JP7414190B2 - Plasticizer for vinyl chloride resin, vinyl chloride resin composition, molded products and laminates thereof - Google Patents

Description

The present invention relates to a plasticizer for vinyl chloride resin, a vinyl chloride resin composition, and molded products and laminates thereof.

Polyvinyl chloride resin (PVC) is one of the typical plastics, and plasticizers are usually added to it to give it properties such as flexibility and low-temperature properties, and to make it easier to process through thermoforming. It is used after softening the vinyl chloride resin.

Plasticizers used in vinyl chloride resins are required to have a variety of properties such as compatibility, cold resistance, and heat resistance. It has been known. Among these, phthalate esters were often used from the viewpoint of price and performance balance.

For applications that require heat resistance that cannot be met by phthalate esters, trimellitic acid esters, which have heat resistance higher than phthalate esters, are used (for example, Patent Document 1). Among them, tri-2-ethylhexyl trimellitate, trinormaloctyl trimellitate, trinormaldecyl trimellitate, triisononyl trimellitate, and triisodecyl trimellitate are plasticizers with extremely high heat resistance. For this reason, it is often used in automobile dashboards, etc.

JP2016-089155A

For plasticizers in vinyl chloride resins used in automobile dashboards and vehicle interior materials, there is an increasing demand for non-migration of the plasticizers into urethane resins. Automobile dashboards include a laminate part of a vinyl chloride resin layer and a urethane resin layer (urethane foam layer).If the plasticizer contained in the vinyl chloride resin layer migrates to the urethane resin layer, the plasticizer in the vinyl chloride resin layer There was a problem in that the amount of plasticizer decreased and flexibility was lost.

If the vinyl chloride resin layer in a car dashboard loses its flexibility, the vinyl chloride resin layer becomes hard pieces and scatters when the airbag is deployed, potentially endangering the interior of the car. The above-mentioned trimellitic acid ester plasticizer has not been able to satisfy the non-migration property.

The problem to be solved by the present invention is to provide a plasticizer for vinyl chloride resin that has excellent heat resistance and non-migration properties.

As a result of intensive studies to solve the above problems, the present inventors found that a plasticizer for vinyl chloride resin, which is a polyester using a specific glycol, can exhibit excellent heat resistance and non-migration properties. The present invention has been completed.

That is, the present invention provides a glycol having 2 to 18 carbon atoms, an aliphatic dicarboxylic acid having 4 to 14 carbon atoms, a monoalcohol having 4 to 18 carbon atoms, and/or a monocarboxylic acid having 2 to 21 carbon atoms. A plasticizer for vinyl chloride resin, which is a polyester that uses an acid as a raw material for reaction, wherein the glycol is an alkylene glycol having 5 to 18 carbon atoms, and the main chain is substituted with one or more methyl groups. The present invention relates to a plasticizer for vinyl chloride resin containing 30 mol% or more of alkylene glycol.

ADVANTAGE OF THE INVENTION According to the present invention, a plasticizer for vinyl chloride resins having excellent heat resistance and non-migration properties can be provided.

An embodiment of the present invention will be described below. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within a range that does not impair the effects of the present invention.

[Plasticizer for vinyl chloride resin]
The plasticizer for vinyl chloride resin of the present invention comprises a glycol having 2 to 18 carbon atoms, an aliphatic dicarboxylic acid having 4 to 14 carbon atoms, a monoalcohol having 4 to 18 carbon atoms, and/or a monoalcohol having 2 to 18 carbon atoms. A plasticizer for vinyl chloride resin, which is a polyester using as a reaction raw material a monocarboxylic acid of It is a glycol and contains 30 mol% or more of an alkylene glycol whose main chain is substituted with one or more methyl groups.
The term "reaction raw material" as used herein means a raw material constituting the polyester of the present invention, and does not include a solvent or catalyst that does not constitute the polyester.

The polyester which is the plasticizer for vinyl chloride resin of the present invention may be hereinafter simply referred to as "the polyester of the present invention".

The glycol having 2 to 18 carbon atoms is preferably an alkylene glycol having 2 to 18 carbon atoms or an oxyalkylene glycol having 2 to 18 carbon atoms.

Examples of the alkylene glycol having 2 to 18 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,2-propanediol. , 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,5-pentanediol , 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3 -Methyl-1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl -1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol and the like.

The alkylene glycol having 2 to 18 carbon atoms is preferably an alkylene glycol having 3 to 10 carbon atoms, more preferably an alkylene glycol having 3 to 6 carbon atoms, and even more preferably 1,2-propanediol. , 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 2-methyl-1,3-propanediol, 3-methyl-1, These are 5-pentanediol and 1,6-hexanediol.

The oxyalkylene glycol having 2 to 18 carbon atoms is, for example, one in which one of the carbon atoms of the alkylene glycol having 2 to 18 carbon atoms has been replaced with an oxygen atom, and includes diethylene glycol, triethylene glycol, tetraethylene glycol, Examples include dipropylene glycol and tripropylene glycol.

The oxyalkylene glycol having 2 to 18 carbon atoms is preferably an oxyalkylene glycol having 3 to 10 carbon atoms, more preferably an oxyalkylene glycol having 4 to 10 carbon atoms, and still more preferably diethylene glycol or triethylene glycol. It is ethylene glycol.

In the present invention, the glycol having 2 to 18 carbon atoms contains 30 mol% or more of an alkylene glycol having 5 to 18 carbon atoms and having one or more methyl groups substituted in the main chain.
The "main chain" herein refers to the longest alkylene chain among the alkylene chains between two hydroxyl groups.

Examples of the alkylene glycol having 5 to 18 carbon atoms and having one or more methyl groups substituted in the main chain include neopentyl glycol, 3-methyl-1,5-pentanediol, etc. .

Among the alkylene glycols having 5 to 18 carbon atoms, the proportion of the alkylene glycol whose main chain is substituted with one or more methyl groups may be 30 mol% or more, preferably 35 mol% or more, More preferably it is 40 mol% or more, and still more preferably 55 mol% or more.

Among the alkylene glycols having 5 to 18 carbon atoms, the upper limit of the proportion of the alkylene glycol whose main chain is substituted with one or more methyl groups is not particularly limited, and is, for example, 100 mol% or less, 90 mol% or less, It is 80 mol% or less or 70 mol% or less.

Glycols having 2 to 18 carbon atoms, which are reaction raw materials for the polyester of the present invention, may be used alone or in combination of two or more.

The aliphatic dicarboxylic acid having 4 to 14 carbon atoms is preferably an alkylene dicarboxylic acid having 4 to 14 carbon atoms, more preferably an alkylene dicarboxylic acid having 6 to 12 carbon atoms.

Examples of the alkylene dicarboxylic acid having 4 to 14 carbon atoms include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid (dodecanedioic acid), cyclohexanedicarboxylic acid, hexahydrophthalic acid, and the like. Can be mentioned. Among these, adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid are more preferred, adipic acid and sebacic acid are even more preferred, and adipic acid is particularly preferred.

The alkylene dicarboxylic acid having 4 to 14 carbon atoms, which is a reaction raw material for the polyester of the present invention, may be used alone or in combination of two or more.

The monoalcohol having 4 to 18 carbon atoms is preferably an aliphatic monoalcohol having 4 to 18 carbon atoms.
Examples of the aliphatic monoalcohol having 4 to 18 carbon atoms include butanol, heptanol, hexanol, cyclohexanol, heptanol, octanol, 2-ethylhexanol, isononyl alcohol, nonanol, decanol, undecanol, dodecanol, and the like.

The monoalcohols having 4 to 18 carbon atoms, which are reaction raw materials for the polyester of the present invention, may be used alone or in combination of two or more.

The monocarboxylic acid having 2 to 21 carbon atoms is preferably an aliphatic monocarboxylic acid having 2 to 21 carbon atoms.
Examples of the aliphatic monocarboxylic acids having 2 to 21 carbon atoms include acetic acid, caproic acid, 2-ethylhexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, and stearin. acid, arachidic acid, etc.

The monocarboxylic acid having 2 to 21 carbon atoms may be a hydrogenated vegetable oil fatty acid. Examples of the hydrogenated vegetable oil fatty acids include hydrogenated coconut oil fatty acids, hydrogenated palm kernel oil fatty acids, hydrogenated palm oil fatty acids, hydrogenated olive oil fatty acids, hydrogenated castor oil fatty acids, hydrogenated rapeseed oil fatty acids, and the like. These are obtained by decomposing and hydrogenating oils obtained from coconut, palm kernel, palm, olive, castor, and rapeseed, respectively. It is a mixture of more than one long chain aliphatic monocarboxylic acid.
Note that the above-mentioned vegetable oil fatty acid without hydrogenation may be used as long as the effects of the present invention are not impaired. Moreover, vegetable oil fatty acids are not limited to those mentioned above.

