Processing stabilizer, resin composition, and organic material stabilizing method

Abstract

To provide a processing stabilizer effective in improving the stability in processing an organic material.SOLUTION: The processing stabilizer contains a compound (I) represented by formula (I) in the figure and a compound (II) represented by formula (II) in the figure, where R1 represents an alkyl group having one or two carbon atoms. The content of the compound (II) is 0.02-10 pts.mass per 100 pts.mass of the compound (I).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a processing stabilizer containing a specific phenolic compound, a resin composition containing the specific phenolic compound, and a method for stabilizing an organic material using the specific phenolic compound. [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 processing stabilizer which is effective in improving the stability during processing of organic materials. [Means for solving the problem]

[0006] In order to solve the above problems, the present inventors conducted extensive research into various compounds and discovered that a mixture of specific phenol compounds is effective in improving the stability of resins, thereby completing the present invention.

[0007] That is, the present invention includes the following preferred embodiments. [1] Formula (I): [ka] and a compound represented by formula (II): [ka] [In formula (II), R 1 represents an alkyl group having 1 to 2 carbon atoms. and a compound (II) represented by the following formula: wherein the content of compound (II) is 0.02 to 10 parts by mass per 100 parts by mass of compound (I). [2] R in formula (II) 1 is a methyl group. [3] Formula (I): [ka] and a compound represented by formula (II): [ka] [In formula (II), R 1 represents an alkyl group having 1 to 2 carbon atoms. and at least one organic material, wherein the content of compound (II) is 0.02 to 10 parts by mass per 100 parts by mass of compound (I). [4] The resin composition according to [3], comprising the processing stabilizer according to [1] or [2] as compounds (I) and (II). [5] The resin composition according to [3] or [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] The organic material comprises a compound of formula (I): [ka] and a compound represented by formula (II): [ka] [In formula (II), R 1 represents an alkyl group having 1 to 2 carbon atoms. In an amount such that the content of compound (II) is 0.02 to 10 parts by mass relative to 100 parts by mass of compound (I), or A method for stabilizing an organic material, comprising adding the processing stabilizer according to [1] or [2] 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 processing stabilizer of the present invention is effective in improving stability during processing of organic materials such as thermoplastic resins, etc. Furthermore, the resin composition of the present invention has high stability. 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] [Processing stabilizer] The processing stabilizer of the present invention has the formula (I): [ka] and a compound represented by formula (II): [ka] [In formula (II), R 1 represents an alkyl group having 1 to 2 carbon atoms. The content of compound (II) is 0.02 to 10 parts by mass per 100 parts by mass of compound (I).

[0011] The compound (I) represented by formula (I) contained in the processing stabilizer of the present invention is a known compound, and can be synthesized, for example, according to the method described in the specification of Japanese Patent No. 3661198. As the compound (I), a compound commercially available as Sumilizer (registered trademark) GA-80 from Sumitomo Chemical Co., Ltd. may be used.

[0012] The processing stabilizer of the present invention contains a compound represented by the above formula (II) in addition to the compound represented by the above formula (I). 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. The processing stabilizer of the present invention may contain, in addition to the compound represented by formula (I), one type of compound represented by formula (II) or may contain two or more types of compounds represented by formula (II).

[0013] The phenol compound represented by formula (II) can be produced by reacting the compound represented by formula (I) with an alkyl halide having an alkyl group having 1 to 2 carbon atoms (e.g., methyl iodide or ethyl iodide) in the presence of nitrogen.

[0014] 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.

[0015] 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. The reaction temperature is usually room temperature.

[0016] In this method, the amount of alkyl halide having an alkyl group having 1 to 2 carbon atoms relative to the compound represented by formula (I) used as a raw material is preferably about 3 times by mol relative to the compound represented by formula (I). The amount of potassium carbonate added is preferably about 3 times by mol relative to the compound represented by formula (I) used as a raw material. As described above, the compound represented by formula (I) can be used as a raw material to produce the compound represented by formula (II).

[0017] In the processing stabilizer of the present invention, the compound (I) and the compound (II) are contained in an amount such that the content of the compound (II) is 0.02 to 10 parts by mass relative to 100 parts by mass of the compound (I). When the content of the compound (II) relative to 100 parts by mass of the compound (I) is less than 0.02 parts by mass, the compound (II) is not substantially contained, so that the synergistic stabilizing effect of the resin composition by using the compound (I) and the compound (II) in combination cannot be obtained. When the content of the compound (II) relative to 100 parts by mass of the compound (I) exceeds 10 parts by mass, the amount of the compound (II) relative to the amount of the compound (I) becomes too large, so that the stabilizing effect of the resin composition cannot be improved synergistically.

