JP2000095909A - Vinyl chloride resin composition stabilized against heat - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vinyl chloride resin composition made proof against initial coloration and black decomposition and therefore giving a molding having improved transparency by using as a stabilizer component a combination comprising a metal salt compound of a carboxylic acid or of an alkylphenol, a β-diketone compound, and the product of thermal melting of a specified phosphoric ester and phosphorous or phosphoric acid. SOLUTION: 100 pts.wt. vinyl chloride resin is mixed with 0.1-5 pts.wt. at least either a metal salt compound of a carboxylic acid or a metal salt of an alkylphenol, at least 0.0005-3 pts.wt. β-diketone compound, and 0.0005-2 pts.wt. product obtained by heating a mixture of a polyoxyethylene organic group ether phosphoric ester represented by the formula with phosphoric or phosphorous acid to obtain the objective vinyl chloride resin composition. In the formula, R is an alkyl, an aryl, an alkylaryl, an arylalkyl, an alkenyl, or the like; n is 4-55; and x is 1 or 2. The metal of the metal salt compound of a carboxylic acid or of an alkylphenol is desirably a combination of barium with zinc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-stabilized vinyl chloride resin composition, and in particular, comprises a combination of a low-toxic or non-toxic metal salt compound and a heat-stabilizing aid. The present invention relates to a thermally stabilized vinyl chloride resin composition.

[0002]

2. Description of the Related Art Vinyl chloride resin compositions have various excellent properties. However, when they are thermoformed, they are decomposed with dehydrochlorination, thereby coloring molded articles and deteriorating their commercial value. There is. For this reason, it has been widely practiced to add various stabilizers thereto to stabilize the heat.

[0003] Components of such stabilizers include, for example, Ba-Z
It is obtained by combining an n-based or Ca-Zn-based metal soap with an organic phosphite compound, a hindered phenol-based antioxidant or an epoxy compound.

Although the above method of adding a stabilizer component for heat stabilization does not pose a problem in terms of toxicity, it is still insufficient in the ability to prevent coloring due to deterioration during thermoforming. Performance improvement was required. For this reason,
Hitherto, many methods have been proposed for further improving the performance of the above-mentioned stabilizer by further adding various stabilizing aids.

The present applicant also discloses a method using a β-diketone compound in JP-B-52-47948 and JP-B-57-9386, and a method using a metal salt compound of β-diketone in JP-B-57-39260. No.61-44899
Proposed a method using a ketoacetonitrile compound, and Japanese Patent Publication Nos. 1-58213 and 1-58214 proposed a method using cyclopentanone and cyclohexanone compounds.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a vinyl chloride resin, which comprises adding a low-toxic or non-toxic metal salt compound and a novel heat stabilizing aid to a vinyl chloride resin. It is intended to improve the thermal stability of the composition, especially the prevention of initial coloration and black decomposition (carbonization), and the transparency of the molded article.

[0007]

According to the present invention, at least one kind of (a) a metal salt compound of (a) a carboxylic acid or an alkylphenol is added to 100 parts by weight of a vinyl chloride resin.
5 parts by weight, (b) 0.0005 to 3 parts by weight of at least one kind of β-diketone compound, and (c) the following general formula: (Wherein R is alkyl, aryl, alkylaryl,
Represents an arylalkyl, alkenyl, cycloalkyl, alkylene or acyl group; n represents 4-55; x represents 1 or 2; ) Is added to the polyoxyethylene organic group ether phosphate represented by the formula (1) and added with phosphoric acid or phosphorous acid. (A) 0.1 to 5 parts by weight of at least one kind of (a) a metal salt compound of a carboxylic acid or an alkylphenol is added to 100 parts by weight of the vinyl chloride-based resin composition. , (B) 0.0005 to 3 parts by weight of at least one β-diketone compound, and (c)
General formula (Wherein R is alkyl, aryl, alkylaryl,
Represents an arylalkyl, alkenyl, cycloalkyl, alkylene or acyl group; n represents 4-55; x represents 1 or 2; ), At least one of 0.0005 to 2 parts by weight of a heated melt obtained by adding phosphoric acid or phosphorous acid to the polyoxyethylene organic group ether phosphoric acid ester and heating; formula _{Mg X Zn Y Al 2 · (} OH) 2X + 2Y + 4 · (CO 3) 1-Z / 2 (ClO 4) Z · mH 2 O (2) ( wherein, x.y and z are each A number that satisfies the condition represented by the following formula is shown, and m represents 0 or an arbitrary number.
0 <X <10, 0 ≦ y <10, 2 ≦ x + y <20, 0 ≦
at least one compound represented by the formula z <2) 0.001
And a metal salt of a metal salt compound of a carboxylic acid or an alkylphenol, wherein the metal of the metal salt compound of carboxylic acid or alkylphenol is barium-zinc, calcium-zinc or 3. The heat-stabilized vinyl chloride resin composition according to claim 1, which is a combination of calcium-magnesium-zinc, wherein the metal salt compound is barium or calcium overbased carboxy. 3. The thermally stabilized vinyl chloride resin composition according to claim 1 or 2, which is a combination of any one of a rate carbonate complex or an overbased alkylphenolate carbonate complex and zinc carboxylate. -The diketone compound is dibenzoylmethane, palmitoylbenzoylmethane or stearoylbenzoylmethane; Claim is either methane 1
Or a thermally stabilized vinyl chloride resin composition according to claim 2 (claim 5); (Wherein R is alkyl, aryl, alkylaryl,
Represents an arylalkyl, alkenyl, cycloalkyl, alkylene or acyl group; n represents 4-55; x represents 1 or 2; The polyoxyethylene organic group ether phosphate represented by the formula (1) is either tridecyl polyoxyethylene (4 to 10) phosphoric acid or nonylphenyl polyoxyethylene (5 to 55) phosphoric acid. 2. A thermally stabilized vinyl chloride resin composition according to claim 2 (claim 6). Hereinafter, these inventions are further described.

