JP2011219592A - Thermoplastic polymer composition and processing stabilizer for thermoplastic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problems wherein a new thermoplastic polymer composition having good processing stability is required.SOLUTION: The thermoplastic polymer composition contains glucose and a thermoplastic polymer. The processing stabilizer for the thermoplastic polymer contains the glucose as an active ingredient. The method for stabilizing the thermoplastic polymer includes a step of mixing 0.0005-5 pts.wt. of the glucose based on 100 pts.wt. of the thermoplastic polymer. The use of the glucose for improving the processing stability of the thermoplastic polymer is also provided.

Description

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

  Thermoplastic polymers are widely used in food packaging containers and household goods because of their excellent transparency and impact resistance. A thermoplastic polymer composition to which various polymer stabilizers are added in order to improve the processing stability of such a thermoplastic polymer is known (for example, Non-Patent Document 1).

Seiichi Honma, 1. Basic Comprehensive Explanation, Molding Technology Useful in the Field-Materials and Molding Technology, Plastic April 2002 issue, 4th volume, published by Kogyo Kenkyukai

  There is a need for new thermoplastic polymer compositions that are excellent in processing stability.

In order to solve this problem, the present inventors have intensively studied, and as a result, have reached the inventions described in the following [1] to [6].
[1] A thermoplastic polymer composition containing glucose and a thermoplastic polymer.
[2] The thermoplastic polymer composition according to [1], which contains 0.01 to 5 parts by weight of glucose 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 resin selected from the group consisting of polyethylene resins, polypropylene resins, and polystyrenes.
[4] A processing stabilizer for thermoplastic polymers containing glucose as an active ingredient.
[5] A method for stabilizing the processing of a thermoplastic polymer, comprising the step of mixing 0.01 to 5 parts by weight of glucose with respect to 100 parts by weight of the thermoplastic polymer.
[6] Use of glucose to improve the processing stability of the thermoplastic polymer.

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

  Hereinafter, the present invention will be described in detail.

  First, a processing stabilizer for thermoplastic polymers containing glucose as an active ingredient will be described.

  Glucose that is commercially available can be used as it is as a processing stabilizer for thermoplastic polymers. Glucose may be anhydrous or hydrated. Glucose may be α-form or β-form. The glucose may be D-form or L-form. Moreover, in the range which does not inhibit the effect of this invention, glucose and a suitable additive can be mixed and it can also be set as the processing stabilizer for thermoplastic polymers.

  Examples of the additive include antioxidants other than glucose, ultraviolet absorbers, light stabilizers, metal deactivators, nucleating agents, lubricants, antistatic agents, flame retardants, fillers, pigments, and inorganic fillers. Etc.

  Examples of the antioxidant include phenolic antioxidants, hydroquinone antioxidants, sulfur antioxidants, and phosphorus antioxidants.

  Here, as the phenolic antioxidant, for example, 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- ( Alkylated monophenols such as 1′-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 bisphenols and derivatives thereof such as -t-butyl-4-hydroxy-2-methylphenyl) pentane and mixtures thereof;

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

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

Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol , Spiroglycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri At least one alcohol selected from the group consisting of methylolpropane and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane; and β- (3,5-di- t Esters composed of a butyl-4-hydroxyphenyl) propionic acid;

2,2′-thiobis (6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,2′-thiobis (4-octylphenol), 4,4′-thiobis Hydroxylated thiodiphenyl ethers 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 isooctyl-3,5-di-t-butyl-4-hydroxybenzyl mercaptoacetate and mixtures thereof (O-benzyl derivative, N-benzyl derivative, S-benzyl derivative);

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 bis (3,5-di-tert-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-t-butyl-4-hydroxybenzyl) phenol and mixtures thereof ;

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 A benzylphosphonate derivative of

Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol , Spiroglycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri At least one alcohol selected from the group consisting of methylolpropane and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane; and β- (5-t-butyl) Esters consisting of 4-hydroxy-3-methylphenyl) propionic acid;

Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol , Spiroglycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri At least one alcohol selected from the group consisting of methylolpropane and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane; and β- (3,5-disic; Esters consisting of hexyl-4-hydroxyphenyl) propionic acid;

Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol , Spiroglycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri At least one alcohol selected from the group consisting of methylolpropane and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane; and 3,5-di-t-butyl Esters consisting of 4-hydroxyphenyl acetic acid;

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 Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid such as mixtures thereof;

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

  Examples of the hydroquinone antioxidant include hydroquinone, 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, 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-tert-butyl-4-hydroxyphenyl) adipate and mixtures thereof.

