Phenolic compounds, stabilizers for organic materials, resin compositions, and methods for stabilizing organic materials

Abstract

This invention relates to a phenolic compound represented by formula (1), in which R 1 It refers to alkyl groups with 1 to 2 carbon atoms.

Description

Technical Field

[0001] This 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 rubbers, mineral oils, lubricants, adhesives, and coatings can deteriorate during manufacturing, processing, and even use due to the effects of heat or oxygen. This deterioration is accompanied by phenomena such as molecular cleavage or cross-linking, which lead to a decrease in the strength and physical properties of organic materials, changes in fluidity, coloring, and a decrease in surface properties. Sometimes, the commercial value can be significantly impaired.

[0003] Various phenolic and phosphorus-based antioxidants have been developed to prevent such heat- or oxygen-induced deterioration, and it is known that adding them to organic materials can stabilize them (Patent Document 1). However, the antioxidants used in the past have sometimes been insufficient in stabilizing the heat- or oxygen-induced deterioration during the processing of organic materials, and compounds with further stabilizing effects are needed.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Publication No. 08-002998. Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] The objective of this invention is to provide new compounds that are effective in improving the thermal stability of organic materials during processing.

[0009] Methods for solving problems

[0010] In order to solve the above-mentioned problems, the inventors conducted detailed research on various compounds and discovered new phenolic compounds, thus completing this invention.

[0011] That is, the present invention includes the following preferred embodiments.

[0012] [1] A phenolic compound, wherein the phenolic compound is represented by formula (1).

[0013] Chemical Formula 1

[0014]

[0015] In equation (1), R 1 It refers to alkyl groups with 1 to 2 carbon atoms.

[0016] [2] A phenolic compound as described in [1], wherein R1 It is a methyl group.

[0017] [3] A stabilizer for organic materials, wherein the stabilizer for organic materials comprises the phenolic compound described in [1] or [2].

[0018] [4] A resin composition comprising the phenolic compound described in [1] or [2] and at least one organic material, or comprising the organic material stabilizer described in [3] and at least one organic material.

[0019] [5] The resin composition as described in [4], wherein the organic material is a thermoplastic resin.

[0020] [6] The resin composition as described in [5], wherein the thermoplastic resin is a polyolefin or an engineering plastic.

[0021] [7] A method for stabilizing an organic material, wherein the phenolic compound described in [1] or [2] or the stabilizer for the organic material described in [3] is added to the organic material.

[0022] [8] The stabilization method as described in [7], wherein the organic material is a thermoplastic resin.

[0023] [9] The stabilization method as described in [8], wherein the thermoplastic resin is a polyolefin or an engineering plastic.

[0024] The effects of the invention

[0025] The phenolic compounds of the present invention are effective in improving the thermal stability of organic materials such as thermoplastic resins during processing. Detailed Implementation

[0026] The embodiments of the present invention will now be described in detail. It should be noted that the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the invention. Furthermore, when a plurality of upper and lower limits are specified for a specific feature, any of these upper and lower limits can be combined to form an appropriate numerical range.

[0027] The present invention provides a phenolic compound represented by formula (1).

[0028] Chemical formula 2

[0029]

[0030] In equation (1), R 1 R represents an alkyl group having 1 to 2 carbon atoms. In formula (1) above, R... 1This indicates an alkyl group with 1 to 2 carbon atoms; specifically, it indicates methyl or ethyl. From the viewpoint of easily stabilizing organic materials such as thermoplastic resins, R... 1 Methyl is preferred.

[0031] The phenolic compound represented by formula (1) can be made to react with -OR in formula (1). 1 Compounds with a -OH group as the base are reacted with haloalkyl groups (e.g., iodomethane or iodoethane) having 1 to 2 carbon atoms in the presence of nitrogen.

[0032] The reaction is usually carried out in an organic solvent. There are no particular limitations on the organic solvent, as long as it does not hinder the reaction; examples include ketone solvents, ether solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and halogenated hydrocarbon solvents. The reaction can be carried out in a single organic solvent, in a mixture of two or more organic solvents, or in a mixture of the organic solvent and other solvents.

[0033] 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.

[0034] The reaction was carried out at room temperature.

[0035] In the case of this method, for -OR in equation (1) 1 The amount of haloalkyl group having an alkyl group having 1 to 2 carbon atoms in compounds with a base portion of -OH group is preferably relative to -OR in formula (1). 1 Compounds with a -OH group at the base are used in amounts of approximately 3 molar times the amount of a haloalkyl group. Additionally, relative to -OR... 1 For compounds with a -OH group as the base, the amount of potassium carbonate added is preferably about 3 moles.

[0036] -OR in formula (1) used as raw material 1 The synthesis methods for compounds with a -OH group are known, for example, they can be synthesized according to the methods described in Japanese Patent No. 3661198, etc.

