Discoloration-inhibiting composition for vinyl chloride resins

Abstract

To provide a discoloration inhibition composition for a vinyl chloride-based resin which can inhibit discoloration of a vinyl chloride-based resin, a stabilizer composition for a vinyl chloride-based resin, a vinyl chloride-based resin composition, a vinyl chloride-based resin molding, a laminate, an automobile interior material, and a method for inhibiting discoloration of a vinyl chloride-based resin.SOLUTION: A discoloration inhibition composition for a vinyl chloride-based resin contains, with respect to 100 pts.mass of the following component (A), 0.1-20,000 pts.mass of the following component (B). Component (A): zinc salt of 2- mercaptobenzothiazole. Component (B): one or more selected from the group of ultraviolet absorbers.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a discoloration-inhibiting composition for vinyl chloride resins (hereinafter also referred to as "discoloration-inhibiting composition"). More specifically, the present invention relates to a discoloration-inhibiting composition for vinyl chloride resins that can inhibit discoloration of vinyl chloride resins due to amines and ultraviolet rays, a stabilizer composition for vinyl chloride resins, a vinyl chloride resin composition, a vinyl chloride resin molded product (hereinafter also referred to as "stabilizer composition," "resin composition," and "molded product," respectively), a laminate, an automotive interior material, and a method for inhibiting discoloration of vinyl chloride resins. [Background technology]

[0002] Vinyl chloride resins have excellent properties such as flame retardancy, chemical resistance, mechanical stability, heat resistance, and weather resistance, and are inexpensive. As a result, they are widely used as a versatile resin material with high utility value, and are particularly widely used as a surface material for automobile interiors.

[0003] Various interior materials are used in automobiles to improve ride comfort. Automotive interior materials typically consist of a surface layer that provides a soft feel (texture), a luxurious feel, and aesthetic appeal, and a base layer that maintains the structure. Furthermore, the surface layer is often lined with a foam layer made of urethane or similar to further enhance the soft feel.

[0004] The surface layer is made of vinyl chloride resin, thermoplastic elastomer, polyolefin such as polyethylene, etc. Among these, vinyl chloride resin is widely used because it can produce a variety of textures from semi-hard to soft depending on the amount of plasticizer added, is easy to mold, and has excellent design properties.

[0005] In interior materials that use vinyl chloride resin, laminates of polyvinyl chloride resin molded bodies and polyurethane foam, backed with urethane resin, particularly polyurethane foam (also known as "polyurethane foam molded bodies"), are often used to create a soft feel.

[0006] However, when vinyl chloride resin is used as a laminate with polyurethane foam, there is a problem that the amine compound used as a catalyst in forming the polyurethane foam molded body migrates into the vinyl chloride resin molded body, causing the vinyl chloride resin molded body to become discolored. To address this problem, methods have been proposed to prevent discoloration of vinyl chloride resin molded bodies caused by the amine compound by blending perchlorate compounds such as sodium perchlorate, barium perchlorate, and perchloric acid-treated hydrotalcite into vinyl chloride resin compositions (Patent Documents 1 and 2). Patent Document 3 also proposes a vinyl chloride resin composition to which a mercaptobenzothiazole compound has been added, and shoes using the same.

[0007] Furthermore, vinyl chloride resins have problems such as discoloration due to sunlight or ultraviolet light and cracks occurring on the surface of molded articles. Therefore, when vinyl chloride resins are used in automobile interior materials, in particular, it has been necessary to suppress discoloration due to ultraviolet light contained in sunlight.

[0008] Furthermore, since the interior of a car can become very hot when parked outdoors, if vinyl chloride resin is used in car interior materials, the components contained in the vinyl chloride resin can volatilize and adhere to the glass surfaces inside the car, causing the problem of fogging. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 5-17648 [Patent Document 2] Japanese Patent Application Publication No. 7-173354 [Patent Document 3] Japanese Patent Application Publication No. 60-233140 Summary of the Invention [Problem to be solved by the invention]

[0010] However, the methods proposed in Patent Documents 1 and 2, in which a perchlorate compound is blended with a vinyl chloride resin composition, did not provide sufficient discoloration suppression. Furthermore, perchlorates, which are also used in gunpowder and explosives, are classified as Class 1 (oxidizing solids) hazardous materials under the Fire Service Act and are constantly at risk of causing explosions or fires due to friction or impact. Furthermore, water pollution caused by perchlorates has been reported in at least 20 U.S. states, and the California Department of Toxic Substances Control (DTSC) has established regulations regarding the handling of perchlorates. Therefore, the use of perchlorate compounds raises numerous safety and environmental concerns. Furthermore, perchlorate compounds cannot be expected to suppress discoloration caused by ultraviolet light. For these reasons, there has been a demand for vinyl chloride resin compositions and automotive interior materials suitable for automotive interior materials that suppress amine-induced discoloration without the use of perchlorate compounds and that also suppress discoloration caused by ultraviolet light.

[0011] Meanwhile, Patent Document 3 proposes a vinyl chloride resin composition containing a mercaptobenzothiazole compound that inhibits discoloration caused by amines, and shoes using the same. However, Patent Document 3 does not take into consideration the effects of multiple factors, such as ultraviolet rays contained in sunlight and high temperatures inside an automobile under the blazing summer sun, which are particularly problematic for automobile interior materials, nor the synergistic effects of these factors. Moreover, the discoloration inhibition performance against these factors is not satisfactory. Furthermore, Patent Document 3 does not at all consider fogging resistance, which is important for automobile interior materials.

[0012] Therefore, an object of the present invention is to provide a discoloration-inhibiting composition for vinyl chloride resins that can inhibit discoloration of vinyl chloride resins, as well as a stabilizer composition for vinyl chloride resins, a vinyl chloride resin composition, a vinyl chloride resin molded product, a laminate, an automotive interior material, and a method for inhibiting discoloration of vinyl chloride resins that use the same. [Means for solving the problem]

[0013] As a result of extensive research aimed at solving the above problems, the present inventors discovered that the combined use of a zinc salt of 2-mercaptobenzothiazole and an ultraviolet absorber can suppress discoloration of vinyl chloride resins and also provide excellent anti-fogging properties, leading to the completion of the present invention.

[0014] That is, the present invention provides a composition comprising 100 parts by mass of a zinc salt of 2-mercaptobenzothiazole as component (A) and 10.0 to 400 parts by mass of one or more kinds selected from the group consisting of ultraviolet absorbers as component (B), The present invention provides a discoloration-inhibiting composition for vinyl chloride resins, wherein the ultraviolet absorber of component (B) is at least one selected from the group consisting of benzotriazole-based ultraviolet absorbers, which are 2-(2-hydroxyphenyl)benzotriazoles, triazine-based ultraviolet absorbers, and benzophenone-based ultraviolet absorbers.

[0016] The discoloration-inhibiting composition for vinyl chloride resins of the present invention is suitable for use in automobile interior materials. The present invention is useful when the automobile interior material is an automobile interior material comprising a laminate of a vinyl chloride resin molded article and a polyurethane foam molded article.

[0017] The present invention also provides a stabilizer composition for vinyl chloride resins, which contains one or more stabilizers for vinyl chloride resins and the discoloration-inhibiting composition for vinyl chloride resins.

[0018] The present invention also provides a vinyl chloride resin composition containing a vinyl chloride resin and the discoloration-inhibiting composition for vinyl chloride resin.

[0019] In the vinyl chloride resin composition of the present invention, the content of the discoloration-inhibiting composition for vinyl chloride resin is preferably 0.001 to 50 parts by mass per 100 parts by mass of the vinyl chloride resin. The vinyl chloride resin composition of the present invention is suitable for powder molding.

[0020] The present invention also provides a vinyl chloride resin molded article obtained from the vinyl chloride resin composition.

[0021] Furthermore, the present invention provides a laminate of a vinyl chloride resin molded product and a polyurethane foam molded product, comprising: The vinyl chloride resin molded article provides a laminate obtained from the vinyl chloride resin composition.

[0022] The present invention also provides an automobile interior material containing the vinyl chloride resin molded article.

[0023] Furthermore, the present invention provides an automobile interior material comprising the above laminate.

[0024] Furthermore, the present invention provides a method for inhibiting discoloration of an automobile interior material including a laminate of a vinyl chloride resin molded product and a polyurethane foam molded product, the method comprising: The present invention also provides a method for inhibiting discoloration, which comprises blending the above-mentioned discoloration-inhibiting composition for vinyl chloride resin with vinyl chloride resin, which is a raw material resin for the vinyl chloride resin molded article. [Effects of the Invention]

[0025] According to the present invention, it is possible to provide a discoloration-inhibiting composition for vinyl chloride resin that can inhibit discoloration of vinyl chloride resin due to amines and ultraviolet light and also impart fogging resistance, as well as a stabilizer composition for vinyl chloride resin, a vinyl chloride resin composition, a vinyl chloride resin molded product, a laminate, an automotive interior material, and a method for inhibiting discoloration of vinyl chloride resin that uses the same.

[0026] The vinyl chloride resin molded article of the present invention is inhibited from discoloring and has excellent fogging resistance, making it suitable for use as an automobile interior material. DETAILED DESCRIPTION OF THE INVENTION

[0027] Hereinafter, embodiments of the present invention will be described in detail.