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

  Examples of phosphorus antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, di Stearyl 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 Triphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-diphenylenediphosphonite, 2,2'-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phos Phyto, 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-oxaphospho Linan, 2,2 ′, 2 ″ -nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra-t-butyl-1,1′-biphenyl-2,2′-diyl) phosphite and its Mixtures of al and 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 Salicylate derivatives such as butyl-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, 2- [3'-t-butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl) phenyl] benzotriazole and mixtures thereof Or 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-te Lamethylbutyl) 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-hydroxyphenyl] propionate, methyl 3- [3-t-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, 3- [3-t- 2- (2′-hydroxyphenyl) benzotriazole such as butyl-5- (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-butylmalonate, bis (1-acryloyl-2,2,6,6-tetramethyl) Ru-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-tert-butyl-4-hydroxyphenyl) propionyloxy] -1- [2 -(3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2,6 , 6-Tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1, 2 3,4-butane tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate,

Mixed esterified product of 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetrabonic acid And 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, and 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl- Mixed esterified product of 4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5 · 5] undecane, 1,2,3 , 4-Butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10 Mixed esterified product of tetraoxaspiro [5.5] undecane, polycondensate of dimethyl succinate and 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) 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-piperi A) polycondensation product of hexamethylenediamine and 1,2-dibromoethane, 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-triazine- 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 Stabilizers;

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 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 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 light stabilizers;

  As the stabilizer, in addition to the above, for example, N, N-dibenzylhydroxyamine, N, N-diethylhydroxyamine, N, N-dioctylhydroxyamine, N, N-dilaurylhydroxyamine, N, N-diamine Hydroxyl such as tetradecylhydroxyamine, N, N-dihexadecylhydroxyamine, N, N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl-N-octadecylhydroxyamine and mixtures thereof Also included are amines.

  Examples of the lubricant include aliphatic hydrocarbons such as paraffin and wax, higher aliphatic acids having 8 to 22 carbon atoms, metal (Al, Ca, Mg, Zn) salts of higher aliphatic acids having 8 to 22 carbon atoms, C8-22 aliphatic alcohol, polyglycol, ester comprising higher fatty acid having 4-22 carbon atoms and aliphatic monohydric alcohol having 4-18 carbon atoms, higher aliphatic amide having 8-22 carbon atoms, silicone Examples include oil and rosin derivatives.

  Examples of metal deactivators include metal deactivators such as thiocarbamates, salicylic acid series, benzotriazole, imidazole, and thiadiazole series.

  Examples of the nucleating agent include metal phosphate-based, benzylidene sorbitol-based, and carboxylic acid metal salt-based nucleating agents.

  Examples of the antistatic agent include nonionic types such as esters, ethers, and hydroxylamines; anionic types such as sulfonates and phosphates; cationic types; amphoteric types.

  Examples of the flame retardant include inorganic flame retardants typified by magnesium hydroxide and aluminum hydroxide, and organic flame retardants typified by halogens and phosphorus.

  Examples of pigments include organic pigments such as azo yellow, isoindolinone, azo, phthalocyanine, selenium, quinacridone, carbon black, petal, yellow lead, molybdate orange, lead normal chromate, molybdenum Examples thereof include inorganic pigments such as lead acid, titanium white, ultramarine blue, bitumen / cobalt blue, titanium yellow, graphite, and zinc white.

  Examples of the filler include carbon black, white carbon, clay, mica, calcium carbonate, talc and the like.

