallyl phosphite, and triallyl phosphite. In the vinyl chloride resin composition of the present invention, both triesters and diesters can be used, but triesters are preferred from the viewpoint of thermal stability. Thioesters can also be used.

[0086] Examples of phosphite ester 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 phosphite, and 2,2'-methylenebis(4,6-tert-butylphenyl). -2-ethylhexyl phosphite, 2,2'-methylenebis(4,6-tertiary butylphenyl)-octadecyl phosphite, 2,2'-ethyldenbis(4,6-ditertiary butylphenyl) fluorophosphite, octyldiphenyl phosphite, diphenyldecyl phosphite, diphenyl(2-ethylhexyl) phosphite, di(decyl)monophenyl phosphite, diphenyltridecyl phosphite, diphenyl(C12-C15 mixed alkyl) phosphite, phenyldiisodecyl phosphite, phenylbis(isotridecyl (Syl) phosphite, triethyl phosphite, tributyl phosphite, tris(2-ethylhexyl) phosphite, tris(decyl) phosphite, trilauryl phosphite, tris(tridecyl) phosphite, trioleyl phosphite, tristearyl phosphite, diethyl phosphite, dibutyl phosphite, dilauryl phosphite, bis(2-ethylhexyl) phosphite, dioleyl phosphite, trilauryl trithiophosphite, bis(neopentyl glycol)-1,4-cyclohexanedimethyl di Phosphite, bis(2,4-diter-butylphenyl)pentaerythritol diphosphite, bis(2,6-diter-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-triter-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, di(tridecyl)pentaerythritol diphosphite, phenyl-4,4'-Isopropylidenediphenol Pentaerythritol Diphosphite, Tetra(C12~15 mixed alkyl)-4,4'-Isopropylidenediphenyl Diphosphite, Hydrogenated-4,4'-Isopropylidenediphenol Polyphosphite, Bis(octylphenyl)-Bis[4,4'-n-Butylidenebis(2-Tertiary butyl-5-methylphenol)]-1,6-Hexanediol Diphosphite, Tetra(tridecyl)-4,4'-n-Butylidenebis(2-Tertiary butyl-5-methylphenol) Diphosphite, Hexa(tridecyl)-1,1,3-Tris(2-methyl-4-hydroxy-5-tertiary butylphenyl)butane Triphosphite, Hexa(tridecyl)-1,1,3-Tris(2-methyl-5-tertiary butyl-4-hydroxyphenyl)butane Triphosphite Examples include phosphites, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol·2,4,6-triter-butylphenol monophosphite, tris[2-terter-butyl-4-(3-terter-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tetra(tridecyl)isopropylidenediphenol diphosphite, tetrakis(2,4-diter-butylphenyl)biphenylenediphosphite, tris(2-[(2,4,8,10-tetrakister-butyldibenzo[d,f][1,3,2]dioxaphosphine-6-yl)oxy]ethyl)amine, and phosphites of 2-ethyl-2-butylpropylene glycol and 2,4,6-triter-butylphenol.

[0087] 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.

[0088] The vinyl chloride resin composition of the present invention may also contain one or more phenolic antioxidants from the viewpoint of thermal stability.

[0089] Examples of phenolic antioxidants include 2,6-diter-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl(3,5-diter-butyl-4-hydroxyphenyl)propionate, distearyl(3,5-diter-butyl-4-hydroxybenzyl)phosphonate, thiodiethylene glycol bis[(3,5-diter-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene bis[(3,5-diter-butyl-4-hydroxyphenyl)propionate], and 1,6-hexamethylene Bis[(3,5-diter-butyl-4-hydroxyphenyl)propionamide], 4,4'-thiobis(6-terter-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-terter-butylphenol), 2,2'-methylenebis(4-ethyl-6-terter-butylphenol), bis[3,3-bis(4-hydroxy-3-terter-butylphenyl)butyric acid] glycol ester, 4,4'-butylidenebis(6-terter-butyl-m-cresol), 2,2'-ethylidenebis(4,6-diter-butylphenol), 2,2'-ethyl Denbis(4-2-butyl-6-3-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-3-butylphenyl)butane, bis[2-3-butyl-4-methyl-6-(2-hydroxy-3-3-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-3-butylbenzyl)isocyanurate, 1,3,5-tris(3,5-di3-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(3,5-di3-butyl-4-hydroxybenzyl (Lu)-2,4,6-trimethylbenzene, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,Examples include 10-tetraoxaspiro[5,5]undecane and triethylene glycol bis[(3-tertiary butyl-4-hydroxy-5-methylphenyl)propionate].