The polyester of the present invention comprises a glycol having 2 to 18 carbon atoms, an aliphatic dicarboxylic acid having 4 to 14 carbon atoms, a monoalcohol having 4 to 18 carbon atoms, and/or a monocarboxylic acid having 2 to 21 carbon atoms. The glycol is an alkylene glycol having 5 to 18 carbon atoms and may contain 30 mol% or more of an alkylene glycol having one or more methyl groups substituted in the main chain, and the present invention Raw materials other than these may be used within a range that does not impair the effect.

The reaction raw materials for the polyester of the present invention are preferably a glycol having 2 to 18 carbon atoms, an aliphatic dicarboxylic acid having 4 to 14 carbon atoms, a monoalcohol having 4 to 18 carbon atoms, and/or a monoalcohol having 2 to 18 carbon atoms. ~21 monocarboxylic acids, more preferably glycols having 2 to 18 carbon atoms, aliphatic dicarboxylic acids having 4 to 14 carbon atoms, monoalcohols having 4 to 18 carbon atoms, and/or or a monocarboxylic acid having 2 to 21 carbon atoms.

（前記式（１）～（３）中、
Ｇは、炭素原子数２～１８のグリコール残基である。
Ａは、炭素原子数２～１２の脂肪族ジカルボン酸残基である。
Ｓ_１１およびＳ_１２は、それぞれ独立に、炭素原子数１～２０のモノカルボン酸残基である。
Ｓ_２１およびＳ_２２は、それぞれ独立に、炭素原子数４～１８のモノアルコール残基である。
Ｓ_３１は、炭素原子数１～２０のモノカルボン酸残基である。
Ｓ_３２は、炭素原子数４～１８のモノアルコール残基である。
ｐ、ｑおよびｒは、それぞれ独立に、整数である。）The polyester of the present invention is a mixture of compounds represented by the following formula (1) with mutually different values of p, a mixture of compounds represented by the following formula (2) with mutually different values of q, and a mixture of compounds represented by the following formula (2) with mutually different values of q. It contains one or more selected from the group consisting of mixtures of different compounds represented by the following formula (3).

(In the above formulas (1) to (3),
G is a glycol residue having 2 to 18 carbon atoms.
A is an aliphatic dicarboxylic acid residue having 2 to 12 carbon atoms.
S ₁₁ and S ₁₂ are each independently a monocarboxylic acid residue having 1 to 20 carbon atoms.
S ₂₁ and S ₂₂ are each independently a monoalcohol residue having 4 to 18 carbon atoms.
S ₃₁ is a monocarboxylic acid residue having 1 to 20 carbon atoms.
S ₃₂ is a monoalcohol residue having 4 to 18 carbon atoms.
p, q and r are each independently an integer. )

In the present invention, "carboxylic acid residue" refers to the remaining organic group of carboxylic acid excluding the carboxyl group. Note that the number of carbon atoms in the "carboxylic acid residue" does not include carbon atoms in the carboxy group.
In the present invention, "alcohol residue" refers to the organic group remaining after removing the hydroxyl group from alcohol.
In the present invention, the term "glycol residue" refers to the organic group remaining after removing the hydroxyl group from glycol.

The glycol residue having 2 to 18 carbon atoms in G is a group corresponding to the glycol having 2 to 18 carbon atoms, which is a reaction raw material for the polyester of the present invention. In G, 30 mol% or more is an alkylene glycol residue having 5 to 18 carbon atoms, and the main chain is substituted with one or more methyl groups.
The aliphatic dicarboxylic acid residue having 2 to 12 carbon atoms in A is a group corresponding to the aliphatic dicarboxylic acid having 4 to 14 carbon atoms, which is a reaction raw material for the polyester of the present invention.
The monocarboxylic acid residues having 1 to 20 carbon atoms in S ₁₁ , S ₁₂ and S ₃₁ are groups corresponding to the monocarboxylic acid having 2 to 21 carbon atoms, which is a reaction raw material for the polyester of the present invention.
The monoalcohol residues having 4 to 18 carbon atoms in S ₂₁ , S ₂₂ and S ₃₂ are groups corresponding to the monoalcohol having 4 to 18 carbon atoms which is a reaction raw material for the polyester of the present invention.

The upper limit of each of p, q and r is, for example, 30, although it is not particularly limited.
The average value of p is, for example, in the range of 3 to 20, the average value of q is in the range of, for example, 3 to 20, and the average value of r is, for example, in the range of 3 to 20.
Note that the average values of p, q, and r can be confirmed from the number average molecular weight of the polyester.

The polyester of the present invention preferably comprises a component of the compound represented by the above formula (1) with p=0, a component of the compound represented by the above formula (2) with q=0, and a component represented by the above formula (3). The total of the components with r=0 in the compound is in the range of 0.5 to 3.0% by mass in area ratio measured by gel permeation chromatography.

The number average molecular weight (Mn) of the polyester of the present invention is 500 to 6,000, preferably 1,000 to 5,000, more preferably 2,000 to 4,000, even more preferably 2 ,000 to 3,700.
The number average molecular weight (Mn) of the polyester of the present invention is confirmed by the method described in Examples.

The acid value of the polyester of the present invention is preferably 2.0 or less, more preferably 1.0 or less.
The hydroxyl value of the polyester of the present invention is preferably 15 or less, more preferably 10 or less.
The viscosity of the polyester of the present invention is preferably 7,000 mPa·s or less, more preferably 5,000 mPa·s or less.
The acid value, hydroxyl value and viscosity of the polyester of the present invention are confirmed by the methods described in Examples.

[Method for producing plasticizer for vinyl chloride resin]
The plasticizer for vinyl chloride resin of the present invention is an alkylene glycol having 5 to 18 carbon atoms, and containing 30 mol% or more of an alkylene glycol having one or more methyl groups substituted in the main chain. 18 glycol, an aliphatic dicarboxylic acid having 4 to 14 carbon atoms, and a monoalcohol having 4 to 18 carbon atoms and/or a monocarboxylic acid having 4 to 21 carbon atoms to synthesize a polyester. Preferably, the polyester obtained is further subjected to a steam stripping treatment.

The polyester represented by the formula (1) can be obtained, for example, by the method shown below.
Method 1: A method in which a monocarboxylic acid, a dicarboxylic acid, and a glycol constituting each residue of the polyester represented by formula (1) are charged all at once, and these are reacted.
Method 2: The dicarboxylic acid and glycol constituting each residue of the polyester represented by formula (1) are reacted under conditions such that the equivalent of the hydroxyl group is greater than the equivalent of the carboxyl group, and the hydroxyl group is attached to the end of the main chain. A method of obtaining a polyester having a polyester resin and then reacting the obtained polyester resin with a monocarboxylic acid constituting S ₁₁ and S ₁₂ .

The polyester represented by the formula (2) can be obtained, for example, by the method shown below.
Method 3: A method in which the monoalcohol, dicarboxylic acid, and glycol constituting each residue of the polyester represented by formula (2) are charged at once and reacted.
Method 4: Dicarboxylic acid constituting each residue of the polyester represented by formula (2) and glycol are reacted under conditions such that the equivalent of the carboxyl group is greater than the equivalent of the hydroxyl group, and the carboxyl group is converted into a main chain. A method of obtaining a polyester having terminals and then reacting the obtained polyester with a monoalcohol constituting S ₂₁ and S ₂₂ .

The polyester represented by the formula (3) can be obtained, for example, by the method shown below.
Method 4: A method in which the monoalcohol, monocarboxylic acid, dicarboxylic acid, and glycol constituting each residue of the polyester represented by formula (3) are charged all at once and reacted.
Method 5: Dicarboxylic acid constituting each residue of the polyester represented by formula (3) and glycol are reacted under conditions such that the equivalent weight of the carboxyl group and the equivalent weight of the hydroxyl group are the same, thereby converting the carboxyl group and the hydroxyl group, respectively. A method in which, after obtaining a polyester having a main chain terminal, the obtained polyester is reacted with a monoalcohol and a monocarboxylic acid constituting S ₃₁ and S ₃₂ .

In the synthesis of polyester, the reaction is preferably carried out in the presence of an esterification catalyst, if necessary, at a temperature range of 180 to 250° C. for 5 to 25 hours.
Note that conditions such as temperature and time for the esterification reaction are not particularly limited and may be set as appropriate.

Examples of the esterification catalyst include titanium catalysts such as tetraisopropyl titanate and tetrabutyl titanate; tin catalysts such as dibutyltin oxide; and organic sulfonic acid catalysts such as p-toluenesulfonic acid.