[0028] [Discoloration-inhibiting composition for vinyl chloride resins] First, the discoloration-inhibiting composition for vinyl chloride resins of the present invention will be described. The discoloration-inhibiting composition of the present invention has the function of inhibiting discoloration of vinyl chloride resins due to amines and ultraviolet light. The discoloration-inhibiting composition of the present invention can also impart fogging resistance. Therefore, as described below, the discoloration-inhibiting composition of the present invention is suitable for use in automotive interior materials, and is particularly suitable for use in automotive interior materials consisting of a laminate of a vinyl chloride resin molded product and a polyurethane foam molded product, as described below.

[0029] The discoloration-inhibiting composition of the present invention contains 0.1 to 20,000 parts by mass of the following component (B) per 100 parts by mass of the following component (A). (A) Component: Zinc salt of 2-mercaptobenzothiazole. Component (B): One or more selected from the group consisting of ultraviolet absorbers.

[0030] First, component (A) will be described. The zinc salt of 2-mercaptobenzothiazole of component (A) preferably has a structure represented by the following formula (1), from the viewpoints of inhibiting discoloration of vinyl chloride resins due to amines and ultraviolet rays, as well as achieving anti-fogging effects. TIFF0007811102000001.tif33153

[0031] As the zinc salt of 2-mercaptobenzothiazole, commercially available products may be used, such as "Suncerer MZ" manufactured by Sanshin Chemical Industry Co., Ltd., "ACCEL MZ" manufactured by Kawaguchi Chemical Industry Co., Ltd., and "Noccela MZ" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.

[0032] Next, the component (B) of the present invention will be described. The component (B) of the present invention is one or more members selected from the group consisting of ultraviolet absorbers.

[0033] Examples of the ultraviolet absorber of component (B) include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and salicylate-based ultraviolet absorbers.

[0034] As the ultraviolet absorber of component (B), from the viewpoint of inhibiting discoloration due to amines and ultraviolet rays, as well as obtaining anti-fogging effects, one or more selected from the group consisting of benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and benzophenone-based ultraviolet absorbers are preferred, and benzotriazole-based ultraviolet absorbers or benzophenone-based ultraviolet absorbers are more preferred.

[0035] Examples of the benzotriazole-based ultraviolet absorber include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-benzotriazolylphenol), 2,2'-methylenebis(4-ethylhydroxy-6-benzotriazolylphenol), 2,2'-Methylenebis(4-methyl-6-benzotriazolylphenol), polyethylene glycol ester of 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole, 2-[2-hydroxy-3-(2-acryloyloxyethyl)-5-methylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-octylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-5-(2-methacryloyloxyethyl)phenyl]benzotriazole Examples of 2-hydroxyphenyl)benzotriazoles include 2-(2-hydroxyphenyl)benzotriazoles such as 2-[2-hydroxy-3-tert-butyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-amyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(3-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-4-(2-methacryloyloxymethyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methacryloyloxy-2-hydroxypropyl)phenyl]benzotriazole, and 2-[2-hydroxy-4-(3-methacryloyloxypropyl)phenyl]benzotriazole.

[0036] Examples of triazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(octyloxy)phenol, 2-(4,6-bis(4-butoxy-2-methylphenyl)-1,3,5-triazin-2-yl)-3,5-dibutoxyphenol, and 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-3,5-dibutoxyphenol. Examples of phenol-containing triazines include 2-(azin-2-yl)-5-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)phenol, 2-(4,6-di([1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol, and 2-methylhexyl-2-(4,(4,6-di([1,1'-biphenyl]-4-yl)-1,3,5-triazin-2-yl)-3-hydroxyphenoxy)propanoate.

[0037] Examples of benzophenone-based ultraviolet absorbers include 2-hydroxybenzophenones such as 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,4-dihydroxybenzophenone, 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone), and 1,4-bis(4-benzoyl-3-hydroxyphenoxy)-butane.

[0038] Examples of benzoate-based ultraviolet absorbers include benzoates such as resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy)benzoate, dodecyl (3,5-di-tert-butyl-4-hydroxy)benzoate, tetradecyl (3,5-di-tert-butyl-4-hydroxy)benzoate, hexadecyl (3,5-di-tert-butyl-4-hydroxy)benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy)benzoate, and behenyl (3,5-di-tert-butyl-4-hydroxy)benzoate.

[0039] Examples of oxanilide-based ultraviolet absorbers include substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide.

[0040] Examples of cyanoacrylate ultraviolet absorbers include ethyl-2-cyano-3,3-diphenylacrylate, 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-α-cyano-β,β-diphenylacrylate, methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate, 4-(2-cyano-3-(4-ethylphenoxy)-3-oxopropenyl)phenyl-4-propylcyclohexane-1-carboxylate, 4-(2- Cyano-3-(4-ethylphenoxy)-3-oxopropenyl)phenyl-4-propyl benzoate, 4-butylphenyl-4-(2-cyano-3-oxo-3-(4-propylphenoxy)propenyl)benzoate, 4-(2-cyano-3-(4-cyanophenoxy)-3-oxopropenyl)phenyl-4-pentyl benzoate, 4-(2-cyano-3-(4-fluorophenoxy)-3-oxopropenyl)phenyl-4-methylcyclohexane-1-carboxylate 4-(2-cyano-3-(4-methoxyphenoxy)-3-oxopropenyl)phenyl-4-hexylcyclohexane-1-carboxylate, 4-(2-cyano-3-(4-ethoxyphenoxy)-3-oxopropenyl)phenyl-4-octylcyclohexane-1-carboxylate, 4-(2-cyano-3-oxo-3-(4-propoxyphenoxy)propenyl)phenyl-4-propylcyclohexane-1-carboxylate, 4-(2-cyano-3-oxo-3 cyanoacrylates such as 4-(4-pentylphenoxy)propenyl)phenyl-4-propylcyclohexane-1-carboxylate, 4-(2-cyano-3-(4-octylphenoxy)-3-oxopropenyl)-4-propylcyclohexane-1-carboxylate, and 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis-[[(2'-cyano-3',3'-diphenylacryloyl)oxy]methyl]propane.

[0041] Examples of salicylate-based ultraviolet absorbers include salicylic acids such as 4-tert-butylphenyl salicylate, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropanolphenyl salicylate.

[0042] Two or more types of ultraviolet absorbers of component (B) may be used in combination.

[0043] From the viewpoint of inhibiting discoloration due to amines and ultraviolet rays, and obtaining anti-fogging effects, preferred ultraviolet absorbers for component (B) include 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol, 2-(4,6-diphenyl)-

[0033] Examples of the 2-hydroxy-4-(octyloxy)phenyl](phenyl)methanone include 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-p-cresol, and 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol.

[0044] The ultraviolet absorber of component (B) may be a commercially available product, and specific examples thereof include those manufactured by ADEKA CORPORATION under the product names "ADK STAB LA-24," "ADK STAB LA-29," "ADK STAB LA-31RG," "ADK STAB LA-31G," "ADK STAB LA-32," "ADK STAB LA-36," "ADK STAB LA-36RG," "ADK STAB LA-46," "ADK STAB LA-F70," "ADK STAB 1413," and "ADK STAB LA-51"; those manufactured by Otsuka Chemical Co., Ltd. under the product names "RUVA-100" and "RUVA93"; and those manufactured by Fairmout under the product names "Mixxim BB / 150" and "Mixxim BB / 200"; product names of Shipro Chemical Co., Ltd.: "Seesorb704", "Seesorb705", "Seesorb706", "Seesorb707", "Seesorb708", "Seesorb709", "Seesorb100", "Seesorb101", "Seesorb104", "Seesorb106", "Seesorb107", "Seesorb151"; product name of Sumitomo Chemical Co., Ltd.: "Sumisorb250"; product names of BASF: "Tinuvin P" and "Tinuvin PS", "Tinuvin109", "Tinuvin213", "Tinuvin234", "Tinuvin234FF", "Tinuvin326", "Tinuvin326FL", "Tinuvin32 7'', ``Tinuvin328'', ``Tinuvin329'', ``Tinuvin329FL'', ``Tinuvin350'', ``Tinuvin360'', ``Tinuvin384'', ``Tinuvin571'', `` Tinuvin1130", "Tinuvin400", "Tinuvin405", "Tinuvin460", "Tinuvin477", "Tinuvin479", "Tinuvin1577", "Tin uvin1577ED”, “Tinuvin1600”, “Chimassorb81”, “Chimassorb81FL”, “Tinuvin120”, “Uvinul3030”, “Uvinul3048”;Examples include Cytec products such as "Cyasorb 1164," "Cyasorb UV-21," "Cyasorb UV-24," "Cyasorb UV-207," "Cyasorb UV-284," and "Cyasorb UV-2126."

[0045] In the discoloration-inhibiting composition of the present invention, the content of the ultraviolet absorber, component (B), is 0.1 to 20,000 parts by mass relative to 100 parts by mass of the zinc salt of 2-mercaptobenzothiazole, component (A). From the viewpoint of obtaining the effects of inhibiting discoloration due to amines and ultraviolet light, as well as fogging resistance, the content is preferably 5.0 to 8,000 parts by mass, more preferably 10.0 to 800 parts by mass, and even more preferably 10.0 to 400 parts by mass.