  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 and N, N′-bis [3- ( 3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionyl] hexamethylenediamine, which 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 and 2,2 ′, 2 ″ -nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra-t-butyl-1,1′-biphenyl-2, 2'-diyl) phosphites, each of which can be used alone or in combination of two or more.

  More preferable ultraviolet absorbers include phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, 4-t -Octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, bis (5-benzoyl-4 -Hydroxy-2-methoxyphenyl) methane, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3', 5'-di- t-butyl-2′-hydroxyphenyl) benzotriazole, 2- 5'-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (3-t-butyl-2-hydroxy-5- Methylphenyl) -5-chlorobenzotriazole, 2- (3′-s-butyl-2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octyloxyphenyl) ) Benzotriazole, 2- (3 ′, 5′-di-t-amyl-2′-hydroxyphenyl) benzotriazole and 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) ) Phenyl] -2H-benzotriazole, each of which may be used alone or in combination of two or more.

  As more preferred hindered amine light stabilizers, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N- Cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5-di-t-butyl) -4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) 2,2-bis (3,5 Di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, 2,2,6,6-tetramethyl-4- Piperidyl methacrylate, 4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -1- [2- (3- (3,5-di-tert-butyl-4--) Hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2, 2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate,

Tetrakis (1,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6 Mixed esterified product of 6-pentamethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol Mixed esterified product, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -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)] and poly [(6- (1 , 1,3,3-tetramethylbutyl) -1,3,5-triazine-2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2 , , 6,6-tetramethyl-4-piperidyl) imino)], and these may be used alone or two or respectively.

  When glucose and an additive are mixed to form a processing stabilizer for a thermoplastic polymer, the stabilizer can be produced by, for example, using a mixer such as a Henschel mixer, a super mixer, or a high speed mixer. The method of mixing is mentioned. The obtained mixture may be further processed into an appropriate shape by extrusion molding, stirring granulation or the like.

  The thermoplastic polymer composition of the present invention contains glucose and a thermoplastic polymer. The amount of glucose used is preferably in the range of 0.001 to 5 parts by weight, more preferably in the range of 0.005 to 3 parts by weight, and in the range of 0.02 to 2 parts by weight with respect to 100 parts by weight of the thermoplastic polymer. More preferably, the range of 0.1-1 weight part is especially preferable.

  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 poly Enylene 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 Group polyester resin, diallyl phthalate prepolymer, silicone resin, 1,2-polybutadiene, polyisoprene, butadiene / acrylonitrile copolymer, ethylene-methyl methacrylate copolymer, etc. Polypropylene resins and polystyrene resins are preferred, and among them, low density polyethylene, polypropylene and styrene-butadiene copolymers More preferable.

  As a method for producing the thermoplastic polymer composition of the present invention, for example, a thermoplastic polymer processing stabilizer containing glucose as an active ingredient and a thermoplastic polymer are mixed, and the resulting mixture is uniaxially or A method of melt-kneading with a multi-screw extruder; a solution obtained by dissolving or suspending, in a solvent, a thermoplastic polymer processing stabilizer containing glucose as an active ingredient in a solution obtained by polymerizing a thermoplastic polymer. And then the solvent is distilled off.

  Here, with respect to 100 parts by weight of the thermoplastic polymer, glucose is preferably 0.0005 to 5 parts by weight, more preferably 0.001 to 3 parts by weight, and even more preferably 0.005 to 2 parts by weight. And a processing stabilizer for thermoplastic polymers.

  Moreover, when the processing stabilizer for thermoplastic polymers consists only of glucose etc., said additive can also be mix | blended separately from the processing stabilizer for thermoplastic polymers. Specifically, there may be mentioned a method in which pellets of glucose, additives and thermoplastic polymer are mixed with a Banbury mixer and then extruded to obtain a pellet-shaped thermoplastic polymer composition.

