JP2012107179A - Thermoplastic polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic polymer composition with further improved processing stability.SOLUTION: The thermoplastic polymer composition contains a thermoplastic polymer, a compound expressed by formula (1), wherein Rand Reach independently represents a 1-8C alkyl group, a 6-12C aryl group or a 7-18C aralkyl group; Rrepresents a hydrogen atom or a 1-3C alkyl group; and Rrepresents a hydrogen atom or a methyl group, and a compound expressed by formula (2), wherein n denotes an integer of 2 or more.

Description

  The present invention relates to a thermoplastic polymer composition and the like.

  Thermoplastic polymers are widely used in food packaging containers and household goods because of their excellent transparency and impact resistance. In the manufacture of such products, the thermoplastic polymer is used as a composition containing it. As such a thermoplastic polymer composition, polybutadiene rubber which is one kind of thermoplastic polymer, 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-) A thermoplastic polymer composition comprising (hydroxyphenyl) ethyl] phenyl acrylate is known (Patent Document 1).

Japanese Laid-Open Patent Publication No. 1-168643 (Example)

  A thermoplastic polymer composition with further improved processing stability is desired.

（式中、Ｒ^１及びＲ^２は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数６〜１２のアリール基又は炭素数７〜１８のアラルキル基を表す。Ｒ^３は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ^４は水素原子又はメチル基を表す。）
で表される化合物、及び、式（２）

（式中、ｎは２以上の整数を表す。）
で表される化合物を含有する熱可塑性ポリマー組成物。
［２］ 式（１）で表される化合物と式（２）で表される化合物との合計重量が、熱可塑性ポリマー１００重量部に対して０．００１〜３重量部である［１］記載の熱可塑性ポリマー組成物。 In order to solve this problem, the present inventors have intensively studied, and as a result, have found a thermoplastic polymer composition having further improved processing stability, and have reached the inventions described in [1] to [11] below.
[1] Thermoplastic polymer, formula (1)

(Wherein R ¹ and R ² each independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. R ³ represents a hydrogen atom or Represents an alkyl group having 1 to 3 carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group.)
And a compound represented by formula (2)

(In the formula, n represents an integer of 2 or more.)
The thermoplastic polymer composition containing the compound represented by these.
[2] The total weight of the compound represented by the formula (1) and the compound represented by the formula (2) is 0.001 to 3 parts by weight with respect to 100 parts by weight of the thermoplastic polymer. Thermoplastic polymer composition.

（式中、Ｒ^１及びＲ^２は、それぞれ独立に、炭素数１〜８のアルキル基、炭素数６〜１２のアリール基又は炭素数７〜１８のアラルキル基を表す。Ｒ^３は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ^４は水素原子又はメチル基を表す。）
で表される化合物と、式（２）

（式中、ｎは２以上の整数を表す。）
で表される化合物とを含有する安定剤組成物。
［４］ 式（１）で表される化合物が、２，４―ジ−ｔ−アミル−６−［１−（３，５−ジ−ｔ−アミル−２−ヒドロキシフェニル）エチル］フェニルアクリレート又は２−ｔ−ブチル−６−（３−ｔ−ブチル−２−ヒドロキシ−５−メチルベンジル）−４−メチルフェニル アクリレートである［３］記載の安定剤組成物。
［５］ 式（２）中のｎが５である［３］又は［４］記載の安定剤組成物。
［６］ 式（２）で表される化合物がｍｙｏ−イノシトール又はｓｃｙｌｌｏ−イノシトールである［３］又は［４］記載の安定剤組成物。
［７］ さらに、式（３）

（式中、Ｒ^５及びＲ^６はそれぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表し、Ｘは、ヘテロ原子及び／又は環状基を含んでいてもよい炭素数１〜２４のｍ価のアルコール残基を表し、ｍは１〜４の整数を表す。ここでアルコール残基とは、アルコールのヒドロキシ基から水素原子を除いた残りの基を表す。）
で表される化合物を含有する［３］〜［６］のいずれか一項記載の安定剤組成物。
［８］ さらに、式（４）〜式（８）からなる群から選ばれる少なくとも一つの式で表される有機リン化合物を含有する［３］〜［７］のいずれか一項記載の安定剤組成物。
式（４）：

（式中、Ｒ^７及びＲ^８は、互いに独立に、水素原子、炭素数１〜９のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表す。）
式（５）：

（式中、Ｒ^９は、水素原子、炭素数１〜９のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表す。）
式（６）：

（式中、Ａ^１は、炭素数１〜１８のアルキル基、炭素数１〜９のアルキル基で置換されていてもよいフェニル基、炭素数５〜８のシクロアルキル基で置換されていてもよいフェニル基、炭素数６〜１２のアルキルシクロアルキル基で置換されていてもよいフェニル基、又は炭素数７〜１２のアラルキル基で置換されていてもよいフェニル基を表す。）
式（７）：

（式中、Ｒ^１０及びＲ^１１は、互いに独立に、水素原子、炭素数１〜９のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表す。Ａ^２は、単結合、硫黄原子、又は炭素数１〜８のアルキリデン基を表す。Ａ^３は炭素数２〜８のアルキレン基を表す。）
式（８）：

（式中、Ｒ^１２及びＲ^１３は、互いに独立に、水素原子、炭素数１〜９のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表す。Ａ^４は、単結合、硫黄原子、又は炭素数１〜８のアルキリデン基を表す。Ａ^５は、炭素数１〜８のアルキル基、炭素数１〜９のアルキル基で置換されていてもよいフェニル基、炭素数５〜８のシクロアルキル基で置換されていてもよいフェニル基、炭素数６〜１２のアルキルシクロアルキル基で置換されていてもよいフェニル基、又は炭素数７〜１２のアラルキル基で置換されていてもよいフェニル基を表す。）
［９］ 式（４）〜式（８）からなる群から選ばれる少なくとも一つの式で表される有機リン化合物が、式（４）で表される化合物である［８］記載の安定剤組成物。 [3] Formula (1)

(Wherein R ¹ and R ² each independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. R ³ represents a hydrogen atom or Represents an alkyl group having 1 to 3 carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group.)
A compound represented by formula (2)

(In the formula, n represents an integer of 2 or more.)
The stabilizer composition containing the compound represented by these.
[4] The compound represented by the formula (1) is 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate or The stabilizer composition according to [3], which is 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate.
[5] The stabilizer composition according to [3] or [4], wherein n in the formula (2) is 5.
[6] The stabilizer composition according to [3] or [4], wherein the compound represented by the formula (2) is myo-inositol or scyllo-inositol.
[7] Furthermore, Formula (3)

(In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and X represents a carbon atom having 1 to 24 carbon atoms which may contain a hetero atom and / or a cyclic group. m represents an alcohol residue, and m represents an integer of 1 to 4. Here, the alcohol residue represents a remaining group obtained by removing a hydrogen atom from a hydroxy group of alcohol.
The stabilizer composition as described in any one of [3]-[6] containing the compound represented by these.
[8] The stabilizer according to any one of [3] to [7], further comprising an organophosphorus compound represented by at least one formula selected from the group consisting of formula (4) to formula (8). Composition.
Formula (4):

(In the formula, R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or a carbon number. 7 to 12 aralkyl groups or phenyl groups are represented.)
Formula (5):

(In the formula, R ⁹ is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or Represents a phenyl group.)
Formula (6):

(In the formula, A ¹ may be substituted with a C 1-18 alkyl group, a phenyl group optionally substituted with a C 1-9 alkyl group, or a C 5-8 cycloalkyl group. It represents a good phenyl group, a phenyl group optionally substituted with an alkylcycloalkyl group having 6 to 12 carbon atoms, or a phenyl group optionally substituted with an aralkyl group having 7 to 12 carbon atoms.)
Formula (7):

(In the formula, R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkyl cycloalkyl group having 6 to 12 carbon atoms, or a carbon number. 7 to 12 represents an aralkyl group or a phenyl group, A ² represents a single bond, a sulfur atom, or an alkylidene group having 1 to 8 carbon atoms, and A ³ represents an alkylene group having 2 to 8 carbon atoms.
Formula (8):

(In the formula, R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkyl cycloalkyl group having 6 to 12 carbon atoms, or a carbon number. Represents an aralkyl group or a phenyl group having 7 to 12. A ⁴ represents a single bond, a sulfur atom, or an alkylidene group having 1 to 8 carbon atoms, and A ⁵ represents an alkyl group having 1 to 8 carbon atoms or 1 carbon atom. A phenyl group which may be substituted with an alkyl group of ˜9, a phenyl group which may be substituted with a cycloalkyl group having 5 to 8 carbon atoms, and a phenyl group which may be substituted with a cycloalkyl group having 6 to 12 carbon atoms Represents a good phenyl group or a phenyl group optionally substituted by an aralkyl group having 7 to 12 carbon atoms.)
[9] The stabilizer composition according to [8], wherein the organic phosphorus compound represented by at least one formula selected from the group consisting of formula (4) to formula (8) is a compound represented by formula (4). object.