[0046] The discoloration inhibitor composition of the present invention preferably further contains a hindered amine light stabilizer in order to inhibit discoloration due to amines and ultraviolet light, as well as to obtain anti-fogging effects. The hindered amine light stabilizer is not particularly limited, and any known compound can be used. Examples of hindered amine light stabilizers include compounds having a 2,2,6,6-tetramethylpiperidyl structure, such as 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) benzoate, and the like. lysyl) sebacate, bis(2,2,6,6-tetramethyl-1-(octyloxy)piperidyl-4-yl) sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, butane-1,2,3,4-tetracarboxylic acid tetrakis(2,2,6,6-tetramethyl-4-piperidinyl), butane-1,2,3,4-tetracarboxylic acid tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl), bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidyl)di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-ditert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidyl Lysinol / diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1-methyl-10-(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and bis(2,2,6,Polycondensation products of 6-tetramethyl-4-piperidyl) sebacate, butanetetracarboxylic acid tetramethyl ester, esters with spiroglycol and N-methylpiperidinol, polycondensation products of butanetetracarboxylic acid, esters with 3-hydroxy-2,2-dimethylpentanal and N-methylpiperidinol, 1,2,3,4-butanetetracarboxylic acid tetramethyl ester, 2,2,6,6-tetramethyl-4-piperidinol and β,β,β',β'-tetramethyl Polycondensation product of tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol, 2,4-dichloro-6-(1,1,3,3-tetramethylbutylamino)-1,3,5-triazine-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, 2,4-dichloro-6-(1,1,3,3-tetramethylbutylamino)-1,3,5-triazine, 1,5,8,12-tetrakis[2,4-biphenyl] 1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino]-s-triazin-6-yl]-1,5,8-12-tetraazadodecane, Examples of the hindered amine light stabilizer include 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, bis{4-(1-octyloxy-2,2,6,6-tetramethyl)piperidyl}decanedionate, and bis{4-(2,2,6,6-tetramethyl-1-undecyloxy)piperidyl)carbonate. The hindered amine light stabilizer may be a mixture of two or more types.

[0047] In terms of inhibiting discoloration due to amines and ultraviolet light, and obtaining anti-fogging effects, preferred hindered amine light stabilizers include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate, and a mixture of 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6- Mixed esters of pentamethyl-4-piperidinol and 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8-10-tetraoxospiro[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-tetraoxospiro[5.5]undecane, Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6 of C12-21 saturated fatty acids and C18 unsaturated fatty acids 1,2,2,6,6-tetramethyl-4-piperidinyl esters of C12-21 saturated fatty acids and C18 unsaturated fatty acids, and 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-tetraoxospiro[5.5]undecane is particularly preferred.

[0048] As the hindered amine-based light stabilizer, commercially available products may be used, for example, those manufactured by ADEKA Corporation under the product names "ADK STAB LA-52", "ADK STAB LA-57", "ADK STAB LA-63P", "ADK STAB LA-68", "ADK STAB LA-72", "ADK STAB LA-77", "ADK STAB LA-77Y", "ADK STAB LA-77G", "ADK STAB LA-81", "ADK STAB LA-82", "ADK STAB LA-87", and "ADK STAB LA-88". A-402AF, ADK STAB LA-40MP, ADK STAB LA-40Si, ADK STAB LA-94, ADK STAB LA-402XP, ADK STAB LA-502XP; BASF product names: Chimassorb 119, Chimassorb 944, Chimassorb 944FDL, Chimassorb 944LD, Chimassorb 2020, Chimassorb 2020FDL, Tinuvin PA144," "Tinuvin765," "Tinuvin770DF," "Tinuvin XT55FB," "Tinuvin622SF," "Tinuvin XT850," "Tinuvin NOR371," "Tinuvin783," "Tinuvin791," "Irgastab FS-210," "Irgastab FS-410," "Tinuvin622," "Tinuvin111," "Tinuvin111FDL," "Tinuvin783FDL," and "Tinuvin791FB"; and Cytec products under the names "Cyasorb UV-3808PP5" and "Cyasorb Cynergy V-703."

[0049] When a hindered amine light stabilizer is contained in the discoloration-inhibiting composition of the present invention, the content thereof is preferably 1.0 to 15,000 parts by mass, more preferably 5.0 to 2,000 parts by mass, and even more preferably 10.0 to 700 parts by mass, per 100 parts by mass of the zinc salt of 2-mercaptobenzothiazole of component (A), in order to obtain the effects of inhibiting discoloration due to amines and ultraviolet rays, as well as fogging resistance.

[0050] [Stabilizer composition for vinyl chloride resin] The discoloration-inhibiting composition of the present invention is also preferably used as a stabilizer composition for vinyl chloride resins in combination with one or more stabilizers for vinyl chloride resins. The stabilizer composition of the present invention is suitably used for automobile interior materials, and is particularly suitably used for automobile interior materials comprising a laminate of a vinyl chloride resin molded article and a polyurethane foam molded article, as described below.

[0051] As a stabilizer for vinyl chloride resins to be used in combination with the discoloration-inhibiting composition, a zinc salt of an organic acid is preferred from the viewpoints of inhibiting discoloration due to amines and ultraviolet light, as well as achieving anti-fogging and thermal stability. Examples of such zinc salts of organic acids include zinc salts of organic carboxylic acids, phenols, or organic phosphoric acids. In the present invention, 2-mercaptobenzothiazole is not included in the organic acids.

[0052] Examples of organic carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexyl acid, neodecanoic acid, capric acid, undecanoic acid, isoundecylic acid, lauric acid, isolauric acid, tridecanoic acid, myristic acid, isomyristic acid, palmitic acid, isopalmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, versatic acid, benzoic acid, monochlorobenzoic acid, and 4-tert-butylbenzoic acid. Acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, toluic acid, dimethylbenzoic acid, 2,4-dimethylbenzoic acid, 3,5-dimethylbenzoic acid, 2,4,6-trimethylbenzoic acid, ethylbenzoic acid, 2-ethylbenzoic acid, 3-ethylbenzoic acid, 4-ethylbenzoic acid, 2,4,6-triethylbenzoic acid, 4-isopropylbenzoic acid, n-propylbenzoic acid, aminobenzoic acid, N,N-dimethylaminobenzoic acid, acetoxybenzoic acid Monocarboxylic acids such as aromatic acid, salicylic acid, p-tert-octyl salicylic acid, elaidic acid, oleic acid, linoleic acid, linolenic acid, myristoleic acid, palmitoleic acid, eleostearic acid, eicosenoic acid, eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, arachidonic acid, docosapentaenoic acid, docosahexaenoic acid, ricinoleic acid, thioglycolic acid, mercaptopropionic acid, and octylmercaptopropionic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, and suberin. Examples of suitable carboxylic acids include dicarboxylic acids such as benzoic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, and thiodipropionic acid, as well as monoesters and monoamide compounds thereof; and di- or triester compounds of tri- or tetracarboxylic acids such as butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid, mellophanic acid, and pyromellitic acid.

[0053] Examples of phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, isooctylphenol, 2-ethylhexylphenol, tert-nonylphenol, decylphenol, tert-octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisohexylphenol, and methyl-tert-octylphenol.

[0054] Examples of organic phosphoric acids include mono- or dioctyl phosphoric acid, mono- or didodecyl phosphoric acid, mono- or dioctadecyl phosphoric acid, mono- or di-(nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, and phosphonic acid stearyl ester.

[0055] The zinc salt of an organic acid may be an acidic salt, a neutral salt, a basic salt, or an overbased complex in which part or all of the base of the basic salt is neutralized with carbonic acid.

[0056] The zinc salt of an organic acid may be composed of two or more organic acids. For example, in the case of a zinc salt of a monovalent organic acid, the same organic acid may constitute the anion site and form a salt with the divalent zinc that constitutes the cation site, or two different monovalent organic acids may constitute the anion site and form a salt with the divalent zinc that constitutes the cation site.

[0057] As the zinc salt, zinc benzoate, zinc toluate, zinc 4-tert-butylbenzoate, zinc stearate, zinc laurate, zinc versatate, zinc octoate, zinc oleate, zinc palmitate, and zinc myristate are preferred from the viewpoints of inhibiting discoloration due to amines and ultraviolet rays, as well as achieving anti-fogging and thermal stability. The zinc salts of organic acids may be used alone or in combination of two or more.

[0058] When the stabilizer composition of the present invention contains a zinc salt of an organic acid, the content thereof is preferably 5 to 20,000 parts by mass, more preferably 10 to 8,000 parts by mass, and even more preferably 20 to 800 parts by mass, per 100 parts by mass of the zinc salt of 2-mercaptobenzothiazole, which is component (A) in the discoloration-inhibiting composition, from the viewpoints of inhibiting discoloration due to amines and ultraviolet rays, as well as achieving anti-fogging and thermal stability effects.

[0059] Furthermore, in the stabilizer composition of the present invention, the stabilizer used in combination with the discoloration-inhibiting composition is preferably one or more selected from the group consisting of barium salts of organic acids and overbased barium carbonate salts, in order to obtain the effects of inhibiting discoloration due to amines and ultraviolet rays, as well as fogging resistance and thermal stability.

