JPH07179702A - Vinyl chloride resin composition for powder molding - Google Patents

Abstract

PURPOSE:To obtain the subject composition good in heat resistance, colorability and moldability and useful for automotive interiors, etc., by adding a silicate salt, a metal perchlorate salt, ammonium perchlorate salt, a specific hydrotalcite, etc., and a beta-diketone compound to a vinyl chloride resin. CONSTITUTION:The objective resin composition is obtained by adding (A) 0.001-10 pts.wt. of at least one of silicate salt compounds of the formula (M is an alkaline earth metal, aluminum: (a) is 1, when M is an alkaline earth metal, and (a) is 3/2, when M is aluminum; (n) is 1-5; (m) is an arbitrary positive integer) (e.g. calcium silicate), (B) 0.001-10 pts.wt. of a metal perchlorate (e.g. barium perchlorate), ammonium perchlorate, perchloric acid-treated hydrotalcite or a perchloric acid-treated silicate salt, and (C) 0.001-10 pts.wt. of at least one of beta-diketone compounds (e.g. dibenzoylmethane) to 100 pts.wt. of a vinyl chloride resin. which is used for powder molding and is excellent in heat resistance, thermal againg resistance, colorability and moldability.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a vinyl chloride resin composition for powder molding, and more particularly to a vinyl chloride resin composition for powder rotary molding or powder slush molding suitable for automobile interior materials. .

[0002]

2. Description of the Related Art In recent years,
As a covering material for automobile interior materials such as crash pads, armrests, headrests, consoles, meter covers, door trims, etc., those that are light and have a soft feeling and have a high-class leather grain pattern or stitch pattern. Is being asked for more.

Conventionally, as these covering materials, a vacuum-molded product of a soft sheet mainly composed of vinyl chloride resin and ABS resin, or a rotational molding or slush of sol mainly composed of vinyl chloride resin for paste and a plasticizer. Molded products (hereinafter referred to as "sol molded products") have been used.
However, although the vacuum-molded product has achieved its purpose in terms of weight reduction, it does not have a soft feeling and only a hard feeling can be obtained.Furthermore, a high-class leather grain pattern or stitch pattern is applied. It has been difficult to shape such a complex shaped article. Further, the vacuum-molded product has a large residual strain at the time of molding, and has a drawback that the molded product is apt to crack when used for a long time.

On the other hand, the sol-molded product has a soft feeling, but its gelling temperature is low, so that it melts quickly in the metal, and phenomena such as flow marks, lips or stringing of the sol occur, resulting in a smooth surface. It has drawbacks such as lack of properties, it takes too long to discharge the sol from the mold, and the thickness of the covering material becomes thick. Further, 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 withstand long-term storage because the viscosity changes with time. .

As a method for solving these drawbacks and problems, a powder molding method has recently been in the limelight. This powder molding method generally includes a fluidized-bed immersion method, an electrostatic coating method, a powder spraying method, a powder rotational molding method, a powder slush molding method, and the like. 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 characterized by the fact that the processing method completes the processing in a short time due to the high temperature. It is required that the mold is gelled, the mold release property is excellent, and the mold contamination is small.

For example, in JP-A-62-270645 and JP-A-1-65157, a chlorine-containing resin for powder molding contains a Ba-Zn stabilizer and a metal salt of perchloric acid or a perchlorate ion type. JP-A-63-125553 proposes to add a basic lead silicate and a perchlorate together. In JP-A-4-359949, it is proposed to add a hydrotalcite compound or a zeolite compound, calcium oxide and a halogen oxyacid salt or a metal salt thereof together, but it is possible to sufficiently improve the above-mentioned drawbacks. There wasn't.

Further, JP-A-53-13659 proposes to add a metal carboxylate or phenolate, a basic inorganic acid salt and a halogen oxyacid salt to a halogen-containing resin in combination. Kaisho 58-12
No. 2951 discloses a halogen-containing resin with an organic acid metal salt,
It has been proposed to add hydrotalcites and halogen oxyacid salts together, and JP-A-61-178874.
Japanese Patent Laid-Open No. 61-113 proposes to add a perchloric acid-treated metal silicate to a halogen-containing resin.
Japanese Patent Laid-Open No. 1-252649 proposes to blend a chlorine-containing polymer with a silicic acid or a silicate containing a perhalogen oxyacid.
JP-A-4-15260 proposes to add a complex salt of dehydroacetic acid and perchloric acid with a metal selected from calcium, magnesium, barium and zinc to a polyvinyl chloride resin. Proposes to compound a polar resin polymer with a complex in which a quaternary ammonium salt-perchloric acid complex is held in a silicate, but these are simply added to a chlorine-containing resin for powder molding. Even if it applied, the above-mentioned fault could not be improved.

