JP5593595B2 - Thermoplastic polymer composition - Google Patents

Description

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

  Thermoplastic polymer compositions are widely used in food packaging containers and household goods. The thermoplastic polymer composition contains 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate in the thermoplastic polymer. And 4,4′-thiobis (6-tert-butyl-m-cresol) (ie, 4,4′-thiobis (2-tert-butyl-5-methyl) A thermoplastic polymer composition containing phenol)) is known (Patent Document 2).

Japanese Patent Laid-Open No. 1-168643 (Example) Japanese Patent Publication No. 40-12171 (Table 1)

  However, the thermoplastic polymer composition is not always satisfactory depending on conditions, and a thermoplastic polymer composition having further improved processing stability is required.

（式（１）中、Ｒ^１、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、炭素数７〜１８のアラルキル基を表し、Ｒ^３は、水素原子、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。）
と、式（２）で表される化合物

（式（２）中、Ｒ^５は、硫黄原子又は酸素原子を表し、Ｒ^６及びＲ^７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、炭素数７〜１８のアラルキル基を表す。）
とを含有する熱可塑性ポリマー組成物であり、該組成物における式（１）で表される化合物と式（２）で表される化合物との重量比が９：１〜１：２の重量比であることを特徴とする熱可塑性ポリマー組成物。 In order to solve this problem, the present inventors diligently studied the thermoplastic polymer composition, and as a result, have reached the inventions described in [1] to [6] below.
[1] a thermoplastic polymer;
Compound represented by formula (1)

(In the formula ^{(1), R 1, R} 2 represent each independently an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, ^{R 3} is (Represents a hydrogen atom or 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 (2), ^{R 5} represents, represents a sulfur atom or an oxygen atom, ^{R 6} and ^{R 7} each independently represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, 7 carbon atoms Represents -18 aralkyl groups.)
The weight ratio of the compound represented by formula (1) and the compound represented by formula (2) in the composition is 9: 1 to 1: 2. A thermoplastic polymer composition characterized in that:

[2] The total content of the compound represented by the formula (1) and the compound represented by the formula (2) is 0.01 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic polymer. The thermoplastic polymer composition according to [1].
[3] The compound represented by the formula (1) is 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate. The thermoplastic polymer according to [1] or [2], wherein the compound represented by the formula (2) is 4,4′-thiobis (2-t-butyl-5-methylphenol) Composition.

（式（１）中、Ｒ^１、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、炭素数７〜１８のアラルキル基を表し、Ｒ^３は、水素原子、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。）
と、式（２）で表される化合物

（式（２）中、Ｒ^５は、硫黄原子又は酸素原子を表し、Ｒ^６及びＲ^７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、炭素数７〜１８のアラルキル基を表す。）
とを９：１〜１：２の重量比で含有することを特徴とするフェノール組成物。 [4] Compound represented by formula (1)

(In the formula ^{(1), R 1, R} 2 represent each independently an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, ^{R 3} is (Represents a hydrogen atom or 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 (2), ^{R 5} represents, represents a sulfur atom or an oxygen atom, ^{R 6} and ^{R 7} each independently represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, 7 carbon atoms Represents -18 aralkyl groups.)
In a weight ratio of 9: 1 to 1: 2.

[5] A method for producing a thermoplastic polymer composition, comprising a step of mixing the phenol composition according to [4] with a thermoplastic polymer.

[6] Use of the phenol composition according to [4] for processing stabilization of 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, it may be referred to as compound (2)), and the weight ratio of compound (1) to compound (2) in the composition is 9: 1 to 1: 2. The weight ratio is preferably 9: 1 to 1: 1, particularly preferably 9: 1 to 2: 1.

In the compound (1), R ¹ and R ² in the formula are each independently, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t - butyl group, n- pentyl group, t-pentyl group _{(-C (CH 3) 2 CH} 2 CH 3), 2- ethylhexyl group, cyclohexyl group an alkyl group having 1 to 8 carbon atoms, for example, such as a phenyl group An aryl group having 6 to 12 carbon atoms, for example, an aralkyl group having 7 to 18 carbon atoms such as a benzyl group.
In particular, an alkyl group having a tertiary carbon such as a t-butyl group and a t-pentyl group is preferable, and a t-pentyl group is particularly preferable.

In Formula (1), R ³ represents a hydrogen atom, for example, an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and a methyl group is particularly preferable.