[0090] You may use only one type of phenolic antioxidant, or you may use two or more types in combination.

[0091] 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 include them due to their toxicity and adverse effects on the environment.

[0092] The vinyl chloride resin composition of the present invention may also contain a hydrotalcite compound.

[0093] Examples of hydrotalcite compounds include those represented by the following general formula (1).

[0094] TIFF0007872668000001.tif8154

[0095] In general formula (1), x1, x2, and y1 are numbers that satisfy the conditions expressed by the following formulas: 0 ≤ x2 / x1 < 10, 2 ≤ x1 + x2 < 20, and 0 ≤ y1 ≤ 2, respectively, and m is 0 or any integer.

[0096] Preferably, hydrotalcite compounds are double salt compounds consisting of magnesium and aluminum, or zinc, magnesium, and aluminum. They may also be dehydrated or treated with perchloric acid. Such hydrotalcite compounds may be natural or synthetic. There are no restrictions on the crystal structure, particle size, etc., of the above hydrotalcite compounds.

[0097] Furthermore, hydrotalcite compounds can also be used in which their surface is 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, or waxes.

[0098] Hydrotalcite compounds may be used individually or in combination of two or more.

[0099] The vinyl chloride resin composition of the present invention may also contain polyhydric alcohol compounds. 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, and the like. Only one type of polyhydric alcohol compound may be used, or two or more types may be used in combination.

[0100] The vinyl chloride resin composition of the present invention may also contain a filler.

[0101] Examples of fillers include calcium carbonate, calcium oxide, calcium hydroxide, zinc hydroxide, zinc carbonate, zinc sulfide, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, sodium aluminosilicate, hydrocalmite, 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, wollonite, potassium titanate, PMF, gypsum fiber, zonolite, MOS, phosphate fiber, glass fiber, carbon fiber, and aramid fiber. These fillers may be used individually or in combination of two or more types.

[0102] The vinyl chloride resin composition of the present invention may also contain a lubricant for ease of processing. Examples of lubricants include hydrocarbon lubricants such as low molecular weight waxes, paraffin wax, polyethylene wax, chlorinated hydrocarbons, and fluorocarbons; natural wax lubricants such as carnauba wax and candelilla wax; fatty acid lubricants such as higher fatty acids such as lauric acid, stearic acid, and behenic acid, or oxy fatty acids such as hydroxystearic acid; aliphatic amide lubricants such as aliphatic amide compounds such as stearylamide, laurylamide, and oleylamide, or alkylene bisaliphatic amides such as methylenebisstearylamide and ethylenebisstearylamide; and fatty acid monohydric alcohol ester compounds such as stearyl stearate, butyl stearate, and distearyl phthalate. Examples of lubricants include fatty acid alcohol ester compounds such as glycerin tristearate, sorbitan tristearate, pentaerythritol tetrastearate, dipentaerythritol hexastearate, polyglycerin polyricinolate, hydrogenated castor oil, or complex ester compounds of monohydric fatty acids and polybasic organic acids with polyhydric alcohols, such as adipic acid / stearic acid ester of dipentaerythritol; aliphatic alcohol lubricants such as stearyl alcohol, lauryl alcohol, palmityl alcohol; metal soaps; montanic acid lubricants such as partially saponified montanic acid esters; acrylic lubricants; and silicone oils. These lubricants may be used individually or in combination of two or more.