[0037] By adding the phenolic compound of the present invention, represented by formula (1), to an organic material, thermal deterioration and oxidative deterioration of the organic material can be reduced, and the organic material can be stabilized, for example, by preventing viscosity reduction or coloring. Therefore, the phenolic compound of the present invention is suitable as an effective component of a stabilizer for organic materials. Therefore, the present invention also provides a stabilizer for organic materials comprising the phenolic compound of the present invention, represented by formula (1), and a method for stabilizing an organic material by adding the phenolic compound of the present invention or the above-mentioned stabilizer for organic materials to the organic material. Furthermore, a stabilized resin composition comprising an organic material and the phenolic compound of the present invention or the stabilizer for organic materials of the present invention is also provided.

[0038] In the above manner, as the phenolic compound of the present invention represented by formula (1), one phenolic compound represented by formula (1) may be used, or two or more phenolic compounds represented by formula (1) may be used in combination.

[0039] As organic materials capable of being stabilized by the phenolic compounds of the present invention, examples include, but are not limited to, the organic materials described below. The organic material may be a single organic material or a mixture of two or more organic materials.

[0040] (1) Polyethylene, such as high-density polyethylene (HD-PE), low-density polyethylene (LD-PE), and linear low-density polyethylene (LLDPE).

[0041] (2) Polypropylene.

[0042] (3) Methylpentene polymer.

[0043] (4) EEA (ethylene / ethyl acrylate copolymer) resin.

[0044] (5) Ethylene / vinyl acetate copolymer resin.

[0045] (6) Polystyrene, such as polystyrene, poly(p-methylstyrene), and poly(α-methylstyrene).

[0046] (7) AS (acrylonitrile / styrene copolymer) resin.

[0047] (8) ABS (acrylonitrile / butadiene / styrene copolymer) resin.

[0048] (9) AAS (Special Acrylic Rubber / Acrylonitrile / Styrene Copolymer) Resin.

[0049] (10) ACS (acrylonitrile / chlorinated polyethylene / styrene copolymer) resin.

[0050] (11) Chlorinated polyethylene, polychloroprene, chlorinated rubber.

[0051] (12) Polyvinyl chloride, polyvinylidene chloride.

[0052] (13) Methacrylic resin.

[0053] (14) Ethylene / vinyl alcohol copolymer resin.

[0054] (15) Fluoropolymer.

[0055] (16) Polyacetal.

[0056] (17) Grafted polyphenylene ether resin and polyphenylene sulfide resin.

[0057] (18) Polyurethane.

[0058] (19) Polyamide.

[0059] (20) Polyester resins, such as polyethylene terephthalate and polybutylene terephthalate. (21) Polycarbonate.

[0060] (22) Polyacrylate.

[0061] (23) Polysulfone, polyether ether ketone, polyether sulfone.

[0062] (24) Aromatic polyester resins and other thermoplastic resins.

[0063] (25) Epoxy resin.

[0064] (26) diallyl phthalate prepolymer.

[0065] (27) Silicone resin.

[0066] (28) Unsaturated polyester resin.

[0067] (29) Acrylic acid modified benzoguanamine resin.

[0068] (30) Benzoguanidine / melamine resin.

[0069] (31) Thermosetting resins such as urea-formaldehyde resin.

[0070] (32) Polybutadiene.

[0071] (33) 1,2-Polybutadiene.

[0072] (34) Polyisoprene.

[0073] (35) Styrene / butadiene copolymer.

[0074] (36) Butadiene / acrylonitrile copolymer.

[0075] (37) Ethylene / propylene copolymer.

[0076] (38) Silicone rubber.

[0077] (39) Epichlorohydrin rubber.

[0078] (40) Acrylic rubber.

[0079] (41) Natural rubber.

[0080] (42) Chlorinated rubber-based coatings.

[0081] (43) Polyester resin coatings.

[0082] (44) Carbamate resin coatings.

[0083] (45) Epoxy resin coatings.

[0084] (46) Acrylic resin coatings.

[0085] (47) Vinyl resin coatings.

[0086] (48) Amino alkyd resin coatings.

[0087] (49) Alkyd resin coatings.

[0088] (50) Nitrocellulose resin coatings.

[0089] (51) Oil-based coatings.

[0090] (52) Wax.

[0091] (53) Lubricating oil, etc.

[0092] Among them, thermoplastic resins are preferred, especially polyethylene such as HD-PE, LD-PE, LLDPE and polyolefins such as polypropylene, polyamide, polyethylene terephthalate, polybutylene terephthalate and engineering plastics such as polycarbonate.

[0093] There are no particular limitations on the polyolefin used. For example, it can be a polyolefin obtained by free radical polymerization or a polyolefin manufactured by polymerization using a catalyst containing a metal from Group IVb, Vb, VIb, or VIII of the periodic table. Examples of catalysts containing this metal include metal complexes having one or more ligands, such as oxides, halogen compounds, alkoxides, esters, aryl groups, etc., coordinated via π or σ bonds. These complexes can be metal complexes directly or supported on substrates such as magnesium chloride, titanium chloride, alumina, and silica. Polyolefins manufactured using, for example, Ziegler-Natta catalysts, TNZ catalysts, metallocene catalysts, and Phillips catalysts are preferred.

