JP5781807B2 - Thermoplastic polymer composition - Google Patents

Description

The present invention relates to a thermoplastic polymer composition , a stabilizer composition for thermoplastic polymer (processing stabilizer 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ｍ価のアルコール残基を表し、ｍは１〜４の整数を表す。ここでアルコール残基とは、アルコールのヒドロキシ基から水素原子を除いた残りの基を表す。）
で表される化合物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. In the manufacture of such products, the thermoplastic polymer is used as a composition containing it. Such a thermoplastic polymer composition includes a thermoplastic polymer and a 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. m represents an alcohol residue, and m represents an integer of 1 to 4. Here, the alcohol residue represents a remaining group obtained by removing a hydrogen atom from a hydroxy group of alcohol.
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.

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

（式中、Ｒ^１及びＲ^２はそれぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表し、Ｘは、ヘテロ原子及び／又は環状基を含んでいてもよい炭素数１〜２４のｍ価のアルコール残基を表し、ｍは１〜４の整数を表す。ここでアルコール残基とは、アルコールのヒドロキシ基から水素原子を除いた残りの基を表す。）
で表される化合物、及び、トレハロースを含有する熱可塑性ポリマー組成物。
［２］ 式（１）で表される化合物とトレハロースとの合計重量が、熱可塑性ポリマー１００重量部に対して０．００１〜３重量部である［１］記載の熱可塑性ポリマー組成物。
［３］ 熱可塑性ポリマーが、スチレン−ブタジエンブロック共重合体である［１］又は［２］記載の熱可塑性ポリマー組成物。 In order to solve this problem, the present inventors have intensively studied, and as a result, have found a thermoplastic polymer composition having further improved processing stability, and have reached the inventions described in [1] to [8] 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. m represents an alcohol residue, and m represents an integer of 1 to 4. Here, the alcohol residue represents a remaining group obtained by removing a hydrogen atom from a hydroxy group of alcohol.
And a thermoplastic polymer composition containing trehalose.
[2] The thermoplastic polymer composition according to [1], wherein the total weight of the compound represented by formula (1) and trehalose is 0.001 to 3 parts by weight with respect to 100 parts by weight of the thermoplastic polymer.
[3] The thermoplastic polymer composition according to [1] or [2], wherein the thermoplastic polymer is a styrene-butadiene block copolymer.

（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ｍ価のアルコール残基を表し、ｍは１〜４の整数を表す。ここでアルコール残基とは、アルコールのヒドロキシ基から水素原子を除いた残りの基を表す。）
で表される化合物とトレハロースとを含有する安定剤組成物。
［５］ 式（１）

（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ｍ価のアルコール残基を表し、ｍは１〜４の整数を表す。ここでアルコール残基とは、アルコールのヒドロキシ基から水素原子を除いた残りの基を表す。）
で表される化合物とトレハロースとからなる安定剤組成物。
［６］ 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［４］又は［５］記載の安定剤組成物。 [4] 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. m represents an alcohol residue, and m represents an integer of 1 to 4. Here, the alcohol residue represents a remaining group obtained by removing a hydrogen atom from a hydroxy group of alcohol.
The stabilizer composition containing the compound represented by these, and trehalose.
[5] 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. m represents an alcohol residue, and m represents an integer of 1 to 4. Here, the alcohol residue represents a remaining group obtained by removing a hydrogen atom from a hydroxy group of alcohol.
And a stabilizer composition comprising trehalose.
[6] 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 [4] or [5], which is tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate].

[7] A method for producing a thermoplastic polymer composition, comprising a step of mixing the stabilizer composition according to any one of [4] to [6] with a thermoplastic polymer.

[8] Use of the stabilizer composition according to any one of [4] to [6] for processing stabilization of a thermoplastic polymer.

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

  Hereinafter, the present invention will be described in detail.

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

  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.

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

  Thermoplastic polymers include polyethylene resins (high density polyethylene (HD-PE), low density polyethylene (LD-PE), linear low density polyethylene (LLDPE), ethylene-vinyl alcohol copolymer (EVOH), ethylene, -Ethyl acrylate copolymer, ethylene-vinyl acetate copolymer (EVA), etc.), polypropylene resin (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. , Styrene - butadiene block copolymer is more preferable.