[0060] First, the barium salt of an organic acid will be described. Examples of the barium salt of an organic acid include barium salts of organic carboxylic acids, phenols, organic phosphoric acids, and the like.

[0061] Examples of organic carboxylic acids, phenols and organic phosphoric acids include those exemplified as zinc salts of organic acids.

[0062] The barium salt of an organic acid may be composed of two or more organic acids. For example, in the case of a barium salt of a monovalent organic acid, the same organic acid may constitute the anion site and form a salt with the divalent barium that constitutes the cation site, or two different monovalent organic acids may constitute the anion site and form a salt with the divalent barium that constitutes the cation site.

[0063] The barium salt of an organic acid may be used alone or in combination of two or more kinds. The barium salt of an organic acid may be an acidic salt, a neutral salt, or a basic salt.

[0064] Next, we will explain overbased barium carbonate. Overbased barium carbonate is a liquid overbased carboxylate / carbonate complex of barium. Unlike a simple mixture of barium carboxylate and barium carbonate, this complex is formed through some kind of interaction between the two. It has the characteristic of exhibiting a homogeneous liquid state in organic solvents while having a high metal content. This complex is composed of barium carboxylate, barium carbonate, and a barium carboxylate-carbonate complex salt. The barium carbonate is at the center, with the barium carboxylate and the barium carboxylate-carbonate complex salts surrounding it, forming a micelle-like structure that allows it to exhibit a homogeneous liquid state in organic solvents.

[0065] These liquid overbased carboxylate / carbonate complexes of barium can be produced, for example, by the production method disclosed in JP-A-2004-238364.

[0066] Furthermore, various commercially available liquid overbased carboxylate / carbonate complexes of barium can be used as they are. Representative commercially available complexes include "Plastistab" manufactured by AM STABILIZERS, USA. TM 2116" (Overbased barium oleate / carbonate complex: specific gravity 1.42-1.53, Ba=33-36%), "Plastistab TM 2513" (Overbased barium oleate / carbonate complex: specific gravity 1.41-1.52, Ba=33-36%), "Plastistab TM 2508" (overbased barium oleate / carbonate complex: specific gravity 1.39 to 1.51, Ba=33 to 36%).

[0067] These overbased barium carbonate salts may be used alone or in combination of two or more.

[0068] When the stabilizer composition of the present invention contains a barium salt of an organic acid or an overbased barium carbonate, the content thereof is preferably 10 to 60,000 parts by mass, more preferably 30 to 10,000 parts by mass, and even more preferably 50 to 2,000 parts by mass, per 100 parts by mass of the zinc salt of 2-mercaptobenzothiazole, which is component (A) in the discoloration-inhibiting composition, in order to obtain the effects of inhibiting discoloration due to amines and ultraviolet rays, as well as fogging resistance and thermal stability.

[0069] Furthermore, in the stabilizer composition of the present invention, the stabilizer used in combination with the discoloration-inhibiting composition is preferably at least one selected from the group consisting of calcium salts of organic acids and overbased calcium carbonate salts, from the viewpoints of inhibiting discoloration due to amines and ultraviolet light, as well as achieving anti-fogging and thermal stability. Examples of such calcium salts of organic acids include calcium salts of organic carboxylic acids, phenols, and organic phosphoric acids.

[0070] Examples of organic carboxylic acids, phenols and organic phosphoric acids include those exemplified as zinc salts of organic acids.

[0071] The calcium salt of an organic acid may be composed of two or more organic acids. For example, in the case of a calcium salt of a monovalent organic acid, the same organic acid may constitute the anion site and form a salt with divalent calcium that constitutes the cation site, or two different monovalent organic acids may constitute the anion site and form a salt with divalent calcium that constitutes the cation site.

[0072] The calcium salt of an organic acid may be used alone or in combination of two or more kinds. The calcium salt of an organic acid may be an acidic salt, a neutral salt, or a basic salt.

[0073] Next, we will explain overbased calcium carbonate. Overbased calcium carbonate is a liquid overbased carboxylate / carbonate complex of calcium. Unlike a simple mixture of calcium carboxylate and calcium carbonate, this complex is formed by some kind of interaction between the two. It has the characteristic of exhibiting a uniform liquid state in organic solvents while having a high metal content. This complex is composed of calcium carboxylate, calcium carbonate, and a complex salt of calcium carboxylate and carbonate. The calcium carbonate is at the center, with the calcium carboxylate and complex salt of calcium carboxylate and carbonate surrounding them, forming a sort of micelle, which allows it to exhibit a uniform liquid state in organic solvents.

[0074] Liquid overbased carboxylate / carbonate complexes of calcium can be produced in the same manner as liquid overbased carboxylate / carbonate complexes of barium. Alternatively, various commercially available complexes can be used as they are. Representative commercially available complexes include, for example, "Plastistab" manufactured by AM STABILIZERS, USA. TM 2265" (overbased calcium oleate / carbonate complex: specific gravity 1.04-1.09, Ca=10%).

[0075] These overbased calcium carbonates may be used alone or in combination of two or more.

[0076] When the stabilizer composition of the present invention contains a calcium salt of an organic acid or an overbased calcium carbonate, the content thereof is preferably 10 to 60,000 parts by mass, more preferably 30 to 10,000 parts by mass, and even more preferably 50 to 2,000 parts by mass, per 100 parts by mass of the zinc salt of 2-mercaptobenzothiazole, which is component (A) in the discoloration-inhibiting composition, from the viewpoints of inhibiting discoloration due to amines and ultraviolet light, as well as achieving anti-fogging and thermal stability.

[0077] Furthermore, in the stabilizer composition of the present invention, a β-diketone compound is preferred as a stabilizer to be used in combination with the discoloration-inhibiting composition, from the viewpoints of inhibiting discoloration due to amines and ultraviolet light, as well as obtaining the effects of fogging resistance and thermal stability. Examples of such β-diketone compounds include acetylacetone, triacetylmethane, 2,4,6-heptatrione, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, distearoylmethane, stearoylacetylmethane, phenylacetylacetylmethane, dicyclohexylcarbonylmethane, benzoylformylmethane, benzoylacetylmethane, dibenzoylmethane, octylbenzoylmethane, and biacetylmethane. Examples of suitable metal salts include bis(4-octylbenzoyl)methane, benzoyldiacetylmethane, 4-methoxybenzoylbenzoylmethane, bis(4-carboxymethylbenzoyl)methane, 2-carboxymethylbenzoylacetyloctylmethane, dehydroacetic acid, ethyl acetoacetate, cyclohexane-1,3-dione, methyl 3,6-dimethyl-2,4-dioxycyclohexane-1-carboxylate, 2-acetylcyclohexanone, dimedone, and 2-benzoylcyclohexane. Metal salts of these salts can also be used. Examples of suitable metal salts include lithium salts, sodium salts, potassium salts, calcium salts, zinc salts, magnesium salts, and aluminum salts. Preferred examples of suitable metal salts include calcium acetylacetone and zinc acetylacetone.

[0078] The β-diketone compound may be used alone or in combination of two or more. Among these β-diketone compounds, dibenzoylmethane, stearoylbenzoylmethane, or acetylacetonate zinc salt is preferred from the viewpoints of amine resistance and thermal stability.

[0079] When a β-diketone compound is contained in the stabilizer composition of the present invention, the content thereof is preferably 10 to 60,000 parts by mass, more preferably 30 to 10,000 parts by mass, and even more preferably 50 to 2,000 parts by mass, per 100 parts by mass of the zinc salt of 2-mercaptobenzothiazole, which is component (A) in the discoloration-inhibiting composition, in order to obtain the effects of inhibiting discoloration due to amines and ultraviolet rays, as well as fogging resistance and thermal stability.

[0080] Furthermore, in the stabilizer composition of the present invention, the stabilizer used in combination with the discoloration-inhibiting composition is preferably one or more phosphite ester compounds, from the viewpoints of inhibiting discoloration due to amines and UV rays, as well as achieving anti-fogging and thermal stability. Examples of such phosphite ester compounds include trialkyl phosphites, dialkyl phosphites, dialkyl monoallyl phosphites, alkyl allyl phosphites, monoalkyl diallyl phosphites, diallyl phosphites, and triallyl phosphites. In the stabilizer composition of the present invention, either triesters or diesters can be used, but triesters are preferred from the viewpoint of thermal stability. Thioesters can also be used.

