Plasticizer composition

Abstract

The present invention provides a plastic resin composition that can impart excellent low-temperature flexibility and heat resistance to a halogen-based resin composition by using the composition. [Solution] The present invention provides a plasticizer composition comprising a specific phthalate diester A and a specific fatty acid ester B, wherein the mass ratio of the amount of phthalate diester A to the amount of fatty acid ester B (phthalate diester A / fatty acid ester B) is greater than 90 / 10 and 99.9 / 0.1 or less; a halogen-based resin composition comprising the plasticizer composition; and a method for producing a plasticizer composition, which comprises a step of mixing the specific phthalate diester A and the specific fatty acid ester B, wherein the mass ratio of the amount of phthalate diester A to the amount of fatty acid ester B (phthalate diester A / fatty acid ester B) is greater than 90 / 10 and 99.9 / 0.1 or less.

Description

[Technical Field]

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

[0002] Halogenated resins such as polyvinyl chloride (PVC) are important general-purpose polymers used in a wide range of fields. For example, halogenated resins are used in various applications such as wallpaper and other interior furnishings; toys and other general-purpose products; and automotive materials such as sealants, as well as in rigid PVC and flexible PVC. When using halogen-based resins, for example, a halogen-based resin composition is prepared by blending a plasticizer, diluent, viscosity reducer, filler such as calcium carbonate, pigment, flame retardant, foaming agent, stabilizer, etc., with the resin powder of the halogen-based resin.

[0003] For example, Patent Document 1 discloses a plasticizer for halogenated resins containing a didecyl phthalate mixture having a linear or branched alkyl group having 10 carbon atoms, wherein the content of di-n-decyl phthalate in the didecyl phthalate mixture is 48 mol% or more and 70 mol% or less. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application No. 2018-042114 [Overview of the project] [Problems that the invention aims to solve]

[0005] Sheet products manufactured from halogen-based resin compositions (for example, leather seats made from soft PVC-containing compositions used in car seats and sofas) sometimes develop a white appearance due to repeated loading, which is known as glaze. Halogen-based resin compositions tend to lose flexibility in low-temperature environments, and repeated loading in low-temperature environments tends to cause whitening. Therefore, to prevent whitening, it is necessary to improve the flexibility of halogen-based resin compositions, and in particular, to improve flexibility at low temperatures (low-temperature flexibility). Furthermore, the plasticizers contained in halogen-based resin compositions volatilize from the surface of the halogen-based resin composition at high temperatures, which can lead to hardening or cracking of the halogen-based resin composition due to the volatilization of the plasticizers. Therefore, plasticizers used in halogen-based resin compositions are required to have heat resistance, meaning they do not volatilize easily even at high temperatures. The present invention relates to a plasticizer composition that, when used in a halogen-based resin composition, can impart excellent low-temperature flexibility and heat resistance, a halogen-based resin composition using the plasticizer composition, and a method for producing the plasticizer composition.

[0006] The present inventors have found that a plasticizer composition containing phthalate diester A and fatty acid ester B in a specific mass ratio can solve the above problem. The present invention relates to the following [1] to [3]. [1] A plasticizer composition comprising a phthalate diester A represented by general formula (I) (hereinafter also referred to as "phthalate diester A") and a fatty acid ester B represented by general formula (II) (hereinafter also referred to as "fatty acid ester B"), wherein the mass ratio of the content of phthalate diester A to the content of fatty acid ester B (phthalate diester A / fatty acid ester B) is greater than 90 / 10 and 99.9 / 0.1 or less. [ka] (In general formula (I), R 1 and R 2is a linear alkyl group having 10 to 14 carbon atoms or a branched alkyl group having 10 to 14 carbon atoms, which may be the same or different from each other. [Chemical formula] (In General Formula (II), R 3 is a linear alkyl group having 5 to 14 carbon atoms or a branched alkyl group having 5 to 14 carbon atoms, and R 4 is a linear alkyl group having 14 to 24 carbon atoms or a branched alkyl group having 14 to 24 carbon atoms, or a linear alkenyl group having 14 to 24 carbon atoms or a branched alkenyl group having 14 to 24 carbon atoms. [2] A halogen-based resin composition containing the plasticizer composition described in [1] above. [3] A method for producing a plasticizer composition, which includes a step of mixing a phthalic acid diester A represented by General Formula (I) and a fatty acid ester B represented by General Formula (II), and the mass ratio of the blending amount of phthalic acid diester A to the blending amount of fatty acid ester B (phthalic acid diester A / fatty acid ester B) is more than 90 / 10 and 99.9 / 0.1 or less. [Chemical formula] (In General Formula (I), R [[ID= 23]] 1 and R 2 are each a linear alkyl group having 10 to 14 carbon atoms or a branched alkyl group having 10 to 14 carbon atoms, which may be the same or different from each other. [Chemical formula] (In General Formula (II), R 3 is a linear alkyl group having 5 to 14 carbon atoms or a branched alkyl group having 5 to 14 carbon atoms, and R 4 is a linear alkyl group having 14 to 24 carbon atoms or a branched alkyl group having 14 to 24 carbon atoms, or a linear alkenyl group having 14 to 24 carbon atoms or a branched alkenyl group having 14 to 24 carbon atoms.

[0007] According to the present invention, there can be provided a plasticizer composition capable of imparting excellent low-temperature flexibility and heat resistance when used in a halogen-based resin composition, a halogen-based resin composition using the plasticizer composition, and a method for producing the plasticizer composition.

[0008] [Plasticizer composition] The plasticizer composition of the present invention contains [1] a phthalic acid diester A represented by the general formula (I) and a fatty acid ester B represented by the general formula (II), and the mass ratio of the content of the phthalic acid diester A to the content of the fatty acid ester B (phthalic acid diester A / fatty acid ester B) is more than 90 / 10 and 99.9 / 0.1 or less.

[0009] [Chemical formula] (In the general formula (I), R 1 and R 2 are each independently a linear alkyl group having from 10 to 14 carbon atoms or a branched alkyl group having from 10 to 14 carbon atoms, which may be the same or different from each other.)

[0010] [Chemical formula] (In the general formula (II), R 3 is a linear alkyl group having from 5 to 14 carbon atoms or a branched alkyl group having from 5 to 14 carbon atoms, and R 4 is a linear alkyl group having from 14 to 24 carbon atoms or a branched alkyl group having from 14 to 24 carbon atoms, or a linear alkenyl group having from 14 to 24 carbon atoms or a branched alkenyl group having from 14 to 24 carbon atoms.)

