JP3511219B2 - Vinyl chloride resin composition for vehicles - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition for vehicles, and more particularly to a vehicle suitable for automobile interior materials having improved thermal stability, heat aging resistance, weather resistance and fogging resistance. The present invention relates to a vinyl chloride resin composition.

[0002]

2. Description of the Related Art Vinyl chloride resins have excellent physical properties such as mechanical strength, chemical resistance, and weather resistance, and are relatively inexpensive. Therefore, they are covering materials for automobile interiors. For this purpose, semi-hard or soft vinyl chloride resin is often used.

However, in recent years, as the thickness has been reduced for cost reduction and the required performance has been upgraded, it has been desired to improve not only processing stability but also heat aging characteristics during use, light resistance characteristics and the like.

Further, the vinyl chloride resin covering material may be lined with urethane in order to give the interior material a soft feeling, and this adversely affects the stability of the vinyl chloride resin. There is a strong demand for improvement.

In recent years, in covering materials such as crash pads, armrests, headrests, consoles, meter covers, door trims, etc., which are used as interior materials for automobiles, they are lightweight and excellent in softness, and also have a high-grade skin-grain pattern or stitch pattern. Those that have been subjected to such things are required even more.

Conventionally, as these covering materials, vacuum molding of a soft sheet mainly composed of vinyl chloride resin and ABS resin, rotational molding of a sol mainly composed of vinyl chloride resin for paste and plasticizer, or Slush moldings (hereinafter referred to as "sol moldings") have been used.
However, although the above-mentioned vacuum-molded product has achieved its purpose in terms of weight reduction, it lacks in soft feeling and can only provide a hard feeling, and further has a high-class skin grain pattern or stitch pattern. It was difficult to shape the applied complex shaped one. Also,
The above vacuum-molded product has a large residual strain at the time of molding, and has a drawback that the molded product is likely to crack when used for a long time.

On the other hand, the above sol molded product has a soft feeling, but its gelation temperature is low, so that it melts quickly in the metal, and phenomena such as flow marks, lips or stringing of the sol occur. It has drawbacks such as lack of smoothness, it takes too long to discharge the sol from the mold, and the covering material becomes thick. Also,
In the case of sol molding, it is difficult to clean the tank and piping when changing colors, and there is a problem that it cannot be stored for a long time because the viscosity changes with time.

As a method for solving these drawbacks and problems, powder molding has recently been in the limelight. This powder molding method generally includes a fluidized dipping method, an electrostatic coating method, a powder spraying method, a powder rotational molding method, or a powder slush molding method. Particularly, for the covering material for automobile interior materials, the powder rotational molding method is used. Alternatively, the powder slush molding method is suitable.

In the powder rotation molding method or the powder slush molding method, a mold at a temperature of 180 ° C. or higher is integrated with a powder supply box and rotated or rocked or jetted to weld the powder to the inner surface of the mold. Then, the unfused powder is automatically or forcibly recovered in the powder supply box.

As a method for heating the die used for the powder molded article, there are a gas heating furnace method, a heat medium oil circulation method, a dipping method in heat medium oil or heat fluidized sand, a high frequency induction heating method and the like. .

The powder composition used in the above-mentioned powder molding method is excellent in thermal stability as well as being promptly gelled in a mold because the processing method completes the processing in a short time due to high temperature. In addition, it is required to have excellent mold release property and low mold contamination.

Further, when it is used as an interior material for automobiles, it may be exposed to relatively high temperatures, and in particular, when it is exposed to the hot sun of midsummer, it may rise to nearly 100 ° C. , Causes defects such as coloring (heat aging). In order to solve this, metal salts of perchloric acid and the like have been used.

For example, JP-A-62-270645 and JP-A-64-65157 propose to add hydrotalcite-treated product of perchloric acid to vinyl chloride resin for powder molding. JP-A-4-359949 proposes to add hydrotalcite or zeolite, calcium oxide and a halogen oxyacid salt or a metal salt thereof to a vinyl chloride resin for powder molding, and JP-A-5-17648. In the publication, it is proposed to add a metal salt of perchloric acid, a metal compound of strong inorganic acid, zeolite and hydrotalcite to the vinyl chloride resin for powder molding. The situation has not been resolved.

