Plasticizer composition

Abstract

To provide a plasticizer composition that is used in a halogen-based resin composition to impart excellent heat resistance to the halogen-based resin composition.SOLUTION: The plasticizer composition comprises: a plasticizer A comprising a phthalate diester; and a plasticizer B containing an isosorbide diester (b1) represented by general formula (II). (In general formula (II), R3 and R4 are linear or branched alkyl groups having mutually different numbers of carbon atoms.)SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a plasticizer composition, a halogen-based resin composition containing the same, and a method for producing the plasticizer composition. [Background technology]

[0002] Halogen-based resins such as polyvinyl chloride (PVC) are important general-purpose polymers used in a variety of fields. For example, PVC is used in a variety of applications, including home interior products such as wallpaper, general-purpose products such as toys, and automotive materials such as sealing materials. When a halogen-based resin is used, for example, a plasticizer, a diluent, a viscosity reducing agent, a filler such as calcium carbonate, a pigment, a flame retardant, a foaming agent, a stabilizer, etc. are blended with resin powder of the halogen-based resin to prepare a halogen-based resin composition.

[0003] However, the plasticizers blended to improve the processability of halogen-based resin compositions have a problem with heat resistance in that they volatilize from the surface of the halogen-based resin composition when exposed to high temperatures, causing cracks and other problems when the halogen-based resin composition hardens.

[0004] Patent Document 1 describes a composition comprising at least one 1,4:3,6-dianhydrohexitol ester (A) with a molar mass of 255 to 345 g.mol relative to the total weight of (A) and (B). -1 and 0.1% by weight to 99% by weight of an ester (A) selected from monoesters and diesters of isosorbide, isomannide and isoidide, and at least one compound (B), wherein the molar mass of the compound (B) is 345 g.mol -1More specifically, a composition is disclosed which comprises 1% to 99.9% by weight of a compound (B) selected from the following: 1,4:3,6-dianhydrohexitol esters selected from mono- and diesters of isosorbide, isomannide and isoidide, 1,4:3,6-dianhydrohexitol ester groups which are groups containing 1 to 24 carbon atoms, preferably 6 to 12 carbon atoms; esters of cyclohexanepolycarboxylic acids; esters of phthalic acid; glycerol esters. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2015-516009 Summary of the Invention [Problem to be solved by the invention]

[0006] Although the composition described in Patent Document 1 has a high plasticization rate, it still has a problem with heat resistance. The present invention relates to a plasticizer composition which, when used in a halogen-based resin composition, gives the halogen-based resin composition excellent heat resistance. [Means for solving the problem]

[0007] The present inventors have found that the above-mentioned problems can be solved by a plasticizer composition containing plasticizer A consisting of a phthalate diester having a structure derived from an alcohol having a specific chain length, and plasticizer B containing an isosorbide diester having a structure derived from a carboxylic acid having a specific chain length. That is, the present invention relates to the following [1] to

[14] . [1] A plasticizer composition comprising a plasticizer A consisting of a phthalic acid diester represented by general formula (I) and a plasticizer B containing an isosorbide diester (b1) represented by general formula (II). [ka] (In general formula (I), R 1 and R 2 are each a straight-chain or branched alkyl group having 8 to 14 carbon atoms, which may be the same or different. [ka] (In general formula (II), R 3 and R 4 are linear or branched alkyl groups each having a different number of carbon atoms. [2] In the isosorbide diester (b1) represented by the general formula (II), R 3 and R 4 and each are a linear or branched alkyl group having 7 to 9 carbon atoms. The plasticizer composition according to [1]. [3] The plasticizer composition according to [1] or [2], wherein the isosorbide diester (b1) represented by the general formula (II) is an isosorbide (octanoic acid / decanoic acid) diester. [4] The plasticizer B further contains an isosorbide diester (b2) represented by general formula (III), The plasticizer composition according to any one of [1] to [3], wherein the content of the isosorbide diester (b1) in the plasticizer B is 10 mass % or more. [ka] (In general formula (III), R 5 and R 6 are linear or branched alkyl groups each having the same number of carbon atoms. [5] In the isosorbide diester (b2) represented by the general formula (III), R 5 and R 6 and each are a linear or branched alkyl group having 7 to 9 carbon atoms. [6] The plasticizer composition according to any one of [1] to [5], wherein a mass ratio of the plasticizer A to the plasticizer B (plasticizer A / plasticizer B) is 5 / 95 or more and 85 / 15 or less. [7] A halogen-based resin composition comprising the plasticizer composition according to any one of [1] to [6]. [8] A method for producing a plasticizer composition, comprising mixing a plasticizer A consisting of a phthalic acid diester represented by general formula (I) with a plasticizer B containing an isosorbide diester (b1) represented by general formula (II). [ka] (In general formula (I), R 1 and R 2 are the same or different linear or branched alkyl groups having 8 to 14 carbon atoms. [ka] (In general formula (II), R 3 and R 4 are linear or branched alkyl groups each having a different number of carbon atoms. [9] The method for producing a plasticizer composition according to [8], wherein the plasticizer B is obtained by esterifying isosorbide and a carboxylic acid raw material containing at least two linear or branched aliphatic carboxylic acids having different carbon numbers.

[10] The method for producing a plasticizer composition according to [9], wherein the linear or branched aliphatic carboxylic acids having different carbon numbers are linear or branched aliphatic carboxylic acids having 8 to 10 carbon atoms.

[11] The method for producing a plasticizer composition according to

[10] , wherein the linear or branched aliphatic carboxylic acid having from 8 to 10 carbon atoms is octanoic acid and decanoic acid.

[12] The method for producing a plasticizer composition according to

[10] or

[11] , wherein a molar ratio of the linear or branched aliphatic carboxylic acid having 8 carbon atoms to the linear or branched aliphatic carboxylic acid having 10 carbon atoms in the carboxylic acid raw material (carboxylic acid having 8 carbon atoms / carboxylic acid having 10 carbon atoms) is 5 / 95 or more and 92 / 8 or less.

[13] The method for producing a plasticizer composition according to any one of [8] to

[12] , wherein the plasticizer A is obtained by esterifying a phthalic acid raw material and an alcohol raw material containing a linear or branched aliphatic alcohol having from 8 to 14 carbon atoms.