The amount of the esterification catalyst to be used may be set as appropriate, but it is usually in the range of 0.001 to 0.1 part by mass based on 100 parts by mass of the total amount of reaction raw materials.

The steam stripping treatment is a treatment in which the obtained polyester is brought into contact with steam to remove unreacted components, catalysts, and low molecular components contained in the polyester. By performing this treatment, the residual amount of the monoalcohol derived from the reaction raw material in the polyester of the present invention can be reduced to less than 1,000 mass ppm.
The residual amount of monoalcohol is measured by the method described in Examples.

It is presumed that the residual amount of monoalcohol derived from the reaction raw material in the polyester of the present invention has a correlation with the odor of the polyester itself, and the odor can be reduced by reducing the residual amount of monoalcohol.
The residual amount of the monoalcohol derived from the reaction raw material in the polyester of the present invention may be, for example, less than 1,000 mass ppm, preferably 900 mass ppm or less, more preferably 800 mass ppm or less, and even more preferably is 700 mass ppm or less.
The lower limit of the residual amount of monoalcohol derived from the reaction raw material in the polyester of the present invention is not particularly limited, but is, for example, 0 mass ppm.

The steam stripping treatment is carried out, for example, by passing the obtained polyester through a stripping tower equipped with a perforated plate from which steam is spouted, and the stripping treatment temperature is, for example, in the range of 100 to 180°C. The processing pressure is preferably set in the range of 0.005 to 0.03 STMkg/hr/kg. The stripping time can be set within a range of 2 to 10 hours, for example.

[Vinyl chloride resin composition]
The vinyl chloride resin composition of the present invention contains the plasticizer for vinyl chloride resin of the present invention and a vinyl chloride resin. In the present invention, the vinyl chloride resin includes a homopolymer of vinyl chloride, a homopolymer of vinylidene chloride, a copolymer containing vinyl chloride as an essential component, a copolymer containing vinylidene chloride as an essential component, and the like.
When the vinyl chloride resin is a copolymer containing vinyl chloride as an essential component or a copolymer containing vinylidene chloride as an essential component, examples of comonomers that can be copolymerized include α- such as ethylene, propylene, and 1-butene. Olefins; Conjugated dienes such as butadiene and isoprene; Vinyl alcohol, styrene, acrylonitrile, vinyl acetate, vinyl propionate, fumaric acid, fumaric esters, maleic acid, maleic esters, maleic anhydride, acrylic acid, acrylic esters, Examples include methacrylic acid, methacrylic esters, isoprenol, and the like.

The degree of polymerization of the vinyl chloride resin is usually 300 to 5,000, preferably 400 to 3,500, and more preferably 700 to 3,000. When the degree of polymerization of the vinyl chloride resin is within this range, a molded article with high heat resistance can be obtained, and a vinyl chloride resin composition with excellent processability can be obtained.

Vinyl chloride resins can be produced by known methods, such as suspension polymerization in the presence of an oil-soluble polymerization catalyst, emulsion polymerization in an aqueous medium in the presence of a water-soluble polymerization catalyst, and the like.
A commercially available vinyl chloride resin may be used. Commercially available vinyl chloride resins include TH-640, TH-700, TH-800 (manufactured by Taiyo PVC Co., Ltd.); S-1004, S-1008, PSH-10 (manufactured by Kaneka Corporation). ;TK-700, TK-800. Examples include TK-1300 (manufactured by Shin-Etsu Polymer Co., Ltd.); ZEST800Z, ZEST1000Z, and ZEST1300Z (manufactured by Shin-Daiichi PVC Co., Ltd.).

The content of the plasticizer for vinyl chloride resin of the present invention in the vinyl chloride resin composition of the present invention is preferably 10 to 150 parts by mass based on 100 parts by mass of the vinyl chloride resin from the viewpoint of compatibility with the vinyl chloride resin. parts, more preferably 30 to 120 parts by weight, still more preferably 50 to 120 parts by weight, particularly preferably 70 to 120 parts by weight.

The vinyl chloride resin composition of the present invention only needs to contain a vinyl chloride resin and a plasticizer for vinyl chloride resin of the present invention, and may contain a plasticizer other than the plasticizer for vinyl chloride resin of the present invention (other plasticizers), and other plasticizers. It may also contain additives and the like.

Examples of the other plasticizers include benzoic acid esters such as diethylene glycol dibenzoate; dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), Phthalic acid esters such as diundecyl phthalate (DUP) and ditridecyl phthalate (DTDP); Terephthalic acid esters such as bis(2-ethylhexyl) terephthalate (DOTP); Isophthalic acid esters such as bis(2-ethylhexyl) isophthalate (DOIP) Acid ester; Pyromellitic acid ester such as tetra-2-ethylhexyl pyromellitate (TOPM); di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-(2 Aliphatic dibasic acid esters such as azelaic acid derivatives such as -ethylhexyl) azelate, diisooctyl azelate, di-n-hexyl azelate; tri-2-ethylhexyl phosphate (TOP), tricresyl phosphate (TCP), etc. phosphoric acid ester; alkyl ester of polyhydric alcohol such as pentaerythritol; polyester with a molecular weight of 800 to 4,000 synthesized by polyesterification of dibasic acid such as adipic acid and glycol; epoxidized soybean oil, epoxidized linseed Epoxidized esters such as oil; alicyclic dibasic acids such as diisononyl hexahydrophthalate; fatty acid glycol esters such as 1,4-butanediol dicapric acid; tributyl acetyl citrate (ATBC); paraffin wax and n-paraffin Examples include chlorinated paraffins obtained by chlorinating; chlorinated fatty acid esters such as chlorinated stearate; and higher fatty acid esters such as butyl oleate.

Among other plasticizers, it is preferable to use one or more selected from trimellitic acid ester plasticizers and sebacic acid derivative plasticizers.

The above trimellitic acid ester plasticizers include trimethyl trimellitate, triethyl trimellitate, tri-n-propyl trimellitate, tri-n-butyl trimellitate, tri-n-pentyl trimellitate, and trimellitate. Tri-n-hexyl, tri-n-heptyl trimellitate, tri-n-octyl trimellitate, tri-n-nonyl trimellitate, tri-n-decyl trimellitate, tri-n-undecyl trimellitate , tri-n-dodecyl trimellitate, tri-n-tridecyl trimellitate, tri-n-tetradecyl trimellitate, tri-n-pentadecyl trimellitate, tri-n-hexadecyl trimellitate, trimellitate tridecyl -n-heptadecyl, tri-n-stearyl trimellitate, tri-n-alkyl trimellitate (here, the number of carbon atoms in the alkyl group of the tri-n-alkyl trimellitate is different from each other in one molecule) linear trimellitic acid esters in which the alkyl group constituting the ester is linear;
Tri-i-propyl trimellitate, tri-i-butyl trimellitate, tri-i-pentyl trimellitate, tri-i-hexyl trimellitate, tri-i-heptyl trimellitate, tri-i-trimellitate i-octyl, tri-(2-ethylhexyl) trimellitate, tri-i-nonyl trimellitate, tri-i-decyl trimellitate, tri-i-undecyl trimellitate, tri-i-dodecyl trimellitate , tri-i-tridecyl trimellitate, tri-i-tetradecyl trimellitate, tri-i-pentadecyl trimellitate, tri-i-hexadecyl trimellitate, tri-i-heptadecyl trimellitate, trimellitate tridecyl -i-Octadecyl, trimellitic acid trialkyl ester (here, the number of carbon atoms of the alkyl group possessed by the trimellitic acid trialkyl ester may be different in one molecule), and an alkyl constituting the ester. Examples include branched trimellitic acid esters having a branched group.

Examples of the sebacic acid derivative plasticizer include di-n-butyl sebacate, di-(2-ethylhexyl) sebacate, diisodecyl sebacate, di-(2-butyloctyl) sebacate, and the like.

The above-mentioned other plasticizers may be used alone or in combination of two or more.

Among the other plasticizers mentioned above, trimellitic acid esters and sebacic acid derivatives are preferred from the viewpoint of obtaining good tensile elongation and cold resistance.

When the other plasticizer is used in the vinyl chloride resin composition of the present invention, the content of the other plasticizer is, for example, 10 to 300 parts by mass per 100 parts by mass of the plasticizer for vinyl chloride resin of the present invention. It is preferably in the range of 20 to 200 parts by mass.

Examples of the other additives include flame retardants, stabilizers, stabilizing aids, colorants, processing aids, fillers, antioxidants (antiaging agents), ultraviolet absorbers, light stabilizers, lubricants, and electrostatic charges. Examples include inhibitors, crosslinking aids, and the like.