[10] A method for producing a thermoplastic polymer composition, comprising a step of mixing the stabilizer composition according to any one of [3] to [9] with a thermoplastic polymer.

[11] Use of the stabilizer composition according to any one of [3] to [9] for processing and stabilizing a thermoplastic polymer.

  The thermoplastic polymer composition of the present invention is excellent in processing stability.

  Hereinafter, the present invention will be described in detail.

  The thermoplastic polymer composition of the present invention comprises a thermoplastic polymer, a compound represented by the formula (1) (hereinafter sometimes referred to as the compound (1)), and a compound represented by the formula (2). (Hereinafter, may be referred to as compound (2)).

In the compound (1), R ¹ and R ² in the formula each independently represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. Examples of R ¹ and R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, t-amyl group. An alkyl group having 1 to 8 carbon atoms such as a group (—C (CH ₃ ) ₂ CH ₂ CH ₃ ), 2-ethylhexyl group and cyclohexyl group, for example, an aryl group having 6 to 12 carbon atoms such as phenyl group, for example, benzyl Examples thereof include aralkyl groups having 7 to 18 carbon atoms such as a group.

  Preferably, an alkyl group having a tertiary carbon such as a t-butyl group and a t-amyl group is used, and a t-amyl group is more preferable.

R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Preferable R ³ includes a hydrogen atom or a methyl group.

R ⁴ represents a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

Specific examples of the compound (1) include, for example, 2,4-di-t-butyl-6- [1- (3,5-di-t-butyl-2-hydroxyphenyl) ethyl] phenyl acrylate, 2, 4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, 2,4-di-t-butyl-6- (3,5 -Di-t-butyl-2-hydroxy-benzyl) phenyl methacrylate, 2,4-di-t-butyl-6- [1- (3,5-di-t-butyl-2-hydroxyphenyl) ethyl] phenyl Methacrylate, 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl methacrylate,
2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl methacrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy- 5-methylbenzyl) -4-methylphenyl acrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-ethylphenyl methacrylate, 2-t-amyl-6 -(3-t-amyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl methacrylate, 2-t-amyl-6- (3-t-amyl-2-hydroxy-5-methylbenzyl) -4 -Methylphenyl acrylate etc. can be mentioned. More preferably, 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate or 2-t-butyl-6- (3 -T-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate and the like.

  2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate is manufactured by Sumilizer GS (F) (registered trademark, manufactured by Sumitomo Chemical Co., Ltd.) Hereinafter, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate is commercially available as compound (1-1)). It is marketed as Sumilizer GM (registered trademark, manufactured by Sumitomo Chemical Co., Ltd., hereinafter may be referred to as compound (1-2)).

  In the compound (2), n represents an integer of 2 or more, preferably 2 to 6, more preferably 5.

  Examples of the compound (2) include 1,2,3-cyclopropanetriol and 1,2,3,4-cyclobutanetetraol. 1,2,3,4,5-cyclopentanepentaol (1,2,3,4,5-cyclopentanepentaol), 1,2,3,4,5,6-cyclohexanehexaol (1,2,3 , 4,5,6-cyclopentanehexaol), 1,2,3,4,5,6,7-cycloheptaneheptaol (1,2,3,4,5,6,7-cycloheptaneheptaol), 1,2, Examples include 3,4,5,6,7,8-cyclooctaneoctaol (1,2,3,4,5,6,7,8-cyclooctaneoctaol).

Preferred are 1,2,3,4,5,6-cyclohexanehexol such as myo-inositol, epi-inositol, allo-inositol, muco-inositol, neo-inositol, chiro-inositol, scyllo-inositol, More preferred are myo-inositol and scyllo-inositol.

  Compound (2) may be a commercially available product. Further, the compound (2) may be an anhydride or a hydrate.

  Thermoplastic polymers include polyethylene resins (high density polyethylene (HD-PE), low density polyethylene (LD-PE), linear low density polyethylene (LLDPE), ethylene-vinyl alcohol copolymer (EVOH), ethylene, -Ethyl acrylate copolymer, ethylene-vinyl acetate copolymer (EVA), etc.), polypropylene resin (propylene homopolymer, propylene-ethylene random copolymer, propylene-α-olefin random copolymer, propylene- Ethylene-α-olefin copolymer, propylene homopolymer component or a copolymer component mainly composed of propylene, and a polypropylene block copolymer composed of a copolymer component of propylene and ethylene and / or α-olefin) , Methylpentene polymer, polystyrene -Based resins (poly (p-methylstyrene), poly (α-methylstyrene), polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), special acrylic rubber-acrylonitrile-styrene copolymer Polymer, acrylonitrile-chlorinated polyethylene-styrene copolymer, etc.), polybutadiene resin (polybutadiene rubber (BR), styrene butadiene copolymer (SBR), styrene-butadiene block copolymer (SBS), BR or SBR or SBS) Impact-modified polystyrene (HI-PS), etc.), chlorinated polyethylene, polychloroprene, chlorinated rubber, polyvinyl chloride, polyvinylidene chloride, methacrylic resin, fluororesin, polyacetal, grafted polyphenylene Ether resin, polyphenylene sulfide resin, polyurethane, polyamide, polyester resin (eg, polyethylene terephthalate, polybutylene terephthalate, etc.), polylactic acid resin (PLA), polycarbonate, polyacrylate, polysulfone, polyetheretherketone, polyethersulfone, aromatic polyester Resin, diallyl phthalate prepolymer, silicone resin, 1,2-polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer, ethylene-methyl methacrylate copolymer, etc. Polyethylene resin, polypropylene Resin, polystyrene resin and polybutadiene resin are preferable, and polyethylene resin and polybutadiene resin are more preferable.

  The total weight of the compound (1) and the compound (2) in the thermoplastic polymer composition of the present invention is preferably 0.001 to 3 parts by weight, more preferably 0.001 to 100 parts by weight of the thermoplastic polymer. 02 to 2 parts by weight, more preferably 0.02 to 1 part by weight, and the weight ratio of the compound (1) to the compound (2) is preferably compound (1): compound (2) = 1000: 1 to 0.05: 1. From the viewpoint of the processing stability of the thermoplastic polymer, more preferably 1000: 1 to 10: 1, more preferably 1000: 1 to 100: 1, and even more preferably from suppressing discoloration of the thermoplastic polymer. 1000: 1 to 200: 1.

  The thermoplastic polymer composition of the present invention may contain additives (except for the compound (1) and the compound (2)) as long as the effects of the present invention are not impaired. Examples of such additives include antioxidants, ultraviolet absorbers, light stabilizers, metal deactivators, nucleating agents, lubricants, antistatic agents, flame retardants, fillers, pigments, inorganic fillers, and the like. be able to.

  Here, examples of the phenolic antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,6-di-t-butylphenol, 2 -T-butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t -Butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-diocudadecyl-4-methylphenol, 2,4 , 6-tricyclohexylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl 6- (1′-methylundecyl-1′-yl) phenol, 2,4-dimethyl-6- (1′-methylheptadecyl-1′-yl) phenol, 2,4-dimethyl-6- (1 Alkylated monophenols such as' -methyltridecyl-1'-yl) phenol and mixtures thereof;

  2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4 -Alkylthiomethylphenols such as nonylphenol and mixtures thereof;

  2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis [4-methyl-6- ( α-methylcyclohexyl) phenol]], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (4-methyl-6-nonylphenol), 2,2′-methylenebis (4 , 6-di-t-butylphenol), 2,2′-ethylidenebis (4,6-di-t-butylphenol), 2,2′-ethylidenebis (4-isobutyl-6-t-butylphenol), 2, 2′-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2′-methylenebis [6- (α, α-dimethylbenzyl) -4 Nonylphenol], 4,4′-methylenebis (6-tert-butyl-2-methylphenol), 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-butylidenebis (3-methyl) -6-tert-butylphenol), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis ( 3-t-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 1,1- Bis (5-t-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis-3′-t-butyl 4'-hydroxyphenyl] butyrate], bis (3-t-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-t-butyl-2'-hydroxy-5'-) Methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-t-) Butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5 Alkylidene bisphenol and its derivatives, such as -t-butyl-4-hydroxy-2-methylphenyl) pentane and mixtures thereof,

  Acylaminophenol derivatives such as 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide, octyl-N- (3,5-di-t-butyl-4-hydroxyphenyl) carbanate and mixtures thereof;

