Phenolic compound, stabilizer for organic material, resin composition, and method for stabilizing organic material

Abstract

To provide a new compound for improving thermal stability when an organic material is processed.SOLUTION: A phenolic compound is represented by formula (1). In the formula, R1 represents an alkyl group having 1 to 2 carbon atoms.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to novel phenolic compounds and their use as stabilizers for organic materials. [Background technology]

[0002] It is known that organic materials such as thermoplastic resins, thermosetting resins, natural or synthetic rubber, mineral oil, lubricating oil, adhesives, and paints deteriorate due to the action of heat, oxygen, and the like during production, processing, and even use. This deterioration can result in a decrease in the strength properties of the organic materials, changes in flow properties, coloration, and deterioration of surface properties due to phenomena such as molecular scission and molecular crosslinking, and can significantly impair their commercial value.

[0003] In order to prevent such deterioration due to heat or oxygen, various phenol-based antioxidants and phosphorus-based antioxidants have been developed, and it is known that adding these to organic materials can stabilize the organic materials (Patent Document 1). However, the antioxidants that have been used so far may not have sufficient stabilizing effect against deterioration due to heat or oxygen when processing organic materials, and compounds with further stabilizing effect are required. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 08-002998 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a novel compound which is effective in improving the thermal stability during processing of organic materials. [Means for solving the problem]

[0006] Means of Solving the Problems The present inventors conducted extensive research into various compounds in order to solve the above problems, and discovered a novel phenol compound, which led to the completion of the present invention.

[0007] That is, the present invention includes the following preferred embodiments. [1] Formula (1): [ka] [In the formula, R 1 represents an alkyl group having 1 to 2 carbon atoms. A phenolic compound represented by the formula: [2] R 1 is a methyl group. [3] A stabilizer for organic materials, comprising the phenol compound according to [1] or [2]. [4] A resin composition comprising the phenol compound according to [1] or [2] or the stabilizer for organic materials according to [3], and at least one organic material. [5] The resin composition according to [4], wherein the organic material is a thermoplastic resin. [6] The resin composition according to [5], wherein the thermoplastic resin is a polyolefin or an engineering plastic. [7] A method for stabilizing an organic material, comprising adding the phenol compound according to [1] or [2] or the stabilizer for organic materials according to [3] to the organic material. [8] The stabilization method according to [7], wherein the organic material is a thermoplastic resin. [9] The stabilization method according to [8], wherein the thermoplastic resin is a polyolefin or an engineering plastic. Effect of the Invention

[0008] The phenolic compound of the present invention is effective in improving the thermal stability during processing of organic materials such as thermoplastic resins. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, the embodiments of the present invention will be described in detail. Note that the scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the spirit of the present invention. In addition, when multiple upper and lower limit values ​​are described for a specific feature, any upper and lower limit values ​​can be combined to form a suitable numerical range.

[0010] The present invention relates to a compound represented by formula (1): [ka] [In the formula, R 1 represents an alkyl group having 1 to 2 carbon atoms. The present invention provides a phenolic compound represented by the formula (1): 1 represents an alkyl group having 1 to 2 carbon atoms, specifically a methyl group or an ethyl group. From the viewpoint of facilitating stabilization of organic materials such as thermoplastic resins, R 1 is preferably a methyl group.

[0011] The phenol compound represented by formula (1) is represented by the formula (1) -OR 1 It can be produced by reacting a compound having an -OH group as the group moiety with an alkyl halide having an alkyl group having 1 to 2 carbon atoms (for example, methyl iodide or ethyl iodide) in the presence of nitrogen.

[0012] The reaction is usually carried out in an organic solvent. The organic solvent is not particularly limited as long as it does not inhibit the reaction, and examples thereof include ketone solvents, ether solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and halogenated hydrocarbon solvents. The reaction may be carried out in one type of organic solvent, in a mixed solvent of two or more types of organic solvents, or in a mixed solvent of the organic solvent and another solvent.

[0013] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of ether solvents include diethyl ether and dibutyl ether. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and ethylbenzene. Examples of aliphatic hydrocarbon solvents include n-hexane, n-heptane, and n-octane. Examples of halogenated hydrocarbon solvents include chloroform, carbon tetrachloride, monochlorobenzene, dichloromethane, 1,2-dichloroethane, and dichlorobenzene.

