plasticizer components

Abstract

Invention details;

Description

Plasticizer Composition

[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.

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

[0003] However, plasticizers that are 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] JP 2015-516009 A (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% to 99% by weight of an ester (A) chosen from the monoesters and diesters of isosorbide, isomannide and isoidide, and at least one compound (B), wherein the molar mass of said compound (B) is 345 g.mol －１ More particularly, compositions are disclosed that comprise from 1% to 99.9% by weight of a compound (B) selected from the following: 1,4:3,6-dianhydrohexitol esters selected from monoesters 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; and glycerol esters.

[0005] The present invention relates to 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).

[0006] (In general formula (I), R １ and R ２ are each a linear or branched alkyl group having 8 to 14 carbon atoms, which may be the same or different.

[0007] (In general formula (II), R ３ and R ４ are linear or branched alkyl groups each having a different number of carbon atoms.

[0008] The composition described in Patent Document 1 has a fast plasticization rate, but still has a problem with heat resistance. The present invention relates to a plasticizer composition that, when used in a halogen-based resin composition, gives the halogen-based resin composition excellent heat resistance.

[0009] The present inventors have found that the above-mentioned problems can be solved by a plasticizer composition containing a plasticizer A consisting of a phthalate diester having a structure derived from an alcohol having a specific chain length, and a plasticizer B containing an isosorbide diester having a structure derived from a carboxylic acid having a specific chain length.

[0010] According to the present invention, it is possible to provide a plasticizer composition that, when used in a halogen-based resin composition, gives the halogen-based resin composition excellent heat resistance.

[0011] [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 number of carbon atoms; and plasticizer B containing an isosorbide diester having a structure derived from a linear or branched aliphatic carboxylic acid having a different number of carbon atoms.

[0012] The plasticizer composition of the present invention exhibits an excellent effect in improving the heat resistance of halogen-containing resin compositions. The reason for this effect is unclear, but is thought to be as follows. The plasticizer composition of the present invention includes plasticizer A, which comprises a phthalate 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, which contains an isosorbide diester having structures derived from linear or branched aliphatic carboxylic acids having two different carbon numbers. It is believed that because plasticizer A comprises a phthalate 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 contains an isosorbide diester having structures derived from linear or branched aliphatic carboxylic acids having two different carbon numbers, a stronger interaction occurs between the phthalate diester and the isosorbide diester than between the phthalate diester and an isosorbide diester having structures derived from the same two carboxylic acids. Therefore, the phthalate diester diffuses uniformly into the halogen-based resin composition together with the isosorbide diester, thereby suppressing bleeding of the plasticizer composition of the present invention from the halogen-based resin composition, and further suppressing evaporation of the plasticizer composition of the present invention from the halogen-based resin composition, which is thought to result in the halogen-based resin composition having high heat resistance.

[0013] [Plasticizer A] In the present invention, plasticizer A comprises a phthalic acid diester represented by general formula (I).

[0014]

[0015] 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.

[0016] R １ and R ２ The linear 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, or an n-tetradecyl group.１ and R ２ Examples of the branched alkyl group having 8 to 14 carbon atoms as R 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, and an isotetradecyl group. Here, "iso-" refers to a structure in which a methyl group is branched at the terminal of the alkyl group. Among these, 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 from 10 to 13 carbon atoms, and more preferably a group selected from an n-decyl group, an n-dodecyl group, and an isotridecyl group.

[0017] 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.

[0018] (Method for Producing 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.

[0019] Examples of the phthalic acid raw material include phthalic acid, phthalic anhydride, and phthalate 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.

[0020] Examples of the alcohol raw material include linear aliphatic alcohols having from 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 from 8 to 14 carbon atoms, such as 2-ethylhexanol, 2-butyloctanol, isooctanol, isononanol, isodecanol, isoundecanol, isododecanol, isotridecanol, and isotetradecanol.

[0021] From the viewpoint of providing excellent heat resistance to the halogen-based resin composition, the molar ratio of linear aliphatic alcohol to 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 preferably 100 / 0 or less, more preferably 100 / 0. The molar ratio of linear aliphatic alcohol to branched aliphatic alcohol in the alcohol raw material (linear aliphatic alcohol / branched aliphatic alcohol) is preferably 70 / 30 or more and 100 / 0 or less, more preferably 80 / 20 or more and 100 / 0 or less, even more preferably 85 / 15 or more and 100 / 0 or less, and still more preferably 100 / 0.