Examples of the flame retardant include inorganic compounds such as aluminum hydroxide, antimony trioxide, magnesium hydroxide, and zinc borate; cresyl diphenyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, and trisdichloropropyl phosphate. Examples include phosphorus compounds such as phate; halogen compounds such as chlorinated paraffin.
When a flame retardant is added to a vinyl chloride resin composition, the amount thereof is usually in the range of 0.1 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin.

Examples of the stabilizer include lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc octylate, zinc laurate, and zinc ricinoleate. , metal soap compounds such as zinc stearate; organotin compounds such as dimethyltin bis-2-ethylhexylthioglycolate, dibutyltin maleate, dibutyltin bisbutyl maleate, dibutyltin dilaurate; antimony mercaptide compounds; lanthanum oxide, water Examples include lanthanoid-containing compounds such as lanthanum oxide.
When a stabilizer is blended into a vinyl chloride resin composition, the amount thereof is usually in the range of 0.1 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin.

Examples of the stabilizing aid include phosphite compounds such as triphenyl phosphite, monooctyldiphenyl phosphite, and tridecyl phosphite; beta-diketone compounds such as acetylacetone and benzoylacetone; glycerin, sorbitol, pentaerythritol, and polyethylene. Examples include polyol compounds such as glycol; perchlorate compounds such as barium perchlorate and sodium perchlorate; hydrotalcite compounds; and zeolites.
When a stabilizing aid is added to a vinyl chloride resin composition, the amount thereof is usually in the range of 0.1 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin.

Examples of the coloring agent include carbon black, lead sulfide, white carbon, titanium white, lithopone, safflower, antimony sulfide, chrome yellow, chrome green, cobalt blue, molybdenum orange, and the like.
When a colorant is added to a vinyl chloride resin composition, the amount of the colorant added is usually in the range of 1 to 100 parts by weight based on 100 parts by weight of the vinyl chloride resin.

Examples of the processing aid include liquid paraffin, polyethylene wax, stearic acid, stearamide, ethylene bisstearamide, butyl stearate, calcium stearate, and the like.
When a processing aid is blended into a vinyl chloride resin composition, the amount thereof is usually in the range of 0.1 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin.

Examples of the filler include metal oxides such as calcium carbonate, silica, alumina, clay, talc, diatomaceous earth, and ferrite; fibers and powders of glass, carbon, and metal; glass spheres, graphite, aluminum hydroxide, and barium sulfate. , magnesium oxide, magnesium carbonate, magnesium silicate, calcium silicate, and the like.
When a filler is blended into a vinyl chloride resin composition, the amount thereof is usually in the range of 1 to 100 parts by mass based on 100 parts by mass of the vinyl chloride resin.

Examples of the antioxidant include 2,6-di-tert-butylphenol, tetrakis[methylene-3-(3,5-tert-butyl-4-hydroxyphenol)propionate]methane, 2-hydroxy-4-methoxy Phenolic compounds such as benzophenone; Sulfur compounds such as alkyl disulfides, thiodipropionic acid esters, and benzothiazole; trisnonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, tris(2,4-di-tert Examples include phosphoric acid compounds such as -butylphenyl) phosphite; organometallic compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate.
When an antioxidant is added to a vinyl chloride resin composition, the amount thereof is usually in the range of 0.2 to 20 parts by weight based on 100 parts by weight of the vinyl chloride resin.

Examples of the ultraviolet absorber include salicylate compounds such as phenyl salicylate and p-tert-butylphenyl salicylate; benzophenones such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-n-methoxybenzophenone; Examples include benzotriazole compounds such as 5-methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, as well as cyanoacrylate compounds.
When an ultraviolet absorber is added to a vinyl chloride resin composition, the amount thereof is usually in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin.

Examples of the light stabilizer include hindered amine light stabilizers. Specifically, for example, 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-Hydryxyphenyl]methyl]butyl malonate, decanedioic acid bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidyl) ester and 1,1-dimethylethyl hydroperoxide reaction product of ,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-4-piperidyl-1,6-hexa Polycondensate of methylene diamine 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. .
When a light stabilizer is added to a vinyl chloride resin composition, the amount thereof is usually in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin.

Examples of the lubricant include silicone, liquid paraffin, paraffin wax, fatty acid metal salts such as metal stearate and metal laurate; fatty acid amide, fatty acid wax, and higher fatty acid wax.
When a lubricant is added to a vinyl chloride resin composition, its amount is usually in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin.

Examples of the antistatic agent include anionic antistatic agents of alkyl sulfonate type, alkyl ether carboxylic acid type, or dialkyl sulfosuccinate type; nonionic antistatic agents such as polyethylene glycol derivatives, sorbitan derivatives, and diethanolamine derivatives; alkylamidoamines. Examples include cationic antistatic agents such as quaternary ammonium salts such as type, alkyldimethylbenzyl type, organic acid salts or hydrochlorides of alkylpyridinium type; amphoteric antistatic agents such as alkylbetaine type and alkylimidazoline type. .
When an antistatic agent is added to a vinyl chloride resin composition, the amount thereof is usually in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin.

Examples of the crosslinking aid include polyfunctional monomers such as tetraethylene glycol dimethacrylate, divinylbenzenediallyl phthalate, triallyl isocyanurate, trimethylolpropane triarylate, tetramethylolmethanetetramethacrylate, and trimethoxyethoxyvinylsilane,
When a crosslinking aid is added to a vinyl chloride resin composition, its amount is usually in the range of 0.5 to 30 parts by weight based on 100 parts by weight of the vinyl chloride resin.

The vinyl chloride resin composition of the present invention can be produced by a known method.
For example, the vinyl chloride resin composition of the present invention can be prepared by mixing the vinyl chloride resin, the vinyl chloride resin plasticizer of the present invention, and any optional components (the other plasticizers and other additives) in a blender, planetary mixer, Banbury mixer, etc. It can be prepared by mixing using a kneader.

A molded article can be obtained by molding the vinyl chloride resin composition of the present invention by a known molding method such as vacuum molding, compression molding, extrusion molding, calendar molding, press molding, blow molding, powder molding, or powder slush molding. I can see it.

Molded products obtained using the vinyl chloride resin composition of the present invention include, for example, insulating tapes, insulating sheets, wiring connectors, conductor coating materials, pipes such as water pipes, pipe fittings, gutters such as rain gutters, window frames, etc. Automotive materials such as siding, flat plates, corrugated plates, automobile underbody coats, dashboards, instrument panels, consoles, door sheets, undercarpets, trunk seats, and door trims, various leathers, decorative sheets, agricultural films, and food packaging. films, various foam products, hoses, medical tubes, food tubes, refrigerator gaskets, packing, wallpaper, flooring, boots, curtains, soles, gloves, water stop plates, toys, decorative boards, blood bags, It can be used for infusion bags, tarpaulins, mats, water-shielding sheets, civil engineering sheets, roofing, waterproof sheets, industrial tapes, glass films, erasers, etc.

[Urethane/vinyl chloride laminate]
The above automobile dashboard includes a laminate portion of a vinyl chloride resin layer and a urethane resin layer, and the molded product obtained using the vinyl chloride resin composition of the present invention is particularly suitable for the vinyl chloride resin layer of the laminate. It is. This is because in the vinyl chloride resin layer using the plasticizer of the present invention, migration of the plasticizer in the vinyl chloride resin layer to the urethane resin layer is reduced, and the flexibility of the vinyl chloride resin layer can be maintained. It is.

The non-migration property of the plasticizer of the present invention can be confirmed by the heating test described in the Examples. Specifically, even after a laminate of a vinyl chloride resin layer containing the plasticizer for vinyl chloride resin of the present invention and a urethane resin layer is subjected to a heat test, the plasticizer of the present invention remains in the vinyl chloride resin layer. The ratio (amount of plasticizer in the vinyl chloride resin layer after the heating test/amount of plasticizer in the vinyl chloride resin layer before the heating test x 100) can be 90% or more.
The upper limit of the residual rate is not particularly limited, but is, for example, 100%.

Hereinafter, the laminate of the vinyl chloride resin layer containing the vinyl chloride resin plasticizer of the present invention and the urethane resin layer will be referred to as the "laminate of the present invention", and each layer will be explained.

The vinyl chloride resin layer is formed by molding the vinyl chloride resin composition of the present invention, and the components contained in the vinyl chloride resin composition and the molding method are as described above.

The thickness of the vinyl chloride resin layer may be set arbitrarily, and is, for example, 0.2 to 2.0 mm, preferably 0.5 to 1.5 mm.

The urethane resin layer is a layer made of polyurethane foam, and can be formed using a foam raw material containing a polyol, a polyisocyanate, a crosslinking agent, a catalyst, a blowing agent, a foam stabilizer, and the like.