[14] The method for producing a plasticizer composition according to

[13] , wherein a molar ratio of linear aliphatic alcohol to branched aliphatic alcohol in the alcohol raw material (linear aliphatic alcohol / branched aliphatic alcohol) is 70 / 30 or more and 100 / 0 or less. Effect of the Invention

[0008] According to the present invention, it is possible to provide a plasticizer composition which, when used in a halogen-based resin composition, gives the halogen-based resin composition excellent heat resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] [Plasticizer composition] The plasticizer composition of the present invention is a plasticizer composition comprising: plasticizer A consisting of a phthalate diester having a structure derived from at least one alcohol selected from linear or branched aliphatic alcohols having a specific carbon number; and plasticizer B containing an isosorbide diester having a structure derived from a linear or branched aliphatic carboxylic acid having a different carbon number.

[0010] The plasticizer composition of the present invention exerts an excellent effect on the heat resistance of a halogen-based resin composition. Although the reason for this effect is not clear, it is believed to be as follows. The plasticizer composition of the present invention contains plasticizer A consisting of a phthalic acid diester having a structure derived from at least one alcohol selected from linear or branched aliphatic alcohols having 8 to 14 carbon atoms, and plasticizer B containing an isosorbide diester having a structure derived from linear or branched aliphatic carboxylic acids having two different carbon numbers. It is considered that by plasticizer A consisting of a phthalic acid diester having a structure derived from at least one alcohol selected from linear or branched aliphatic alcohols having 8 to 14 carbon atoms and plasticizer B containing an isosorbide diester having a structure derived from linear or branched aliphatic carboxylic acids having two different carbon numbers, a stronger interaction is generated between the phthalic acid diester and the isosorbide diester than the interaction between the phthalic acid diester and an isosorbide diester having structures derived from the same two carboxylic acids. Therefore, since the phthalate diester diffuses uniformly into the halogen-based resin composition together with the isosorbide diester, bleeding of the plasticizer composition of the present invention from the halogen-based resin composition is suppressed, and further, evaporation of the plasticizer composition of the present invention from the halogen-based resin composition is suppressed, which is thought to result in the halogen-based resin composition having high heat resistance.

[0011] [Plasticizer A] In the present invention, the plasticizer A comprises a phthalic acid diester represented by the general formula (I).

[0012] [ka]

[0013] In general formula (I), R 1 and R 2 are each a straight-chain or branched alkyl group having 8 to 14 carbon atoms, which may be the same or different.

[0014] R 1 and R 2The straight-chain alkyl group having 8 to 14 carbon atoms as R is an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, and an n-tetradecyl group. 1 and R 2 Examples of the branched alkyl group having 8 to 14 carbon atoms as the alkyl group include a 2-ethylhexyl group, a 2-butyloctyl group, an isooctyl group, an isononyl group, an isodecyl group, an isoundecyl group, an isododecyl group, an isotridecyl group, an isotetradecyl group, etc. Here, "iso-" refers to a structure in which a methyl group is branched at the terminal of the alkyl group. Among them, R 1 and R 2 From the viewpoint of providing excellent heat resistance to the halogen-based resin composition, the alkyl group is preferably a group selected from linear or branched alkyl groups having 10 to 13 carbon atoms, and more preferably a group selected from an n-decyl group, an n-dodecyl group, and an isotridecyl group.

[0015] The phthalic acid diester represented by general formula (I) constituting the plasticizer A may be one type or two or more types. Preferably, the phthalic acid diester represented by general formula (I) constituting the plasticizer A is one type or two types.

[0016] (Production method of plasticizer A) Plasticizer A is obtained by esterifying a phthalic acid raw material with an alcohol raw material containing a linear or branched aliphatic alcohol having 8 to 14 carbon atoms.

[0017] Examples of the phthalic acid raw material include phthalic acid, phthalic anhydride, and phthalic acid esters such as dimethyl phthalate. From the viewpoints of availability and productivity, one or more selected from phthalic acid and phthalic anhydride are preferred, and phthalic anhydride is more preferred.

[0018] Examples of the alcohol raw material include linear aliphatic alcohols having 8 to 14 carbon atoms, such as 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, and 1-tetradecanol; and branched aliphatic alcohols having 8 to 14 carbon atoms, such as 2-ethylhexanol, 2-butyloctanol, isooctanol, isononanol, isodecanol, isoundecanol, isododecanol, isotridecanol, and isotetradecanol.

[0019] From the viewpoint of providing an excellent heat resistance of the halogen-based resin composition, the molar ratio of the linear aliphatic alcohol to the branched aliphatic alcohol in the alcohol raw material (linear aliphatic alcohol / branched aliphatic alcohol) is preferably 70 / 30 or more, more preferably 80 / 20 or more, even more preferably 85 / 15 or more, and is preferably 100 / 0 or less, more preferably 100 / 0.

[0020] The amount of the alcohol raw material charged at the start of the esterification reaction is preferably in excess of the stoichiometric amount. The stoichiometric amount of the alcohol raw material in the esterification reaction is the theoretical ratio for producing a phthalic acid diester, and is twice the molar amount of the phthalic acid raw material used. That is, from the viewpoint of promoting the reaction and completing the reaction, the amount of the alcohol raw material charged is preferably 2.0 times by mole or more, more preferably 2.1 times by mole or more, even more preferably 2.2 times by mole or more, and is preferably 3.0 times by mole or less, more preferably 2.7 times by mole or less, and even more preferably 2.5 times by mole or less, relative to 1 mole of the phthalic acid raw material. It is preferable to reduce the water content of the alcohol raw material used as much as possible. If the alcohol raw material contains a large amount of water, it may poison the catalyst described below and reduce the catalytic activity.

[0021] As the esterification reaction catalyst, any known esterification catalyst having esterification ability can be used, and an organometallic catalyst is preferred. Examples of the organometallic catalyst include one or more selected from organotin compounds such as tin tetraethylate, butyltin maleate, dimethyltin oxide, monobutyltin oxide, dibutyltin oxide, and dioctyltin oxide, organotitanium compounds such as titanium tetraisopropoxide, and organozinc compounds such as zinc acetate, etc. Among these, from the viewpoint of productivity, organotitanium compounds are preferred, and one or more selected from titanium tetraisopropoxide, titanium tetra-n-butoxide, and titanium tetra-2-ethylhexyl oxide are preferred.

[0022] The amount of the catalyst used varies depending on the type thereof, but from the viewpoint of fully exerting catalytic activity, it is preferably 0.01 part by mass or more, more preferably 0.015 parts by mass or more, and even more preferably 0.02 parts by mass or more, relative to 100 parts by mass of the total amount of the phthalic acid raw material and the alcohol raw material supplied to the reactor, and from the viewpoint of catalyst addition efficiency, it is preferably 2 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less.

