Plasticizer for vinyl chloride resin, vinyl chloride resin composition and molded article thereof

Abstract

Provided is a plasticizer for a vinyl chloride resin, which has a low freezing point and can impart both of heat resistance and cold resistance to a vinyl chloride resin molded product. More specifically, a plasticizer for a vinyl chloride resin is provided, which comprises a polyester produced using, as reaction starting materials, 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 and / or a monocarboxylic acid having 2 to 21 carbon atoms, in which the glycol comprises 1,5-pentanediol and an alkylene glycol that has an alkylene chain having a branch having 3 to 18 carbon atoms, and the content ratio of the 1,5-pentanediol in the glycol is 5 to 90 mol%.

Description

[Technical field]

[0001] The present invention relates to a plasticizer for vinyl chloride resin, a vinyl chloride resin composition and a molded article thereof. [Background technology]

[0002] Polyvinyl chloride resin (PVC) is one of the most common plastics. It is usually made flexible by adding a plasticizer before use in order to give it properties such as flexibility and low-temperature properties, and to facilitate thermoforming processability.

[0003] Plasticizers used in polyvinyl chloride resins are required to have various properties such as compatibility, cold resistance, and heat resistance, and higher alkyl esters of polybasic acids such as phthalates, adipates, trimellitates, etc. Among them, phthalates are generally used as plasticizers for polyvinyl chloride resins from the viewpoint of the balance between price and performance.

[0004] Automobile dashboards generally contain a laminate structure of a urethane resin layer and a polyvinyl chloride resin layer. For applications requiring heat resistance, such as dashboards, the heat resistance of phthalate ester plasticizers is insufficient, and polyester-based plasticizers are therefore used instead of the phthalate ester plasticizers (e.g., Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 3-66727 Summary of the Invention [Problem to be solved by the invention]

[0006] Polyester plasticizers using 1,5-pentanediol as the glycol can impart heat and cold resistance to the resulting molded products, but because the freezing point of the polyester is high, there is a problem that when used in automobile dashboards, part of the plasticizer crystallizes and bleeds, impairing the plasticizing performance. If the plasticizing performance of the plasticizer is impaired by this crystallization and bleeding, the polyvinyl chloride resin layer may break into hard fragments and fly off when the airbag is deployed, creating a danger inside the vehicle.

[0007] The problem to be solved by the present invention is to provide a plasticizer for polyvinyl chloride resin which has a low freezing point and is capable of imparting both heat resistance and cold resistance to polyvinyl chloride resin molded articles. Another problem to be solved by the present invention is to provide a molded article made of a vinyl chloride resin composition in which bleeding of a plasticizer is suppressed and which can exhibit both heat resistance and cold resistance. [Means for solving the problem]

[0008] Means for Solving the Problems The present inventors conducted intensive research to solve the above problems and discovered that a plasticizer for polyvinyl chloride resin, which is a polyester using a specific glycol including 1,5-pentanediol, exhibits a low freezing point and can impart sufficient heat resistance and cold resistance to the resulting molded article, thereby completing the present invention.

[0009] That is, the present invention relates to the following plasticizers for vinyl chloride resins, etc. 1. A plasticizer for polyvinyl chloride resin, which is a polyester obtained by reacting glycol having 2 to 18 carbon atoms, aliphatic dicarboxylic acid having 4 to 14 carbon atoms, and monoalcohol having 4 to 18 carbon atoms and / or monocarboxylic acid having 2 to 21 carbon atoms as reaction raw materials, The glycol comprises 1,5-pentanediol and an alkylene glycol having a branched alkylene chain having 3 to 18 carbon atoms; A plasticizer for polyvinyl chloride resin, wherein the content of the 1,5-pentanediol in the glycol is within a range of 5 to 90 mol %. 2. A plasticizer for polyvinyl chloride resin according to 1, having a freezing point of 15°C or lower. 3. The plasticizer for polyvinyl chloride resin according to 1 or 2, wherein the alkylene glycol is one or more selected from the group consisting of 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol and 3-methyl-1,5-pentanediol. 4. The plasticizer for vinyl chloride resin according to any one of 1 to 3, 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. 5. The plasticizer for vinyl chloride resin according to any one of 1 to 4, wherein the monoalcohol is one or more selected from the group consisting of octanol, 2-ethylhexanol and isononyl alcohol. 6. The plasticizer for vinyl chloride resin according to any one of 1 to 5, wherein the monocarboxylic acid is one or more selected from the group consisting of 2-ethylhexanoic acid, hydrogenated coconut oil fatty acid, and lauric acid. 7. The plasticizer for vinyl chloride resin according to any one of 1 to 6, wherein the number average molecular weight of the polyester is in the range of 500 to 4,000. 8. A vinyl chloride resin composition comprising the plasticizer for vinyl chloride resin according to any one of 1 to 7 and vinyl chloride resin. 9. The vinyl chloride resin composition according to 8, wherein the content of the plasticizer for vinyl chloride resin is in the range of 10 to 150 parts by mass per 100 parts by mass of the vinyl chloride resin. 10. A molded article of the vinyl chloride resin composition according to 8 or 9. 11. A laminate of a urethane resin layer and a vinyl chloride resin layer, 8. A laminate comprising the vinyl chloride resin layer comprising the plasticizer for vinyl chloride resin according to any one of 1 to 7. Effect of the Invention

[0010] The present invention provides a plasticizer for polyvinyl chloride resin which has a low freezing point and can impart both heat resistance and cold resistance to polyvinyl chloride resin molded articles. According to the present invention, it is possible to provide a molded article of a vinyl chloride resin composition in which bleeding of a plasticizer is suppressed and which is capable of exhibiting both heat resistance and cold resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] An embodiment of the present invention will be described below. The present invention is not limited to the following embodiment, and can be implemented by making appropriate modifications within the scope that does not impair the effects of the present invention.

[0012] [Plasticizer for polyvinyl chloride resin] The vinyl chloride resin plasticizer of the present invention is a polyester produced by reacting glycol having 2 to 18 carbon atoms, aliphatic dicarboxylic acid having 4 to 14 carbon atoms, and monoalcohol having 4 to 18 carbon atoms and / or monocarboxylic acid having 2 to 21 carbon atoms as reaction raw materials. The term "reactive raw materials" as used herein means raw materials that constitute the polyester of the present invention, and does not include solvents or catalysts that do not constitute the polyester.

[0013] In the present invention, the glycol having 2 to 18 carbon atoms as the reaction raw material contains 1,5-pentanediol and an alkylene glycol having a branched alkylene chain having 3 to 18 carbon atoms, and the content of 1,5-pentanediol in the glycol is in the range of 5 to 90 mol %. The content of 1,5-pentanediol can be adjusted to fall within the above range by appropriately adjusting the amounts of the reaction raw materials charged.