[0103] The vinyl chloride resin composition of the present invention may also contain processing aids 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 individually or in combination of two or more.

[0104] The vinyl chloride resin composition of the present invention may further contain other additives commonly used in vinyl chloride resins, such as sulfur-based antioxidants, epoxy compounds, impact modifiers, reinforcing agents, zeolite compounds, perchlorates, magnesium salts of organic acids, overbasic magnesium carbonate salts, flame retardants, flame retardant aids, pigments, stabilizing aids, and the like.

[0105] Examples of sulfur-based antioxidants include dialkylthiodipropionates 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 individually or in combination of two or more.

[0106] Examples of epoxy compounds include epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, epoxidized safflower oil, and other epoxidized animal and vegetable oils; 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, and tris(E). Examples include 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 individually or in combination of two or more.

[0107] Examples of impact modifiers 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, and silicone rubber. Examples of the diene used in the ethylene-propylene-diene copolymer rubber (EPDM) include 1,4-hexanediene, dicyclopentadiene, methylenenorbornene, ethylidenenorbornene, and propenylnorbornene. These impact modifiers may be used individually or in combination of two or more types.

[0108] The reinforcing agent can be in the form of fibers, plates, granules, or powders commonly used to reinforce synthetic resins. Specifically, it can be an inorganic fibrous reinforcing material such as glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, warlastenite, sepiolite, asbestos, slag fiber, zonolite, elestadite, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, and boron fiber, as well as polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate fiber, kenaf, ramie, cotton, jute, hemp, and rhinoceros. Examples of reinforcing agents include organic fibrous reinforcing agents such as sieves, flax, linen, silk, Manila hemp, sugarcane, wood pulp, paper waste, recycled paper, and wool; and plate-like or granular reinforcing agents such as glass flakes, non-swelling mica, graphite, metal foil, ceramic beads, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, fine silica, feldspar powder, potassium titanate, shirasu balloons, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon dioxide, gypsum, novaculite, dawsonite, and white clay. These reinforcing agents may be coated or bundled with thermoplastic resins such as ethylene / vinyl acetate copolymers or thermosetting resins such as epoxy resins, or treated with coupling agents such as aminosilanes or epoxysilanes. These reinforcing agents may be used individually or in combination of two or more.

[0109] Zeolite compounds are aluminosilicates of alkali or alkaline earth metals that have a unique three-dimensional zeolite crystal structure. Typical examples include type A, type X, type Y, and type P zeolites, monodenite, analcite, sodalite aluminosilicates, clinobutyrolite, erionite, and chabacite. These zeolite compounds can be either hydrated (containing crystal water, so-called zeolite water) or anhydrous (with crystal water removed), and their particle size can range from 0.1 to 50 μm, with a particularly preferred size of 0.5 to 10 μm. These zeolite compounds may be used individually or in combination of two or more.

[0110] Examples of perchlorates include metal perchlorates, ammonium perchlorates, and perchloric acid-treated silicates. Examples of metals that make up these metal salts include lithium, sodium, potassium, calcium, magnesium, strontium, barium, zinc, cadmium, lead, and aluminum. Metal perchlorates may be anhydrous or hydrated, or dissolved in alcohol-based or ester-based solvents such as butyl diglycol and butyl diglycol adipate, or their dehydrated forms. These perchlorates may be used individually or in combination of two or more types.

[0111] This section explains magnesium salts of organic acids. Examples of magnesium salts of organic acids include magnesium salts of organic carboxylic acids, phenols, and organic phosphoric acids.

[0112] Examples of organic carboxylic acids include barium salts of organic acids. Examples of phenols include barium salts of organic acids. Examples of organic phosphoric acids include barium salts of organic acids. Magnesium salts of organic acids 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 anionic moiety and form a salt with divalent magnesium which forms a cation moiety, or two different monovalent organic acids may form anionic moieties and form a salt with divalent magnesium which forms a cation moiety. Magnesium salts of organic acids may be used by one type or by two or more types in combination.