[0011] The plasticizer composition of the present invention can impart excellent low-temperature flexibility and heat resistance when used in a halogen-based resin composition. The reason for such an effect is not clear, but it is considered as follows. The plasticizer composition of the present invention, by containing phthalate diester A, is thought to impart low-temperature flexibility to the resulting halogen-based resin composition without impairing its heat resistance. Furthermore, the plasticizer composition of the present invention, by containing fatty acid ester B, is thought to further improve the low-temperature flexibility of the resulting halogen-based resin composition. Furthermore, the plasticizer composition of the present invention can be made to have excellent low-temperature flexibility and heat resistance in the resulting halogen-based resin composition if the mass ratio of the content of phthalate diester A to the content of fatty acid ester B (phthalate diester A / fatty acid ester B) is greater than 90 / 10 and less than or equal to 99.9 / 0.1.

[0012] In the present invention, the mass ratio of the content of phthalate diester A to the content of fatty acid ester B (phthalate diester A / fatty acid ester B) is greater than 90 / 10, preferably 91 / 9 or more, more preferably 92 / 8 or more, even more preferably 94 / 6 or more, even more preferably 95.5 / 4.5 or more, and even more preferably 96.5 / 3.5 or more, and from the viewpoint of improving the heat resistance of the halogen-based resin composition, it is 99.9 / 0.1 or less, preferably 99.5 / 0.5 or less, more preferably 99 / 1 or less, even more preferably 98 / 2 or less, even more preferably 97.5 / 2.5 or less, even more preferably 97 / 3 or less, and even more preferably 96.5 / 3.5 or less. The mass ratio of the content of phthalate diester A to the content of fatty acid ester B (phthalate diester A / fatty acid ester B) is preferably 91 / 9 to 99.9 / 0.1, more preferably 91 / 9 to 99.5 / 0.5, even more preferably 91 / 9 to 99 / 1, and even more preferably 91 / 9 to 98 / 2, from the viewpoint of achieving both improved heat resistance and improved low-temperature flexibility of the halogenated resin composition. Furthermore, the mass ratio of the content of phthalate diester A to the content of fatty acid ester B (phthalate diester A / fatty acid ester B) is preferably 91 / 9 to 99.9 / 0.1, more preferably 92 / 8 to 99.5 / 0.5, even more preferably 94 / 6 to 99 / 1, and even more preferably 95.5 / 4.5 to 99 / 1, from the viewpoint of improving the heat resistance of the halogenated resin composition. Furthermore, the mass ratio of the content of phthalate diester A to the content of fatty acid ester B (phthalate diester A / fatty acid ester B) is preferably 91 / 9 to 99 / 1, more preferably 91 / 9 to 98 / 2, even more preferably 92 / 8 to 97.5 / 2.5, even more preferably 94 / 6 to 97 / 3, and even more preferably 94 / 6 to 96.5 / 3.5, from the viewpoint of improving the low-temperature flexibility of the halogenated resin composition.

[0013] <Diester Phthalate A> In the present invention, phthalate diester A has a structure represented by the above general formula (I). Phthalate diester A may be a single type or a mixture of two or more types, but from the viewpoint of improving the low-temperature flexibility of the halogen-based resin composition, a mixture of two or more types is preferred.

[0014] In phthalate diester A, R in general formula (I) 1 and R 2 These are linear alkyl groups having 10 to 14 carbon atoms or branched alkyl groups having 10 to 14 carbon atoms, which may be the same or different from each other.

[0015] (linear alkyl group) R 1 and R 2 In this composition, the linear alkyl group having 10 to 14 carbon atoms is preferably a linear alkyl group having 11 to 14 carbon atoms, from the viewpoint of improving the heat resistance of the halogen-based resin composition. Furthermore, from the viewpoint of improving compatibility with the halogen-based resin, it is preferable to include a linear alkyl group having 10 carbon atoms.

[0016] The linear alkyl group having 11 to 14 carbon atoms is preferably one or more selected from n-undecyl, n-dodecyl, n-tridecyl, and n-tetradecyl groups. Among these, the linear alkyl group having 11 to 12 carbon atoms is more preferably a linear alkyl group having 11 to 12 carbon atoms, and even more preferably an n-dodecyl group, from the viewpoint of improving the heat resistance of the halogen-based resin composition and improving compatibility with the halogen-based resin.

[0017] Examples of linear alkyl groups having 10 carbon atoms include n-decyl groups, and it is preferable to include a linear alkyl group having 10 carbon atoms from the viewpoint of improving compatibility with halogen-based resins.

[0018] (Branched alkyl group) The branched alkyl groups in R1 and R2 are preferably one or more selected from 2-propylheptyl group, 2-butyloctyl group, isodecyl group, isoundecyl group, isododecyl group, isotridecyl group, and isotetradecyl group. Here, "iso-" refers to a structure in which a methyl group is branched at the end of the alkyl group. Among these, the carbon number is between 10 and 14. Branched As for the alkyl group, from the viewpoint of improving compatibility with halogen-based resins, it is more preferable to have 10 to 12 carbon atoms. Branched It is an alkyl group, and more preferably a 2-propylheptyl group.

[0019] (Composition of phthalate diester A) In the present invention, when phthalate diester A is a mixture of two or more types, the R in general formula (I) in the total amount of phthalate diester A 1 and R 2The content of the phthalate diester, in which at least one of the atoms is a linear alkyl group having 10 to 14 carbon atoms, is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more, from the viewpoint of improving the heat resistance of the halogen-based resin composition, and preferably 90 mol% or less, even more preferably 88 mol% or less, and even more preferably 86 mol% or less, from the viewpoint of improving compatibility with the halogen-based resin.

[0020] In the present invention, when phthalate diester A is a mixture of two or more types, the R in general formula (I) in the total amount of phthalate diester A 1 and R 2 The content of phthalate diesters, both of which are linear alkyl groups having 10 to 14 carbon atoms, is preferably 20 mol% or more, more preferably 25 mol% or more, and even more preferably 30 mol% or more, from the viewpoint of improving the heat resistance of the halogen-based resin composition, and preferably 50 mol% or less, even more preferably 45 mol% or less, and even more preferably 40 mol% or less, from the viewpoint of improving compatibility with the halogen-based resin.

[0021] In the present invention, when phthalate diester A is a mixture of two or more types, the R in general formula (I) in the total amount of phthalate diester A 1 and R 2 The content of phthalate diesters in which at least one of the atoms is a linear alkyl group having 11 to 14 carbon atoms is preferably 50 mol% or more, more preferably 55 mol% or more, even more preferably 60 mol% or more, even more preferably 65 mol% or more, even more preferably 70 mol% or more, even more preferably 75 mol% or more, and even more preferably 78 mol% or more, and from the viewpoint of improving the heat resistance of the halogen-based resin composition, it is preferably 95 mol% or less, more preferably 90 mol% or less, even more preferably 85 mol% or less, even more preferably 83 mol% or less, and even more preferably 80 mol% or less.