[0014] The polyester, which is a plasticizer for vinyl chloride resin of the present invention, can have a freezing point of 15° C. or less, and can suppress crystallization of the plasticizer. Here, the "freezing point" is a value measured by the method described in the Examples. Hereinafter, the polyester which is the plasticizer for vinyl chloride resin of the present invention may be simply referred to as the "polyester of the present invention."

[0015] 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.

[0016] 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, 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-dimethyl butyl pentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylol heptane), 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.

[0017] The oxyalkylene glycol having 2 to 18 carbon atoms is, for example, an alkylene glycol having 2 to 18 carbon atoms in which one of the carbon atoms is replaced with an oxygen atom, and examples of the oxyalkylene glycol include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol.

[0018] In the present invention, the glycols used as reaction raw materials include 1,5-pentanediol and alkylene glycol having a branched alkylene chain having 3 to 18 carbon atoms, and the content of 1,5-pentanediol in the glycol is in the range of 5 to 90 mol %.

[0019] The lower limit of the content of 1,5-pentanediol in glycol, which is the reaction raw material, is 5 mol % or more, and preferably 10 mol % or more, 15 mol % or more, 20 mol % or more, 25 mol % or more, or 30 mol % or more. Similarly, the upper limit of the content of 1,5-pentanediol in glycol, which is the reaction raw material, is 90 mol % or less, and preferably 85 mol % or less, 80 mol % or less, 75 mol % or less, 60 mol % or less, or 55 mol % or less. The content of 1,5-pentanediol is preferably in the range of 10 to 80 mol %, more preferably in the range of 20 to 60 mol %.

[0020] 1,5-pentanediol is available derived from biological resources, and by appropriately selecting reaction raw materials other than 1,5-pentanediol, the polyvinyl chloride resin plasticizer of the present invention can be made to have a high biomass content.

[0021] Examples of alkylene glycols having a branched alkylene chain having 3 to 18 carbon atoms (hereinafter, may be simply referred to as "branched alkylene glycols") include 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol.

[0022] The lower limit of the content of branched alkylene glycol in the glycol that is the reaction raw material is not particularly limited, but is, for example, 10 mol % or more, preferably 30 mol % or more, and more preferably 50 mol % or more. Similarly, the upper limit of the content of branched alkylene glycol in the glycol that is the reaction raw material is not particularly limited, but is, for example, 95 mol % or less, preferably 90 mol % or less, more preferably 70 mol % or less, and even more preferably 50 mol % or less.

[0023] The glycol as the reaction raw material may contain 1,5-pentanediol and branched alkylene glycol, and may contain glycols other than 1,5-pentanediol and branched alkylene glycol.

[0024] The glycol as the raw material of the reaction may be substantially composed of, for example, 1,5-pentanediol and branched alkylene glycol. Here, "substantially composed" means that the total content of 1,5-pentanediol and branched alkylene glycol in the glycol as the raw material of the reaction is 80 mol % or more, 90 mol % or more, or 95 mol % or more, and preferably the glycol as the raw material of the reaction is composed only of 1,5-pentanediol and branched alkylene glycol.

[0025] The aliphatic dicarboxylic acid having 4 to 14 carbon atoms is preferably an alkylene dicarboxylic acid having 4 to 14 carbon atoms, and more preferably an alkylene dicarboxylic acid having 6 to 12 carbon atoms.

[0026] Examples of the alkylene dicarboxylic acid having 4 to 14 carbon atoms include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecane dicarboxylic acid (dodecanedioic acid), cyclohexane dicarboxylic acid, hexahydrophthalic acid, etc. Among these, adipic acid, azelaic acid, sebacic acid, and dodecane diacid are more preferred, adipic acid and sebacic acid are even more preferred, and adipic acid is particularly preferred.

[0027] 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 kinds.

[0028] 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, and dodecanol.

[0029] The monoalcohol having 4 to 18 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 kinds.

[0030] 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 acid having 2 to 21 carbon atoms include acetic acid, caproic acid, 2-ethylhexanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, and arachidic acid.

[0031] The monocarboxylic acid having 2 to 21 carbon atoms may be a hydrogenated vegetable oil fatty acid. Examples of the hydrogenated vegetable oil fatty acid include hydrogenated coconut oil fatty acid, hydrogenated palm kernel oil fatty acid, hydrogenated palm oil fatty acid, hydrogenated olive oil fatty acid, hydrogenated castor oil fatty acid, and hydrogenated rapeseed oil fatty acid. These are obtained by decomposing and hydrogenating oils obtained from coconut, palm kernel, palm, olive, castor, and rapeseed, respectively, and are all mixtures of two or more long-chain aliphatic monocarboxylic acids including an aliphatic monocarboxylic acid having 8 to 21 carbon atoms. In addition, the above vegetable oil fatty acids that have not been hydrogenated may be used as long as the effects of the present invention are not impaired. Also, the vegetable oil fatty acids are not limited to the above.

[0032] The polyester of the present invention is prepared by using, as reaction raw materials, 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 and / or a monocarboxylic acid having 2 to 21 carbon atoms. The glycol may include 1,5-pentanediol and an alkylene glycol having a branched alkylene chain having 4 to 18 carbon atoms, and reaction raw materials other than these may also be used as long as the effects of the present invention are not impaired.

[0033] The reaction raw materials for the polyester of the present invention preferably consist essentially of 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 and / or a monocarboxylic acid having 2 to 21 carbon atoms, and more preferably consist solely of 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 and / or a monocarboxylic acid having 2 to 21 carbon atoms.

[0034] The polyester of the present invention contains at least one compound selected from the group consisting of a mixture of compounds represented by the following formula (1) having different p values, a mixture of compounds represented by the following formula (2) having different q values, and a mixture of compounds represented by the following formula (3) having different r values. [ka] (In the above formulas (1) to (3), G is a glycol residue having 2 to 18 carbon atoms. A is a residue of an aliphatic dicarboxylic acid 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 32is a monoalcohol residue having 4 to 18 carbon atoms. p, q and r are each independently an integer.

[0035] In the present invention, the term "carboxylic acid residue" refers to the remaining organic group of a carboxylic acid, excluding the carboxyl group. The number of carbon atoms in the "carboxylic acid residue" does not include the carbon atoms in the carboxy group. In the present invention, the term "alcohol residue" refers to an organic group remaining after removing a hydroxyl group from an alcohol. In the present invention, the term "glycol residue" refers to an organic group remaining after removing a hydroxyl group from a glycol.

[0036] The glycol residue having 2 to 18 carbon atoms for 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. The residue of an aliphatic dicarboxylic acid having 2 to 12 carbon atoms for A is a group corresponding to an aliphatic dicarboxylic acid having 4 to 14 carbon atoms which is a reaction raw material for the polyester of the present invention. S 11 , S 12 and S 31 The monocarboxylic acid residue having 1 to 20 carbon atoms is a group corresponding to the monocarboxylic acid having 2 to 21 carbon atoms which is a reaction raw material for the polyester of the present invention. S 21 , S 22 and S 32 The monoalcohol residue having 4 to 18 carbon atoms is a group corresponding to the monoalcohol having 4 to 18 carbon atoms which is a reaction raw material for the polyester of the present invention.