[0022] 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 or more by mole, more preferably 2.1 times or more by mole, even more preferably 2.2 times or more by mole, and 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 the phthalic acid raw material. The amount of the alcohol raw material charged is preferably 2.0 times or more by mole and 3.0 times or less by mole, more preferably 2.1 times or more by mole and 2.7 times or less by mole, and even more preferably 2.2 times or more by mole and 2.5 times or less by mole, 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.

[0023] As the esterification reaction catalyst, any known esterification catalyst having esterification ability can be used, but 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. Among these, organotitanium compounds are preferred from the viewpoint of productivity, and one or more selected from titanium tetraisopropoxide, titanium tetra-n-butoxide, and titanium tetra-2-ethylhexyloxide are preferred.

[0024] The amount of catalyst used varies depending on the type, but from the viewpoint of fully exerting catalytic activity, it is preferably 0.01 parts 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 fed 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. The amount of catalyst used is preferably 0.01 parts by mass or more and 2 parts by mass or less, more preferably 0.015 parts by mass or more and 1 part by mass or less, and even more preferably 0.02 parts by mass or more and 0.5 parts by mass or less, relative to 100 parts by mass of the total amount of the phthalic acid raw material and the alcohol raw material.

[0025] The esterification reaction can be carried out under alcohol reflux using a known reaction apparatus equipped with equipment 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. 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. The reaction temperature is preferably 100°C or higher and 280°C or lower, more preferably 130°C or higher and 260°C or lower, and even more preferably 150°C or higher and 240°C or lower. A reaction temperature of 100°C or higher allows the reaction to proceed rapidly, while a reaction temperature of 280°C or lower can suppress the production of reaction by-products. The reaction pressure is usually preferably 13.3 kPa or higher in absolute pressure and atmospheric pressure or lower. The reaction pressure can be set based on the vapor pressure of the alcohol raw material used. Specifically, it is preferable to adjust the pressure to a level at which the reaction mixture maintains a boiling state, and further, it is preferable to adjust the pressure to a level at which the by-product water can be removed from 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 on 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 generation of by-products can be suppressed, and the quality of plasticizer A can be improved.

[0026] 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, thereby increasing the reaction rate to nearly 100%. After separating the excess alcohol raw material, the reaction mixture is post-treated by a known method such as alkali washing, water washing, adsorption of impurities, or distillation, thereby obtaining plasticizer A as a phthalic acid diester represented by general formula (I).

[0027] [Plasticizer B] In the present invention, plasticizer B contains an isosorbide diester (b1) represented by general formula (II). Note that the isosorbide diester (b1) represented by general formula (II) may have any stereoisomer, and from the viewpoint of cost, it is preferable that it has a stereostructure derived from D-sorbitol.

[0028]

[0029] In general formula (II), R ３ and R ４ are linear or branched alkyl groups each having a different number of carbon atoms.

[0030] R ３ and R ４ The linear or branched alkyl group as R ３ and R ４ and R are linear or branched alkyl groups having different carbon numbers, and preferably linear or branched alkyl groups having 7 to 9 carbon atoms. Examples of linear alkyl groups having 7 to 9 carbon atoms include n-heptyl, n-octyl, and n-nonyl groups. ３ and R ４ Examples of the branched alkyl group having 7 to 9 carbon atoms as R include a 2-ethylhexyl group, an isoheptyl group, an isooctyl group, and an isononyl group. ３ and R ４ From the viewpoint of providing excellent heat resistance to the halogen-based resin composition, the isosorbide 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.

[0031] 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.

[0032] 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.

[0033]

[0034] 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 from 7 to 9 carbon atoms, and more preferably a straight-chain or branched alkyl group having the same number of carbon atoms, from 7 to 9 carbon atoms.

[0035] R ５ and R ６ As the straight chain alkyl group, R ３ and R ４ The groups are preferably selected from linear or branched alkyl groups having 7 to 9 carbon atoms.

[0036] The isosorbide diester (b2) represented by general formula (III) contained in plasticizer B may be one type or two or more types. Preferably, the isosorbide diester (b2) represented by general formula (III) contained in plasticizer B is one type or two types, and more preferably, the isosorbide diester (b2) represented by general formula (III) contained in plasticizer B is two types.

[0037] The plasticizer B preferably contains an isosorbide diester (b1) represented by the general formula (II) and an isosorbide diester (b2) represented by the general formula (III), and more preferably consists of the isosorbide diester (b1) represented by the general formula (II) and the isosorbide diester (b2) represented by the general formula (III).