[0081] Examples of the phosphite ester compounds include triphenyl phosphite, tricresyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(mono- and di-mixed nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, diphenyl phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, 2,2'-methylenebis(4,6-tert-butylphenyl) octyl phosphite, )-2-ethylhexyl phosphite, 2,2'-methylenebis(4,6-tert-butylphenyl)-octadecyl phosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, octyldiphenyl phosphite, diphenyldecyl phosphite, diphenyl(2-ethylhexyl) phosphite, di(decyl)monophenyl phosphite, diphenyltridecyl phosphite, diphenyl(C12-C15 mixed alkyl) phosphite, phenyldiisodecyl phosphite, phenylbis(isotride sil) phosphite, triethyl phosphite, tributyl phosphite, tris(2-ethylhexyl) phosphite, tris(decyl) phosphite, trilauryl phosphite, tris(tridecyl) phosphite, trioleyl phosphite, tristearyl phosphite, diethyl phosphite, dibutyl phosphite, dilauryl phosphite, bis(2-ethylhexyl) phosphite, dioleyl phosphite, trilauryl trithiophosphite, bis(neopentyl glycol)-1,4-cyclohexanedimethyl di Phosphite, bis(2,4-ditert-butylphenyl)pentaerythritol diphosphite, bis(2,6-ditert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tritert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, di(tridecyl)pentaerythritol diphosphite, phenyl-4,4'-Isopropylidenediphenol pentaerythritol diphosphite, tetra(C12-15 mixed alkyl)-4,4'-isopropylidenediphenyl diphosphite, hydrogenated 4,4'-isopropylidenediphenol polyphosphite, bis(octylphenyl)bis[4,4'-n-butylidenebis(2-tert-butyl-5-methylphenol)]-1,6-hexanediol diphosphite, tetra(tridecyl)-4,4'-n-butylidenebis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane triphosphite Examples include triphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol·2,4,6-tri-tert-butylphenol monophosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tetra(tridecyl)isopropylidenediphenol diphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphite, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, and phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol.

[0082] The phosphite ester compound may be used alone or in combination of two or more. Among these phosphite ester compounds, from the viewpoint of thermal stability, it is preferable to use a phosphite ester compound having 12 to 80 carbon atoms, more preferably a phosphite ester compound having 12 to 46 carbon atoms, even more preferably a phosphite ester compound having 12 to 36 carbon atoms, and particularly preferably a phosphite ester compound having 18 to 30 carbon atoms.

[0083] When a phosphite ester compound is contained in the stabilizer composition of the present invention, the content thereof is preferably 5 to 60,000 parts by mass, more preferably 20 to 6,000 parts by mass, and even more preferably 40 to 2,000 parts by mass, per 100 parts by mass of the zinc salt of 2-mercaptobenzothiazole, which is component (A) in the discoloration-inhibiting composition, from the viewpoints of inhibiting discoloration due to amines and ultraviolet rays, as well as obtaining the effects of fogging resistance and thermal stability.

[0084] Furthermore, in the stabilizer composition of the present invention, the stabilizer used in combination with the discoloration-inhibiting composition is preferably one or more phenolic antioxidants, from the viewpoints of inhibiting discoloration due to amines and ultraviolet light, as well as achieving anti-fogging and thermal stability. Examples of such phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene bis[(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide], 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid ]glycol esters, 4,4'-butylidenebis(6-tert-butyl-m-cresol), 2,2'-ethylidenebis(4,6-ditert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3, 5-Tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], etc.

[0085] The phenolic antioxidant may be used alone or in combination of two or more. Among these phenolic antioxidants, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] or octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate is preferred from the viewpoint of thermal stability.

[0086] When a phenolic antioxidant is contained in the stabilizer composition of the present invention, the content thereof is preferably 1 to 2,000 parts by mass, more preferably 2 to 200 parts by mass, and even more preferably 4 to 100 parts by mass, per 100 parts by mass of the zinc salt of 2-mercaptobenzothiazole, which is component (A) in the discoloration-inhibiting composition, from the viewpoints of inhibiting discoloration due to amines and ultraviolet light, as well as obtaining the effects of fogging resistance and thermal stability.

[0087] Furthermore, in the stabilizer composition of the present invention, the stabilizer used in combination with the discoloration-inhibiting composition is preferably one or more inorganic auxiliary agents, from the viewpoints of inhibiting discoloration due to amines and ultraviolet rays, as well as achieving anti-fogging and thermal stability. Examples of such inorganic auxiliary agents include hydrotalcite compounds and zeolite compounds.

[0088] The hydrotalcite compound may be a compound represented by the following general formula (2).

[0089] Mg x1Zn x2 Al2(OH) 2x1+2x2+4 (CO3) 1-y1 / 2 (ClO4) y1 mH2O···(2)

[0090] In general formula (2), x1, x2, and y1 each represent numbers satisfying the conditions represented by the following formulas: 0≦x2 / x1<10, 2≦x1+x2<20, 0≦y1≦2, and m represents 0 or any integer.

[0091] As the hydrotalcite compound, a double salt compound composed of magnesium and aluminum, or zinc, magnesium, and aluminum, is preferably used. It may also be a compound from which water of crystallization has been dehydrated. Such a hydrotalcite compound may be a natural product or a synthetic product. There are no limitations on the crystal structure, crystal particle size, etc., of the hydrotalcite compound.

[0092] Furthermore, the hydrotalcite compound may be one whose surface is coated with a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal salt of oleic acid, an organic sulfonic acid metal salt such as an alkali metal salt of dodecylbenzenesulfonic acid, a higher fatty acid amide, a higher fatty acid ester, or a wax.

[0093] However, among hydrotalcite compounds, those containing perchlorate anions or those treated with perchlorate can be used in the stabilizer composition of the present invention, but their use is not preferred from the viewpoints of safety and the environment.

[0094] The hydrotalcite compound may be used alone or in combination of two or more kinds.

[0095] Zeolite compounds are aluminosilicates of alkali or alkaline earth metals having a unique three-dimensional zeolite crystal structure, and representative examples include A-, X-, Y-, and P-type zeolites, monodenite, analcite, sodalite-group aluminosilicates, clinobutyrolite, erionite, and chabazite. These zeolite compounds may be either hydrated compounds containing water of crystallization (so-called zeolite water) or anhydrous compounds from which the water of crystallization has been removed. Zeolite compounds having a particle size of 0.1 to 50 μm can be used, with 0.5 to 10 μm being particularly preferred. Zeolite compounds may be used alone or in combination of two or more types.

[0096] The inorganic auxiliary may be used alone or in combination of two or more kinds, and a hydrotalcite compound and a zeolite compound may be used in combination.

[0097] When an inorganic auxiliary is contained in the stabilizer composition of the present invention, the content thereof is preferably 5 to 80,000 parts by mass, more preferably 20 to 8,000 parts by mass, and even more preferably 50 to 4,000 parts by mass, per 100 parts by mass of the zinc salt of 2-mercaptobenzothiazole, which is component (A) in the discoloration-inhibiting composition, from the viewpoint of obtaining the effects of inhibiting discoloration due to amines and ultraviolet rays, as well as fogging resistance and thermal stability.

[0098] [Vinyl chloride resin composition] Next, the vinyl chloride resin composition of the present invention will be described.

[0099] The vinyl chloride resin composition of the present invention is characterized in that the discoloration-inhibiting composition of the present invention is blended with a vinyl chloride resin.

[0100] The vinyl chloride resin in the vinyl chloride resin composition of the present invention is not particularly limited in terms of its polymerization method, which may be bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. Examples of vinyl chloride resins include polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride ... Examples of vinyl chloride resins include ethylene-vinyl acetate terpolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, and vinyl chloride-various vinyl ether copolymers, as well as blends thereof and other chlorine-free synthetic resins such as acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, ethylene-vinyl acetate copolymers, ethylene-ethyl (meth)acrylate copolymers, and blends, block copolymers, and graft copolymers with polyesters. These vinyl chloride resins may be mixtures of two or more types, or may be mixtures with other synthetic resins. Polyvinyl chloride is preferred as the vinyl chloride resin, as it inhibits discoloration due to amines and ultraviolet rays, and provides anti-fogging properties. Polyvinyl chloride, particularly polyvinyl chloride for powder molding, is particularly preferred.

[0101] In the vinyl chloride resin composition of the present invention, the amount of the discoloration-inhibiting composition of the present invention used is preferably 0.001 to 50 parts by mass, more preferably 0.005 to 50 parts by mass, even more preferably 0.1 to 20 parts by mass, still more preferably 0.1 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass, per 100 parts by mass of vinyl chloride resin, from the viewpoint of imparting an effect of inhibiting discoloration due to amines and UV rays to the vinyl chloride resin and from the viewpoint of obtaining anti-fogging effects. If the amount of the discoloration-inhibiting composition used is less than 0.001 part by mass, the inhibition of discoloration due to amines and UV rays may be insufficient, and even if it exceeds 50 parts by mass, the improvement in effect is small and may even have a negative impact on other performance properties.

[0102] In the vinyl chloride resin composition of the present invention, the discoloration-inhibiting composition of the present invention may be blended into the vinyl chloride resin as the stabilizer composition, or may be blended into the vinyl chloride resin separately from the stabilizer for the vinyl chloride resin and other components to be blended.

[0103] The vinyl chloride resin composition of the present invention preferably contains a plasticizer. Examples of the plasticizer include phthalate-based plasticizers such as dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate; adipate-based plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, and di(butyldiglycol) adipate; phosphate-based plasticizers such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri(isopropylphenyl)phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri(butoxyethyl)phosphate, and octyldiphenyl phosphate; ethylene glycol, diethylene Polyester-based plasticizers are those that use polyhydric alcohols such as glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, and neopentyl glycol, and dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid, and optionally a monohydric alcohol or monocarboxylic acid as a stopper; other examples include tetrahydrophthalic acid-based plasticizers, azelaic acid-based plasticizers, sebacic acid-based plasticizers, stearic acid-based plasticizers, citric acid-based plasticizers, trimellitic acid-based plasticizers, pyromellitic acid-based plasticizers, and biphenylene polycarboxylic acid-based plasticizers. These plasticizers may be used alone or in combination of two or more.