[0037] The upper limit of each of p, q and r is, but is not particularly limited to, 30, for example. The average value of p is in the range of 3 to 20, for example; the average value of q is in the range of 3 to 20, for example; and the average value of r is in the range of 3 to 20, for example. The average values ​​of p, q and r can be confirmed from the number average molecular weight of the polyester.

[0038] In the polyester of the present invention, the total amount of the compound represented by formula (1) where p=0, the compound represented by formula (2) where q=0, and the compound represented by formula (3) where r=0 is preferably within a range of 0.5 to 3.0 mass % in terms of area ratio measured by gel permeation chromatography.

[0039] The number average molecular weight (Mn) of the polyester of the present invention is, for example, 500 to 6,000, preferably 500 to 4,000, more preferably 1,000 to 4,000, and further preferably 1,000 to 3,700. The number average molecular weight (Mn) of the polyester of the present invention is confirmed by the method described in the Examples.

[0040] The acid value of the polyester of the present invention is preferably 2.0 or less, and more preferably 1.0 or less. The hydroxyl value of the polyester of the present invention is preferably 15 or less, and more preferably 10 or less. The viscosity of the polyester of the present invention is preferably 7,000 mPa·s or less, and 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 the examples.

[0041] [Method of manufacturing plasticizer for polyvinyl chloride resin] The plasticizer for vinyl chloride resin of the present invention can be produced by reacting a glycol having 2 to 18 carbon atoms (the glycol contains 1,5-pentanediol and an alkylene glycol having a branched alkylene chain having 4 to 18 carbon atoms, and the content of 1,5-pentanediol in the glycol is in the range of 5 to 90 mol %) with 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 2 to 21 carbon atoms to synthesize a polyester.

[0042] The polyester represented by the formula (1) can be obtained, for example, by the method shown below. Method 1: A method in which the monocarboxylic acid, dicarboxylic acid and glycol constituting the respective residues of the polyester represented by formula (1) are charged all at once and reacted. Method 2: The dicarboxylic acid and glycol constituting each residue of the polyester represented by formula (1) are reacted under conditions in which the equivalent of the hydroxyl group is greater than the equivalent of the carboxyl group to obtain a polyester having a hydroxyl group at the end of the main chain, and then the obtained polyester resin is mixed with S 11 and S 12 A method of reacting a monocarboxylic acid constituting the compound (I) with a monocarboxylic acid constituting the compound (I).

[0043] 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 the respective residues of the polyester represented by formula (2) are charged all at once and reacted. Method 4: The dicarboxylic acid and glycol constituting each residue of the polyester represented by formula (2) are reacted under conditions in which the equivalent of the carboxyl group is greater than the equivalent of the hydroxyl group to obtain a polyester having a carboxyl group at the end of the main chain, and then the obtained polyester is mixed with S 21 and S 22 A method of reacting with a monoalcohol constituting the compound.

[0044] 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 the respective residues of the polyester represented by formula (3) are charged all at once and reacted. Method 5: The dicarboxylic acid and glycol constituting each residue of the polyester represented by formula (3) are reacted under conditions in which the equivalent weight of the carboxyl group and the equivalent weight of the hydroxyl group are the same to obtain a polyester having a carboxyl group and a hydroxyl group at the end of the main chain, respectively, and then the obtained polyester is mixed with S 31 and S 32 A method of reacting a monoalcohol and a monocarboxylic acid which constitute the above-mentioned compound.

[0045] In the synthesis of the polyester, the reaction may be carried out, as necessary, in the presence of an esterification catalyst at a temperature range of, for example, 180 to 250° C. for 5 to 25 hours. The conditions of the esterification reaction, such as temperature and time, are not particularly limited and may be set appropriately.

[0046] Examples of the esterification catalyst include titanium-based catalysts such as tetraisopropyl titanate and tetrabutyl titanate; tin-based catalysts such as dibutyltin oxide; and organic sulfonic acid-based catalysts such as p-toluenesulfonic acid.

[0047] The amount of the esterification catalyst used may be appropriately determined, but is usually preferably within the range of 0.001 to 0.1 part by mass relative to 100 parts by mass of the total amount of the reaction raw materials.

[0048] The resulting polyester is preferably further subjected to a steam stripping treatment. The steam stripping treatment is a treatment in which the polyester obtained is brought into contact with water vapor to remove unreacted components, catalyst and low molecular weight components contained in the polyester.

[0049] The steam stripping treatment is carried out, for example, by passing the polyester through a stripping tower equipped with a perforated plate from which steam is ejected, and the stripping temperature is set, for example, in the range of 100 to 180° C., and the stripping pressure is set in the range of 0.005 to 0.03 STMkg / hr / kg. The stripping time can be set, for example, in the range of 2 to 10 hours.

[0050] [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-olefins such as ethylene, propylene, and 1-butene; conjugated dienes such as butadiene and isoprene; vinyl alcohol, styrene, acrylonitrile, vinyl acetate, vinyl propionate, fumaric acid, fumaric acid esters, maleic acid, maleic acid esters, maleic acid anhydride, acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, and isoprenol.

[0051] 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 product having high heat resistance can be obtained, and a vinyl chloride resin composition having excellent processability can be obtained.

[0052] The vinyl chloride resin can be produced by a known method, for example, 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, or the like. Commercially available vinyl chloride resins may be used. Commercially available vinyl chloride resins include TH-640, TH-700, and TH-800 (all manufactured by Taiyo Vinyl Corporation); S-1004, S-1008, and PSH-10 (all manufactured by Kaneka Corporation); TK-700, TK-800, and TK-1300 (all manufactured by Shin-Etsu Polymer Co., Ltd.); ZEST800Z, ZEST1000Z, and ZEST1300Z (all manufactured by Shin-Daiichi Vinyl Corporation).

[0053] The content of the plasticizer for vinyl chloride resin of the present invention in the vinyl chloride resin composition of the present invention is, from the viewpoint of compatibility with vinyl chloride resin, etc., preferably in the range of 10 to 150 parts by mass, more preferably in the range of 30 to 120 parts by mass, even more preferably in the range of 50 to 120 parts by mass, and particularly preferably in the range of 70 to 120 parts by mass, relative to 100 parts by mass of vinyl chloride resin.

[0054] The vinyl chloride resin composition of the present invention only needs to contain a vinyl chloride resin and the plasticizer for vinyl chloride resin of the present invention, and may also contain plasticizers other than the plasticizer for vinyl chloride resin of the present invention (other plasticizers), other additives, etc.