  The thermoplastic polymer composition thus obtained can be further molded and processed into products such as films, molding materials and pipes.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1
100 parts by weight of polypropylene (manufactured by Sumitomo Chemical Co., Ltd.), 0.05 part by weight of calcium stearate, and 0.1 part by weight of D-glucose are dry blended, and a 30 mmΦ single-screw extruder manufactured by Tanabe Plastics [model number: VS30-28, L / D = 28] was extruded at 230 ° C. and a rotation speed of 50 rpm to obtain a thermoplastic polymer composition of the present invention.

  A melt flow rate (hereinafter referred to as MFR) of the thermoplastic polymer composition obtained in Example 1 was used under the conditions of a temperature of 270 ° C. and a load of 2.16 kg using a techno-seven melt indexer (model number: L217-E14011). It was 10.3 g / 10 min.

(Comparative Example 1)
A thermoplastic polymer composition was obtained in the same manner as in Example 1 except that D-glucose was not used, and the MFR was measured to be 26.6 g / 10 min.

  In the case of polypropylene, the smaller the MFR value, the better the processing stability. That is, from Example 1 and Comparative Example 1, the thermoplastic polymer composition of the present invention containing D-glucose and polypropylene is superior in processing stability to the polypropylene composition not containing D-glucose. I understand.

(Example 2)
100 parts by weight of low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd.), 0.05 part by weight of calcium stearate, and 0.1 part by weight of D-glucose are dry blended, and a 30 mmφ single screw extruder manufactured by Tanabe Plastics [ Model No .: VS30-28, L / D = 28], and extruded under the conditions of 230 ° C. and rotation speed of 50 rpm to obtain the thermoplastic polymer composition of the present invention.

  The MFR of the thermoplastic polymer composition obtained in Example 1 was measured under the conditions of a temperature index of 270 ° C. and a load of 2.16 kg using a Techno Seven melt indexer (model number: L217-E14011). It was 1 g / 10 minutes.

(Comparative Example 2)
A thermoplastic polymer composition was obtained in the same manner as in Example 2 except that D-glucose was not used, and the MFR measured was 7.7 g / 10 min.

  In the case of low density polyethylene, the larger the MFR value, the better the processing stability. That is, from Example 2 and Comparative Example 2, the thermoplastic polymer composition of the present invention containing D-glucose and low-density polyethylene is more process stable than the low-density polyethylene composition not containing D-glucose. It turns out that it is excellent.

(Example 3)
100 parts by weight of a styrene-butadiene block copolymer (Asahi Kasei Co., Ltd .: Asaflex (registered trademark) 830) and 0.24 parts by weight of D-glucose were mixed, and Labo Plast Mill (Toyo Seiki Seisakusho Co., Ltd.) 4C-150) was kneaded under a nitrogen atmosphere at 250 ° C. and a rotation speed of 50 rpm to obtain a thermoplastic polymer composition of the present invention.

  When the kneading in Example 3 was continued and the time until the torque of the lab plast mill reached the maximum value was measured as the build-up time, it was 96 minutes.

(Comparative Example 3)
The build-up time was 46 minutes as measured in the same manner as in Example 3 except that D-glucose was not used.

  In the case of a styrene-butadiene block copolymer, the longer the build-up time, the better the processing stability. That is, from Example 3 and Comparative Example 3, the thermoplastic polymer composition of the present invention containing D-glucose and a styrene-butadiene block copolymer is a styrene-butadiene block copolymer containing no D-glucose. It can be seen that the processing stability is superior to that of the composition.

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

Claims (6)

A thermoplastic polymer composition comprising glucose and a thermoplastic polymer. The thermoplastic polymer composition according to claim 1, comprising 0.0005 to 5 parts by weight of glucose 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 resin selected from the group consisting of a polyethylene resin, a polypropylene resin, and a polystyrene resin. A processing stabilizer for thermoplastic polymers containing glucose as an active ingredient. A method for stabilizing the processing of a thermoplastic polymer, comprising the step of mixing 0.0005 to 5 parts by weight of glucose with respect to 100 parts by weight of the thermoplastic polymer. Use of glucose to improve the processing stability of thermoplastic polymers.