[0113] Furthermore, the magnesium salt of the organic acid may be an acidic salt, a neutral salt, or a basic salt.

[0114] This section describes overbasic magnesium carbonate salts. Overbasic magnesium carbonate salts are liquid overbasic carboxylate / carbonate complexes of magnesium. Unlike simple mixtures of magnesium, magnesium carboxylate, and magnesium carbonate, these complexes are formed through some kind of interaction, and they have the characteristic of exhibiting a uniform liquid state in organic solvents while having a high metal content. This complex is composed of magnesium carboxylate, magnesium carbonate, and a complex salt of magnesium carboxylic acid and carbonic acid as its constituent components. Magnesium carbonate is at the center, with magnesium carboxylate and the complex salt surrounding it, forming something like micelles, which allows it to exhibit a uniform liquid state in organic solvents.

[0115] Liquid overbasic carboxylate / carbonate complexes of magnesium can be prepared in the same manner as liquid overbasic carboxylate / carbonate complexes of barium, an organic acid. Alternatively, commercially available complexes can be used as is.

[0116] These perbasic magnesium carbonate salts may be used individually or in combination of two or more types.

[0117] Examples of flame retardants and flame retardant additives include triazine ring-containing compounds, metal hydroxides, other inorganic phosphorus, halogenated flame retardants, silicon-based flame retardants, phosphate ester flame retardants, condensed phosphate ester flame retardants, intomescent flame retardants, antimony oxides such as antimony trioxide, other inorganic flame retardant additives, and organic flame retardant additives.

[0118] 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.

[0119] Examples of metal hydroxides include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, and Kissmer 5A (magnesium hydroxide: manufactured by Kyowa Chemical Industry Co., Ltd.).

[0120] Examples of phosphate ester-based flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, trixylenyl phosphate, octyldiphenyl phosphate, xylenyldiphenyl phosphate, trisisopropylphenyl phosphate, 2-ethylhexyldiphenyl phosphate, t-butylphenyldiphenyl phosphate, bis-(t-butylphenyl)phenyl phosphate, tris-(t-butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis-(isopropylphenyl)diphenyl phosphate, and tris-(isopropylphenyl) phosphate.

[0121] Examples of condensed phosphate ester flame retardants include 1,3-phenylenebis(diphenyl phosphate), 1,3-phenylenebis(dixylenyl phosphate), and bisphenol A bis(diphenyl phosphate). Examples of intomessent flame retardants include ammonium salts and amine salts of (poly)phosphates, such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, ammonium pyrophosphate, melamine pyrophosphate, and piperazine pyrophosphate.

[0122] Other inorganic flame retardant additives include, for example, inorganic compounds such as titanium dioxide, aluminum oxide, magnesium oxide, and talc, as well as surface-treated products thereof. Various commercially available products can be used, such as TIPAQUE R-680 (titanium dioxide: manufactured by Ishihara Sangyo Co., Ltd.) and Kyowa Mag 150 (magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.).

[0123] These flame retardants and flame retardant enhancers may be used individually or in combination of two or more types.

[0124] Examples of pigments include white pigments such as titanium dioxide, and blue pigments such as ultramarine blue and phthalocyanine blue.

[0125] Examples of stabilizing agents include diphenylthiourea, anilinodithiotriazine, melamine, benzoic acid, cinnamic acid, and p-ter-butylbenzoic acid.

[0126] Furthermore, if necessary, the vinyl chloride resin composition of the present invention may contain additives commonly used in vinyl chloride resins, such as crosslinking agents, antistatic agents, antifogging agents, plate-out prevention agents, surface treatment agents, fluorescent agents, antifungal agents, disinfectants, metal deactivators, mold release agents, etc., to the extent that they do not impair the effects of the present invention. These optional components may be used individually or in combination of two or more.

[0127] The vinyl chloride resin composition of the present invention can be prepared by stirring and mixing the polyester plasticizer, vinyl chloride resin, and other components as needed using an agitator such as a mortar mixer, Henschel mixer, Banbury mixer, or ribbon blender to obtain a mixed powder of the vinyl chloride resin composition.