[0023] The esterification reaction can be carried out under reflux of the alcohol using a known reaction apparatus equipped with a facility capable of refluxing the alcohol raw material. The reaction temperature varies depending on the type of alcohol raw material, etc., but from the viewpoint of reactivity, it is preferably 100° C. or higher, more preferably 130° C. or higher, and even more preferably 150° C. or higher, and from the viewpoint of yield, it is preferably 280° C. or lower, more preferably 260° C. or lower, and even more preferably 240° C. or lower. When the reaction temperature is 100° C. or higher, the reaction proceeds quickly, and when the reaction temperature is 280° C. or lower, the production of reaction by-products can be suppressed. The reaction pressure is preferably 13.3 kPa or more in absolute pressure and normal pressure or less. The reaction pressure can be set according to the vapor pressure of the alcohol raw material used. Specifically, the reaction pressure is adjusted to a pressure at which the reaction mixture is kept boiling, and more preferably, the pressure is adjusted to a pressure at which the by-product water can be removed outside the system. The reaction time varies depending on the phthalic acid raw material, alcohol raw material, reaction temperature, amount of catalyst used, etc., but from the viewpoint of reactivity, it is preferably 1 hour or more, more preferably 2 hours or more. If the reaction time is sufficient, the load in the separation process of unreacted phthalic acid raw material and phthalic acid monoester which is a reaction intermediate is reduced. On the other hand, from the viewpoint of yield, the reaction time is preferably 24 hours or less, more preferably 10 hours or less. If the reaction time is short, the production of by-products can be suppressed and the quality of plasticizer A can be improved.

[0024] In the esterification reaction under the above reaction conditions, the water produced is removed from the reaction system by azeotropy with the alcohol raw material, the reaction rate is increased to nearly 100%, and the excess alcohol raw material is separated. After that, the reaction is post-treated by a known method such as alkali washing, water washing, adsorption of impurities, distillation, etc., to obtain plasticizer A as a phthalic acid diester represented by general formula (I).

[0025] [Plasticizer B] In the present invention, the plasticizer B contains an isosorbide diester (b1) represented by the general formula (II). The isosorbide diester (b1) represented by the general formula (II) may have any stereoisomer, and from the viewpoint of cost, it is preferable that the isosorbide diester (b1) has a stereostructure derived from D-sorbitol.

[0026] [ka]

[0027] In general formula (II), R 3 and R 4 are linear or branched alkyl groups each having a different number of carbon atoms.

[0028] R 3 and R 4 The linear or branched alkyl group as R 3 and R 4 The alkyl groups may be linear or branched alkyl groups having different carbon numbers, and are preferably linear or branched alkyl groups having 7 to 9 carbon atoms. The linear alkyl group having 7 to 9 carbon atoms includes an n-heptyl group, an n-octyl group, and an n-nonyl group. 3 and R 4 Examples of the branched alkyl group having 7 to 9 carbon atoms include a 2-ethylhexyl group, an isoheptyl group, an isooctyl group, and an isononyl group. Among them, R 3 and R 4 From the viewpoint of providing excellent heat resistance to the halogen-based resin composition, the alkyl group is preferably a group selected from linear or branched alkyl groups having 7 or 9 carbon atoms, and more preferably a group selected from an n-heptyl group and an n-nonyl group. A preferred example of the isosorbide diester (b1) is isosorbide (octanoic acid / decanoic acid) diester.

[0029] The isosorbide diester (b1) represented by the general formula (II) contained in the plasticizer B may be one type or two or more types. Preferably, the isosorbide diester (b1) represented by the general formula (II) contained in the plasticizer B is one type.

[0030] The plasticizer B may further contain an isosorbide diester (b2) represented by the general formula (III). The isosorbide diester (b2) represented by the general formula (III) may have any stereoisomer, and from the viewpoint of cost, it is preferable that the isosorbide diester (b2) has a stereostructure derived from D-sorbitol.

[0031] [ka]

[0032] In general formula (III), R 5 and R 6 are each a straight-chain or branched alkyl group having the same number of carbon atoms, preferably a straight-chain or branched alkyl group having 7 to 9 carbon atoms, and more preferably a straight-chain or branched alkyl group having the same number of carbon atoms, 7 to 9.

[0033] R 5 and R 6 As the straight chain alkyl group, R 3 and R 4 Of these, a group selected from linear or branched alkyl groups having 7 to 9 carbon atoms is preferred.

[0034] The isosorbide diester (b2) represented by general formula (III) contained in the plasticizer B may be one type or two or more types. Preferably, the isosorbide diester (b2) represented by general formula (III) contained in the plasticizer B is one type or two types, and more preferably, the isosorbide diester (b2) represented by general formula (III) contained in the plasticizer B is two types.

[0035] Plasticizer B preferably contains an isosorbide diester (b1) represented by general formula (II) and an isosorbide diester (b2) represented by general formula (III), and preferably consists of an isosorbide diester (b1) represented by general formula (II) and an isosorbide diester (b2) represented by general formula (III).

[0036] From the viewpoint of providing excellent heat resistance to the halogen-based resin composition, the content of the isosorbide diester (b1) in the plasticizer B is preferably 10 mass% or more, more preferably 13 mass% or more, and even more preferably 15 mass% or more, and is preferably 100 mass% or less, more preferably 80 mass% or less, and even more preferably 60 mass% or less. The content of the isosorbide diester (b1) in the plasticizer B can be measured by a gas chromatography method or the like. Specifically, it is measured by the method described in the examples.

[0037] (Production method of plasticizer B) Plasticizer B is obtained by esterifying isosorbide with two types of linear or branched aliphatic carboxylic acids having different carbon numbers.

[0038] Examples of the carboxylic acid raw material include linear aliphatic carboxylic acids having 8 to 10 carbon atoms, such as octanoic acid, nonanoic acid, and decanoic acid; and branched aliphatic carboxylic acids having 8 to 10 carbon atoms, such as 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, and isodenic acid. Of these, the carboxylic acid raw material is preferably a linear aliphatic carboxylic acid having 8 to 10 carbon atoms, and more preferably octanoic acid and decanoic acid. It is preferable to reduce the water content of the carboxylic acid raw material used as much as possible. If the carboxylic acid raw material contains a large amount of water, it may poison the catalyst described below and reduce the catalytic activity.

[0039] When the plasticizer B is an isosorbide diester (b1) represented by the general formula (II), one type of linear or branched aliphatic carboxylic acid having 8 to 10 carbon atoms is charged at 1.0 to 1.1 times the molar amount per mole of isosorbide in which one of the two hydroxyl groups of isosorbide is protected by a protecting group to generate an isosorbide monoester in which one hydroxyl group is protected, and the isosorbide monoester isolated after deprotection is subjected to an esterification reaction in which a linear or branched aliphatic carboxylic acid having 8 to 10 carbon atoms different from the above is charged at 1.0 to 1.1 times the molar amount to obtain the isosorbide diester (b1) represented by the general formula (II). Examples of the protecting group include those usually used as protecting groups for hydroxyl groups.