Further, Japanese Patent Application Laid-Open No. 53-11948 proposes to add an organic acid metal salt and halogen oxyacid salts together, and Japanese Patent Application Laid-Open No. 58-122951 discloses perchloric acid. It has been proposed to add a salt, an organic acid salt and a hydrotalcite compound to a chlorine-containing resin, and JP-A-59-140261 proposes perchloric acid-treated hydrotalcites. 61-
JP-A-34042 proposes to add a zinc salt of an organic acid, zeolite and a metal salt of halogenoxygen acid to a chlorine-containing resin, and JP-A-4-136054 discloses an alkali metal salt of perchlorate and an alkali salt of perchlorate. It has been proposed to add an earth metal salt to a chlorine-containing resin in combination, and see Japanese Patent Application Laid-Open No. 4-1.
Japanese Patent No. 73854 discloses that a metal salt of perchloric acid and a hydrotalcite treated with perchloric acid or a silicate treated with perchloric acid are used in combination with a chlorine-containing resin. Has proposed to add a zinc compound, a phosphite ester, a perchloric acid-containing hydrotalcite and a piperidine compound together to a chlorine-containing resin, but no sufficient effect is obtained yet.

In addition to these physical properties, vinyl chloride resin additives such as plasticizers and stabilizers are volatilized from the resin, causing a phenomenon (fogging) of adhering to vehicle windows and causing fogging. This improvement is also required because the cloudiness of car windows has a significant impact on safety.

Further, in Japanese Patent Laid-Open No. 2-86631,
A molded body composed of a urethane foam containing a phosphoric acid ester and a chlorine-containing resin containing a trimellitic acid ester has been proposed. In JP-A-2-138355 and JP-A-2-209941, trimellitic acid is disclosed. It has been proposed to add an ester plasticizer to a chlorine-containing resin for powder molding. JP-A-6-279642 discloses a powder slush containing suspension-polymerized vinyl chloride and pyromellitic acid ester. A chlorine-containing resin composition for molding has been proposed, but one having satisfactory performance has not yet been obtained.

Therefore, the object of the present invention is to provide excellent heat stability, heat aging resistance, and fogging resistance, and even when it is used for powder molding, gelation, demolding, mold contamination, etc. Another object of the present invention is to provide a vinyl chloride resin composition for vehicles that has excellent moldability.

[0018]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that vinyl chloride resins, compounds having a specific zeolite crystal structure or hydrotalcite compounds, perchlorates, specific cyclic organic compounds. It has been found that a vinyl chloride resin composition containing a phosphite compound and a trimellitic acid ester compound or a pyromellitic acid ester compound can achieve the above object.

The present invention has been made on the basis of the above-mentioned findings, and at least one kind selected from the group consisting of 100 parts by weight of vinyl chloride resin, (a) an aluminosilicate having a zeolite crystal structure and a hydrotalcite compound.
001 to 10 parts by weight, at least one selected from the group consisting of (b) metal salt of perchloric acid, ammonium salt of perchloric acid and hydrotalcite treated with perchloric acid 0.001 to 1
0 parts by weight, (c) the following [Chemical Formula 2] (the same as the above [Chemical Formula 1])
0.001 to 10 parts by weight of an organic phosphite compound represented by the general formula (I) and (d)
It is intended to provide a vinyl chloride resin composition for a vehicle, which contains 5 to 200 parts by weight of at least one selected from the group consisting of a trimellitic acid ester compound and a pyromellitic acid ester compound.

[0020]

[Chemical 2]

The vinyl chloride resin composition for vehicles of the present invention will be described in detail below.

The component (a) used in the present invention is at least one selected from the group consisting of aluminosilicates having a zeolite crystal structure (hereinafter referred to as "zeolite compound") and hydrotalcite compounds.

The above-mentioned zeolite compound is an aluminosilicate of an alkali or alkaline earth metal having a unique three-dimensional zeolite crystal structure, of which typical examples are A-type, X-type, Y-type and P-type zeolites. Monodenite, analsite, aluminosilicate of sodalite group, clinobutilite, erionite, chabazite, etc. can be mentioned, and water-containing substances or water of crystallization having water of crystallization of these zeolite compounds (so-called zeolite water) can be removed. Any of the above anhydrides may be used, and those having a particle size of 0.1 to 50 μm can be used, and those having a particle size of 0.5 to 10 μm are particularly preferable.

The hydrotalcite compound is a carbonate double salt compound of magnesium and / or zinc and aluminum, preferably the following general formula (II)
Is a compound represented by.