[0128] Furthermore, a pelletized vinyl chloride resin composition can also be obtained by melt-molding the polyester plasticizer, vinyl chloride resin, and other components of the present invention using a kneader such as a conical twin-screw extruder, parallel twin-screw extruder, single-screw extruder, cone-type kneader, or roll kneader.

[0129] Alternatively, the polyester plasticizer, vinyl chloride paste resin, and other components of the present invention can be uniformly mixed using a mixer such as a pony mixer, butterfly mixer, planetary mixer, ribbon blender, kneader, dissolver, twin-screw mixer, Henschel mixer, or three-roll mill, and defoamed under reduced pressure as needed to obtain a paste-like vinyl chloride resin composition.

[0130] The vinyl chloride resin composition of the present invention exhibits excellent weather resistance and saltwater resistance, making it suitable for applications requiring weather resistance and saltwater resistance.

[0131] Next, the molded article of the present invention will be described. A molded article obtained from the vinyl chloride resin composition of the present invention can be formed into a desired shape by melt molding the vinyl chloride resin composition (in the form of a blended powder or pellets) according to the present invention using conventionally known methods such as vacuum molding, compression molding, extrusion molding, injection molding, calendering, press molding, blow molding, and powder molding.

[0132] On the other hand, the aforementioned paste-like vinyl chloride resin composition can be molded into a desired shape by molding using conventionally known methods such as spread molding, dipping molding, gravure molding, slush molding, and screen processing.

[0133] The shape of the molded body is not particularly limited, but examples include rod-shaped, sheet-shaped, film-shaped, plate-shaped, cylindrical, circular, elliptical, star-shaped, polygonal, and so on.

[0134] The vinyl chloride resin composition of the present invention and the molded articles obtained therefrom can be used in a wide range of industrial fields, including electrical and electronic communications, agriculture, forestry and fisheries, mining, construction, food, textiles, clothing, medical, coal, petroleum, rubber, leather, automobiles, precision instruments, timber, building materials, civil engineering, furniture, printing, and musical instruments.

[0135] More specifically, the vinyl chloride resin composition and its molded articles of the present invention are used in applications such as printers, personal computers, word processors, keyboards, PDAs (personal digital assistants), telephones, photocopiers, facsimile machines, ECRs (electronic cash registers), calculators, electronic organizers, cards, holders, stationery, and other office and OA equipment; washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting fixtures, game consoles, irons, kotatsu (heated tables), and other home appliances; AV equipment such as TVs, VTRs, video cameras, radio cassette players, tape recorders, MiniDiscs, CD players, speakers, and liquid crystal displays; electrical and electronic components and communication equipment such as connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulating materials, LED encapsulating materials, electric wires, cables, transformers, deflection yokes, distribution boards, clocks, and other electrical and electronic components; automotive interior and exterior materials; printing plates, adhesive films, bottles, food containers, food packaging films, pharmaceutical and medical wrap films, product packaging films, agricultural films, agricultural sheets, and greenhouse films.

[0136] Furthermore, the resin composition and its molded articles of the present invention can be used for seats (filling, upholstery, etc.), belts, headliners, convertible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, wheel covers, mattress covers, airbags, insulating materials, handrails, handrail straps, wire insulation materials, electrical insulating materials, paints, coatings, upholstery materials, flooring materials, corner walls, carpets, wallpaper, wall coverings, exterior materials, interior materials, roofing materials, decking materials, wall materials, column materials, baseboards, and fence materials. It can be used for a wide range of applications, including materials, frameworks and moldings, window and door profiles, shingles, paneling, terraces, balconies, soundproofing boards, insulation boards, window materials, and other building and construction materials for automobiles, vehicles, ships, aircraft, buildings, houses, and civil engineering materials, as well as everyday items and sports equipment such as clothing, curtains, sheets, nonwoven fabrics, plywood, synthetic fiberboards, carpets, doormats, partition curtains, sheets, buckets, hoses, powder transport hoses, containers, eyeglasses, bags, cases, goggles, skis, rackets, tents, musical instruments, and more.