The polyol is not particularly limited, and any known polyol used in the production of polyurethane foam can be used. Specific examples of the polyol include polyether polyols such as polypropylene glycol (PPG), polyethylene glycol (PEG), and polyoxytetramethylene glycol (PTMG); polyester polyols, polymer polyols, etc.; is preferred.
One type of polyol may be used alone, or two or more types may be used in combination.

As the polyisocyanate, diphenylmethane diisocyanate (hereinafter sometimes abbreviated as "MDI") type and tolylene diisocyanate (hereinafter sometimes abbreviated as "TDI") type may be used in combination.
Examples of the MDI type include 2,2'-MDI, 2,4'-MDI, 4,4'-MDI, polymethylene polyphenylene polyisocyanate, and urethane modified products thereof.
Examples of the TDI type include 2,4-TDI, 2,6-TDI, and carbodiimide modified products thereof.

As the crosslinking agent, any crosslinking agent that is normally used in the production of polyurethane foam can be used without particular limitation. As this crosslinking agent, a compound having a molecular weight of less than 500 and having at least two active hydrogen groups, such as a low molecular weight alcohol, a low molecular weight amine, or a low molecular weight amino alcohol, can be used. The crosslinking agent is preferably a low molecular weight amino alcohol that reacts slowly with isocyanate groups, more preferably diethanolamine.

Only one type of crosslinking agent may be used, or two or more types may be used in combination.
The blending amount of the crosslinking agent is preferably 10 parts by mass or less, particularly 5 parts by mass or less (usually 1 part by mass or more), based on 100 parts by mass of the polyol.

As the catalyst, any catalyst that is normally used in the production of polyurethane foam can be used without particular limitation. As this catalyst, tertiary amines, diazabicycloalkene compounds and their salts, organometallic compounds, etc. can be used, and tertiary amines are preferred.

Examples of the tertiary amine include triethylenediamine, triethylamine, tri-n-butylamine, bis(2-dimethylaminoethyl)ether, N,N,N',N'-tetramethylhexamethylenediamine, and 1,2-dimethylimidazole. etc. Examples of organometallic compounds include metal salts of various metals such as tin, lead, and zirconium and organic acids such as octenoic acid and naphthenic acid, such as dibutyltin dilaurate, dibutyltin diacetylacetonate, and zirconium tetraacetylacetonate. can be mentioned. These catalysts may be used alone or in combination of two or more. The amount of the catalyst blended is preferably 0.03 to 2.0 parts by weight, particularly 0.03 to 1.5 parts by weight, based on 100 parts by weight of the polyol. When the amount of the catalyst is 0.03 to 2.0 parts by mass, the foam raw material can be easily cured and the moldability is good.

As the blowing agent, any blowing agent that is normally used in the production of polyurethane foam can be used without particular limitation. Water is often used as the blowing agent, and in addition to water, there are two other types of blowing agents, for example, inert low boiling point solvents and reactive blowing agents.

Examples of the inert low-boiling solvent include dichloromethane, hydrochlorofluorocarbon, hydrofluorocarbon, isopentane, and the like.

Examples of the reactive blowing agent include azo compounds that decompose at temperatures higher than room temperature to generate gas. These blowing agents may be used alone or in combination of two or more. The amount of the blowing agent blended is preferably 1.0 to 5.0 parts by weight, particularly 1.5 to 4.0 parts by weight, based on 100 parts by weight of the polyol. If the amount of the blowing agent is 1.0 to 5.0 parts by mass, the foam will be a closed-cell type, and no caving or the like will occur on the surface of the foam.

As the foam stabilizer, any foam stabilizer that is normally used in the production of polyurethane foam can be used without particular limitation. Examples of the foam stabilizer include polydimethylsiloxane/polyalkylene oxide block copolymers and vinylsilane/polyalkylene polyol copolymers.

The foam stabilizer may be used alone or in combination of two or more.
The amount of the foam stabilizer added is preferably 3.0 parts by mass or less, particularly 2.0 parts by mass or less (usually 0.5 parts by mass or more), based on 100 parts by mass of the polyol.

In the production of polyurethane foam, which becomes the urethane resin layer, antioxidants, anti-aging agents such as ultraviolet absorbers, fillers such as calcium carbonate and barium sulfate, internal mold release agents, flame retardants, plasticizers, colorants, and antiseptics are used. Various additives and auxiliaries such as fungicides can be used as necessary.

The method for forming the polyurethane foam layer is not particularly limited, and for example, a foam raw material is placed in the space between the upper mold and the lower mold under conditions such that the isocyanate index is 70 to 140, particularly 80 to 120, by vacuum forming or the like. It can be formed by injection, reaction, and curing. Further, if necessary, the foam raw material and/or the mold can be heated to accelerate the reaction and curing. Further, the foam raw material is injected into the space between the molds, preferably coated with a mold release agent, using at least one mixing head, and is usually reacted at a temperature range of, for example, room temperature to about 70°C, to form the foam. , can be formed by curing.

The thickness of the urethane resin layer may be set arbitrarily, and is, for example, 5 to 15 mm, preferably 7 to 12 mm.

Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples.
Note that the present invention is not limited to the following examples.

In the Examples of the present application, the acid value and viscosity values are values evaluated by the following methods.
<Method for measuring acid value>
It was measured by a method according to JIS K0070-1992.
<Method of measuring viscosity>
It was measured by a method according to JIS K6901-1986.

In the Examples of the present application, the number average molecular weight of polyester is a value converted to polystyrene based on GPC measurement, and the measurement conditions are as follows.
[GPC measurement conditions]
Measuring device: High-speed GPC device “HLC-8320GPC” manufactured by Tosoh Corporation
Column: "TSK GURDCOLUMN SuperHZ-L" manufactured by Tosoh Corporation + "TSK gel SuperHZM-M" manufactured by Tosoh Corporation + "TSK gel SuperHZM-M" manufactured by Tosoh Corporation + "TSK gel SuperHZ-2000" manufactured by Tosoh Corporation + “TSK gel SuperHZ-2000” manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: “EcoSEC Data Analysis version 1.07” manufactured by Tosoh Corporation
Column temperature: 40℃
Developing solvent: Tetrahydrofuran Flow rate: 0.35 mL/min Measurement sample: 7.5 mg of the sample was dissolved in 10 ml of tetrahydrofuran, and the resulting solution was filtered with a microfilter to obtain the measurement sample.
Sample injection volume: 20μl
Standard sample: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual for the above-mentioned "HLC-8320GPC".

(Monodisperse polystyrene)
"A-300" manufactured by Tosoh Corporation
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
"F-288" manufactured by Tosoh Corporation

(Example 1: Synthesis of polyester plasticizer A)
In a reaction vessel, 597 g (4.09 mol) of adipic acid, 448 g (3.80 mol) of 3-methyl 1,5-pentanediol, 177 g (1.23 mol) of isononyl alcohol, and 0% of tetraisopropyl titanate as an esterification catalyst were added. 06 g was charged into a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised stepwise to 230° C. while stirring under a nitrogen stream. Heating was continued at 230° C. until the acid value became 4 or less, and the water produced was continuously removed. After the reaction, excess isononyl alcohol was distilled off under reduced pressure at 230 to 200°C to obtain polyester plasticizer A (Mn 2,734, acid value 0.5, viscosity 3,000 mPa・s (25°C), isononyl alcohol 945 g of the product was obtained (content: 1920 ppm by mass).

The residual amount of isononyl alcohol in the obtained polyester plasticizer A was measured by GC under the following conditions:
Measuring equipment: GC-2010PLUS (manufactured by Shimadzu Corporation)
Column: DB-5 (0.25mm x 30m x 0.25μm)
Vaporization chamber temperature: 250℃
Detector temperature: 320℃
Column temperature conditions: 40°C (10°C/min) → 250°C (20°C/min) → 315 (held for 34 minutes)
Sample concentration: 50mg/ml acetone

(Preparation of vinyl chloride resin composition (1))
100 parts by mass of vinyl chloride resin (polymerization degree 1,000, ZEST1000Z, manufactured by Shin Daiichi PVC Co., Ltd.), 50 parts by mass of the obtained polyester plasticizer A, filler (Greg MP-677D (calcium/zinc-based composite stable (manufactured by Nichishin Boeki Co., Ltd.) were mixed to obtain a vinyl chloride resin composition (1). The following evaluations were performed using the obtained vinyl chloride resin composition (1).

(Evaluation of plasticizing performance of plasticizer)
After kneading the vinyl chloride resin composition (1) prepared with two rolls heated to 170°C for 10 minutes, a molded product with a thickness of 1.0 mm is obtained from the vinyl chloride resin composition (1) after kneading. A 1.0 mm thick sheet was produced by molding using a mold (1.0 mm thick mold) and a press heated to 170°C.

