JP2011032461A - Thermoplastic polymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problem that processing stability of a thermoplastic polymer composition is deteriorated by action of heat and oxygen depending on the condition in molding processing. <P>SOLUTION: The thermoplastic polymer composition includes a thermoplastic polymer, a compound represented by formula (1) (wherein R<SP>1</SP>and R<SP>2</SP>each independently represents a hydrogen atom or a 1-6C alkyl group, X represents an n-valent 1-24C alcohol residual group which may contain a hetero atom and/or a cyclic group, m represents an integer of 1-4, and here, the alcohol residual group represents a group in which H is removed from OH of alcohol) and a compound represented by formula (2): C<SB>n</SB>H<SB>2n+2</SB>O<SB>n</SB>(2) (wherein n represents an integer of 4-12). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

（式中、Ｒ^１及びＲ^２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ｎ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ＯＨからＨを除いた基を表す。）
で表される化合物とを含有する熱可塑性ポリマー組成物（特許文献１〜３）が知られている。 Thermoplastic polymers are widely used in food packaging containers and household goods because of their excellent transparency and impact resistance. As a thermoplastic polymer composition, a thermoplastic polymer and formula (1)

(In the formula, R ¹ and R ² 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. represents an n-valent alcohol residue, and m represents an integer of 1 to 4. Here, the alcohol residue represents a group obtained by removing H from OH of an alcohol.)
A thermoplastic polymer composition (Patent Documents 1 to 3) containing a compound represented by the formula is known.

JP 59-25826 US Pat. No. 3,644,482 U.S. Pat. No. 3,308,059

  Depending on the conditions during molding, the processing stability of the thermoplastic polymer composition may be deteriorated by the action of heat, oxygen, or the like.

（式中、Ｒ^１及びＲ^２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ｎ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ＯＨからＨを除いた基を表す。）
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り、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重量部である熱可塑性ポリマー組成物。 In order to solve such problems, 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 [6] below.
[1] Thermoplastic polymer, formula (1)

(In the formula, R ¹ and R ² 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. represents an n-valent alcohol residue, and m represents an integer of 1 to 4. Here, the alcohol residue represents a group obtained by removing H from OH of an alcohol.)
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.)
The total weight of the compound represented by Formula (1) and the compound represented by Formula (2) is 100 parts by weight of the thermoplastic polymer. A thermoplastic polymer composition in an amount of 0.001 to 3 parts by weight.

（式中、Ｒ^１及びＲ^２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ｎ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ＯＨからＨを除いた基を表す。）
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。
［３］ 式（１）で表される化合物が、ｎ−オクタデシル−β−（４’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）プロピオネート、３，９−ビス［２−｛３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ｝−１，１−ジメチルエチル］−２，４，８，１０−テトラオキサスピロ［５・５］ウンデカン又はペンタエリスリトールテトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］であることを特徴とする［２］記載の安定剤組成物。
［４］ 式（２）で表される化合物がアリトール、イジトール、ガラクチトール、ソルビトール、タリトール又はマンニトールである［２］又は［３］記載の安定剤組成物。 [2] Formula (1)

(In the formula, R ¹ and R ² 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. represents an n-valent alcohol residue, and m represents an integer of 1 to 4. Here, the alcohol residue represents a group obtained by removing H from OH of an alcohol.)
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.
[3] The compound represented by the formula (1) is n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate, 3,9-bis [2- { 3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5 · 5] undecane or pentaerythritol The stabilizer composition according to [2], which is tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate].
[4] The stabilizer composition according to [2] or [3], wherein the compound represented by the formula (2) is allitol, iditol, galactitol, sorbitol, taritol, or mannitol.

[5] A method for producing a thermoplastic polymer composition, comprising a step of mixing the stabilizer composition according to any one of [2] to [4] with a thermoplastic polymer.

[6] Use of the stabilizer composition according to any one of [2] to [4] for stabilizing the processing 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 may be referred to as compound (2)).

  In the compound (1), the alkyl group having 1 to 6 carbon atoms includes 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.

  Examples of the compound (1) include 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-trioxabici B [2,2,2] esters with mono- or polyhydric alcohols, such as octane 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,

  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 mixtures of these and the like.

  As compound (1), n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate (manufactured by BASF, Irganox (registered trademark) 1076, hereinafter, compound ( 1-1)), 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 Co., Ltd., Smither (registered trademark) GA-80, hereinafter may be referred to as compound (1-2)) or pentaerythritol tetrakis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF, Irganox (registered trademark) 1010, hereinafter referred to as compound (1-3) Bet there) is preferred.