[0040] As the esterification reaction catalyst, the esterification reaction catalysts mentioned in the method for producing plasticizer A can be used, and an organic titanium compound is preferable, and one or more selected from titanium tetraisopropoxide, titanium tetra-n-butoxide, and titanium tetra-2-ethylhexyloxide are preferable.

[0041] The amount of catalyst used varies depending on the type, but from the viewpoint of fully exerting catalytic activity, it is preferably 0.01 part by mass or more, more preferably 0.02 part by mass or more, and even more preferably 0.03 part by mass or more, relative to 100 parts by mass of the total amount of isosorbide and carboxylic acid raw materials supplied to the reactor, and from the viewpoint of catalyst addition efficiency, it is preferably 2 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.1 part by mass or less. The esterification reaction can be carried out using a known reaction apparatus. From the viewpoint of reactivity, the reaction temperature is preferably 100° C. or higher, more preferably 130° C. or higher, and even more preferably 150° C. or higher, and from the viewpoint of yield, it is preferably 280° C. or lower, more preferably 260° C. or lower, and even more preferably 240° C. or lower. When the reaction temperature is 100° C. or higher, the reaction proceeds quickly, and when the reaction temperature is 280° C. or lower, the production of reaction by-products can be suppressed. The reaction pressure is preferably 13.3 kPa or more in absolute terms and normal pressure or less. Specifically, it is preferable to adjust the pressure to a level that allows the by-product water to be removed from the system. The reaction time varies depending on the isosorbide, the carboxylic acid raw material, the reaction temperature, the amount of catalyst used, etc., but from the viewpoint of reactivity, it is preferably 1 hour or more, more preferably 2 hours or more. If the reaction time is sufficient, the load in the separation process of the unreacted phthalic acid raw material and the reaction intermediate phthalic acid monoester is reduced. On the other hand, from the viewpoint of yield, the reaction time is preferably 24 hours or less, more preferably 10 hours or less. If the reaction time is short, the production of by-products can be suppressed and the quality of the plasticizer B can be improved.

[0042] In the esterification reaction, under the above reaction conditions, the water produced is removed from the reaction system, the reaction rate is increased to nearly 100%, and the excess carboxylic acid raw material is separated. After that, the reaction is post-treated by a known method such as alkali washing, water washing, adsorption of impurities, distillation, etc., to obtain the isosorbide diester (b1) represented by general formula (II) as the plasticizer B.

[0043] When the plasticizer B contains the isosorbide diester (b1) represented by the general formula (II) and the isosorbide diester (b2) represented by the general formula (III), a carboxylic acid raw material containing two kinds of linear or branched aliphatic carboxylic acids having from 8 to 10 carbon atoms can be used. In this case, the esterification catalyst used, the reaction conditions, etc. can be the same as those of the above-mentioned esterification reaction. When the plasticizer B contains the isosorbide diester (b1) represented by the general formula (II) and the isosorbide diester (b2) represented by the general formula (III), the amount of the carboxylic acid raw material charged at the start of the esterification reaction is preferably in excess of the stoichiometric amount. The stoichiometric amount of the carboxylic acid raw material in the esterification reaction is the theoretical ratio for producing an isosorbide diester, and is twice the molar amount of the isosorbide used. That is, the amount of the carboxylic acid raw material charged is preferably 2.0 times or more by mole, more preferably 2.1 times or more by mole, even more preferably 2.2 times or more by mole, and even more preferably 2.3 times or more by mole, and is preferably 3.0 times or less by mole, more preferably 2.7 times or less by mole, and even more preferably 2.5 times or less by mole, relative to 1 mole of isosorbide, from the viewpoint of promoting the reaction and completing the reaction.

[0044] The molar ratio of the linear or branched aliphatic carboxylic acid having 8 carbon atoms to the linear or branched aliphatic carboxylic acid having 10 carbon atoms in the carboxylic acid raw material (carboxylic acid having 8 carbon atoms / carboxylic acid having 10 carbon atoms) is preferably 5 / 95 or more, more preferably 8 / 92 or more, even more preferably 10 / 90 or more, and is preferably 92 / 8 or less, more preferably 90 / 10 or less, even more preferably 85 / 15 or less, from the viewpoint of the halogen-based resin composition exhibiting excellent heat resistance and from the viewpoint of reducing production costs.

[0045] In addition, since there is almost no difference in the reaction rate between a linear or branched aliphatic carboxylic acid having 8 to 10 carbon atoms and isosorbide, the molar contents of the isosorbide diester (b1) and the isosorbide diester (b2) in plasticizer B obtained by the esterification reaction can be estimated from the content (mol %) of the linear or branched aliphatic carboxylic acid having 8 to 10 carbon atoms in the carboxylic acid raw material. For example, when the carboxylic acid raw material contains a linear aliphatic carboxylic acid having 8 carbon atoms (hereinafter also referred to as "C8 carboxylic acid") and a linear aliphatic carboxylic acid having 10 carbon atoms (hereinafter also referred to as "C10 carboxylic acid"), and the content of the linear aliphatic carboxylic acid having 8 carbon atoms in the carboxylic acid raw material is α mol %, and the content of the linear aliphatic carboxylic acid having 10 carbon atoms is (100-α) mol %, the content of isosorbide C8 carboxylic acid and C10 carboxylic acid diester (b1-1) in plasticizer B obtained by esterification reaction is 2 × [(α / 100) × (1-α / 100)] × 100 mol %, and the content of isosorbide C8 carboxylic acid diester (b2-1) is (α / 100) 2 × 100 mol%, the content of isosorbide C10 carboxylic acid diester (b2-2) is (1-α / 100) 2 ]×100 mol %. In addition, since the molecular weight of b1-1 is 426.59, the molecular weight of b2-1 is 398.54, and the molecular weight of b2-2 is 454.65, the contents (mass %) of the isosorbide diester (b1) and the isosorbide diester (b2) in the plasticizer B can be calculated from the contents (mol %) of these.

[0046] [Other ingredients] The plasticizer composition of the present invention may contain a compound that is usually used as a plasticizer for halogen-based resins. Examples of the plasticizer, from the viewpoint of high compatibility with halogen-based resins, include phthalate ester-based plasticizers of alcohols having 1 to 7 carbon atoms, such as dimethyl phthalate, diethyl phthalate, and dibutyl phthalate; trimellitate ester-based plasticizers of alcohols having 6 to 10 carbon atoms, such as tris(2-ethylhexyl) trimellitate, trioctyl trimellitate, and tridecyl trimellitate; adipate ester-based plasticizers, azelaate ester-based plasticizers, sebacate ester-based plasticizers, phosphate ester-based plasticizers, polyester-based plasticizers, epoxy-based plasticizers, fatty acid ester-based plasticizers, and pyromellitate ester-based plasticizers.