The obtained sheet was evaluated for 100% modulus (tensile stress at 100% elongation) and elongation at break according to JIS K6251:2010. Specifically, using a 1.0 mm thick sheet, a tensile test was conducted under the following conditions, and the 100% modulus and elongation at break were evaluated. The results are shown in Table 1.
The elongation at break is expressed as a percentage by dividing the value obtained by subtracting the initial distance between chucks, 20 mm, from the distance between chucks when a 1.0 mm thick sheet tensilely breaks, by the distance between chucks, 20 mm.
Measuring equipment: Tensilon universal material testing machine (manufactured by Orientec Co., Ltd.)
Sample shape: Dumbbell size 3 Distance between chucks: 20mm
Tensile speed: 200mm/min Measurement atmosphere: Temperature 23 degrees, humidity 50%

The lower the 100% modulus value, the higher the effect of plasticizing the vinyl chloride resin. Further, the higher the elongation at break, the higher the effect of plasticizing the vinyl chloride resin.

(Evaluation of heat resistance performance of molded products)
After kneading the vinyl chloride resin composition (1) prepared with two rolls heated to 170°C for 10 minutes, a molded product with a thickness of 1.0 mm is obtained from the vinyl chloride resin composition (1) after kneading. A 1.0 mm thick sheet was produced by molding using a mold (1.0 mm thick mold) and a press heated to 170°C. A dumbbell test piece having a dumbbell shape No. 3 was prepared from the prepared sheet having a thickness of 1.0 mm in accordance with JIS K6251:2010.

The produced dumbbell test piece was subjected to a heat aging test at 136°C for 168 hours in accordance with JISK6257:2017. The mass of the dumbbell test piece before and after the heat aging test was measured, and the weight loss rate ((mass before heat aging test - mass after heat aging test)/mass before heat aging test) was calculated. The results are shown in Table 1.
The smaller the weight loss rate, the more the polyester plasticizer A remains in the molded product even after the heat aging test, and the heat resistance effect of the polyester plasticizer A can be expected.

For the dumbbell test piece after the heat aging test, the elongation at break was evaluated in the same manner as in the evaluation of the plasticization effect, and the elongation rate of the dumbbell test piece after the heat aging test was divided by the elongation rate of the dumbbell test piece before the heat aging test. The elongation rate was evaluated as "remaining elongation rate." The results are shown in Table 1.
The higher the residual elongation rate, the more the plasticizing effect can be maintained even after the heat aging test, and it can be said that the vinyl chloride resin composition has excellent heat resistance.

(Evaluation of low temperature flexibility of molded product)
After kneading the vinyl chloride resin composition (1) prepared with two rolls heated to 170°C for 10 minutes, a molded product with a thickness of 1.0 mm is obtained from the vinyl chloride resin composition (1) after kneading. A 1.0 mm thick sheet was produced by molding using a mold (1.0 mm thick mold) and a press heated to 170°C.
Regarding the obtained sheet, a test piece was prepared according to the test method specified in JIS K6773:2007, and the flexibility temperature (unit: °C) was evaluated using a Crashberg flexibility temperature measurement tester. The results are shown in Table 1. The lower the softness temperature, the better the cold resistance.

(Evaluation of non-migration of plasticizer)
After kneading the vinyl chloride resin composition (1) prepared with two rolls heated to 170°C for 10 minutes, a molded product with a thickness of 1.0 mm is obtained from the vinyl chloride resin composition (1) after kneading. A 1.0 mm thick sheet was produced by molding using a mold (1.0 mm thick mold) and a press heated to 170°C.
The obtained 1.0 mm thick sheet was punched out into a size of 6.0 mm x 38 mm to obtain a test piece. This test piece was placed on two acrylonitrile-butadiene-styrene resin (ABS) plates, two high-impact polystyrene resin (HIPS) plates, two acrylonitrile-styrene resin (AS) plates, and two polyurethane resin (PU) plates. ) They were sandwiched between plates and held at 70° C. for 72 hours while applying a load of 0.22 kg/cm ² . The degree of contamination caused by the transfer of plasticizer to each of the ABS board, HIPS board, AS board, and PU board was visually evaluated using the following criteria. The results are shown in Table 1.
○: There is no trace of migration to the resin board, or even if there is a trace, the trace disappears by wiping with ethanol-impregnated gauze. ×: There is clearly a trace of plasticizer migration, and the trace does not disappear even with wiping with ethanol-impregnated gauze.

(Evaluation of compatibility of plasticizer)
After kneading the vinyl chloride resin composition (1) prepared with two rolls heated to 170°C for 10 minutes, a molded product with a thickness of 1.0 mm is obtained from the vinyl chloride resin composition (1) after kneading. A 1.0 mm thick sheet was produced by molding using a mold (1.0 mm thick mold) and a press heated to 170°C. Two 1.0 mm thick sheets were cut from this sheet into a size of 5 cm x 5 cm. The two produced sheets were stacked and left for 30 days at 70° C. and 95% relative humidity. Thereafter, the condition of the surface of the sheet and the surface where the sheets overlapped was evaluated according to the following evaluation criteria. The results are shown in Table 1.
〇: Visually check the surface of the sheet and the surface where the sheets overlap, and if no foreign matter (bleed) such as powder or viscous material is found, and check the surface of the sheet and the surface where the sheets overlap. Even if you touch it, you can't check the bleed.
×: Bleeding can be confirmed by visually checking the surface of the sheet and the surface where the sheets overlap, or bleeding can be confirmed by touching the surface of the sheet and the surface where the sheets overlap with a finger.

(Evaluation of plasticizer odor)
Put 100g of plasticizer in a 225ml glass bottle and leave it at room temperature for about 2 hours, then insert the suction port of the sensor (Shin Cosmos Electric Co., Ltd. portable odor sensor XP-329) into the 8mm hole in the inner lid and start measurement. The value was read after 3 minutes and evaluated using the following evaluation criteria. The smaller the sensor value, the less odor there is.
1: Sensor value is less than 100 2: Sensor value is 100 or more and less than 300 3: Sensor value is 300 or more and less than 500 4: Sensor value is 500 or more

(Evaluation of residual amount of plasticizer)
<Manufacture of vinyl chloride resin molded sheets>
After kneading the vinyl chloride resin composition (1) prepared with two rolls heated to 170°C for 10 minutes, a molded product with a thickness of 1.0 mm is obtained from the vinyl chloride resin composition (1) after kneading. A 1.0 mm thick sheet was produced by molding using a mold (1.0 mm thick mold) and a press heated to 170°C.

<Formation of laminate>
50 parts of propylene glycol PO (propylene oxide)/EO (ethylene oxide) block adduct (hydroxyl value 28, terminal EO unit content 10%, internal EO unit content 4%), glycerin PO/EO block 50 parts of adduct (hydroxyl value 21, content of terminal EO unit = 14%), 2.5 parts of water, ethylene glycol solution of triethylenediamine (manufactured by Tosoh Corporation, trade name "TEDA-L33"). A polyol mixture was prepared by mixing 0.2 parts of triethanolamine, 1.2 parts of triethanolamine, 0.5 parts of triethylamine, and 0.5 parts of a foam stabilizer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "F-122"). I got it. A liquid mixture was prepared by mixing the obtained polyol mixture and polymethylene polyphenylene polyisocyanate (polymeric MDI) at a ratio giving an index of 98.
Pour the prepared liquid mixture onto a vinyl chloride resin molded sheet placed in a mold of 200 mm x 300 mm x 10 mm, and cover the mold with an aluminum plate of 348 mm x 255 mm x 10 mm. The mold was sealed. By sealing the mold and leaving it for 5 minutes, a polyurethane foam molding (thickness: 9 mm, density: 0.18 g/cm ³ ) was formed on the vinyl chloride resin molded sheet (thickness: 1 mm) as the skin. The lined laminate was formed in a mold. This laminate was taken out from the mold to produce a laminate consisting of a foamed urethane resin layer and a vinyl chloride resin layer.

The obtained laminate was placed in an oven and heated for 600 hours at a temperature of 130°C. After heating, only the vinyl chloride resin layer was peeled off from the laminate, and the peeled vinyl chloride resin layer equivalent to 20 mg was dissolved in tetrahydrofuran (THF). The obtained THF solution was analyzed under the above-mentioned GPC measurement conditions to measure the plasticizer content (%) in the vinyl chloride resin layer after the heat treatment. The plasticizer content obtained in the measurement was divided by the plasticizer content in the vinyl chloride resin layer before heat treatment to calculate the plasticizer residual rate.