[0022] In the present invention, when phthalate diester A is a mixture of two or more types, the R in general formula (I) in the total amount of phthalate diester A 1 and R 2 The content of phthalate diesters, both of which are linear alkyl groups having 11 to 14 carbon atoms, is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 12 mol% or more, even more preferably 15 mol% or more, even more preferably 18 mol% or more, even more preferably 20 mol% or more, even more preferably 23 mol% or more, even more preferably 25 mol% or more, and even more preferably 28 mol% or more, and from the viewpoint of improving compatibility with halogenated resins, it is preferably 55 mol% or less, more preferably 50 mol% or less, even more preferably 45 mol% or less, even more preferably 40 mol% or less, even more preferably 35 mol% or less, and even more preferably 30 mol% or less.

[0023] In the present invention, when phthalate diester A is a mixture of two or more types, the R in general formula (I) in the total amount of phthalate diester A 1 and R 2 The content of the phthalate diester, in which at least one of the atoms is a linear alkyl group having 10 carbon atoms, is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, from the viewpoint of improving compatibility with halogen-based resins, and from the viewpoint of improving the heat resistance of the halogen-based resin composition, it is preferably 30 mol% or less, more preferably 25 mol% or less, even more preferably 20 mol% or less, even more preferably 15 mol% or less, even more preferably 10 mol% or less, even more preferably 5 mol% or less, and even more preferably 0 mol%.

[0024] In the present invention, when phthalate diester A is a mixture of two or more types, the R in general formula (I) in the total amount of phthalate diester A 1 and R 2The content of the phthalate diester, in which both are linear alkyl groups having 10 carbon atoms, is preferably 0.5 mol% or more, more preferably 0.8 mol% or more, and even more preferably 1 mol% or more, from the viewpoint of improving compatibility with halogen-based resins, and from the viewpoint of improving the heat resistance of the halogen-based resin composition, it is preferably 10 mol% or less, more preferably 5 mol% or less, even more preferably 3 mol% or less, even more preferably 2 mol% or less, even more preferably 1 mol% or less, and even more preferably 0 mol%.

[0025] In the present invention, when phthalate diester A is a mixture of two or more types, the R in general formula (I) in the total amount of phthalate diester A 1 and R 2 At least one of them has 10 carbon atoms Branched The content of the alkyl group, which is a phthalic acid diester, is preferably 50 mol% or more, more preferably 55 mol% or more, and even more preferably 60 mol% or more, from the viewpoint of improving compatibility with halogen-based resins, and from the viewpoint of improving the low-temperature flexibility of the halogen-based resin composition, it is preferably 80 mol% or less, more preferably 75 mol% or less, and even more preferably 70 mol% or less.

[0026] In the present invention, when phthalate diester A is a mixture of two or more types, the R in general formula (I) in the total amount of phthalate diester A 1 and R 2 The content of the phthalic acid diester, in which both are branched alkyl groups having 10 carbon atoms, is preferably 5 mol% or more, more preferably 10 mol% or more, and more preferably 15 mol% or more, from the viewpoint of improving compatibility with halogen-based resins, and preferably 30 mol% or less, more preferably 25 mol% or less, and even more preferably 20 mol% or less, from the viewpoint of improving the low-temperature flexibility of the halogen-based resin composition.

[0027] <Fatty acid ester B> In the present invention, fatty acid ester B has a structure represented by the above general formula (II). Fatty acid ester B may be a single type or a mixture of two or more types.

[0028] In fatty acid ester B, R in general formula (II) 3 R is a linear alkyl group having 5 to 14 carbon atoms or a branched alkyl group having 5 to 14 carbon atoms, 4 This is a linear alkyl group having 14 to 24 carbon atoms, a branched alkyl group having 14 to 24 carbon atoms, or a linear alkenyl group having 14 to 24 carbon atoms, or a branched alkenyl group having 14 to 24 carbon atoms. In fatty acid ester B, R in general formula (II) 3 From the viewpoint of improving the low-temperature flexibility of the halogen-based resin composition, it is preferably a linear alkyl group having 6 to 12 carbon atoms, or a branched alkyl group having 6 to 12 carbon atoms, and more preferably a linear alkyl group having 8 to 12 carbon atoms. In addition, in fatty acid ester B, R in general formula (II) 4 From the viewpoint of improving the low-temperature flexibility of the halogen-based resin composition, the linear alkyl group having 16 to 22 carbon atoms is preferred, more preferably a linear alkenyl group having 16 to 22 carbon atoms, and even more preferably a linear alkenyl group having 16 to 20 carbon atoms. In other words, in fatty acid ester B, preferably R in general formula (II) 3 R is a linear alkyl group having 6 to 12 carbon atoms, or a branched alkyl group having 6 to 12 carbon atoms, 4 is a linear alkyl group having 14 to 24 carbon atoms, or a linear alkenyl group having 16 to 22 carbon atoms, more preferably R in general formula (II). 3 R is a linear alkyl group having 6 to 12 carbon atoms, or a branched alkyl group having 6 to 12 carbon atoms, 4 is a linear alkenyl group having 16 to 22 carbon atoms, and more preferably R in general formula (II). 3 R is a linear alkyl group having 6 to 12 carbon atoms, 4 is a linear alkenyl group having 16 to 22 carbon atoms, and more preferably R in general formula (II). 3 R is a linear alkyl group having 8 to 12 carbon atoms,4 This is a linear alkenyl group having 16 to 20 carbon atoms.

[0029] Specific examples of fatty acid ester B include saturated fatty acid esters and unsaturated fatty acid esters. Examples of saturated fatty acid esters include octyl stearate, isooctyl stearate, decyl stearate, isodecyl stearate, 2-propylheptyl stearate, octyl palmitate, isooctyl palmitate, decyl palmitate, isodecyl palmitate, 2-propylheptyl palmitate, dodecyl palmitate, and isododecyl palmitate. Examples of unsaturated fatty acid esters include octyl oleate, isooctyl oleate, decyl oleate, isodecyl oleate, 2-propylheptyl oleate, dodecyl oleate, isododecyl oleate, octyl linoleate, isooctyl linoleate, decyl linoleate, isodecyl linoleate, 2-propylheptyl linoleate, octyl linoleate, isooctyl linoleate, decyl linolenate, isodecyl linolenate, 2-propylheptyl linoleate, hexyl erucate, isohexyl erucate, octyl erucate, and isooctyl erucate. Among these, fatty acid ester B is preferably an unsaturated fatty acid ester, more preferably at least one selected from octyl oleate, decyl oleate, and dodecyl oleate, even more preferably at least one selected from octyl oleate and decyl oleate, and even more preferably octyl oleate.