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

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

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

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

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

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

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

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

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

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

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

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

  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 Riphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-diphenylenediphosphonite, 2,2'-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite 2,2'-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, bis (2,4 -Di-t-butyl-6-methylphenyl) methyl phosphite, 2- (2,4,6-tri-t-butylphenyl) -5-ethyl-5-butyl-1,3,2-oxaphosphorinane 2,2 ', 2 "-nitrilo [triethyl-tris (3,3', 5,5'-tetra-t-butyl-1,1'-biphenyl-2,2'-diyl) phosphite and the same Mixtures of the like.

  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-t-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4- Hydroxyphenyl] propionate, methyl 3- [3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, 3- [3-tert-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-piperidyl) Decandioate, 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, , 4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic Mixed esterified product of an acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol,

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

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

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

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

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

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

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

（式中、Ｒ^３及びＲ^４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^５は水素原子又は炭素数１〜３のアルキル基を表し、Ｒ^６は水素原子又はメチル基を表す。）、
式（４）：

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

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

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

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

（式中、Ｒ^１２及びＲ^１３は、互いに独立に、水素原子、炭素数１〜９のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表す。Ａ^４は、単結合、硫黄原子、又は炭素数１〜８のアルキリデン基を表す。Ａ^５は、炭素数１〜８のアルキル基、炭素数１〜９のアルキル基で置換されていてもよいフェニル基、炭素数５〜８のシクロアルキル基で置換されていてもよいフェニル基、炭素数６〜１２のアルキルシクロアルキル基で置換されていてもよいフェニル基、又は炭素数７〜１２のアラルキル基で置換されていてもよいフェニル基を表す。）
式（９）：

〔式中、Ｒ^１４、Ｒ^１５、Ｒ^１７及びＲ^１８は、それぞれ独立に水素原子、炭素数１〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表し、Ｒ^１６は水素原子又は炭素数１〜８のアルキル基を表し、Ｘは単結合、硫黄原子又は式（９−Ｉ）
式（９−Ｉ）：

（式中、Ｒ^１９は水素原子、炭素数１〜８のアルキル基または炭素数５〜８のシクロアルキル基を示す。）で示される２価の基を表し、Ａは炭素数２〜８のアルキレン基または式（９−ＩＩ）

（式中、Ｒ^２０は単結合または炭素数１〜８のアルキレン基を表し、＊は酸素原子側に結合していることを表す。）で示される２価の基を表し、Ｙ、Ｚはいずれか一方がヒドロキシ基、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基または炭素数７〜１２のアラルキルオキシ基を表し、他方が水素原子または炭素数１〜８のアルキル基を表す。〕 Among these additives, phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, ultraviolet absorbers, and hindered amine light stabilizers are preferably used. More preferably, it is a phenol-based antioxidant or a phosphorus-based antioxidant, and more preferably a compound represented by the formula (3) among the phenol-based antioxidants, or a formula (4) among the phosphorus-based antioxidants. ~ Organic phosphorus compound represented by at least one formula selected from the group consisting of formula (9).
Formula (3):

(In the formula, R ³ and R ⁴ 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. R ⁵ represents a hydrogen atom or Represents an alkyl group having 1 to 3 carbon atoms, and R ⁶ represents a hydrogen atom or a methyl group).
Formula (4):

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

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

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

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

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

[In formula, R <^14> , R <^15> , R <^17> and R <^18> are respectively independently a hydrogen atom, a C1-C8 alkyl group, a C5-C8 cycloalkyl group, and a C6-C12 alkylcyclohexane. Represents an alkyl group, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group, R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and X represents a single bond, a sulfur atom, or a formula (9-1)
Formula (9-I):

(Wherein R ¹⁹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms), and A represents a group having 2 to 8 carbon atoms. Alkylene group or formula (9-II)

(In the formula, R ²⁰ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and * represents a bond to the oxygen atom side.) Y, Z are Either one represents a hydroxy group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Represents. ]

In the above formula (3), R ³ and R ⁴ 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 ³ and R ⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, t-amyl group. An alkyl group having 1 to 8 carbon atoms such as a group (—C (CH ₃ ) ₂ CH ₂ CH ₃ ), 2-ethylhexyl group and cyclohexyl group, for example, an aryl group having 6 to 12 carbon atoms such as phenyl group, for example, benzyl Examples thereof include aralkyl groups having 7 to 18 carbon atoms such as a group.