(Example 2: Synthesis of polyester plasticizer B)
In a reaction vessel, 597 g (4.09 mol) of adipic acid, 448 g (3.80 mol) of 3-methyl 1,5-pentanediol, 177 g (1.23 mol) of isononyl alcohol, and 0% of tetraisopropyl titanate as an esterification catalyst were added. 06 g was charged into a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised stepwise to 230° C. while stirring under a nitrogen stream. Heating was continued at 230° C. until the acid value became 4 or less, and the water produced was continuously removed. After the reaction, excess isononyl alcohol was distilled off under reduced pressure at 230 to 200°C to obtain a polyester.
The obtained polyester was subjected to a steam stripping treatment by supplying steam at 160°C for 1 hour at a rate of 0.015 STM kg/hr/kg per unit resin throughput, and polyester plasticizer B (Mn2,738, acid value 0.5, viscosity 2,990 mPa·s (25° C.), and isononyl alcohol content 1562 mass ppm).

A vinyl chloride resin composition (2) was prepared and evaluated in the same manner as in Example 1, except that plasticizer B was used instead of plasticizer A. The results are shown in Table 1.

(Example 3: Synthesis of polyester plasticizer C)
In a reaction vessel, 597 g (4.09 mol) of adipic acid, 448 g (3.80 mol) of 3-methyl 1,5-pentanediol, 177 g (1.23 mol) of isononyl alcohol, and 0% of tetraisopropyl titanate as an esterification catalyst were added. 06 g was charged into a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised stepwise to 230° C. while stirring under a nitrogen stream. Heating was continued at 230° C. until the acid value became 4 or less, and the water produced was continuously removed. After the reaction, excess isononyl alcohol was distilled off under reduced pressure at 230 to 200°C to obtain a polyester.
The obtained polyester was subjected to a steam stripping treatment by supplying steam at 160°C for 2 hours at a rate of 0.015 STM kg/hr/kg per unit resin throughput, and polyester plasticizer C (Mn2,697, acid value 0.6, viscosity 2,980 mPa·s (25° C.), and isononyl alcohol content 792 mass ppm).

A vinyl chloride resin composition (3) was prepared and evaluated in the same manner as in Example 1, except that plasticizer C was used instead of plasticizer A. The results are shown in Table 1.

(Example 4: Synthesis of polyester plasticizer D)
In a reaction vessel, 597 g (4.09 mol) of adipic acid, 448 g (3.80 mol) of 3-methyl 1,5-pentanediol, 177 g (1.23 mol) of isononyl alcohol, and 0% of tetraisopropyl titanate as an esterification catalyst were added. 06 g was charged into a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised stepwise to 230° C. while stirring under a nitrogen stream. Heating was continued at 230° C. until the acid value became 4 or less, and the water produced was continuously removed. After the reaction, excess isononyl alcohol was distilled off under reduced pressure at 230 to 200°C to obtain a polyester.
The obtained polyester was subjected to a steam stripping treatment by supplying steam at 160°C for 5 hours at a rate of 0.015 STM kg/hr/kg per unit resin throughput, and polyester plasticizer D (Mn2,794, acid value 0.7, viscosity 2,943 mPa·s (25° C.), and isononyl alcohol content 522 mass ppm).

A vinyl chloride resin composition (4) was prepared and evaluated in the same manner as in Example 1, except that plasticizer D was used instead of plasticizer A. The results are shown in Table 1.

(Example 5: Synthesis of polyester plasticizer E)
In a reaction vessel, 597 g (4.09 mol) of adipic acid, 265 g (2.25 mol) of 3-methyl 1,5-pentanediol, 80 g (0.77 mol) of neopentyl glycol, and 73 g (73 mol) of 1,4-butanediol were added. 0.81 mol), 114 g (0.88 mol) of 2-ethylhexanol, 54 g (0.08 mol) of coconut oil, 0.06 g of tetraisopropyl titanate as an esterification catalyst, a thermometer, a stirrer, and a reflux condenser. The mixture was charged into a four-necked flask with an internal volume of 2 liters, and the temperature was raised stepwise to 230°C while stirring under a nitrogen stream. Heating was continued at 230° C. until the acid value became 4 or less, and the water produced was continuously removed. After the reaction, excess 2-ethylhexanol was distilled off under reduced pressure at 230 to 200°C to obtain a polyester.
The obtained polyester was subjected to a steam stripping treatment by supplying steam at 160°C for 2 hours at a rate of 0.015 STM kg/hr/kg per unit resin throughput, and polyester plasticizer E (Mn2,995, acid value 0.6, viscosity 2,910 mPa·s (25° C.), and 2-ethylhexanol content 693 mass ppm).

A vinyl chloride resin composition (5) was prepared and evaluated in the same manner as in Example 1, except that plasticizer E was used instead of plasticizer A. The results are shown in Table 1.

(Example 6: Synthesis of polyester plasticizer F)
In a reaction vessel, 657 g (4.50 mol) of adipic acid, 231 g (2.57 mol) of 2-methyl-1,3-propanediol, 154 g (1.49 mol) of neopentyl glycol, and 194 g (1.5 mol) of isononyl alcohol were added. 35 mol) and 0.06 g of tetraisopropyl titanate as an esterification catalyst were charged into a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and the mixture was heated at 230°C with stirring under a nitrogen stream. The temperature was gradually raised to . Heating was continued at 230° C. until the acid value became 4 or less, and the water produced was continuously removed. After the reaction, excess isononyl alcohol was distilled off under reduced pressure at 230 to 200°C to obtain a polyester.
The obtained polyester was subjected to a steam stripping treatment by supplying steam at 160°C for 2 hours at a rate of 0.015 STM kg/hr/kg per unit resin throughput, and the polyester plasticizer F (Mn2,182, acid value 0.2, viscosity 3,140 mPa·s (25° C.), and isononyl alcohol content 753 mass ppm).

A vinyl chloride resin composition (6) was prepared and evaluated in the same manner as in Example 1, except that plasticizer F was used instead of plasticizer A. The results are shown in Table 1.

(Example 7: Synthesis of polyester plasticizer G)
In a reaction vessel, 615 g (4.21 mol) of adipic acid, 70 g (0.78 mol) of 1,4-butanediol, 322 g (3.10 mol) of neopentyl glycol, and 177 g (1.36 mol) of 2-ethylhexanol. , 56 g (0.08 mol) of coconut oil, and 0.06 g of tetraisopropyl titanate as an esterification catalyst were charged into a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and the mixture was heated with a nitrogen stream. The temperature was raised stepwise to 230°C while stirring at the bottom. Heating was continued at 230° C. until the acid value became 4 or less, and the water produced was continuously removed. After the reaction, excess 2-ethylhexanol was distilled off under reduced pressure at 230 to 200°C to obtain a polyester.
The obtained polyester was subjected to a steam stripping treatment by supplying steam at 160° C. for 2 hours at a rate of 0.015 STM kg/hr/kg per unit resin throughput to remove polyester plasticizer G (Mn2,144, acid value 0.6, viscosity 2,950 mPa·s (25° C.), 2-ethylhexanol content 461 mass ppm).

A vinyl chloride resin composition (7) was prepared and evaluated in the same manner as in Example 1, except that plasticizer G was used instead of plasticizer A. The results are shown in Table 1.

(Example 8: Synthesis of polyester plasticizer H)
In a reaction vessel, 672 g (4.60 mol) of adipic acid, 236 g (2.62 mol) of 1,4-butanediol, 182 g (1.75 mol) of neopentyl glycol, 133 g (0.92 mol) of isononyl alcohol, 0.06 g of tetraisopropyl titanate as an esterification catalyst was charged into a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was gradually raised to 230°C while stirring under a nitrogen stream. The temperature rose. Heating was continued at 230° C. until the acid value became 4 or less, and the water produced was continuously removed. After the reaction, excess isononyl alcohol was distilled off under reduced pressure at 230 to 200°C to obtain a polyester.
The obtained polyester was subjected to a steam stripping treatment by supplying steam at 160°C for 2 hours at a rate of 0.015 STM kg/hr/kg per unit resin throughput, and a polyester plasticizer H (Mn2,770, acid value 0.6, viscosity 9,810 mPa·s (25° C.), and isononyl alcohol content 669 mass ppm).

A vinyl chloride resin composition (8) was prepared and evaluated in the same manner as in Example 1, except that plasticizer H was used instead of plasticizer A. The results are shown in Table 1.

