JPH06263915A - Plasticizer composition and thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having processability, heat resistance, vaporization resistance and cold resistance, comprising a specific butanetetracarboxylic acid ester and a specific ester compound. CONSTITUTION:The objective composition comprises (A) a 1,2,3,4- butanetetracarboxylic acid ester of formula I (R<1> to R<4> are straight-chain or branched-chain 1-6C alkyl or alkenyl)(preferably an ester of 4-13C alcohol such as hexyl alcohol) and (B) an ester compound selected from an ester compound of formula II or formula III and an epoxy-containing ester compound. The compound of formula II is preferably obtained from trimellitic acid and/or trimellitic anhydride and a 4-10C aliphatic alcohol such as n-octyl alcohol and a 2-8C aliphatic diol such as 1,6-hexanediol as raw materials. An epoxy compound of dioleyl tetrahydrophthalate is preferable as the epoxy group-containing ester compound of the component B.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plasticizer composition having excellent processability, heat resistance, volatility resistance and cold resistance and a thermoplastic resin composition containing the plasticizer composition.

[0002]

2. Description of the Related Art Halogen-containing resin compositions are inexpensive and have excellent performance. Therefore, in soft systems, leather, films, sheets, tubes, hoses, compounds, etc., and in hard systems, corrugated sheets, flat plates, It is a general-purpose material used in a wide variety of deck materials, gutters, pipes, joints, films, sheets, containers, etc., and various characteristics are required depending on its application. The selection of the plasticizer is important for satisfying such properties.

For example, heat resistant wires, automobile members, marking films and the like are required to have heat resistance, volatility resistance (fogging resistance) and cold resistance.

As the plasticizer selected when heat resistance and volatility resistance are required, dialkyl phthalates (having 7 to 13 carbon atoms) such as diisodecyl phthalate, diundecyl phthalate and ditridecyl phthalate, trimellitic acid. Trialkyl trimellitates such as trioctyl and triisodecyl trimellitate (C7-11) and molecular weight 1000
Approximately about 3000 polyester plasticizers are exemplified.

On the other hand, when cold resistance is required, dialkyl adipate (having 7 carbon atoms) such as diisononyl adipate, diisodecyl adipate, and ditridecyl adipate.
~ 13) are used.

However, a plasticizer which can satisfy all of the various properties such as processability, heat resistance, volatility resistance and cold resistance has not yet been known, and by developing a plasticizer having the various properties together, A halogen-containing resin composition applicable to a wide range of uses can be obtained.

A vinyl chloride resin composition containing a tetraester of 1,2,3,4-butanetetracarboxylic acid (hereinafter abbreviated as "BTC") as a plasticizer is known (Japanese Patent Publication No. 47-47). 18219).

The ester was found by our study to be a compound having properties such as volatility resistance and cold resistance. However, the ester has low compatibility with halogen-containing resins, especially polyvinyl chloride resin, and has processability. There were some points left to be improved in.

Generally, in order to enhance the compatibility, a compound having a strong polarity and a relatively low molecular weight is blended, but this method impairs the volatility resistance, which is not intended by the present invention.

[0010]

DISCLOSURE OF THE INVENTION The present invention provides a plasticizer composition which can satisfy all of the characteristics of processability, heat resistance, volatility resistance and cold resistance, and by extension, a heat composition which can be applied to a wider range of applications. An object is to provide a plastic resin composition.

[0011]

Means for Solving the Problems As a result of intensive studies to solve such problems, the present inventors have found that a halogen-containing resin can be obtained by using a predetermined ester of BTC in combination with a specific ester compound. Not only that, they have found that the intended purpose can be achieved for various thermoplastic resins, and have completed the present invention based on such findings.

That is, the plasticizer composition according to the present invention is characterized by containing a compound (A component) belonging to group A and a compound (component B) belonging to group B below.