[0055] Examples of the other plasticizers include benzoic acid esters such as diethylene glycol dibenzoate; phthalic acid esters such as dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), 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); pyromellitic acid esters such as tetra-2-ethylhexyl pyromellitic acid (TOPM); di-2-ethylhexyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-(2-ethylhexyl) azelate, and diisooctyl azelate. Examples of the fatty acid esters include aliphatic dibasic acid esters such as azelaic acid derivatives such as di-n-hexyl azelate; phosphate esters such as tri-2-ethylhexyl phosphate (TOP) and tricresyl phosphate (TCP); alkyl esters of polyhydric alcohols such as pentaerythritol; polyesters having a molecular weight of 800 to 4,000 synthesized by polyesterification of a dibasic acid such as adipic acid with a glycol; epoxidized esters such as epoxidized soybean oil and epoxidized linseed oil; alicyclic dibasic acids such as diisononyl hexahydrophthalate; fatty acid glycol esters such as 1,4-butanediol dicaprate; acetyl tributyl citrate (ATBC); chlorinated paraffin obtained by chlorinating paraffin wax or n-paraffin; chlorinated fatty acid esters such as chlorinated stearic acid ester; and higher fatty acid esters such as butyl oleate.

[0056] Among other plasticizers, it is preferable to use one or more plasticizers selected from trimellitic acid ester plasticizers and sebacic acid derivative plasticizers.

[0057] The trimellitic acid ester plasticizers include trimethyl trimellitate, triethyl trimellitate, tri-n-propyl trimellitate, tri-n-butyl trimellitate, tri-n-pentyl trimellitate, tri-n-hexyl trimellitate, tri-n-heptyl trimellitate, tri-n-octyl trimellitate, tri-n-nonyl trimellitate, tri-n-decyl trimellitate, tri-n-undecyl trimellitate, tri-n-dodecyl ... linear trimellitic acid esters in which the alkyl group constituting the ester is linear, such as tri-n-tridecyl trimellitate, tri-n-tetradecyl trimellitate, tri-n-pentadecyl trimellitate, tri-n-hexadecyl trimellitate, tri-n-heptadecyl trimellitate, tri-n-stearyl trimellitate, and tri-n-alkyl trimellitate (wherein the number of carbon atoms of the alkyl group in the trimellitic acid tri-n-alkyl ester may be different from each other in one molecule); Tri-i-propyl trimellitate, tri-i-butyl trimellitate, tri-i-pentyl trimellitate, tri-i-hexyl trimellitate, tri-i-heptyl trimellitate, tri-i-octyl trimellitate, 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, tri-i-octadecyl trimellitate, and trialkyl trimellitate (wherein the number of carbon atoms of the alkyl group in the trialkyl trimellitate may be different from each other in one molecule) are examples of branched trimellitic acid esters in which the alkyl group constituting the ester is branched.

[0058] Examples of the sebacic acid derivative plasticizers include di-n-butyl sebacate, di-(2-ethylhexyl) sebacate, diisodecyl sebacate, and di-(2-butyloctyl) sebacate.

[0059] The above other plasticizers may be used alone or in combination of two or more kinds.

[0060] Among the above-mentioned other plasticizers, trimellitic acid esters and sebacic acid derivatives are preferred from the viewpoint of obtaining good tensile elongation and cold resistance.

[0061] 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, in the range of 10 to 300 parts by mass, and preferably in the range of 20 to 200 parts by mass, per 100 parts by mass of the plasticizer for vinyl chloride resin of the present invention.

[0062] Examples of the other additives include flame retardants, stabilizers, stabilization aids, colorants, processing aids, fillers, antioxidants (antiaging agents), UV absorbers, light stabilizers, lubricants, antistatic agents, crosslinking aids, and the like.

[0063] Examples of the flame retardant include inorganic compounds such as aluminum hydroxide, antimony trioxide, magnesium hydroxide, and zinc borate; phosphorus compounds such as cresyl diphenyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, and trisdichloropropyl phosphate; and halogen compounds such as chlorinated paraffin. When a flame retardant is blended into a vinyl chloride resin composition, the blending amount is usually in the range of 0.1 to 20 parts by mass per 100 parts by mass of the vinyl chloride resin.

[0064] Examples of the stabilizer include metal soap compounds such as lithium stearate, magnesium stearate, magnesium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc octoate, zinc laurate, zinc ricinoleate, and zinc stearate; organic tin compounds such as dimethyltin bis-2-ethylhexylthioglycolate, dibutyltin maleate, dibutyltin bisbutylmaleate, and dibutyltin dilaurate; antimony mercaptide compounds; and lanthanoid-containing compounds such as lanthanum oxide and lanthanum hydroxide. When a stabilizer is blended into a vinyl chloride resin composition, the blending amount is usually in the range of 0.1 to 20 parts by mass per 100 parts by mass of the vinyl chloride resin.

[0065] Examples of the stabilizing aid include phosphite compounds such as triphenyl phosphite, monooctyl diphenyl phosphite, and tridecyl phosphite; beta diketone compounds such as acetyl acetone and benzoyl acetone; polyol compounds such as glycerin, sorbitol, pentaerythritol, and polyethylene glycol; perchlorate compounds such as barium perchlorate and sodium perchlorate; hydrotalcite compounds; and zeolites. When a stabilizing aid is blended into a vinyl chloride resin composition, the blending amount is usually in the range of 0.1 to 20 parts by mass per 100 parts by mass of the vinyl chloride resin.

[0066] Examples of the colorant include carbon black, lead sulfide, white carbon, titanium white, lithopone, safflower, antimony sulfide, chrome yellow, chrome green, cobalt blue, and molybdenum orange. When a colorant is blended into a vinyl chloride resin composition, the blending amount is usually within the range of 1 to 100 parts by mass per 100 parts by mass of the vinyl chloride resin.

[0067] Examples of the processing aid include liquid paraffin, polyethylene wax, stearic acid, stearic acid amide, ethylene bis stearic acid amide, butyl stearate, calcium stearate, and the like. When the processing aid is blended into the vinyl chloride resin composition, the blending amount is usually in the range of 0.1 to 20 parts by mass per 100 parts by mass of the vinyl chloride resin.

[0068] 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, metal, and the like; glass spheres, graphite, aluminum hydroxide, barium sulfate, magnesium oxide, magnesium carbonate, magnesium silicate, and calcium silicate. When a filler is blended into a vinyl chloride resin composition, the blending amount is usually within the range of 1 to 100 parts by mass per 100 parts by mass of the vinyl chloride resin.

[0069] Examples of the antioxidant include phenolic compounds such as 2,6-di-tert-butylphenol, tetrakis[methylene-3-(3,5-tert-butyl-4-hydroxyphenol)propionate]methane, and 2-hydroxy-4-methoxybenzophenone; sulfur compounds such as alkyl disulfides, thiodipropionic acid esters, and benzothiazole; phosphoric acid compounds such as trisnonylphenyl phosphite, diphenylisodecyl phosphite, triphenyl phosphite, and tris(2,4-di-tert-butylphenyl)phosphite; and organometallic compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate. When an antioxidant is blended into a vinyl chloride resin composition, the blending amount is usually in the range of 0.2 to 20 parts by mass per 100 parts by mass of the vinyl chloride resin.