In formula (1), R ⁴ represents a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

  Specific examples of the compound (1) include 2,4-di-t-butyl-6- [1- (3,5-di-t-butyl-2-hydroxyphenyl) ethyl] phenyl acrylate, 2- [1 -(2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 2,4-di-t-butyl-6- [1- (3 5-di-t-butyl-2-hydroxyphenyl) ethyl] phenyl methacrylate, 2,4-di-t-pentyl 6- [1- (3,5-di-t-pentyl 2-hydroxyphenyl) ethyl] phenyl Methacrylate, 2,4-di-t-butyl-6- [1- (3,5-di-t-butyl-2-hydroxyphenyl) propyl] phenyl acrylate, 2-t-butyl-6- (3-t -Butyl-2-hydroxy-5-me Rubenzyl) -4-methylphenyl methacrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-ethylbenzyl) -4-ethylphenyl methacrylate, 2-t-pentyl-6- (3 -T-pentyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl methacrylate, 2-t-pentyl-6- (3-t-pentyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl An acrylate etc. are mentioned. 2- [1- (2-Hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, because it gives the thermoplastic polymer particularly good processing stability 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate is preferred. 2- [1- (2-Hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate is manufactured by Sumilizer GS (F) (registered trademark, manufactured by Sumitomo Chemical Hereinafter, it may be referred to as the compound (1-1)) and is commercially available. 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate Is marketed as Sumilizer GM (registered trademark, manufactured by Sumitomo Chemical Co., Ltd.).

In the compound (2), R ⁵ in the formula represents a sulfur atom or an oxygen atom. In particular, a sulfur atom is preferable.

In formula (2), each R ⁶ independently represents, for example, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n- An alkyl group having 1 to 8 carbon atoms such as a pentyl group, a t-pentyl group, a 2-ethylhexyl group and a cyclohexyl group; for example, an aryl group having 6 to 12 carbon atoms such as a phenyl group; for example, 7 carbon atoms such as a benzyl group Represents -18 aralkyl groups. A methyl group is particularly preferable.

In formula (2), each R ⁷ is independently, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n- Alkyl groups having 1 to 8 carbon atoms such as pentyl group, t-pentyl group, 2-ethylhexyl group and cyclohexyl group, for example, aryl groups having 6 to 12 carbon atoms such as phenyl group, for example, 7 to 7 carbon atoms such as benzyl group 18 aralkyl groups are represented. In particular, a t-butyl group is preferable.
R ⁶ and R ⁷ may be the same as or different from each other.

  Specific examples of the compound (2) include, for example, 4,4′-thiobis (2-tert-butyl-5-methylphenol), 4,4′-thiobis (3,6-methylphenol), 4,4 ′. -Thiobis (3,6-t-butylphenol) and the like. 4,4'-thiobis (2-t-butyl-5-methylphenol) is commercially available as WX-R (registered trademark, manufactured by Sumitomo Chemical Co., Ltd., hereinafter sometimes referred to as compound (2-1)).

  In the thermoplastic polymer composition of the present invention, the compound (1) and the compound (2) may be added to the thermoplastic polymer, respectively, or after preparing the phenol composition containing the compound (1) and the compound (2). The phenol composition may be blended with the thermoplastic polymer.

Hereinafter, the phenol composition will be described.
The phenol composition of the present invention comprises the compound (1) and the compound (2) in a weight ratio of 9: 1 to 1: 2, preferably 9: 1 to 1: 1, particularly preferably 9: 1. Contained in a weight ratio of ˜2: 1.
The phenol composition may be a mixture composed only of the compound (1) and the compound (2), and contains additives other than the compound (1) and the compound (2) as long as the effects of the present invention are not impaired. It may be a composition.
Examples of the additive include an antioxidant other than the compound (1) and the compound (2), an ultraviolet absorber, a light stabilizer, a metal deactivator, a nucleating agent, a lubricant, an antistatic agent, a flame retardant, A filler, a pigment, an inorganic filler, etc. can be mentioned.
The phenol composition is preferably such that the total weight of the compound (1), the compound (2) and the additive is 50% or more, particularly preferably 90% or more.

  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;

  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′-thiobis Hydroxylated thiodiphenyl ether such as (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-pentylhydroquinone. 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) phosphite, 6- [3- (3-t -Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyl-dibenzo [d, f] [1,3,2] dioxaphosphine and their A mixture etc. are mentioned.

  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-pentyl2'-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. Of these additives other than compounds (1) and (2), those preferably used are phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants other than compounds (1) and (2), UV absorber, hindered amine light stabilizer.