Group A: 1, 2, represented by the general formula (1)
3,4-butane tetracarboxylic acid ester

[Chemical 4] [In formula, R < ¹ >, R < ² >, R < ³ >, R < ⁴ > is same or different and represents a linear or branched C1-C36 alkyl group or alkenyl group. ]

Group B: Ester compound (B-1 component) represented by the general formula (2) or ester compound (B-2 component) represented by the general formula (3) and epoxy group-containing ester compound (B- 1 or 2 selected from the group consisting of 3 components)
More than one ester compound

[0015]

[Chemical 5] [In the formula, R ⁵ , R ⁶ , R ⁷ , and R ⁸ are the same or different and each represent a linear or branched alkyl group or alkenyl group having 4 to 36 carbon atoms. R ⁹ is a linear, branched, alicyclic or aromatic C 2 -C 3 which may contain an ether group.
6 represents a hydrocarbon group. ]

[0016]

[Chemical 6] [In the formula, R ¹⁰ and R ¹¹ are the same or different and each represent a linear or branched alkyl group or alkenyl group having 4 to 36 carbon atoms. R ¹² represents a linear, branched, alicyclic or aromatic hydrocarbon group having 2 to 36 carbon atoms which may contain an ether group. n represents an integer of 2 to 20. ]

The component A compound can be obtained by esterifying BTC and / or its acid anhydride with one or more kinds of predetermined aliphatic alcohols by a conventional method.

Examples of the predetermined aliphatic alcohol include straight chain or branched chain saturated or unsaturated alcohols having 1 to 36 carbon atoms, and more specifically, ethyl alcohol, butyl alcohol, amyl alcohol. , Hexyl alcohol, heptyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, alfol 610 (Vistachemical / Far East Co., Ltd.), Lineball 79, 911
(Shell Chemical Co., Ltd.), Diadol 79, 911 (manufactured by Mitsubishi Kasei Co., Ltd.) and other saturated alcohols; octenyl alcohol, undecenyl alcohol, hexadecenyl alcohol, octadecenyl alcohol, linoleyl alcohol, lino An unsaturated alcohol such as renyl alcohol is exemplified.

Among them, an ester prepared by using an alcohol having 4 to 13 carbon atoms as an alcohol component is preferable. If the carbon number is less than 4, the volatility resistance decreases and the carbon number is 13
If it exceeds, the cold resistance is good, but the workability and gelation property tend to be significantly reduced.

The B-1 component compound is esterified by a conventional method using (a) trimellitic acid and / or its acid anhydride, (b) a predetermined aliphatic alcohol and (c) a predetermined diol as raw materials. It is obtained by doing. At this time, the respective raw materials are charged in a molar ratio of about a: b: c = 2: 4: 1.

The reaction is preferably carried out by charging each of the raw materials in a molar number corresponding to one time. However, after the trimellitic acid and the diol are esterified in advance, an aliphatic alcohol is added to complete the esterification. It may be a method.

In addition to the compound represented by the general formula (2), its oligomer and trialkyl trimellitate are contained as impurities in the reaction product depending on the charged molar ratio of the raw materials. This trialkyl ester tends to slightly lower the heat resistance.

The aliphatic alcohol used is B
The same alcohol as the above-mentioned aliphatic alcohol can be exemplified as a raw material of TC ester.

The diols used have an alkylene group which may contain an ether group and have 2 to 36 carbon atoms.
Is a linear or branched aliphatic, alicyclic or aromatic diol.

Examples of the aliphatic diol include ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, neopentyl glycol, hexamethylene glycol, methylpentyl glycol, heptyl glycol, octyl glycol, butylmethylpropyl glycol, nonyl glycol and decyl. Chain diols such as glycol, undecyl glycol, dodecyl glycol, tridecyl glycol, and geometric isomers thereof, as well as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, etc. Examples of ether group-containing diols include

Examples of the alicyclic diol include alicyclic diols such as cyclohexanediol, cyclohexanedimethanol and hydrogenated bisphenol A, and their alkylene oxide adducts.

Examples of the aromatic diol include xylylene glycol, bisphenol A and their alkylene oxide adducts.

As a more effective B-1 compound, an ester having an aliphatic diol having 2 to 8 carbon atoms and an aliphatic alcohol having 4 to 10 carbon atoms as alcohol components is exemplified.

The B-2 component compound can be obtained by esterification with orthophthalic acid (anhydride), isophthalic acid, terephthalic acid, diols and aliphatic alcohol. At this time, it is preferable that the diols and the dicarboxylic acid are previously reacted under a charge of a molar ratio to obtain a desired molecular weight, and then an esterification reaction with an aliphatic alcohol is performed.