  β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid and methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1, 6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) Oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane And so Esters of mono- or polyhydric alcohols, such as mixtures of al,

  2,2′-thiobis (6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,2′-thiobis (4-octylphenol), 4,4′- Hydroxylated thiodiphenyl ether such as thiobis (2-methyl-6-tert-butylphenol), 4,4 ′-(2,6-dimethyl-4-hydroxyphenyl) disulfide,

  3,5,3 ′, 5′-tetra-t-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tris (3,5-di-t -Butyl-4-hydroxybenzyl) amine, bis (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide Benzyl derivatives such as O-benzyl derivatives, N-benzyl derivatives, S-benzyl derivatives, etc., isooctyl-3,5-di-t-butyl-4-hydroxybenzyl mercaptoacetate and mixtures thereof

  2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2-n-octylthio-4,6-bis (4 -Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2-n-octylthio-4,6-bis (4-hydroxy-3,5-di-t-butylphenoxy)- 1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-phenoxy) -1,3,5-triazine, tris (4-tert-butyl-3-hydroxy) -2,6-dimethylbenzyl) isocyanurate, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-t-butyl-4) -Hydroxyphenylethyl) -1,3,5 Triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylpropyl) -1,3,5-triazine, tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate , Triazine derivatives such as tris [2- (3 ′, 5′-di-t-butyl-4′-hydroxycinnamoyloxy) ethyl] isocyanurate and mixtures thereof;

  Dioctadecyl-2,2-bis (3,5-di-t-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-t-butyl-4-hydroxy-5-methylbenzyl) malonate, di Dodecyl mercaptoethyl-2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2 Hydroxybenzylated malonate derivatives such as hydroxybenzylated malonate derivatives such as bis (3,5-di-t-butyl-4-hydroxybenzyl) malonate and mixtures thereof,

  1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,4-bis (3,5-di-t-butyl-4 -Hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-tert-butyl-4-hydroxybenzyl) phenol and mixtures thereof, aromatic hydroxybenzyl derivatives,

  Dimethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-t-butyl-4 -Hydroxybenzylphosphonate, dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoester, and mixtures thereof Benzylphosphonate derivatives,

  β- (5-t-butyl-4-hydroxy-3-methylphenyl) propionic acid and methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1, 6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) Oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane And Esters of mono- or polyhydric alcohols such as mixtures thereof,

  β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3- Thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane and Esters of mono- or polyhydric alcohols such as a mixture of these,

  3,5-di-t-butyl-4-hydroxyphenylacetic acid and methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thia Undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane and mixtures thereof Esters of mono- or polyhydric alcohol,

  N, N′-bis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionyl] hydrazine, N, N′-bis [3- (3 ′, 5′-di-) t-butyl-4′-hydroxyphenyl) propionyl] hexamethylenediamine, N, N′-bis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionyl] trimethylenediamine and Β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid amides such as mixtures thereof, etc.

  Examples include tocopherols such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof.

  Examples of hydroquinone and alkylated hydroquinone antioxidants include 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, and 2,5-di-t-amylhydroquinone. 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4 -Hydroxyphenyl stearate, bis (3,5-di-t-butyl-4-hydroxyphenyl) adipate and mixtures thereof.

  Examples of the sulfur antioxidant include dilauryl 3,3′-thiodipropionate, tridecyl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thio. Examples include dipropionate, lauryl stearyl 3,3′-thiodipropionate, neopentanetetrayltetrakis (3-laurylthiopropionate), and the like.

  Examples of phosphorus antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl. Pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphos Phyto, tetrakis (2,4-di-t-butylphenyl) -4,4'-diphenylenediphosphonite, 2,2'-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite 2,2'-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, bis (2,4 -Di-t-butyl-6-methylphenyl) methyl phosphite, 2- (2,4,6-tri-t-butylphenyl) -5-ethyl-5-butyl-1,3,2-oxaphosphorinane 2,2 ′, 2 ″ -nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra-t-butyl-1,1′-biphenyl-2,2′-diyl) phosphites and their blend Etc.

  Examples of the ultraviolet absorber include phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, 4-t- Octylphenyl salicylate, bis (4-t-butylbenzoyl) resorcinol, benzoylresorcinol, hesisadecyl 3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, octadecyl 3 ′, 5′-di-t-butyl- Salicylate derivatives such as 4′-hydroxybenzoate, 2-methyl-4,6-di-t-butylphenyl 3 ′, 5′-di-t-butyl-4′-hydroxybenzoate and mixtures thereof;

  2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, bis (5-benzoyl-4-hydroxy-2- 2-hydroxybenzophenone derivatives such as methoxyphenyl) methane, 2,2 ′, 4,4′-tetrahydroxybenzophenone and mixtures thereof;

  2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3 ′, 5′-di-t-butyl-2′-hydroxyphenyl) benzotriazole, 2- (5′-t-butyl-2) '-Hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzo Triazole, 2- (3′-s-butyl-2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-t-amyl-2'-hydroxyphenyl) benzotriazole, 2- [2'-hydroxy-3', 5'-bis (α, α-di Methylbenzyl) phenyl] -2H-benzotriazole, 2-[(3′-t-butyl-2′-hydroxyphenyl) -5 ′-(2-octyloxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2 -[3'-t-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl] -5-chlorobenzotriazole, 2- [3'-t-butyl-2' -Hydroxy-5 '-(2-methoxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2- [3'-t-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl) phenyl] benzo Triazole, 2- [3′-tert-butyl-2′-hydroxy-5- (2-octyloxycarbonylethyl) phenyl] ben Triazole, 2- [3′-t-butyl-2′-hydroxy-5 ′-[2- (2-ethylhexyloxy) carbonylethyl] phenyl] benzotriazole, 2- [2-hydroxy-3- (3,4) , 5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3′-dodecyl) -2'-hydroxy-5'-methylphenyl) benzotriazole and 2- [3'-t-butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl) phenyl] benzotriazole, 2 , 2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethyl Til) phenol, 2,2′-methylenebis [4-t-butyl-6- (2H-benzotriazol-2-yl) phenol], poly (3-11) (ethylene glycol) and 2- [3′-t -Butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl] benzotriazole condensate, poly (3-11) (ethylene glycol) and methyl 3- [3- (2H-benzotriazole- 2-yl) -5-tert-butyl-4-hydroxyphenyl] propionate condensate, 2-ethylhexyl 3- [3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, octyl 3- [3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4- Droxyphenyl] propionate, methyl 3- [3-t-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, 3- [3-t-butyl-5 2- (2′-hydroxyphenyl) benzotriazole such as-(5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionic acid and mixtures thereof.

  Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ((2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1, 2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2,2, 6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl) -4-piperidyl) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-butyl malonate, bis (1-acryloyl-2,2,6,6-tetramethyl- 4-piperidyl) 2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1,2,2,6,6-pentamethyl-4-piperidyldecane Diate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -1- [2- ( 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2,6,6 -Tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1, 2, 3, -Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid Mixed esterified product of 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol,

  Mixed esterified product of 1,2,3,4-butanetetrabonic acid and 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5 · 5] Mixed esterified product with undecane, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethyl) Ethyl) -2,4,8,10-tetraoxaspiro [5 · 5] undecane mixed ester, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2, , 6-tetramethylpiperidine polycondensate, poly [(6-morpholino-1,3,5-triazine-2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl) Imino) hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)], poly [(6- (1,1,3,3-tetramethylbutyl) imino-1,3,5 -Triazine-2,4-diyl ((2,2,6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)), N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane polycondensate, N, N ′, 4,7-tetrakis [4 , 6-Bis (N-butyl-N- (2,2,6 6-tetramethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10 diamine, N, N ′, 4-tris [4,6-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine N, N ′, 4,7-tetrakis [4,6-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -1,3,5- Triazin-2-yl] -4,7-diazadecane-1,10-diamine, N, N ′, 4-tris [4,6-bis (N-butyl-N- (1,2,2,6,6) -Pentamethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7- Hindered amine light stabilizers such as diazadecane-1,10-diamine and mixtures thereof;

  Ethyl α-cyano-β, β-diphenyl acrylate, isooctyl α-cyano-β, β-diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α- Acrylate-based light such as cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline and mixtures thereof Stabilizer,

  Nickel complex of 2,2′-thiobis- [4- (1,1,3,3-tetramethylbutyl) phenol], nickel dibutyldithiocarbamate, nickel salt of monoalkyl ester, nickel complex of ketoxime and mixtures thereof, etc. Nickel-based light stabilizers,

  4,4'-dioctyloxy oxanilide, 2,2'-diethoxy oxanilide, 2,2'-dioctyloxy-5,5'-di-t-butylanilide, 2,2'-didodecyloxy -5,5'-di-t-butylanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl- Oxamide-based light stabilizers such as 2′-ethoxyanilide, 2-ethoxy-5,4′-di-t-butyl-2′-ethyloxanilide and mixtures thereof;

  2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazine, 2- [2,4-dihydroxyphenyl-4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine , 2- [2 Hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- ( 2- (2-hydroxyphenyl) -1 such as 2-hydroxy-3-octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and mixtures thereof , 3,5-triazine-based light stabilizer and the like.