[0094] Engineering plastics are not particularly limited. Polyamide resins are resins with amide bonds in their polymer chains, as long as they can be melted by heating. Polyamide resins can be manufactured by any method, such as the condensation reaction of diamines and dicarboxylic acids, the condensation reaction of aminocarboxylic acids, and the ring-opening polymerization of lactams. Examples of polyamide resins include nylon 66, nylon 69, nylon 610, nylon 612, poly-bis-(p-aminocyclohexyl)methane laurylamide, nylon 46, nylon 6, nylon 12, and copolymers of nylon 66 and nylon 6, such as nylon 66 / 6 and nylon 6 / 12. Polyester resins are resins with ester bonds in their polymer chains, as long as they can be melted by heating. Examples include polyesters obtained by the condensation polymerization of dicarboxylic acids and dihydroxy compounds. Polyester resins can also be either homopolymers or copolymers. Polycarbonate resin is a resin with carbonate bonds in its polymer chain. It can be obtained by heating and melting. For example, polycarbonate precursors such as methyl carbonate and diphenyl carbonate can be reacted with aromatic hydroxyl compounds or aromatic hydroxyl compounds and a small amount of polyhydroxyl compounds in the presence of a solvent, acid acceptor, and molecular weight regulator. Polycarbonate resin can be linear, branched, or a copolymer.

[0095] When an organic material is stabilized by adding the phenolic compound of the present invention represented by formula (1), from the viewpoint of stabilizing the organic material, the content of the phenolic compound of the present invention is generally 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and more preferably 0.05 parts by mass or more, relative to 100 parts by mass of the organic material. Furthermore, from the viewpoint of efficiently stabilizing the organic material and being economical, the content of the phenolic compound of the present invention is generally 5 parts by mass or less, preferably 3 parts by mass or less, and more preferably 1 part by mass or less, relative to 100 parts by mass of the organic material.

[0096] When a phenolic compound represented by formula (1) is added to an organic material, other additives can also be added to the organic material as needed, such as phenolic antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, ultraviolet absorbers, light stabilizers, peroxide scavengers, polyamide stabilizers, hydroxylamines, lubricants, plasticizers, flame retardants, nucleating agents, metal deactivators, antistatic agents, pigments, fillers, pigments, anti-caking agents, surfactants, processing aids, foaming agents, emulsifiers, gloss agents, calcium stearate, hydrotalcite, and other neutralizing agents, and further, 9,10-dihydro-9-oxa-10-phosphaphenanthrene (9,10-Dihydro-9-oxa-10-phosphaphenanthrene) Coloring modifiers such as 10-oxide, and auxiliary stabilizers such as benzofurans and indoline compounds described in US patents 4325853, 4338244, 5175312, 5216053, 5252643, 4316611, DE-A-4316622, 4316876, EP-A-589839, and EP-A-591102. These additives can be added to organic materials simultaneously with the phenolic compounds of the present invention, or at a different stage than the phenolic compounds of the present invention. One additive can be used, or two or more additives can be used in combination.

[0097] Examples of phenolic antioxidants include, for example, the substances described below. These compounds can be used alone or in combination of two or more as phenolic antioxidants.

[0098] (1) Examples of alkylated monophenols

[0099] 2,6-Di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 2,6-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecane 2,4,6-Tricyclohexylphenol, 2,6-Di-tert-butyl-4-methoxymethylphenol, 2,6-dinonyl-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'-methyltetrazyl-1'-yl)phenol, and mixtures thereof.

[0100] (2) Examples of alkylthiomethylphenols

[0101] 2,4-Dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-bis(dodecylthiomethyl-4-nonylphenol) and mixtures thereof.

[0102] (3) Examples of hydroquinone and alkylated hydroquinone

[0103] 2,6-Di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-pentylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate, and mixtures thereof.

[0104] (4) Examples of tocopherol

[0105] α-Tocopherol, β-Tocopherol, γ-Tocopherol, δ-Tocopherol, and mixtures thereof.

[0106] (5) Examples of hydroxylated diphenyl thioethers

[0107] 2,2'-Thiobis(6-tert-butylphenol), 2,2'-Thiobis(4-methyl-6-tert-butylphenol), 2,2'-Thiobis(4-octylphenol), 4,4'-Thiobis(3-methyl-6-tert-butylphenol), 4,4'-Thiobis(2-methyl-6-tert-butylphenol), 4,4'-Thiobis(3,6-di-tert-pentylphenol), 4,4'-(2,6-dimethyl-4-hydroxyphenyl) disulfide, etc.

[0108] (6) Examples of alkylene bisphenols and their derivatives

[0109] 2,2'-Methylenebis(4-methyl-6-tert-butylphenol), 2,2'-Methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-Methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-Methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-Methylenebis(4-methyl-6-nonylphenol), 2,2'-Methylenebis(4,6-di-tert-butylphenol), 2,2'-Ethylbis(4,6-di-tert-butylphenol), 2,2'-Ethylbis(4-isobutyl-6-tert-butylphenol) 2,2'-Methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-Methylenebis[4,6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-Methylenebis(6-tert-butyl-2-methylphenol), 4,4'-Methylenebis(2,6-di-tert-butylphenol), 4,4'-Butylbis(3-methyl-6-tert-butylphenol), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-phenyl)cyclohexane 1,1,3-Tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-dodecyl mercaptobutane, ethylene glycol bis[3,3-bis-3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)biscyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethylphenyl) 2,2-Di(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,4-di-tert-pentyl-6-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]phenyl acrylate, and mixtures thereof.