[0070] Examples of the ultraviolet absorber include salicylate-based compounds such as phenyl salicylate and p-tert-butylphenyl salicylate; benzophenone-based compounds such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-n-methoxybenzophenone; benzotriazole-based compounds such as 5-methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole; and cyanoacrylate-based compounds. When an ultraviolet absorbent is blended into a vinyl chloride resin composition, the blending amount is usually within the range of 0.1 to 10 parts by mass per 100 parts by mass of the vinyl chloride resin.

[0071] The light stabilizer may be, for example, a hindered amine light stabilizer.Specific examples of the light stabilizer include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidylsebacate (mixture), bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, bis(2,2,6,6-decanedioate), Tetramethyl-1(octyloxy)-4-piperidyl) ester and reaction products of 1,1-dimethylethyl hydroperoxide with octane, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, ester mixture of 2,2,6,6-tetramethyl-4-piperidinol and higher fatty acids, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethanetetracarboxylate), (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 Examples include 1,3,5-triazine, a polycondensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, and 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. When a light stabilizer is blended into a vinyl chloride resin composition, the blending amount is usually within the range of 0.1 to 10 parts by mass per 100 parts by mass of the vinyl chloride resin.

[0072] Examples of the lubricant include silicone, liquid paraffin, paraffin wax, metal salts of fatty acids such as metal stearates and metal laurates; fatty acid amides, fatty acid waxes, and higher fatty acid waxes. When a lubricant is blended into a vinyl chloride resin composition, the blending amount is usually in the range of 0.1 to 10 parts by mass per 100 parts by mass of the vinyl chloride resin.

[0073] Examples of the antistatic agent include anionic antistatic agents of the 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; cationic antistatic agents such as quaternary ammonium salts of the alkyl amidoamine type, alkyl dimethyl benzyl type, and organic acid salts or hydrochlorides of alkyl pyridinium type; and amphoteric antistatic agents such as alkyl betaine type and alkyl imidazoline type. When an antistatic agent is blended into a vinyl chloride resin composition, the blending amount is usually within the range of 0.1 to 10 parts by mass per 100 parts by mass of the vinyl chloride resin.

[0074] Examples of the crosslinking aid include polyfunctional monomers such as tetraethylene glycol dimethacrylate, divinylbenzene diallyl phthalate, triallyl isocyanurate, trimethylolpropane triallylate, tetramethylolmethane tetramethacrylate, and trimethoxyethoxyvinylsilane. When a crosslinking aid is blended into a vinyl chloride resin composition, the blending amount is usually in the range of 0.5 to 30 parts by mass per 100 parts by mass of the vinyl chloride resin.

[0075] 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 a vinyl chloride resin, the plasticizer for vinyl chloride resin of the present invention, and optional components (the other plasticizers and the other additives described above) using a kneading machine such as a blender, a planetary mixer, or a Banbury mixer.

[0076] Molded articles can be obtained by molding the vinyl chloride resin composition of the present invention by known molding methods such as vacuum molding, compression molding, extrusion molding, calendar molding, press molding, blow molding, powder molding, and powder slush molding.

[0077] Molded articles obtained using the vinyl chloride resin composition of the present invention can be used for, for example, insulating tape, insulating sheet, wiring connector, conductor wire covering material, pipes such as water pipes, pipe joints, gutters such as rain gutters, window frame siding, flat plates, corrugated plates, automobile underbody coatings, dashboards, instrument panels, consoles, door sheets, undercarpets, trunk sheets, automobile interior materials such as door trims, various types of leather, decorative sheets, agricultural films, food packaging films, various foam products, hoses, medical tubes, food tubes, refrigerator gaskets, packings, wallpaper, flooring materials, boots, curtains, shoe soles, gloves, water stops, toys, decorative panels, blood bags, infusion bags, tarpaulins, mats, waterproof sheets, civil engineering sheets, roofing, waterproof sheets, industrial tapes, glass films, erasers, and the like.

[0078] [Urethane / vinyl chloride laminate] The above-mentioned automobile dashboard contains a laminate portion of a vinyl chloride resin layer and a urethane resin layer, and a molded article obtained using the vinyl chloride resin composition of the present invention is particularly suitable for the vinyl chloride resin layer of the laminate. Hereinafter, a laminate of a vinyl chloride resin layer containing the plasticizer for vinyl chloride resin of the present invention and a urethane resin layer will be referred to as the "laminate of the present invention," and each layer will be described.

[0079] The vinyl chloride resin layer is formed from the vinyl chloride resin composition of the present invention, and the components contained in the vinyl chloride resin composition and the forming method are as described above.

[0080] The thickness of the vinyl chloride resin layer may be set arbitrarily and is, for example, 0.2 to 2.0 mm, and preferably 0.5 to 1.5 mm.

[0081] 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 foaming agent, a foam stabilizer, and the like.

[0082] 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, and polymer polyols, with polyether polyols and polymer polyols being preferred. The polyols may be used alone or in combination of two or more kinds.

[0083] As the polyisocyanate, it is preferable to use a diphenylmethane diisocyanate (hereinafter sometimes abbreviated as "MDI") type and a tolylene diisocyanate (hereinafter sometimes abbreviated as "TDI") type in combination. Examples of MDI-based resins include 2,2'-MDI, 2,4'-MDI, 4,4'-MDI, polymethylene polyphenylene polyisocyanate, and urethane-modified versions of these. Examples of TDI-based resins include 2,4-TDI, 2,6-TDI, and carbodiimide-modified versions of these.

[0084] The crosslinking agent can be any crosslinking agent that is normally used in the production of polyurethane foam, without any particular limitations. As the crosslinking agent, a compound having a molecular weight of less than 500 and 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 an isocyanate group, and more preferably diethanolamine.

[0085] The crosslinking agent may be used alone or in combination of two or more kinds. The amount of the crosslinking agent is preferably 10 parts by mass or less, particularly preferably 5 parts by mass or less (usually 1 part by mass or more), based on 100 parts by mass of the polyol.

[0086] The catalyst can be any catalyst that is generally used in the production of polyurethane foam without any particular limitation. As the catalyst, tertiary amines, diazabicycloalkene compounds and their salts, organometallic compounds, etc. can be used, and tertiary amines are preferred.

[0087] Examples of the tertiary amine include triethylenediamine, triethylamine, tri-n-butylamine, bis(2-dimethylaminoethyl)ether, N,N,N',N'-tetramethylhexamethylenediamine, and 1,2-dimethylimidazole. Examples of the organometallic compound include metal salts of various metals such as tin, lead, and zirconium with organic acids such as octenic acid and naphthenic acid, such as dibutyltin dilaurate, dibutyltin diacetylacetonate, and zirconium tetraacetylacetonate. These catalysts may be used alone or in combination of two or more. The amount of the catalyst is preferably 0.03 to 2.0 parts by mass, particularly 0.03 to 1.5 parts by mass, based on 100 parts by mass of polyol. If the amount of the catalyst is 0.03 to 2.0 parts by mass, the foam raw material is easily cured and has good moldability.