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

R ⁵ 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 ⁵ includes a hydrogen atom or a methyl group.

R ⁶ represents a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

  Examples of the compound represented by the formula (3) (hereinafter sometimes referred to as the compound (3)) include 2,4-di-t-amyl-6- [1- (3,5-di). -T-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate is Sumilizer GS (F) (registered trademark, manufactured by Sumitomo Chemical Co., Ltd., hereinafter may be referred to as compound (3-1)), 2-t-butyl- 6- (3-t-Butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate is Sumilizer GM (registered trademark, manufactured by Sumitomo Chemical Co., Ltd., hereinafter may be referred to as compound (3-2)). Is mentioned.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the compound (9), examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹⁴ , R ¹⁵ , R ¹⁷ and R ¹⁸ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n -Butyl group, i-butyl group, sec-butyl group, t-butyl group, t-pentyl group, i-octyl group, t-octyl group, 2-ethylhexyl group can be mentioned.

  Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the alkylcycloalkyl group having 6 to 12 carbon atoms include 1-methylcyclopentyl group, 1-methylcyclohexyl group, and 1-methyl-4-i-propylcyclohexyl group. Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, an α-methylbenzyl group, and an α, α-dimethylbenzyl group.

R ¹⁴ , R ¹⁵ and R ¹⁷ are preferably each independently an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms or an alkylcycloalkyl group having 6 to 12 carbon atoms. More preferably, R ¹⁴ and R ¹⁷ are each independently a t-alkyl group such as a t-butyl group, a t-pentyl group or a t-octyl group, a cyclohexyl group or a 1-methylcyclohexyl group. R ¹⁵ is independently carbon such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, t-pentyl group, etc. It is preferably a C 1-5 alkyl group, more preferably a methyl group, a t-butyl group or a t-pentyl group. R ¹⁸ is a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, t-pentyl group, etc. 5 is preferably an alkyl group or a hydrogen atom, more preferably a methyl group or a hydrogen atom.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹⁶ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t -Butyl group, t-pentyl group, i-octyl group, t-octyl group, 2-ethylhexyl group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- An alkyl group having 1 to 5 carbon atoms such as a butyl group, a sec-butyl group, a t-butyl group, or a t-pentyl group or a hydrogen atom is preferable, and a methyl group or a hydrogen atom is more preferable.

X represents a single bond, a sulfur atom or a divalent group represented by the formula (9-I). Examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹⁹ in the formula (9-1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group. , Sec-butyl group, t-butyl group, t-pentyl group, i-octyl group, t-octyl group and 2-ethylhexyl group. Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group. , A cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. R ⁶ is preferably a C 1-5 alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, or an i-butyl group, or a hydrogen atom. X is preferably a single bond or a divalent group represented by the formula (9-I), and more preferably a single bond.

A represents an alkylene group having 2 to 8 carbon atoms or a divalent group represented by the above formula (9-II), and an alkylene group having 2 to 8 carbon atoms is preferable. Group, propylene group, butylene group, pentamethylene group, hexamethylene group, octamethylene group, 2,2-dimethyl-1,3-propylene group and the like, and propylene group is more preferable. The divalent group represented by the formula (9-II) is bonded to the oxygen atom and the benzene nucleus, but * indicates that it is bonded to the oxygen atom. Examples of the alkylene group having 1 to 8 carbon atoms represented by R ²⁰ include methylene group, ethylene group, propylene group, butylene group, pentamethylene group, hexamethylene group, octamethylene group, 2,2-dimethyl-1, A 3-propylene group etc. are mentioned. Such R ²⁰ is preferably a single bond or an ethylene group.

  One of Y and Z represents a hydroxy group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other is a hydrogen atom or carbon. The alkyl group of number 1-8 is shown. Here, examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, and t-butyl. Group, t-pentyl group, i-octyl group, t-octyl group and 2-ethylhexyl group. Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, t-butoxy group, t -Pentyloxy group, i-octyloxy group, t-octyloxy group, 2-ethylhexyloxy group may be mentioned. Examples of the aralkyloxy group having 7 to 12 carbon atoms include benzyloxy group, α-methylbenzyloxy group, α, α-dimethylbenzyloxy group.