[0038] From the viewpoint of ensuring excellent heat resistance of the halogen-based resin composition, the content of the isosorbide diester (b1) in the plasticizer B is preferably 10% by mass or more, more preferably 13% by mass or more, even more preferably 15% by mass or more, and preferably 100% by mass or less, more preferably 80% by mass or less, and even more preferably 60% by mass or less. The content of the isosorbide diester (b1) in the plasticizer B is preferably 10% by mass or more and 100% by mass or less, more preferably 13% by mass or more and 80% by mass or less, and even more preferably 15% by mass or more and 60% by mass or less. The content of the isosorbide diester (b1) in the plasticizer B can be measured by gas chromatography or the like. Specifically, it is measured by the method described in the examples.

[0039] (Method for Producing Plasticizer B) Plasticizer B can be obtained by esterifying isosorbide with two types of linear or branched aliphatic carboxylic acids having different carbon numbers.

[0040] Examples of the carboxylic acid raw material include linear aliphatic carboxylic acids having from 8 to 10 carbon atoms, such as octanoic acid, nonanoic acid, and decanoic acid; and branched aliphatic carboxylic acids having from 8 to 10 carbon atoms, such as 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, and isodenic acid. Among these, the carboxylic acid raw material is preferably a linear aliphatic carboxylic acid having from 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.

[0041] When plasticizer B is an isosorbide diester (b1) represented by general formula (II), one kind of linear or branched aliphatic carboxylic acid having from 8 to 10 carbon atoms is charged in an amount of from 1.0 to 1.1 times by mole per mole of isosorbide in which one of the two hydroxyl groups of isosorbide is protected with a protecting group to produce an isosorbide monoester in which one hydroxyl group is protected, and the isosorbide monoester isolated after deprotection is then subjected to an esterification reaction in which a different linear or branched aliphatic carboxylic acid having from 8 to 10 carbon atoms is charged in an amount of from 1.0 to 1.1 times by mole to produce isosorbide diester (b1) represented by general formula (II). Examples of the protecting group include those typically used as protecting groups for hydroxyl groups.

[0042] As the esterification reaction catalyst, the esterification reaction catalysts exemplified in the method for producing plasticizer A can be used, and an organic titanium compound is preferred, and one or more selected from titanium tetraisopropoxide, titanium tetra-n-butoxide, and titanium tetra-2-ethylhexyloxide are preferred.

[0043] The amount of catalyst used varies depending on the type, but from the viewpoint of fully exerting catalytic activity, it is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and even more preferably 0.03 parts 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. 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 parts by mass or less. The amount of catalyst used is preferably 0.01 parts by mass or more and 2 parts by mass or less, more preferably 0.02 parts by mass or more and 1 part by mass or less, and even more preferably 0.03 parts by mass or more and 0.1 parts by mass or less, relative to 100 parts by mass of the total amount of isosorbide and carboxylic acid raw materials. 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 more, more preferably 130°C or more, and even more preferably 150°C or more. From the viewpoint of yield, it is preferably 280°C or less, more preferably 260°C or less, and even more preferably 240°C or less. The reaction temperature is preferably 100°C or higher and 280°C or lower, more preferably 130°C or higher and 260°C or lower, and even more preferably 150°C or higher and 240°C or lower. A reaction temperature of 100°C or higher allows the reaction to proceed quickly, while a reaction temperature of 280°C or lower can suppress the generation of reaction by-products. The reaction pressure is usually preferably 13.3 kPa or higher in absolute pressure and atmospheric pressure or lower. 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, carboxylic acid raw material, reaction temperature, amount of catalyst used, etc., but from the viewpoint of reactivity, it is preferably 1 hour or longer, more preferably 2 hours or longer. A sufficient reaction time reduces the load on the separation process of unreacted phthalic acid raw material and the reaction intermediate phthalate monoester. On the other hand, from the viewpoint of yield, the reaction time is preferably 24 hours or shorter, more preferably 10 hours or shorter. A shorter reaction time can suppress the generation of by-products and improve the quality of plasticizer B.

[0044] In the esterification reaction under the above reaction conditions, the generated water 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 mixture 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 the general formula (II) as the plasticizer B.

[0045] When plasticizer B contains an isosorbide diester (b1) represented by general formula (II) and an isosorbide diester (b2) represented by general formula (III), a carboxylic acid raw material containing two linear or branched aliphatic carboxylic acids having from 8 to 10 carbon atoms can be used. In this case, the esterification catalyst used, reaction conditions, etc. can be the same as those for the above-mentioned esterification reaction. When plasticizer B contains an isosorbide diester (b1) represented by general formula (II) and an isosorbide diester (b2) represented by 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, from the viewpoint of promoting the reaction and completing the reaction, the amount of the carboxylic acid 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, still more preferably 2.3 times by mole or more, and 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 isosorbide. The amount of the carboxylic acid raw material charged is preferably 2.0 times by mole or more and 3.0 times by mole or less, more preferably 2.1 times by mole or more and 2.7 times by mole or less, even more preferably 2.2 times by mole or more and 2.5 times by mole or less, and even more preferably 2.3 times by mole or more and 2.5 times by mole or less, relative to 1 mole of isosorbide.

