Mixtures of phenolic and inorganic materials with antimicrobial activity

[0001] [Technical field to which the invention belongs] The present invention is a combination of a phenolic compound and an inorganic compound that show excellent antimicrobial activity when mixed with a base resin, and the mixture does not show a negative effect due to the use of only one of them. It is about. Plastic articles made from such resins by various methods are endowed with long-term antimicrobial activity and exhibit excellent resistance to fading and, above all, maintenance of physical properties upon exposure to UV irradiation. [0002] [Conventional technology] Triclosan or brand name Irgaguard, Ciba Specialty Chemicals Inc. , 2,4,4'-Trichloro-2'-hydroxydiphenyl ether is a known antimicrobial agent for plastic applications. It is known to have high activity against a large number of Gram-positive and Gram-negative bacteria. It can be used as a raw material or through a masterbatch of various polymer substrates such as LDPE, HDPE, MDPE, PP, ABS, SAN, PS, polyacrylate, PMMA, polyamide, polyester, PVC, latex, PUR, TPU, It can be mixed with UP, UF, etc. The trade name Irgaguard exhibits high activity on the surface of plastic articles, and the activity remains after repeated cleaning of the plastic articles. In addition, the trade name Irgaguard has a good toxicity profile. [0003] [Problems to be Solved by the Invention] The disadvantage of the trade name Irgaguard is that the plastic articles formed using it show strong fading during weathering. For example, a polypropylene sample containing the trade name Irgaguard is 63 ° C, 035 W / m.²Fades within a few hours in the xenon arc weatherometer. In addition, machining at temperatures above 250 ° C is problematic due to the volatility of the trade name Irgaguard. [0004] Silver-based materials such as colloidal silver, silver nitrate, silver sulfate, silver chloride, silver complexes and zeolites containing silver ions are known antimicrobial agents for plastic articles. Silver compounds show high activity against microorganisms, and they have a good toxicity profile. High processing temperatures (higher than 300 ° C) are possible with silver compounds. [0005] The disadvantage of silver-based antimicrobial agents is that plastic articles containing them often show fading during weather resistance, and the activity on the surface of said articles is often lost after repeated cleaning. [0006] Surprisingly, the combination of certain phenolic substances and certain inorganic substances has the disadvantage of using either the trade name Irgaguard or silver-based antimicrobial agents alone in plastic articles. At the same time, it was found to impart excellent long-term antimicrobial activity to the article. [0007] An object of the present invention is to provide a mixture of novel antimicrobial agents for plastics applications. [0008] Another object of the present invention is to have antimicrobial activity, yet to exhibit excellent resistance to fading, to be processed at high temperatures, and to maintain physical properties during weather resistance, especially when exposed to UV light. To provide a plastic article or film to be used. [0009] [Means for solving problems] The present invention describes a) the following equation (I): [Chemical 2]<img file="JP4880147B2_D0001.tif" />[In the formula, n represents 0 or 1 and represents R₁And R₂Represents a hydrogen atom or a chlorine atom R₃Represents a hydrogen atom or a hydroxyl group R₄, R₅And R₆Represents a hydrogen atom or a chlorine atom R₇Represents a hydroxyl group, and X is -O-group or -CH₂-Represents a group], as well as at least one phenolic antimicrobial compound. b) At least one selected from the group consisting of zinc oxide, copper and copper compounds, silver, colloidal silver, silver nitrate, silver sulfate, silver chloride, silver complexes, metal-containing zeolites and surface-modified metal-containing zeolites. Consists of inorganic anti-microbial compounds, and It relates to a novel mixture of antimicrobial agents for plastics applications, with a ratio of component a): component b) of about 1: 9 to about 9: 1. [0010] BEST MODE FOR CARRYING OUT THE INVENTION Preferred phenolic anti-microbial compounds of component a) are o-benzyl-phenol, 2-benzyl-4-chloro-phenol, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, 4,4'-dichloro- 2-Hydroxydiphenyl ether, 5-chloro-2-hydroxy-diphenyl-methane, mono-chloro-o-benzyl-phenol, 2,2'-methylenebis- (4-chloro-phenol) and 2,4,6-trichlorophenol Is. [0011] The most preferred phenolic antimicrobial compounds of component a) are 2,4,4'-trichloro-2'-hydroxydiphenyl ether and 4,4'-dichloro-2-hydroxydiphenyl ether. [0012] Of particular importance is a mixture of antimicrobial agents for plastics applications, wherein the inorganic antimicrobial compound is a metal-containing zeolite or a surface-modified metal-containing zeolite. [0013] The metal-containing zeolite of component b) is, for example, as described in US Pat. Nos. 4,775585, 4911898, 4911899 and 6071542, the disclosure of which is hereby referred to. It is taken in. Zeolites are usually aluminosilicates with a three-dimensionally grown skeletal structure, and usually Al as a base.₂O₃XM with_{2 / n}O Al₂O₃ YSiO₂ ZH₂O (in the equation, M represents an ion-exchangeable metal ion, which is usually a monovalent or divalent metal ion; n corresponds to the valence of the metal; x represents the coefficient of the metal oxide; y represents the coefficient of silica; and z represents the number of crystalline waters). The zeolite of the present invention is at least 150 m²It has a specific surface area of / g. [0014] Antibacterial metals used in metal-containing zeolites include silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium, cobalt, nickel, zirconium, or two or more combinations of the metals. .. Preferred are silver, copper, zinc and zirconium or combinations thereof. Particularly preferred metals are silver alone or a combination of silver with copper, zinc or zirconium. [0015] A particularly preferred metal-containing zeolite of component b) is a surface-modified metal-containing zeolite according to United States Patent No. 6071542. [0016] The inorganic antimicrobial compound of the most important component b) is a surface-modified metal-containing zeolite whose metal is selected from the group consisting of silver and a combination of silver and copper, zinc or zirconium. [0017] Particularly preferred are antimicrobial agents in which component a) is 2,4,4'-trichloro-2'-hydroxydiphenyl ether and component b) is a surface-modified silver-containing zeolite. It is a mixture. The term "silver-containing" includes combinations of silver with other metals such as zinc, copper and zirconium. BACTEKILLER BM-102GA (manufactured by Kanebo Co., Ltd.) is a surface-modified silver-containing zeolite based on United States Patent No. 6071542. [0018] In addition to zeolites, antibacterial metals such as silver, silver compounds and silver complexes are used for other inert materials such as SiO.