  Particularly preferred phenolic antioxidants other than the compounds (1) and (2) include 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,4. -Dioctylthiomethyl-6-methylphenol, 2,2'-thiobis (6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4 -Ethyl-6-t-butylphenol), 2,2′-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol]], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (4,6-di-t-butylphenol), 2,2′-ethylidenebis (4,6-di-t-butylphenol), 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, 1,1,3-tris (5-tert-butyl) -4-hydroxy-2-methylphenyl) butane, ethylene glycol bis [3,3-bis-3′-t-butyl-4′-hydroxyphenyl] butyrate],

  2,4,6-tris (3,5-di-t-butyl-4-phenoxy) -1,3,5-triazine, tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) Isocyanurate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tris [2- (3 ′, 5′-di-tert-butyl-4′-hydroxycinnamoyloxy) ethyl] Isocyanurate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, di-n-octadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, 3,5-di-t -Calcium salt of butyl-4-hydroxybenzylphosphonic acid monoester, n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate Neopentanetetrayltetrakis (3,5-di-t-butyl-4-hydroxycinnamate), thiodiethylenebis (3,5-di-t-butyl-4-hydroxycinnamate), 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,6-dioxaoctamethylenebis (3,5-di-t-butyl-4- Hydroxycinnamate), hexamethylene bis (3,5-di-t-butyl-4-hydroxycinnamate), triethylene glycol bis (5-t-tyl-4-hydroxy-3-methylcinnamate), 3, 9-bis [2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetrao Xaspiro [5 · 5] undecane, 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 and the like, and these may be used alone or in combination of two or more.

  Particularly preferred phosphorus antioxidants include tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearyl 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, 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) fluoro Sulphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl 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) phosphite, 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyl-dibenzo [d, f] [1,3,2] dioxaphosphepine and the like can be mentioned, and these can be used alone or in combination of two or more.

  Preferred 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, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, bis (5-benzoyl-4 -Hydroxy-2-methoxyphenyl) methane, 2,2 ', 4,4'-tetrahydroxybenzophenone, 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-chlorobenzotriazole, 2- (3′-s-butyl-2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octyloxyphenyl) ) Benzotriazole, 2- (3 ′, 5′-di-t-pentyl-2′-hydroxyphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) ) Phenyl] -2H-benzotriazole and the like, and these may be used alone or in combination of two or more.

  Preferred examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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-butylmalonate, bis (1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) 2,2-bis (3,5-di-t-butyl-4- Hydroxybenzyl) -2-butylmalonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-tert-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) 1,2,3,4-butanetetracarboxylate,

  Tetrakis (1,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6 Mixed esterified product of 6-pentamethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol Mixed esterified product, 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] undecane mixed ester, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-te Mixed esterified product of tramethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, dimethyl succinate and Polycondensate with 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 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) -1,3,5-triazine-2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2 , 2,6 , 6-tetramethyl-4-piperidyl) imino)] and the like, and these may be used alone or in combination of two or more.

  As a method for producing the phenol composition, for example, the compound (1), the compound (2) and, if necessary, the above additives are mixed in a mixer such as a mortar, a Henschel mixer, a super mixer, a high speed mixer or the like. For example, a method of further extruding the mixture of compound (1), compound (2) and additive, for example, a method of further stirring and granulating the mixture of compound (1), compound (2) and additive, etc. It is done.

  The thermoplastic polymer composition of the present invention usually contains a total of 0.01 to 5 parts by weight of the compound (1) and the compound (2), preferably 0.02 to 100 parts by weight of the thermoplastic polymer. 2 parts by weight, particularly preferably 0.02 to 1 part by weight is contained.

  Here, examples of the thermoplastic polymer include polypropylene resins such as ethylene-propylene copolymers, polyethylene resins (high density polyethylene (HD-PE), low density polyethylene (LD-PE), and linear low density. Polyethylene (LLDPE), methylpentene polymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, polystyrene (poly (p-methylstyrene), polystyrene such as poly (α-methylstyrene), Acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, special acrylic rubber-acrylonitrile-styrene copolymer, acrylonitrile-chlorinated polyethylene-styrene copolymer, styrene-butadiene copolymer), chlorinated polyethylene , Poly Loroprene, chlorinated rubber, polyvinyl chloride, polyvinylidene chloride, methacrylic resin, ethylene-vinyl alcohol copolymer, fluororesin, polyacetal, grafted polyphenylene ether resin, polyphenylene sulfide resin, polyurethane, polyamide, polyester resin (for example, polyethylene terephthalate) , Polybutylene terephthalate, etc.), polycarbonate, polyacrylate, polysulfone, polyether ether ketone, polyether sulfone, aromatic polyester resin, diallyl phthalate prepolymer, silicone resin, 1,2-polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer And ethylene-methyl methacrylate copolymer. Especially, because of good moldability, polyethylene Of these resins, polypropylene resins, polypropylene resins, and polystyrenes are preferable, and polypropylene resins, acrylonitrile-butadiene-styrene copolymers, and styrene-butadiene copolymers are particularly preferable.