[0046] 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, and even more preferably 85 / 15 or less, from the viewpoint of the halogen-based resin composition exhibiting excellent heat resistance and reducing production costs. The molar ratio (carboxylic acid having 8 carbon atoms / carboxylic acid having 10 carbon atoms) is preferably 5 / 95 or more and 92 / 8 or less, more preferably 8 / 92 or more and 90 / 10 or less, and even more preferably 10 / 90 or more and 85 / 15 or less, from the viewpoint of the halogen-based resin composition exhibiting excellent heat resistance and reducing production costs.

[0047] Furthermore, 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. Therefore, 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 / C10 carboxylic acid diester (b1-1) in plasticizer B obtained by the 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.

[0048] [Other Components] The plasticizer composition of the present invention may contain a compound that is usually used as a plasticizer for halogen-based resins. Examples of plasticizers that have 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, etc.

[0049] 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% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and preferably 100% by mass or less, more preferably 100% by mass. The total content of plasticizer A and plasticizer B in the plasticizer composition of the present invention is preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, even more preferably 95% by mass or more and 100% by mass or less, and still more preferably 100% by mass.

[0050] 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, and even more preferably 75 / 25 or less. The mass ratio (plasticizer A / plasticizer B) is preferably 5 / 95 or more and 85 / 15 or less, more preferably 10 / 90 or more and 80 / 20 or less, and even more preferably 15 / 85 or more and 75 / 25 or less.

[0051] (Method for Producing Plasticizer Composition) The plasticizer composition of the present invention can be obtained by mixing a plasticizer A consisting of a phthalate diester represented by general formula (I), a plasticizer B containing an isosorbide diester (b1) represented by general formula (II), and, if necessary, the other components described above. Plasticizer A and plasticizer B can be mixed 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 other components described above, the other components can be added to a mixture of plasticizer A and plasticizer B and mixed, or the components can be mixed sequentially. The plasticizer composition can be prepared by mixing plasticizer A, plasticizer B, and, if necessary, the other components described above, using a mixer such as a hand mixer, a lab mixer, a mortar mixer, a Henschel mixer, a Banbury mixer, or a ribbon blender.

[0052] [Halogen-Based Resin Composition] The halogen-based resin composition of the present invention contains the plasticizer composition and a halogen-based resin.

[0053] [Halogen-Based Resin] In the present invention, the term "halogen-based resin" refers to a homopolymer or copolymer of a halogen-containing monomer, or a polymer modified with a halogen. Examples of halogen-based resins include vinyl chloride resins such as vinyl chloride resin, ethylene-vinyl chloride copolymer, vinyl acetate-vinyl chloride copolymer, and polyurethane-grafted polyvinyl chloride copolymer, vinylidene chloride resin, chlorinated polyethylene, chlorinated polypropylene, chlorosulfonated polyethylene, and chloroprene rubber, which are readily available. Examples of halogen-based resins include vinyl chloride resin, vinylidene chloride, and chloroprene rubber, which are flexible. The halogen-based resin composition of the present invention preferably contains at least one selected from vinyl chloride resin, vinylidene chloride resin, and chloroprene rubber.

[0054] (Vinyl chloride resin) Examples of vinyl chloride resins include vinyl chloride homopolymers (vinyl chloride resins), copolymers of vinyl chloride with a copolymerizable monomer (hereinafter also referred to as "vinyl chloride copolymers"), and graft copolymers in which vinyl chloride is graft-copolymerized onto a polymer other than the vinyl chloride copolymer. 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, and butylene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as butyl vinyl ether and cetyl vinyl ether; (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and phenyl (meth)acrylate; aromatic vinyls such as styrene and α-methylstyrene; vinyl halides such as vinylidene chloride and vinyl fluoride; and N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide. Furthermore, from the viewpoint of easy availability, polymers other than vinyl chloride copolymers may be any polymers 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, and the like.

[0055] [Additives] The halogen-based resin composition may contain additives such as basic inorganic fillers, stabilizers, processing aids, colorants, antioxidants, ultraviolet absorbers, antistatic agents, and lubricants, as needed, within the range that does not impair the effects of the present invention.