[0047] From the viewpoint of enabling the halogen-based resin composition to exhibit excellent heat resistance, the total content of plasticizer A and plasticizer B in the plasticizer composition of the present invention is preferably 80 mass% or more, more preferably 90 mass% or more, even more preferably 95 mass% or more, and is preferably 100 mass% or less, more preferably 100 mass%.

[0048] From the viewpoint of providing excellent heat resistance to the halogen-based resin composition, the mass ratio of the plasticizer A to the plasticizer B in the plasticizer composition (plasticizer A / plasticizer B) is preferably 5 / 95 or more, more preferably 10 / 90 or more, even more preferably 15 / 85 or more, and is preferably 85 / 15 or less, more preferably 80 / 20 or less, even more preferably 75 / 25 or less.

[0049] (Method of producing plasticizer composition) The plasticizer composition of the present invention is obtained by mixing a plasticizer A consisting of a phthalic acid diester represented by general formula (I), a plasticizer B containing an isosorbide diester (b1) represented by general formula (II), and, if necessary, the above-mentioned other components. The mixing of plasticizer A and plasticizer B may be performed by adding plasticizer B to plasticizer A and mixing them, or by adding plasticizer A to plasticizer B and mixing them. When the plasticizer composition contains the above-mentioned other components, the above-mentioned other components may be added to a mixture of plasticizer A and plasticizer B and mixed, or each component may be mixed sequentially. The plasticizer composition can be prepared by mixing plasticizer A, plasticizer B, and, if necessary, the other components described above, with a mixer such as a hand mixer, a lab mixer, a mortar mixer, a Henschel mixer, a Banbury mixer, or a ribbon blender.

[0050] [Halogen-based resin composition] The halogen-based resin composition of the present invention contains the above plasticizer composition and a halogen-based resin.

[0051] [Halogen-based resin] In the present invention, the halogen-based resin means a homopolymer, copolymer, or polymer modified by halogen of a monomer containing a halogen. Examples of the halogen-based resin include vinyl chloride resins such as vinyl chloride resins, ethylene-vinyl chloride copolymers, vinyl acetate-vinyl chloride copolymers, polyurethane graft polyvinyl chloride copolymers, vinylidene chloride resins, chlorinated polyethylene, chlorinated polypropylene, chlorosulfonated polyethylene, and chloroprene rubber, from the viewpoint of easy availability. Examples of the halogen-based resin include vinyl chloride resins, vinylidene chloride, and chloroprene rubber, from the viewpoint of flexibility. The halogen-based resin composition of the present invention preferably contains one or more selected from vinyl chloride resins, vinylidene chloride resins, and chloroprene rubber.

[0052] (Vinyl chloride resin) Examples of vinyl chloride resins include vinyl chloride homopolymers (vinyl chloride resins), copolymers of vinyl chloride with monomers copolymerizable therewith (hereinafter also referred to as "vinyl chloride copolymers"), and graft copolymers in which vinyl chloride is graft-copolymerized onto polymers other than the vinyl chloride copolymers. From the viewpoint of ease of copolymerization, the monomer copolymerizable with vinyl chloride may be any monomer having a reactive double bond in the molecule, and examples thereof include α-olefins such as ethylene, propylene, butylene, etc.; vinyl esters such as vinyl acetate, vinyl propionate, etc.; vinyl ethers such as butyl vinyl ether, cetyl vinyl ether, etc.; esters of (meth)acrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, phenyl (meth)acrylate, etc.; aromatic vinyls such as styrene, α-methylstyrene, etc.; vinyl halides such as vinylidene chloride, vinyl fluoride, etc.; and N-substituted maleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, etc. In addition, from the viewpoint of easy availability, polymers other than vinyl chloride copolymers may be those that can be graft-copolymerized with vinyl chloride, and examples thereof include ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-ethyl acrylate copolymer, ethylene-ethyl acrylate-carbon monoxide copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, acrylonitrile-butadiene copolymer, polyurethane, etc.

[0053] [Additives] The halogen-based resin composition may contain additives such as a basic inorganic filler, a stabilizer, a processing aid, a colorant, an antioxidant, an ultraviolet absorber, an antistatic agent, and a lubricant, as necessary, within the range that does not impair the effects of the present invention.

[0054] Examples of the basic inorganic filler include calcium carbonate, talc, calcium silicate, alumina, etc. The basic inorganic filler may be used alone or in combination of two or more. From the viewpoint of economy, the basic inorganic filler preferably contains calcium carbonate.

[0055] When the halogen-based resin composition of the present invention contains a basic inorganic filler, the content of the basic inorganic filler is, from the viewpoint of reducing the cost of the halogen-based resin composition, preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and is preferably 150 parts by mass or less, more preferably 140 parts by mass or less, even more preferably 130 parts by mass or less, per 100 parts by mass of the halogen-based resin.

[0056] 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 octylate, zinc laurate, zinc ricinoleate, and zinc stearate, organic tin compounds such as dimethyltin bis-2-ethylhexylthioglycolate, dibutyltin maleate, dibutyltin bisbutylmaleate, and dibutyltin dilaurate, and antimony mercaptide compounds. The content of the stabilizer is 0.1 to 20 parts by mass relative to 100 parts by mass of the halogen-based resin.

[0057] Examples of the processing aid include liquid paraffin, polyethylene wax, stearic acid, stearic acid amide, ethylene bis stearic acid amide, butyl stearate, calcium stearate, etc. The content of the processing aid is 0.1 to 20 parts by mass with respect to 100 parts by mass of the halogen-based resin.

[0058] Examples of the colorant include carbon black, lead sulfide, white carbon, titanium white, lithopone, red iron oxide, antimony sulfide, chrome yellow, chrome green, cobalt blue, molybdenum orange, etc. The content of the colorant is 1 to 100 parts by mass relative to 100 parts by mass of the halogen-based resin.

[0059] 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, diphenyl isodecyl phosphite, triphenyl phosphite, and tris(2,4-di-tert-butylphenyl)phosphite, and organometallic compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate. The content of the antioxidant is 0.2 to 20 parts by mass relative to 100 parts by mass of the halogen-based resin.