[0030] <Other ingredients> The plasticizer composition of the present invention may also contain other plasticizers that are commonly used as plasticizers for halogen-based resins. Other plasticizers that have high compatibility with halogenated resins include, for example, phthalate ester plasticizers of C1-C9 alcohols such as dimethyl phthalate, diethyl phthalate, and dibutyl phthalate (preferably phthalate ester plasticizers of C1-C7 alcohols); trimellitic acid ester plasticizers of C6-C10 alcohols such as tris(2-ethylhexyl) trimellitic acid, trioctyl trimellitic acid, and tridecyl trimellitic acid; adipic acid ester plasticizers, azelaic acid ester plasticizers, sebatic acid ester plasticizers, phosphate ester plasticizers, polyester plasticizers, epoxy plasticizers, fatty acid ester plasticizers other than the above fatty acid ester B, pyromellitic acid ester plasticizers, and the like.

[0031] The total content of phthalate diester A and fatty acid ester 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, preferably 100% by mass or less, and more preferably 100% by mass or less, from the viewpoint of improving compatibility with halogen-based resins and improving the low-temperature flexibility and heat resistance of halogen-based resin compositions.

[0032] [Halogenated resin composition] The halogen-based resin composition of the present invention comprises the plasticizer composition of the present invention described above, and more specifically, comprises the plasticizer composition of the present invention described above and a halogen-based resin.

[0033] In the present invention, a halogenated resin means a monomer homopolymer, copolymer, or halogen-modified polymer containing a halogen. Examples of halogenated resins, from the viewpoint of availability, include vinyl chloride resins such as vinyl chloride resin, ethylene-vinyl chloride copolymer, vinyl acetate-vinyl chloride copolymer, and polyurethane-grafted polyvinyl chloride copolymer, as well as vinylidene chloride resin, chlorinated polyethylene, chlorinated polypropylene, chlorosulfonated polyethylene, and chloroprene rubber. Examples of halogenated resins, from the viewpoint of flexibility, include vinyl chloride resin, vinylidene chloride, and chloroprene rubber. The halogenated resin composition of the present invention preferably contains one or more selected from vinyl chloride resin, vinylidene chloride resin, and chloroprene rubber.

[0034] <Vinyl chloride resin> Examples of vinyl chloride resins include vinyl chloride homopolymers (vinyl chloride resins), copolymers of vinyl chloride with copolymerizable monomers (hereinafter also referred to as "vinyl chloride copolymers"), and graft copolymers obtained by graft copolymerizing vinyl chloride with polymers other than the vinyl chloride copolymer. The monomers copolymerizable with vinyl chloride mentioned above can be any monomer having a reactive double bond in its molecule, from the viewpoint of ease of copolymerization. Examples 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; esters of (meth)acrylic acid 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, as polymers other than vinyl chloride copolymers, any polymer that can graft copolymerize vinyl chloride is acceptable, from the viewpoint of ease of availability. Examples 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, and polyurethane.

[0035] <Additives> The halogenated resin composition may optionally contain additives such as basic inorganic fillers, stabilizers, processing aids, colorants, antioxidants, ultraviolet absorbers, antistatic agents, and lubricants, to the extent that the effects of the present invention are not impaired.

[0036] Examples of basic inorganic fillers include calcium carbonate, talc, calcium silicate, and alumina. A single basic inorganic filler may be used, or two or more may be mixed. Preferably, the basic inorganic filler contains calcium carbonate from an economic standpoint.

[0037] 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, from the viewpoint of reducing the cost of the halogen-based resin composition, per 100 parts by mass of the halogen-based resin.

[0038] 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 dimethyl tin bis-2-ethylhexyl thioglycolate, dibutyl tin maleate, dibutyl tin bis-butyl maleate, and dibutyl tin dilaurate; and antimony mercaptide compounds. The stabilizer content is 0.1 to 20 parts by mass per 100 parts by mass of halogenated resin.

[0039] Examples of processing aids include liquid paraffin, polyethylene wax, stearic acid, stearate amide, ethylenebisstearate amide, butyl stearate, and calcium stearate. The content of the processing aid is 0.1 to 20 parts by mass per 100 parts by mass of halogenated resin.

[0040] Examples of colorants include carbon black, lead sulfide, white carbon, titanium white, lithopone, red iron oxide, antimony sulfide, chromium yellow, chromium green, cobalt blue, and molybdenum orange. The colorant content is 1 to 100 parts by mass per 100 parts by mass of halogen-based resin.

[0041] 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; sulfuric compounds such as alkyl disulfides, thiodipropionates, and benzothiazoles; 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 antioxidant content is 0.2 to 20 parts by mass per 100 parts by mass of halogenated resin.

[0042] Examples of UV absorbers 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 UV absorber content is 0.1 to 10 parts by mass per 100 parts by mass of halogenated resin.

[0043] 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 and alkyldimethylbenzyl type, and organic acid salts or hydrochlorides of the alkylpyridinium type; and amphoteric antistatic agents such as alkyl betaine type and alkylimidazoline type. The content of the antistatic agent is 0.1 to 10 parts by mass per 100 parts by mass of halogenated resin.

[0044] Examples of lubricants include silicones, liquid paraffins, paraffin waxes, fatty acids such as stearic acid and lauric acid and their metal salts, fatty acid amides, fatty acid waxes, and higher fatty acid waxes. The lubricant content is 0.1 to 10 parts by mass per 100 parts by mass of halogenated resin.

[0045] The halogen-based resin composition of the present invention is useful as an interior decorative agent for vehicles such as instrument panel surfaces, leather seats, and wire harnesses; as an adhesive, sealant, paint, plastisol, foam, synthetic leather, pipes such as water pipes, building materials, wallpaper, flooring, floor coverings, insulation materials, roofing membranes, and other interior building materials; as a packaging material such as food packaging film; as an agricultural material such as agricultural film; as an automotive-related material such as sealing material and undercoat material; as a substrate protection material, fabric covering material, wire covering material, 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.