The molecular weight of the component is 500 to 30.
00 is recommended, and more preferably 800 to 2000
Is. If it is more than 3000, the cold resistance tends to be impaired, and if it is less than 500, the volatility resistance tends to be poor.

The diols and aliphatic alcohols used are the same as the raw materials used in the ester compound represented by the general formula (2).

As a more effective B-2 compound, an ester comprising an aliphatic diol having 2 to 8 carbon atoms and an aliphatic alcohol having 4 to 10 carbon atoms as an alcohol component is exemplified.

Examples of the B-3 component compound include epoxidized natural unsaturated fatty acid triglycerides such as soybean oil and linseed oil, and alkyl (or alkenyl) tetrahydrophthalic acid having 4 to 22 carbon atoms (preferably 8 to 18 carbon atoms). Examples include epoxidized products of esters. Recommended compounds include epoxides of dioleyl tetrahydrophthalate.

The mixing ratio of the A component and the B component, which are essential components of the present invention, is not particularly limited as long as both are contained, but the content of the A component in the plasticizer composition is usually 5 to 95.
% By weight, and more preferably the component A is contained in a ratio of 20 to 80% by weight.

The type and content of the B component can be appropriately selected according to the characteristics to be emphasized. For example, the plasticizer composition containing 1 to 5% by weight of the component B-3 has the performance as a heat resistance stabilizer for a halogen-containing resin.

In the plasticizer composition according to the present invention, conventionally known plasticizers can be used in combination as long as the performance thereof is not impaired.

Examples of such plasticizers include phthalic acid di (2-
Phthalates such as ethylhexyl), diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate,
Aromatic polybasic acid ester-based plasticizers such as trimellitate-based trioctyl trimellitate, triisodecyl trimellitate, and trialkyl trimellitate (mixed alkyl having 7 to 9 or 9 to 11 carbon atoms); dioctyl adipate and adipine Adipate-based plasticizers such as diisononyl acid, dioctyl maleate and the like, fumarate-based dioctyl fumarate and the like, azelate-based dioctyl azelate and sebacate-based aliphatic dibasic ester plasticizers such as dioctyl sebacate; Phosphoric acid-based plasticizers such as tricresyl phosphate and trixylenyl phosphate; epoxy-based plasticizers such as butyl epoxystearate, octyl epoxystearate and epoxy resins; polyester-based plasticizers and the like.

The thermoplastic resin used in the present invention may be a halogen-containing resin. Examples of the halogen-containing resin include homopolymers of halogen-containing compounds such as vinyl chloride and vinylidene chloride, and copolymers of monomers copolymerizable with the halogen-containing compounds.

Examples of the monomer copolymerizable with the halogen-containing compound include vinyl acetate, vinyl propionate, vinyl laurate, and other vinyl esters, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth).
(Meth) acrylic acid esters such as acrylate, maleic acid esters such as dibutyl maleate and diethyl malate, vinyl ethers, (meth) acrylonitrile,
Examples include vinyl cyanide, α-olefins such as ethylene, propylene and styrene, vinylidene chloride, vinyl halides and the like. Here, the weight ratio of the above monomers is, for example, 3 to 30% by weight, preferably 5 to 15% by weight.

The degree of polymerization of such homopolymers and copolymers is about 400 to 12000, preferably 600 to 9
It is about 000.

Other thermoplastic resins include vinyl acetate resins, polystyrene resins, acrylonitrile-styrene resins, acrylonitrile-butadiene-sterene resins, chloroprene resins, polyvinyl alcohol resins, polyacrylic resins, butyral resins. In addition to urethane resins and silicone resins, various heat resistant thermoplastic resins and thermoplastic elastomers can be exemplified.

Examples of the heat-resistant thermoplastic resin include chlorinated PVC, aromatic polyamides such as terephthalic acid and aliphatic diamines or xylylenediamine and aliphatic dicarboxylic acids, aliphatic polyamides, polycarbonates, polyacetals, and polyethylene terephthalate. , Polybutylene terephthalate, polyarylate, and liquid crystal polymer.