[0018] The content of compound (II) in the processing stabilizer of the present invention relative to 100 parts by mass of compound (I) is preferably 0.02 parts by mass or more, more preferably 0.04 parts by mass or more, and even more preferably 0.09 parts by mass or more, from the viewpoint of measurability during use and of easily enhancing the synergistic stabilizing effect of the resin composition by using compound (I) and compound (II) in combination, and is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less, from the viewpoint of efficiently stabilizing the resin composition.

[0019] The amount of compound (I) and compound (II) contained in the processing stabilizer of the present invention is not particularly limited as long as they are contained in the above ratio, and may be appropriately set according to the mode of adding the processing stabilizer to the resin, but from the viewpoint of resin stabilization, based on the total weight of the processing stabilizer, it is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 90 mass% or more. In addition, the upper limit of the amount of compound (I) and compound (II) contained in the processing stabilizer may be 100 mass% or less based on the total weight of the processing stabilizer.

[0020] By adding the processing stabilizer of the present invention to an organic material such as a thermoplastic resin, the thermal and oxidative deterioration of the organic material can be reduced, and the organic material can be stabilized, for example, the viscosity reduction and coloring can be prevented. The processing stabilizer may be a material containing only the compound (I) represented by the above formula (I) and the compound (II) represented by the above formula (II) in the above ratio, or may be a material containing at least one other additive that can be contained in the resin composition described later in addition to the compound (I) and the compound (II). The processing stabilizer of the present invention may also be a material containing at least one organic material in addition to the compound (I) and the compound (II). Such a material is also called, for example, a master batch.

[0021] [Method for stabilizing resin composition and organic material] By adding the processing stabilizer of the present invention to an organic material, or by adding a specific ratio of the compound (I) represented by formula (I) and the compound (II) represented by formula (II), the thermal deterioration and oxidative deterioration of the organic material can be reduced, and the organic material can be stabilized, for example, preventing a decrease in viscosity. It is also believed that coloring can be prevented. Therefore, the processing stabilizer of the present invention is suitable as a stabilizer for organic materials. The present invention also provides a method for stabilizing an organic material, which comprises adding a specific ratio of a compound (I) represented by formula (I) and a compound (II) represented by formula (II) in addition to the above-mentioned processing stabilizer. Furthermore, the present invention also provides a stabilized resin composition containing an organic material and the processing stabilizer of the present invention, or a specific ratio of a compound (I) represented by formula (I) and a compound (II) represented by formula (II).

[0022] Examples of organic materials that can be stabilized by the processing stabilizer of the present invention include, but are not limited to, the following organic materials: The organic material may be one type of organic material or a mixture of two or more types of organic materials.

[0023] (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,

[0024] (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,

[0025] (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,

[0026] (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,

[0027] (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.

[0028] 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, etc. are preferably used.

[0029] 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.

[0030] 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.

[0031] The organic material can be stabilized by adding the compound (I) represented by formula (I) and the compound (II) represented by formula (II) to the organic material. In this case, the compounds (I) and (II) are added to the organic material in an amount such that the content of the compound (II) is 0.02 to 10 parts by mass relative to 100 parts by mass of the compound (I). The content of the compound (II) relative to 100 parts by mass of the compound (I) is preferably 0.02 parts by mass or more, more preferably 0.04 parts by mass or more, and even more preferably 0.09 parts by mass or more from the viewpoint of measurability during use and from the viewpoint of easily enhancing the synergistic stabilizing effect of the resin composition by using the compound (I) and the compound (II) in combination, and is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less from the viewpoint of efficiently stabilizing the resin composition.

[0032] The compound (I) represented by formula (I) and the compound (II) represented by formula (II) may be added to the organic material by adding the processing stabilizer of the present invention. In either case, the compound (I) and the compound (II) are contained in the organic material in a specific quantitative ratio.

[0033] When a processing stabilizer or a compound (I) represented by formula (I) and a compound (II) represented by formula (II) are added to an organic material to stabilize the organic material, the total weight of the compound (I) represented by formula (I) and the compound (II) represented by formula (II) is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.05 parts by mass or more, per 100 parts by mass of the organic material, from the viewpoint of stabilizing the organic material. Also, the total weight of the compound (I) represented by formula (I) and the compound (II) represented by formula (II) is usually 5 parts by mass or less, preferably 3 parts by mass or less, and more preferably 1 part by mass or less, per 100 parts by mass of the organic material, from the viewpoint of efficiently stabilizing the organic material and being economical.

[0034] When the phenolic compound represented by the formula (I) and the compound represented by the formula (II) are added to an organic material, other additives may be added to the organic material as necessary, such as a phenolic 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, etc. Neutralizing agents such as calcium and hydrotalcite, color improving agents 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, and 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 compounds (I) and (II) contained in the resin composition of the present invention, or can be added to the organic material at a stage separate from the compounds (I) and (II) contained in the resin composition 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.