Mg _x1 Zn _x2 Al ₂ (OH) _{2 (X1 + X2) + 4} · CO ₃ · mH ₂ O (II) (wherein x1 and x2 are numbers satisfying the conditions represented by the following formulas, respectively) And m is a real number, 0 ≦ x2 / x1 <
10,2 ≦ x1 + x2 <20)

The above-mentioned hydrotalcite compound is
It may be a natural product or a synthetic product. As a method of synthesizing the above-mentioned synthetic product, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, and Japanese Patent Publication No.
Known methods such as those described in JP-A-9129 and JP-A-61-174270 can be exemplified. Further, in the present invention, the hydrotalcite compound can be used without being limited by the crystal structure, crystal particle system, presence or absence of crystal water, and the amount thereof.

The above-mentioned hydrotalcite compound is
The surface is coated with a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an oleic acid alkali metal salt, an organic sulfonic acid metal salt such as a dodecylbenzenesulfonic acid alkali metal salt, a higher fatty acid amide, a higher fatty acid ester or wax. Things can also be used.

The content of the component (a) (the zeolite compound and / or the hydrotalcite compound) is 0.00 based on 100 parts by weight of the vinyl chloride resin.
It is 1 to 10 parts by weight, preferably 0.05 to 5 parts by weight. If the content is less than 0.001 part by weight, the effect is almost nonexistent, and if it exceeds 10 parts by weight, the effect of increasing the amount is not exerted, and rather, defects such as large coloring occur.

The component (b) used in the present invention is at least one selected from the group consisting of metal salts of perchloric acid, ammonium salts of perchloric acid and hydrotalcite treated with perchloric acid.

Examples of the metal constituting the metal salt of perchlorate include lithium, sodium, potassium, calcium, magnesium, strontium, barium, zinc, cadmium, lead and aluminum. The metal salt of perchloric acid may be an anhydrous salt or a hydrated salt, or may be a salt thereof dissolved in an alcohol solvent or an ester solvent such as butyl diglycol or butyl diglycol adipate, or a dehydrated product thereof.

The ammonium perchlorate salt may be an anhydrous salt or a hydrous salt.

The perchloric acid-treated hydrotalcite is a perchloric acid-modified product obtained by substituting perchloric acid for part or all of the carbonic acid in the hydrotalcite compound of component (a).

The surface of the perchloric acid-treated hydrotalcite is a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, or an organic sulfonic acid metal such as an alkali metal dodecylbenzenesulfonate. Those coated with salt, higher fatty acid amide, higher fatty acid ester or wax can also be used.

The above-mentioned perchloric acid-treated hydrotalcite is
For example, hydrotalcite can be easily produced by adding hydrotalcite to a dilute aqueous solution of perchloric acid, stirring the mixture, and then, if necessary, filtering, dehydrating, or drying.
In this case, the molar ratio of the hydrotalcite to the perchloric acid can be set arbitrarily, but generally, the ratio is 0.1 to 2 mol of perchloric acid per 1 mol of hydrotalcite. It is preferable to use.

The content of the component (b) (metal salt of perchlorate, ammonium salt of perchlorate and / or hydrotalcite treated with perchloric acid) is 0.001 to 100 parts by weight of vinyl chloride resin. 10 parts by weight, preferably 0.0
1 to 5 parts by weight. If the content is less than 0.001 part by weight, the effect is hardly seen, and if it exceeds 10 parts by weight, the effect is not improved, and even heat resistance, colorability and the like are adversely affected.

The component (c) used in the present invention is at least one kind of the organic phosphite compound represented by the general formula (I).

In the above general formula (I), the alkyl group having 1 to 9 carbon atoms represented by R ₁ includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, Groups such as tertiary amyl, hexyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, and the like,
As the alkyl group having 1 to 4 carbon atoms represented by R ₂ ,
Examples include groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl and the like.