Under these circumstances, it has been demanded to provide a powder composition which is excellent in heat stability, heat aging property and coloring property, and is excellent in moldability such as gelling property, mold release property and mold stain property. .

Therefore, an object of the present invention is to provide a powder composition which is excellent in heat stability, heat aging property and coloring property, and excellent in moldability such as gelling property, mold release property and mold stain property. Especially.

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a chlorinated product obtained by adding a specific silicate compound, a perchlorate compound and a β-diketone compound to a vinyl chloride resin in combination. We have found that a vinyl-based resin composition can achieve the above objects, and completed the present invention.

That is, the present invention is based on the vinyl chloride resin 100.
In parts by weight, (a) the following [Chemical formula 2] (the same as the above [Chemical formula 1])
0.001 to 10 parts by weight of a silicate compound represented by the general formula (I), (b) a metal salt of perchloric acid,
0.001 to 10 parts by weight of ammonium salt of perchloric acid, hydrotalcite treated with perchloric acid or chlorate treated with perchloric acid, and 0.001 to 10 parts by weight of at least one (c) β-diketone compound are added. The present invention provides a vinyl chloride resin composition for powder molding.

[0014]

[Chemical 2]

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

The vinyl chloride resin used in the present invention is a vinyl chloride polymer produced by a suspension polymerization method, a bulk polymerization method or an emulsion polymerization method, or ethylene, propylene, vinyl acetate and the like which can be copolymerized with vinyl chloride. However, the present invention is not limited to this, but is not limited to this, or a graft copolymer of ethylene, a vinyl acetate copolymer and vinyl chloride, or a mixture of two or more kinds of these polymers.

In the composition of the present invention, at least one of the silicate compounds represented by the above general formula (I) which is the component (a) is used.

In the above general formula (I), M represents an alkaline earth metal or aluminum, and examples of the alkaline earth metal include magnesium, calcium, barium and strontium, and magnesium, calcium and aluminum are particularly preferable. . Further, in the general formula (I), n represents a number of 1 to 5. When n is less than 1, coloring property is lowered, and when n is more than 5, synergistic effect with other components on thermal stability and moldability is poor.

The silicate compound may be a natural product or a synthetic product.

The amount of the silicate compound added is 0.001 to 10 parts by weight, based on 100 parts by weight of the vinyl chloride resin.
It is preferably 0.01 to 5 parts by weight. If the addition amount is less than 0.001 part by weight, a sufficient effect cannot be obtained, and even if it is used in an amount exceeding 10 parts by weight, the effect is not improved.

As the metal component constituting the metal salt of perchloric acid, which is one of the component (b) used in the present invention, lithium, sodium, potassium, strontium, barium, zinc, cadmium, lead, aluminum, etc. Can be exemplified, the metal salt of perchloric acid composed of these metals,
It may be an anhydride or a hydrous salt, or may be one dissolved in an alcohol or ester solvent such as butyl diglycol or butyl diglycol adipate, or its dehydrated product.

The ammonium salt of perchloric acid, which is one of the components (b) used in the present invention, may be anhydrous or hydrated.

The perchloric acid-treated hydrotalcite, which is one of the component (b) used in the present invention, is a perchloric acid-modified product obtained by replacing part or all of the carbonic acid of the hydrotalcite compound with perchloric acid. Is.

Here, the hydrotalcite compound is
It is a carbonate double salt compound of magnesium and / or zinc and aluminum, and is usually represented by the general formula (I
The compound represented by I) is used.

[0025]

[Chemical 3]

The hydrotalcite compound may be a natural product or a synthetic product. As a method for synthesizing the synthetic product, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, and Japanese Patent Publication No. 51-29129.
The publicly known methods described in JP-A No. 61-174270 and JP-A No. 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 size, presence or absence of crystal water, and the amount thereof.