[0056] 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 includes calcium carbonate.

[0057] When the halogen-based resin composition of the present invention contains a basic inorganic filler, the content of the basic inorganic filler is 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 preferably 150 parts by mass or less, more preferably 140 parts by mass or less, and even more preferably 130 parts by mass or less, relative to 100 parts by mass of the halogen-based resin, from the viewpoint of reducing the cost of the halogen-based resin composition. When the halogen-based resin composition of the present invention contains a basic inorganic filler, the content of the basic inorganic filler is preferably 1 part by mass or more and 150 parts by mass or less, more preferably 3 parts by mass or more and 140 parts by mass or less, and even more preferably 5 parts by mass or less, relative to 100 parts by mass of the halogen-based resin.

[0058] Examples of stabilizers 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, organotin 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 per 100 parts by mass of the halogen-based resin.

[0059] Examples of processing aids include liquid paraffin, polyethylene wax, stearic acid, stearic acid amide, ethylene bisstearic acid amide, butyl stearate, calcium stearate, etc. The content of the processing aid is 0.1 to 20 parts by mass per 100 parts by mass of the halogen-based resin.

[0060] Examples of colorants 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 per 100 parts by mass of the halogen-based resin.

[0061] Examples of antioxidants 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. The content of the antioxidant is 0.2 to 20 parts by mass per 100 parts by mass of the halogen-based resin.

[0062] 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.

[0063] Examples of antistatic agents 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 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 per 100 parts by mass of the halogen-based resin.

[0064] Examples of lubricants 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 per 100 parts by mass of the halogen-based resin.

[0065] [Method for 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 involve mixing a plasticizer composition containing plasticizer A and plasticizer B, or may involve 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 plasticizer, halogen-based resin, and various additives may be mixed together or sequentially. The halogen-based resin composition may be prepared by mixing the plasticizer, halogen-based resin, and various additives, if necessary, using a mixer such as a mortar mixer, a lab mixer, a Henschel mixer, a Banbury mixer, or a ribbon blender, to obtain a mixed powder of the halogen-based resin composition. Furthermore, a halogen-based resin composition in the form of a mixed powder, pellets, or paste can be obtained by melt molding using a kneader such as a conical twin-screw extruder, a parallel twin-screw extruder, a single-screw extruder, a co-kneader-type kneader, a roll kneader, etc. The mixing and melt molding conditions may be any conditions that are used in a typical method for producing a halogen-based resin composition.

[0066] The mixed powder or pellets of the halogen-based resin composition can be molded into a desired shape by known methods such as extrusion molding, injection molding, calendar molding, press molding, blow molding, etc. Furthermore, the paste-like halogen-based resin composition can be molded into a desired shape by known methods such as spread molding, dipping molding, gravure molding, screen processing, etc.

[0067] The halogen-based resin composition of the present invention is useful as an automotive interior decorative material such as an instrument panel skin, leather seat, or wire harness; an adhesive, a sealant, a paint, a plastisol, a foam, a synthetic leather, a pipe such as a water pipe, a building material, a wallpaper material, a floor material, a floor covering material, a heat insulating material, a roofing membrane material, or other residential interior goods; a packaging material such as a food packaging film; an agricultural material such as an agricultural film; an automotive material such as a sealant or undercoat material; a substrate protective material, a fabric covering material, an electric wire covering material, various leathers, various foam products, general hoses, gaskets, packings, boots, toys, food packaging material, and medical supplies such as tubes and blood bags.

[0068] The present invention includes the following aspects [1] to

[14] : [1] A plasticizer composition comprising a plasticizer A consisting of a phthalate diester represented by general formula (I) and a plasticizer B containing an isosorbide diester (b1) represented by general formula (II). (In general formula (I), R １ and R ２ are each a linear or branched alkyl group having 8 to 14 carbon atoms, which may be the same or different. (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 represent a linear or branched alkyl group having from 7 to 9 carbon atoms. [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 composition according to any one of [1] to [3], wherein the plasticizer B further contains an isosorbide diester (b2) represented by the general formula (III), and the content of the isosorbide diester (b1) in the plasticizer B is 10 mass% or more. (In general formula (III), R ５ and R ６are 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 from 7 to 9 carbon atoms. [6] The plasticizer composition according to any one of [1] to [5], wherein the mass ratio of the plasticizer A to the plasticizer B (plasticizer A / plasticizer B) is from 5 / 95 to 85 / 15. [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 phthalate diester represented by general formula (I) with a plasticizer B containing an isosorbide diester (b1) represented by general formula (II). (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. (In general formula (II), R ３ and R ４are 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 with a carboxylic acid raw material containing at least two linear or branched aliphatic carboxylic acids having different numbers of carbon atoms.