  As the stabilizer, in addition to the above, for example, N, N-dibenzylhydroxyamine, N, N-diethylhydroxyamine, N, N-dioctylhydroxyamine, N, N-dilaurylhydroxyamine, N, N-ditetra Hydroxylamines such as decylhydroxyamine, N, N-dihexadecylhydroxyamine, N, N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl-N-octadecylhydroxyamine and mixtures thereof And so on.

  Examples of the lubricant include aliphatic hydrocarbons such as paraffin and wax, higher aliphatic acids having 8 to 22 carbon atoms, metals (Al, Ca, Mg, Zn) salts of higher aliphatic acids having 8 to 22 carbon atoms, carbon An aliphatic alcohol having 8 to 22 carbon atoms, polyglycol, an ester of a higher fatty acid having 4 to 22 carbon atoms and an aliphatic monohydric alcohol having 4 to 18 carbon atoms, a higher aliphatic amide having 8 to 22 carbon atoms, silicone oil, Examples include rosin derivatives.

（式中、Ｒ^５及びＲ^６はそれぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表し、Ｘは、ヘテロ原子及び／又は環状基を含んでいてもよい炭素数１〜２４のｍ価のアルコール残基を表し、ｍは１〜４の整数を表す。ここでアルコール残基とは、アルコールのヒドロキシ基から水素原子を除いた残りの基を表す。）
で表される化合物（以下、化合物（３）と記すことがある）である。 Among these additives, phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, ultraviolet absorbers, and hindered amine light stabilizers are preferably used. More preferably, it is a phenolic antioxidant and / or a phosphorus antioxidant, and a more preferable phenolic antioxidant is represented by the formula (3).

(In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and X represents a carbon atom having 1 to 24 carbon atoms which may contain a hetero atom and / or a cyclic group. m represents an alcohol residue, and m represents an integer of 1 to 4. Here, the alcohol residue represents a remaining group obtained by removing a hydrogen atom from a hydroxy group of alcohol.
(Hereinafter, may be referred to as compound (3)).

  In the compound (3), examples of the alkyl group having 1 to 6 carbon atoms include 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Linear alkyl group, i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, t-hexyl group, etc., branched alkyl group having 3 to 6 carbon atoms, cyclopentyl And a cycloalkyl group having 3 to 6 carbon atoms such as a cyclohexyl group.

  Examples of the monovalent alcohol residue having 1 to 24 carbon atoms include methanol, ethanol, n-propanol, i-propanol, n-butanol, t-butanol, n-hexanol, n-octanol, n-decanol, and n-dodecanol. , N-tetradecanol, n-hexadecanol, and n-octadecanol.

  Examples of the residue of the divalent alcohol having 1 to 24 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, diethylene glycol, triethylene glycol, 3,9-bis And a residue of (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane.

  Examples of the residue of a trivalent alcohol having 1 to 24 carbon atoms include a glycerol residue.

  Examples of the residue of a tetravalent alcohol having 1 to 24 carbon atoms include erythritol and pentaerythritol.

  Among the compounds (3), n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate (manufactured by BASF Japan, Irganox (registered trademark)) is even more preferable. 1076, hereinafter may be referred to as compound (3-1))), 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1 , 1-Dimethylethyl] -2,4,8,10-tetraoxaspiro [5 · 5] undecane (manufactured by Sumitomo Chemical, Smither (registered trademark) GA-80), pentaerythritol tetrakis [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate] (BASF Japan, Irganox (registered trademark) 1010).

  The amount of the compound (3) added in the thermoplastic polymer composition of the present invention is preferably 0.001 to 3 parts by weight, more preferably 0.02 to 2 parts by weight with respect to 100 parts by weight of the thermoplastic polymer composition. It is.

（式中、Ｒ^７及びＲ^８は、互いに独立に、水素原子、炭素数１〜９のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表す。）
式（５）：

（式中、Ｒ^９は、水素原子、炭素数１〜９のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表す。）
式（６）：

（式中、Ａ^１は、炭素数１〜１８のアルキル基、炭素数１〜９のアルキル基で置換されていてもよいフェニル基、炭素数５〜８のシクロアルキル基で置換されていてもよいフェニル基、炭素数６〜１２のアルキルシクロアルキル基で置換されていてもよいフェニル基、又は炭素数７〜１２のアラルキル基で置換されていてもよいフェニル基を表す。）
式（７）：

（式中、Ｒ^１０及びＲ^１１は、互いに独立に、水素原子、炭素数１〜９のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表す。Ａ^２は、単結合、硫黄原子、又は炭素数１〜８のアルキリデン基を表す。Ａ^３は炭素数２〜８のアルキレン基を表す。）
式（８）：

（式中、Ｒ^１２及びＲ^１３は、互いに独立に、水素原子、炭素数１〜９のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表す。Ａ^４は、単結合、硫黄原子、又は炭素数１〜８のアルキリデン基を表す。Ａ^５は、炭素数１〜８のアルキル基、炭素数１〜９のアルキル基で置換されていてもよいフェニル基、炭素数５〜８のシクロアルキル基で置換されていてもよいフェニル基、炭素数６〜１２のアルキルシクロアルキル基で置換されていてもよいフェニル基、又は炭素数７〜１２のアラルキル基で置換されていてもよいフェニル基を表す。） A more preferred phosphorus antioxidant is an organic phosphorus compound represented by at least one formula selected from the group consisting of the following formulas (4) to (8).
Formula (4):

(In the formula, R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or a carbon number. 7 to 12 aralkyl groups or phenyl groups are represented.)
Formula (5):

(In the formula, R ⁹ is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or Represents a phenyl group.)
Formula (6):

(In the formula, A ¹ may be substituted with a C 1-18 alkyl group, a phenyl group optionally substituted with a C 1-9 alkyl group, or a C 5-8 cycloalkyl group. It represents a good phenyl group, a phenyl group optionally substituted with an alkylcycloalkyl group having 6 to 12 carbon atoms, or a phenyl group optionally substituted with an aralkyl group having 7 to 12 carbon atoms.)
Formula (7):

(In the formula, R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkyl cycloalkyl group having 6 to 12 carbon atoms, or a carbon number. 7 to 12 represents an aralkyl group or a phenyl group, A ² represents a single bond, a sulfur atom, or an alkylidene group having 1 to 8 carbon atoms, and A ³ represents an alkylene group having 2 to 8 carbon atoms.
Formula (8):

(In the formula, R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkyl cycloalkyl group having 6 to 12 carbon atoms, or a carbon number. Represents an aralkyl group or a phenyl group having 7 to 12. A ⁴ represents a single bond, a sulfur atom, or an alkylidene group having 1 to 8 carbon atoms, and A ⁵ represents an alkyl group having 1 to 8 carbon atoms or 1 carbon atom. A phenyl group which may be substituted with an alkyl group of ˜9, a phenyl group which may be substituted with a cycloalkyl group having 5 to 8 carbon atoms, and a phenyl group which may be substituted with a cycloalkyl group having 6 to 12 carbon atoms Represents a good phenyl group or a phenyl group optionally substituted by an aralkyl group having 7 to 12 carbon atoms.)

In the formula (4), examples of the alkyl group having 1 to 9 carbon atoms represented by R ⁷ and R ⁸ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, Examples include i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, t-amyl group (—C (CH ₃ ) ₂ CH ₂ CH ₃ ), 2-ethylhexyl group and the like. Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group and a cyclohexyl group. Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include 2-methylcyclopentyl group and 2-methylcyclohexyl group. Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group and cumyl group (also referred to as 2-phenylpropan-2-yl group).

  Examples of the organic phosphorus compound represented by the formula (4) (hereinafter sometimes referred to as the compound (4)) include tris (2,4-di-t-butylphenyl) phosphite (manufactured by BASF). Irgaphos (registered trademark) 168, hereinafter may be referred to as compound (4-1).), Tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite and the like. Of these, compound (4-1) is preferred.

In the formula (5), the alkyl group having 1 to 9 carbon atoms represented by ^{R 9,} for example, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl Group, sec-butyl group, t-butyl group, n-pentyl group, t-amyl group (—C (CH ₃ ) ₂ CH ₂ CH ₃ ), 2-ethylhexyl group and the like. Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group and a cyclohexyl group. Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include 2-methylcyclopentyl group and 2-methylcyclohexyl group. Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group and cumyl group (also referred to as 2-phenylpropan-2-yl group).