Further, as the thermoplastic elastomer (TPE), styrene-based TPE such as styrene and butadiene or isoprene, olefin-based TPE such as PP and α-olefin rubber, urethane-based TPE such as urethane and ester or ether, and high polymerization degree PVC. And partially crosslinked PVC and crosslinked NRB
PVC-based TPE and PB such as polymer alloys of PVC and PVC
Examples include T and polyester-based TPE such as polytetramethylene glycol and polycaprolactone, polyamide-based TPE such as nylon and polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and butadiene-based TPE based on syndiotactic-1,2-polybutadiene. It

The elastomer is not limited to thermoplasticity, and vulcanized elastomer can be exemplified. For example, natural rubber, isobutylene rubber, styrene-butadiene rubber,
Butadiene rubber, chloroprene rubber, butyl rubber, ethylene propylene rubber, ethylene vinyl acetate copolymer, chlorosulfonated polyethylene, chlorinated polyethylene, epichlorohydrin rubber, nitrile butadiene rubber, nitrile isoprene rubber, acrylic rubber, urethane rubber, polynorbornene rubber, hydrogen Nitrile butadiene rubber and the like.

The blending amount of the plasticizer composition according to the present invention can be appropriately selected according to the kind of the thermoplastic resin, the desired characteristics and the use of the resin composition, but usually 100 weight% of the thermoplastic resin is used. About 1 to 250 parts by weight are blended with respect to parts.

For example, the compounding amount of the plasticizer composition according to the present invention with respect to 100 parts by weight of the halogen-containing resin is 1 to 2 depending on the application of the resin composition such as soft, semi-hard, and hard.
It is appropriately selected within the range of 00 parts by weight. More specifically,
In the case of soft blending, it is used in the range of about 30 to 150 parts by weight. Further, about 1 to 5 parts by weight is used in the case of a hard mixture, and about 10 to 20 parts by weight is applied in the case of a semi-hard mixture. If the amount is less than 1 part by weight, it is difficult to obtain a predetermined effect, and if the amount is more than 200 parts by weight, the slipperiness is increased so that the workability is deteriorated and bleeding out may occur.

The thermoplastic resin composition according to the present invention may be mixed with conventionally known auxiliary materials.

For example, a stabilizer such as metal soap, tribasic lead sulfate, organotin, silicic acid-based or epoxy-based plasticizer can be used in combination with the halogen-based resin composition.

The stabilizer is usually a halogen-containing resin 100.
It is used in an amount of 0.1 to 10 parts by weight, preferably 1 to 6 parts by weight, based on parts by weight. If the amount is less than 0.1 parts by weight, it is difficult to obtain the desired effect, and if the amount is more than 10 parts by weight, the lubricity is strong and the cohesiveness is extremely poor.

Further, a lubricant, a flame retardant, a filler, a foaming agent, an antistatic agent, an antifogging agent, a bactericide, a processing aid, an antioxidant, a light stabilizer, a pigment, as long as the predetermined effects are not impaired. Additives such as zeolites, cross-linking agents and surface treatment agents can be added depending on the purpose.

Examples of the antistatic agent include alkyl sulphate type, polyethylene glycol ether sulphate type, alkyl amide sulphate type, alkyl sulphonate type, alkyl amide sulphonate type,
Anionic surfactants such as alkyl ether sulfonate type, alkyl aryl sulfonate type, alkyl phosphite type, and alkyl phosphate type,

Quaternary ammonium salts of alkylamidoamine type, alkyltrimethyl type, alkyldimethylbenzyl type, alkylamide type, compounds represented by the following formula,
Alkyloxazoline-type, alkylimidazoline-type, aminoethylimidazoline-type, dihydroindole-type, alkylaminotriazole-type, alkyldioxane-type carbonates, hydrochlorides, perchlorates, acetates, citrates,
A cationic surfactant such as an alkylpyridinium salt, an alkylamidopyridinium salt, or an alkyl ether pyridinium salt,

Amphoteric surfactants such as betaine type, imidozoline type, sulfuric acid ester type, sulfonic acid type and phosphoric acid ester type,

Alkyl ether type, alkyl aryl ether type, alkyl thioether type, amide type, polyhydric alcohol type such as glycerin, sorbitan monoalkyl ester type or monoglyceride type ester type or their alkylene oxide adducts, polyethyleneimine type Examples of nonionic surfactants are as follows.

Among them, the cationic surfactant represented by the following formula is particularly effective.