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

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

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

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

[10] or

[11] , wherein 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 (8 carbon atom carboxylic acid / 10 carbon atom carboxylic acid) 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 with 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 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 from 70 / 30 to 100 / 0.

[0069] In the following Production Examples, Examples and Comparative Examples, "parts" and "%" are "parts by mass" and "% by mass" unless otherwise specified.

[0070] [Production of Plasticizers] (Production of Plasticizer A) Production Example 1 (Production of Plasticizer A1) Into a 1 L four-neck flask were charged 148.1 g (1.00 mol) of phthalic anhydride (Kanto Chemical Co., Inc.), 317.8 g (2.00 mol) of n-decanol (Kao Corporation, trade name: Kalcol 1098), 79.4 g (0.43 mol) of n-dodecanol (Kao Corporation, trade name: Kalcol 2098), and 0.14 g of titanium tetraisopropoxide (Fujifilm Wako Pure Chemical Industries, Ltd.), which were mixed and heated. The mixture was maintained at 230°C under atmospheric pressure for 2.5 hours to carry out a reaction while distilling off water. After completion of the reaction, the mixture was cooled to 90°C, and 11.0 g of distilled water was added, followed by stirring at 90°C for 1 hour. Thereafter, the temperature was raised to 215°C, and excess alcohol was distilled off under reduced pressure conditions of approximately 270 Pa (absolute pressure). Thereafter, the pressure was returned to normal and the mixture was cooled to 90°C. The mixture was then subjected to suction filtration using filter paper covered with a filter aid, thereby obtaining Plasticizer A1 as a phthalate diester mixture.

[0071] Using a 10% solution of plasticizer A1 dissolved in n-hexane, the content of phthalate diesters with different alcohol residues (hereinafter also referred to as "different alkyl phthalate diesters") in the phthalate diesters was quantified from the ratio of peak areas in a chromatogram obtained by the gas chromatography method described below. In the quantification, the ratio of the peak area derived from n-decyl / n-dodecyl phthalate to the total area of ​​peaks derived from phthalate diesters, excluding peaks detected in a short time due to 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. Note that, because 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 shown below. Measurement equipment: Agilent 8890 (gas chromatograph, manufactured by Agilent Technologies Inc.) Column: DB-1ht (manufactured by Agilent Technologies Inc.) (length 30 m, inner diameter 0.25 mm, film thickness 0.10 μm) Carrier gas: He (constant flow mode) Split ratio: 50:1 Detector: FID Injection port temperature: 330°C Detector temperature: 330°C Measurement temperature conditions: 100°C → temperature increase at 10°C / min → hold at 350°C for 10 minutes Detection sensitivity: uptake rate, 20 Hz Minimum peak width, 0.01 min Injection volume: 1 μl (split method) Quantification of different alkyl diesters

[0072] 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 the 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 (trade name: Tridecanol, manufactured by KH Neochem Co., Ltd.). The content of n-decyl / isotridecyl phthalate in plasticizer A2 was measured in the same manner as for plasticizer A1, but the chromatogram peaks overlapped, making it impossible to measure the content.

[0073] 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. The results are shown in Table 1.

[0074]

[0075] (Production of Plasticizer B) Production Example 4 (Production of Plasticizer B1) Into a 1 L four-neck flask were added 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, trade name: Lunac 8-98), 201.4 g (1.17 mol) of decanoic acid (manufactured by Kao Corporation, trade name: Lunac 10-98), and 0.28 g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), which were mixed, heated, and maintained at 230°C under atmospheric pressure for 5.5 hours to carry out a reaction while distilling off water. After completion of the reaction, the mixture was cooled to 90°C, and 11.6 g of distilled water was added, followed by stirring at 90°C for 1 hour. Thereafter, the temperature was raised to 245 ° C., and under reduced pressure conditions of about 400 Pa (absolute pressure), excess fatty acids were distilled off, and then the mixture was returned to normal pressure and cooled to 90 ° C., and suction filtered using filter paper covered with a filter aid to obtain plasticizer B1 as an isosorbide diester mixture. The theoretical content of isosorbide (octanoic acid / decanoic acid) diester, which is the isosorbide diester (b1) in plasticizer B1, calculated from the respective molar concentrations relative to the total of octanoic acid and decanoic acid used, was 49.9% by mass, and the actual measured value of the content of isosorbide (octanoic acid / decanoic acid) diester in plasticizer B1 by gas chromatography was 50.4%. Note that the measurement by gas chromatography was carried out under the same conditions as for plasticizer A1.