Among the organophosphorus compounds represented by the formula (9) (hereinafter sometimes referred to as the compound (9)), R ¹⁴ and R ¹⁷ are a t-alkyl group, a cyclohexyl group, or a 1-methylcyclohexyl group, and R ¹⁵ is an alkyl group having 1 to 5 carbon atoms, R ⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁶ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X is a single atom. It is a bond, and A is preferably an alkylene group having 2 to 8 carbon atoms.

  In the stabilizer composition of the present invention, a single compound may be used as the compound (9), or two or more kinds of compounds may be used in combination.

  Examples of the compound (9) include 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1, 3, 2] dioxaphosphepine [Sumitomo Chemical Co., Ltd., Sumilizer (registered trademark) GP, hereinafter referred to as compound (9-1)]. )], 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g ] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] Dibenzo [d, f] [1,3,2] dioxaphosphine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propoxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -12 -Dibenzo [d, g] [1,3,2] dioxaphosphocine, 2,4,8,10-tetra-t-pentyl-6- [3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -dibenzo [d, f] [1,3,2] dioxaphosphine, 2,10-dimethyl-4,8- Di-t-butyl-6- (3,5-di-t-butyl-4-hydroxybenzoyloxy) -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4 8,10-tetra-t-butyl-6- (3,5-di-t-butyl-4- Droxybenzoyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3 -(3-Methyl-4-hydroxy-5-t-butylphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra- t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocine, 2, 10-diethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3 , 2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl Tyl-6- [2,2-dimethyl-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -dibenzo [d, f] [1,3,2] dioxaphosphine Etc., and the compound (9-1) is preferable.

  Of the compounds (3) to (9), the compound (3), the compound (4) or the compound (9) is even more preferable.

  The additive amount selected from the group consisting of compound (3) to compound (9) in the thermoplastic polymer composition of the present invention is preferably 0.001 to 3 with respect to 100 parts by weight of the thermoplastic polymer composition. Part by weight, more preferably 0.02 to 2 parts by weight.

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

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

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

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

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

  The stabilizer composition of this invention contains a compound (1) and a compound (2). Preferably, it consists of compound (1) and compound (2). Here, consisting of the compound (1) and the compound (2) means that the total weight of the compound (1) and the compound (2) is 99% or more of the entire stabilizer composition.

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

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

  Preferred additives are as described above, and the additive amount selected from the group consisting of compound (3) to compound (9) in the stabilizer composition of the present invention is based on 100 parts by weight of the stabilizer composition. The amount is preferably 0 to 90 parts by weight, more preferably 0.1 to 80 parts by weight.

  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 obtained by blending the stabilizer composition of the present invention with polyurethane is useful for obtaining polyurethane elastic fibers. The stabilizer composition of the present invention can be added at any stage of producing the polyurethane elastic fiber, but is preferably added after the polyurethane polymerization and before the spinning stage. Polyurethane elastic fibers can be fiberized by dry, wet or melt spinning methods.

  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.

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

In the following examples, the following compounds (3) to (9) were used.
Compound (3-1): 2,4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd., Smither (registered) Trademark) GS (F))
Compound (3-2): 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Sumilizer (registered trademark) GM)
Compound (4-1): Tris (2,4-di-t-butylphenyl) phosphite (manufactured by BASF, Irgaphos (registered trademark) 168)
Compound (5-1): Tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylene diphosphonite (manufactured by Clariant, Sandstub (registered trademark) P-EPQ)
Compound (6-1): Bis (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol diphosphite (manufactured by ADEKA, ADEKA STAB (registered trademark) PEP-36)
Compound (6-2): Bis (2,4-di-t-butylphenyl) -pentaerythritol diphosphite (manufactured by GE Plastics, Ultranox (registered trademark) 626)
Compound (6-3): bis (2,4-dicumylphenyl) -pentaerythritol diphosphite (manufactured by Dover Chemical Co., Doverphos S9228T)
Compound (7-1): 2,2 ′, 2 ″ -nitrilotriethyl-tris (3,3 ′, 5,5′-tetra-t-butyl-1,1′-biphenyl-2,2′-diyl ) Phosfight (BASF, Irgaphos (registered trademark) 12)
Compound (8-1): 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (manufactured by ADEKA, ADEKA STAB (registered trademark) HP-10)
In each of the following examples, the following was used as compound (9).
Compound (9-1): 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [ 1,3,2] Dioxaphosphepine (Sumitomo Chemical Co., Sumilizer (registered trademark) GP)

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

Reference example 1
A composition was prepared by mixing 0.2 part of the compound (1-1) and 0.3 part of the compound (3-1).