  Examples of the organophosphorus compound represented by the formula (5) (hereinafter sometimes referred to as the compound (5)) include tetrakis (2,4-di-t-butylphenyl) -4,4-biphenyl. Range Phosphonite (manufactured by Clariant, Sandstub (registered trademark) P-EPQ, hereinafter sometimes referred to as compound (5-1)), tetrakis (2,4-di-t-butyl-5-methyl) Phenyl) -4,4-biphenylenediphosphonite (API, Yoshinox (registered trademark) GSY-P101) and the like. Of these, compound (5-1) is preferred.

In the formula (6), the alkyl group having 1 to 18 carbon atoms represented by ^{A 1,} for example, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl Group, t-butyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group and the like.

  Examples of the phenyl group which may be substituted with an alkyl group having 1 to 9 carbon atoms include a phenyl group, a 2-methylphenyl group, a 4-methylphenyl group, a 2-t-butylphenyl group, and a 4-t-butylphenyl group. 2-n-nonylphenyl group, 4-n-nonylphenyl group, 2,4-di-t-butylphenyl group, 2,4-di-n-nonylphenyl group, 2,6-di-t-butyl Phenyl group, 2-t-butyl-4-methylphenyl group, 2-t-butyl-4-ethylphenyl group, 2,5-di-t-butylphenyl group, 2,6-di-t-butyl-4 -A methylphenyl group etc. are mentioned.

  Examples of the phenyl group which may be substituted with a cycloalkyl group having 5 to 8 carbon atoms include 2-cyclopentylphenyl group, 2-cyclohexylphenyl group, 4-cyclohexylphenyl group, 2,4-dicyclohexylphenyl group and the like. .

  Examples of the phenyl group which may be substituted with an alkylcycloalkyl group having 6 to 12 carbon atoms include 2- (2-methylcyclohexyl) phenyl group, 4- (2-methylcyclohexyl) phenyl group, and 2,4-di- (2-methylcyclohexyl) phenyl group and the like can be mentioned.

  Examples of the phenyl group which may be substituted with an aralkyl group having 7 to 12 carbon atoms include 2-benzylphenyl group, 2-cumylphenyl group, 4-cumylphenyl group, and 2,4-dicumylphenyl group.

  Examples of the organic phosphorus compound represented by the formula (6) (hereinafter sometimes referred to as the compound (6)) include distearyl pentaerythritol diphosphite (manufactured by Adeka Corporation, Adeka Stub (registered trademark) PEP-). 8), bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol diphosphite (manufactured by ADEKA, ADEKA STAB (registered trademark) PEP-36, hereinafter referred to as compound (6-1)) ), Bis (2,4-di-t-butylphenyl) -pentaerythritol diphosphite (manufactured by GE Plastics, Ultranox (registered trademark) 626, hereinafter referred to as compound (6-2)) ), Bis (2,4-dicumylphenyl) -pentaerythritol diphosphite (Dover Chemical, Doverfo S9228T hereinafter sometimes referred to as compound (6-3).) Can be mentioned. Of these, compounds (6-1), (6-2) and (6-3) are preferred.

In the formula (7), examples of the alkyl group having 1 to 9 carbon atoms represented by R ¹⁰ and R ¹¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, Examples include i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, t-amyl group (—C (CH ₃ ) ₂ CH ₂ CH ₃ ), 2-ethylhexyl group and the like. Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group and a cyclohexyl group. Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include 2-methylcyclopentyl group and 2-methylcyclohexyl group. Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group and cumyl group (also referred to as 2-phenylpropan-2-yl group).

Examples of the alkylidene group represented by C 1-8 of A ² include a methylidene group, an ethylidene group, a propane-1-ylidene group, a propane-2-ylidene group, and an n-butane-1-ylidene group. It is done.

The alkylene group having 2 to 8 carbon atoms represented by A ^3, an ethylene group, a propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, 2,2-dimethyl-1, A 3-propylene group is mentioned.

  The organophosphorus compound represented by the formula (7) (hereinafter sometimes referred to as the compound (7)) is 2,2 ′, 2 ″ -nitrilotriethyl-tris (3,3 ′, 5, 5′-tetra-t-butyl-1,1′-biphenyl-2,2′-diyl) phosphite (manufactured by BASF, Irgaphos (registered trademark) 12, hereinafter may be referred to as compound (7-1) .) Is preferred.

In the formula (8), examples of the alkyl group having 1 to 9 carbon atoms represented by R ¹² and R ¹³ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, Examples include i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, t-amyl group (—C (CH ₃ ) ₂ CH ₂ CH ₃ ), 2-ethylhexyl group and the like. Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group and a cyclohexyl group. Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include 2-methylcyclopentyl group and 2-methylcyclohexyl group. Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group.

Examples of the alkylidene group having 1 to 8 carbon atoms represented by A ⁴ include a methylidene group, an ethylidene group, a propane-1-ylidene group, a propane-2-ylidene group, and an n-butane-1-ylidene group. It is done.

Examples of the alkyl group having 1 to 8 carbon atoms represented by A ^5, for example, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, An n-hexyl group, an n-octyl group, etc. are mentioned. Examples of the phenyl group which may be substituted with an alkyl group having 1 to 9 carbon atoms include a phenyl group, a 2-methylphenyl group, a 4-methylphenyl group, a 2-t-butylphenyl group, and 4-t-butyl. Phenyl group, 2-n-nonylphenyl group, 4-n-nonylphenyl group, 2,4-di-t-butylphenyl group, 2,4-di-n-nonylphenyl group, 2,6-di-t -Butylphenyl group, 2-t-butyl-4-methylphenyl group, 2-t-butyl-4-ethylphenyl group, 2,5-di-t-butylphenyl group, 2,6-di-t-butyl A -4-methylphenyl group etc. are mentioned.

  Examples of the phenyl group which may be substituted with a cycloalkyl group having 5 to 8 carbon atoms include 2-cyclopentylphenyl group, 2-cyclohexylphenyl group, 4-cyclohexylphenyl group, 2,4-dicyclohexylphenyl group and the like. .

  Examples of the phenyl group which may be substituted with an alkylcycloalkyl group having 6 to 12 carbon atoms include 2- (2-methylcyclohexyl) phenyl group, 4- (2-methylcyclohexyl) phenyl group, and 2,4-di- (2-methylcyclohexyl) phenyl group and the like can be mentioned.

  Examples of the phenyl group which may be substituted with an aralkyl group having 7 to 12 carbon atoms include 2-benzylphenyl group, 2-cumylphenyl group, 4-cumylphenyl group, and 2,4-dicumylphenyl group.

  Examples of the organophosphorus compound represented by the formula (8) (hereinafter sometimes referred to as the compound (8)) include 2,2-methylenebis (4,6-di-t-butylphenyl) octylphos. Phyto (manufactured by Adeka, Adeka Stub (registered trademark) HP-10, hereinafter may be referred to as compound (8-1)) is preferred.

  Of the compounds (4) to (8), the compound (4) is more preferable, and the compound (4-1) is more preferable.

  The total amount of the organic phosphorus compound selected from the compounds (4) to (8) in the thermoplastic polymer composition of the present invention is preferably 0.001 to 3 weights per 100 parts by weight of the thermoplastic polymer composition. Parts, more preferably 0.02 to 2 parts by weight.

  As a method for producing the thermoplastic polymer composition of the present invention, for example, when kneading the thermoplastic polymer, a method of separately blending the compound (1), the compound (2) and, if necessary, an additive, for example, , A step of producing a stabilizer composition by mixing the compound (1), the compound (2) and an additive as necessary, and a step of mixing the stabilizer composition obtained in the above step with a thermoplastic polymer. The method of including is mentioned. From the viewpoint of dispersibility of the compound (1) and the compound (2) in the thermoplastic polymer, the latter method is preferable.

  Here, as the process for producing the stabilizer composition, the method exemplified in the production method for the stabilizer composition described later is similarly exemplified.

  The step of mixing the stabilizer composition with the thermoplastic polymer will be described in more detail. For example, after the thermoplastic polymer and the stabilizer composition are dry blended, the mixture is melt-kneaded with a single-screw or multi-screw extruder and then extruded. A method for obtaining pellets of a thermoplastic polymer composition, for example, a method in which a solution obtained by dissolving a stabilizer composition in a solvent such as cyclohexane is added to a polymer solution after completion of polymerization of a thermoplastic polymer, and a solvent is removed. Is mentioned.