[0035] 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.

[0036] (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.

[0037] (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.

[0038] (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.

[0039] (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.

[0040] (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.

[0041] (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.

[0042] (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.

[0043] (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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] (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.

[0048] 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,

[0049] 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 mixed esters of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[(6-morpholino-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)], poly[(6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl]((2,2,6,6-tetramethyl-4-piperidyl)imino)], 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,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',4,7-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.

[0050] (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 complex of ketoximes and mixtures thereof.

[0051] (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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] Examples of fillers include calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, carbon black, carbon fibers, zeolites, and mixtures thereof.

[0059] 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,

[0060] 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), 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.

[0061] 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.

[0062] 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.

[0063] 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,

[0064] 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.

[0065] The processing stabilizer of the present invention, or a specific ratio of the compound (I) represented by formula (I) and the compound (II) represented by formula (II), and 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, in the case of adding the processing stabilizer of the present invention, when the organic material is a solid polymer, the processing stabilizer of the present invention and / or other additives added as required can be dry-blended directly with the solid polymer, or the processing stabilizer of the present invention and / or other additives added as required can be added to the solid polymer in the form of a masterbatch. When the organic material is a liquid polymer, in addition to the above-mentioned addition method, the processing stabilizer 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., an oil), in addition to the above-mentioned addition methods, the processing stabilizer of the present invention and / or other additives added as needed can be added directly to the organic material and dissolved therein, or the processing stabilizer of the present invention and / or other additives added as needed can be added in a dissolved or suspended state in a liquid medium.

[0066] The processing stabilizer of the present invention has excellent performance as a stabilizer for various organic materials including thermoplastic resins such as polyolefins. Organic materials to which the processing stabilizer of the present invention has been added, and organic materials to which a specific ratio of compound (I) represented by formula (I) and compound (II) represented by formula (II) has been added, are stable against thermal degradation, oxidative degradation, and the like during production, processing, and use, and become high-quality products. EXAMPLES

[0067] The present invention will be described in more detail below by showing examples, but the present invention is not limited to these.

[0068] 1 H-NMR measurements Equipment: Bruker AV-300M Measurement solvent: CDCl 3

[0069] 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.

[0070] Synthesis Example 1: Phenol compound represented by formula (II) (R 1 Synthesis of methyl Sumilizer (registered trademark) GA-80 was added in an amount of 10 g (13.5 mmol, chemical formula C 43 H 64 O 10 The mixture was charged with 1.87 g (13.5 mmol) of potassium carbonate and 1.92 g (13.5 mmol) of methyl iodide (Exact Mass: 740.45, molecular weight 740.98), 100 mL of acetone, 1.87 g (13.5 mmol) of potassium carbonate, and 1.92 g (13.5 mmol) of methyl iodide, and stirred overnight at room temperature. Since the ratio of the raw material to the product was approximately 8:2 by LC, 1 equivalent each of potassium carbonate and methyl iodide were added, and the mixture was stirred at room temperature for 6 hours. An additional 1 equivalent each of potassium carbonate and methyl iodide were added, and the mixture was stirred overnight, after which the mixture was 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 monomethoxy compound (1) (chemical formula: C) represented by the following formula (II) 1-MeO. 44 H 66 O 10 4.5 g of the dimethoxy compound represented by the following formula DMeO (chemical formula: C 45 H 68 O 10 2.9 g of the compound (exact mass: 768.48, molecular weight: 769.03) was obtained. [ka]

[0071] Purity (LC) Model: LC-20A Column: L-column2 ODS (5μm, 4.6mmφ, 150mm) Injection volume: 5μL (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: 1.0 mL / min Column temperature: 40°C Measurement wavelength: UV, 280nm Purity: 99.3% (1-MeO), 97.4% (DMeO)

[0072] 1 H-NMR (1-MeO, 300MHz, CDCl 3 ) δ0.91 (d, J = 1.8Hz, 12H, CH 3 ), δ1.37 (s, 9H, C(CH 3 ) 3 ), δ1.40 (s, 9H, C(CH 3 ) 3 ), δ2.22 (s, 3H, ArCH 3 ), δ2.29 (s, 3H, ArCH 3 ), δ2.57 - 2.64 (m, 4H, CH 2 ), δ2.82 - 2.89 (m, 4H, CH 2 ), δ3.22 - 3.27 (dd, J = 11.7Hz, 1.5Hz, 2H, CH 2 ), δ3.40 - 3.55 (m, 4H, CH 2 ), δ3.74 (s, 3H, OCH 3 ), δ3.92 (d, J = 2.1Hz, 4H, COOCH 2 ), δ4.18 (d, J = 2.4Hz, 2H, CH), δ4.47 (m, 2H, CH 2),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)