₂, TiO₂And it is expected that it can be supported on glass. [0019] The novel antimicrobial mixture of components a) and b) may be mixed into the plastic resin before it is subjected to manufacturing processes such as film blowing, rotomoulding, fiber spinning and the like. The mixture of components a) and b) makes it possible to set required processing conditions such as high temperature, for example temperatures above 200 ° C. [0020] Plastic films, fibers and articles containing a mixture of the antimicrobial agents of the present invention consisting of components a) and b) are suitable for field exposure; they are resistant to outdoor exposure and UV degradation. [0021] [0021] A mixture of antimicrobial agents consisting of components a) and b) exhibits good long-term activity and a good toxicity profile. [0022] Plastic samples containing Triclosan undergo strong fading in a very short time when exposed to field exposure. A plastic sample containing the composition of the present invention consisting of components a) and b) shows only minimal color change. [0023] Triclosan Plastic samples containing, show reduced photostability. A plastic sample containing the composition of the present invention consisting of components a) and b) exhibits the same physical properties as a control preparation containing no antimicrobial agent. [0024] The plastic films, fibers and articles of the present invention are conveniently used in applications that require long-term hygienic activity on the surface, such as medical devices, handrails, door handles and the like. The plastic films, fibers and articles of the present invention are used, for example, in hospitals, homes, public research institutes, ventilation systems, air purification and air conditioning systems, and waste treatment systems. Plastic articles exposed to outdoor exposure, which may contain a mixture of antimicrobial agents of the present invention, are, for example, waste containers, swimming pool equipment, outdoor swing devices, slides, etc., as well as stadium seats. [0025] The plastic films, fibers and articles of the present invention exhibit high antimicrobial activity on the surface. This antimicrobial activity remains after repeated washing. [0026] The compositions, plastic films, fibers and articles of the invention, ie, polymer substrates, may also contain one or more of the following additives: [0027]<u style="single">1. Antioxidant</u><u style="single">1.1. Alkylated monophenol</u>For example, 2,6-ditertiary butyl-4-methylphenol, 2-third butyl-4,6-dimethylphenol, 2,6-ditertiary butyl-4-ethylphenol, 2,6-ditertiary. Butyl-4-n-butylphenol, 2,6-ditertiary butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol , 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-ditertiary butyl-4-methoxymethylphenol, with linear or branched side chains Some nonylphenols, such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadeci) -1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltrideci-1'-yl) phenol and mixtures thereof. [0028]<u style="single">1.2. Alkylthiomethylphenol</u>For example, 2,4-dioctylthiomethyl-6-tertiary butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl -4-Nonylphenol. [0029]<u style="single">1.3. Hydroquinone and Alkylated Hydroquinone</u>For example, 2,6-ditertiary butyl-4-methoxyphenol, 2,5-ditertiary butylhydroquinone, 2,5-ditertiary amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2, 6-Ditertiary Butylhydroquinone, 2,5-Ditertiary Butyl-4-Hydroxyanisole, 3,5-Ditertiary Butyl-4-Hydroxyanisole, 3,5-Ditertiary Butyl-4-hydroxyphenylsteer Rate, bis (3,5-ditertiary butyl-4-hydroxyphenyl) adipate. [0030]<u style="single">1.4. Tocopherol</u>For example, α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E). [0031]<u style="single">1.5. Hydroxylated thiodiphenyl ether</u>For example, 2,2'-thiobis (6-tertiary butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tertiary butyl-3-methylphenol) ), 4,4'-thiobis (6-tertiary butyl-2-methylphenol), 4,4'-thiobis (3,6-disecond amylphenol), 4,4'-bis (2,6-) Dimethyl-4-hydroxyphenyl) disulfide. [0032]<u style="single">1.6. Alkylidene bisphenol</u>For example, 2,2'-methylenebis (6-tertiary butyl-4-methylphenol), 2,2'-methylenebis (6-third butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl -6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2' -Methylenebis (4,6-di-tertiary butylphenol), 2,2'-etylidenebis (4,6-dithird butylphenol), 2,2'-etiridenbis (6-third butyl-4-isobutylphenol) ), 2,2'-Methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4' -Methylenebis (2,6-ditertiary butylphenol), 4,4'-Methylenebis (6-third butyl-2-methylphenol), 1,1-bis (5-third butyl-4-hydroxy-2-) Methylphenyl) butane, 2,6-bis (3-tertiary butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tertiary butyl-4-hydroxy- 2-Methylphenyl) butane, 1,1-bis (5-tertiary butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol-bis [3,3-bis (3') -3rd Butyl-4'-Hydroxyphenyl) Butylate], Bis (3-3rd Butyl-4-Hydroxy-5-Methylphenyl) Dicyclopentadiene, Bis [2- (3'-3rd Butyl-2'-Hydroxy) -5'-Methylbenzyl) -6-Triary Butyl-4-Methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-) Di-tertiary butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tertiary butyl-4-hydroxy-2-methylphenyl) -4-n-dodecyl mercaptobutane, 1,1,5,5-Tetra (5-tertiary butyl-4-hydroxy-2-methylphenyl) pentane. [0033]<u style="single">1.7. O-, N- and S-benzyl compounds</u>For example, 3,5,3', 5'-tetra ternary butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3, 5-Ditertiary Butylbenzyl Mercaptoacetate, Tris (3,5-Ditertiary Butyl-4-Hydroxybenzyl) Amine, Bis (4-Third Butyl-3-Hydroxy-2,6-dimethylbenzyl) Dithioterephthalate, Bis (3,5-ditertiary butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-ditertiary butyl-4-hydroxybenzyl mercaptoacetate. [0034]<u style="single">1.8. Hydroxybenzylated malonate</u>For example, dioctadecyl-2,2-bis (3,5-ditertiary butyl-2-hydroxybenzyl) malonate, dioctadecil-2- (3-tertiary butyl-4-hydroxy-5-methylbenzyl) malonate, Didodecyl mercaptoethyl-2,2-bis (3,5-ditertiary butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2 -Bis (3,5-ditertiary butyl-4-hydroxybenzyl) malonate. [0035]<u style="single">1.9. Aromatic hydroxybenzyl compound</u>For example, 1,3,5-tris (3,5-ditertiary butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-ditertiary butyl-4). -Hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-ditertiary butyl-4-hydroxybenzyl) phenol. [0036]<u style="single">1.10. Triazine compound</u>For example, 2,4-bis (octyl mercapto) -6- (3,5-ditertiary butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl mercapto-4,6-bis ( 3,5-Di-tertiary butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl mercapto-4,6-bis (3,5-di-tertiary butyl-4-hydroxyphenoxy)- 1,3,5-triazine, 2,4,6-tris (3,5-ditertiary butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5) -Di-tertiary butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tertiary butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris ( 3,5-Ditertiary Butyl-4-Hydroxyphenylethyl) -1,3,5-Triazine, 1,3,5-Tris (3,5-Ditertiary Butyl-4-hydroxyphenylpropionyl) -Hexahydro- 1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate. [0037]<u style="single">1.11. Benzyl phosphonate</u>For example, dimethyl 2,5-ditertiary butyl-4-hydroxybenzylphosphonate, diethyl3,5-ditertiary butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-ditertiary butyl-4-hydroxybenzylphosphonate. , Calcium salt of monoethyl ester of dioctadecyl 5-tertiary butyl-4-hydroxy-3-methylbenzylphosphonate, 3,5-ditrithibyl-4-hydroxybenzylphosphonic acid. [0038]<u style="single">1.12. Acylaminophenol</u>For example, 4-hydroxylaurate anilide, 4-hydroxystearic acid anilide, octyl N- (3,5-di-tertiary butyl-4-hydroxyphenyl) -carbamate. [0039]<u style="single">1.13. Ester of β- (3,5-ditertiary butyl-4-hydroxyphenyl) propionic acid with the following monohydric or polyhydric alcohols</u>Examples of alcohols: methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylpropane , 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane. [0040]<u style="single">1.14. Ester of β- (5-tertiary butyl-4-hydroxy-3-methylphenyl) propionic acid and the following monohydric or polyhydric alcohols</u>Examples of alcohols: methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylpropan , 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane, 3,9-bis [2- {3- (3-tertiary butyl-4-hydroxy-5-) Methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane. [0041]<u style="single">1.15. Ester of β- (3,5-dicyclocyclohexyl-4-hydroxyphenyl) propionic acid with the following monohydric or polyhydric alcohols</u>Examples of alcohols: methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene 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. [0042]<u style="single">1.16.3,5-Ester of tertiary butyl-4-hydroxyphenylacetic acid with the following monohydric or polyhydric alcohols</u>Examples of alcohols: methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene 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. [0043]<u style="single">1.17. Amide of β- (3,5-ditertiary butyl-4-hydroxyphenyl) propionic acid</u>For example, N, N'-bis (3,5-ditertiary butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N'-bis (3,5-ditertiary butyl-4-hydroxyphenylpropionyl) Trimethylenediamide, N, N'-bis (3,5-ditertiary butyl-4-hydroxyphenylpropionyl) hydrazide, N, N'-bis [2- (3- [3,5-ditertiary butyl-) 4-Hydroxyphenyl] propionyloxy) ethyl] oxamide [trade name Naugard XL-1 provided by Uniroyal]. [0044]<u style="single">1.18. Ascorbic acid (vitamin C)</u> 【0045】<u style="single">1.19. Amine-based antioxidant</u>For example, N, N'-diisopropyl-p-phenylenediamine, N, N'-disecondary butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N , N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine , N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3 -Dimethylbutyl) -N'-Phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-Toluene Sulfamoyl) Diphenylamine, N, N'-dimethyl-N, N'-disecondary butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1 -Naphthylamine, N- (4-tertiary octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, eg p, p'-ditertiary octyldiphenylamine, 4-n-butylaminophenol, 4-Butylylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-ditertiary butyl-4-dimethyl Aminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis [(2-2-bis Methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1',,3'-Dimethylbutyl) phenyl] amine, tertiary octylated N-phenyl-1-naphthylamine, mono- and dialkylated tertiary butyl / tertiary octyldiphenylamine mixture, mono- and dialkylated nonyldiphenylamine mixture, mono- And a mixture of dialkylated dodecyldiphenylamine, a mixture of mono- and dialkylated isopropyl / isohexyldiphenylamine, a mixture of mono- and dialkylated tertiary butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4 -Benzothiazine, phenothiazine, mono- and dialkylated tributyl / tertiary octylphenothiazine mixture, mono- and dialkylated tertiary octylphenothiazine mixture, N-allylphenothiazine, N, N, N', N'-tetraphenyl -1,4-diaminobute-2-ene. [0046]<u style="single">2. UV absorber and light stabilizer</u><u style="single">2.1.2-(2'-Hydroxyphenyl</u><u style="single">) </u><u style="single">Benzotriazole</u>For example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3', 5'-ditertiary butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-third Butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3', 5'-di Tertiary butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tertiary butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3' -Secondary butyl-5'-Third butyl-2'-Hydroxyphenyl) Benzotriazole, 2- (2'-Hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3', 5'-dith Triamyl-2'-hydroxyphenyl) benzotriazole, 2- (3', 5'-bis (α, α,)α-Dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tertiary butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-3rd Butyl-5'-[2- (2-Ethylhexyloxy) carbonylethyl] -2'-Hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-3rd Butyl-2 '-Hydroxy-5'-(2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tertiary butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl) phenyl) Bentriazole, 2- (3'-3rd Butyl-2'-Hydroxy-5'-(2-octyloxycarbonylethyl) phenyl) Bentriazole, 2- (3'-3rd Butyl-5'-[2- (2-Ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tertiary butyl -2'-Hydroxy-5'-(2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazole- 2-Ilphenol]; 2- [3'-3rd Butyl-5'-(2-methoxycarbonylethyl) -2'-Hydroxyphenyl] -2H-benzotriazole and polyethylene glycol 300 ester exchange product; Expression: [R-CH₂CH₂-COO-CH₂CH₂-]₂(In the formula, R represents the 3'-tertiary butyl-4'-hydroxy-5'-2H-benzotriazole-2-ylphenyl group), 2- [2'-hydroxy-3'- (α, α-dimethylbenzyl) -5'-(1,1,3,3-tetramethylbutyl) phenyl] benzotriazole; 2- [2'-hydroxy-3'-(1,1,3,3-) Tetramethylbutyl) -5'-(α, α-dimethylbenzyl) phenyl] benzotriazole. [0047]<u style="single">2.2.2-Hydroxybenzophenone</u>For example, 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2', 4'-trihydroxy and 2'-hydroxy-4,4'- Dimethoxy derivative. [0048]<u style="single">2.3. Substituted and unsubstituted benzoic acid esters</u>For example, 4-third butylphenyl salicylate, phenylsalicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-third butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-ditertiary butylphenyl. 