[0088] The foaming agent can be any foaming agent that is generally used in the production of polyurethane foam, without any particular limitation. Water is often used as the foaming agent, and in addition to water, two types of foaming agents, for example, an inactive low boiling point solvent and a reactive foaming agent, can be used.

[0089] Examples of the inert low boiling point solvent include dichloromethane, hydrochlorofluorocarbons, hydrofluorocarbons, isopentane, and the like.

[0090] The reactive foaming agent may be, for example, an azo compound, which decomposes at a temperature higher than room temperature to generate gas. These foaming agents may be used alone or in combination of two or more. The amount of the foaming agent is preferably 1.0 to 5.0 parts by mass, particularly 1.5 to 4.0 parts by mass, based on 100 parts by mass of polyol. If the amount of the foaming agent is 1.0 to 5.0 parts by mass, a closed-cell type foam is obtained, and no depressions or the like are formed on the foam surface.

[0091] The foam stabilizer may be any foam stabilizer that is generally used in the production of polyurethane foam, including, without limitation, polydimethylsiloxane / polyalkylene oxide block copolymers and vinylsilane / polyalkylene polyol copolymers.

[0092] The foam stabilizer may be used alone or in combination of two or more kinds. The blend amount of the foam stabilizer is preferably 3.0 parts by mass or less, particularly preferably 2.0 parts by mass or less (usually 0.5 parts by mass or more), based on 100 parts by mass of the polyol.

[0093] In producing the polyurethane foam that becomes the urethane resin layer, various additives and auxiliaries such as antioxidants, ultraviolet absorbers, and other anti-aging agents, fillers such as calcium carbonate and barium sulfate, internal mold release agents, flame retardants, plasticizers, colorants, and anti-fungal agents can be used as necessary.

[0094] The method for forming the polyurethane foam layer is not particularly limited, and for example, the polyurethane foam layer can be formed by injecting a foam raw material into the space between the upper and lower molds under conditions such that the isocyanate index is 70 to 140, particularly 80 to 120, and reacting and curing the foam raw material by vacuum molding or the like. If necessary, the foam raw material and / or the mold can be heated to promote the reaction and curing. Furthermore, 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, foamed, and cured at a temperature range of, for example, room temperature to about 70°C.

[0095] The thickness of the urethane resin layer may be set arbitrarily and is, for example, 5 to 15 mm, and preferably 7 to 12 mm. EXAMPLES

[0096] The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

[0097] In the examples of the present application, the acid value, viscosity and freezing point were evaluated by the following methods. <Acid value measurement method> The measurement was performed according to the method of JIS K0070-1992. <Method of measuring viscosity> The measurement was performed according to the method of JIS K6901-1986. <Method of measuring freezing point> The measurement was performed according to a method in accordance with ASTM D7346.

[0098] In the examples of the present application, the number average molecular weight of the polyester is a value calculated in terms of polystyrene based on GPC measurement, and the measurement conditions are as follows. [GPC measurement conditions] Measurement equipment: Tosoh Corporation's high-speed GPC equipment "HLC-8320GPC" 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: Tosoh Corporation "EcoSEC Data Analysis Version 1.07" Column temperature: 40℃ Developing solvent: Tetrahydrofuran Flow rate: 0.35mL / min Measurement sample: 7.5 mg of the sample was dissolved in 10 ml of tetrahydrofuran, and the resulting solution was filtered through a microfilter to prepare a measurement sample. Sample injection volume: 20 μl Standard sample: In accordance with the measurement manual for the above-mentioned "HLC-8320GPC," the following monodisperse polystyrene with known molecular weight was used.

[0099] (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

[0100] (Example 1: Synthesis of polyester plasticizer A) A reaction vessel was charged with 292g (2.00 mol) of adipic acid, 26g (0.34 mol) of 1,2-propanediol, 141g (1.36 mol) of 1,5-pentanediol, 105g (0.81 mol) of 2-ethylhexanol, and 0.02g of tetraisopropyl titanate as an esterification catalyst in a four-neck flask with an internal volume of 2 liters equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was gradually increased to 230°C while stirring under a nitrogen stream. Heating was continued at 230°C until the acid value was 4 or less, and the generated water was continuously removed. After the reaction, the excess 2-ethylhexanol was distilled off under reduced pressure at 230-200°C to obtain 445g of polyester plasticizer A (Mn 1,522, acid value 0.2, viscosity 790mPa·s (25°C), freezing point 6°C).

[0101] (Example 2: Synthesis of polyester plasticizer B) A reaction vessel was charged with 292g (2.00 mol) of adipic acid, 64g (0.85 mol) of 1,2-propanediol, 88g (0.85 mol) of 1,5-pentanediol, 105g (0.81 mol) of normal octanol, and 0.02g of tetraisopropyl titanate as an esterification catalyst in a four-neck flask with an internal volume of 2 liters equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was gradually increased to 230°C while stirring under a nitrogen stream. Heating was continued at 230°C until the acid value was 4 or less, and the generated water was continuously removed. After the reaction, the excess normal octanol was distilled off under reduced pressure at 230 to 200°C to obtain 441g of polyester plasticizer B (Mn 1,582, acid value 0.5, viscosity 770mPa·s (25°C), freezing point -22°C).

[0102] (Example 3: Synthesis of polyester plasticizer C) A reaction vessel was charged with 292g (2.00 mol) of adipic acid, 107g (1.19 mol) of 2-methyl-1,3-propanediol, 53g (0.51 mol) of 1,5-pentanediol, 105g (0.81 mol) of normal octanol, and 0.02g of tetraisopropyl titanate as an esterification catalyst in a four-neck flask with an internal volume of 2 liters equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was gradually increased to 230°C while stirring under a nitrogen stream. Heating was continued at 230°C until the acid value was 4 or less, and the generated water was continuously removed. After the reaction, the excess normal octanol was distilled off under reduced pressure at 230 to 200°C to obtain 448g of polyester plasticizer C (Mn 1,515, acid value 0.2, viscosity 780mPa·s (25°C), freezing point -19°C).

[0103] (Example 4: Synthesis of polyester plasticizer D) Adipic acid 292g (2.00 mol), 1,2-propanediol 101g (1.33 mol), 1,5-pentanediol 139g (1.33 mol), hydrogenated coconut oil fatty acid 174g (0.85 mol), and tetraisopropyl titanate 0.02g as an esterification catalyst were charged into a 2-liter four-neck flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was gradually increased to 230°C while stirring under a nitrogen stream. Heating was continued at 230°C until the acid value was 4 or less, and the generated water was continuously removed to obtain 575g of polyester plasticizer D (Mn 1,621, acid value 0.3, viscosity 766mPa·s (25°C), freezing point 10°C).