[0137] In particular, the vinyl chloride resin composition of the present invention and the molded articles obtained therefrom have excellent weather resistance and saltwater resistance, making them suitable for outdoor use and applications affected by ultraviolet rays from sunlight. For example, they can be suitably used in building materials such as exterior materials, roofing materials, and window materials, automotive interior and exterior materials, boats, ships, outdoor sports equipment, outdoor leisure equipment, tents, agricultural films, agricultural sheets, greenhouse films, marking films, and the like. [Examples]

[0138] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0139] The polyester-based plasticizer of the present invention was manufactured according to the manufacturing example below. In the manufacturing example below, the number-average molecular weight of the polyester-based plasticizer was measured using the <Method for Measuring Number-Average Molecular Weight> below, the viscosity was measured using the <Method for Measuring Viscosity> below, the acid value was measured using the <Method for Measuring Acid Value> below, and the hydroxyl value was measured using the <Method for Measuring Hydroxyl Value> below.

[0140] <Method for measuring number-average molecular weight> A sample prepared by dissolving 50 mg of the sample in 10 mL of THF was analyzed using a semi-micro GPC column (SHODEX KF-402.5, manufactured by Showa Denko K.K.) and a differential refractometer detector to separate the peaks. The average molecular weight was then calculated in polystyrene equivalent.

[0141] <Viscosity measurement method> After attaching the rotor and measuring container appropriate to the viscosity of the sample to be measured to the B-type viscometer, immerse the measuring container in a constant temperature water bath set to 25°C. Leave it until the sample reaches the constant temperature, then select the rotation speed appropriate to the viscosity. Perform the measurement for the specified time and read the measurement value displayed on the automatically calculated digital display.

[0142] <Method for measuring acid value> The sample is accurately weighed to the nearest 10 mg and thoroughly dissolved in a neutral toluene / ethanol solution. A few drops of phenolphthalein indicator are added, and the mixture is titrated with 0.1 N KOH aqueous solution.

[0143] <Method for measuring hydroxyl value> Weigh the sample accurately to the nearest 10 mg into a container and dissolve thoroughly in 10 mL of TEP (triethyl phosphate). Add 15 mL of reagent A and stir well, then add 20 mL of reagent D and let stand for 5 minutes. Add 50 mL of neutral isopropyl alcohol, add a few drops of phenolphthalein indicator, and titrate with 1.0 N KOH aqueous solution.

[0144] <Manufacturing of polyester-based plasticizers> [Manufacturing Example 1] A polyester-based plasticizer was prepared using components (A) to (C) listed in Table 1, in the composition ratio (mass%) shown in Table 1. Specifically, an esterification reaction was carried out at 200-230°C under normal pressure and reduced pressure using tetraisopropoxytitanium as a catalyst to obtain the polyester-based plasticizer-1 of the present invention. The number-average molecular weight, viscosity, acid value, and hydroxyl value of the obtained polyester-based plasticizer-1 were measured. The results are shown in Table 1.

[0145] [Manufacturing Examples 2-8] In the same manner as in Production Example 1, polyester plasticizers were prepared using components (A) to (C) listed in Table 1, in the composition ratios (mass%) listed in Table 1. Specifically, esterification reactions were carried out at 200-230°C under normal pressure and reduced pressure using tetraisopropoxytitanium as a catalyst to obtain polyester plasticizers-2 to 8 of the present invention. The number-average molecular weight, viscosity, acid value, and hydroxyl value of the obtained polyester plasticizers-2 to 8 were measured. The results are shown in Table 1.