[0046] <Method for producing halogenated resin compositions> The method for producing the halogenated resin composition of the present invention includes the step of mixing a plasticizer composition, a halogenated resin, and various additives as needed. The mixing of the plasticizer composition may involve mixing a plasticizer composition containing phthalate diester A and fatty acid ester B, or by using phthalate diester A and fatty acid ester B separately and mixing them so that the resulting halogenated resin composition contains a plasticizer composition containing phthalate diester A and fatty acid ester B. If the halogenated resin composition contains various additives, the mixing of the plasticizer composition, halogenated resin, and various additives may involve adding them all at once, or mixing each component sequentially. Halogenated resin compositions can be prepared by mixing a plasticizer composition, a halogenated resin, and various additives as needed using a stirrer such as a mortar mixer, lab mixer, Henschel mixer, Banbury mixer, or ribbon blender to obtain a mixed powder of halogenated resin compositions. Alternatively, halogenated resin compositions can be obtained in the form of mixed powder, pellets, or paste by melt molding using a kneader such as a conical twin-screw extruder, parallel twin-screw extruder, single-screw extruder, cone-type kneader, or roll kneader. The mixing and melt molding conditions can be any conditions used in a typical halogen-based resin composition manufacturing method.

[0047] Mixed powders or pellets of halogen-based resin compositions can be molded into desired shapes by known methods such as extrusion molding, injection molding, calendering, press molding, and blow molding. Furthermore, paste-like halogen-based resin compositions can be molded into desired shapes by known methods such as spread molding, dipping molding, gravure molding, and screen molding.

[0048] [Method for producing plasticizer compositions] The method for producing the plasticizer composition of the present invention comprises a step of mixing a phthalate diester A represented by the above general formula (I) and a fatty acid ester B represented by the above general formula (II), wherein the mass ratio of the amount of phthalate diester A to the amount of fatty acid ester B (phthalate diester A / fatty acid ester B) is greater than 90 / 10 and 99.9 / 0.1 or less. The mixture of phthalate diester A and fatty acid ester B may be made by adding fatty acid ester B to phthalate diester A and mixing, or by adding phthalate diester A to fatty acid ester B and mixing. If the plasticizer composition contains the above-mentioned other components, the above-mentioned other components may be added to a mixture of fatty acid ester B and fatty acid ester B and mixed, or each component may be mixed sequentially. A plasticizer composition can be prepared by mixing phthalate diester A, fatty acid ester B, and other components as needed using a stirrer such as a hand mixer, lab mixer, mortar mixer, Henschel mixer, Banbury mixer, or ribbon blender.

[0049] In the method for producing the plasticizer composition of the present invention, phthalate diester A is obtained by esterifying a phthalate raw material with an alcohol raw material containing a linear aliphatic alcohol having 10 to 14 carbon atoms or a branched aliphatic alcohol having 10 to 14 carbon atoms.

[0050] (Phthalic acid raw material) Examples of phthalic acid raw materials for phthalic acid diester A include phthalic acid, phthalic anhydride, phthalic acid esters such as dimethyl phthalate, etc. However, from the viewpoint of availability and productivity, one or more selected from phthalic acid and phthalic anhydride are preferred, and phthalic anhydride is more preferred.

[0051] (Alcohol raw material) In the present invention, the alcohol raw material for phthalate diester A includes a linear aliphatic alcohol having 10 to 14 carbon atoms or a branched aliphatic alcohol having 10 to 14 carbon atoms.

[0052] [Linear aliphatic alcohols] From the viewpoint of improving the heat resistance of the halogenated resin composition, it is preferable to include a linear aliphatic alcohol having 11 to 14 carbon atoms as the linear aliphatic alcohol having 10 to 14 carbon atoms. Furthermore, from the viewpoint of improving compatibility with the halogenated resin, it is preferable to include a linear aliphatic alcohol having 10 carbon atoms.

[0053] Preferably, the linear aliphatic alcohol having 11 to 14 carbon atoms is one or more selected from 1-undecanol, 1-dodecanol, 1-tridecanol, and 1-tetradecanol. Among these, the linear aliphatic alcohol having 11 to 12 carbon atoms is more preferably a linear aliphatic alcohol having 11 to 12 carbon atoms, and even more preferably 1-dodecanol, from the viewpoint of improving the heat resistance of the halogen-based resin composition and improving compatibility with the halogen-based resin.

[0054] Examples of linear aliphatic alcohols having 10 carbon atoms include 1-decanol, and it is preferable to include a linear aliphatic alcohol having 10 carbon atoms from the viewpoint of improving compatibility with halogenated resins.

[0055] [Branched aliphatic alcohols] Preferably, branched aliphatic alcohols having 10 to 14 carbon atoms include one or more selected from 2-propyl-1-heptanol, 2-butyl-1-octanol, isodecanol, isoundecanol, isododecanol, isotridecanol, and isotetradecanol. Among these, branched aliphatic alcohols having 10 to 14 carbon atoms are more preferably branched aliphatic alcohols having 10 to 12 carbon atoms, and even more preferably 2-propyl-1-heptanol, from the viewpoint of improving compatibility with halogenated resins.

[0056] In the present invention, the alcohol raw material for phthalate diester A preferably contains both a linear aliphatic alcohol having 10 to 14 carbon atoms and a branched aliphatic alcohol having 10 to 14 carbon atoms, from the viewpoint of improving compatibility with halogenated resins and improving the low-temperature flexibility and heat resistance of halogenated resin compositions. That is, in the present invention, the alcohol raw material for phthalate diester A preferably contains a linear aliphatic alcohol having 10 to 14 carbon atoms and a branched aliphatic alcohol having 10 to 14 carbon atoms, more preferably contains a linear aliphatic alcohol having 10 carbon atoms, a linear aliphatic alcohol having 11 to 14 carbon atoms and a branched aliphatic alcohol having 10 to 14 carbon atoms, even more preferably contains a linear aliphatic alcohol having 10 carbon atoms, a linear aliphatic alcohol having 11 to 12 carbon atoms and a branched aliphatic alcohol having 10 to 12 carbon atoms, and even more preferably contains 1-decanol, 1-dodecanol, and 2-propyl-1-heptanol. Furthermore, when prioritizing the improvement of the heat resistance of the halogenated resin composition, the alcohol raw material of phthalate diester A preferably contains a linear aliphatic alcohol having 11 to 12 carbon atoms and a branched aliphatic alcohol having 10 to 12 carbon atoms, and more preferably contains 1-dodecanol and 2-propyl-1-heptanol.

[0057] In the present invention, the molar ratio of the amount of linear aliphatic alcohol having 10 to 14 carbon atoms to the amount of branched aliphatic alcohol having 10 to 14 carbon atoms in the alcohol raw material of phthalate diester A (amount of branched aliphatic alcohol / amount of linear aliphatic alcohol) is preferably 50 / 50 or more, more preferably 55 / 45 or more, from the viewpoint of improving compatibility with halogen-based resins, and preferably 70 / 30 or less, more preferably 65 / 35 or less, from the viewpoint of improving the low-temperature flexibility of the halogen-based resin composition and improving the heat resistance of the halogen-based resin composition.