[Chemical 7] [In the formula, R ¹³ has 8 to 8 carbon atoms which may have an amide group.
24 represents an alkyl group or an alkenyl group. R ¹⁴ represents a hydrogen atom or an alkyl group or alkenyl group having 1 to 18 carbon atoms. A represents an oxyalkylene group having 2 to 3 carbon atoms. o and p are positive integers, and 2 ≦ o + p ≦ 8. X represents an alkyl sulfonate ion such as chlorine, bromine, iodine, perchlorate ion, monomethyl sulfate ester or the like, or an alkylaryl sulfonate ion such as dodecylbenzene sulfonate ion or the like. ]

[0056]

[Chemical 8] [In the formula, R ¹⁵ has 8 to 8 carbon atoms which may have an amide group.
24 represents an alkyl group or an alkenyl group. R ¹⁶ , R ¹⁷
Are the same or different and represent a hydrogen atom or an alkyl group or an alkenyl group having 1 to 18 carbon atoms. A has 2 to 2 carbon atoms
3 represents an oxyalkylene group. q is a positive integer.
Y represents an alkylsulfonate ion such as chlorine, bromine, iodine, perchlorate ion, monomethylsulfate ester or an alkylarylsulfonate ion such as dodecylbenzenesulfonate ion. ]

The thermoplastic resin composition according to the present invention is kneaded using a conventionally known device such as a heat roll, a Banbury mixer, a Henschel mixer, a ribbon blender, and is subjected to calender molding, extrusion molding, injection molding, etc. according to each field. It is molded by the above-mentioned molding method and provided for each use.

For example, the halogen-containing resin composition is thus applied as a resin material for semi-rigid or hard products such as pipes, corrugated sheets, flat plates, films, sheets, gutters, deck materials, containers and floor materials. , General soft products such as soft sheet, soft film, leather, tube, long flooring,
It is applied to gaskets, packings, floor materials, etc.

[0059]

EXAMPLES The present invention will be described in detail below with reference to examples. The characteristics of the resin composition in each example were measured and evaluated by the following methods.

Workability: The degree of transparency of the sheet obtained by kneading the resin composition obtained by kneading the resin composition using a heated two roll heated at 160 ° C. and observing the degree of transparency is as follows. It is evaluated according to the standard. ◯: Good (transparent), Δ: Slightly good, ×: Poor (large turbidity)

Heat resistance: A predetermined resin composition was kneaded with two hot rolls to prepare a 0.8 mm-thick masticated sheet, which was then cut into a predetermined size to give a test piece. .
The change in color tone of the test piece at 180 ° C. was visually observed in a gear oven and evaluated according to the following criteria. A: No change, B: yellowing, C: slightly browning, D: browning, E: blackening

Volatilization resistance: Using the same test piece as in the heat resistance test, the weight loss ratio (% by weight) before and after heating the test piece in a gear oven (180 ° C.) is measured.

Cold resistance: Crashberg method (JIS K 674
Based on 5).

The component A used in each example is abbreviated as follows. BTC / C8: BTC tetraoctyl BTC / F18: BTC tetraoleyl

Production Example 1 Trimellitic anhydride 3 was placed in a 2-liter four-necked flask.
84 g (2.0 mol), 1,6-hexanediol 11
8 g (1.0 mol) and n-octyl alcohol 520
g (4.0 mol) was charged, and the mixture was heated and dehydrated for 4 hours with stirring at 150 ° C. in the presence of an acid catalyst (p-toluenesulfonic acid) to obtain the target esterified product (acid value 0.1, ester value 350). , Hereinafter referred to as "main ester 1".) 944 g
Got

Production Example 2 384 g (2.0 mol) of trimellitic anhydride, 1,4
-Cyclohexanedimethanol 144 g (1.0 mol)
And 520 g (4.0 mol) of n-octyl alcohol were heated and stirred in the same manner as in Production Example 1, and the target esterified product (acid value 0.1, ester value 344, hereinafter referred to as "present ester 2"). 970 g were obtained.

Production Example 3 384 g (2.0 mol) of trimellitic anhydride, 316 g of adduct of 2 mol of ethylene oxide with bisphenol A
(1.0 mol) and n-octyl alcohol 520 g
(4.0 mol), and heated and stirred according to Production Example 1,
Target esterified product (acid value 0.3, ester value 29
1, hereinafter referred to as "main ester 3". ) 1140 g were obtained.