[0104] Among these plasticizers, at least one selected from the group consisting of trimellitic acid-based plasticizers, which are trimellitic acid ester compounds, and pyromellitic acid-based plasticizers, which are pyromellitic acid ester compounds, is preferred from the viewpoint of suppressing discoloration due to amines and ultraviolet rays, as well as achieving anti-fogging effects.

[0105] As the trimellitic acid ester compound or pyromellitic acid ester compound, a triester compound or tetraester compound of trimellitic acid or pyromellitic acid with a monohydric alcohol is used, respectively.

[0106] Examples of monohydric alcohols used to produce trimellitic acid triester compounds or pyromellitic acid tetraester compounds include linear or branched alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, pentyl alcohol, isopentyl alcohol, hexanol, isohexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, isononyl alcohol, decanol, isodecanol, undecanol, dodecanol, tridecanol, isotridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, henicosanol, and docosanol, as well as mixtures thereof.

[0107] In the vinyl chloride resin composition of the present invention, the content of the plasticizer is preferably 5 to 200 parts by mass, and more preferably 10 to 100 parts by mass, per 100 parts by mass of the vinyl chloride resin, from the viewpoints of suppressing discoloration due to amines and discoloration due to ultraviolet light, and obtaining anti-fogging effects.

[0108] The vinyl chloride resin composition of the present invention preferably contains one or more stabilizers for vinyl chloride resins. The stabilizers may be blended as a stabilizer composition or may be blended individually.

[0109] Furthermore, other additives that are usually used in vinyl chloride resin compositions, such as epoxy compounds, polyhydric alcohol compounds, and fillers, can be added to the vinyl chloride resin composition of the present invention.

[0110] Examples of epoxy compounds include bisphenol and novolac epoxy resins, epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, epoxidized safflower oil, epoxidized tall oil fatty acid octyl, epoxidized linseed oil fatty acid butyl, methyl, butyl, 2-ethylhexyl, or stearyl epoxy stearate, tris(epoxypropyl)isocyanurate, 3-(2-xenoxy)-1,2-epoxypropane, epoxidized polybutadiene, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl-6-methylepoxycyclohexane carboxylate, and bis(3,4-epoxycyclohexyl)adipate. One type of epoxy compound may be used alone, or two or more types may be used in combination.

[0111] Examples of polyhydric alcohol compounds include pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, neopentyl glycol, trimethylolpropane, ditrimethylolpropane, 1,3,5-tris(2-hydroxyethyl)isocyanurate, polyethylene glycol, glycerin, diglycerin, mannitol, maltitol, lactitol, sorbitol, erythritol, xylitol, xylose, sucrose, trehalose, inositol, fructose, maltose, lactose, etc. Only one type of polyhydric alcohol compound may be used, or two or more types may be used in combination.

[0112] Examples of fillers include calcium carbonate, calcium oxide, calcium hydroxide, zinc hydroxide, zinc carbonate, zinc sulfide, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, sodium aluminosilicate, hydrocalumite, aluminum silicate, magnesium silicate, calcium silicate, zeolite, activated clay, talc, clay, red iron oxide, asbestos, antimony trioxide, silica, glass beads, mica, sericite, glass flakes, asbestos, wollastonite, potassium titanate, PMF (processed mineral fiber), gypsum fiber, zonolite, MOS (magnesium hydroxide sulfate hydrate, a fibrous magnesium compound), phosphate fiber, glass fiber, carbon fiber, and aramid fiber. These fillers may be used alone or in combination of two or more.

[0113] The vinyl chloride resin composition of the present invention may further contain, as necessary, additives typically used in vinyl chloride resins, such as crosslinking agents, foaming agents, antistatic agents, antifogging agents, antiplate-out agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, antifungal agents, bactericides, metal deactivators, release agents, pigments, processing aids, solvents, etc., within the range that does not impair the effects of the present invention. These optional components may be used alone or in combination of two or more.

[0114] Examples of lubricants include hydrocarbon-based lubricants such as low molecular weight wax, paraffin wax, polyethylene wax, chlorinated hydrocarbons, and fluorocarbons; natural wax-based lubricants such as carnauba wax and candelilla wax; fatty acid-based lubricants such as higher fatty acids such as lauric acid, stearic acid, and behenic acid, or oxyfatty acids such as hydroxystearic acid; fatty amide-based lubricants such as stearylamide, laurylamide, and oleylamide, or alkylene bisfatty amides such as methylene bisstearylamide and ethylene bisstearylamide; and fatty acid monohydric alcohol ester compounds such as stearyl stearate, butyl stearate, and distearyl phthalate. Examples of lubricants include fatty acid alcohol ester lubricants such as fatty acid polyhydric alcohol ester compounds such as glycerin tristearate, sorbitan tristearate, pentaerythritol tetrastearate, dipentaerythritol hexastearate, polyglycerin polyricinoleate, and hydrogenated castor oil, and complex ester compounds of monobasic fatty acids and polybasic organic acids with polyhydric alcohols, such as dipentaerythritol adipic acid-stearic acid ester; fatty alcohol lubricants such as stearyl alcohol, lauryl alcohol, and palmityl alcohol; metal soaps; montanic acid lubricants such as partially saponified montanic acid ester; acrylic lubricants; and silicone oils. These lubricants may be used alone or in combination of two or more.

[0115] Examples of pigments include white pigments such as titanium dioxide, and blue pigments such as ultramarine blue and phthalocyanine blue.

[0116] Examples of processing aids include homopolymers or copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; copolymers of the above alkyl methacrylates with alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate; copolymers of the above alkyl methacrylates with aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; and copolymers of the above alkyl methacrylates with vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. These processing aids may be used alone or in combination of two or more.

[0117] The vinyl chloride resin composition of the present invention may further contain other additives typically used in vinyl chloride resins, such as sulfur-based antioxidants, impact modifiers, reinforcing materials, perchlorates, magnesium salts of organic acids, overbased magnesium carbonates, flame retardants, and flame retardant aids, within limits that do not impair the effects of the present invention.

[0118] Examples of sulfur-based antioxidants include dialkyl thiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid, and β-alkyl mercaptopropionic acid esters of polyols such as pentaerythritol tetra(β-dodecylmercaptopropionate). These sulfur-based antioxidants may be used alone or in combination of two or more.

[0119] Examples of impact resistance improvers include polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer rubber, methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene graft copolymer, acrylonitrile-styrene-butadiene copolymer rubber, acrylonitrile-styrene-butadiene graft copolymer, styrene-butadiene-styrene block copolymer rubber, styrene-isoprene-styrene copolymer rubber, styrene-ethylene-butylene-styrene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber (EPDM), silicone-containing acrylic rubber, silicone / acrylic composite rubber graft copolymer, silicone rubber, etc. Examples of dienes in the ethylene-propylene-diene copolymer rubber (EPDM) include 1,4-hexadiene, dicyclopentadiene, methylene norbornene, ethylidene norbornene, propenyl norbornene, etc. These impact modifiers may be used alone or in combination of two or more.

[0120] The reinforcing agent may be a fibrous, plate-like, granular, or powdery material typically used to reinforce synthetic resins. Specific examples of the reinforcing agent include inorganic fibrous reinforcing materials such as glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, sepiolite, asbestos, slag fiber, zonolite, elestadite, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, and boron fiber; polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate fiber, kenaf, ramie, cotton, and jute. Examples of suitable reinforcing materials include organic fibrous reinforcing materials such as hemp, sisal, flax, linen, silk, Manila hemp, sugarcane, wood pulp, wastepaper, recycled paper, and wool; and plate-like or granular reinforcing materials such as glass flakes, non-swelling mica, graphite, metal foil, ceramic beads, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, finely powdered silicic acid, feldspar powder, potassium titanate, silicic acid balloons, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dawsonite, and clay. These reinforcing materials may be coated or bundled with a thermoplastic resin such as ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or may be treated with a coupling agent such as an aminosilane or an epoxysilane. These reinforcing materials may be used alone or in combination.

[0121] Examples of perchlorates include metal perchlorates, ammonium perchlorate, and perchlorate-treated silicates. Metals constituting these metal salts include lithium, sodium, potassium, calcium, magnesium, strontium, barium, zinc, cadmium, lead, and aluminum. Metal perchlorates may be anhydrous or hydrated, or may be dissolved in alcohol-based or ester-based solvents such as butyl diglycol or butyl diglycol adipate, or may be dehydrated products thereof. These perchlorates may be used alone or in combination. However, in the resin composition of the present invention, the use of perchlorates is not preferred from the viewpoints of safety and the environment.

[0122] The magnesium salts of organic acids are described below: Examples of magnesium salts of organic acids include magnesium salts of organic carboxylic acids, phenols, organic phosphoric acids, and the like.

[0123] Examples of organic carboxylic acids, phenols and organic phosphoric acids include those exemplified as zinc salts of organic acids.

[0124] The magnesium salt of an organic acid may be composed of two or more organic acids. For example, in the case of a magnesium salt of a monovalent organic acid, the same organic acid may constitute the anion site and form a salt with the divalent magnesium that constitutes the cation site, or two different monovalent organic acids may constitute the anion site and form a salt with the divalent magnesium that constitutes the cation site.