  The obtained thermoplastic polymer composition may be molded by supplying it to a molding machine in a molten state without cooling. The molding method is not particularly limited, and for example, a molding method such as an injection molding method, an extrusion molding method, an extrusion blow molding method, an injection blow molding method, or a biaxial stretch blow molding method can be used.

  By cooling after molding, a thermoplastic polymer molded article comprising the thermoplastic polymer composition of the present invention is obtained. Examples of thermoplastic polymer moldings that can be obtained include coil bobbins, connectors, switches, resistor parts, sockets, relays, capacitor cases, fuses, motors, microwave ovens, printed boards, IC manufacturing equipment, electronic parts such as lamps, and air outlets. Automotive parts such as garnish, hood vents, distributor caps, exhaust gas control valves, mechanical parts such as gears and cams, watch parts such as base plates, camera parts such as bottom lids, lens barrels and levers, and parts for leisure goods such as reels , Household appliances housing, lighting and wiring equipment, film, bottle, fiber, septic tank, toilet bowl, bathtub, unit bath, water tank, ship, chemical tank, pipe, corrugated sheet, flat plate, paint, decorative plate, electrical component encapsulant, Examples include resin concrete.

  The stabilizer composition of this invention contains a compound (1) and a compound (2).

  The stabilizer composition of the present invention contains compound (1) and compound (2) in a weight ratio of preferably 1000: 1 to 0.05: 1 (compound (1): compound (2)). From the viewpoint of the processing stability of the thermoplastic polymer, more preferably from 1000: 1 to 10: 1, from the viewpoint of suppressing discoloration of the thermoplastic polymer, more preferably from 1000: 1 to 100: 1, and even more preferably. 1000: 1 to 200: 1.

  The stabilizer composition of the present invention can be used as it is as a processing stabilizer for thermoplastic polymers. Moreover, said additive may be included in the range which does not inhibit the effect of this invention.

  Preferable additives are as described above, and the amount of the compound (3) added in the stabilizer composition of the present invention is preferably 0 to 90 parts, more preferably 0.8 parts, relative to 100 parts by weight of the stabilizer composition. 1 to 80 parts.

  As a method for producing the stabilizer composition of the present invention, for example, compound (1), compound (2) and, if necessary, the above additives are mixed in a mixer such as a Henschel mixer, a super mixer, or a high speed mixer. For example, a method for further extruding a mixture of compound (1), compound (2) and additive, for example, a method for further stirring and granulating the mixture of compound (1), compound (2) and additive, etc. Is mentioned.

  Hereinafter, the present invention will be described in more detail with reference to Examples, Reference Examples and Comparative Examples. Parts and% mean weight basis unless otherwise specified. The melt flow rate is referred to as MFR.

In the following examples, the following was used as compound (1).
Compound (1-1): 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., Smither (registered) Trademark) GS (F))
Compound (1-2): 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Sumilizer (registered trademark) GM)

In the following examples, the following was used as the compound (2).
Compound (2-1): myo-inositol

In each of the following examples, the following was used as compound (3).
Compound (3-1): n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate (manufactured by BASF Japan, Irganox (registered trademark) 1076)
Compound (3-2): 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 8,10-tetraoxaspiro [5.5] undecane (manufactured by Sumitomo Chemical, Smither (registered trademark) GA-80)
Compound (3-3): Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (BASF Japan, Irganox (registered trademark) 1010)

In each of the following examples, the following was used as the compound (4).
Compound (4-1): Tris (2,4-di-t-butylphenyl) phosphite (manufactured by BASF, Irgaphos (registered trademark) 168)

In the following examples, the following are used as the compound (5) to the compound (8), respectively.
Compound (5-1): Tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylene diphosphonite (manufactured by Clariant, Sandstub (registered trademark) P-EPQ)
Compound (6-1): Bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol diphosphite (manufactured by Adeka, Adekastab (registered trademark) PEP-36)
Compound (6-2): Bis (2,4-di-t-butylphenyl) -pentaerythritol diphosphite (manufactured by GE Plastics, Ultranox (registered trademark) 626)
Compound (6-3): bis (2,4-dicumylphenyl) -pentaerythritol diphosphite (manufactured by Dover Chemical Co., Doverphos S9228T)
Compound (7-1): 2,2 ′, 2 ″ -nitrilotriethyl-tris (3,3 ′, 5,5′-tetra-t-butyl-1,1′-biphenyl-2,2′-diyl ) Phosfight (BASF, Irgaphos (registered trademark) 12)
Compound (8-1): 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (manufactured by ADEKA, ADEKA STAB (registered trademark) HP-10)

Example 1 (Production of stabilizer composition)
A stabilizer composition was produced by mixing 0.3 part of the compound (1-1) and 0.01 part of the compound (2-1).

Example 2 (Production of stabilizer composition)
A stabilizer composition was produced by mixing 0.3 part of the compound (1-1), 0.01 part of the compound (2-1) and 0.2 part of the compound (3-1).

Example 3 (Production of stabilizer composition)
A stabilizer composition was produced by mixing 0.3 part of the compound (1-2), 0.01 part of the compound (2-1) and 0.2 part of the compound (3-1).

Reference Example 1 (Production of stabilizer composition)
A stabilizer composition was produced by mixing 0.3 part of the compound (1-1) and 0.2 part of the compound (3-1).

Example 4 (Production of thermoplastic polymer composition)
After dry blending 100 parts of a styrene-butadiene block copolymer manufactured by Asahi Kasei as a thermoplastic polymer and 0.31 part of the stabilizer composition obtained in Example 1, the resulting resin composition was prepared by using a screw diameter of 30 mm. A strand obtained by kneading and extruding at 230 ° C. and a screw rotation speed of 50 rpm using a single screw extruder (manufactured by Tanabe Plastics Co., Ltd., VS30-28 type extruder) is cut with a pelletizer to produce pellets of a thermoplastic polymer composition. Obtained.

Example 5 (Production of thermoplastic polymer composition)
In Example 4, a thermoplastic polymer composition was obtained in the same manner as in Example 4 except that 0.51 part of the stabilizer composition obtained in Example 2 was used instead of the stabilizer composition obtained in Example 1. A product pellet was obtained.

Example 6 (Production of thermoplastic polymer composition)
In Example 4, a thermoplastic polymer composition was obtained in the same manner as in Example 4 except that 0.51 part of the stabilizer composition obtained in Example 3 was used instead of the stabilizer composition obtained in Example 1. A product pellet was obtained.

Reference example 2
In Example 4, a thermoplastic polymer composition was obtained in the same manner as in Example 4 except that 0.5 part of the stabilizer composition obtained in Reference Example 1 was used instead of the stabilizer composition obtained in Example 1. A product pellet was obtained.

Comparative Example 1
In Example 4, instead of the stabilizer composition obtained in Example 1, the pellets of the thermoplastic polymer composition were obtained in the same manner as in Example 4 except that 0.3 part of compound (1-1) was used. Obtained.

Test Example 1 (Processing stability test)
For the pellets obtained in Examples 4, 5, and 6, Reference Example 2 and Comparative Example 1, a retention MFR test was performed as an evaluation of workability during operation during extrusion. The test was performed in accordance with JIS K 7210. The inside of a melt indexer (L217-E14011, manufactured by Techno Seven) was set at 270 ° C., and the thermoplastic polymer composition was charged into the cylinder at a load of 2.16 kg. The measurement was carried out by measuring the MFR and then measuring the MFR at a load of 2.16 kg after allowing the thermoplastic polymer composition to stay in the cylinder for 30 minutes. The results are shown in Table 1.

The MFR fluctuation rate in Table 1 is a value obtained by the following equation. In the case of a styrene-butadiene block copolymer, the smaller the MFR variation rate, the better the workability.

MFR fluctuation rate (%) =
Absolute value of (MFR value after staying for 30 minutes-MFR value before staying) / MFR value before staying × 100

Example 7 (Production of thermoplastic polymer composition)
After dry blending 100 parts of nylon 6 (manufactured by Ube Industries Co., Ltd.) and the total amount of the stabilizer composition obtained in Example 1, the obtained resin composition was mixed with a single screw extruder (Tanabe Plastics) having a screw diameter of 30 mm. A strand obtained by kneading and extruding at 280 ° C. and a screw rotation speed of 50 rpm using a VS30-28 type extruder manufactured by Komatsu Ltd. was cut with a pelletizer to obtain pellets of a thermoplastic polymer composition.

Comparative Example 3
In Example 7, in place of the stabilizer composition obtained in Example 1, 0.1 parts of compound (1-1) was used, and the pellets of the thermoplastic polymer composition were obtained in the same manner as in Example 7. Obtained.

