JP2010270310A - Stabilizer composition and thermoplastic polymer composition containing the composition - Google Patents

Abstract

（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）
Ｃ_ｎＨ_２ｎ＋２Ｏ_ｎ （２）
（式中、ｎは４〜１２の整数を表す。）
で表される化合物とを含有することを特徴とする安定剤組成物。
【選択図】なしThere is a need for a thermoplastic polymer composition having further improved processing stability.
SOLUTION: 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)
C _n H _{2n + 2} O _n (2)
(In the formula, n represents an integer of 4 to 12.)
The stabilizer composition characterized by including the compound represented by these.
[Selection figure] None

Description

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

Thermoplastic polymers are widely used in food packaging containers and household goods because of their excellent transparency and impact resistance. However, these thermoplastic polymers have a problem that the processing stability deteriorates due to a decrease in fluidity during molding.
As a thermoplastic polymer composition having excellent processing stability, 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl) is added to polybutadiene rubber which is a kind of thermoplastic polymer. A thermoplastic polymer composition containing (2-hydroxyphenyl) ethyl] phenyl acrylate has been proposed (Patent Document 1).

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

  Recently, there has been a demand for thermoplastic polymer compositions having further improved processing stability.

（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）
Ｃ_ｎＨ_２ｎ＋２Ｏ_ｎ （２）
（式中、ｎは４〜１２の整数を表す。）
で表される化合物とを含有することを特徴とする安定剤組成物。 In order to solve this problem, the present inventors have intensively studied, and as a result, have arrived at the inventions described in [1] to [6] below.
[1] 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)
C _n H _{2n + 2} O _n (2)
(In the formula, n represents an integer of 4 to 12.)
The stabilizer composition characterized by including the compound represented by these.

[2] 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 [1], which is 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate.

[3] The stabilizer composition according to [1] or [2], wherein the compound represented by the formula (2) is allitol, iditol, galactitol, sorbitol, taritol, or mannitol.

（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）
Ｃ_ｎＨ_２ｎ＋２Ｏ_ｎ （２）
（式中、ｎは４〜１２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であって、
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重量部であることを特徴とする熱可塑性ポリマー組成物。 [4] 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)
C _n H _{2n + 2} O _n (2)
(In the formula, n represents an integer of 4 to 12.)
A thermoplastic polymer composition containing a compound represented by:
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. Polymer composition.

[5] A method for producing a thermoplastic polymer composition, comprising a step of mixing the stabilizer composition according to any one of [1] to [3] with a thermoplastic polymer.
[6] Use of the stabilizer composition according to any one of [1] to [3] for processing and stabilizing a thermoplastic polymer.

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

Hereinafter, the present invention will be described in detail.
The stabilizer composition of the present invention comprises a compound represented by the formula (1) (hereinafter sometimes referred to as the compound (1)) and a compound represented by the formula (2) (hereinafter referred to as the compound (2). May be included).

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, and t-amyl. 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 is an integer of 4 to 12, preferably 5 to 8, and more preferably 6.

  Examples of the compound (2) include sugar alcohols having 4 to 12 carbon atoms such as erythritol, threitol, arabinitol, xylitol, adonitol, allitol, iditol, galactitol, sorbitol, thalitol, mannitol, boremitol, perseitol, octitol and the like. be able to.

The compound (2) may be an optically active substance such as D-form or L-form, or an optically inactive substance such as DL-form.
As the compound (2), a sugar alcohol having n of 6 such as allitol, iditol, galactitol, sorbitol, tallitol or mannitol represented by the Fisher projection formula is preferable, and sorbitol or mannitol is more preferable.

  The stabilizer composition of the present invention preferably contains compound (1) and compound (2) in a weight ratio of 9: 1 to 1: 9 (compound (1): compound (2)), and 8: More preferably, it is contained in a weight ratio of 2 to 2: 8.

The stabilizer composition of the present invention can be used as it is as a processing stabilizer for thermoplastic polymers. Moreover, what added an appropriate additive in the range which does not inhibit the effect of this invention may be contained in the stabilizer composition of this invention.
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.
In the stabilizer composition of the present invention, the total weight of the compound (1), the compound (2) and the additive is preferably 50% or more, more 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′- 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. Of these additives other than compound (1) and compound (2), those preferably used are phenolic antioxidants other than compound (1) and compound (2), phosphorus antioxidants, sulfur antioxidants. Agents, UV absorbers, hindered amine light stabilizers.

  Particularly preferred phenolic antioxidants other than compound (1) and compound (2) include 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2, 4-dioctylthiomethyl-6-methylphenol, 2,2′-thiobis (6-tert-butylphenol), 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 (4,6-di-t-butylphenol), 2,2′-ethylidenebis (4,6-di-t-butylphenol), , 4′-methylenebis (6-tert-butyl-2-methylphenol), 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-t) -Butylphenol), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1,3-tris (5- t-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) The phosphite etc. are mentioned, These can each use individually or 2 types 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-amyl-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 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.