[0014] The reaction is carried out at room temperature.

[0015] In this method, -OR in formula (1) 1 The amount of alkyl halide having an alkyl group having 1 to 2 carbon atoms relative to the compound having an -OH group is determined by dividing the alkyl halide by the -OR 1 It is preferable to use about 3 times the molar amount of the compound having the -OH group. 1 The amount is preferably about 3 times by mole relative to the compound having a -OH group as a radical portion.

[0016] The -OR in formula (1) used as a raw material 1 Methods for synthesizing compounds in which the group moiety is a -OH group are known, and the compounds can be synthesized according to the method described in, for example, Japanese Patent No. 3661198.

[0017] By adding the phenolic compound of the present invention represented by formula (1) to an organic material, the thermal and oxidative degradation of the organic material can be reduced, and the organic material can be stabilized, for example, viscosity reduction and coloring can be prevented. Therefore, the phenolic compound of the present invention is suitable as an active ingredient of a stabilizer for organic materials. Therefore, the present invention also provides a stabilizer for organic materials containing the phenolic compound of the present invention represented by formula (1), and a method for stabilizing an organic material, which comprises adding the phenolic compound of the present invention or the stabilizer for organic materials to an organic material. Furthermore, a stabilized resin composition is also provided, which contains an organic material and the phenolic compound of the present invention or the stabilizer for organic materials of the present invention.

[0018] In the above embodiment, as the phenol compound of the present invention represented by formula (1), one type of phenol compound represented by formula (1) may be used, or two or more types of phenol compounds represented by formula (1) may be used in combination.

[0019] Examples of organic materials that can be stabilized by the phenolic compound of the present invention include, but are not limited to, the following: The organic material may be one type of organic material or a mixture of two or more types of organic materials.

[0020] (1) Polyethylene, such as high density polyethylene (HD-PE), low density polyethylene (LD-PE), linear low density polyethylene (LLDPE), (2) Polypropylene, (3) methylpentene polymers, (4) EEA (ethylene / ethyl acrylate copolymer) resin, (5) ethylene / vinyl acetate copolymer resin, (6) Polystyrenes, such as polystyrene, poly(p-methylstyrene), poly(α-methylstyrene), (7) AS (acrylonitrile / styrene copolymer) resin, (8) ABS (acrylonitrile / butadiene / styrene copolymer) resin, (9) AAS (special acrylic rubber / acrylonitrile / styrene copolymer) resin, (10) ACS (acrylonitrile / chlorinated polyethylene / styrene copolymer) resin,

[0021] (11) Chlorinated polyethylene, polychloroprene, chlorinated rubber, (12) Polyvinyl chloride, polyvinylidene chloride, (13) methacrylic resin, (14) ethylene / vinyl alcohol copolymer resin, (15) Fluorine resin, (16) Polyacetal, (17) Grafted polyphenylene ether resins and polyphenylene sulfide resins, (18) polyurethane, (19) polyamide, (20) Polyester resins, such as polyethylene terephthalate, polybutylene terephthalate,

[0022] (21) polycarbonate, (22) polyacrylate, (23) Polysulfone, polyetheretherketone, polyethersulfone, (24) Thermoplastic resins such as aromatic polyester resins, (25) epoxy resin, (26) diallyl phthalate prepolymer, (27) silicone resin, (28) unsaturated polyester resins, (29) Acrylic modified benzoguanamine resin, (30) benzoguanamine / melamine resin, (31) Thermosetting resins such as urea resins,

[0023] (32) polybutadiene, (33) 1,2-polybutadiene, (34) polyisoprene, (35) styrene / butadiene copolymers, (36) butadiene / acrylonitrile copolymer, (37) ethylene / propylene copolymers, (38) silicone rubber, (39) epichlorohydrin rubber, (40) acrylic rubber, (41) Natural rubber,

[0024] (42) Chlorinated rubber paints, (43) Polyester resin paint, (44) Urethane resin paint, (45) Epoxy resin paint, (46) Acrylic resin paint, (47) Vinyl resin paints, (48) Amino alkyd resin paints, (49) Alkyd resin paints, (50) Nitrocellulose resin paint, (51) Oil-based paints, (52) wax, (53) Lubricants, etc.