[0058] In the present invention, the amount of linear aliphatic alcohol having 11 to 14 carbon atoms in the alcohol raw material of phthalate diester A is preferably 30 mol% or more, more preferably 35 mol% or more, and even more preferably 40 mol% or more, from the viewpoint of improving the heat resistance of the halogen-based resin composition, and preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less, from the viewpoint of improving compatibility with the halogen-based resin.

[0059] In the present invention, the amount of linear aliphatic alcohol having 10 carbon atoms in the alcohol raw material of phthalate diester A is preferably 3 mol% or more, more preferably 5 mol% or more, and even more preferably 8 mol% or more, from the viewpoint of improving compatibility with halogen-based resins, and from the viewpoint of improving the heat resistance of the halogen-based resin composition, it is preferably 25 mol% or less, more preferably 20 mol% or less, even more preferably 15 mol% or less, even more preferably 10 mol% or less, even more preferably 5 mol% or less, even more preferably 3 mol% or less, and even more preferably 0 mol%.

[0060] In the present invention, the alcohol raw material of phthalate diester A has 10 to 14 carbon atoms. BranchedFrom the viewpoint of improving compatibility with the halogenated resin composition, the amount of aliphatic alcohol blended is preferably 30 mol% or more, more preferably 35 mol% or more, and even more preferably 40 mol% or more. From the viewpoint of heat resistance with the halogenated resin, it is preferably 55 mol% or less, more preferably 50 mol% or less, and even more preferably 45 mol% or less.

[0061] It is preferable that the amount of alcohol raw material charged at the start of the esterification reaction is in excess of the stoichiometric amount. The stoichiometric amount of alcohol raw material in the esterification reaction is the theoretical proportion that produces the phthalate diester, and is twice the molar amount of the phthalate raw material used. In other words, the amount of alcohol raw material added is preferably 2.0 times the amount of phthalic acid raw material or more, more preferably 2.1 times the amount of phthalic acid raw material or more, more preferably 2.2 times the amount of phthalic acid raw material or more, preferably 3.0 times the amount or less, more preferably 2.7 times the amount or less, and more preferably 2.5 times the amount or less, from the viewpoint of promoting the reaction and completing the reaction. It is preferable to keep the water content of the alcohol raw material as low as possible. By keeping the water content of the alcohol raw material as low as possible, it is possible to prevent the water from poisoning the esterification reaction catalyst described later, and to suppress the decrease in catalytic activity.

[0062] In order to obtain phthalate diester A in the present invention, it is preferable to use an esterification reaction catalyst when esterifying the phthalate raw material and the alcohol raw material. As the esterification reaction catalyst, any known esterification catalyst having esterification ability can be used, but an organometallic catalyst is preferred. Examples of organometallic catalysts include one or more selected from organotin compounds such as tin tetraethylate, butylsutsumalate, 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-ethylhexyl oxide are preferred.

[0063] The amount of esterification reaction catalyst used varies depending on the type, but from the viewpoint of fully exhibiting 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, per 100 parts by mass of the total amount of phthalic acid raw material and 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.

[0064] The esterification reaction to obtain phthalate diester A in the present invention can be carried out under reflux of alcohol using a known reaction apparatus equipped with facilities that can reflux the alcohol raw material. The reaction temperature varies depending on the type of alcohol raw material, 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. 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 formation of reaction byproducts. The reaction pressure is usually preferably 13.3 kPa or higher in absolute pressure and below atmospheric pressure. The reaction pressure can be set by the vapor pressure of the alcohol raw material used. Specifically, it is preferable to adjust the pressure to maintain a boiling state in the reaction mixture, and further, to adjust it to a pressure that allows for the removal of by-product water from the system. The reaction time varies depending on the phthalic acid raw material, alcohol raw material, reaction temperature, and amount of catalyst used, 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 burden on the separation step of unreacted phthalic acid raw material and phthalic acid monoester, which is a reaction intermediate, will be 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 formation of by-products can be suppressed and the quality of phthalic acid diester A can be improved. [Examples]

[0065] In the following manufacturing examples, embodiments, and comparative examples, "parts" and "%" refer to "parts by mass" and "mass%" respectively, unless otherwise specified.

[0066] [Manufacturing of plasticizer compositions] Manufacturing Example A1 (Production of Diester Phthalate A1) In a 1L four-necked flask, 148.1g (1.00 mol) of phthalic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as the phthalic acid raw material, 37.0g (0.23 mol) of 1-decanol (manufactured by Kao Corporation, trade name: Calcol 1098), 164.6g (1.04 mol) of 2-propyl-1-heptanol (manufactured by BASF), and 209.9g (1.13 mol) of 1-dodecanol (manufactured by Kao Corporation, trade name: Calcol 2098), along with 0.17g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), were added and mixed. The reaction was carried out at 230°C under atmospheric pressure for 2.5 hours, with water being removed by distillation. After the reaction was complete, the mixture was cooled to 80°C, 11.2g of distilled water was added, and the mixture was stirred at 80°C for 1 hour. Subsequently, the temperature was raised to 215°C, and the excess alcohol was removed by distillation under reduced pressure of approximately 400 Pa. After returning to atmospheric pressure and cooling to 80°C, the mixture was filtered by suction using filter paper lined with a filtration aid to obtain phthalate diester A1. The obtained phthalate diester A1 is shown in Table 1.

[0067] Manufacturing Example A2 (Production of Diester A2 Phthalate) Phthalate diester A2 was obtained in the same manner as in production example A1, except that the amounts of each component were changed to the amounts shown in Table 1.

[0068] <Measurement of the composition of phthalate diester A> The compositions of phthalate diesters A1 and A2 obtained in production examples A1 and A2 were measured by gas chromatography under the following conditions. (Preparation of samples for measurement) Each of the phthalate diesters A1 and A2 obtained in production examples A1 and A2 was dissolved in n-hexane to prepare a 10% by mass hexane solution, which was used as the measurement sample. (Measurement conditions) • Measurement device: Agilent 8890 (gas chromatograph, manufactured by Agilent Technologies, Inc.) • Column: DB-1HT (manufactured by 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: Heat from 100°C → increase at 10°C / min → hold at 350°C for 10 minutes • Detection sensitivity: Acquisition speed, 20Hz • Minimum peak width, 0.01 min • Injection volume: 0.1 μl (split method) (Quantitative determination of phthalate diesters with each structure) Standard samples consisting only of phthalate diesters having the structures listed in Table 1 below were prepared, and the detection time of each standard sample by gas chromatography was measured under the above conditions. Based on the detection time of each standard sample measured, the phthalate diesters of each structure contained in the measurement sample were identified. The proportion of each phthalate diester having a particular structure in the measurement sample was determined by the ratio of the peak area of ​​each phthalate diester having a particular structure to the total area excluding the peaks detected in a short time due to n-hexane or unreacted substances.