The monovalent group having 1 to 30 carbon atoms represented by R ₃ includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,
Tert-butyl, amyl, tert-amyl, hexyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, tert-nonyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, terracosyl, Alkyl group such as triacontyl, alkyl group having an ether bond such as methoxyethyl, butoxyethyl, methoxyethoxyethyl, butoxyethoxyethyl, phenyl,
Examples thereof include aryl groups such as tolyl, xylyl, 4-tert-butylphenyl, 4-octylphenyl, 4-nonylphenyl, and 2,4-di-tert-butylphenyl, which are divalent groups having 2 to 20 carbon atoms. Is ethylene glycol, diethylene glycol, triethylene glycol, 1,2
-Propanediol, 1,3-propanediol, 2-
Methyl-1,3-propanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 3,9-bis (1,1-dimethyl-2) -Hydroxyethyl) -2,
An example is a residue obtained by removing two hydroxyl groups from glycols such as 4,8,10-tetraoxaspiro [5.5] undecane. Triethanolamine is a trivalent group having 3 to 20 carbon atoms. , Triisopropanolamine, glycerin trimethylolpropane, tris (2-hydroxyethyl) isocyanerate, and other polyhydric alcohols with three hydroxyl groups removed.

Therefore, the organic phosphite compound which is the above-mentioned component (c) is, for example,
Examples thereof include compounds No. 1 to No. 9 of [Chemical formula 11].

[0040]

[Chemical 3]

[0041]

[Chemical 4]

[0042]

[Chemical 5]

[0043]

[Chemical 6]

[0044]

[Chemical 7]

[0045]

[Chemical 8]

[0046]

[Chemical 9]

[0047]

[Chemical 10]

[0048]

[Chemical 11]

The content of the component (c) (organic phosphite ester compound) is 0.001 to 10 parts by weight, preferably 0.0 to 100 parts by weight of the vinyl chloride resin.
It is 1 to 1 part by weight. When the content is less than 0.001 part by weight, the effect of improving thermal stability, heat aging resistance, etc. is small,
If it exceeds 10 parts by weight, the fogging resistance may be reduced.

In the present invention, the zeolite compound and / or the hydrotalcite compound as the component (a), the perchlorates as the component (b), and the component (c).
The organic phosphite compound as a component is used as a stabilizer, and can be blended in the vinyl chloride resin separately, but they can be mixed and used. It can also be used as a so-called composite stabilizer containing other stabilizer components depending on the above.

The component (d) used in the present invention is at least one selected from the group consisting of trimellitic acid ester compounds and pyromellitic acid ester compounds.

As the trimellitic acid ester compound or the pyromellitic acid ester compound, a triester compound or a tetraester compound of trimellitic acid or pyromellitic acid and a monohydric alcohol is used, respectively.

Examples of the monohydric alcohol used for producing the trimellitic acid triester compound or the pyromellitic acid tetraester compound include, for example, methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, Dibutyl alcohol, tertiary butyl alcohol, pentyl alcohol, isopentyl alcohol, hexanol, isohexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, isononyl alcohol, decanol, isodecanol, undecanol, dodecanol, tridecanol, isotrideca. Nole, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, Kosanoru, Hen'ikosanoru, linear or alcohols and mixtures of these branches, such as docosanol and the like.

Component (d) (trimellitic acid ester compound and / or pyromellitic acid ester compound)
The content of 5 is 5 parts with respect to 100 parts by weight of vinyl chloride resin.
˜200 parts by weight, preferably 10 to 100 parts by weight. If the content is less than 5 parts by weight, the effect of improving the cold resistance is small, and if it exceeds 200 parts by weight, the fogging resistance is lowered, and plate-out, bleeding, etc. may occur.

The vinyl chloride resin used in the present invention is not particularly limited to the polymerization method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization, and examples thereof include polyvinyl chloride and 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-acrylonitryl copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer , Vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, chloride Vinyl chloride resins such as nyl-maleic acid ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-various vinyl ether copolymers, and their blends or others. Blends with chlorine-free synthetic resins such as acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, ethylene-vinyl acetate copolymers, ethylene-ethyl (meth) acrylate copolymers, polyesters, etc. Examples thereof include products, block copolymers, graft copolymers and the like.

In the composition of the present invention, other additives usually used in vinyl chloride resin compositions such as metal salts of organic carboxylic acids, phenols and organic phosphoric acids, epoxy compounds, β-diketos. Compounds, polyhydric alcohols, phosphorus-based antioxidants other than the organic phosphite compounds of the general formula (I), phenol-based and sulfur-based antioxidants, ultraviolet absorbers, hindered amine-based light stabilizers, Other inorganic metal compounds and the like can be added.