[0025] Among these, thermoplastic resins, particularly polyolefins such as polyethylene, for example, HD-PE, LD-PE, LLDPE and polypropylene, polyamides, engineering plastics such as polyethylene terephthalate, polybutylene terephthalate and polycarbonate are preferably used.

[0026] The polyolefin is not particularly limited, and may be, for example, one obtained by radical polymerization, or one produced by polymerization using a catalyst containing a metal of group IVb, Vb, VIb or VIII of the periodic table. Examples of catalysts containing such metals include metal complexes having one or more ligands, such as oxides, halides, alcoholates, esters, aryls, etc., coordinated by π or σ bonds. These complexes may be metal complexes as they are, or may be supported on a substrate such as magnesium chloride, titanium chloride, alumina, or silicon oxide. As polyolefins, those produced using, for example, Ziegler-Natta catalysts, TNZ catalysts, metallocene catalysts, Phillips catalysts, etc. are preferably used.

[0027] Engineering plastics are not particularly limited. The polyamide resin may be any one that has an amide bond in the polymer chain and can be melted by heating. The polyamide resin may be one produced by any method, for example, one produced by a condensation reaction between diamines and dicarboxylic acids, a condensation reaction between aminocarboxylic acids, or a ring-opening polymerization of lactams. Examples of polyamide resins include nylon 66, nylon 69, nylon 610, nylon 612, poly-bis-(p-aminocyclohexyl)methandodecamide, nylon 46, nylon 6, nylon 12, nylon 66 / 6, which is a copolymer of nylon 66 and nylon 6, and nylon 6 / 12. The polyester resin may be any one that has an ester bond in the polymer chain and can be melted by heating, for example, polyester obtained by polycondensation of dicarboxylic acids and dihydroxy compounds. The polyester resin may be either a homopolyester or a copolyester. The polycarbonate resin may be any resin having a carbonate bond in the polymer chain and capable of being melted by heating, and may be, for example, a polycarbonate obtained by reacting an aromatic hydroxy compound or a small amount of a polyhydroxy compound with a carbonate precursor such as phosgene or diphenyl carbonate in the presence of a solvent, an acid acceptor, and a molecular weight modifier. The polycarbonate resin may be linear or branched, or may be a copolymer.

[0028] When the phenol compound of the present invention represented by formula (1) is added to an organic material to stabilize the organic material, the content of the phenol compound of the present invention is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, relative to 100 parts by mass of the organic material, from the viewpoint of stabilizing the organic material. Moreover, the content of the phenol compound of the present invention is usually 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 1 part by mass or less, relative to 100 parts by mass of the organic material, from the viewpoint of efficiently stabilizing the organic material and being economical.

[0029] When the phenol compound represented by formula (1) is added to an organic material, other additives may be added to the organic material as necessary, such as a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, an ultraviolet absorber, a light stabilizer, a peroxide scavenger, a polyamide stabilizer, a hydroxylamine, a lubricant, a plasticizer, a flame retardant, a nucleating agent, a metal deactivator, an antistatic agent, a pigment, a filler, a pigment, an antiblocking agent, a surfactant, a processing aid, a foaming agent, an emulsifier, a gloss agent, calcium stearate, hydrotalcite, etc. Neutralizing agents such as 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, color improvers such as 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, and auxiliary stabilizers such as benzofurans and indolines described in U.S. Patents 4,325,853, 4,338,244, 5,175,312, 5,216,053, 5,252,643, 4,316,611, DE-A-4,316,622, 4,316,876, EP-A-589,839, and EP-A-591,102 can also be added. These additives can be added to the organic material simultaneously with the phenolic compound of the present invention, or can be added to the organic material at a stage different from that of the phenolic compound of the present invention. As the additive, one type of additive may be used, or two or more types of additives may be used in combination.

[0030] Examples of the phenol-based antioxidant include the following: As the phenol-based antioxidant, the following compounds may be used alone or in combination of two or more kinds. (1) Examples of alkylated monophenols 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-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundecyl-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadecyl-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridecyl-1'-yl)phenol and mixtures thereof.