Test example 2 (processing stability test)
In Test Example 1, instead of the pellets obtained in Examples 4, 5, and 6, Reference Example 2 and Comparative Example 1, respectively, the pellets obtained in Example 7 and Comparative Example 3 were used, and the temperature in the cylinder was set to 285. The MFR fluctuation rate was determined in the same manner as in Test Example 1 except that the temperature was changed to ° C. The results are shown in Table 2.
In the case of nylon 6, the smaller the MFR fluctuation rate, the better the processing stability.

Example 8 (Production of stabilizer composition)
A stabilizer composition was produced by mixing 0.1 part of the compound (1-2) and 0.01 part of the compound (2-1).

Example 9 (Production of thermoplastic polymer composition)
After dry blending 100 parts of polyurethane [manufactured by Nippon Milactolan Co., Ltd.] and the total amount of the stabilizer composition obtained in Example 8, the obtained resin composition was mixed with a single screw extruder (Tanabe Plastics Co., Ltd.) having a screw diameter of 30 mm. The strand obtained by kneading and extruding at 200 ° C. and a screw rotation speed of 50 rpm using a VS30-28 type extruder) was cut with a pelletizer to obtain a pellet of a thermoplastic polymer composition.

Comparative Example 4
In Example 9, in place of the stabilizer composition obtained in Example 8, the pellets of the thermoplastic polymer composition were obtained in the same manner as in Example 9 except that 0.1 part of compound (1-2) was used. Obtained.

Test Example 3 (Processing stability test)
In Test Example 1, instead of the pellets obtained in Examples 4, 5, 6, Reference Example 2 and Comparative Example 1, respectively, the pellets obtained in Example 9 and Comparative Example 4 were used, and the temperature in the cylinder was set to 200. The MFR fluctuation rate was determined in the same manner as in Test Example 1 except that the temperature was changed to ° C. The results are shown in Table 3.
In the case of polyurethane, the smaller the MFR fluctuation rate, the better the processing stability.

Example 10 (Production of thermoplastic polymer composition)
After dry blending 100 parts of a styrene butadiene elastomer (manufactured by Asahi Kasei Chemicals) and the total amount of the stabilizer composition obtained in Example 1, the resulting resin composition was mixed with a single-screw extruder having a screw diameter of 30 mm ( A strand obtained by kneading and extrusion at 200 ° C. and a screw speed of 50 rpm using a Tanabe Plastics Co., Ltd. (VS30-28 type extruder) was cut with a pelletizer to obtain a pellet of a thermoplastic polymer composition.

Comparative Example 5
A pellet of a thermoplastic polymer composition was obtained in the same manner as in Example 2 except that 0.1 part of the compound (1-1) was used instead of the total amount of the stabilizer composition obtained in Example 1.

Test Example 4 (Processing stability test)
In Test Example 1, instead of the pellets obtained in Examples 4, 5, 6, Reference Example 2 and Comparative Example 1, respectively, the pellets obtained in Example 10 and Comparative Example 5 were used, and the temperature in the cylinder was set to 285. The MFR fluctuation rate was determined in the same manner as in Test Example 1 except that the temperature was changed to ° C. The results are shown in Table 4.
In the case of a styrene butadiene block elastomer, it can be said that the smaller the MFR fluctuation rate, the better the processing stability.

Example 11 (Production of Stabilizer Composition)
Stabilizer by mixing 0.03 part of compound (1-1), 0.005 part of compound (2-1), 0.2 part of compound (3-3) and 0.2 part of compound (4-1) A composition was prepared.

Example 12 (Production of thermoplastic polymer composition)
After dry blending 100 parts of a styrene-butadiene block copolymer manufactured by Chevron Phillips as a thermoplastic polymer and the total amount of the stabilizer composition obtained in Example 11, the resulting resin composition was prepared with a screw diameter of 30 mm. A strand obtained by kneading and extruding at 230 ° C. and a screw rotation speed of 50 rpm using a single screw extruder (VS30-28 type extruder manufactured by Tanabe Plastics) is cut with a pelletizer to obtain pellets of a thermoplastic polymer composition. It was.

Reference example 3
A stabilizer composition was prepared by mixing 0.03 part of the compound (1-1), 0.2 part of the compound (3-3) and 0.2 part of the compound (4-1).

Comparative Example 6
In Example 12, the thermoplastic polymer composition was obtained in the same manner as in Example 11 except that the total amount of the stabilizer composition obtained in Reference Example 3 was used instead of the stabilizer composition obtained in Example 11. Pellets were obtained.

Test Example 5 (Processing stability test)
Test Example 1 except that the pellets obtained in Example 11 and Comparative Example 6 were used in place of the pellets obtained in Examples 4, 5, and 6, Reference Example 2 and Comparative Example 1, respectively. The MFR fluctuation rate was obtained in the same manner as described above. The results are shown in Table 5.

Examples 13 to 19 (Production of Stabilizer Composition)
The compound (1-1) and the compound (2-1) were mixed at the ratio shown in Table 6 in the same manner as in Example 1 to obtain stabilizer compositions.

Example 20 (Production of thermoplastic polymer composition)
After dry blending 100 parts of an electrochemically produced styrene-butadiene block copolymer and 0.2 part of the stabilizer composition obtained in Example 13 as a thermoplastic polymer, the obtained resin composition was screwed to a screw diameter of 30 mm. A strand obtained by kneading and extruding at 230 ° C. and a screw rotation speed of 50 rpm using a single screw extruder (manufactured by Tanabe Plastics Co., Ltd., VS30-28 type extruder) is cut with a pelletizer to produce pellets of a thermoplastic polymer composition. Obtained.

Examples 21-26 (Production of thermoplastic polymer composition)
In Example 20, it replaced with the stabilizer composition obtained in Example 13, and it carried out similarly to Example 20 except using 0.2 parts of stabilizer compositions obtained in Examples 14-19, respectively. A pellet of thermoplastic polymer composition was obtained.

Comparative Example 7
In Example 20, a pellet of a thermoplastic polymer composition was obtained in the same manner as in Example 20 except that 0.2 part of the compound (1-1) was used.

Test Example 6
In Test Example 1, except that the pellets obtained in Examples 20 to 26 and Comparative Example 7 were used in place of the pellets obtained in Examples 4, 5, 6, Reference Example 2 and Comparative Example 1, respectively, In the same manner as in Test Example 1, the MFR was measured to determine the MFR fluctuation rate. The results are shown in Table 7.

Examples 27 and 28 (Production of stabilizer composition)
The compound (1-1) and the compound (2-1) were mixed at the ratio shown in Table 8 in the same manner as in Example 1 to obtain a stabilizer composition.

Example 29 (Production of thermoplastic polymer composition)
After dry blending 100 parts of an electrochemically produced styrene-butadiene block copolymer and 0.51 part of the stabilizer composition obtained in Example 27 as a thermoplastic polymer, the resulting resin composition was treated with a screw diameter of 30 mm. A strand obtained by kneading and extruding at 230 ° C. and a screw rotation speed of 50 rpm using a single screw extruder (manufactured by Tanabe Plastics Co., Ltd., VS30-28 type extruder) is cut with a pelletizer to produce pellets of a thermoplastic polymer composition. Obtained.

Example 30 (Production of thermoplastic polymer composition)
In Example 29, a thermoplastic polymer composition was prepared in the same manner as in Example 29 except that 0.71 part of the stabilizer composition obtained in Example 28 was used instead of the stabilizer composition obtained in Example 27. A product pellet was obtained.

Test Example 7
In Test Example 1, except that the pellets obtained in Examples 29 and 30 were used in place of the pellets obtained in Examples 4, 5, 6, Reference Example 2 and Comparative Example 1, respectively, Test Example 1 and Similarly, MFR was measured and MFR fluctuation rate was obtained. The results are shown in Table 9.

Examples 31-117 (Production of Stabilizer Composition)
The compounds shown in Tables 10 to 12 are mixed in the same manner as in Example 1 to obtain a stabilizer composition. Thermoplastic polymers in which these stabilizer compositions are blended are excellent in processing stability.