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

As the perchloric acid-treated silicate which is one of the components (b) used in the present invention, metal silicates such as calcium silicate, magnesium silicate, barium silicate and zinc silicate, and various siliceous clay minerals or The treated products, for example, kaolin, bentonite, mica powder, talc, diatomaceous earth, acid clay, activated clay and zeolite treated natural or synthetic silicates such as those treated with a perchloric acid aqueous solution, these perchloric acid treatment Among silicates, calcium silicate,
Particularly preferred are treated products of magnesium silicate, barium silicate, kaolin, bentonite, talc, acid clay, activated clay and zeolite.

The above-mentioned perchloric acid-treated hydrotalcite or perchloric acid-treated silicate is, for example, added to a dilute aqueous solution of perchloric acid in the hydrotalcite or silicate, and optionally stirred with heating, and thereafter, if necessary. Depending on the filtration,
It can be easily produced by dehydration or drying. The molar ratio of the hydrotalcite or silicate to perchloric acid can be set arbitrarily, but in general, 0.1 to 2 mol of perchloric acid is used per 1 mol of hydrotalcite or silicate. It is preferable to use it in such a ratio that

Among the above-mentioned component (b), perchloric acid, ammonium perchlorate is particularly excellent in powder moldability, and is used in combination with all of the component (b) in the present invention or other perchlorates. It is preferable to use.

The addition amount of the metal salt of perchloric acid, ammonium salt of perchloric acid, hydrotalcite treated with perchloric acid or silicate treated with perchloric acid is 0.001 with respect to 100 parts by weight of vinyl chloride resin. -10 parts by weight, preferably 0.
01 to 5 parts by weight. If the addition amount is less than 0.001 part by weight, a sufficient effect cannot be obtained, and even if it is used in an amount exceeding 10 parts by weight, the effect is not improved.

Β- which is the component (c) used in the present invention
Examples of the diketone compound include dehydroacetic acid, acetyltetralone, benzoyltetralone, 2-benzoylcyclohexanone, dibenzoylmethane, benzoyl-4-chlorobenzoylmethane, bis (4-methylbenzoyl) methane, 4-tertiarybutylbenzoyl. -4-methoxybenzoylmethane, benzoyl-4-isopropylbenzoylmethane, bis (4-methoxybenzoyl) methane, acetylbenzoylmethane, acetylbenzoylallylmethane, propionyl-3-methoxycarbonylbenzoylmethane, isovaleroylbenzoylmethane,
Octanoyl benzoyl methane, palmitoyl benzoyl methane, stearoyl benzoyl methane, dipivaloyl methane, distearoyl methane etc. are mentioned. Further, metal salts of these β-diketone compounds (lithium, sodium, potassium, magnesium, calcium, barium, zinc, etc.) can be similarly used.

The amount of the β-diketone compound added is 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the addition amount is less than 0.001 part by weight, a sufficient effect cannot be obtained, and even if it is used in an amount exceeding 10 parts by weight, the effect is not improved.

Further, in the present invention, the silicate compound of the above-mentioned component (a) used as a stabilizer, the ammonium salt of perchloric acid of the above-mentioned component (b), and the metal salt of perchloric acid, hydrochloric acid treated with perchloric acid. The site- or perchloric acid-treated silicate and the β-diketone compound as the component (c) can be separately blended with the vinyl chloride resin, or they can be mixed and used. In this case, If necessary, it can also be used as a so-called composite stabilizer containing other stabilizer components and the like.

In addition, the composition of the present invention may be used in combination with other stabilizers, plasticizers and other additives which are usually used in vinyl chloride resin compositions for powder molding.

Other stabilizers usable in the present invention include:
Organic carboxylic acids, metal salts of phenols and organic phosphoric acids, epoxy compounds, organic phosphite compounds, phenol-based or sulfur-based antioxidants, ultraviolet absorbers,
Examples thereof include hindered amine light stabilizers, pure organic stabilizers, hydrotalcite compounds, zeolite compounds and other inorganic compounds.