[0110] (7) Examples of O-, N- and S-benzyl derivatives

[0111] 3,5,3',5'-Tetratert-butyl-4,4'-dihydroxybenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tris(3,5-ditert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-ditert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-ditert-butyl-4-hydroxybenzyl mercaptoacetate, and mixtures thereof.

[0112] (8) Examples of hydroxybenzyl malonate derivatives

[0113] Dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecyl mercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, and mixtures thereof.

[0114] (9) Examples of aromatic hydroxybenzyl derivatives

[0115] 1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-tert-butyl-4-hydroxybenzyl)phenol, and mixtures thereof.

[0116] (10) Examples of triazine derivatives

[0117] 2,4-Bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-triazine, 2-n-octylthio-4,6-bis(4-hydroxy-3,5-di-tert-butylaniline)-1,3,5-triazine, 2-n-octylthio-4,6-bis(4-hydroxy-3,5-di-tert-butylphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-phenoxy)-1,3,5-triazine, tris(4-tert-butyl-3-hydroxy-2,6- Dimethylbenzyl) isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylpropyl)-1,3,5-triazine, tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate, tris[2-(3',5'-di-tert-butyl-4'-hydroxycinnamoyloxy)ethyl] isocyanurate, and mixtures thereof.

[0118] (11) Examples of benzyl phosphate derivatives

[0119] Calcium salts of dimethyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphate, diethyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzyl phosphate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoester, and mixtures thereof.

[0120] (12) Examples of acylaminophenol derivatives

[0121] 4-Hydroxylauroyl aniline, 4-hydroxystearoyl aniline, octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate and mixtures thereof.

[0122] (13) Examples of esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with the following mono- or polyols

[0123] Methanol, ethanol, octanol, octadecyl alcohol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spirocyclohexane, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thioundecyl alcohol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, and mixtures thereof.

[0124] (14) Examples of esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with the following mono- or polyols

[0125] Methanol, ethanol, octanol, octadecyl alcohol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spirocyclohexane, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thioundecyl alcohol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, and mixtures thereof.

[0126] (15) Examples of esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with the following mono- or polyols

[0127] Methanol, ethanol, octanol, octadecyl alcohol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spirocyclohexane, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thioundecyl alcohol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, and mixtures thereof.

[0128] (16) Examples of esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with the following mono- or polyols

[0129] Methanol, ethanol, octanol, octadecyl alcohol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spirocyclohexane, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thioundecyl alcohol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2,2,2]octane, and mixtures thereof.

[0130] (17) Examples of amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid

[0131] N,N'-bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyl]hydrazine, N,N'-bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyl]hexamethylenediamine, N,N'-bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyl]trimethylenediamine, and mixtures thereof.

[0132] Examples of sulfur-based antioxidants include, for example, the substances described below.

[0133] Dilaurate 3,3'-thiodipropionate, tridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearate 3,3'-thiodipropionate, lauryl / stearyl 3,3'-thiodipropionate, neopentanetetramethyltetra(3-lauryl thiopropionate), etc.

[0134] Examples of phosphorus-based antioxidants include the substances described below. These compounds can be used alone or in combination of two or more.

[0135] Triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, trilauryl phosphite, tris(octadecyl) phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetra(2,4-di-tert-butylphenyl)-4,4'-diphenylene diphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)2- Ethylhexyl phosphite, 2,2'-ethylidene bis(4,6-di-tert-butylphenyl)fluorophosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, 2-(2,4,6-tri-tert-butylphenyl)-5-ethyl-5-butyl-1,3,2-oxophosphacyclohexane, 2,2',2”-nitro[triethyl-tri(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphacycloheptadecene, and mixtures thereof, etc.

[0136] Examples of ultraviolet absorbers include the substances described below. These compounds can be used alone or in combination of two or more.

[0137] (1) Examples of salicylate derivatives

[0138] Phenyl salicylate, 4-tert-butylphenyl salicylate, 2,4-di-tert-butylphenyl 3',5'-di-tert-butyl-4'-hydroxybenzoic acid, 4-tert-butylphenyl salicylate, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, hexadecyl 3',5'-di-tert-butyl-4'-hydroxybenzoic acid, octadecyl 3',5'-di-tert-butyl-4'-hydroxybenzoic acid, 2-methyl-4,6-di-tert-butylphenyl 3',5'-di-tert-butyl-4'-hydroxybenzoic acid ester, and mixtures thereof.

[0139] (2) Examples of 2-hydroxybenzophenone derivatives

[0140] 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.