[0104] (Example 5: Synthesis of polyester plasticizer E) In a reaction vessel, 404g (2.00 mol) of sebacic acid, 61g (0.80 mol) of 1,2-propanediol, 83g (0.80 mol) of 1,5-pentanediol, 130g (1.00 mol) of 2-ethylhexanol, and 0.02g of tetraisopropyl titanate as an esterification catalyst were charged into a 2-L four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was gradually increased to 230°C while stirring under a nitrogen stream. Heating was continued at 230°C until the acid value was 4 or less, and the generated water was continuously removed. After the reaction, excess 2-ethylhexanol was distilled off under reduced pressure at 230-200°C to obtain 570g of polyester plasticizer E (Mn 1,560, acid value 0.3, viscosity 588mPa·s (25°C), freezing point -2°C).

[0105] (Example 6: Synthesis of polyester plasticizer F) In a reaction vessel, 404g (2.00 mol) of sebacic acid, 61g (0.80 mol) of 1,2-propanediol, 83g (0.80 mol) of 1,5-pentanediol, 130g (1.00 mol) of normal octanol, and 0.02g of tetraisopropyl titanate as an esterification catalyst were charged into a four-necked flask with an internal volume of 2 liters equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was gradually increased to 230°C while stirring under a nitrogen stream. Heating was continued at 230°C until the acid value was 4 or less, and the generated water was continuously removed. After the reaction, excess normal octanol was distilled off under reduced pressure at 230 to 200°C to obtain 572g of polyester plasticizer F (Mn 1,435, acid value 0.6, viscosity 506 mPa·s (25°C), freezing point 4°C).

[0106] (Example 7: Synthesis of polyester plasticizer G) In a reaction vessel, 303g (1.50 mol) of sebacic acid, 143g (1.88 mol) of 1,2-propanediol, 22g (0.21 mol) of 1,5-pentanediol, 162g (0.79 mol) of hydrogenated coconut oil fatty acid, and 0.02g of tetraisopropyl titanate as an esterification catalyst were charged into a 2-liter four-neck flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was gradually increased to 230°C while stirring under a nitrogen stream. Heating was continued at 230°C until the acid value was 4 or less, and the generated water was continuously removed to obtain 523g of polyester plasticizer G (Mn 1,390, acid value 0.2, viscosity 590mPa·s (25°C), freezing point 14°C).

[0107] (Comparative Example 1: Synthesis of polyester plasticizer A') A reaction vessel was charged with 292g (2.00 mol) of adipic acid, 6.4g (0.10 mol) of 1,2-propanediol, 166g (1.60 mol) of 1,5-pentanediol, 109g (0.84 mol) of 2-ethylhexanol, and 0.02g of tetraisopropyl titanate as an esterification catalyst in a four-neck flask with an internal volume of 2 liters equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was gradually increased to 230°C while stirring under a nitrogen stream. Heating was continued at 230°C until the acid value was 4 or less, and the generated water was continuously removed. After the reaction, the excess 2-ethylhexanol was distilled off under reduced pressure at 230-200°C to obtain 452g of polyester plasticizer A' (Mn 1,588, acid value 0.3, viscosity 703mPa·s (25°C), freezing point 26°C).

[0108] (Comparative Example 2: Synthesis of polyester plasticizer B') A reaction vessel was charged with 292g (2.00 mol) of adipic acid, 77g (0.85 mol) of 1,4-butanediol, 88g (0.85 mol) of 1,5-pentanediol, 109g (0.84 mol) of 2-ethylhexanol, and 0.02g of tetraisopropyl titanate as an esterification catalyst in a 2-L four-neck flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was gradually increased to 230°C while stirring under a nitrogen stream. Heating was continued at 230°C until the acid value was 4 or less, and the generated water was continuously removed. After the reaction, the excess 2-ethylhexanol was distilled off under reduced pressure at 230-200°C to obtain 452g of polyester plasticizer B' (Mn 1,518, acid value 0.3, viscosity 650mPa·s (25°C), freezing point 34°C).

[0109] (Comparative Example 3: Synthesis of polyester plasticizer C') A reaction vessel was charged with 292g (2.00 mol) of adipic acid, 129g (1.70 mol) of 1,2-propanediol, 109g (0.84 mol) of 2-ethylhexanol, and 0.02g of tetraisopropyl titanate as an esterification catalyst in a 2-L four-neck 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. Heating was continued at 230°C until the acid value was 4 or less, and the generated water was continuously removed. After the reaction, the excess 2-ethylhexanol was distilled off under reduced pressure at 230-200°C to obtain 421g of polyester plasticizer C' (Mn 1,421, acid value 0.5, viscosity 590mPa·s (25°C), freezing point -35°C).

[0110] (Preparation of vinyl chloride resin composition (1)) 100 parts by mass of vinyl chloride resin (polymerization degree 1,000, ZEST1000Z, manufactured by Shin-Daiichi Vinyl Corporation), 50 parts by mass of the obtained polyester plasticizer A, and 4 parts by mass of a filler (Greg MP-677D (calcium / zinc-based composite stabilizer), manufactured by Nitshin Trading Co., Ltd.) were mixed to obtain a vinyl chloride resin composition (1). The obtained vinyl chloride resin composition (1) was used to carry out the following evaluations. The results are shown in Table 1.

[0111] (Evaluation of the plasticizing performance of plasticizers) The vinyl chloride resin composition (1) prepared with two rolls heated to 170°C was kneaded for 10 minutes, and then the kneaded vinyl chloride resin composition (1) was molded using a mold capable of producing a molded product with a thickness of 1.0 mm (a 1.0 mm-thick mold) and a press machine heated to 170°C to produce a sheet with a thickness of 1.0 mm.

[0112] The 100% modulus (tensile stress at 100% elongation) and breaking elongation of the obtained sheet were evaluated according to JIS K6251: 2010. Specifically, a tensile test was carried out under the following conditions using a 1.0 mm thick sheet, and the 100% modulus and breaking elongation were evaluated. The results are shown in Table 1. The breaking elongation was calculated by subtracting the initial chuck distance of 20 mm from the chuck distance when the 1.0 mm thick sheet broke in tension, and dividing the result by the chuck distance of 20 mm, and expressing it as a percentage. Measuring equipment: Tensilon universal material testing machine (manufactured by Orientec Co., Ltd.) Sample shape: Dumbbell shape No. 3 Chuck distance: 20mm Tensile speed: 200mm / min Measurement environment: Temperature 23 degrees, humidity 50%

[0113] The lower the 100% modulus value, the greater the effect of plasticizing polyvinyl chloride resin. Also, the higher the breaking elongation percentage, the greater the effect of plasticizing polyvinyl chloride resin.