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

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, and 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-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cuminic acid, n-propylbenzoic acid, aminobenzoic acid, N, N-dimethylaminobenzoic acid, acetoxybenzoic acid, Salicylic acid, p-tertiary octyl salicylic acid, elaidic acid, oleic acid Acid, linoleic acid, linolenic acid,
Monovalent carboxylic acids such as thioglycolic acid, mercaptopropionic acid and octylmercaptopropionic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid Acid, terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid,
Maleic acid, fumaric acid, citraconic acid, metaconic acid,
Divalent carboxylic acids such as itaconic acid, aconitic acid, thiodipropionic acid or their monoesters or monoamide compounds; butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid, melophanoic acid, pyromellitic acid Examples thereof include di- or triester compounds of trivalent or tetravalent carboxylic acids.

The above-mentioned phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol,
Octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, isooctylphenol, 2-ethylhexylphenol,
Examples thereof include tertiary nonylphenol, decylphenol, tertiary octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisofuxylphenol, and methyltertiaryoctylphenol.

The above-mentioned organic phosphates include mono- or di-octyl, -decyl, -dodecyl, -tridecyl, -tetradecyl, -hexadecyl, -octadecyl, -phenyl, -tolyl, -xylyl, -octylphenyl,-. Examples include nonylphenyl phosphoric acid, pyrophosphoric acid, phosphorous acid, and the like.

The metal salts of the above-mentioned carboxylic acids, phenols and organic phosphoric acids are overbased obtained by neutralizing a part or all of the bases of acidic salts, neutral salts, basic salts or basic salts with carbonic acid. It may be a complex.

The addition amount of the metal salt of the above-mentioned organic carboxylic acid, phenols and organic phosphoric acid is the vinyl chloride resin 1
It is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, relative to 00 parts by weight.

Examples of the epoxy compound include bisphenol type and novolac type epoxy resins, epoxidized natural fats and oils such as epoxidized soybean oil and epoxidized linseed oil, and epoxidized unsaturated fatty acids such as epoxidized tall oil fatty acid octyl. And an alicyclic epoxy compound such as vinylcyclohexene diepoxy.

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 organic phosphite compound include diphenyldecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite,
Tridecyl phosphite, tris (2-ethylhexyl) phosphite, tributyl phosphite, dilauryl acid phosphite, dibutyl acid phosphite, tris (dinonylphenyl) phosphite, trilauryl trithiophosphite, trilauryl phosphite, bis (Neopentyl glycol) -1,4-cyclohexane dimethyl phosphite, distearyl pentaerythritol diphosphite, diphenyl acid phosphite, tetradecyl-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, di-mixed 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
4'-n-butylidene bis (2-tert-butyl-5-methylphenol)]-1,6-hexanediol diphosphite, phenyl-4,4'-isopropylidene diphenol pentaerythritol diphosphite, phenyldiisodecyl Phosphite, tetratridecyl (2-
Tert-butyl-5-methylphenol) diphosphite,
Tris (2,4-ditert-butylphenyl) phosphite and the like can be mentioned.

The amount of the organic phosphite compound added is
The amount is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

Examples of the phenolic antioxidants 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-hexamethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-di-tert-butyl) -4-Hydroxyphenyl) propionic 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 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-4-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-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-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] and the like.

The amount of the above-mentioned phenolic antioxidant added is
The amount is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

Examples of the sulfur-based antioxidant include
Examples thereof include dialkyl thiodipropioates such as dilauryl thiodipropionate, dimyristyl and distearyl, and β-alkylmercaptopropionic acid esters of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate).

The amount of the above sulfur-based antioxidant added is preferably 0.01 with respect to 100 parts by weight of the vinyl chloride resin.
10 to 10 parts by weight, more preferably 0.05 to 5 parts by weight.

Examples of the ultraviolet absorber include, for example, 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.

The amount of the ultraviolet absorber added is preferably 0.01 to 1 with respect to 100 parts by weight of the vinyl chloride resin.
It is 0 part by weight, more preferably 0.05 to 5 parts by weight.

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 amount of the hindered amine light stabilizer added is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin.
Parts by weight.

As the above-mentioned pure organic stabilizing aid, phenols such as bisphenol A and hydrogenated bisphenol A; pentaerythritol, dipentaerythritol,
Polyalcohols such as dipentaerythritol adipate, mannitol and sorbitol, and their ester compounds or partial ester compounds; 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic acid didodecyl ester, 2-phenyl Examples include organic nitrogen-containing compounds such as indole and melamine.

The amount of the above-mentioned pure organic stabilization aid added is preferably 0.0 based on 100 parts by weight of the vinyl chloride resin.
The amount is 01 to 5 parts by weight, more preferably 0.005 to 3 parts by weight.