  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.

  Compound (II) may be a commercially available product. Compound (II) 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 (crystalline propylene homopolymer, propylene-ethylene random copolymer, propylene-α-olefin random copolymer, A propylene-ethylene-α-olefin copolymer, 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 Etc.), methylpentene polymer, poly Polystyrene (poly (p-methylstyrene), poly (α-methylstyrene), 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 High impact polystyrene (HI-PS) modified with SBS), chlorinated polyethylene, polychloroprene, chlorinated rubber, polyvinyl chloride, polyvinylidene chloride, methacrylic resin, fluororesin, polyacetal, grafted polyphene Nylene 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 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, even more preferably 0.05 to 0.8 parts by weight, particularly preferably 0.08 to 0.7 parts by weight, The weight ratio of compound (1) to compound (2) is preferably compound (1): compound (2) = 99.9: 0.1 to 5:95, more preferably 98: 2 to 10:90. is there.

  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;

  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,

  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.

  Among these additives, phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, ultraviolet absorbers, and hindered amine light stabilizers are preferably used.

  More preferred phenolic antioxidants 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), 4,4'-methylenebis (6-t-butyl) Ru-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.

  More preferable 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) fluor B Phosphite, 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) phosphites and the like, and these may be used alone or in combination of two or more.

  More preferable ultraviolet absorbers include, for example, 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.

  More preferable 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-cyclohexyl) Oxy-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) propionyl Oxy) 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) -Mixed esterified product of 2,4,8,10-tetraoxaspiro [5.5] undecane, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6- 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-tetramethyl-4-piperidyl) imino)] and the like, which may be used singly or two or respectively.

  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 may contain compound (1) and compound (2) in a weight ratio of 99.9: 0.1 to 5:95 (compound (1): compound (2)). Preferably, it is contained in a weight ratio of 98: 2 to 10:90.

  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 and Comparative Examples. Parts and% mean weight basis unless otherwise specified. The melt flow rate is referred to as MFR.

Example 1 (Production of stabilizer composition)
As compound (1), n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate (manufactured by BASF Japan, Irganox (registered trademark) 1076, hereinafter, compound (1) -1))) and 0.42 part of mannitol as compound (2) were mixed to prepare a stabilizer composition.

Examples 2 and 3 (Production of stabilizer composition)
In Example 1, the compound (1-1) was used in amounts of 0.30 parts and 0.12 parts, respectively, and mannitol was used in amounts of 0.30 parts and 0.48 parts, respectively. A stabilizer composition was produced in the same manner as described above.

Example 4 (Production of thermoplastic polymer composition)
After dry blending 100 parts of Asahi Kasei styrene-butadiene block copolymer and 0.6 parts of the stabilizer composition obtained in Example 1 as a thermoplastic polymer, the resulting resin composition was screwed into a 30 mm screw diameter. 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 5 and 6 (Production of thermoplastic polymer composition)
In Example 4, Example 4 was used except that 0.6 part of the stabilizer composition obtained in Examples 2 and 3 was used instead of 0.6 part of the stabilizer composition obtained in Example 1. In the same manner as above, pellets of a thermoplastic polymer composition were obtained.

Comparative Example 1
In Example 4, the thermoplastic polymer was obtained in the same manner as in Example 4 except that 0.6 part of the compound (1-1) was used instead of 0.6 part of the stabilizer composition obtained in Example 1. A pellet of the composition was obtained.

Test Example 1 (Processing stability test)
The pellets obtained in Examples 4 to 6 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.
The processing stability improvement rate in Table 1 is a value obtained by the following equation.

(Processing stability improvement rate) = (MFR value measured in Example−MFR value measured in Comparative Example 1) / MFR value measured in Comparative Example 1 × 100

Example 7 (Production of stabilizer composition)
3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8, as compound (1) 0.1 parts of 10-tetraoxaspiro [5.5] undecane (manufactured by Sumitomo Chemical Co., Ltd., Sumilizer (registered trademark) GA-80, hereinafter sometimes referred to as compound (1-2)), and compound (2) A stabilizer composition was prepared by mixing with 0.1 part of mannitol.

Example 8 (Production of stabilizer composition)
In Example 7, a stabilizer composition was produced in the same manner as in Example 7 except that sorbitol was used as the compound (2).