[0031] (2) Examples of alkylthiomethylphenols 2,4-dioctylthiomethyl-6-t-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol, and mixtures thereof. (3) Examples of hydroquinone and alkylated 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-t-butyl-4-hydroxyphenyl)adipate, and mixtures thereof.

[0032] (4) Examples of tocopherols α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof. (5) Examples of hydroxylated thiodiphenyl ethers 2,2'-thiobis(6-t-butylphenol), 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol), 4,4'-thiobis(3,6-di-t-amylphenol), 4,4'-(2,6-dimethyl-4-hydroxyphenyl) disulfide, etc.

[0033] (6) Examples of alkylidene bisphenols and their derivatives 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-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[4,6-(α,α- dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(6-t-butyl-2-methylphenol), 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(5-t-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-t-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-t-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-Tetra(5-t-butyl-4-hydroxy-2-methylphenyl)pentane, 2-t-butyl-6-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,4-di-t-pentyl-6-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]phenyl acrylate and mixtures thereof.

[0034] (7) Examples of O-, N- and S-benzyl derivatives 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, isooctyl-3,5-di-t-butyl-4-hydroxybenzyl mercaptoacetate, and mixtures thereof. (8) Examples of hydroxybenzylated malonate derivatives Dioctadecyl-2,2-bis(3,5-di-t-butyl-2-hydroxybenzyl)malonate, dioctadecyl-2-(3-t-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecylmercaptoethyl-2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate, and mixtures thereof. (9) Examples of aromatic hydroxybenzyl derivatives 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.

[0035] (10) Examples of triazine derivatives 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-t-butyl-4-phenoxy)-1,3,5-triazine, tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)iso cyanurate, 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-t-butyl-4-hydroxyphenylpropyl)-1,3,5-triazine, tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, tris[2-(3',5'-di-t-butyl-4'-hydroxycinnamoyloxy)ethyl]isocyanurate and mixtures thereof.

[0036] (11) Examples of benzylphosphonate derivatives Dimethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salts of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoester, and mixtures thereof. (12) Examples of acylaminophenol derivatives 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide, octyl-N-(3,5-di-t-butyl-4-hydroxyphenyl)carbamate, and mixtures thereof. (13) Examples of esters of β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid with the following monohydric or polyhydric alcohols Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, and mixtures thereof.

[0037] (14) Examples of esters of β-(5-t-butyl-4-hydroxy-3-methylphenyl)propionic acid with the following monohydric or polyhydric alcohols Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, and mixtures thereof. (15) Examples of esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with the following monohydric or polyhydric alcohols Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, and mixtures thereof.

[0038] (16) Examples of esters of 3,5-di-t-butyl-4-hydroxyphenylacetic acid with the following monohydric or polyhydric alcohols: Methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, and mixtures thereof. (17) Examples of amides of β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic 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 mixtures thereof.

[0039] Examples of sulfur-based antioxidants include the following: Dilauryl 3,3'-thiodipropionate, tridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3,3'-thiodipropionate, neopentanetetrayltetrakis (3-laurylthiopropionate), etc.

[0040] Examples of phosphorus-based antioxidants include the following: As the phosphorus-based antioxidant, the following compounds may be used alone or in combination of two or more kinds. Triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-t-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-t-butylphenyl)pentaerythritol Diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-t-butylphenyl)-4,4'-diphenylene diphosphonite, 2,2'-methylenebis(4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, 2,2'-ethylidenebis(4,6-di-t-butylphenyl) fluoro phosphite, bis(2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, bis(2,4-di-t-butyl-6-methylphenyl) methyl phosphite, 2-(2,4,6-tri-t-butylphenyl)-5-ethyl-5-butyl-1,3,2-oxaphosphorinane, 2,2',2''-nitrilo[triethyl-tris(3,3',5,5'-tetra-t-butyl-1,1'-biphenyl-2,2'-diyl] Phosphite, 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1,3,2]dioxaphosphepine, and mixtures thereof.