[0069] Manufacturing Example B1 (Manufacturing of Octyl Oleate) In a 1L four-necked flask, 282.46g (1.0 mol) of oleic acid (manufactured by Kao Corporation, trade name: Lunac OV) as the fatty acid raw material, 156.28g (1.2 mol) of 1-octanol (manufactured by Kao Corporation, trade name: Calcol 0898) as the alcohol raw material, and 0.07g of titanium tetraisopropoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added and mixed. The reaction was carried out under atmospheric pressure while distilling off the water. After the reaction was complete, the mixture was cooled to 80°C, distilled water was added, and the mixture was stirred at 80°C for 1 hour. Then, the temperature was raised, and the excess alcohol was distilled off under reduced pressure. After that, the pressure was returned to normal and the mixture was cooled to 80°C. The mixture was then filtered by suction using filter paper lined with a filtration aid to obtain octyl oleate.

[0070] Manufacturing Example B2 (Production of Decyl Oleate) Decyl oleate was obtained in the same manner as in Production Example B1, except that 189.94 g (1.2 mol) of 1-decanol (manufactured by Kao Corporation, trade name: Calcol 1098) was used as the alcohol raw material.

[0071] Manufacturing Example B3 (Manufacturing of Dodecyl Oleate) Dodecyl oleate was obtained in the same manner as in Production Example B1, except that 223.61 g (1.2 mol) of 1-dodecanol (manufactured by Kao Corporation, trade name: Calcol 2098) was used as the alcohol raw material.

[0072] Manufacturing Example B4 (Manufacturing of Tetradecyl Oleate) Tetradecyl oleate was obtained in the same manner as in Production Example B1, except that 257.27 g (1.2 mol) of 1-tetradecanol (manufactured by Kao Corporation, trade name: Calcol 4098) was used as the alcohol raw material.

[0073] Manufacturing Example B5 (Production of 2-propylheptyl stearate) 2-propylheptyl stearate was obtained in the same manner as in Production Example B1, except that 284.48 g (1.0 mol) of stearic acid (manufactured by Kao Corporation, product name: Lunac S-98) was used as the fatty acid raw material, and 189.95 g (1.2 mol) of 2-propyl-1-heptanol (manufactured by BASF) was used as the alcohol raw material.

[0074] [Table 1]

[0075] In Table 1, R in the structure of phthalate diester A 1 or R 2 The details are as follows: • 2PH: 2 propylheptyl groups nC10: n-decyl group nC12: n-dodecyl group

[0076] Example 1-1 (Production of Plasticizer Composition 1) 95.0 g of phthalate diester A1 and 5.0 g of octyl oleate as fatty acid ester B were weighed out and mixed visually until homogeneous to obtain plasticizer composition 1. The composition of the obtained plasticizer composition 1 is shown in Table 2.

[0077] Examples 1-2 to 1-4, Comparative Examples 1-1 to 1-3 (Production of plasticizer compositions 2-4 and 11-13) Plasticizer compositions 2-4 and 11-13 were obtained in the same manner as in Example 1-1, except that the content of phthalate diester A1 and fatty acid ester B were changed as shown in Table 2. The plasticizer composition 11 of Comparative Example 1-1 contains 100% by mass of phthalate diester A1 and does not contain fatty acid ester B. The plasticizer composition 13 of Comparative Example 1-3 contains isobutyl oleate (manufactured by Kao Corporation, product name: Vinisizer 30) instead of fatty acid ester B.

[0078] Examples 1-5 (Production of Plasticizer Composition 5) 91.7 g of phthalate diester A2 and 8.3 g of octyl oleate as fatty acid ester B were weighed out and mixed visually until homogeneous to obtain plasticizer composition 5. The composition of the obtained plasticizer composition 5 is shown in Table 2.

[0079] Examples 1-6 (Production of Plasticizer Composition 6) Plasticizer composition 6 was obtained in the same manner as in Examples 1-5, except that octyl oleate was replaced with decyl oleate as fatty acid ester B.

[0080] Examples 1-7 (Production of Plasticizer Composition 7) Plasticizer composition 7 was obtained in the same manner as in Examples 1-5, except that octyl oleate was replaced with dodecyl oleate as fatty acid ester B.

[0081] Examples 1-8 (Production of Plasticizer Composition 8) Plasticizer composition 8 was obtained in the same manner as in Examples 1-5, except that octyl oleate was replaced with tetradecyl oleate as fatty acid ester B.

[0082] Examples 1-9 (Production of Plasticizer Composition 9) In Examples 1-5, plasticizer composition 9 was obtained with the composition shown in Table 2, except that the content of phthalate diester A2, the content of fatty acid ester B, and the fatty acid ester B were changed from octyl oleate to 2-propylheptyl stearate.

[0083] [Table 2]

[0084] [Manufacturing of halogenated resin compositions] Examples 2-1 to 2-9, Comparative Examples 2-1 to 2-4 (Halogenated Resin Compositions 1 to 4 and 11 to 14) 100 parts of polyvinyl chloride resin (average degree of polymerization 1400, manufactured by Shin-Daiichi Vinyl Chloride Co., Ltd., product name: ZEST1400) were mixed at room temperature using a stirring rod with 60 parts of the plasticizer composition shown in Table 3, 20 parts of calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., product name: Whiteon H), 2 parts of Ca / Mg / Zn-based stabilizer for polyvinyl chloride resin (manufactured by ADEKA Corporation, product name: ADEKA Stab RUP-103), and 0.5 parts of lubricant (manufactured by Kao Corporation, product name: Lunac S-70V). The mixture was then kneaded at 17.5 rpm and 160°C using a 4-inch open roll type kneader (manufactured by Nishimura Machinery Co., Ltd.) to induce gelation, and kneading was continued for 5 minutes after gelation to obtain a halogen-based resin composition. The unformed sheet produced as described above was preheated at 175°C for 4.5 minutes, then pressurized at 20 MPa for 1.5 minutes, and further cooled at 15°C for 2 minutes to obtain a molded sheet of halogen-based resin composition with a thickness of 0.8 mm. Note that the halogen-based resin composition 14 in Comparative Example 2-4 does not contain a plasticizer composition.