[0076] 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 replaced with 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 plasticizer B2, calculated from the molar concentrations of the octanoic acid and decanoic acid relative to the total amount of the octanoic acid and decanoic acid used, was 19.7 mass%, and the actual content of the isosorbide (octanoic acid / decanoic acid) diester in plasticizer B2 measured by gas chromatography was 18.5%. Note that the gas chromatography measurement was performed under the same conditions as for plasticizer A1.

[0077] 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 isosorbide (octanoic acid / decanoic acid) diester, which is the isosorbide diester (b1) in plasticizer B3, calculated from the molar concentrations of the octanoic acid and decanoic acid relative to the total amount, was 29.9 mass%, and the actual content of isosorbide (octanoic acid / decanoic acid) diester in plasticizer B3 measured by gas chromatography was 31.7%. Note that the gas chromatography measurement was performed under the same conditions as for plasticizer A1.

[0078] 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 274.6 g (1.90 mol) of octanoic acid was used instead of octanoic acid and decanoic acid.

[0079] 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.

[0080]

[0081] [Production of Plasticizer Compositions] Example 1 (Production of Plasticizer Composition 1) 50.0 g of Plasticizer A1 and 50.0 g of Plasticizer B1 were weighed out and mixed until visually homogeneous, thereby obtaining Plasticizer Composition 1.

[0082] Examples 2 to 8 and Comparative Examples 1 to 7 (Production of Plasticizer Compositions 2 to 8 and 11 to 17) Plasticizer compositions 2 to 8 and 11 to 17 were obtained in the same manner as in Example 1, except that the types and blending ratios of plasticizer A and plasticizer B were changed as shown in Table 3. In Table 3, didecyl phthalate (manufactured by Kao Corporation, product name: Vinicizer 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.

[0083]

[0084] [Production of Halogen-Based Resin Compositions] 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-Dai-Ichi Vinyl Corporation, product name: ZEST1400) was 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: Adekastab 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. The mixture was then kneaded using a 4-inch open-roll kneader (manufactured by Nishimura Machinery Co., Ltd.) at a rotation speed of 17 rpm and 170°C 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, then pressed 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.

[0085] [Measurement] [Evaluation of heat resistance] A molded sheet of each halogen-based resin composition was punched out into a No. 3 dumbbell shape as specified in JIS K6251:2017, and the test piece was placed in a gear aging tester (manufactured by Ueshima Seisakusho Co., Ltd., product name: AG-103) as specified in JIS K 7212:1999 at 100°C for 100 hours, after which the mass loss rate (%) was measured. The closer the value is to zero, the better the heat resistance. The results are shown in Table 4.

[0086]

[0087] As shown in Table 4, the plasticizer composition of the present invention exhibits excellent heat resistance when used in a halogen-based resin composition. Furthermore, a comparison of the results of Example 9 with those of Examples 10 and 11 reveals that increasing the content of plasticizer A in the plasticizer composition improves the heat resistance of the halogen-based resin composition. Furthermore, a comparison of the results of Example 9 with those of Examples 12 and 13 reveals that increasing the content of plasticizers b1 and b2, which contain a large number of decanoic acid-derived groups in plasticizer B, improves the heat resistance of the halogen-based resin composition. Meanwhile, a comparison of the results of Example 9 with those of Examples 14 to 16 reveals that the type of plasticizer A does not significantly affect the heat resistance of the halogen-based resin composition. Meanwhile, the halogen-based resin composition 11 of Comparative Example 8, which used plasticizer composition 11 containing di-n-hexyl phthalate (plasticizer A11) and isosorbide dioctanoate (plasticizer B11), exhibited significantly inferior heat resistance. Furthermore, the halogen-based resin composition 12 of Comparative Example 9, which used plasticizer composition 12 containing plasticizer A1 and isosorbide didecanoate (plasticizer B12), the halogen-based resin composition 13 of Comparative Example 10, which used plasticizer composition 13 containing plasticizer A1 and isosorbide dioctanoate (plasticizer B11), and the halogen-based resin composition 14 of Comparative Example 11, which used plasticizer composition 14 containing plasticizer A1 and isosorbide dioctanoate (plasticizer B11) and isosorbide didecanoate (plasticizer B12), all had poor heat resistance. Furthermore, the halogen-based resin composition 15 of Comparative Example 12, which used plasticizer composition 15 containing di-n-hexyl phthalate (plasticizer A11) and plasticizer B1, the halogen-based resin composition 16 of Comparative Example 13, which used plasticizer composition 16 containing di-n-hexyl phthalate (plasticizer A11) and plasticizer B2, and the halogen-based resin composition 17 of Comparative Example 14, which used plasticizer composition 17 containing di-n-hexyl phthalate (plasticizer A11) and plasticizer B3, all had extremely poor heat resistance. From a comparison with the results of Examples 1, 14, and 15, it can be seen that the R １ and R ２ It 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