3,5-Ditertiary Butyl-4-Hydroxybenzoate, Hexadecyl 3,5-Ditertiary Butyl-4-Hydroxybenzoate, Octadecyl 3,5-Ditertiary Butyl-4-Hydroxybenzoate, 2-Methyl-4, 6-Ditertiary butylphenyl 3,5-Ditertiary butyl-4-hydroxybenzoate. [0049]<u style="single">2.4. Acrylate</u>For example, 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-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindrin. [0050]<u style="single">2.5. Nickel compounds</u>For example, a nickel complex of 2,2'-thiobis [4- (1,1,3,3-tetramethylbutyl) phenol], such as a 1: 1 or 1: 2 complex, n-butylamine, triethanolamine. Or with or without an additional ligand such as N-cyclohexyldiethanolamine, nickel dibutyl dithiocarbamate; monoalkyl ester, eg, methyl 4-hydroxy-3,5-ditetrabutylbenzylphosphonic acid or Nickel salt of ethyl ester; a nickel complex of ketoxim, for example 2-hydroxy-4-methyl-phenylundecyl ketoxim, a nickel complex of 1-phenyl-4-lauroyl-5-hydroxypyrazole, and other ligands. With or without. [0051]<u style="single">2.6. Steric hindrance amine</u>For example, 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 (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4- Piperidine) n-butyl-3,5-ditertiary butyl-4-hydroxybenzylmalonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid Condensation products of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tertiary octylamino-2,6-dichloro-1,3,5- Linear or cyclic condensation product with triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)- 1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2 , 6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2 -(2-Hydroxy-3,5-ditertiary butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4 -Dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, N, N'- Linear or cyclic condensation product of bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 2 -Chloro-4,6-bis (4-n-butylamino-2,2,Condensation product of 6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 2-chloro-4,6-di (4-n-) Condensation product of butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3 -Dodecyl-7,7,9,9-Tetramethyl-1,3,8-Triazaspiro [4.5] Decane-2,4-dione, 3-Dodecyl-1- (2,2,6,6-Tetramethyl- 4-Pihelidine) pyrridine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrridine-2,5-dione, 4-hexadecyloxy- Mixture with 4-stearyloxy-2,2,6,6-tetramethylpiperazine, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino Condensation product with -2,6-dichloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine and Condensation product of 4-butylamino-2,2,6,6-tetramethylpiperidine [CAS Reg. No [136504-96-6]]; 1,6-hexanediamine and 2,4,6-trichloro-1 , 3,5-Triazine and the condensation product of N, N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine [CAS Reg. No [192268-64-7]]; N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecyl succinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dodecyl succinimide, 2-undecyl -7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4.5] decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1 -Oxa-3,8-Diaza-4-oxo-spiro [4.5] Reaction product of decane and epichlorohydrin, 1,1-bis (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethene, N , N'-bisformyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, 4-methoxymethylenemalonic acid and 1,2,2,6,6-pentamethyl Diester with -4-hydroxypiperidine, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, maleic anhydride-α-olefin copolymer and 2, Reaction product with 2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine. [0052] Steric hindrance amines are described in GB-A-2301106 as components Ia), Ib), Ic), Id), Ie), If), Ig), Ih), Ii), Ij), Ik) or Il). Light stabilizers 1-a-1,1-a-2,1-b-1,1-c- listed on pages 68 to 73 of GB-A-2301106. 1,1-d-1,1-d-2,1-d-3,1-e-1,1-f-1,1-g-1,1-g-2 or 1-k-1 There may be. [0053] The steric hindrance amine is one of the compounds described in EP-A-0782994, eg, the compounds of claims 10 or 38, or Examples 1-12, or D-1 to D-5 thereof. It may be. [0054]<u style="single">2.7. Steric hindrance amine in which a nitrogen atom is substituted with an alkoxy group substituted with a hydroxyl group</u>For example, 1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 1- (2-hydroxy-2-methylpropoxy) -4-hexa Decanoyloxy-2,2,6,6-tetramethylpiperidine, 1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidine reaction product with carbon radicals from tertiary amyl alcohol, 1- (2-Hydroxy-2-methylpropoxy) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 1- (2-hydroxy-2-methylpropoxy) ) -4- oxo-2,2, 6,6-Tetramethylpiperidin, bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) sevacate, bis (1- (2-hydroxy-) 2-Methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin -4-yl) succinate, bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) glutarate and 2,4-bis {N- [1 -(2-Hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine-4-yl] -N-butylamino} -6- (2-hydroxyethylamino) -s-like triazine Compound. [0055]<u style="single">2.8. Oxamide</u>For example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-dithird butoxanilide, 2,2'-didodecyloxy. -5,5'-Ditertiary butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tertiary butyl -2'-Etoxanilide and a mixture of the compound with 2-ethoxy-2'-ethyl-5,4'-ditertiary butoxanilide, a mixture of o- and p-methoxy-disubstituted oxanilide and o- and p-ethoxy. -A mixture of disubstituted oxanilides. [0056]<u style="single">2.9.2- (2-Hydroxyphenyl) -1,3,5-triazine</u>For example, 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-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) ) -1,3,5-triazine, 2- [2-Hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3, 5-Triazine, 2- [2-Hydroxy-4- (2-Hydroxy-3-octyloxypropyloxy) Phenyl]-4,6-bis (2,4-dimethyl) -1,3,5-Triazine, 2 -[4- (Dodecyloxy / Tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2 -Hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- Hexyloxy) Phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-Hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4, 6-Tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6 -Phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2, 4-Dimethylphenyl) -1,3,5-triazine. [0057]<u style="single">3. Metal activator</u>For example, N, N'-diphenyloxamide, N-salicyral-N'-salicyloyl hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-ditertiary butyl- 4-Hydrazinephenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoil bisphenylhydrazide, N, N'-diacetylazido Poyldihydrazide, N, N'-bis (salicyloyl) oxalyldihydrazide, N, N'-bis (salicyloyl) thiopropionyldihydrazide. [0058] [0058]<u style="single">4. Phosfit and phosphonite</u>For example, Triphenylphosfit, Diphenylalkylphosfit, Phenyldialkylphosfit, Tris (nonylphenyl) phosfit, Trilauryl phosfit, Trioctadecyl phosfit, Distearyl pentaerythritol diphosfit, Tris (2,4-di Tertiary Butylphenyl) Phenyl Phenyl, Diisodecylpentaerytritol Diphosfit, Bis (2,4-Ditertiary