[0141] (3) Examples of 2-(2'-hydroxyphenyl)benzotriazole

[0142] 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-(3',5'-di-tert-pentyl-2'-hydroxyphenyl)benzotriazole, 2-[2'-hydroxy-3',3'-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-[(3'-tert-butyl) [2'-hydroxyphenyl)-5'-(2-octyloxycarbonylethyl)phenyl]-5-chlorobenzotriazole, 2-[3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl]-5-chlorobenzotriazole, 2-[3'-tert-butyl-3'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl]-5-chlorobenzotriazole, 2-[3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl]benzotriazole, 2-[3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl]benzotriazole, 2-[3'-tert-butyl-2'-hydroxy-5'-[2-(2-ethylhexyloxy)carbonylethyl]phenyl]benzotriazole, 2-[2-hydroxyphenyl]-5'-hydroxyphenyl]-5'-(2-octyloxycarbonylethyl)phenyl]benzotriazole, 2-[2-hydroxyphenyl]-5'-hydroxyphenyl]-5'-(2-ethylhexyloxy)carbonylethyl] ... [3'-(3,4,5,6-tetrahydrophthalimidemethyl)-5-methylphenyl]benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole and a mixture of 2-[3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenyl]benzotriazole, 2,2'-methylenebis[6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[4-tert-butyl-6-(2H-benzotriazole-2-yl)phenol], poly(3-11)(ethylene glycol) and 2-[3'-tert-butyl-2'-hydroxy- Condensations of 5'-(2-methoxycarbonylethyl)phenyl]benzotriazole, condensations of poly(3-11)(ethylene glycol) and methyl 3-[3-(2H-benzotriazole-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionate, 2-ethylhexyl 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate, octyl 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate, methyl 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate, 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate, and mixtures thereof.

[0143] Examples of light stabilizers include the substances described below. These compounds can be used alone or in combination of two or more.

[0144] (1) Examples of hindered amine light stabilizers

[0145] bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) succinate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(N-octoxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(N-benzyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1-acryloyl-2,2,6,6-tetramethyl-4-piperidinyl) 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-1-[2-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy)ethyl]-2,2,6,6-tetramethylpiperidine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidinyl)amino-N-(2,2,6,6-tetramethyl-4-piperidinyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylic acid ester , tetra(1,2,2,6,6-pentamethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylic acid ester, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecaneol, mixed esters of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecaneol, 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, 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol Mixed esters of alcohols and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxazolo[5.5]undecane, 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-piperidinyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidinyl)imino)], poly[(6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl((2,2,6,6-tetramethyl-4-piperidinyl)imino)hexamethylene ...[6-Tetramethyl-4-piperidinyl)imino], N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine and 1,2-dibromoethane condensation polymer, N,N',4,7-tetra[4,6-bis(n-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-1,3,5-triazin-2-yl]-4,7-diazadecyl-1,10-diamine, N,N',4-tris[4,6-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-1,3,5-tris]-1,3,5-tris]-4,7-diazadecyl-1,10-diamine [Azine-2-yl]-4,7-diazadecyl-1,10-diamine, N,N',4,7-tetra[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino)-1,3,5-triazine-2-yl]-4,7-diazadecyl-1,10-diamine, N,N',4-tris[4,6-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino)-1,3,5-triazine-2-yl]-4,7-diazadecyl-1,10-diamine, and mixtures thereof.

[0146] (2) Examples of acrylate-based light stabilizers

[0147] Ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-methyl cinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-methyl ester-p-methoxycinnamate, and N-(β-methyl ester-β-cyanovinyl)-2-methylindoline and mixtures thereof.

[0148] (3) Examples of nickel-based light stabilizers

[0149] Nickel complexes of 2,2'-thiobis-[4-(1,1,3,3-tetramethylbutyl)phenol], nickel dibutyl dithiocarbamates, nickel salts of monoalkyl esters, nickel complexes of ketoximes, and mixtures thereof.

[0150] (4) Examples of oxalamide-based light stabilizers

[0151] 4,4'-Dioctyloxyoxalaniline, 2,2'-Diethoxyoxalaniline, 2,2'-Dioctyloxy-5,5'-di-tert-butylaniline, 2,2'-bisdodecyloxy-5,5'-di-tert-butylaniline, 2-ethoxy-2'-ethyloxalaniline, N,N'-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2'-ethoxyaniline, 2-ethoxy-5,4'-di-tert-butyl-2'-ethyloxalaniline, and mixtures thereof.

[0152] (5) Examples of 2-(2-hydroxyphenyl)-1,3,5-triazine light stabilizers

[0153] 2,4,6-Tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylyl)-1,3,5-triazine, 2-[2,4-dihydroxyphenyl-4,6-bis(2,4-dimethylyl]-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4- Methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylyl)-1,3,5-triazine, and mixtures thereof.

[0154] Examples of metal deactivators include, for example, the substances described below.

[0155] N,N'-diphenyloxamide, N-salicylic aldehyde-N'-salicylic hydrazide, N,N'-bis(salicylic acid)hydrazide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, 3-salicylic acid amino-1,2,4-triazole, bis(benzylmethyl)oxalyl dihydrazide, oxalaniline, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-bis(salicylic acid)oxalyl dihydrazide, N,N'-bis(salicylic acid)thiopropionyl dihydrazide, and mixtures thereof.