Examples 118-239 (Production of Thermoplastic Polymer Composition)
In Example 4, as the thermoplastic polymer and the stabilizer composition, the thermoplastic polymer composition was prepared in the same manner as in Example 4 except that 100 parts of the thermoplastic polymer described in Tables 13 to 16 and the stabilizer composition were used. Obtain pellets. The resulting thermoplastic polymer composition is excellent in processing stability.
In Tables 13 to 16, each thermoplastic polymer has the following meaning.
In Tables 8 to 11, each thermoplastic polymer has the following meaning.
P-1: High density polyethylene (HDPE) (excluding P-44 to P-49)
P-2: Low density polyethylene (LDPE) (excluding P-50 to P-57)
P-3: Linear low density polyethylene (LLDPE) (excluding P-58 to P-64)
P-4: Ethylene-ethyl acrylate copolymer (EEA)
P-5: Ethylene-vinyl acetate copolymer (EVA)
P-6: Polypropylene (PP) (excluding P-65 to P-71)
P-7: Propylene-ethylene random copolymer P-8: Propylene-α-olefin random copolymer P-9: Propylene-ethylene-α-olefin copolymer P-10: Polystyrene (PS)
P-11: Acrylonitrile-styrene copolymer (SAN)
P-12: Acrylonitrile-butadiene-styrene copolymer (ABS)
P-13: Special acrylic rubber-acrylonitrile-styrene copolymer P-14: Acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS)
P-15: Polybutadiene rubber (BR)
P-16: Styrene butadiene copolymer (SB)
P-17: Styrene butadiene block copolymer (SBS)
P-18: Chlorinated polyethylene (CPE)
P-19: Polychloroprene P-20: Chlorinated rubber P-21: Polyvinyl chloride (PVC)
P-22: Polyvinylidene chloride (PVDC)
P-23: Methacrylic resin P-24: Fluororesin P-25: Polyacetal (POM)
P-26: Grafted polyphenylene ether resin P-27: Polyphenylene sulfide resin (PPS)
P-28: Polyamide (PA) (excluding P-74 to P-78)
P-29: Polyethylene terephthalate (PET)
P-30: Polybutylene terephthalate (PBT)
P-31: Polylactic acid (PLA)
P-32: Polycarbonate (PC)
P-33: Polyacrylate P-34: Polysulfone (PPSU)
P-35: Polyetheretherketone (PEEK)
P-36: Polyethersulfone (PES)
P-37: Aromatic polyester P-38: Diallyl phthalate prepolymer P-39: Silicone resin (SI)
P-40: 1,2-polybutadiene P-41: polyisoprene P-42: butadiene / acrylonitrile copolymer (NBR)
P-43: Ethylene-methyl methacrylate copolymer (EMMA)
P-44: High density polyethylene (HDPE) with MFR of 40 g / 10 min
P-45: High density polyethylene (HDPE) with an MFR of 20 g / 10 min
P-46: High density polyethylene (HDPE) with an MFR of 10 g / 10 min
P-47: High density polyethylene (HDPE) with an MFR of 5 g / 10 min
P-48: High density polyethylene (HDPE) with MFR of 1 g / 10 min
P-49: High density polyethylene (HDPE) with MFR of 0.1 g / 10 min
P-50: Low density polyethylene (LDPE) with an MFR of 75 g / 10 min
P-51: Low density polyethylene (LDPE) with an MFR of 50 g / 10 min
P-52: Low density polyethylene (LDPE) with MFR of 25 g / 10 min
P-53: Low density polyethylene (LDPE) with an MFR of 10 g / 10 min
P-54: Low density polyethylene (LDPE) with an MFR of 5 g / 10 min
P-55: Low density polyethylene (LDPE) with an MFR of 2 g / 10 min
P-56: Low density polyethylene (LDPE) with an MFR of 1 g / 10 min
P-57: Low density polyethylene (LDPE) with MFR of 0.1 g / 10 min
P-58: Linear low density polyethylene (LLDPE) with MFR of 100 g / 10 min
P-59: Linear low density polyethylene (LLDPE) with an MFR of 50 g / 10 min
P-60: Linear low density polyethylene (LLDPE) with MFR of 25 g / 10 min
P-61: Linear low density polyethylene (LLDPE) with an MFR of 10 g / 10 min
P-62: Linear low density polyethylene (LLDPE) with MFR of 5 g / 10 min
P-63: Linear low density polyethylene (LLDPE) with MFR of 1 g / 10 min
P-64: Linear low density polyethylene (LLDPE) with MFR of 0.1 g / 10 min
P-65: Polypropylene (PP) with MFR of 100 g / 10 min
P-66: Polypropylene (PP) with an MFR of 50 g / 10 min
P-67: Polypropylene (PP) with MFR of 25 g / 10 min
P-68: Polypropylene (PP) with an MFR of 10 g / 10 min
P-69: Polypropylene (PP) with an MFR of 5 g / 10 min
P-70: Polypropylene (PP) with an MFR of 1 g / 10 min
P-71: Polypropylene (PP) with an MFR of 0.1 g / 10 min
P-72: Styrene ethylene butylene styrene block copolymer (SEBS)
P-73: Styrene isoprene styrene block copolymer (SIS)
P-74: Nylon 610 (Ny610)
P-75: Nylon 612 (Ny612)
P-76: Nylon 11 (Ny11)
P-77: Nylon 12 (Ny12)
P-78: Nylon MXD6 (NyMXD6)

  The thermoplastic polymer composition of the present invention is excellent in processing stability.

Claims (11)

Thermoplastic polymer, formula (1)

(Wherein R ¹ and R ² each independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. R ³ represents a hydrogen atom or Represents an alkyl group having 1 to 3 carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group.)
And a compound represented by formula (2)

(In the formula, n represents an integer of 2 or more.)
The thermoplastic polymer composition containing the compound represented by these.   The thermoplastic resin according to claim 1, wherein the total weight of the compound represented by formula (1) and the compound represented by formula (2) is 0.001 to 3 parts by weight with respect to 100 parts by weight of the thermoplastic polymer. Polymer composition. Formula (1)

(Wherein R ¹ and R ² each independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. R ³ represents a hydrogen atom or Represents an alkyl group having 1 to 3 carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group.)
A compound represented by formula (2)

(In the formula, n represents an integer of 2 or more.)
The stabilizer composition containing the compound represented by these.   The compound represented by the formula (1) is 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate or 2-t The stabilizer composition according to claim 3, which is -butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate.   The stabilizer composition according to claim 3 or 4, wherein n in the formula (2) is 5.   The stabilizer composition according to claim 3 or 4, wherein the compound represented by the formula (2) is myo-inositol or scyllo-inositol. Furthermore, Formula (3)

(In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and X represents a carbon atom having 1 to 24 carbon atoms which may contain a hetero atom and / or a cyclic group. m represents an alcohol residue, and m represents an integer of 1 to 4. Here, the alcohol residue represents a remaining group obtained by removing a hydrogen atom from a hydroxy group of alcohol.
The stabilizer composition as described in any one of Claims 3-6 containing the compound represented by these. Furthermore, the stabilizer composition as described in any one of Claims 3-7 containing the organophosphorus compound represented by the at least 1 formula chosen from the group which consists of Formula (4)-Formula (8).
Formula (4):

(In the formula, R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, or a carbon number. 7 to 12 aralkyl groups or phenyl groups are represented.)
Formula (5):

(In the formula, R ⁹ is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or Represents a phenyl group.)
Formula (6):

(In the formula, A ¹ may be substituted with a C 1-18 alkyl group, a phenyl group optionally substituted with a C 1-9 alkyl group, or a C 5-8 cycloalkyl group. It represents a good phenyl group, a phenyl group optionally substituted with an alkylcycloalkyl group having 6 to 12 carbon atoms, or a phenyl group optionally substituted with an aralkyl group having 7 to 12 carbon atoms.)
Formula (7):

(In the formula, R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkyl cycloalkyl group having 6 to 12 carbon atoms, or a carbon number. 7 to 12 represents an aralkyl group or a phenyl group, A ² represents a single bond, a sulfur atom, or an alkylidene group having 1 to 8 carbon atoms, and A ³ represents an alkylene group having 2 to 8 carbon atoms.
Formula (8):

(In the formula, R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkyl cycloalkyl group having 6 to 12 carbon atoms, or a carbon number. Represents an aralkyl group or a phenyl group having 7 to 12. A ⁴ represents a single bond, a sulfur atom, or an alkylidene group having 1 to 8 carbon atoms, and A ⁵ represents an alkyl group having 1 to 8 carbon atoms or 1 carbon atom. A phenyl group which may be substituted with an alkyl group of ˜9, a phenyl group which may be substituted with a cycloalkyl group having 5 to 8 carbon atoms, and a phenyl group which may be substituted with a cycloalkyl group having 6 to 12 carbon atoms Represents a good phenyl group or a phenyl group optionally substituted by an aralkyl group having 7 to 12 carbon atoms.)   The stabilizer composition according to claim 8, wherein the organic phosphorus compound represented by at least one formula selected from the group consisting of formula (4) to formula (8) is a compound represented by formula (4).   The manufacturing method of the thermoplastic polymer composition characterized by including the process of mixing the stabilizer composition as described in any one of Claims 3-9 with a thermoplastic polymer.   Use of the stabilizer composition according to any one of claims 3 to 9 for process stabilization of a thermoplastic polymer.