Butylphenyl) Pentaerythitol Diphosfit, Bis (2,4-Dicumylphenyl) Pentaerythitol diphosfit, Bis (2,6-ditertiary butyl-4-methylphenyl) pentaerythritol diphosfit, diisodecyloxypentaerytritor diphosfit, bis (2,4-ditertiary butyl-6-methylphenyl) pentaerythritol diphosfit , Bis (2,4,6-tris tertiary butylphenyl) pentaerythritol diphosfit, tristearyl sorbitol triphosfit, tetrakis (2,4-ditertiary butylphenyl) -4,4'-biphenylenediphosphonite, 6-Isooctyloxy-2,4,8,10-Tetra Tertiary Butyl-12H-Dibenz [d, g] -1,3,2-Dioxaphosphocin, Bis (2,4-Ditertiary Butyl- 6-Methylphenyl) Methylphosfit, Bis (2,4-Ditertiary butyl-6-Methylphenyl) Ethylphosfit, 6-Fluoro-2,4,8,10-Tetratertiary butyl-12-methyl- Dibenz [d, g] -1,3,2-dioxaphosphocin, 2,2', 2 "-Nitrilo [Triethyltris (3,3', 5,5'-Tetratertiary butyl-1,1' -Biphenyl-2,2'-diyl) phosfit], 2-ethylhexyl (3,3', 5,5'-tetratertiary butyl-1,1'-biphenyl-2,2'-diyl) phosfit, 5-Butyl-5-Ethyl-2- (2,4,6-tritertiary butylphenoxy) -1,3,2-dioxaphosphylan. [0059] The following phosfits are particularly preferred. Tris (2,4-ditertiary butylphenyl) phosfit [trade name Irgafos 168, manufactured by Ciba Specialty Chemicals Inc.], Tris (nonylphenyl) phosfit, by the following formula Represented phosfit: [Chemical 3]<img file="JP4880147B2_D0002.tif" />[Chemical 4]<img file="JP4880147B2_D0003.tif" /> 【0060】<u style="single">5. Hydroxylamine</u>For example, N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N- N, N-dialkyl derived from dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, hydrogenated beef amine Hydroxylamine. [0061]<u style="single">6. Nitron</u>For example, N-benzyl-α-phenyl-nitrone, N-ethyl-α-methyl-nitrone, N-octyl-α-heptyl-nitrone, N-lauryl-α-undecyl-nitrone, N-tetradecyl-α-tridecyl- Nitron, N-Hexadecyl-α-Pentadecyl-Nitrone, N-Octadecyl-α-Hexadecyl-Nitrone, N-Hexadecyl-α-Heptadecyl-Nitrone, N-Octadecyl-α-Pentadecyl-Nitrone, N-Heptadecyl-α-Heptadecil- Nitrone, N-octadecyl-α-hexadecyl-nitrone, nitrone derived from N, N-dialkylhydroxylamine derived from hydrogenated beef fat amine. [0062]<u style="single">7. Amine oxide</u>For example, amine oxide derivatives, didecylmethylamine oxides, tridecylamine oxides, tridodecylamine oxides and trihexadecylamine oxides disclosed in United States Patent Nos. 5844029 and 5880191. [0063]<u style="single">8. Benzofuran and indolinone</u>For example, those disclosed in US4325863, US4338244, US5175312, US5216052, US5252643, DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102, or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-ditertiary butylbenzofuran-2-one, 5,7-ditertiary butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran -2-one, 3,3'-bis [5,7-ditertiary butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5,7-ditertiary butyl- 3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-ditertiary butylbenzofuran-2-one, 3- (3,5-) Dimethyl-4-pivaloyloxyphenyl) -5,7-ditertiary butylbenzofuran-2-one, 3- (3,4-dimethylphenyl) -5,7-ditertiary butylbenzofuran-2-one, 3- (2,3-Dimethylphenyl) -5,7-ditertiary butyl-benzofuran-2-one. [0064]<u style="single">9. Thio synergist</u>For example, dilaurylthiodipropionate or distearylthiodipropionate. [0065]<u style="single">10. Peroxide sweeping agent</u>For example, β-thiodipropionic acid esters such as lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole or 2-mercaptobenzimidazole zinc salt, zinc dibutyldithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis (β-dodecyl mercapto). ) Propionate. [0066]<u style="single">11. Polyamide stabilizer</u>For example, copper salts in combination with iodides and / or phosphorus compounds and divalent manganese salts. [0067]<u style="single">12. Basic auxiliary stabilizer</u>For example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts of higher fatty acids and alkaline earth metal salts such as calcium stearate, zinc stearate, magnesium base. Henate, magnesium stearate, sodium ricinolate and potassium palmitate, antimony pyrocatecolate or zinc pyrocatecolate. [0068]<u style="single">13. Nuclear agent</u>For example, inorganic substances such as talc, metal oxides such as titanium dioxide or magnesium oxide, preferably alkaline earth metal phosphates, carbonates or sulfates, organic compounds such as mono- or polycarboxylic acids and salts thereof. , For example, 4-tertiary butyl benzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers). Particularly preferred are 1,3: 2,4-bis (3', 4'-dimethylbenzidene) sorbitol, 1,3: 2,4-di (paramethyl-dibenzylidene) sorbitol, and 1,3: 2, 4-Di (benzylidene) sorbitol. [0069]<u style="single">14. Fillers and strengtheners</u>For example, calcium carbonate, silicate, glass fiber, fiberglass, asbestos, talc, porcelain clay, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood powder, and other natural powders or fibers. ,Synthetic fibers. [0070]<u style="single">15. Other additives</u>For example, plasticizers, lubricants, emulsifiers, pigments, dyes, rheology additives, catalysts, flow regulators, optical brighteners, slip agents, crosslinkers, crosslinking boosters, halogen sweepers, smoke proofs. Agents, flameproofing agents, antioxidants, clearing agents such as substituted and unsubstituted bisbendylidene sorbitol, benzoxazineone UV absorbers such as 2,2'-p-phenylene-bis (3,1-benzoxazine-) 4-on), trade name Cyasorb 3638 (CAS # 18600-59-4), and foaming agent. [0071]<u style="single">16. Other killing agents</u>For example, 3,5-dimethyl-tetrahydro-1,3,5-2H-thiodiazine-2-thione, bis-tributyltin oxide, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, Antifungal agents such as N-butyl-benz-isothiazolin, 10,10'-oxybisphenoxyarcin, zinc 2-pyridinethiol-1-oxide, and 2-methylthio-4-cyclopropylamino-6- (α, β) -Dimethylpropylamino) -s-triazine, 2-methylthio-4-cyclopropylamino-6-tertiary butylamino-s-triazine, 2-methylthio-4-ethylamino-6- (α, α-dimethylpropylamino-6-) )-S-Algae killing agents such as triazine. [0072] Other preferred additives are antioxidants, UV absorbers, sterically damaging amines, phosfits and phosphonite, hydroxylamines, nitrons, benzofuran-2-ones, thiosynergists, polyamide stabilizers, metal stearate, nucleating agents, It is selected from the group consisting of fillers, strengthening agents, lubricants, emulsifiers, dyes, pigments, optical brighteners, flame retardants, antistatic agents and foaming agents. [0073] Generally, the polymer substrate of the plastic resin having the antimicrobial activity of the present invention can be selected from the following group. [0074] 1. Monoolefin and diolefin polymers such as polypropylene, polyisobutylene, polybute-1-ene, poly-4-methylpente-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, and cycloolefin polymers such as cyclopentene or norbornene. Polymers, polyethylene (which may be crosslinked if desired), such as high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene. (MDPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), (VLDPE) and (ULDPE). [0075] Polyolefins, i.e. the monoolefins exemplified in the previous paragraph, preferably polyethylene and polypropylene polymers, can be prepared by different methods and, above all, by the methods described below. [0076] a) Radical polymerization (usually performed under high pressure and elevated temperature). b) Catalytic polymerization usually using a catalyst containing one or more metals of the Periodic Table Group IVb, Vb, VIb or VIII. The metal usually has one or more ligands and may typically be π- or σ-coordinated oxides, halides, alcoholates, esters, ethers, amines. , Alkyl, alkenyl and / or aryl. The metal complex may be in free form or may be supported on a substrate, typically activated magnesium chloride, titanium trichloride, alumina or silicon oxide. The catalyst may be soluble or insoluble in the polymerization medium. The catalyst may be used alone in the polymerization, or another activator, typically a metal alkyl, a metal hydride, a metal alkyl halide, a metal alkyl oxide or a metal alkyl oxane may be used. , The metal is an element of the groups Ia, IIa and / or IIIa of the periodic table. The activator may be conveniently modified with another ester, ether, amine or silyl ethers. The catalyst system is usually a Phillips catalyst, a Standard Oil Indiana catalyst, a Ziegler (-Natta) catalyst, a TNZ catalyst, and a metallocene catalyst. Or called a single site catalyst (SSC). [0077] Polymer mixtures described in 2.1., Such as polypropylene and polyisobutylene mixtures, polypropylene and polyethylene mixtures (eg PP / HDPE, PP / LDPE) and different types of polyethylene mixtures (eg LDPE / HDPE). [0078] 3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures with their low density polyethylene (LDPE), propylene / Bute-1-ene copolymer, propylene / isobutylene copolymer, ethylene / bute-1-ene copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, ethylene / vinylcyclohexane copolymer , Ethylene / cycloolefin copolymers (eg, ethylene / norbornen COC), ethylene / 1-olefin copolymers (1-olefins are generated in the field), propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / vinylcyclohexene copolymers, ethylene / Alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers or ethylene / acrylic acid copolymers and salts thereof (ionomers), and terpolymers of ethylene and propylene and diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; And mixtures of the copolymers with each other and the polymers described in 1. above, such as polypropylene / ethylene-propylene-polymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers such as polyamide. [0079] 4. A hydrocarbon resin (eg, 5 to 9 carbon atoms) containing a hydrogenated modified product (eg, a tackifier) and a mixture of polyalkylene and starch. [0080] [0080] The homopolymers and copolymers from 1. to 4 may have any three-dimensional structure including syndiotactics, isotactics, hemiisotactics or atactics; atactic polymers are preferred. .. Stereoblock polymers are also included. [0081] 5. Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene). [0082] 6. Includes all isomers of styrene, α-methylstyrene, vinyltoluene, especially all isomers of p-vinyltoluene, ethylstyrene, propylstyrene, vinylbiphenyl, vinylnaphthalene, and vinylanthracene, and mixtures thereof. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers. Homopolymers and copolymers may have any three-dimensional structure including syndiotactics, isotactics, hemiisotactics or atactics; atactic polymers are preferred. Stereo block polymers are also included. [0083] 6a. Copolymers comprising the above-mentioned vinyl aromatic monomers and comonomer selected from ethylene, propylene, diene, nitrile, acid, maleic anhydride, maleimide, vinyl acetate and vinyl chloride or acrylic derivatives thereof and mixtures thereof, for example, styrene. / Butadiene copolymer, styrene / acrylonitrile copolymer, styrene / ethylene copolymer (interpolymer), styrene / alkyl methacrylate copolymer, styrene / butadiene / alkyl acrylate copolymer, styrene / butadiene / alkyl methacrylate copolymer, styrene / maleic anhydride copolymer, styrene / acrylonitrile / Methyl acrylate copolymers; Impact resistant mixtures made from styrene copolymers and other polymers such as polyacrylates, diene polymers or ethylene / propylene / dienter polymers; and block copolymers of styrene, such as styrene / butadiene / styrene. Block copolymer, styrene / isoprene / styrene block copolymer, styrene / ethylene / butylene / styrene block copolymer or styrene / ethylene / propylene / styrene block copolymer. [0084] 6b. In particular, it is derived from the hydrogenation of the polymers described in 6., including polycyclohexylethylene (PCHE), which is often produced by hydrogenation of atactic polystyrene, often described as polyvinylcyclohexane (PVCH). Hydrogenated aromatic polymer. [0085] A hydrogenated aromatic polymer derived from the hydrogenation of the polymer described in 6c.6a. [0086] Homopolymers and copolymers may have any three-dimensional structure including syndiotactics, isotactics, hemiisotactics or atactics; atactic polymers are preferred. Stereo block polymers are also included. [0087] 7. Graft copolymers of vinyl aromatic monomers such as styrene or α-methylstyrene, eg styrene graft copolymers to polybutadiene, styrene graft copolymers to polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) to polybutadiene Styrene) graft copolymer; Styrene, acrylonitrile and methyl methacrylate graft copolymer to polybutadiene; Styrene and maleic anhydride graft copolymer to polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide graft copolymer to polybutadiene; Styrene and maleimide to polybutadiene Graft copolymer; Styrene and alkyl acrylate or methacrylate graft copolymer for polybutadiene; Styrene and acrylonitrile graft copolymer for ethylene / propylene / dienter polymer; Styrene and acrylonitrile graft copolymer for polyalkyl acrylate or polyalkyl methacrylate; Styrene and acrylonitrile graft copolymer for acrylate / butadiene copolymer Grafted copolymers of styrene and acrylonitrile, and mixtures with the copolymers described in 6. for example, copolymer mixtures known as ABS polymers, MBS polymers, ASA polymers or AES polymers. [0088] 8. Halogen-containing polymers such as polyvinylidene, rubber chloride, chloride and isobutylene bromide-isoprene copolymer (halobutyl rubber), chloride or sulfochlorinated polyethylene, ethylene and ethylene chloride copolymers, epichlorohydrin homo-and copolymers, especially halogens. Polymers from vinyl compounds contained, such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene chloride, polyvinylidene chloride, and their copolymers, such as vinyl chloride / vinyl chlorideden copolymers, vinyl chloride / vinyl acetate