The hydrotalcite compound is a double salt compound consisting of magnesium (and zinc) represented by the general formula (II) and aluminum, and is surface-treated in the same manner as the perchloric acid-treated hydrotalcite. But it is okay.

The amount of the hydrotalcite compound added is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin.
Parts by weight.

The above-mentioned zeolite compound is an aluminosilicate of an alkali or alkaline earth metal having a unique three-dimensional zeolite crystal structure, and its representative examples are A-type, X-type, Y-type and P-type zeolites. Examples include monodenite, analsite, aluminosilicate of sodalite group, clinobuchilorite, erionite, chabazite, etc., and remove water-containing substances or water of crystallization having crystal water of these zeolite compounds (so-called zeolite water). 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 amount of the above zeolite compound added is preferably 0.01 with respect to 100 parts by weight of the vinyl chloride resin.
10 to 10 parts by weight, more preferably 0.05 to 5 parts by weight.

Other inorganic compounds that can be used in the present invention include calcium phosphate, calcium oxide, magnesium phosphate, magnesium oxide, magnesium hydroxide and the like.

As the plasticizer that can be used in the present invention, any plasticizer usually used for vinyl chloride resins can be used. 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, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri Phosphorus such as (butoxyethyl) phosphate octyldiphenylphosphate Over preparative plasticizing system; 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 as a dibasic acid, Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. were used, and monohydric alcohols and monocarboxylic acids were used as stoppers as needed. Polyester plasticizer, epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized safflower oil, epoxidized methyl stearate, -butyl, -2-
Epoxy plasticizers such as ethylhexyl, -stearyl ester, epoxidized polybutadiene, epoxidized tall oil fatty acid ester, and epoxidized linseed oil fatty acid ester; other, tetrahydrophthalic acid plasticizer, azelaic acid plasticizer, sebacic acid plasticizer Agents, stearic acid plasticizers, citric acid plasticizers, trimellitic acid plasticizers and the like.

In addition, if necessary, the composition of the present invention may include, for example, a crosslinking agent, a filler, a pigment, a foaming agent, an antistatic agent, an antiplate-out agent, a surface treatment agent, a lubricant, a flame retardant, and a fluorescent agent. Agents, photo-deteriorating agents, mildew-proofing agents, bactericides, non-metal stabilizers, processing aids, release agents and the like.

The vinyl chloride resin composition for powder molding of the present invention is produced, for example, as follows. The vinyl chloride resin produced by the suspension polymerization or bulk polymerization method is added to the above-mentioned essential components (a), (b) and (c), and, if necessary, a plasticizer, an organic carboxylic acid, an organic compound. Metallic salts of phosphoric acids or phenols, lubricants such as hydroxy fatty acid oligoesters or salts thereof, other additives, etc. are evenly dispersed with a mixer such as a super mixer, or when adding a fluidity improver, dry After blending, after cooling with a cooling mixer or the like, a fluidity improver is added, and the surface of the dry blended vinyl chloride resin is uniformly coated to obtain a composition.

[0065]

[Examples] The composition of the present invention and its stabilizing effect are specifically described below with reference to Examples. However, the invention is not limited to these examples.

Example 1 A vinyl chloride resin composition having the following [formulation] was dried up at 110 ° C. for 1 hour in a gear oven and then stirred for 15 minutes using a raider to prepare a compound. The chromium mirror plate is put in a gear oven at 300 ° C. for about 15 minutes and taken out, and when the mirror plate reaches 240 ° C., the compound is rapidly spread to a uniform thickness and the molded sheet is left for 10 seconds. The mold is turned upside down, left as it is for 30 seconds, then immersed in a water tank and cooled.
The gelation state of the sheet at that time was evaluated according to the following evaluation criteria.

[Evaluation Criteria] ◎ Completely gelled ○ Although gelled, granules remained inside △ Gelled but surface irregularity × Ungelled portion

Further, the gelled sheet prepared here is used for 24
Put it in a gear oven at 0 ℃ and decompose it (heat stability)
Was measured. Further, the initial coloring property of this gelled sheet and the coloring property (heat aging property) after accelerated deterioration for 500 hours in a 130 ° C. oven were evaluated in 10 grades [Evaluation criteria:
Good 1 ←-→ 10 bad (relative comparison).