Examples of the metal which constitutes the metal salt of the above organic carboxylic acid, phenols and organic phosphoric acids include lithium, potassium, sodium, calcium, barium, magnesium, strontium, zinc, tin, cesium, aluminum or organic tin. can give.

Examples of the organic carboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid,
Enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, neodecanoic acid, capric acid, undecanoic acid,
Lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid,
Monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-ditert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cuminic acid, n-propylbenzoic acid Acid, aminobenzoic acid, N, N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid, p-tertiary octylsalicylic acid, elaidic acid, oleic acid, linoleic acid, linoleic acid, thioglycolic acid, mercaptopropionic acid, octylmercapto Monovalent carboxylic acids such as propionic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, Divalent carboxylic acids such as fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, and thiodipropionic acid or their monoesters or monoamide compounds; butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid And di- or triester compounds of trivalent or tetravalent carboxylic acids such as melophanoic acid and pyromellitic acid.

Examples of the above-mentioned phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol. , Isooctylphenol, 2-ethylhexylphenol, tertiary nonylphenol, decylphenol, tertiary octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisofuxylphenol, methyl tertiary octylphenol, etc. To be

Examples of the above-mentioned 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, phosphon. Examples thereof include acid stearyl esters.

The metal salts of the above organic carboxylic acids, phenols and organic phosphoric acids are acid salts, neutral salts, basic salts or bases of basic salts partially or wholly neutralized with carbonic acid. It may be a basic complex.

The amount of the metal salt of the above-mentioned organic carboxylic acid, phenol or organic phosphoric acid added is preferably 0.01 to 10 parts by weight, more preferably 0.05, based on 100 parts by weight of the vinyl chloride resin. ~ 5 parts by weight.

Examples of the epoxy compound include bisphenol type and novolac type epoxy resins, epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, and epoxidized. Safflower oil, epoxidized tall oil fatty acid octyl, epoxidized linseed oil fatty acid butyl, epoxy methyl stearate, -butyl, -2-ethylhexyl or -stearyl, tris (epoxypropyl) isocyanurate, 3- (2-xenoxy)- 1,
2-epoxypropane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) ) Examples include adipate.

The amount of the epoxy compound added is preferably 0.01 to 100 parts by weight of the vinyl chloride resin.
20 parts by weight, more preferably 0.05 to 10 parts by weight.

Examples of the above β-diketo compound include:
Examples thereof include dehydroacetic acid, dibenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, and the metal salts thereof are also useful.

Examples of the polyhydric alcohol include pentaerythritol, dipentaerythritol, sorbitol, mannitol, trimethylolpropane, ditrimethylolpropane, pentaerythritol or a partial ester of stearic acid of dipentaerythritol, bis (dipentaethathritol). ) Adipate, glycerin, diglycerin, tris (2-hydroxyethyl) isocyanurate and the like can be mentioned.

Examples of the phosphorus-based antioxidant include, for example,
Diphenyldecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tributyl phosphite, dilauryl acid phosphite, dibutyl acid phosphite, tris (di Nonylphenyl) phosphite, trilauryltrithiophosphite, trilaurylphosphite, bis (neopentylglycol) -1,4-cyclohexanedimethylphosphite, distearylpentaerythritol diphosphite, bis (2,4-ditertiary) Butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diphenylacid phosphite, tetrade Le-1,1,3-tris (2 '
-Methyl-5'-tert-butyl-4'-hydroxyphenyl) butanediphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidenediphenyldiphosphite, tris (4-hydroxy-2, 5-di-tert-butylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, hydrogenated-4,4'-
Isopropylidene diphenol polyphosphite, diphenyl bis [4,4'-n-butylidene bis (2-tert-butyl-5-methylphenol)] thiodiethanol diphosphite, bis (octylphenyl) bis [4,4 '-N-butylidene bis (2-tert-butyl-5
-Methylphenol)]-1,6-hexanediol diphosphite, phenyl-4,4'-isopropylidene diphenol pentaerythritol diphosphite,
Phenyldiisodecyl phosphite, tetratridecyl [4,4'-n-butylidene bis (2-tertiary butyl-5]
-Methylphenol)] diphosphite, hexatridecyl [1,1,3-tris (2-tert-butyl-5-methyl-4-hydroxyphenyl) butane] triphosphite, tris (2,4-di-tert-butylphenyl) ) Examples include phosphite.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol and 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-hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-sec. Tributylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid]
Glycol ester, 4,4'-butylidene bis (6-
Tert-butyl-m-cresol), 2,2'-ethylidene bis (4,6-di-tert-butylphenol), 2,2'-
Ethylidene bis (4-tert-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-)
Hidoxybenzyl) isocyanurate, 1,3,5-
Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-
Tris [(3,5-ditert-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-tertiary 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] and the like.