copolymers or vinylidene chloride / Vinyl acetate copolymer. [0089] 9. Polymers derived from α, β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates; polymethylmethacrylates, polyacrylamides and polyacrylonitriles with improved impact resistance using butyl acrylates. [0090] Copolymers of the monomers described in 10.9. With each other or with other unsaturated monomers, such as acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymers or acrylonitrile / alkyl methacrylate / butadiene. Tarpolymer. [0091] 11. Polymers derived from unsaturated alcohols and amines or acyl derivatives thereof or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; And their copolymers with the olefins described in 1. above. [0092] 12. Homopolymers and copolymers of cyclic ethers, such as copolymers with polyalkylene glycols, polyethylene oxides, polypropylene oxides or bisglycidyl ethers. [0093] 13. Polyoxymethylene, such as polyoxymethylene and their polyoxymethylene containing ethylene oxide as a comonomer; polyacetal modified with thermoplastic polyurethane, acrylate or MBS. [0094] 14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with polystyrene polymers or polyamides. [0095] 15. Polyurethanes derived from polyethers, polyesters or polybutadienes having a terminal hydroxyl group as one component and aliphatic or aromatic polyisocyanates as other components, and their precursors. [0096] 16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or equivalent lactams such as polyamide 4, polyamide 6, polyamide 6/6,6 / 10,6 / 9,6 / 12 , 4/6, 12/12, Polyamide 11, Polyamide 12, m-Aromatic polyamide starting from xylenediamine and adipic acid; with hexamethylenediamine and isophthalic acid and / or terephthalic acid and elastomer as modifier Polyamides produced without or without, such as poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and further, the polyamide is conjugated with a polyolefin, olefin copolymer, ionomer or chemically. Copolymerized with or grafted elastomers; or copolymers with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; and polyamides or copolyamides modified with EPDM or ABS; and fused during processing Polyamide (RIM-polyamide type). [0097] 17. Polyurea, polyimide, polyamide-imide, polyetherimide, polyesterimide, polyhydantoin and polybenzimidazole. [0098] 18. Polyesters derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids or equivalent lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN). And polyhydroxybenzoates, and block copolyether esters derived from polyethers with hydroxy end groups; and polyesters further modified with polycarbonate or MBS. [0099] 19. Polycarbonate and polyester carbonate. [0100] 20. Polyketone. [0101] 21. Polysulfone, polyethersulfone and polyetherketone. [0102] 22. Cross-linked polymers derived from aldehyde as one component and phenol, urea and melamine as other components, such as phenol / formaldehyde resin, urea / formaldehyde resin and melamine / formaldehyde resin. [0103] 23. Dry and non-dry alkyd resins. [0104] 24. Unsaturated polyester resins derived from saturated and unsaturated dicarboxylic acids, polyhydric alcohols and vinyl compounds as cross-linking agents, and their halogen-containing modified forms with even lower flames. [0105] 25. Crosslinkable acrylic resin derived from substituted acrylates such as epoxy acrylates, urethane acrylates or polyester acrylates. [0106] 26. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins. [0107] 27. Crosslinked epoxy resins derived from aliphatic, alicyclic, heterocyclic or aromatic glycidyl compounds such as bisphenol A and bisphenol F diglycidyl ethers, which are conventional curing agents such as acid anhydride. Those that are crosslinked with a substance or amine in the presence or absence of an accelerator. [0108] 28. Natural polymers such as cellulose, rubber, gelatin and chemically modified derivatives of the same type, such as cellulose acetate, cellulose propionate and cellulose butyrate, or cellulose ethers such as methyl cellulose; and rosin and its derivatives. [0109] 29. Polymer formulations (polyblends) described above, such as PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC. [0110] 30. Oils based on natural and synthetic organic materials, such as mineral oils, animal and vegetable fats, oils and waxes, or synthetic esters (eg, phthalates, adipates, phosphates or trimellites), which are pure monomeric compounds or mixtures of said compounds. , Fats and waxes, and mixtures of synthetic esters and mineral oils of any weight ratio, typically mixtures used as spinning compositions, and aqueous emulsions of said materials. [0111] 31. Aqueous emulsions of natural or synthetic rubber, such as natural latex or latex of carboxylated styrene / butadiene copolymer. [0112] 32. Polysiloxanes, such as the soft, hydrophobic polysiloxanes described in United States Patent No. 4259467; and the hard polyorganosiloxanes described in United States Patent No. 4355147. [0113] 33. Polyketimine in combination with unsaturated acrylic polyacetoacetate resin or unsaturated acrylic acid resin. Unsaturated acrylic resins include urethane acrylates, polyether acrylates, vinyl or acrylic copolymers with suspended unsaturated groups and acrylicized melamines. Polyketimine is produced from polyamines and ketones in the presence of acid catalysts. [0114] 34. A radiation curable composition comprising an ethylenically unsaturated monomer or oligomer and a polyunsaturated aliphatic oligomer. [0115] 35. Epoxy melamine resin, eg, a photostable epoxy resin crosslinked with an epoxy functional co-etherified high solid melamine resin such as LSE-4103 [Monsanto]. [0116] Preferably, the plastic resin is polyethylene (eg LDPE, HDPE or MDPE), polypropylene, acrylonitrile-butadiene-styrene copolymer (ABS), styrene-acrylonitrile copolymer (SAN), polystyrene (PS), polymethylmethacrylate (PMMA). , Polyethylene terephthalate (PET), polyamide, polyvinyl chloride (PVC), polymer latex, polyurethane (PUR), thermoplastic polyurethane (TPU), urea formaldehyde resin (UF) and unsaturated polyester (UP) To. [0117] The present invention A) Polymer substrate and B) A mixture of the above antimicrobial agents in an effective antimicrobial amount It also relates to an antimicrobial polymer composition comprising. [0118] The effective antimicrobial amount of component (B) is, for example, 0.005% to 10%, based on the weight of component (A). [0119] The present invention also relates to a plastic film, fiber or article consisting of a novel mixture of component a) and component b). [0120] The mixture of component a) and component b) is preferably present in the antimicrobial plastic film, fiber or article in an amount of about 0.005% to about 10% by weight based on the plastic material. An amount of about 0.01% to about 5% by weight or about 0.05% to about 3% by weight of