[0041] Examples of the ultraviolet absorbing agent include the following: As the ultraviolet absorbing agent, the following compounds may be used alone or in combination of two or more kinds. (1) Examples of salicylate derivatives 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, hexadecyl 3',5'-di-t-butyl-4'-hydroxybenzoate, octadecyl 3',5'-di-t-butyl-4'-hydroxybenzoate, 2-methyl-4,6-di-t-butylphenyl 3',5'-di-t-butyl-4'-hydroxybenzoate, and mixtures thereof. (2) Examples of 2-hydroxybenzophenone derivatives 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 and mixtures thereof.

[0042] (3) Examples of 2-(2'-hydroxyphenyl)benzotriazole 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(3',5'-di-t-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-t-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(3'-s-butyl-2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-t-amyl-2'-hydroxyphenyl)benzotriazole 2-[2'-hydroxy-3',3'-bis(α,α-dimethylbenzyl)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-3'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl]-5-chlorobenzotriazole, 2-[3'-t-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl] Benzotriazole, 2-[3'-t-butyl-2'-hydroxy-5-(2-octyloxycarbonylethyl)phenyl]benzotriazole, 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-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole and 2-[3'-t-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenyl]benzotriazole mixture, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)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 condensation product, poly(3-11)(ethylene glycol) and methyl 3-[3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl]propionate condensation product, 2-ethylhexyl 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, octyl 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, methyl 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, 3-[3-t-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionic acid and mixtures thereof.

[0043] Examples of the light stabilizer include the following: As the light stabilizer, the following compounds may be used alone or in combination of two or more kinds. (1) Examples of hindered amine light stabilizers 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-4-piperidyl) 2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) decanedioate, 2,2,6,6-tetramethyl-4-piperidyl Methacrylate, 4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-1-[2-(3-(3,5-di-t-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)propionyl Pionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol,

[0044] Mixed esters of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5·5]undecane, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5·5]undecane, dimethyl Polycondensation product of 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-tetramethyl N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 1,2-dibromoethane polycondensate, N,N',4,7-tetrakis[4,6- Bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, N,N',4-tris[4,6-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, N, N',4,7-tetrakis[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, N,N',4-tris[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine and mixtures thereof.

[0045] (2) Examples of acrylate-based light stabilizers Ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, 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-methylindoline and mixtures thereof. (3) Examples of nickel-based light stabilizers Nickel complex of 2,2'-thiobis-[4-(1,1,3,3-tetramethylbutyl)phenol], nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, nickel complexes of ketoximes, and mixtures thereof.

[0046] (4) Examples of oxamide light stabilizers 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 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-t-butyl-2'-ethoxyanilide, 2-ethoxy-5,4'-di-t-butyl-2'-ethyloxanilide, and mixtures thereof. (5) Examples of 2-(2-hydroxyphenyl)-1,3,5-triazine light stabilizers 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-bi 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-hydroxy-3-octyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and mixtures thereof.

[0047] Examples of metal deactivators include the following: N,N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-t-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-bis(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide, and mixtures thereof.

[0048] Peroxide scavengers include, for example, esters of β-thiodipropionic acid, mercaptobenzimidazole, zinc salts of 2-mercaptobenzimidazole, zinc salts of dibutyldithiocarbamic acid, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate, and mixtures thereof. Polyamide stabilizers include, for example, copper or divalent manganese salts of iodides or phosphorus compounds, and mixtures thereof.

[0049] Examples of hydroxyamines include N,N-dibenzylhydroxyamine, N,N-diethylhydroxyamine, N,N-dioctylhydroxyamine, N,N-dilaurylhydroxyamine, N,N-ditetradecylhydroxyamine, N,N-dihexadecylhydroxyamine, N,N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl-N-octadecylhydroxyamine, and mixtures thereof.

[0050] Examples of the neutralizing agent include calcium stearate, zinc stearate, magnesium stearate, hydrotalcite (basic magnesium aluminum hydroxycarbonate hydrate), melamine, amines, polyamides, polyurethanes, and mixtures thereof.

[0051] Examples of lubricants include aliphatic hydrocarbons such as paraffin and wax, higher fatty acids having 8 to 22 carbon atoms, metal (Al, Ca, Mg, Zn) salts of higher fatty acids having 8 to 22 carbon atoms, aliphatic alcohols having 8 to 22 carbon atoms, polyglycols, esters of higher fatty acids having 4 to 22 carbon atoms and aliphatic monohydric alcohols having 4 to 18 carbon atoms, higher aliphatic amides having 8 to 22 carbon atoms, silicone oils, and rosin derivatives.