(Example 9: Synthesis of polyester plasticizer I)
In a reaction vessel, 579 g (3.97 mol) of adipic acid, 167 g (1.85 mol) of 1,4-butanediol, 289 g (2.78 mol) of neopentyl glycol, 176 g (0.88 mol) of lauric acid, and ester. 0.06 g of tetraisopropyl titanate as a catalyst was charged into a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was gradually raised to 230°C while stirring under a nitrogen stream. It was warm. Heating was continued at 230° C. until the acid value became 4 or less, and the water produced was continuously removed. After the reaction, the pressure was reduced at 230 to 200°C to obtain polyester.
The obtained polyester was subjected to a steam stripping treatment by supplying steam at 160°C for 2 hours at a rate of 0.015 STM kg/hr/kg per unit resin throughput, and polyester plasticizer I (Mn 2,400, acid value 0.4, viscosity 4,350 mPa·s (25°C)).

A vinyl chloride resin composition (9) was prepared and evaluated in the same manner as in Example 1 except that Plasticizer I was used instead of Plasticizer A. The results are shown in Table 1.

(Comparative Example 1: Synthesis of polyester plasticizer I)
In a reaction vessel, 597 g (4.09 mol) of adipic acid, 308 g (4.05 mol) of 1,2-propanediol, 138 g (1.23 mol) of 2-ethylhexanol, and 0.06 g of tetraisopropyl titanate as an esterification catalyst. The mixture was charged into a 2-liter four-neck flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised stepwise to 230° C. while stirring under a nitrogen stream. Heating was continued at 230° C. until the acid value became 4 or less, and the water produced was continuously removed. After the reaction, excess 2-ethylhexanol was distilled off under reduced pressure at 230 to 200°C to obtain polyester plasticizer I (Mn 2,242, acid value 0.2, viscosity 3,250 mPa・s (25°C), 2- 861 g of ethylhexanol (content: 3929 ppm by mass) was obtained.

A vinyl chloride resin composition (1') was prepared and evaluated in the same manner as in Example 1 except that Plasticizer I was used instead of Plasticizer A. The results are shown in Table 2.

(Comparative Example 2: Synthesis of polyester plasticizer J)
In a reaction vessel, 657 g (4.50 mol) of adipic acid, 275 g (3.06 mol) of 1,4-butanediol, 106 g (1.02 mol) of neopentyl glycol, 194 g (1.35 mol) of isononyl alcohol, 0.06 g of tetraisopropyl titanate as an esterification catalyst was charged into a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was gradually raised to 230°C while stirring under a nitrogen stream. The temperature rose. Heating was continued at 230° C. until the acid value became 4 or less, and the water produced was continuously removed. After the reaction, excess isononyl alcohol was distilled off under reduced pressure at 230 to 200°C to obtain polyester plasticizer J (Mn 2,031, acid value 0.6, viscosity 2,940 mPa・s (25°C), isononyl alcohol content 3260 mass ppm) was obtained.

A vinyl chloride resin composition (2') was prepared and evaluated in the same manner as in Example 1, except that plasticizer J was used instead of plasticizer A. The results are shown in Table 2.

(Comparative Example 3: Synthesis of polyester plasticizer K)
In a reaction vessel, 667 g (4.57 mol) of adipic acid, 374 g (4.16 mol) of 2-methyl-1,3-propanediol, 194 g (1.35 mol) of isononyl alcohol, and tetraisopropyl titanate as an esterification catalyst were added. 0.06 g was charged into a 2-liter four-necked flask equipped with a thermometer, stirrer, and reflux condenser, and the temperature was raised stepwise to 230° C. with stirring under a nitrogen stream. Heating was continued at 230° C. until the acid value became 4 or less, and the water produced was continuously removed. After the reaction, excess isononyl alcohol was distilled off under reduced pressure at 230 to 200°C to obtain polyester plasticizer K (Mn 2,725, acid value 0.2, viscosity 3,228 mPa・s (25°C), isononyl alcohol content 4011 mass ppm) was obtained.

A vinyl chloride resin composition (3') was prepared and evaluated in the same manner as in Example 1, except that plasticizer K was used instead of plasticizer A. The results are shown in Table 2.

(Comparative Example 4: Synthesis of polyester plasticizer L)
In a reaction vessel, 489 g (3.35 moles) of adipic acid, 427 g (3.62 moles) of 3-methyl-1,5-pentanediol, 35 g (0.27 moles) of 2-ethylhexanol, and 222 g (0.2 moles) of coconut oil were added. 34 mol), 0.06 g of tetraisopropyl titanate as an esterification catalyst was charged into a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and heated to 230°C while stirring under a nitrogen stream. The temperature was gradually raised to . Heating was continued at 230° C. until the acid value became 4 or less, and the water produced was continuously removed. After the reaction, excess 2-ethylhexanol was distilled off under reduced pressure at 230 to 200°C to obtain polyester plasticizer L (Mn 2,814, acid value 0.6, viscosity 1,552 mPa・s (25°C), 2-ethylhexanol). 919 g of the product was obtained (content: 1211 ppm by mass).

A vinyl chloride resin composition (4') was prepared and evaluated in the same manner as in Example 1, except that plasticizer L was used instead of plasticizer A. The results are shown in Table 2.

Tables 1 and 2 show that excellent heat resistance and non-migration properties can be obtained by using a polyester containing a specific amount of a specific polyol as a plasticizer for vinyl chloride resin. It can also be seen that odor can be reduced by steam stripping to reduce the amount of monoalcohol remaining.

Claims (13)

A polyester containing a glycol having 2 to 18 carbon atoms, an aliphatic dicarboxylic acid having 4 to 14 carbon atoms, and a monoalcohol having 4 to 18 carbon atoms as reaction raw materials, or a glycol having 2 to 18 carbon atoms. , a plasticizer for vinyl chloride resin, which is a polyester made of aliphatic dicarboxylic acid having 4 to 14 carbon atoms, a monoalcohol having 4 to 18 carbon atoms, and an aliphatic monocarboxylic acid having 2 to 21 carbon atoms as reaction raw materials. A drug,
The glycol is an alkylene glycol having 5 to 18 carbon atoms, and contains 30 mol% or more of an alkylene glycol substituted with one or more methyl groups in the main chain,
A plasticizer for vinyl chloride resin , wherein the content of the monoalcohol having 4 to 18 carbon atoms in the polyester is less than 1,000 ppm by mass . The plasticizer for vinyl chloride resin according to claim 1, wherein the alkylene glycol is one or more selected from the group consisting of neopentyl glycol and 3-methyl-1,5-pentanediol. The plasticizer for vinyl chloride resin according to claim 1 , wherein the aliphatic dicarboxylic acid having 4 to 14 carbon atoms is one or more selected from the group consisting of adipic acid and sebacic acid. The glycol having 2 to 18 carbon atoms is 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, The plasticizer for vinyl chloride resin according to claim 1 , which is one or more selected from the group consisting of neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. agent. The plasticizer for vinyl chloride resin according to claim 1 , wherein the monoalcohol having 4 to 18 carbon atoms is one or more selected from the group consisting of octanol, 2-ethylhexanol, and isononyl alcohol. The vinyl chloride resin according to claim 1 , wherein the aliphatic monocarboxylic acid having 4 to 21 carbon atoms is one or more selected from the group consisting of 2-ethylhexanoic acid, hydrogenated coconut oil fatty acid, and lauric acid. plasticizer. The plasticizer for vinyl chloride resin according to claim 1, wherein the aliphatic monocarboxylic acid having 4 to 21 carbon atoms contains a hydrogenated vegetable oil fatty acid. The plasticizer for vinyl chloride resin according to claim 1, wherein the polyester has a number average molecular weight in the range of 2,000 to 4,000. A vinyl chloride resin composition comprising the plasticizer for vinyl chloride resin according to any one of claims 1 to 8 and a vinyl chloride resin. The vinyl chloride resin composition according to claim 9, wherein the content of the vinyl chloride resin plasticizer is in the range of 10 to 150 parts by mass based on 100 parts by mass of the vinyl chloride resin. A molded article of the vinyl chloride resin composition according to claim 9 . Alkylene glycols having 5 to 18 carbon atoms, containing 30 mol% or more of alkylene glycols having one or more methyl groups substituted in the main chain, and glycols having 4 to 14 carbon atoms. Synthesize a polyester by reacting an aliphatic dicarboxylic acid with a monoalcohol having 4 to 18 carbon atoms and/or an aliphatic monocarboxylic acid having 4 to 21 carbon atoms,
A method for producing a plasticizer for vinyl chloride resin, in which the synthesized polyester is subjected to a steam stripping treatment after removing residual reaction raw materials under reduced pressure . A laminate of a urethane resin layer and a vinyl chloride resin layer,
The vinyl chloride resin layer contains the plasticizer for vinyl chloride resin according to any one of claims 1 to 8,
A laminate having a plasticizer residual rate of 90% or more in the vinyl chloride resin layer of the laminate after a heating test at a temperature of 130° C. for 600 hours.