  Here, the polypropylene-based resin means a polyolefin containing a structural unit derived from propylene. Specifically, a crystalline propylene homopolymer, a propylene-ethylene random copolymer, a propylene-α-olefin random copolymer. Polypropylene block comprising a polymer, a propylene-ethylene-α-olefin copolymer, a propylene homopolymer component or a copolymer component mainly composed of propylene, and a copolymer component of propylene and ethylene and / or α-olefin A copolymer etc. are mentioned.

  In the present invention, when a polypropylene resin is used as the thermoplastic polymer, one type of polypropylene resin may be used, or two or more types may be blended and used.

  The α-olefin is usually an α-olefin having 4 to 12 carbon atoms, such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and the like. More preferred are 1-butene, 1-hexene, and 1-octene.

  Examples of the propylene-α-olefin random copolymer include a propylene-1-butene random copolymer, a propylene-1-hexene random copolymer, and a propylene-1-octene random copolymer.

  Examples of the propylene-ethylene-α-olefin copolymer include propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, and propylene-ethylene-1-octene copolymer. It is done.

  As a copolymer component mainly composed of propylene in a 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 Examples thereof include a propylene-ethylene copolymer component, a propylene-1-butene copolymer component, a propylene-1-hexene copolymer component, and the like, and a copolymer component of propylene and ethylene and / or an α-olefin. As, for example, propylene-ethylene copolymer component, propylene-ethylene-1-butene copolymer component, propylene-ethylene-1-hexene copolymer component, propylene-ethylene-1-octene copolymer component, propylene -1-butene copolymer component, propylene-1-hex Examples thereof include a cene copolymer component and a propylene-1-octene copolymer component. The content of ethylene and / or α-olefin having 4 to 12 carbon atoms in the copolymer component of propylene and ethylene and / or α-olefin is usually 0.01 to 20% by weight.

  Examples of the polypropylene block copolymer comprising a propylene homopolymer component or a copolymer component mainly composed of propylene and a copolymer component of propylene and ethylene and / or α-olefin include, for example, a propylene-ethylene block Copolymer, (propylene)-(propylene-ethylene) block copolymer, (propylene)-(propylene-ethylene-1-butene) block copolymer, (propylene)-(propylene-ethylene-1-hexene) block Copolymer, (propylene)-(propylene-1-butene) block copolymer, (propylene)-(propylene-1-hexene) block copolymer, (propylene-ethylene)-(propylene-ethylene-1-butene) ) Block copolymer, (propylene-ethylene)-(polymer Pyrene-ethylene-1-hexene) block copolymer, (propylene-ethylene)-(propylene-1-butene) block copolymer, (propylene-ethylene)-(propylene-1-hexene) block copolymer, Propylene-1-butene)-(propylene-ethylene) block copolymer, (propylene-1-butene)-(propylene-ethylene-1-butene) block copolymer, (propylene-1-butene)-(propylene- (Ethylene-1-hexene) block copolymer, (propylene-1-butene)-(propylene-1-butene) block copolymer, (propylene-1-butene)-(propylene-1-hexene) block copolymer Etc.

  In the present invention, when a polypropylene resin is used as the thermoplastic polymer, it is preferable to use a crystalline propylene homopolymer, a propylene homopolymer component or a copolymer component mainly composed of propylene, propylene, ethylene and / or carbon number. It is a polypropylene block copolymer comprising a copolymer component of 4 to 12 α-olefin. More preferably, it is a polypropylene block copolymer comprising a propylene homopolymer component or a copolymer component mainly composed of propylene and a copolymer component of propylene and ethylene and / or an α-olefin having 4 to 12 carbon atoms. is there.