[0052] Examples of nucleating agents include the following: sodium 2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate, [2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate]dihydroxyaluminum, bis[2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate]hydroxyaluminum, tris[2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate]aluminum, sodium Bis(4-t-butylphenyl)phosphate, metal salts of benzoic acid such as sodium benzoate, aluminum pt-butylbenzoate, 1,3:2,4-bis(O-benzylidene)sorbitol, 1,3:2,4-bis(O-methylbenzylidene)sorbitol, 1,3:2,4-bis(O-ethylbenzylidene)sorbitol, 1,3-O-3,4-dimethylbenzylidene-2,4-O-benzylidene sorbitol, 1,3-O-benzyl benzylidene-2,4-O-3,4-dimethylbenzylidene sorbitol, 1,3:2,4-bis(O-3,4-dimethylbenzylidene) sorbitol, 1,3-Op-chlorobenzylidene-2,4-O-3,4-dimethylbenzylidene sorbitol, 1,3-O-3,4-dimethylbenzylidene-2,4-Op-chlorobenzylidene sorbitol, 1,3:2,4-bis(Op-chlorobenzylidene) sorbitol and mixtures thereof.

[0053] Examples of fillers include calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, carbon black, carbon fibers, zeolites, and mixtures thereof.

[0054] Among these additives, those preferably used are phenol-based antioxidants, phosphorus-based antioxidants, ultraviolet absorbers, hindered amine-based light stabilizers, peroxide scavengers and neutralizing agents. Particularly preferred phenolic antioxidants include the following compounds: 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,2'-thiobis(6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-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-2-methylphenol), 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(5-t-butyl-4-hydroxy-2-methylphenyl)butane, 1,1,3-tris(5-t-butyl-4-hydroxy-2-methylphenyl)butane, ethylene glycol Bis[3,3-bis-3'-t-butyl-4'-hydroxyphenyl)butyrate], 2-t-butyl-6-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,4-di-t-pentyl-6-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]phenyl acrylate,

[0055] 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-t-butyl-4-hydroxybenzyl)isocyanurate, tris[2-(3',5'-di-t-butyl-4'-hydroxycinnamoyloxy)ethyl]isocyanurate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, di-n-octadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoester, n-octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, neopentanetetrayltetrakis(3,5-di-t-butyl-4-hydroxycinnamate), thiodiethylene bis(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-dioxaoctamethylene bis(3,5-di-t-butyl-4-hydroxycinnamate), hexamethylene bis(3,5-di-t-butyl-4-hydroxycinnamate), triethylene glycol Bis(5-t-butyl-4-hydroxy-3-methylcinnamate), 3,9-bis[2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl]-2,4,4,10-tetraoxaspiro[5 5]undecane, N,N'-bis[3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionyl]hydrazine, N,N'-bis[3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionyl]hexamethylenediamine, etc.

[0056] Particularly preferred phosphorus-based antioxidants include the following compounds: 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) fluorophosphite, bis(2,4-di-t-butyl-6-methylphenyl) Ethyl phosphite, 2-(2,4,6-tri-t-butylphenyl)-5-ethyl-5-butyl-1,3,2-oxaphosphorinane, 2,2',2''-nitrilo[triethyl-tris(3,3',5,5'-tetra-t-butyl-1,1'-biphenyl-2,2'-diyl)phosphite, 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1,3,2]dioxaphosphepine, and the like.

[0057] Particularly preferred examples of the ultraviolet absorber include the following compounds: 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)benzotriazo benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(3'-s-butyl-2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-t-amyl-2'-hydroxyphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, and the like.

[0058] Particularly preferred light stabilizers include the following compounds: 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-t-butyl-4-hydroxyphenyl)propionyloxy]-1-[2-(3-(3,5-di-t-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,

[0059] Tetrakis(1,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl- Mixed esters of 4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5·5]undecane, mixed esters of 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-tetraoxaspiro[5·5]undecane, dimethyl Polycondensation products of 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)-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)], etc.