Examples of the above sulfur-based antioxidants include:
Examples thereof include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl and distearyl, and β-alkylmercaptopropionate esters of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate).

Examples of the ultraviolet absorber include 2,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis (2-
2-hydroxybenzophenones such as (hydroxy-4-methoxybenzophenone); 2- (2′-hydroxy-)
5'-methylphenyl) benzotriazole, 2-
(2'-Hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- ( 2'-hydroxy-5'-tertiary octylphenyl) benzotriazole, 2- (2'-hydroxy-3'.5'-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tertiary octyl-)
2- (2'- such as 6-benzotriazolyl) phenol
Hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,
4-di-tert-butylphenyl-3 ', 5'-di-tert-butyl-4'-hydroxybenzoate, hexadecyl-3,
Benzoates such as 5-di-tert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano Examples include cyanoacrylates such as -β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, and 2 , 2,6,6-Tetramethyl-4-piperidyl benzoate, N- (2,
2,6,6-Tetramethyl-4-piperidyl) dodecyl succinimide, 1-[(3,5-ditert-butyl-4-
Hydroxyphenyl) propionyloxyethyl]-
2,2,6,6-tetramethyl-4-piperidyl-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis (2,2,6,6-tetramethyl-
4-piperidyl) sebacate, bis (1, 2, 2, 6,
6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4-
Hydroxybenzyl) malonate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetra Carboxylate, tetra (1,2,2,6,6-pentamethyl-4
-Piperidyl) butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl).
Di (tridecyl) butane tetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) butane tetracarboxylate, 3,9-bis [1,1-dimethyl-2 -{Tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.
5] Undecane, 3,9-bis [1,1-dimethyl-2
-{Tris (1,2,2,6,6-pentamethyl-4-
Piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,5,8,12-tetrakis [4,6-bis {N- (2 , 2,6,6-Tetramethyl-4-piperidyl) butylamino} -1,3,5-
Triazin-2-yl] -1,5,8,12-tetraazadodecane, 1- (2-hydroxyethyl) -2,2
6,6-Tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tertiary octylamino-4,6-dichloro-s-triazine / N, N′-bis (2,2,2
6,6-Tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N'-bis (2,2,6,6-
Examples thereof include tetramethyl-4-piperidyl) hexamethylenediamine / dibromoethane condensate.

The above-mentioned inorganic metal compounds include, for example, oxides, hydroxides, halides, carbonates, sulfates, nitrates and silicic acids of the metal species exemplified as the metal constituting the metal salts such as the organic carboxylic acids. Examples thereof include salts, inorganic acid salts such as phosphates, and basic salts thereof.

In the composition of the present invention, the trimellitic acid ester compound and / or pyromellitic acid ester compound of the above-mentioned component (d) is used as a plasticizer having excellent heat resistance, heat aging resistance, and fogging property. In addition to the above, a small amount of a plasticizer usually used for vinyl chloride resins can be used if necessary. 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, dioctyl terephthalate; dioctyl avipate, diisononyl adipate. Adipate plasticizers such as diisodecyl adipate and di (butyldiglycol) adipate; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl)
Phosphate plasticizer systems such as phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri (butoxyethyl) phosphate octyldiphenyl phosphate; as polyhydric alcohols ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol,
1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, neopentyl glycol and the like, and oxalic acid, malonic acid, as dibasic acid, Polyester plastic using succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc., with monohydric alcohol or monocarboxylic acid as a stopper if necessary Agents; other, tetrahydrophthalic acid plasticizers, azelaic acid plasticizers, sebacic acid plasticizers,
Examples thereof include stearic acid-based plasticizers, citric acid-based plasticizers, biphenyltetracarboxylic acid ester-based plasticizers, and chlorine-based plasticizers.

Further, the composition of the present invention contains, if necessary, an impact resistance improver, a cross-linking agent, a filler, a foaming agent, an antistatic agent, an antifogging agent, a plate-out prevention agent, a surface treatment agent, Lubricants, flame retardants, fluorescent agents, antifungal agents, bactericides, metal deactivators,
Release agents, pigments, processing aids and the like can be added.