Example 2 (Production of thermoplastic polymer composition)
After dry blending 100 parts of Asahi Kasei styrene-butadiene block copolymer and 0.51 part of the stabilizer composition obtained in Example 1 as a thermoplastic polymer, the resulting resin composition was screwed to a screw diameter of 30 mm. A strand obtained by kneading and extruding at 230 ° C. and a screw rotation speed of 50 rpm using a single screw extruder (manufactured by Tanabe Plastics Co., Ltd., VS30-28 type extruder) is cut with a pelletizer to produce pellets of a thermoplastic polymer composition. Obtained.

Reference example 2
In Example 2, the thermoplastic polymer composition was prepared in the same manner as in Example 4 except that 0.5 part of the composition obtained in Reference Example 1 was used instead of the stabilizer composition obtained in Example 1. Pellets were obtained.

Test Example 1 (Processing stability test)
The pellets obtained in Example 2 and Reference Example 2 were each subjected to a retention MFR test as an evaluation of processability during operation during extrusion. The test is based on JIS K 7210, the inside of a cylinder of a melt indexer (L217-E14011, manufactured by Techno Seven) is set to 270 ° C., and the thermoplastic polymer composition is filled in the cylinder at a load of 2.16 kg. The measurement was carried out by measuring the MFR and then measuring the MFR at a load of 2.16 kg after allowing the thermoplastic polymer composition to stay in the cylinder for 30 minutes. The results are shown in Table 1.

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

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

Example 3 (Production of stabilizer composition)
A stabilizer composition was produced by mixing 0.1 part of the compound (1-2) and 0.1 part of the compound (2).

Example 4 (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 3, 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.

Comparative Example 1
In Example 4, in place of the stabilizer composition obtained in Example 3, the pellets of the thermoplastic polymer composition were obtained in the same manner as in Example 3 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 Example 4 and Comparative Example 1, 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.

Examples 5-7 (Production of Stabilizer Composition)
Compound (1-1), Compound (2), Compound (3-1) and Compound (4-1) were mixed at a weight ratio shown in Table 3 to produce a stabilizer composition.

Example 8 (Production of thermoplastic polymer composition)
After dry blending 100 parts of an electrochemically produced styrene-butadiene block copolymer and 0.21 part of the stabilizer composition obtained in Example 5 as a thermoplastic polymer, the resulting resin composition was treated with a screw diameter. Thermoplastic polymer composition pellets obtained by kneading and extruding a strand obtained by kneading and extrusion at 230 ° C. and a screw rotation speed of 50 rpm using a 30 mm single screw extruder (VS30-28 type extruder manufactured by Tanabe Plastics) Got.

Example 9 (Production of thermoplastic polymer composition)
In Example 8, in place of the stabilizer composition obtained in Example 5, 0.41 part of the stabilizer composition obtained in Example 6 was used, and the thermoplasticity was the same as in Example 8. Polymer composition pellets were obtained.

Example 10 (Production of thermoplastic polymer composition)
In Example 8, in place of 0.71 part of the stabilizer composition obtained in Example 7 instead of the stabilizer composition obtained in Example 5, the thermoplasticity was the same as in Example 8. Polymer composition pellets were obtained.

Comparative Example 2 (Production of thermoplastic polymer composition)
In Example 8, instead of the stabilizer composition obtained in Example 5, pellets of a thermoplastic polymer composition were used in the same manner as in Example 8, except that 0.2 part of compound (1-1) was used. Got.

Test Example 3 (Processing stability test)
For the pellets obtained in Examples 8 to 10 and Comparative Example 2, the MFR value was measured in the same manner as in Test Example 1 to determine the MFR fluctuation rate. The results are shown in Table 4.

Examples 11-78 (Production of Stabilizer Composition)
As the compound (1), the compound (2), the compound (3), the organic phosphorus compound and the compound (9), the compounds described in Tables 5 and 6 are mixed to obtain a stabilizer composition.