As a manufacturing method of a thermoplastic polymer composition, for example, when kneading a thermoplastic polymer, a method in which compound (1), compound (2) and additives are separately blended as necessary, for example, compound ( 1), a method comprising mixing a compound (2) and, if necessary, a phenol composition by mixing an additive, and a step of mixing the phenol composition obtained in the above step with a thermoplastic polymer, etc. It is done. From the viewpoint of dispersibility of the compound (1) and the compound (2) in the thermoplastic polymer, the latter method is preferable.
The step of mixing the phenol composition with the thermoplastic polymer will be described in more detail. For example, after the thermoplastic polymer and the phenol composition are dry blended, the mixture is melt-kneaded with a single-screw or multi-screw extruder and then extruded. Examples thereof include a method for obtaining polymer pellets, for example, a method in which a solution in which a phenol composition is dissolved in a solvent such as cyclohexane is added to a polymer solution after the completion of polymerization of a thermoplastic polymer to remove the solvent.

  The thermoplastic polymer composition of the present invention is excellent in processing stability such as a decrease in fluidity during molding and a suppression of the generation of fish eye gel.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these. Parts and% mean weight basis unless otherwise specified.

<Example 1>
(Production Example 1 of phenol composition)
As compound (1), 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate (Sumilyzer GS (F), registered trademark) , Manufactured by Sumitomo Chemical Co., Ltd.), that is, 0.45 parts of compound (1-1) and 4,4′-thiobis (2-t-butyl-5-methylphenol) (similarizer WX-R, (Registered trademark, manufactured by Sumitomo Chemical Co., Ltd.), that is, 0.05 part of compound (2-1) was mixed in a mortar to prepare a phenol composition.

(Production Example 1 of Thermoplastic Polymer Composition)
Propylene-ethylene block copolymer (hereinafter may be referred to as PP · EP as a thermoplastic polymer. MI (230 ° C., load 2.16 kg): 3 g / 10 min, manufactured by Sumitomo Chemical Co., Ltd.) 100 parts and the above phenol composition After dry blending 0.5 part of the product, it was kneaded at 230 ° C. with a screw rotation speed of 50 rpm using a 30 mm diameter single screw extruder (VS30-28 type extruder, manufactured by Tanabe Plastics). Pellets were obtained.

(Processing stability test)
About the pellet obtained by (Manufacturing example 1 of a thermoplastic polymer composition), 230 degreeC and 2.16kg conditions using a melt indexer (L217-E14011, the Techno Seven company make) based on JISK7210. The melt flow rate (MFR) value was measured below. In addition, when a thermoplastic polymer is PP * EP, it means that processing stability is so high that the measured MFR value is small.
The test results are shown in Table 1.

＊１：比較例１のＭＦＲ値を１００とした場合のＭＦＲ値の相対比

* 1: Relative ratio of MFR value when MFR value of Comparative Example 1 is 100

<Example 2 , Reference Example 1 , Comparative Examples 1-2>
As a phenol composition, the compound (1-1) and the compound (1-2) were performed in the same manner as in Example 1 except that the number of parts shown in Table 1 was used. The results are summarized in Table 1.
Examples 1 and 2 are compared with a thermoplastic polymer composition containing only compound (1-1) (Comparative Example 1) and a thermoplastic polymer composition containing only compound (2-1) (Comparative Example 2). It can be seen that both have excellent processing stability.

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

Claims (5)

A thermoplastic polymer;
Compound represented by formula (1)

(In the formula ^{(1), R 1, R} 2 represent each independently an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, ^{R 3} is (Represents a hydrogen atom or 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 (2), ^{R 5} represents, represents a sulfur atom or an oxygen atom, ^{R 6} and ^{R 7} each independently represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, 7 carbon atoms Represents -18 aralkyl groups.)
The weight ratio of the compound represented by formula (1) to the compound represented by formula (2) in the composition is 9: 1 to 2 : 1, A thermoplastic polymer characterized in that the total content of the compound represented by the formula (1) and the compound represented by the formula (2) is 0.01 to 5 parts by mass with respect to 100 parts by mass of the plastic polymer. Composition. The compound represented by the formula (1) is 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, The compound represented by (2) is 4,4′-thiobis (2-t-butyl-5-methylphenol).
The thermoplastic polymer composition according to claim 1. Compound represented by formula (1)

(In the formula ^{(1), R 1, R} 2 represent each independently an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, ^{R 3} is A hydrogen atom, 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 the formula (2)

(In the formula (2), ^{R 5} represents, represents a sulfur atom or an oxygen atom, ^{R 6} and ^{R 7} each independently represent an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, 7 carbon atoms Represents -18 aralkyl groups.)
In a weight ratio of 9: 1 to 2 : 1. A phenol composition for thermoplastic polymers .   A method for producing a thermoplastic polymer composition, comprising the step of mixing the phenol composition according to claim 3 with a thermoplastic polymer.   Use of the phenolic composition according to claim 3 for process stabilization of thermoplastic polymers.