The composition of the present invention is preferably used for powder molding, and can be suitably used mainly for vehicle applications such as a covering material for automobile interiors.

[0076]

EXAMPLES Hereinafter, the composition of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples given below.

Example 1 A vinyl chloride resin composition having the following composition was dried up in a gear oven at 110 ° C. for 1 hour, and then stirred for 15 minutes using a raker to prepare a compound. Approximately 1 chrome mirror plate in a 300 ° C gear oven
After putting it in for 5 minutes and taking it out, when the mirror plate reached 240 ° C., the compound was rapidly spread to a uniform thickness.
Let stand for a second. The mold is turned upside down, left as it is for 30 seconds, then immersed in a water tank and cooled. The gelation state at that time was evaluated according to the following evaluation criteria.

[Evaluation Criteria] ◎ Completely gelled ○ Although gelled, granular materials remain inside △ Gelled but the surface has irregularities × There is an ungelled part

The sheet prepared here (thickness 1.8
mm) was placed in a gear oven at 240 ° C., and the decomposition time was measured. Further, this sheet was evaluated for its colorability (heat aging property) after accelerated deterioration for 500 hours in an oven at 130 ° C. in 5 grades and evaluated as good 1-5 bad.

The sheet before deterioration promotion and 130 ° C.
The sheet after the deterioration promotion for 500 hours in the oven of JIS
Tensile test according to K 7113, residual elongation (%)
I asked.

Furthermore, in order to evaluate the fogging property, 50
A mm × 50 mm sheet was placed in a 1-liter flask, covered with a glass plate, and heated in an oil bath maintained at 100 ° C. for 5 hours, and cloudiness (haze) on the glass plate was measured with a haze meter.

The results are shown in Table 1 below.

[0083] [Distribution] Weight part Suspension polymerization PVC 90 Paste PVC 10 Tri (2-ethylhexyl) trimellitate 65 Epoxidized soybean oil 5 Zinc stearate 0.2 Test compound (see [Table 1] below) [Table 1] Sodium A-type zeolite (NA-Z) 3.0 4,4'-butylidene bis (6-tert-butyl-m-cresol) 0.2 Compound No. 2 0.8

[0084]

[Table 1]

Example 2 A sheet having the following composition was prepared in the same manner as in Example 1, the decomposition time at 240 ° C. was measured, the heat aging resistance was evaluated, the elongation residual ratio was measured, and the haze was measured. did. The results are shown in [Table 2] below.

[0086] [Distribution] Weight part Suspension polymerization PVC 90 Paste PVC 10 Tri (2-ethylhexyl) trimellitate 65 Epoxidized soybean oil 5 Zinc stearate 0.2 Sodium A-type zeolite (NA-Z) 3.0 C-HT 1.0 Perchloric acid sodium salt 0.1 4,4'-butylidene bis (6-tert-butyl-m-cresol) 0.2 Test compound (see Table 2 below) 1.0

[0087]

[Table 2]

Example 3 A sheet was prepared in the same manner as in Example 1 with the following composition, and urethane foam was injected into the molded sheet on the chrome mirror surface plate at a constant thickness to prepare a urethane backing sheet. Place the sheet in an oven at 120 ° C for 300 hours and 4 hours.
The degree of coloration of the sheet after 50 hours was measured using a Hunter colorimeter, and the color difference (ΔE) from the original was determined and used as the colorability when exposed at a relatively low temperature.

Further, the elongation residual ratio of the sheet was determined before and after the deterioration was accelerated for 300 hours in an oven at 120 ° C. The urethane backing was completely removed before the measurement.

The results are shown in [Table 3] below.

[0091] (Combined) Weight part Suspension polymerization PVC 100 Tri (C7-9 mixed alkyl) trimellitate 65 Epoxidized linseed oil 5 Bisphenol A diglycidyl ether 3 Zinc stearate 0.3 Test compound (shown in [Table 3] below) [Table 3] Perchloric acid treated hydrotalcite (C-HT) 1.0 Compound No. 1 0.5 Tetra (1,2,2,6,6-pentamethyl-4-0.2 Piperidyl) butane tetracarboxylate Ammonium perchlorate 0.1

[0092]

[Table 3]

Example 4 The following composition was used, which was heated at 170 ° C. in a calendering machine.
Raise 0.4mm sheet and press 1mm.
I made a laminated sheet of. The haze was measured using this sheet in the same manner as in Example 1. A urethane backing sheet was prepared by injecting urethane foam with a constant thickness. Using this sheet, the elongation residual ratio was measured in the same manner as in Example 3. The results are shown in [Table 4] below.