[0125] The magnesium salt of an organic acid may be used alone or in combination of two or more kinds. The magnesium salt of an organic acid may be an acidic salt, a neutral salt, or a basic salt.

[0126] This section explains overbased magnesium carbonate. Overbased magnesium carbonate is a liquid overbased carboxylate / carbonate complex of magnesium. Unlike a simple mixture of magnesium, a carboxylate, and magnesium carbonate, this complex is formed through some kind of interaction. It has the characteristic of exhibiting a homogeneous liquid state in organic solvents despite its high metal content. This complex is composed of magnesium carboxylate, magnesium carbonate, and a complex salt of magnesium carboxylate and carbonate. The magnesium carbonate is at the center, surrounded by the carboxylate and complex salt of magnesium carboxylate and carbonate, forming a micelle-like structure that allows it to exhibit a homogeneous liquid state in organic solvents.

[0127] Liquid overbased carboxylate / carbonate complexes of magnesium can be prepared in the same manner as liquid overbased carboxylate / carbonate complexes of barium, or commercially available complexes can be used as is.

[0128] These overbased magnesium carbonates may be used alone or in combination of two or more.

[0129] Examples of flame retardants and flame retardant aids include triazine ring-containing compounds, metal hydroxides, other inorganic phosphorus, halogen-based flame retardants, silicone-based flame retardants, phosphate ester-based flame retardants, condensed phosphate ester-based flame retardants, intumescent-based flame retardants, antimony oxides such as antimony trioxide, other inorganic flame retardant aids, and organic flame retardant aids.

[0130] Examples of triazine ring-containing compounds include melamine, ammeline, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylenediguanamine, norbornenediguanamine, methylenediguanamine, ethylenedimelamine, trimethylenedimelamine, tetramethylenedimelamine, hexamethylenedimelamine, and 1,3-hexylenedimelamine.

[0131] Examples of metal hydroxides include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, and Kismer 5A (magnesium hydroxide: manufactured by Kyowa Chemical Industry Co., Ltd.).

[0132] Examples of phosphate ester-based flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trixylenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, trisisopropylphenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis-(t-butylphenyl)phenyl phosphate, tris-(t-butylphenyl)phosphate, isopropylphenyl diphenyl phosphate, bis-(isopropylphenyl)diphenyl phosphate, and tris-(isopropylphenyl)phosphate.

[0133] Examples of condensed phosphate ester flame retardants include 1,3-phenylene bis(diphenyl phosphate), 1,3-phenylene bis(dixylenyl phosphate), bisphenol A bis(diphenyl phosphate), etc. Examples of intumescent flame retardants include ammonium salts and amine salts of (poly)phosphoric acids, such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, ammonium pyrophosphate, melamine pyrophosphate, and piperazine pyrophosphate.

[0134] Other inorganic flame retardant aids include, for example, inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, and talc, and surface-treated products thereof. For example, various commercially available products such as TIPAQUE R-680 (titanium oxide: manufactured by Ishihara Sangyo Kaisha Ltd.) and Kyowamag 150 (magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.) can be used.

[0135] These flame retardants and flame retardant auxiliaries may be used alone or in combination of two or more.

[0136] The vinyl chloride resin composition of the present invention may contain a lead-based stabilizer, a cadmium-based stabilizer, or a tin-based stabilizer, but it is preferable not to contain them in view of toxicity and adverse effects on the environment.

[0137] The vinyl chloride resin composition of the present invention may further contain a stabilizing agent typically used in vinyl chloride resins, provided that the effects of the present invention are not impaired. Examples of such stabilizing agents include diphenylthiourea, anilinodithiotriazine, melamine, benzoic acid, cinnamic acid, and p-tert-butylbenzoic acid.

[0138] The vinyl chloride resin composition of the present invention can be prepared by stirring and mixing the discoloration-inhibiting composition of the present invention, a vinyl chloride resin, and, if necessary, a stabilizer, a plasticizer, and various additives, using a stirrer such as a mortar mixer, a Henschel mixer, a Banbury mixer, or a ribbon blender, thereby obtaining a mixed powder of the vinyl chloride resin composition.

[0139] Furthermore, a pellet-shaped vinyl chloride resin composition can also be obtained by melt-molding the discoloration-inhibiting composition of the present invention, a vinyl chloride resin, and, if necessary, a stabilizer, a plasticizer, and various additives, using a kneader such as a conical twin-screw extruder, a parallel twin-screw extruder, a single-screw extruder, a co-kneader-type kneader, or a roll kneader.

[0140] Alternatively, a paste-like vinyl chloride resin composition can be obtained by uniformly mixing the discoloration-inhibiting composition of the present invention, a paste-like vinyl chloride resin, and, if necessary, a stabilizer, a plasticizer, and various additives, using a mixer such as a pony mixer, a butterfly mixer, a planetary mixer, a ribbon blender, a kneader, a dissolver, a twin-screw mixer, a Henschel mixer, or a three-roll mill, and, if necessary, degassing the mixture under reduced pressure.

[0141] [Vinyl chloride resin molded body] Next, the vinyl chloride resin molded article of the present invention will be described.

[0142] The vinyl chloride resin molded article of the present invention can be obtained by melt-molding the vinyl chloride resin composition of the present invention (in the form of blended powder or pellets) into a desired shape using a conventionally known method such as vacuum molding, compression molding, extrusion molding, injection molding, calendar molding, press molding, blow molding, or powder molding.

[0143] On the other hand, a vinyl chloride resin composition in paste form can be molded into a desired shape by molding using a conventionally known method such as spread molding, dipping molding, gravure molding, slush molding, or screen processing.

[0144] In the present invention, from the viewpoint of obtaining the effects of inhibiting discoloration due to amines and ultraviolet rays, as well as fogging resistance, a molded article obtained by powder molding such as powder slush molding, fluidized bed molding, or powder rotational molding using the vinyl chloride resin composition of the present invention is preferred, and among these, a molded article obtained by powder slush molding is particularly preferred. Thus, the vinyl chloride resin composition of the present invention is suitable for powder molding.

[0145] The shape of the molded product is not particularly limited, but examples thereof include rod-like, sheet-like, film-like, plate-like, cylindrical, circular, elliptical, star-like, and polygonal shapes.

[0146] [Laminate] The vinyl chloride resin molded article of the present invention is useful when it is laminated with a molded article using polyurethane, particularly a polyurethane foam molded article, in order to obtain the effects of inhibiting discoloration due to amines and ultraviolet rays, as well as fogging resistance.

[0147] Molded articles using polyurethane, particularly polyurethane foam molded articles, may be any conventionally known article and may be obtained, for example, as follows: That is, raw materials for polyurethane foam molded articles containing polyols, polyisocyanates, a blowing agent, and a catalyst are reacted, foamed, and cured.

[0148] As the polyol, a polyether polyol or a polyester polyol is used. As the polyether polyol, polypropylene glycol, polytetramethylene glycol, polyether polyols formed by addition polymerization of propylene oxide and ethylene oxide with a polyhydric alcohol, modified products thereof, etc. are used. As the polyhydric alcohol, glycerin, dipropylene glycol, etc. are mentioned. As the polyester polyol, condensation polyester polyols obtained by reacting polycarboxylic acids such as adipic acid and phthalic acid with polyols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin, as well as lactone polyester polyols and polycarbonate polyols are used.

[0149] Polyisocyanates are compounds having a plurality of isocyanate groups, and specific examples thereof include tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate, xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), and modified products thereof.

[0150] The foaming agent is used to foam the polyurethane resin to form a polyurethane foam molded article, and examples of the foaming agent include water, pentane, cyclopentane, hexane, cyclohexane, dichloromethane, and carbon dioxide gas.

[0151] The catalyst is used to promote the urethane reaction between polyols and polyisocyanates. Examples of the catalyst include triethylenediamine, dimethylethanolamine, N,N',N'-trimethylaminoethylpiperazine, triphenylamine, triethylamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N-methylmorpholine, N-ethylmorpholine, N-acetylmorpholine, N-octylmorpholine, N-phenylmorpholine, N-hydroxylethylmorpholine, N-hydroxylmethylmorpholine, 4,4'-dithiodimorpholine, dimethylpiperazine, and the like. Preferred amine catalysts are tertiary amines such as piperazine, N,N,N',N'-tetramethylpropanediamine, trimethylaminoethylpiperazine, N,N-dimethylethanolamine, dimethylhexadecylamine, 1-(2-ethylhexenyl)piperazine, tri-n-octylamine, trimethylamine, N,N'-dimethylbenzylamine, triethanolamine, 1,2,4-trimethylpiperazine, N-methyldicyclohexylamine, and methyldicyclohexylamine.

[0152] The present invention is preferable because it is excellent in imparting the effect of inhibiting discoloration of vinyl chloride resins caused by the amine catalyst that promotes the urethane reaction.

[0153] The vinyl chloride resin molded article of the present invention and the laminate of the vinyl chloride resin molded article and the polyurethane foam molded article are useful and preferable as automotive interior materials because they are effective in inhibiting discoloration due to amines and ultraviolet rays, as well as providing anti-fogging properties.