[0156] Examples of peroxide scavengers include, for example, esters of β-thiodipropionic acid, mercaptobenzimidazole, zinc salts of 2-mercaptobenzimidazole, zinc salts of dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetra(β-dodecylmercapto)propionate, and mixtures thereof.

[0157] Examples of polyamide stabilizers include, for example, copper or divalent manganese salts of iodides or phosphorus compounds, and mixtures thereof.

[0158] Examples of hydroxylamines include, for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-bistetradecylhydroxylamine, N,N-bishexadecylhydroxylamine, N,N-bisoctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, and mixtures thereof.

[0159] Examples of neutralizing agents include, for example, calcium stearate, zinc stearate, magnesium stearate, hydrotalcite (basic magnesium-aluminum-hydroxy-carbonate hydrate), melamine, amines, polyamides, polyurethanes, and mixtures thereof.

[0160] Examples of lubricants include, for example, aliphatic hydrocarbons such as paraffin wax and wax, higher fatty acids with 8 to 22 carbon atoms, metal (Al, Ca, Mg, Zn) salts of higher fatty acids with 8 to 22 carbon atoms, aliphatic alcohols with 8 to 22 carbon atoms, polyethylene glycols, esters of higher fatty acids with 4 to 22 carbon atoms and aliphatic monohydric alcohols with 4 to 18 carbon atoms, higher aliphatic amides with 8 to 22 carbon atoms, silicone oils, rosin derivatives, etc.

[0161] Examples of nucleating agents include, for instance, the following substances: sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, aluminum bis(4,6-di-tert-butylphenyl)phosphate, aluminum bis(4,6-di-tert-butylphenyl)phosphate, aluminum tris(2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, sodium bis(4-tert-butylphenyl)phosphate, sodium benzoate and other benzoate metal salts, aluminum p-tert-butylbenzoate, 1,3:2,4-bis(O-benzylmethyl)sorbitol, 1,3:2,4-bis(O-methylbenzylmethyl)sorbitol, 1,3:2,4-bis(O-)benzylmethyl)sorbitol, etc. Sorbitol, 1,3-O-3,4-dimethylbenzyl-2,4-O-benzylmethyl sorbitol, 1,3-O-benzyl-2,4-O-3,4-dimethylbenzylmethyl sorbitol, 1,3:2,4-bis(O-3,4-dimethylbenzyl) sorbitol, 1,3-O-p-chlorobenzyl-2,4-O-3,4-dimethylbenzylmethyl sorbitol, 1,3-O-3,4-dimethylbenzyl-2,4-O-p-chlorobenzylmethyl sorbitol, 1,3:2,4-bis(O-p-chlorobenzyl) sorbitol, and mixtures thereof.

[0162] Examples of fillers include, for example, calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, carbon black, carbon fibers, zeolites, and mixtures thereof.

[0163] Among these additives, phenolic antioxidants, phosphorus antioxidants, ultraviolet absorbers, hindered amine light stabilizers, peroxide scavengers, and neutralizers are preferred.

[0164] The following compounds are examples of particularly preferred phenolic antioxidants.

[0165] 2,6-Di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,2'-thiobis(6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylbis(4,6-di-tert-butylphenol), 4,4'-methylenebis(6-methyl-6-tert-butylphenol) -tert-butyl-2-methylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, ethylene glycol bis[3,3-bis-3'-tert-butyl-4'-hydroxyphenyl)butyrate], 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,4-di-tert-pentyl-6-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]phenyl acrylate, 2,4, 6-Tris(3,5-di-tert-butyl-4-phenoxy)-1,3,5-triazine, tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, tris[2-(3',5'-di-tert-butyl-4'-hydroxycinnamoyloxy)ethyl]isocyanurate, diethyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphate, di-n-octadecyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphate, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoester, n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, neopentanetetramethyltetra(3,5-di-tert-butyl-4-hydroxycinnamate), thiodimethyl... Ethyl bis(3,5-di-tert-butyl-4-hydroxycinnamate), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,6-dioxaoctamethylene bis(3,5-di-tert-butyl-4-hydroxycinnamate), hexamethylene bis(3,5-di-tert-butyl-4-hydroxycinnamate), triethylene glycol bis(5-tert-butyl-4-hydroxy-3-methylcinnamate), 3,9-bis[2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl]-2,4,4,10-tetraoxaspiro[5·5]undecane, N,N'-bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyl]hydrazine, N,N'-bis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyl]hexamethylenediamine, etc.

[0166] In addition, the following compounds are particularly preferred phosphorus-based antioxidants.

[0167] Tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, distearate pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tetra(2,4-di-tert-butylphenyl)-4,4'-diphenylene diphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)2-ethylhexyl phosphite, 2,2'-ethylhexylbis(4,6-di-tert-butylphenyl)2-ethylhexyl phosphite, Tert-butylphenyl)fluorophosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 2-(2,4,6-tri-tert-butylphenyl)-5-ethyl-5-butyl-1,3,2-oxophosphazene, 2,2',2"-nitro[triethyl-tri(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphazene, etc.

[0168] The following compounds are examples of particularly preferred ultraviolet absorbers.