Production Example 4 Using 740 g (5.0 mol) of orthophthalic anhydride and 416 g (4.0 mol) of neopentyl glycol, the mixture was heated and stirred in the same manner as in Production Example 1 to give an ester obtained by dehydration reaction. 260 g (2.0 mol) of 2-ethylhexyl alcohol was added, and dehydration reaction was performed to obtain 1300 g of a desired esterified product (acid value 1.2, ester value 421, hereinafter referred to as "present ester 4").

Examples 1 to 6 and Comparative Examples 1 to 6 With respect to 100 parts by weight of a polyvinyl chloride resin (trade name "Zeon 101EP", manufactured by Nippon Zeon Co., Ltd.), the plasticizer composition and stabilizer shown in Table 1 were used. 3 parts by weight of (calcium stearate / zinc stearate mixture) was mixed to prepare a resin composition, and the workability, heat resistance, volatility resistance and cold resistance of this resin composition were evaluated. The results obtained are shown in Table 1. The epoxidized product of dioleyl tetrahydrophthalate is abbreviated as "main ester 5". When the processability of the resin composition (Comparative Example 6) in which “this ester 5” was blended alone was evaluated,
Plate out was observed in the sample.

[Table 1]

Example 7 A resin composition was prepared by blending 100 parts by weight of chloroprene rubber with the plasticizer composition shown in Table 2, and the processability, heat resistance, volatility resistance and cold resistance of this resin composition were evaluated. evaluated. The results obtained are shown in Table 1.

Example 8 With respect to 100 parts by weight of a vinyl chloride / vinyl acetate copolymer,
A resin composition was prepared by blending the plasticizer composition shown in Table 2, and the processability, heat resistance, volatility resistance and cold resistance of this resin composition were evaluated. The results obtained are shown in Table 2.

Example 9 A resin composition was prepared by blending 100 parts by weight of a silicone resin with the plasticizer composition shown in Table 2, and the processability, heat resistance, volatility resistance and cold resistance of this resin composition were evaluated. evaluated. The results obtained are shown in Table 2.

[Table 2]

Example 10 A resin composition was prepared by adding 2 parts by weight of an ethylene oxide addition type quaternary ammonium perchlorate as an antistatic agent to the resin composition of Example 5, and the processability and heat resistance of this resin composition were prepared. Example 5 was evaluated for the heat resistance, volatility resistance and cold resistance.
Various properties equivalent to those obtained were obtained, and no harmful effect was observed by applying the antistatic agent. The surface resistivity of this product was measured according to JIS K 6723, and an excellent antistatic ability of 10 ¹⁰ level was recognized.

[0074]

The thermoplastic resin composition containing the plasticizer composition according to the present invention can have excellent processability, heat resistance, volatility resistance and cold resistance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshifumi Fujitani 13 Yakura-cho, Yashimajima, Fushimi-ku, Kyoto-shi, Kyoto

Claims (2)

[Claims] 1. A plasticizer composition comprising a compound belonging to group A and a compound belonging to group B below. Group A: 1,2,3,4-butanetetracarboxylic acid ester represented by the general formula (1) [In formula, R < ¹ >, R < ² >, R < ³ >, R < ⁴ > is same or different and represents a linear or branched C1-C36 alkyl group or alkenyl group. Group B: one or more ester compounds selected from the group consisting of ester compounds represented by the general formula (2) or general formula (3) and epoxy group-containing ester compounds [In the formula, R ⁵ , R ⁶ , R ⁷ , and R ⁸ are the same or different and each represent a linear or branched alkyl group or alkenyl group having 4 to 36 carbon atoms. R ⁹ is a linear, branched, alicyclic or aromatic C 2 -C 3 which may contain an ether group.
6 represents a hydrocarbon group. ] [Chemical 3] [In the formula, R ¹⁰ and R ¹¹ are the same or different and each represent a linear or branched alkyl group or alkenyl group having 4 to 36 carbon atoms. R ¹² represents a linear, branched, alicyclic or aromatic hydrocarbon group having 2 to 36 carbon atoms, which may contain an ether group. n represents an integer of 2 to 20. ] 2. A thermoplastic resin composition comprising a thermoplastic resin and the plasticizer composition according to claim 1.