Examples 79-134 (Production of Thermoplastic Polymer Composition)
In Example 4, the thermoplastic polymer composition was changed in the same manner as in Example 4 except that 100 parts of the thermoplastic polymer described in Tables 7 and 8 and the stabilizer composition were used as the thermoplastic polymer and stabilizer composition. Obtain pellets. The resulting thermoplastic polymer composition is excellent in processing stability.

In Tables 7 and 8, each thermoplastic polymer has the following meaning.
P-1: High density polyethylene (HDPE)
P-2: Low density polyethylene (LDPE)
P-3: Linear low density polyethylene (LLDPE)
P-4: Ethylene-vinyl alcohol copolymer (EVOH)
P-5: Ethylene-ethyl acrylate copolymer (EEA)
P-6: Ethylene-vinyl acetate copolymer (EVA)
P-7: Propylene-ethylene random copolymer P-8: Propylene-α-olefin random copolymer P-9: Propylene-ethylene-α-olefin copolymer P-10: Polystyrene (PS)
P-11: Acrylonitrile-styrene copolymer (SAN)
P-12: Acrylonitrile-butadiene-styrene copolymer (ABS)
P-13: Special acrylic rubber-acrylonitrile-styrene copolymer P-14: Acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS)
P-15: Polybutadiene rubber (BR)
P-16: Styrene butadiene copolymer (SB)
P-17: Styrene butadiene block copolymer (SBS)
P-18: Chlorinated polyethylene (CPE)
P-19: Polychloroprene P-20: Chlorinated rubber P-21: Polyvinyl chloride (PVC)
P-22: Polyvinylidene chloride (PVDC)
P-23: Methacrylic resin P-24: Fluororesin P-25: Polyacetal (POM)
P-26: Grafted polyphenylene ether resin P-27: Polyphenylene sulfide resin (PPS)
P-28: Polyurethane (PU)
P-29: Polyamide (PA)
P-30: Polyethylene terephthalate (PET)
P-31: Polybutylene terephthalate (PBT)
P-32: Polylactic acid (PLA)
P-33: Polycarbonate (PC)
P-34: Polyacrylate P-35: Polysulfone (PPSU)
P-36: Polyetheretherketone (PEEK)
P-37: Polyethersulfone (PES)
P-38: Aromatic polyester P-39: Diallyl phthalate prepolymer P-40: Silicone resin (SI)
P-41: 1,2-polybutadiene P-42: polyisoprene P-43: butadiene / acrylonitrile copolymer (NBR)
P-44: Ethylene-methyl methacrylate copolymer (EMMA)

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

Claims (8)

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. m represents an alcohol residue, and m represents an integer of 1 to 4. Here, the alcohol residue represents a remaining group obtained by removing a hydrogen atom from a hydroxy group of alcohol.
And a trehalose , wherein the thermoplastic polymer is a polypropylene-based resin or a polybutadiene-based resin .   The thermoplastic polymer composition according to claim 1, wherein the total weight of the compound represented by formula (1) and trehalose is 0.001 to 3 parts by weight with respect to 100 parts by weight of the thermoplastic polymer.   The thermoplastic polymer composition according to claim 1 or 2, wherein the thermoplastic polymer is a styrene-butadiene block copolymer. 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. m represents an alcohol residue, and m represents an integer of 1 to 4. Here, the alcohol residue represents a remaining group obtained by removing a hydrogen atom from a hydroxy group of alcohol.
The processing stabilizer composition for polypropylene-type resins or polybutadiene-type resins containing the compound represented by these, and trehalose. 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. m represents an alcohol residue, and m represents an integer of 1 to 4. Here, the alcohol residue represents a remaining group obtained by removing a hydrogen atom from a hydroxy group of alcohol.
A processing stabilizer composition for a polypropylene resin or a polybutadiene resin comprising a compound represented by formula (2) and trehalose. 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-tert-butyl-4-hydroxyphenyl) propionate]. A process comprising mixing the processing stabilizer composition according to any one of claims 4 to 6 with a thermoplastic polymer , wherein the thermoplastic polymer is a polypropylene-based resin or a polybutadiene-based resin. And a method for producing a thermoplastic polymer composition. Use of the processing stabilizer composition according to any one of claims 4 to 6, wherein the thermoplastic polymer is a polypropylene-based resin or a polybutadiene-based resin for processing stabilization of the thermoplastic polymer .