[0073] Example 1: Preparation of resin composition 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, 0.1 parts by mass of Sumilizer (registered trademark) GA-80, which is a compound represented by formula (I), and 0.00005 parts by mass of the compound (1) obtained in Synthesis Example 1. The obtained mixture was kneaded using a twin-screw extruder (model: BTN32-S2-36-L, manufactured by Plastics Engineering Research Institute Co., Ltd.) with 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 MFR of the obtained pellet (1) was measured according to the above-mentioned measurement method. The ratio (also referred to as MFR ratio) of the MFR of the obtained pellet (1) to the MFR of the pellet of the resin composition of Comparative Example 1 described later was calculated. The results are shown in Table 1. The smaller the MFR ratio, the higher the stabilization effect of the resin.

[0074] Comparative Example 1 Except for not adding compound (2), pellets of a resin composition were obtained in the same manner as in Example 1. The MFR of the obtained pellets was measured in the same manner as in Example 1. The obtained results are shown in Table 1.

[0075] [Examples 2 to 6 and Comparative Example 2] Pellets of the resin composition were obtained in the same manner as in Example 1, except that the amount of compound (2) relative to 100 parts by mass of compound (1) contained in the resin composition was changed as shown in Table 1. The MFR of the obtained pellets and the ratio (also referred to as MFR ratio) to the MFR of the pellets of the resin composition of Comparative Example 1 were calculated in the same manner as in Example 1. The results are shown in Table 1.

[0076] [Table 1]

[0077] Example 7: Preparation of processing stabilizer 100 parts by mass of GA-80 and 0.1 part by mass of the compound (1) obtained in Synthesis Example 1 are ground in a mortar to obtain a mixed powder, thereby obtaining the processing stabilizer (1) of the present invention.

[0078] Example 8: Preparation of resin composition 100 parts by mass of polypropylene resin (manufactured by Sumitomo Chemical Co., Ltd., MFR: 25 g / 10 min) is dry-blended with 0.05 parts by mass of calcium stearate and the processing stabilizer (1) obtained in Example 7. The mixture obtained is kneaded under air atmosphere, temperature 230°C, and screw rotation speed 100 rpm using a twin-screw extruder (model: BTN32-S2-36-L, manufactured by Plastics Engineering Research Institute Co., Ltd.) to obtain pellets of the resin composition of the present invention. In the above, the pellets of the resin composition obtained by blending 100 parts by mass of polypropylene resin with 0.1001 parts by mass of the processing stabilizer (1) obtained in Example 7 are considered to have an MFR ratio similar to that of the pellets of the resin composition obtained in Example 2.

[0079] It was confirmed that the resin composition of the present invention, which contains the compound (I) represented by formula (I) and the compound (II) represented by formula (II) in a specific ratio, has a low MFR in the pellets after the kneading operation, and is capable of suppressing the decomposition of the resin, which is thought to be caused by the action of heat, oxygen, etc. during processing. In contrast, in the case of the resin composition of Comparative Example 1, which contains the compound (I) represented by formula (I) but does not contain the compound (II) represented by formula (II), and Comparative Example 2, which contains them but not in a specific ratio, the decomposition of the resin due to the kneading operation could not be sufficiently suppressed.

Claims

1. Formula (I): 【Chemistry 1】 and a compound (I) represented by formula (II): 【Chemistry 2】 [In formula (II), R １ represents an alkyl group having 1 to 2 carbon atoms. and a compound (II) represented by the following formula: wherein the content of compound (II) is 0.02 to 10 parts by mass per 100 parts by mass of compound (I).

2. R in formula (II) １ The processing stabilizer of claim 1 , wherein is a methyl group.

3. Formula (I): 【Transformation 3】 and a compound (I) represented by formula (II): 【Chemistry 4】 [In formula (II), R １ represents an alkyl group having 1 to 2 carbon atoms. and at least one organic material, wherein the content of compound (II) is 0.02 to 10 parts by mass per 100 parts by mass of compound (I).

4. 4. The resin composition according to claim 3, comprising the processing stabilizer according to claim 1 or 2 as compounds (I) and (II).

5. 4. The resin composition according to claim 3, 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. The organic material comprises a compound of formula (I): 【Transformation 5】 and a compound (I) represented by formula (II): 【Transformation 6】 [In formula (II), R １ represents an alkyl group having 1 to 2 carbon atoms. and a compound (II) represented by the formula (I) in an amount such that the content of the compound (II) is 0.02 to 10 parts by mass relative to 100 parts by mass of the compound (I), or A method for stabilizing an organic material, comprising adding the processing stabilizer according to claim 1 or 2 to the organic material.

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

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

Images