[0060] Examples of the ultraviolet absorber include salicylate compounds such as phenyl salicylate and p-tert-butylphenyl salicylate, benzophenone compounds such as 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy-4-n-methoxybenzophenone, benzotriazole compounds such as 5-methyl-1H-benzotriazole and 1-dioctylaminomethylbenzotriazole, and cyanoacrylate compounds. The content of the ultraviolet absorber is 0.1 to 10 parts by mass relative to 100 parts by mass of the halogen-based resin.

[0061] Examples of the antistatic agent include anionic antistatic agents of the alkylsulfonate 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 alkylamidoamine type, alkyldimethylbenzyl type, and alkylpyridinium type organic acid salts or hydrochlorides, and amphoteric antistatic agents such as alkylbetaine type and alkylimidazoline type. The content of the antistatic agent is 0.1 to 10 parts by mass relative to 100 parts by mass of the halogen-based resin.

[0062] Examples of the lubricant include silicone, liquid paraffin, paraffin wax, fatty acids such as stearic acid and lauric acid and their metal salts, fatty acid amides, fatty acid wax, higher fatty acid wax, etc. The content of the lubricant is 0.1 to 10 parts by mass relative to 100 parts by mass of the halogen-based resin.

[0063] [Method of producing halogen-based resin composition] The method for producing a halogen-based resin composition of the present invention includes a step of mixing a plasticizer composition, a halogen-based resin, and, if necessary, various additives. The mixing of the plasticizer composition may be performed by mixing a plasticizer composition containing a plasticizer A and a plasticizer B, or by using plasticizer A and plasticizer B separately, and mixing them so that the resulting halogen-based resin composition contains a plasticizer composition containing plasticizer A and plasticizer B. When the halogen-based resin composition contains various additives, the mixing of the plasticizer, the halogen-based resin, and the various additives may be performed by adding them all at once, or by mixing each component sequentially. The halogen-based resin composition can be prepared by mixing the plasticizer, the halogen-based resin, and, if necessary, various additives with a stirrer such as a mortar mixer, a lab mixer, a Henschel mixer, a Banbury mixer, a ribbon blender, etc., to obtain a mixed powder of the halogen-based resin composition. In addition, the halogen-based resin composition can be obtained in the form of a mixed powder, pellets, or paste by melt molding with a kneader such as a conical twin-screw extruder, a parallel twin-screw extruder, a single-screw extruder, a co-kneader type kneader, or a roll kneader. The mixing and melt molding conditions may be those used in a normal method for producing a halogen-based resin composition.

[0064] The mixed powder or pellets of the halogen-based resin composition can be molded into a desired shape by a known method such as extrusion molding, injection molding, calendar molding, press molding, blow molding, etc. Also, the paste-like halogen-based resin composition can be molded into a desired shape by a known method such as spread molding, dipping molding, gravure molding, screen processing, etc.

[0065] The halogen-based resin composition of the present invention is useful as: automotive interior decorative agents such as instrument panel skins, leather seats, and wire harnesses; adhesives, sealants, paints, plastisols, foams, synthetic leather, pipes such as water pipes, building materials, wallpaper materials, flooring materials, floor covering materials, heat insulating materials, roofing membrane materials, and other residential interior products; packaging materials such as food packaging films; agricultural materials such as agricultural films; automotive materials such as sealing materials and undercoats; base protection materials, fabric covering materials, electric wire covering materials, various types of leather, various foam products, general hoses, gaskets, packings, boots, toys, food packaging materials, and medical supplies such as tubes and blood bags. EXAMPLES

[0066] In the following Production Examples, Examples and Comparative Examples, "parts" and "%" are "parts by mass" and "% by mass" unless otherwise specified.

[0067] [Production of plasticizer] (Production of Plasticizer A) Production Example 1 (Production of Plasticizer A1) A 1 L four-neck flask was charged with 148.1 g (1.00 mol) of phthalic anhydride (manufactured by Kanto Chemical Co., Ltd.), 317.8 g (2.00 mol) of n-decanol (manufactured by Kao Corporation, product name: Kalcol 1098), 79.4 g (0.43 mol) of n-dodecanol (manufactured by Kao Corporation, product name: Kalcol 2098), and 0.14 g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), mixed, heated, and maintained at 230° C. under atmospheric pressure for 2.5 hours to carry out a reaction while distilling off water. After the reaction was completed, the mixture was cooled to 90° C., 11.0 g of distilled water was added, and the mixture was stirred at 90° C. for 1 hour. The mixture was then heated to 215° C. and the excess alcohol was distilled off under reduced pressure of about 270 Pa (absolute pressure), after which the pressure was returned to normal and the mixture was cooled to 90° C. The mixture was subjected to suction filtration using filter paper covered with a filter aid to obtain a phthalic acid diester mixture, Plasticizer A1.

[0068] Using a 10% solution of plasticizer A1 dissolved in n-hexane, the content of phthalate diesters with different alcohol residues in the phthalate diesters (hereinafter also referred to as "different alkyl phthalate diesters") was quantified from the ratio of the peak areas of the chromatogram obtained by the following gas chromatography method. In the quantification, the ratio of the peak area derived from n-decyl / n-dodecyl phthalate to the total area of ​​the peaks derived from phthalate diesters, excluding peaks detected in a short time derived from n-hexane and unreacted substances, was calculated and used as the content of different alkyl phthalate diesters in plasticizer A1, as shown in Table 1. Since the relative sensitivity of each component in the phthalate diester mixture in the gas chromatography method described below is approximately the same, the ratio of the peak areas in the obtained chromatogram can be considered to be approximately the same as the mass ratio of each component in the phthalate diester mixture. The measurement conditions for the gas chromatography method are as follows. Measurement equipment: Agilent 8890 (gas chromatograph, manufactured by Agilent Technologies, Inc.) Column: DB-1ht (Agilent Technologies, Inc.) (Length 30m, inner diameter 0.25mm, film thickness 0.10μm) Carrier gas: He (constant flow mode) Split ratio: 50:1 Detector: FID ·Inlet temperature: 330℃ Detector temperature: 330℃ Measurement temperature conditions: 100℃ → Heat up at 10℃ / min → Hold at 350℃ for 10 minutes Detection sensitivity: acquisition speed, 20Hz Minimum peak width: 0.01min Injection volume: 1 μl (split method) Quantitative analysis of different alkyl diesters

[0069] Production Example 2 (Production of Plasticizer A2) Plasticizer A2 was obtained in the same manner as in Production Example 1, except that 155.5 g (1.05 mol) of phthalic anhydride was used and n-decanol and n-dodecanol were changed to 336.2 g (2.12 mol) of n-decanol and 64.3 g (0.32 mol) of isotridecanol (manufactured by KH Neochem Co., Ltd., product name: Tridecanol). When the content of n-decyl / isotridecyl phthalate in plasticizer A2 was measured in the same manner as for plasticizer A1, the peaks in the chromatogram overlapped, making it impossible to measure the content.