[0060] The phenolic compound of the present invention represented by formula (1) and / or other additives added as required can be added to the organic material using any known method and device for obtaining a homogeneous mixture. For example, when the organic material is a solid polymer, the phenolic compound of the present invention and / or other additives added as required can be dry blended directly with the solid polymer, or the phenolic compound and / or other additives added as required can be added to the solid polymer in the form of a master batch. When the organic material is a liquid polymer, in addition to the above-mentioned addition method, the phenolic compound of the present invention and / or other additives added as required can be blended in the form of a solution or dispersion into the polymer solution during or immediately after polymerization. On the other hand, when the organic material is a liquid other than a solid polymer (e.g., oil, etc.), in addition to the above-mentioned addition method, the phenolic compound of the present invention and / or other additives added as required can be directly added to the organic material and dissolved therein, or the phenolic compound of the present invention and / or other additives added as required can be added in a dissolved or suspended state in a liquid medium.

[0061] The phenol compound of the present invention represented by formula (1) has excellent performance as a stabilizer for various organic materials including thermoplastic resins such as polyolefins. Organic materials to which the phenol compound of the present invention is added are stable against thermal and oxidative degradation during production, processing, and use, and become high-quality products. EXAMPLES

[0062] The present invention will be described in more detail below by showing examples, but the present invention is not limited to these.

[0063] 1 H-NMR measurements Equipment: Bruker AV-300M Measurement solvent: CDCl3

[0064] Measuring MFR The MFR was measured using a melt indexer (model L246-3537, Techno Seven Co., Ltd.) at a temperature of 230°C and a load of 21.18 N. Polypropylene resin undergoes decomposition during thermal processing, causing its MFR to increase. Therefore, the more the MFR of a polypropylene resin composition containing a stabilizer is not easily increased by thermal processing, the better the processing stability of the resin composition.

[0065] Yellow Index (YI) Measurement The pellets obtained in the examples and comparative examples were pressed using a press (Kansai Roll Co., Ltd., "PEW-5040") at a temperature of 230°C to obtain a sheet having a thickness of 1 mm. The yellow index (YI) of the obtained sheet was measured using a color difference meter (Minolta Co., Ltd., "CM-3500d"). The smaller the YI value, the more the discoloration is suppressed.

[0066] Example 1: Phenolic compound represented by formula (1) (R 1 Synthesis of methyl Sumilizer (registered trademark) GA-80 10g (13.5mmol), acetone 100mL, potassium carbonate 1.87g (13.5mmol) and methyl iodide 1.92g (13.5mmol) were charged and stirred overnight at room temperature. Since the ratio of raw materials to products was about 8:2 by LC, potassium carbonate and methyl iodide were added in an amount of 1 equivalent each and stirred at room temperature for 6 hours. Potassium carbonate and methyl iodide were further added in an amount of 1 equivalent each and stirred overnight, then filtered and the residue was concentrated to obtain a crude product. The residue was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate system) to obtain 4.5g of compound (1) represented by the following formula (1-MeO) and 2.9g of dimethoxy body (DMeO). Compound (1) represented by formula (1-MeO) is the phenolic compound of the present invention. The obtained dimethoxy body was used in the comparative resin composition in Comparative Example 3 described later. [ka]

[0067] Purity (LC) Model: LC-20A Column: L-column2 ODS (5 μm, 4.6 mm φ, 150 mm) Injection volume: 5 μL (each methanol solution) Mobile phase: Solution A water / acetic acid = 1000 / 1 (v / v) Solution B: Methanol / THF / acetic acid = 930 / 70 / 1 (v / v / v) Gradient:Time(min.) 0 7 37 47 B conc.(%)70 70 100 100 Flow rate: 1.0mL / min Column temperature: 40°C Measurement wavelength: UV, 280nm Purity: 99.3% (1-MeO) 97.4%(DMeO)