[0146] [Examples 1-7, Reference Examples 1-2, Comparative Examples 1-8] 100 parts by mass of vinyl chloride resin (ZEST 1000Z, manufactured by Shin-Daiichi Vinyl Chloride Co., Ltd., average degree of polymerization 1000), 2.5 parts by mass of barium / zinc liquid stabilizer (ADEKA AC-285, manufactured by ADEKA Corporation), and the polyester plasticizers-1 to 8 of the present invention listed in Table 1 below were mixed in the amounts (parts by mass) listed in Tables 2 to 4. The mixture was roll-kneaded at 160°C × 20 rpm (roll rotation speed) × 11 minutes (kneading time) × 0.3 mm (sheet thickness) to produce sheets of 1.2 mm or 0.7 mm thickness. The following tests were performed using the obtained sheets. The results are shown in Tables 2 to 4.

[0147] In addition, comparative plasticizers 1 to 4 were used as comparative plasticizers. Comparative plasticizer 1 was bis(2-ethylhexyl) o-phthalate (DOP), comparative plasticizer 2 was diisononyl o-phthalate (DINP), comparative plasticizer 3 was diisononyl isophthalate (DINIP), and comparative plasticizer 4 was diundecyl o-phthalate (DUP). Sheets were prepared and tested in the same manner as in the examples. The results are shown in Tables 2 to 4.

[0148] <Weather resistance and saltwater resistance tests> Using the obtained roll-kneaded sheet, 1.0 mm thick test specimens were prepared by pressing at 180°C for 5 minutes at 1.0 mm, or 0.5 mm thick test specimens were prepared by pressing at 180°C for 5 minutes at 0.5 mm. Tensile tests were performed at 25°C in accordance with JIS K7113, and the initial tensile strength, elongation, and 100% modulus were measured. The results are shown in Tables 2-4.

[0149] Furthermore, the test specimens were exposed to the outdoors for 6 months, 12 months, 18 months, and 24 months (up to 18 months in Examples 3-7, Reference Example 2, and Comparative Examples 5-8) at an outdoor exposure test site located approximately 200m from the sea in Shizuoka City, Shizuoka Prefecture. Tensile tests were also performed on the outdoor-exposed specimens to determine the elongation retention rate. The outdoor exposure test site used is a location heavily affected by salinity from the sea. The closer the elongation retention rate is to 100%, the better the weather resistance and saltwater resistance. The results are shown in Tables 2-4.

[0150] Furthermore, the surface condition of the test specimens, including discoloration, staining, and crack formation, was visually evaluated due to outdoor exposure. The evaluation criteria were on a 5-point scale, with 1 representing the initial surface condition and increasing numerical values ​​indicating worsening condition. The results are shown in Tables 2-4.

[0151] [Table 1] Component (A): Dibasic acid component Ingredient (B): Glycol component Component (C): Terminal termination component

[0152] [Table 2] (Test specimen sheet thickness: 1.0 mm)

[0153] [Table 3] (Test specimen sheet thickness: 0.5 mm)

[0154] [Table 4] (Test specimen sheet thickness: 0.5 mm)

[0155] The results shown in Tables 1-4 clearly demonstrate that the polyester-based plasticizer of the present invention exhibits excellent weather resistance and saltwater resistance. Furthermore, it is clear that a vinyl chloride resin composition containing the polyester-based plasticizer of the present invention can provide a molded article with excellent weather resistance and saltwater resistance.

Claims

1. A polyester-based plasticizer obtained from a dibasic acid component (A), a glycol component (B), and a terminal termination component (C), The dibasic acid component (A) contains isophthalic acid, The glycol component (B) contains one or more selected from the group consisting of neopentyl glycol, 3-methyl-1,5-pentanediol, 1,2-propanediol, and 2-methyl-1,3-propanediol. A polyester-based plasticizer characterized in that the end-termination component (C) is one or more selected from the group consisting of monohydric alcohols.

2. The polyester-based plasticizer according to claim 1, wherein the dibasic acid component (A) is isophthalic acid.

3. A polyester-based plasticizer according to claim 1 or 2, wherein the viscosity at 25°C is 50 to 5000 mPa·s.

4. A vinyl chloride resin composition characterized by containing a polyester plasticizer according to any one of claims 1 to 3.

5. A molded article characterized by comprising the vinyl chloride resin composition described in claim 4.

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