[0154] [Automotive interior materials] The automotive interior material of the present invention may comprise the vinyl chloride resin molded article of the present invention or the laminate of the present invention. In particular, the automotive interior material of the present invention preferably comprises a surface layer made of a laminate composed of a vinyl chloride resin molded article and a polyurethane foam molded article, and a substrate layer for maintaining the structure. Known substrate layers, such as polypropylene resin molded articles and ABS resin (acrylonitrile-butadiene-styrene copolymer resin) molded articles, are used as the substrate layer.

[0155] Examples of automotive interior materials include instrument panels, door trims, console boxes, glove boxes, pillar trims, dashboards, trunk trims, seats, ceiling materials, automatic transmission shifters, armrests, headrests, floor carpets, wire harnesses, various moldings, sashes, sealing materials, weather strips, gaskets, undercoat materials, etc. In particular, automotive interior materials using the laminate of the present invention are very useful and preferable as, for example, instrument panels, door trims, seats, ceiling materials, etc.

[0156] [Method to prevent discoloration] The discoloration suppression method of the present invention is a method for suppressing discoloration of an automobile interior material comprising a laminate of a vinyl chloride resin molded body and a polyurethane foam molded body, in which the discoloration suppression composition for vinyl chloride resin of the present invention is blended with a vinyl chloride resin that is the raw material resin for the vinyl chloride resin molded body. [Example]

[0157] The present invention will be specifically described below using examples, but the present invention is not limited to the following examples.

[0158] [Examples 1 to 8, Comparative Examples 1 to 3] 100 parts by mass of vinyl chloride resin (TK-1300 (average degree of polymerization 1300) manufactured by Shin-Etsu Chemical Co., Ltd.), 70 parts by mass of Adeka Cizer C-8L (trimellitic acid-based plasticizer, manufactured by ADEKA Corporation), 5 parts by mass of epoxidized soybean oil (epoxy compound), 0.2 parts by mass of Adekastab LS-12 (lubricant, manufactured by ADEKA Corporation), 0.3 parts by mass of zinc stearate (stabilizer, zinc salt of organic acid), 1.04 parts by mass of Mizuka Riser DS (inorganic auxiliary, zeolite, manufactured by Mizusawa Industrial Chemicals Co., Ltd.), 0.21 parts by mass of dibenzoylmethane (β-diketone compound), and further a discoloration-inhibiting composition having the composition shown in Table 1 were mixed in the amounts (parts by mass) shown in Table 1 to obtain the vinyl chloride resin compositions of each example. The zinc salt of 2-mercaptothiazole used as component (A) was a zinc salt of 2-mercaptothiazole having the structure represented by the following formula (1): The ultraviolet absorbers used as component (B) were B-1 to B-4 shown below.

[0159] Component (A) TIFF0007811102000002.tif33153

[0160] (B) Component B-1: [2-hydroxy-4-(octyloxy)phenyl](phenyl)methanone (benzophenone-based ultraviolet absorber, Adeka Stab 1413, manufactured by ADEKA Corporation) B-2: 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (benzotriazole-based ultraviolet absorber, Adeka STAB LA-29, manufactured by ADEKA Corporation) B-3: 2-(2H-benzotriazol-2-yl)-p-cresol (benzotriazole-based ultraviolet absorber, Adeka STAB LA-32, manufactured by ADEKA Corporation) B-4: 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol (benzotriazole-based ultraviolet absorber, Adeka STAB LA-36, manufactured by ADEKA Corporation)

[0161] Next, a sheet was produced by powder slush molding. That is, the obtained vinyl chloride resin composition was heated to 110°C in a Henschel mixer, then cooled to 50°C and dried up. The obtained dry-up compound was sprinkled onto a textured mold heated to a surface temperature of 250°C and left to melt for 15 seconds. After shaking off the excess compound, the mold was placed in an oven set to 250°C and left to stand for 45 seconds. The mold was removed from the oven and cooled with water to obtain a vinyl chloride resin sheet with a thickness of 1 mm.

[0162] A 10 mm thick polyurethane foam backing was applied to the obtained vinyl chloride resin sheet to prepare a laminate. The obtained laminate was subjected to the following "amine resistance test" and "ultraviolet light resistance test." The results are shown in Table 1. A sample containing no discoloration-inhibiting composition was designated Comparative Example 1 and evaluated in the same manner as in each Example. Furthermore, a sample containing no component (B) of the discoloration-inhibiting composition was designated Comparative Example 2, and a sample containing no component (A) was designated Comparative Example 3, both of which were evaluated in the same manner as in each Example. The results are shown in Table 1.

[0163] The vinyl chloride resin sheet obtained was then subjected to the following fogging resistance test. The results are shown in Table 1. A sample containing no discoloration-inhibiting composition was designated Comparative Example 1 and evaluated in the same manner as in each of the Examples. Furthermore, a sample containing no component (B) of the discoloration-inhibiting composition was designated Comparative Example 2, and a sample containing no component (A) was designated Comparative Example 3, both of which were evaluated in the same manner as in each of the Examples. The results are shown in Table 1.

[0164] <Amine resistance test> First, the yellowness index of the obtained vinyl chloride resin sheet was measured. Next, the obtained laminate was placed in an oven at 115°C for 200 hours, and then the vinyl chloride resin sheet and the polyurethane foam were separated. The yellowness index of the vinyl chloride resin sheet was measured to determine the color difference (ΔE). The smaller the value, the better the amine resistance. The yellowness index was measured in accordance with JIS K7373.

[0165] <UV resistance test> The resulting laminate was subjected to an accelerated UV resistance test for 5 days (120 hours) under the following test conditions using a metal weather tester (model KU-R5NCI, manufactured by Daipla Wintes Co., Ltd.). After 1 day, 3 days, and 5 days, the coloration state of the laminate was visually inspected from the vinyl chloride resin sheet side and rated on a 10-point scale from 1 to 10. A rating of 1 indicates no coloration and the best UV resistance, while an increase in the number indicates coloration and poor UV resistance, with a rating of 10 indicating the poorest UV resistance.

[0166] (Test conditions) Light source: Water-cooled metal halide lamp Irradiance: 75mW / cm 2 Irradiation conditions: Light only, BP 63℃, humidity 50%RH, no rain.

[0167] <Fogging resistance test> The obtained vinyl chloride resin sheet was cut into 50 mm x 50 mm pieces, placed in a 1-liter flask, covered with a glass plate, and heated in an oil bath maintained at 100°C. After heating for 3 hours, the stains on the glass plate were visually observed and rated on a 5-point scale from 1 to 5. A rating of 1 indicates no fogging and the best fogging resistance, with increasing numbers indicating worsening fogging, and a rating of 5 indicating the worst fogging resistance.

[0168] [Table 1]

[0169] The results shown in Table 1 clearly show that the discoloration-inhibiting composition of the present invention exhibits excellent effects in inhibiting discoloration of vinyl chloride resins caused by amines and by ultraviolet rays, and also has excellent fogging resistance.

Claims

1. A composition comprising, as component (A), 100 parts by mass of a zinc salt of 2-mercaptobenzothiazole, and as component (B), 10.0 to 400 parts by mass of one or more selected from the group consisting of ultraviolet absorbers; A discoloration-inhibiting composition for vinyl chloride resins, wherein the ultraviolet absorber of component (B) is at least one selected from the group consisting of benzotriazole-based ultraviolet absorbers, which are 2-(2-hydroxyphenyl)benzotriazoles, triazine-based ultraviolet absorbers, and benzophenone-based ultraviolet absorbers.

2. 2. The discoloration-inhibiting composition for vinyl chloride resins according to claim 1, which is used for automobile interior materials.

3. 3. The discoloration-inhibiting composition for vinyl chloride resin according to claim 2, wherein the automobile interior material is a laminate of a vinyl chloride resin molded article and a polyurethane foam molded article.

4. A stabilizer composition for vinyl chloride resins, comprising one or more stabilizers for vinyl chloride resins and the discoloration-inhibiting composition for vinyl chloride resins according to any one of claims 1 to 3.

5. A vinyl chloride resin composition comprising a vinyl chloride resin and the discoloration-inhibiting composition for vinyl chloride resins according to any one of claims 1 to 3.

6. 6. The vinyl chloride resin composition according to claim 5, wherein the content of the discoloration-inhibiting composition for vinyl chloride resin is 0.001 to 50 parts by mass per 100 parts by mass of the vinyl chloride resin.

7. 7. The vinyl chloride resin composition according to claim 5, which is for powder molding.

8. A vinyl chloride resin molded article obtained from the vinyl chloride resin composition according to any one of claims 5 to 7.

9. A laminate of a vinyl chloride resin molded body and a polyurethane foam molded body, A laminate, wherein the vinyl chloride resin molded article is obtained from the vinyl chloride resin composition according to any one of claims 5 to 7.

10. An automobile interior material comprising the vinyl chloride resin molded article according to claim 8.

11. An automobile interior material comprising the laminate according to claim 9.

12. A method for inhibiting discoloration of an automobile interior material including a laminate of a vinyl chloride resin molded product and a polyurethane foam molded product, comprising: A method for inhibiting discoloration, comprising blending the discoloration inhibiting composition for vinyl chloride resin according to any one of claims 1 to 3 with vinyl chloride resin, which is a raw material resin for the vinyl chloride resin molded article.

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