[0068] 1 H-NMR (300MHz, CDCl3) δ0.91(d,J=1.8Hz,12H,CH3),δ1.37(s,9H,C(CH3)3),δ1.40(s,9H,C(CH3)3),δ2.22(s,3H,ArCH3),δ2.29(s ,3H,ArCH3),δ2.57-2.64(m,4H,CH2),δ2.82-2.89(m,4H,CH2),δ3.22-3.27(dd,J=11.7Hz,1.5Hz,2H,CH2), δ3.40-3.55(m,4H,CH2),δ3.74(s,3H,OCH3),δ3.92(d,J=2.1Hz,4H,COOCH2),δ4.18(d,J=2.4Hz,2H,CH),δ4 .47(m,2H,CH2),δ4.67(s,1H,ArOH),δ6.83(d,J=1.8Hz,1H,Ar),δ6.88(d,J=2.1Hz,1H,Ar),δ6.96(m,2H,Ar)

[0069] Example 2: Preparation of pellets of a resin composition containing a phenolic compound represented by formula (1) 100 parts by mass of polypropylene resin (manufactured by Sumitomo Chemical Co., Ltd., MFR: 25 g / 10 min) was dry-blended with 0.05 parts by mass of calcium stearate and 0.1 parts by mass of the compound (1) obtained in Example 1. The resulting mixture was kneaded using a twin-screw extruder (model: BTN32-S2-36-L, manufactured by Plastics Engineering Research Institute Co., Ltd.) having a cylinder diameter of 32 mm under conditions of a temperature of 230° C. and a screw rotation speed of 100 rpm in an air atmosphere to obtain pellets (1) of the resin composition of the present invention. The pellets (1) obtained were kneaded five times in an air atmosphere at a temperature of 280°C and a screw rotation speed of 100 rpm using a single screw extruder (model: VS30-28, manufactured by Tanabe Plastics Co., Ltd.) with a cylinder diameter of 30 mm to obtain pellets, and this operation was repeated five times to obtain pellets (2) after five kneading operations. The MFR and YI of the obtained pellets (2) were measured according to the above-mentioned measurement methods. The results are shown in Table 1.

[0070] Comparative Example 1 Pellets were prepared after five kneading operations in the same manner as in Example 2, except that compound (1) was not added. The MFR and YI of the obtained pellets were measured according to the above-mentioned measurement method. The obtained results are shown in Table 1.

[0071] Comparative Example 2 Pellets were prepared after five kneading operations in the same manner as in Example 2, except that 0.1 parts by mass of GA-80 used as a raw material in Example 1 was added instead of compound (1). The MFR and YI of the obtained pellets were measured according to the above-mentioned measurement method. The obtained results are shown in Table 1.

[0072] Comparative Example 3 Instead of compound (1), 0.1 parts by mass of the dimethoxy compound obtained in the manufacturing method described in Example 1 was added, and the pellets were prepared after five kneading operations in the same manner as in Example 2. The MFR and YI of the obtained pellets were measured according to the above-mentioned measuring method. The obtained results are shown in Table 1.

[0073] [Table 1]

[0074] The resin composition of Example 2 had a low MFR in the pellets (2) obtained after five repeated kneading operations, and it was confirmed that decomposition of the resin, which is believed to be caused by the action of heat or oxygen during processing, was suppressed. It was also confirmed that the YI was low, and coloring of the resin was prevented. In contrast, in the cases of Comparative Examples 1 to 3 in which the phenol compound of the present invention was not added, both the suppression of resin decomposition and the prevention of coloring could not be sufficiently improved after five repeated kneading operations.

Claims

1. Formula (1): 【Chemistry 1】 [In the formula, R １ represents an alkyl group having 1 to 2 carbon atoms. A phenolic compound represented by the formula:

2. R １ The phenolic compound according to claim 1 , wherein is a methyl group.

3. A stabilizer for organic materials comprising the phenolic compound according to claim 1 or 2.

4. A resin composition comprising the phenolic compound according to claim 1 or 2 or the stabilizer for organic materials according to claim 3, and at least one organic material.

5. 5. The resin composition according to claim 4, wherein the organic material is a thermoplastic resin.

6. The resin composition according to claim 5 , wherein the thermoplastic resin is a polyolefin or an engineering plastic.

7. A method for stabilizing an organic material, comprising adding the phenol compound according to claim 1 or 2 or the stabilizer for organic materials according to claim 3 to the organic material.

8. 8. The method of claim 7, wherein the organic material is a thermoplastic resin.

9. 9. The method of claim 8, wherein the thermoplastic resin is a polyolefin or an engineering plastic.

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