[0169] Phenyl salicylate, 4-tert-butylphenyl salicylate, 3',5'-di-tert-butyl-4'-hydroxybenzoic acid-2,4-di-tert-butylphenyl ester, 4-tert-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 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-tert-butyl-2'- 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-(3',5'-ditert-pentyl-2'-hydroxyphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, etc.

[0170] The following compounds are examples of particularly preferred light stabilizers.

[0171] bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(N-octoxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(N-benzyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butylmalonate, bis(1-acryloyl-2,2,6,6-tetramethyl-4-piperidinyl)2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl) 2-Butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidinyl)succinate, 2,2,6,6-tetramethyl-4-piperidinyl methacrylate, 4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-1-[2-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy)ethyl]-2,2,6,6-tetramethylpiperidin, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidinyl)amino-N-(2,2,6,6-tetramethyl-4-piperidinyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)1,2,3,4-butanetetracarboxylate, tetrakis(1,2,6,6-pentamethyl-4-piperidinyl) 1,2,3,4-Butanetetracarboxylic acid ester, a mixed ester of 1,2,3,4-butanetetracarboxylic acid with 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecaneol, a mixed ester of 1,2,3,4-butanetetracarboxylic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecaneol, a mixed ester 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, 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, and 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 (2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, condensation polymers 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-piperidinyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidinyl)imino)], poly[(6-(1,1,3,3-tetramethylbutyl)-1,3,5-triazine-2,4-diyl)((2,2,6,6-tetramethyl-4-piperidinyl)imino)hexamethylene((2,2,6,6-tetramethyl-4-piperidinyl)imino)], etc.

[0172] All known methods and apparatus for obtaining homogeneous mixtures can be used to add the phenolic compound of the present invention, represented by formula (1), and / or other additives as needed, to an organic material. For example, when the organic material is a solid polymer, the phenolic compound of the present invention and / or other additives as needed can be directly dry-mixed into the solid polymer, or the phenolic compound and / or other additives as needed 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-described addition methods, the phenolic compound of the present invention and / or other additives as needed can be incorporated into the polymer solution during or immediately after polymerization in the form of a solution or dispersion. On the other hand, when the organic material is a liquid other than a solid polymer (e.g., oil), in addition to the above-described addition methods, the phenolic compound of the present invention and / or other additives as needed can be directly added to the organic material to dissolve it, or the phenolic compound of the present invention and / or other additives as needed can be added in a state where they are dissolved or suspended in a liquid medium.

[0173] The phenolic compound of the present invention, represented by formula (1), has excellent properties as a stabilizer for various organic materials, mainly composed of thermoplastic resins such as polyolefins. Organic materials containing the phenolic compound of the present invention are stable against thermal and oxidative degradation during manufacturing, processing, and even use, and are high-quality products.

[0174] Example

[0175] The following examples illustrate the invention in more detail, but the invention is not limited thereto.

[0176] 1 H-NMR measurement

[0177] Device: Bruker AV-300M.

[0178] Solvent used for determination: CDCl3.

[0179] Determination of melt flow rate (MFR)

[0180] MFR was determined using a melt indexer (model L246-3537, manufactured by TECHNOLSEVEN CO.,LTD.) at a temperature of 230°C and a load of 21.18 N.

[0181] Polypropylene resin decomposes during thermal processing, increasing its molecular weight ratio (MFR). Therefore, the less likely a polypropylene resin composition with added stabilizers is to experience an increase in MFR due to thermal processing, the better its processing stability.

[0182] Measurement of Yellow Index (YI)

[0183] The particles obtained in the examples and comparative examples were stamped using a stamping press (Kansai Roll Co., Ltd. "PEW-5040") at a temperature of 230°C to obtain sheets with a thickness of 1 mm. The yellow index (YI) of the obtained sheets was measured using a colorimeter (Minolta Co., Ltd. "CM-3500d"). It can be said that the smaller the YI value, the more suppressed the discoloration.

[0184] Example 1: Phenolic compound (R) represented by formula (1) 1 Synthesis of (=methyl)

[0185] Add SUMILIZER (registered trademark) GA-80 (chemical formula: C 43 H 64 O 10 10 g (13.5 mmol) of acetone, 100 mL of potassium carbonate, 1.87 g (13.5 mmol, molecular weight: 138.20) and 1.92 g (13.5 mmol, molecular weight: 141.94) of methyl iodide (MeI) were stirred overnight at room temperature. Since the ratio of reactants to products in LC was approximately 8:2, equal amounts of potassium carbonate and methyl iodide were added to each, and the mixture was stirred at room temperature for 6 hours. After adding equal amounts of potassium carbonate and methyl iodide to each and stirring overnight, the mixture was filtered, and the residue was concentrated to obtain the crude product. The residue was purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate system) to obtain 4.5 g of compound (1) represented by the following formula (1-MeO) and 2.9 g of dimethoxyform (DMeO) represented by the following formula (DMeO). Compound (1), represented by formula (1-MeO), is the phenolic compound of the present invention. The resulting dimethoxylated form was used in the comparative resin composition of Comparative Example 3 described later. It should be noted that the chemical formula of compound (1), represented by formula (1-MeO), is C. 44 H 66 O 10 The exact mass is 754.47, and the molecular weight is 755.00. Furthermore, the chemical formula of the dimethoxyl form represented by (DMeO) is C. 45 H 68 O 10 The exact mass is 768.48, and the molecular weight is 769.03.