[0094] (Combined) Weight part Suspension polymerization PVC 100 Test compound (see Table 4 below) 65 Epoxidized linseed oil 5 Bisphenol A diglycidyl ether 3 Zinc stearate 0.3 HT-1 1.0 NaA zeolite 2.0 Tetra (1,2,2,6,6-pentamethyl-4-0.2 Piperidyl) butane tetracarboxylate Compound No. 1 1.0 Ammonium perchlorate 0.1

[0095]

[Table 4]

From the results of [Table 1] to [Table 4], the following is clear. A vinyl chloride resin, a zeolite compound and / or a hydrotalcite compound, a perchlorate, an organic phosphite compound of the general formula (I), and a trimellitic acid ester compound and / or a pyromellitic acid ester compound. If even one of them is lacking (comparative example), it does not have satisfactory performance. For example, when no zeolite compound or hydrotalcite compound is used (Comparative Examples 1-2,1-3,1-5,1-6,1
-8,3-1 to 3-3) is inferior in heat stability, heat aging resistance, gelation property, etc. and does not use perchlorates (Comparative Example 1
-1 to 1-4,3-3,3-5) is inferior in heat aging resistance and colorability, and when a specific cyclic organic phosphite ester is replaced with another organic phosphite ester (comparison For example 1-8,2-2,2-3),
When the trimellitic acid ester compound or pyromellitic acid ester compound is not used due to poor thermal stability, heat aging resistance, fogging resistance, etc. (Comparative Examples 4-1, 4-2),
It is particularly inferior in physical properties such as thermal stability and heat aging resistance, and inferior in fogging property.

On the other hand, a vinyl chloride resin, a zeolite compound and / or a hydrotalcite compound,
The vinyl chloride resin composition of the present invention comprising a combination of perchlorates, the organic phosphite compound of the general formula (I), and a trimellitic acid ester compound and / or a pyromellitic acid ester compound (Examples 1-1 ~ 1-6,2-
1 to 2-7, 3-1 to 3-10, 4-1 to 4-3) have excellent thermal stability, heat aging resistance, and fogging resistance.

[0098]

The vinyl chloride resin composition for a vehicle according to the present invention (claim 1) is excellent in thermal stability, heat aging resistance and fogging resistance. The vinyl chloride resin composition for a vehicle according to the present invention (claim 2) has excellent moldability such as gelling property, demolding property and mold staining property when used for powder molding process, and therefore is suitable for automobiles. It can be suitably used for vehicle applications such as interior covering materials.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasuhiro Kishimoto 5-2-13 Shirahata, Urawa-shi, Saitama Asahi Denka Kogyo Co., Ltd. (56) Reference JP-A-6-279640 (JP, A) Sho 62-39652 (JP, A) JP 5-156106 (JP, A) JP 4-81444 (JP, A) JP 64-36655 (JP, A) JP 6-100625 (JP , A) JP 5-65379 (JP, A) JP 5-17648 (JP, A) JP 62-270645 (JP, A) JP 64-65157 (JP, A) JP 4-359949 (JP, A) JP-A-2-284946 (JP, A) JP-A-3-172336 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 27/06

Claims (2)

(57) [Claims] 1. A vinyl chloride resin 100 parts by weight, (a)
0.001 to 10 parts by weight of at least one selected from the group consisting of aluminosilicate having a zeolite crystal structure and a hydrotalcite compound, (b) metal salt of perchloric acid, ammonium perchlorate, and hydrochlor treated with perchloric acid 0.001 to 10 parts by weight of at least one selected from the group consisting of sites, (c) 0.001 to 10 parts by weight of at least one organic phosphite compound represented by the general formula (I) of the following [Chemical formula 1] 5 to 20 parts by weight and at least one selected from the group consisting of (d) trimellitic acid ester compounds and pyromellitic acid ester compounds.
A vinyl chloride resin composition for vehicles comprising 0 part by weight. [Chemical 1] 2. The vinyl chloride resin composition for vehicles according to claim 1, which is used for powder molding.