DEPCT6920 / 03 / 25691. Plasticizer components: plasticizer A containing phthalic acid diester represented by general formula (I); and plasticizer B containing isosorbide diester (b1) represented by general formula (II): [Formula 1](Chemical Formula)(I) in general formula (I), each R1 and R2 are straight-chain or branched-chain alkyl groups of 8 or more carbon atoms and 14 or fewer carbon atoms, and are identical or different, [Formula 2](Chemical Formula)(II) in general formula (II), each R3 and R4 are groups 1. A straight-chain or branched alkyl group of varying carbon atoms.

2. A plasticizer component according to claim 1, in which the isosorbide diester (b1) represented by general formula (II), each R3 and R4 is a straight-chain or branched alkyl group of 7 or more carbon atoms and 9 or fewer carbon atoms.

3. A plasticizer component according to claim 1 or 2, in which the isosorbide diester (b1) represented by general formula (II) is an isosorbide (octanoic acid / decanoic acid) diester. 4.A plasticizer composition under one of the claims 1 through 3, where plasticizer B also contains an isosorbide diester (b2) substituted by general formula (III), and the amount of isosorbide diester (b1) in plasticizer B is 10 percent by mass or more: [Formula 3](Chemical formula)(III) In general formula (III), each R5 and R6 is a straight-chain or branched-chain alkyl group of equal number of carbon atoms.

5. A plasticizer composition under claim 4, where in the isosorbide diester (b2) substituted by General formula(III), R5 and R6 each represent a straight-chain or branched-chain alkyl groups of 7 or more carbon atoms and 9 or fewer carbon atoms.

6. A plasticizer composition according to one of the claims 1 through 5, in which the mass ratio of plasticizer A to plasticizer B (plasticizer A / plasticizer B) is 5 / 95 or more and 85 / 15 or less.

7. A halogen-based resin composition incorporating one of the plasticizer compositions of claims 1 through 6. 8.Methods for the production of plasticizer components, consisting of a mixture of phthalic acid diesters represented by general formula (I); and plasticizer B containing isosorbide diesters (b1) represented by general formula (II): [Formula 1](Chemical Formula)(I) in general formula (I), each R1 and R2 is a straight-chain or branched alkyl group with 8 or more carbon atoms and 14 or fewer carbon atoms, and are identical or different; [Formula 2](Chemical Formula)(II) in general formula (II), each R3 and R4 is a straight-chain or branched alkyl group with different numbers of carbon atoms.

9. Methods for the production The method for producing the plasticizer composition according to claim 8, which consists of an esterified isosorbide and a carboxylic acid feedstock containing at least two aliphatic carboxylic acids of straight or branched chain with different carbon counts to obtain plasticizer B10. The method for producing the plasticizer composition according to claim 9, where the aliphatic carboxylic acids of straight or branched chain with different carbon counts are aliphatic carboxylic acids of straight or branched chain with 8 or more carbon atoms and 10 or fewer carbon atoms.11.Methods for the production of plasticizer components under claim 10, where aliphatic carboxylic acids of the straight or branched chain with 8 or more carbon atoms and 10 or fewer carbon atoms are octanoic acids and decanoic acids; 12. Methods for the production of plasticizer components under claim 10 or 11, where the molar ratio of aliphatic carboxylic acids of the straight or branched chain with 8 carbon atoms to aliphatic carboxylic acids of the straight or branched chain with 10 or fewer carbon atoms is octanoic acid and decanoic acid.

13. A method for the production of plasticizer components under any of the claims 8 to 12, which involves the esterification of phthalic acid raw materials and alcohol raw materials containing aliphatic alcohols of the straight-chain or branched-chain type with 8 or more carbon atoms and 14 or fewer carbon atoms, in order to obtain plasticizer A14.Methods for the production of plasticizer components according to claim 13, where the molar ratio of straight-chain aliphatic alcohol to branched-chain aliphatic alcohol in the alcohol raw material (straight-chain aliphatic alcohol / branched-chain aliphatic alcohol) is 70 / 30 or more and 100 / 0 or less;