[0186] Chemical formula 3

[0187]

[0188] Purity (LC).

[0189] Model: LC-20A.

[0190] Chromatographic column: L-column 2ODS (5μm, 4.6mmφ, 150mm).

[0191] Injection volume: 5 μL (each methanol solution).

[0192] Mobile phase: Solution A is water / acetic acid = 1000 / 1 (v / v); Solution B is methanol / tetrahydrofuran (THF) / acetic acid = 930 / 70 / 1 (v / v / v).

[0193] Gradient: Time (minutes) 0 7 37 47;

[0194] B concentration (%) 70 70 100 100.

[0195] Flow rate: 1.0 mL / min.

[0196] Column temperature: 40℃.

[0197] Measurement wavelength: UV, 280nm.

[0198] Purity: 99.3% (1-MeO); 97.4% (DMeO).

[0199] 1 H-NMR (300MHz, CDCl3)

[0200] δ0.91 (d, J=1.8Hz, 12H, CH3), δ1.37 (s, 9H, C(CH3)3), δ1.40

[0201] (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).

[0202] Example 2: Preparation of particles of a resin composition comprising a phenolic compound represented by formula (1)

[0203] 0.05 parts by weight of calcium stearate and 0.1 parts by weight of compound (1) obtained in Example 1 were dry-mixed into 100 parts by weight of polypropylene resin (manufactured by Sumitomo Chemical Co., Ltd., MFR: 25 g / 10 min). Under air conditions, the mixture was kneaded using a twin-screw extruder (model: BTN32-S2-36-L, manufactured by PLABOR Research Laboratory of Plastics Technology Co., Ltd.) with a barrel diameter of 32 mm at a temperature of 230°C and a screw speed of 100 rpm to obtain granules (1) of the resin composition of the present invention.

[0204] In an air environment, the obtained granules (1) were compounded using a single-screw extruder (model: VS30-28, manufactured by Tanabe Plastics Machinery Co., Lid.) with a barrel diameter of 30 mm at a temperature of 280°C and a screw speed of 100 rpm. This operation was repeated 5 times to obtain granules (2) after 5 compounding operations. The MFR and YI of the obtained granules (2) were measured according to the above-described method. The results are shown in Table 1.

[0205] Comparative Example 1

[0206] Except for the absence of compound (1), the process was the same as in Example 2, resulting in granules after 5 mixing operations. The MFR and YI of the granules were measured according to the above-described method. The results are shown in Table 1.

[0207] Comparative Example 2

[0208] Except for the addition of 0.1 parts by weight of GA-80, which was used as a raw material in Example 1, to replace compound (1), the process was carried out in the same manner as in Example 2, and granules were prepared after 5 mixing operations. The MFR and YI of the obtained granules were measured according to the above-described determination method. The results are shown in Table 1.

[0209] Comparative Example 3

[0210] Except for adding 0.1 parts by weight of the dimethoxyl body obtained in the manufacturing method described in Example 1 to replace compound (1), the process was carried out in the same manner as in Example 2 to prepare granules after 5 mixing operations. The MFR and YI of the obtained granules were measured according to the above-described determination method. The results are shown in Table 1.

[0211] Table 1

[0212] MFR [g / 10min] YI Example 2 (1-MeO) 135.9 0.41 Comparative Example 1 (No Additives) 867.3 0.47 Comparative Example 2 (GA-80) 94.7 0.58 Comparative Example 3 (Dimethoxy form) 583.3 0.29

[0213] For the resin composition of Example 2, the MFR in the particles (2) after five repeated mixing operations was low, confirming that it could suppress resin decomposition, which is believed to be caused by heat, oxygen, etc. during processing. In addition, YI was also low, confirming that it could prevent resin discoloration. In contrast, in Comparative Examples 1 to 3 without the addition of the phenolic compounds of the present invention, the effects of suppressing resin decomposition and preventing discoloration were not sufficiently improved after five mixing operations.

Claims

1. A phenolic compound, wherein, The phenolic compound is represented by formula (1): Chemical Formula 1 In equation (1), R 1 It refers to alkyl groups with 1 to 2 carbon atoms.

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

3. A stabilizer for organic materials, wherein, The stabilizer for the organic material comprises the phenolic compound of claim 1.

4. A resin composition, wherein, The resin composition comprises the phenolic compound of claim 1 or 2 and at least one thermoplastic resin, or comprises the organic material stabilizer of claim 3 and at least one thermoplastic resin.

5. The resin composition of claim 4, wherein, Thermoplastic resins are polyolefins or engineering plastics.

6. A method for stabilizing organic materials, wherein, Add the phenolic compound of claim 1 or 2 or the stabilizer for organic materials of claim 3 to an organic material, wherein the organic material is a thermoplastic resin.

7. The method for stabilizing organic materials as described in claim 6, wherein, Thermoplastic resins are polyolefins or engineering plastics.

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