[0070] Production Example 3 (Production of Plasticizer A3) Plasticizer A3 was obtained in the same manner as in Production Example 1, except that n-decanol and n-dodecanol were changed to 208.0 g (1.31 mol) of n-decanol and 208.0 g (1.12 mol) of n-dodecanol. The content of n-decyl / n-dodecyl phthalate in Plasticizer A3 was measured in the same manner as for Plasticizer A1, and the results are shown in Table 1.

[0071] [Table 1]

[0072] (Production of Plasticizer B) Production Example 4 (Production of Plasticizer B1) A 1 L four-neck flask was charged with 155.0 g (1.06 mol) of isosorbide (manufactured by Tokyo Chemical Industry Co., Ltd.), 201.4 g (1.40 mol) of octanoic acid (manufactured by Kao Corporation, product name: Lunac 8-98), 201.4 g (1.17 mol) of decanoic acid (manufactured by Kao Corporation, product name: Lunac 10-98), and 0.28 g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), mixed, heated, and maintained at 230°C under atmospheric pressure for 5.5 hours to carry out a reaction while distilling off water. After the reaction was completed, the mixture was cooled to 90° C., 11.6 g of distilled water was added, and the mixture was stirred at 90° C. for 1 hour. The mixture was then heated to 245° C., and excess fatty acid was distilled off under reduced pressure of about 400 Pa (absolute pressure), after which the mixture was returned to normal pressure and cooled to 90° C., and filtered by suction using filter paper covered with a filter aid to obtain a plasticizer B1 as an isosorbide diester mixture. The theoretical content of the isosorbide (octanoic acid / decanoic acid) diester, which is the isosorbide diester (b1) in the plasticizer B1, calculated from the molar concentration of each of the octanoic acid and decanoic acid relative to the total amount of the used acids, was 49.9% by mass, and the actual content of the isosorbide (octanoic acid / decanoic acid) diester in the plasticizer B1 measured by gas chromatography was 50.4%. The measurement by gas chromatography was carried out under the same conditions as for the plasticizer A1.

[0073] Production Example 5 (Production of Plasticizer B2) Plasticizer B2 was obtained in the same manner as in Production Example 4, except that octanoic acid and decanoic acid were changed to 43.1 g (0.30 mol) of octanoic acid and 388.6 g (2.26 mol) of decanoic acid. The theoretical content of the isosorbide (octanoic acid / decanoic acid) diester, which is the isosorbide diester (b1) in the plasticizer B2, calculated from the molar concentration of each of the octanoic acid and decanoic acid relative to the total amount of the used acids, was 19.7% by mass, and the actual content of the isosorbide (octanoic acid / decanoic acid) diester in the plasticizer B2 measured by gas chromatography was 18.5%. The measurement by gas chromatography was carried out under the same conditions as for the plasticizer A1.

[0074] Production Example 6 (Production of Plasticizer B3) Plasticizer B3 was obtained in the same manner as in Production Example 4, except that 115.2 g (0.79 mol) of isosorbide was used and octanoic acid and decanoic acid were changed to 227.1 g (1.57 mol) of octanoic acid and 56.8 g (0.33 mol) of decanoic acid. The theoretical content of the isosorbide (octanoic acid / decanoic acid) diester, which is the isosorbide diester (b1) in the plasticizer B3, calculated from the molar concentration of each of the octanoic acid and decanoic acid relative to the total amount of the used acids, was 29.9% by mass, and the actual content of the isosorbide (octanoic acid / decanoic acid) diester in the plasticizer B3 measured by gas chromatography was 31.7%. The measurement by gas chromatography was carried out under the same conditions as for the plasticizer A1.

[0075] Comparative Production Example 1 (Production of Plasticizer B11) Plasticizer B11 was obtained in the same manner as in Production Example 4, except that 116.0 g (0.79 mol) of isosorbide was used and octanoic acid and decanoic acid were changed to 274.6 g (1.90 mol) of octanoic acid.

[0076] Comparative Production Example 2 (Production of Plasticizer B12) Plasticizer B12 was obtained in the same manner as in Production Example 4, except that 181.0 g (1.24 mol) of isosorbide was used and 509.3 g (2.96 mol) of decanoic acid was used instead of octanoic acid and decanoic acid.

[0077] [Table 2]

[0078] [Production of plasticizer composition] Example 1 (Production of Plasticizer Composition 1) 50.0 g of Plasticizer A1 and 50.0 g of Plasticizer B1 were weighed out, and these were mixed until visually homogenous, to obtain Plasticizer Composition 1.

[0079] Examples 2 to 8 and Comparative Examples 1 to 7 (Production of Plasticizer Compositions 2 to 8 and 11 to 17) In the same manner as in Example 1, except that the types and compounding ratios of plasticizer A and plasticizer B were changed as shown in Table 3, plasticizer compositions 2 to 8 and 11 to 17 were obtained. In Table 3, didecyl phthalate (manufactured by Kao Corporation, product name: Vinycizer 105) was used as plasticizer A4, and dihexyl phthalate (manufactured by Tokyo Chemical Industry Co., Ltd., product name: dihexyl phthalate) was used as plasticizer A11.

[0080] [Table 3]

[0081] [Production of halogen-based resin composition] Examples 9 to 16 and Comparative Examples 8 to 14 (Production of Halogen-Based Resin Compositions 1 to 8 and 11 to 17) 100 parts of vinyl chloride resin (average degree of polymerization 1400, manufactured by Shin-Daiichi Vinyl Corporation, product name: ZEST1400) were mixed with 80 parts of the plasticizer composition shown in Table 4, 2 parts of a Ca / Mg / Zn-based stabilizer for vinyl chloride resin (manufactured by ADEKA Corporation, product name: Adeka STAB RUP-103), and 0.5 parts of a lubricant (manufactured by Kao Corporation, product name: Lunac S-70V) using a stirring rod at room temperature. Then, the mixture was kneaded at a rotation speed of 17 rpm and 170°C using a 4-inch open roll kneader (manufactured by Nishimura Machinery Co., Ltd.) to gel, and kneading was continued for 5 minutes after gelation to obtain a halogen-based resin composition. The unformed sheets produced above were preheated at 160°C for 5 minutes, pressurized at 20 MPa for 2 minutes, and further cooled at 15°C for 2 minutes to obtain molded sheets of halogen-based resin compositions 1 to 8 and 11 to 17 having a thickness of 0.8 mm.