  The thermoplastic polymer composition of the present invention is a thermoplastic polymer composition containing a thermoplastic polymer, compound (1) and compound (2), and is the sum of the compound (1) and the compound (2). The weight is preferably 0.001 to 3 parts by weight, more preferably 0.02 to 2 parts by weight, and still more preferably 0.02 to 1 part by weight with respect to 100 parts by weight of the thermoplastic polymer. The weight ratio of (1) to the compound (2) is preferably compound (1): compound (2) = 9: 1 to 1: 9, more preferably 2: 8 to 8: 2. And

  Here, as the thermoplastic polymer, polyethylene resin (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 (crystalline propylene homopolymer, propylene-ethylene random copolymer, 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 Copolymer), methylpentene polymer , Polystyrene resins (poly (p-methylstyrene), poly (α-methylstyrene), etc., acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), special acrylic rubber-acrylonitrile-styrene Copolymer, acrylonitrile-chlorinated polyethylene-styrene copolymer, etc.), polybutadiene resin (polybutadiene rubber (BR), styrene butadiene copolymer (SBR), styrene-butadiene block copolymer (SBS), BR or SBR) Or impact-resistant polystyrene (HI-PS) modified with SBS), chlorinated polyethylene, polychloroprene, chlorinated rubber, polyvinyl chloride, polyvinylidene chloride, methacrylic resin, fluororesin, polyacetal, grafting Polyphenylene ether resin, polyphenylene sulfide resin, polyurethane, polyamide, polyester resin (eg, polyethylene terephthalate, polybutylene terephthalate, etc.), polylactic acid resin (PLA), polycarbonate, polyacrylate, polysulfone, polyether ether ketone, polyether sulfone, aromatic Polyester resin, diallyl phthalate prepolymer, silicone resin, 1,2-polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer, ethylene-methyl methacrylate copolymer, and the like. From the good moldability, polyethylene resin, Polypropylene resins, polystyrene resins and polybutadiene resins are preferred, and ethylene resins and polybutadiene resins are more preferred. Arbitrariness.

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 a step of producing a stabilizer composition by mixing the compound (2) and, if necessary, an additive, and a step of mixing the stabilizer composition obtained in the above step with a thermoplastic polymer, etc. 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 a process of manufacturing a stabilizer composition, the method illustrated by the manufacturing method of the said stabilizer composition is illustrated similarly.

  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.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. Parts and% mean weight basis unless otherwise specified.

Example 1 (Production of stabilizer composition)
As compound (1), 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate (Sumilyzer GS (F), registered trademark) , Manufactured by Sumitomo Chemical Co., Ltd., which may hereinafter be referred to as compound (1-1)) was mixed with 0.48 part, and mannitol (0.12 part) was mixed as compound (2) to prepare a stabilizer composition.

Example 2 (Production of stabilizer composition)
As compound (1), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (Sumilyzer GM, registered trademark, manufactured by Sumitomo Chemical Co., Ltd., hereinafter referred to as compound) A stabilizer composition was prepared by mixing 0.48 part of (sometimes referred to as (1-2)) and 0.12 part of sorbitol as compound (2).

Example 3 (Production of thermoplastic polymer composition)
After dry blending 100 parts of Asahi Kasei styrene-butadiene block copolymer and 0.6 part of the stabilizer composition obtained in Example 1, a 30 mm diameter single screw extruder (VS30-28, manufactured by Tanabe Plastics Co., Ltd.). The mixture was kneaded using a mold extruder at 230 ° C. and a screw rotation speed of 50 rpm to obtain pellets of a thermoplastic polymer composition.

Examples 4 and 5 (Production of thermoplastic polymer composition) and Comparative Example 1
In Example 3, the pellets of the thermoplastic polymer composition were prepared in the same manner as in Example 3 except that the number of parts of compound (1-1) and mannitol in the stabilizer composition used was the number of parts shown in Table 1, respectively. Obtained.

Test Example 1 (Processing stability test)
The pellets obtained in Examples 3 to 5 and Comparative Example 1 were subjected to a stay MFR test as an evaluation of processability during operation during extrusion. The test was performed in accordance with JIS K 7210, the temperature of the melt indexer (L217-E14011, manufactured by Techno Seven) was set at 270 ° C., the thermoplastic polymer composition was retained in the cylinder for 30 minutes, and the load was 2. This was done by measuring the MFR at 16 kg. The results are shown in Table 1. The larger the MFR value, the better the processing stability under static conditions.
The processing stability improvement rate in Table 1 is a value obtained by the following equation.

Example 6 (Production of thermoplastic polymer composition)
In Example 3, except that the stabilizer composition obtained in Example 2 was used instead of the stabilizer composition obtained in Example 1, the pellets of the thermoplastic polymer composition were prepared in the same manner as in Example 3. Obtained.

Example 7 (Production of thermoplastic polymer composition) and Comparative Example 2
In Example 6, the pellets of the thermoplastic polymer composition were prepared in the same manner as in Example 6 except that the number of parts of compound (1-2) and sorbitol in the stabilizer composition used was the number of parts shown in Table 2, respectively. Obtained.

Test example 2 (processing stability test)
In the same manner as in Test Example 1, the pellets obtained in Examples 6 and 7 and Comparative Example 2 were subjected to a residence MFR test as an evaluation of processability during operation during extrusion. The results are shown in Table 2.

  The thermoplastic polymer composition containing the stabilizer composition of the present invention is effective in improving the processing stability.

Claims (6)

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)
C _n H _{2n + 2} O _n (2)
(In the formula, n represents an integer of 4 to 12.)
The stabilizer composition characterized by including 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 1, which is -butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate.   The stabilizer composition according to claim 1 or 2, wherein the compound represented by the formula (2) is allitol, iditol, galactitol, sorbitol, taritol or mannitol. 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)
C _n H _{2n + 2} O _n (2)
(In the formula, n represents an integer of 4 to 12.)
A thermoplastic polymer composition containing a compound represented by:
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. Polymer composition.   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 1-3 with a thermoplastic polymer.   Use of the stabilizer composition according to any one of claims 1 to 3 for the process stabilization of a thermoplastic polymer.