the mixture of components a) and b) with respect to the plastic material is particularly preferred. [0121] A mixture of component a) and component b) and optionally another additive may be added to the plastic resin, eg polyolefin, separately or mixed with each other. If desired, the individual components of the additive mixture can be mixed with each other in a molten state prior to blending into the plastic material (molten blending). [0122] Incorporation of a mixture of ingredients a) and b) into the plastic material with another desired additive is a known method such as dry mixing in powder form or wet mixing in solution or suspension form. It is done in. Ingredients a) and b) and the desired other additives are, for example, before or after molding, or in addition, a dissolved or dispersed stabilizer mixture is applied to the plastic material and, if desired, then a solvent. May be blended with or without evaporation. A mixture of ingredients a) and b) and another desired additive may be added to the plastic material, for example, in the form of a masterbatch containing the ingredients at a concentration of about 2.5% to about 70% by weight. Good; by such an operation, the polymer can be used in the form of powders, granules, solutions, suspensions or in the form of latex. [0123] When added to plastic resin in the form of a masterbatch or concentrated solution, the mixture of component a) and component b) of this novel antimicrobial agent is LDPE, HDPE, MDPE, PP, ABS, SAN, PS, acrylate. , PMMA, polyamide, polyester, PVC, latex, styrene, polyol, TPU, unsaturated ester, urea, paraformaldehyde, emulsified aqueous solution and the like. The total concentration of the concentration of the component a) + the concentration of the component b) in the carrier is from about 2.5% by weight to about 70% by weight based on the weight of the carrier. [0124] Ingredients a) and b) and other desired additives may be added before, during or after polymerization or cross-linking. [0125] Ingredients a) and b) and other desired additives may be incorporated into the plastic material in pure form or in the form encapsulated in wax, oil or polymer. [0126] Ingredients a) and b) and other desired additives may be sprayed onto the plastic material. They can also be diluted with other additives (eg, the conventional additives described above) or monomers or melts thereof, so that they can be sprayed onto the plastic material together with the additives. .. The addition by spraying during the inactivation of the polymerization catalyst has particular advantages, which can be done, for example, using the steam used for inactivation. [0127] In the case of spherically polymerized polyolefins, for example, it may be advantageous to spray component a) and component b) together with other additives, if desired. [0128] The present invention also relates to a method of stabilizing an antimicrobial polymer against fading, which comprises blending the polyol with a mixture of the above antimicrobial agents in an effective antimicrobial amount. [0129] A preferred embodiment of the present invention is the use of a mixture of the above antimicrobial agents to stabilize the polymeric substrate against fading. [0130] [Effects of Examples and Inventions] The present invention will be described in more detail with reference to the following examples. The following examples should not be construed as limiting the invention in any way. It is clear that the present invention includes modifications or improvements of a particular embodiment without departing from the ideas and categories of the present invention. Parts and% depend on weight. [0131]<u style="single">Example 1</u>: Stabilization of polyethylene High density polyethylene, Borealis MS6591, is dry blended with the antimicrobial agents listed in Table 1 below. Concentration is% by weight based on HDPE. The mixture is compounded at a maximum temperature of 220 ° C. using a twin shaft screw. The sample is injection molded into a 2 mm plaque at a maximum temperature of 220 ° C. This plaque is spray cycle, 63 ° C, 0.35W / m²Then, it is subjected to accelerated exposure in the Ci65 xenon arc weatherometer. Measure the yellowness index according to ASTM D-1925-77. A low YI value indicates a small fading, and a high YI value indicates a severe fading of the sample. The results are shown in Table 1 below. [table 1]<img file="JP4880147B2_D0004.tif" />a) Comparative example b) Examples of the present invention c) Trademark Irgaguard B1000 is a 2,4,4'-trichloro-2'-hydroxydiphenyl ether manufactured by Ciba Specialty Chemicals Inc. d) BM-102GA (manufactured by Kanebo Co., Ltd.) is a silver-containing zeolite with a modified surface. [0132] The formulations of the present invention using a combination of antimicrobial agents consisting of component a) and component b) provide excellent resistance to yellowing during accelerated exposure. [0133]<u style="single">Example 2</u>: Stabilization of polypropylene The polypropylene homopolymer, Montell Profax 6301, is dry blended with the antimicrobial agents listed in Table 2 below. The concentration is% by weight based on polypropylene. The mixture is then formulated with 0.06% brand name Irgastab FS-301, 0.06% brand name Tinuvin 783 and 0.05% calcium stearate. A polypropylene sample is spun into fibers at 260 ° C. This fiber is spray cycle, 63 ° C, 0.35W / m²Then, it is subjected to accelerated exposure in the Ci65 xenon arc weatherometer. Measure the yellowness index according to ASTM D-1925-77. A low YI value indicates a small fading, and a high YI value indicates a severe fading of the sample. The results are shown in Table 2 below. [Table 2]<img file="JP4880147B2_D0005.tif" />a) Comparative example b) Examples of the present invention c) Trademark Irgaguard B1000 is a 2,4,4'-trichloro-2'-hydroxydiphenyl ether manufactured by Ciba Specialty Chemicals Inc. d) BM-102GA (manufactured by Kanebo Co., Ltd.) is a silver-containing zeolite with a modified surface. [0134] The formulation of the present invention using a combination of an antimicrobial activator consisting of component a) and component b) provides excellent resistance to yellowing during accelerated exposure. [0135] Trademark name Tinuvin 783 is a steric hindrance amine marketed by Ciba Specialty Chemicals, Inc., Trademark name Tinuvin 622 and Trademark Chimassorb 944: [Chemical 5]<img file="JP4880147B2_D0006.tif" />(In the formula, m represents a number in the range 2 to 200). [0136] The brand name Irgastab FS-301 manufactured by Ciba Specialty Chemicals is a combination of the brand name Irgafos 168 and the brand name Irgastab FS-042. The trade name Irgafos 168 is Tris (2,4-ditrimeric butylphenyl) phosfit. Brand name Irgastab FS-042 is an N, N-di (alkyl) hydroxylamine produced by direct oxidation of N, N-di (hydrogenated beef tallow) amine.