[0082] [measurement] [Heat resistance evaluation] The molded sheets of each halogen-based resin composition were punched out into a No. 3 dumbbell shape as specified in JIS K6251:2017 to obtain test pieces, and the mass loss rate (%) was measured before and after leaving the test pieces at 100°C for 100 hours in a gear-type aging tester (manufactured by Ueshima Seisakusho Co., Ltd., product name: AG-103) as specified in JIS K 7212:1999. The closer the value is to zero, the better the heat resistance. The results are shown in Table 4.

[0083] [Table 4]

[0084] As shown in Table 4, it is understood that the plasticizer composition of the present invention exhibits excellent heat resistance when used in a halogen-based resin composition. In addition, from a comparison of the results of Example 9 with Examples 10 and 11, it is understood that the heat resistance of the halogen-based resin composition is improved by increasing the content of plasticizer A in the plasticizer composition. Furthermore, from a comparison of the results of Example 9 with Examples 12 and 13, it is understood that the heat resistance of the halogen-based resin composition is improved by increasing the content of plasticizers b1 and b2 containing a large number of groups derived from decanoic acid in plasticizer B. On the other hand, from a comparison of the results of Example 9 with Examples 14 to 16, it is understood that the type of plasticizer A does not have much effect on the heat resistance of the halogen-based resin composition. On the other hand, the halogen-based resin composition 11 of Comparative Example 8, which used the plasticizer composition 11 containing di-n-hexyl phthalate (plasticizer A11) and isosorbide dioctanoate (plasticizer B11), was extremely poor in heat resistance. Also, the halogen-based resin composition 12 of Comparative Example 9, which used the plasticizer composition 12 containing plasticizer A1 and isosorbide dioctanoate (plasticizer B12), the halogen-based resin composition 13 of Comparative Example 10, which used the plasticizer composition 13 containing plasticizer A1 and isosorbide dioctanoate (plasticizer B11), and the halogen-based resin composition 14 of Comparative Example 11, which used the plasticizer composition 14 containing plasticizer A1, isosorbide dioctanoate (plasticizer B11), and isosorbide dioctanoate (plasticizer B12), were all poor in heat resistance. Furthermore, the halogen-based resin composition 15 of Comparative Example 12, which uses a plasticizer composition 15 containing di-n-hexyl phthalate (plasticizer A11) and a plasticizer B1, the halogen-based resin composition 16 of Comparative Example 13, which uses a plasticizer composition 16 containing di-n-hexyl phthalate (plasticizer A11) and a plasticizer B2, and the halogen-based resin composition 17 of Comparative Example 14, which uses a plasticizer composition 17 containing di-n-hexyl phthalate (plasticizer A11) and a plasticizer B3, all have extremely poor heat resistance. From the comparison with the results of Examples 1, 14, and 15, it can be seen that the R 1 and R 2It has been found that the number of carbon atoms in the alkyl group affects the heat resistance of the halogen-based resin composition containing the plasticizer composition of the present invention.

Claims

1. A plasticizer composition comprising a plasticizer A consisting of a phthalic acid diester represented by general formula (I) and a plasticizer B containing an isosorbide diester (b1) represented by general formula (II). 【Chemistry 1】 (In general formula (I), R １ and R ２ are each a straight-chain or branched alkyl group having 8 to 14 carbon atoms, which may be the same or different. 【Chemistry 2】 (In general formula (II), R ３ and R ４ are linear or branched alkyl groups each having a different number of carbon atoms.

2. In the isosorbide diester (b1) represented by the general formula (II), R ３ and R ４ and each are a linear or branched alkyl group having 7 to 9 carbon atoms. The plasticizer composition according to claim 1 .

3. The plasticizer composition according to claim 2, wherein the isosorbide diester (b1) represented by the general formula (II) is an isosorbide (octanoic acid / decanoic acid) diester.

4. The plasticizer B further contains an isosorbide diester (b2) represented by general formula (III), The plasticizer composition according to claim 1, wherein the content of the isosorbide diester (b1) in the plasticizer B is 10 mass% or more. 【Chemistry 3】 (In general formula (III), R ５ and R ６ are linear or branched alkyl groups each having the same number of carbon atoms.

5. In the isosorbide diester (b2) represented by the general formula (III), R ５ and R ６ and each represent a linear or branched alkyl group having 7 to 9 carbon atoms. The plasticizer composition according to claim 4 .

6. The plasticizer composition according to claim 1 , wherein a mass ratio of the plasticizer A to the plasticizer B (plasticizer A / plasticizer B) is 5 / 95 or more and 85 / 15 or less.

7. A halogen-based resin composition comprising the plasticizer composition according to any one of claims 1 to 6.

8. A method for producing a plasticizer composition, comprising mixing a plasticizer A consisting of a phthalic acid diester represented by general formula (I) with a plasticizer B containing an isosorbide diester (b1) represented by general formula (II). 【Chemistry 4】 (In general formula (I), R １ and R ２ are each the same or different linear or branched alkyl groups having 8 to 14 carbon atoms. 【Chemistry 5】 (In general formula (II), R ３ and R ４ are linear or branched alkyl groups each having a different number of carbon atoms.

9. The method for producing a plasticizer composition according to claim 8, wherein the plasticizer B is obtained by esterifying isosorbide and a carboxylic acid raw material containing at least two linear or branched aliphatic carboxylic acids having different carbon numbers.

10. The method for producing a plasticizer composition according to claim 9, wherein the linear or branched aliphatic carboxylic acids having different carbon numbers are linear or branched aliphatic carboxylic acids having 8 to 10 carbon atoms.

11. The method for producing a plasticizer composition according to claim 10, wherein the linear or branched aliphatic carboxylic acid having from 8 to 10 carbon atoms is octanoic acid and decanoic acid.

12. The method for producing a plasticizer composition according to claim 10 or 11, wherein a molar ratio of the linear or branched aliphatic carboxylic acid having 8 carbon atoms to the linear or branched aliphatic carboxylic acid having 10 carbon atoms in the carboxylic acid raw material (carboxylic acid having 8 carbon atoms / carboxylic acid having 10 carbon atoms) is 5 / 95 or more and 92 / 8 or less.

13. The method for producing a plasticizer composition according to claim 8, wherein the plasticizer A is obtained by esterifying a phthalic acid raw material and an alcohol raw material containing a linear or branched aliphatic alcohol having a carbon number of 8 to 14.

14. The method for producing a plasticizer composition according to claim 13, wherein a molar ratio of linear aliphatic alcohol to branched aliphatic alcohol in the alcohol raw material (linear aliphatic alcohol / branched aliphatic alcohol) is 70 / 30 or more and 100 / 0 or less.

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