[0085] [Evaluation of low-temperature flexibility] Test specimens were prepared from molded sheets of each halogen-based resin composition according to the test method specified in JIS K 6773:1999, and the flexibility temperature (unit: °C) was evaluated using a Crushberg flexibility temperature tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd., product name: No. 170-AUTO). A lower flexibility temperature indicates superior low-temperature flexibility. The results are shown in Table 3.

[0086] [Evaluation of heat resistance] Test specimens of molded sheets of each halogen-based resin composition, punched into a No. 3 dumbbell shape as specified in JIS K6251:2017, were subjected to 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 percentage of mass loss before and after this period was measured. A value closer to zero indicates superior heat resistance. The results are shown in Table 3.

[0087] [Table 3]

[0088] Tables 2 and 3 show that plasticizer compositions 1 to 9 of Examples 1-1 to 1-9, in which the mass ratio of phthalate diester A content to fatty acid ester B content (phthalate diester A / fatty acid ester B) is greater than 90 / 10 and less than or equal to 99.9 / 0.1, can impart excellent low-temperature flexibility and heat resistance when used in halogenated resin compositions 1 to 9 (Examples 2-1 to 2-9). On the other hand, the plasticizer composition 11 of Comparative Example 1-1, which did not contain fatty acid ester B, exhibited inferior low-temperature flexibility even when used in the halogenated resin composition 11 (Comparative Example 2-1). Furthermore, the plasticizer composition 12 of Comparative Example 1-2, in which the mass ratio of the content of phthalate diester A to the content of fatty acid ester B (phthalate diester A / fatty acid ester B) was 90 / 10 or less, and the plasticizer composition 13 of Comparative Example 1-3, which contained isobutyl oleate instead of fatty acid ester B, exhibited poor heat resistance even when used in halogenated resin compositions 12 and 13 (Comparative Examples 2-2 and 2-3). The halogenated resin composition 14 of Comparative Example 2-4, which did not contain a plasticizer composition, exhibited poor low-temperature flexibility and heat resistance.

Claims

1. Diester phthalate A, represented by general formula (I), It contains fatty acid ester B represented by general formula (II), A plasticizer composition in which the mass ratio of the content of phthalate diester A to the content of fatty acid ester B (phthalate diester A / fatty acid ester B) is greater than 90 / 10 and less than or equal to 99.9 / 0.

1. 【Chemistry 1】 (In general formula (I), R １ and R ２ These are linear alkyl groups or branched alkyl groups having 10 to 14 carbon atoms, which may be the same or different from each other. 【Chemistry 2】 (In general formula (II), R ３ R is a linear alkyl group having 5 to 14 carbon atoms or a branched alkyl group having 5 to 14 carbon atoms, ４ (This is a linear alkyl group having 14 to 24 carbon atoms, a branched alkyl group having 14 to 24 carbon atoms, or a linear alkenyl group having 14 to 24 carbon atoms, or a branched alkenyl group having 14 to 24 carbon atoms.)

2. The plasticizer composition according to claim 1, wherein the phthalate diester A is a mixture of two or more types.

3. In the total amount of the phthalate diester A, R in general formula (I) １ and R ２ The plasticizer composition according to claim 2, wherein the content of a phthalate diester in which at least one of the members is a linear alkyl group having 11 or more carbon atoms and 14 carbon atoms is 50 mol% or more and 95 mol% or less.

4. In the total amount of the phthalate diester A, R in general formula (I) １ and R ２ The plasticizer composition according to claim 2, wherein the content of a phthalate diester in which both are linear alkyl groups having 11 or more carbon atoms and 14 or fewer carbon atoms is 5 mol% or more and 55 mol% or less.

5. In the fatty acid ester B, in the general formula (II), R ３ is a linear alkyl group having 5 to 14 carbon atoms, and R ４ is a linear alkenyl group having 14 to 24 carbon atoms, The plasticizer composition according to claim 1.

6. A halogen-based resin composition comprising the plasticizer composition according to any one of claims 1 to 5.

7. Diester phthalate A, represented by general formula (I), The process includes a step of mixing with fatty acid ester B represented by general formula (II), A method for producing a plasticizer composition in which the mass ratio of the amount of phthalate diester A to the amount of fatty acid ester B (phthalate diester A / fatty acid ester B) is greater than 90 / 10 and less than or equal to 99.9 / 0.

1. 【Transformation 3】 (In general formula (I), R １ and R ２ These are linear alkyl groups or branched alkyl groups having 10 to 14 carbon atoms, which may be the same or different from each other. 【Chemistry 4】 (In general formula (II), R ３ R is a linear alkyl group having 5 to 14 carbon atoms or a branched alkyl group having 5 to 14 carbon atoms, ４ (This is a linear alkyl group having 14 to 24 carbon atoms, a branched alkyl group having 14 to 24 carbon atoms, or a linear alkenyl group having 14 to 24 carbon atoms, or a branched alkenyl group having 14 to 24 carbon atoms.)

8. The method for producing the plasticizer composition according to claim 7, wherein the phthalate diester A is obtained by esterifying a phthalate raw material with an alcohol raw material containing a linear aliphatic alcohol having 10 to 14 carbon atoms or a branched aliphatic alcohol having 10 to 14 carbon atoms.

9. A method for producing a plasticizer composition according to claim 8, wherein the alcohol raw material includes a linear aliphatic alcohol having 10 to 14 carbon atoms and a branched aliphatic alcohol having 10 to 14 carbon atoms.

10. A method for producing a plasticizer composition according to claim 8, wherein the mol ratio (amount of linear aliphatic alcohol / amount of branched aliphatic alcohol) of the amount of linear aliphatic alcohol having 10 to 14 carbon atoms to the amount of branched aliphatic alcohol having 10 to 14 carbon atoms in the alcohol raw material is 50 / 50 or more and 70 / 30 or less.

11. A method for producing a plasticizer composition according to claim 8, wherein the amount of linear aliphatic alcohol having 11 to 14 carbon atoms in the alcohol raw material is 30 mol% to 70 mol%.

12. In the fatty acid ester B mentioned above, in general formula (II), R ３ R is a linear alkyl group having 5 to 14 carbon atoms, ４ A method for producing a plasticizer composition according to any one of claims 7 to 11, wherein is a linear alkenyl group having 14 or more carbon atoms and 24 or fewer carbon atoms.

13. A method for producing a halogen-based resin composition, comprising the step of mixing a plasticizer composition according to any one of claims 1 to 5 with a halogen-based resin.

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