The results are shown in [Table 1] below.

[Composition] Parts by Weight Suspension Polymerized PVC 90 Paste PVC 10 Di (C9-11 mixed alkyl) phthalate 65 Epoxidized soybean oil 5 Zinc stearate 0.3 Alkamizer 1 ^{* 1} 1.0 Calcium silicate 0 .5 (Compositional formula: CaO.SiO ₂ .2H ₂ O) Test compound (shown in [Table 1] below) [Table 1] Tetra (C12-15 mixed alkyl) bisphenol A 1.0 diphosphite dibenzoylmethane 0.05 * 1: Synthetic hydrotalcite manufactured by Kyowa Chemical Industry

[0071]

[Table 1]

Example 2 A gelled sheet was prepared in the same manner as in Example 1 by the following [formulation], and the gelled state was evaluated. When the temperature reached 60 ° C. in the cooling stage, the gelled sheet was peeled off, and the degree of haze of the chromium mirror plate and the degree of peeling of the sheet were examined to evaluate the demolding property and the mold fouling property in 10 grades respectively. Evaluation criteria: good 1 ← →→ 10 bad].

Further, a urethane lining sheet was prepared by injecting urethane foam with a constant thickness into a molded sheet on a mirror plate made of chrome. This sheet was placed in an oven at 120 ° C., the coloring degree of the sheet after 300 hours and 450 hours was measured using a Hunter colorimeter, and the color difference (ΔE) from the original was obtained, and the sheet was exposed at a relatively low temperature. The coloring property was used.

The results are shown in Table 2 below.

(Combined) parts by weight suspension polymerization PVC 100 tri (C7-9 mixed alkyl) trimellitate 65 epoxidized linseed oil 5 bisphenol A diglycidyl ether 3 calcium stearate 1.5 basic zinc octylate 1.0 test compound (Indicated in [Table 2] below) 1.0 Na-A type zeolite 2.0 Di (tridecyl) phenylphosphite 1.0 Tetra (2,2,6,6-tetramethyl-4-0.2 piperidyl) Butane tetracarboxylate Ammonium perchlorate 0.2 Barium perchlorate 0.2 Dibensoylmethane 0.05

[0076]

[Table 2]

Example 3 A gelled sheet was prepared in the same manner as in Example 1 by the following [formulation], and the heat stability and heat aging resistance of this gelled sheet were tested.

The results are shown in [Table 3] below.

[Composition] Parts by Weight Suspension Polymerized PVC 90 Paste PVC 10 Di (C9-11 Mixed Alkyl) Phthalate 65 Epoxidized Soybean Oil 5 Zinc Stearate 0.3 Ammonium Perchlorate 0.3 Alkamizer 50. 3 Alkamizer 1 1.0 Calcium silicate 0.5 (Compositional formula: CaO · 2SiO ₂ · 2H ₂ O) Tetra (C12-15 mixed alkyl) bisphenol A 1.0 Diphosphite Test compound 0.05

[0080]

[Table 3]

As is clear from the above [Table 1] to [Table 3], when a silicate compound, a perchlorate and a β-diketone compound were added together to the vinyl chloride resin (Example 1- 1 to 3-5), heat stability and gelation property during processing are unexpectedly unexpected when used alone or when only two kinds of them are used (Comparative Examples 1-1 to 3-1). , Performances such as mold fouling property, demolding property, workability after working, heat stability, and heat aging property are remarkably excellent.

[0082]

INDUSTRIAL APPLICABILITY The vinyl chloride resin composition for powder molding of the present invention is excellent in heat stability, heat aging property and coloring property, and has moldability such as gelling property, mold staining property and demolding property. It is an excellent one.

Claims (1)

[Claims] 1. To 100 parts by weight of vinyl chloride resin,
(A) 0.001 to 10 parts by weight of at least one silicate compound represented by the following general formula (I) represented by the general formula (I), (b)
Metal salt of perchloric acid, ammonium salt of perchloric acid, hydrotalcite treated with perchloric acid or silicate treated with perchloric acid 0.001 to 10 parts by weight and (c) at least one kind of β-diketone compound 0.001 A vinyl chloride resin composition for powder molding, which is obtained by adding 10 parts by weight. [Chemical 1]