[0114] (Evaluation of heat resistance of molded products) The vinyl chloride resin composition (1) prepared with two rolls heated to 170°C was kneaded for 10 minutes, and then the kneaded vinyl chloride resin composition (1) was molded using a mold (1.0 mm thick mold) capable of producing a molded product with a thickness of 1.0 mm and a press machine heated to 170°C to produce a sheet with a thickness of 1.0 mm. From the 1.0 mm thick sheet produced, a dumbbell test piece with a dumbbell shape No. 3 was produced according to JIS K6251:2010.

[0115] The prepared dumbbell test pieces were subjected to a heat aging test at 136°C for 168 hours in accordance with JIS K6257:2017. The masses of the dumbbell test pieces before and after the heat aging test were 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 polyester plasticizer A remains in the molded product even after the heat aging test, and the heat resistance effect of polyester plasticizer A can be expected.

[0116] The dumbbell test pieces after the heat aging test were evaluated for breaking elongation in the same manner as in the evaluation of the plasticizing effect, and the elongation of the dumbbell test pieces after the heat aging test / the elongation of the dumbbell test pieces before the heat aging test was evaluated as the "retained elongation rate." The results are shown in Table 1. The higher the residual elongation, the more the plasticizing effect can be maintained even after a heat aging test, and the more excellent the heat resistance of the vinyl chloride resin composition.

[0117] (Evaluation of low-temperature flexibility of molded products) The vinyl chloride resin composition (1) prepared with two rolls heated to 170°C was kneaded for 10 minutes, and then the kneaded vinyl chloride resin composition (1) was molded using a mold capable of producing a molded product with a thickness of 1.0 mm (a 1.0 mm-thick mold) and a press machine heated to 170°C to produce a sheet with a thickness of 1.0 mm. Test pieces were prepared from the obtained sheets in accordance with the test method specified in JIS K6773:2007, and the pliability temperature (unit: °C) was evaluated using a Crashberg pliability temperature measuring tester. The results are shown in Table 1. The lower the pliability temperature, the better the cold resistance.

[0118] (Evaluation of plasticizer compatibility) The vinyl chloride resin composition (1) prepared with two rolls heated to 170°C was kneaded for 10 minutes, and then the kneaded vinyl chloride resin composition (1) was molded using a mold (1.0 mm thick mold) capable of obtaining a molded product of 1.0 mm thickness and a press machine heated to 170°C to produce a sheet of 1.0 mm thickness. Two 1.0 mm thick sheets were cut from this sheet to a size of 5 cm x 5 cm. The two sheets thus prepared were stacked and left for 30 days under conditions of 70°C and 95% relative humidity. Thereafter, the condition of the surface of the sheet and the surface where the sheets overlap each other was evaluated according to the following evaluation criteria. The results are shown in Table 1. Good: The surface of the sheet and the surface where the sheets overlap are visually inspected and no powdery, viscous or other foreign matter (bleed) is found. In addition, no bleeding is found when the surface of the sheet and the surface where the sheets overlap are touched with a finger. ×: Bleeding was confirmed by visually inspecting the surfaces of the sheets and the surfaces where the sheets overlap, or by touching the surfaces of the sheets and the surfaces where the sheets overlap with a finger.

[0119] Vinyl chloride resin compositions were prepared and evaluated in the same manner as in Example 1, except that a plasticizer shown in Table 1 was used instead of Plasticizer A. The results are shown in Table 1.

[0120] [Table 1]

[0121] From the results in Table 1, it can be seen that bleeding is effectively suppressed and sufficient plasticizing effect, heat resistance, and cold resistance are obtained in the plasticizer using 1,5-pentanediol and branched alkylene glycol having 3 to 18 carbon atoms. On the other hand, it can be seen that bleeding occurs in the plasticizer of Comparative Example 1, which contains a large amount of 1,5-pentanediol, and the plasticizer of Comparative Example 2, which contains 1,5-pentanediol but does not contain branched alkylene glycol having 3 to 18 carbon atoms. It can also be seen that the plasticizer of Comparative Example 3, which does not use 1,5-pentanediol, is inferior in heat resistance and cold resistance to the plasticizers of Examples 1-7 and Comparative Examples 1-2, which use 1,5-pentanediol.

Claims

1. A plasticizer for polyvinyl chloride resin, which is a polyester obtained by reacting glycol having 2 to 18 carbon atoms, aliphatic dicarboxylic acid having 4 to 14 carbon atoms, and monoalcohol having 4 to 18 carbon atoms and / or monocarboxylic acid having 2 to 21 carbon atoms as reaction raw materials, The glycol comprises 1,5-pentanediol and an alkylene glycol having a branched alkylene chain having 3 to 18 carbon atoms; the total content of the 1,5-pentanediol and the alkylene glycol having a branched alkylene chain having 3 to 18 carbon atoms in the glycol is 90 mol % or more, the alkylene glycol having a branched alkylene chain having 3 to 18 carbon atoms is at least one selected from the group consisting of 1,2-propanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol; A plasticizer for polyvinyl chloride resin, wherein the content of the 1,5-pentanediol in the glycol is within a range of 5 to 90 mol %.

2. 2. The polyvinyl chloride resin plasticizer according to claim 1, having a freezing point of 15° C. or lower.

3. 3. The plasticizer for vinyl chloride resin according to claim 1, wherein the aliphatic dicarboxylic acid having 4 to 14 carbon atoms is at least one selected from the group consisting of adipic acid and sebacic acid.

4. 3. The plasticizer for vinyl chloride resin according to claim 1, wherein the monoalcohol is at least one selected from the group consisting of octanol, 2-ethylhexanol and isononyl alcohol.

5. 3. The plasticizer for vinyl chloride resin according to claim 1, wherein the monocarboxylic acid is at least one selected from the group consisting of 2-ethylhexanoic acid, hydrogenated coconut oil fatty acid, and lauric acid.

6. 3. The plasticizer for vinyl chloride resin according to claim 1 or 2, wherein the polyester is a polyester produced by reacting the glycol having 2 to 18 carbon atoms, the aliphatic dicarboxylic acid having 4 to 14 carbon atoms, and the monoalcohol having 4 to 18 carbon atoms as reaction raw materials.

7. 3. The plasticizer for vinyl chloride resin according to claim 1, wherein the number average molecular weight of the polyester is in the range of 500 to 4,000.

8. A vinyl chloride resin composition comprising the plasticizer for vinyl chloride resin according to claim 1 or 2 and a vinyl chloride resin.

9. 9. The vinyl chloride resin composition according to claim 8, wherein the content of the vinyl chloride resin plasticizer is in the range of 10 to 150 parts by mass per 100 parts by mass of the vinyl chloride resin.

10. A molded article made from the vinyl chloride resin composition according to claim 8.

11. A laminate of a urethane resin layer and a vinyl chloride resin layer, A laminate, wherein the vinyl chloride resin layer comprises the plasticizer for vinyl chloride resin according to claim 1 or 2.

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