Example 9 (Production of thermoplastic polymer composition)
After dry blending 100 parts of polypropylene manufactured by Sumitomo Chemical as a thermoplastic polymer and 0.2 part of the stabilizer composition obtained in Example 7, the resulting resin composition was converted into a single screw extruder having 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 Tanabe Plastic Co., Ltd. (VS30-28 type extruder) was cut with a pelletizer to obtain a pellet of a thermoplastic polymer composition.

Example 10 (Production of thermoplastic polymer composition)
In Example 9, a thermoplastic polymer composition was obtained in the same manner as in Example 9, except that 0.2 parts of the stabilizer composition obtained in Example 8 was used instead of the stabilizer composition obtained in Example 7. A product pellet was obtained.

Comparative Example 2
In Example 9, in place of the stabilizer composition obtained in Example 7, 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 2 (processing stability test)
For each of the pellets obtained in Examples 9 and 10 and Comparative Example 2, a retention MFR test was performed as an evaluation of processability during operation during extrusion. The test is based on JIS K 7210, the inside of the cylinder of the melt indexer (L217-E14011, manufactured by Techno Seven) is set to 270 ° C., the thermoplastic polymer composition is filled in the cylinder, and the thermoplastic is contained in the cylinder. This was carried out by measuring the MFR at a load of 2.16 kg after allowing the polymer composition to stay for 30 minutes. The results are shown in Table 2.

In the case of polypropylene, workability is better when the MFR is smaller after 30 minutes of residence.

Example 11 (Production of Stabilizer Composition)
As compound (1), pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, Irganox (registered trademark) 1010, hereinafter, compound (1-3) )) And 0.1 part of mannitol as compound (2) were mixed to prepare a stabilizer composition.

Example 12 (Production of Stabilizer Composition)
In Example 11, a stabilizer composition was produced in the same manner as in Example 11 except that sorbitol was used as the compound (2).

Example 13 (Production of thermoplastic polymer composition)
After dry blending 100 parts of polyethylene manufactured by Sumitomo Chemical as a thermoplastic polymer and 0.11 part of the stabilizer composition obtained in Example 11, the resulting resin composition was converted into a single screw extruder having 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 Tanabe Plastic Co., Ltd. (VS30-28 type extruder) was cut with a pelletizer to obtain a pellet of a thermoplastic polymer composition.

Example 14 (Production of thermoplastic polymer composition)
In Example 13, the thermoplastic polymer composition was the same as Example 13 except that 0.11 part of the stabilizer composition obtained in Example 12 was used instead of the stabilizer composition obtained in Example 13. A product pellet was obtained.

Comparative Example 3
In Example 13, instead of the stabilizer composition obtained in Example 11, pellets of the thermoplastic polymer composition were obtained in the same manner as in Example 13, except that 0.1 part of compound (1-3) was used. Obtained.

Test Example 3 (Processing stability test)
The pellets obtained in Examples 12 and 13 and Comparative Example 3 were each 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 3.

In the case of polyethylene, the greater the MFR change retention, the better the processing stability.
MFR retention rate (%) = MFR for 30 minutes of residence / MFR before residence × 100

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

Claims (6)

Thermoplastic polymer, formula (1)

(In the formula, R ¹ and R ² 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. represents an n-valent alcohol residue, and m represents an integer of 1 to 4. Here, the alcohol residue represents a group obtained by removing H from OH of an alcohol.)
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.)
The total weight of the compound represented by Formula (1) and the compound represented by Formula (2) is 100 parts by weight of the thermoplastic polymer. A thermoplastic polymer composition in an amount of 0.001 to 3 parts by weight. Formula (1)

(In the formula, R ¹ and R ² 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. represents an n-valent alcohol residue, and m represents an integer of 1 to 4. Here, the alcohol residue represents a group obtained by removing H from OH of an alcohol.)
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 n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate, 3,9-bis [2- {3- ( 3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5 · 5] undecane or pentaerythritol tetrakis [3 -(3,5-Di-t-butyl-4-hydroxyphenyl) propionate].   The stabilizer composition according to claim 2 or 3, wherein the compound represented by the formula (2) is allitol, iditol, galactitol, sorbitol, taritol or mannitol.   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 2-4 with a thermoplastic polymer.   Use of the stabilizer composition according to any one of claims 2 to 4 for the process stabilization of a thermoplastic polymer.