[0008] The invention of claim 1 provides at least one metal salt compound of carboxylic acid or alkylphenol.
To 5 parts by weight, at least 0.0005 to 3 parts by weight of at least one kind of β-diketone compound, (Wherein R is alkyl, aryl, alkylaryl,
Represents an arylalkyl, alkenyl, cycloalkyl, alkylene or acyl group; n represents 4-55; x represents 1 or 2; ), At least one kind of a heated melt obtained by adding phosphoric acid or phosphorous acid to the polyoxyethylene organic group ether phosphate ester and heating and combining the three components with 0.0005 to 2 parts by weight. And a heat-stabilized vinyl chloride resin composition.

The metal of the metal salt compound used in the present invention is:
It is sodium, potassium, magnesium, calcium, barium or zinc, and is used in two or more of these. In this case, the combination of metals is preferably barium-zinc or calcium-zinc. The organic residue bonded to the metal is a carboxylic acid or an alkylphenol.

The carboxylic acids include saturated or unsaturated aliphatic carboxylic acids having 2 to 22 carbon atoms, cyclic or heterocyclic carboxylic acids having 7 to 16 carbon atoms, hydroxy acids or alkoxy acids having 2 to 10 carbon atoms. Yes, for example, acetic acid, propionic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, isodecanoic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid,
12-hydroxystearic acid, behenic acid, carbon number 15
~ 16 trialkylacetic acids, oleic acids, linoleic acids,
Ricinoleic acid, adipic acid, sebacic acid, benzoic acid, toluic acid, xylylic acid, pt-butylbenzoic acid, phthalic acid, phthalic acid monoester, salicylic acid, or a mixed carboxylic acid thereof.

The alkylphenol is, for example, p-
t-butylphenol, pt-octylphenol,
Nonylphenol, dinonylphenol, decylphenol and dodecylphenol.

These carboxylic acid metal salt compounds and alkylphenol metal salt compounds may be acidic salts or neutral salts, and may be basic salts or overbased salts. The amount of the metal salt compound is 0.1 to 5 parts by weight per 100 parts by weight of the vinyl chloride resin.
Parts by weight, preferably 0.3 to 3 parts by weight. If the amount is less than 0.1 part by weight, the thermal stability is not sufficient. If the amount exceeds 5 parts by weight, plate-out, bloom or bleeding occurs, and the transparency is also deteriorated.

The β-diketone compound of the stabilizer component (b) of claim 1 is, for example, dehydroacetic acid, cyclohexane-
1,3-dione, 2-acetylcyclopentanone, 2-
Benzoylcyclopentanone, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, acetylstearoylmethane, acetylacetone, benzoylacetone, palmitoylbenzoylmethane, stearoylbenzoylmethane, dibenzoylmethane, tribenzoylmethane, 4-methoxybenzoyl-benzoylmethane,
Bis (4-methoxybenzoylmethane), 4-chlorobenzoyl-benzoylmethane, benzoyltrifluoroacetone, thenoyltrifluoroacetone, palmitoyltetralone, stearoyltetralone, and benzoyltetralone.

The β-diketone compound may be a metal complex salt, and the metal constituting the complex salt is sodium, calcium, barium or zinc. The amount of these β-diketone compounds added is
0.0005 to 3 parts by weight, preferably 0.005 to 1 part by weight, per 0 parts by weight. If the amount is less than 0.0005 parts by weight, the effect of preventing coloring is not sufficient, and if it exceeds 3 parts by weight, black decomposition (carbonization) is promoted.

The stabilizer component (c) according to the first aspect of the present invention.
Is converted to phosphoric acid or phosphorous acid by the general formula (Wherein R is alkyl, aryl, alkylaryl,
Represents an arylalkyl, alkenyl, cycloalkyl, alkylene or acyl group; n represents 4-55; x represents 1 or 2; ), And dissolved by heating with addition of a polyoxyethylene organic group ether phosphate.

This polyoxyethylene organic group ether phosphate is originally poor in reactivity with a metal salt, but is converted into a highly reactive compound by heating and dissolving it with phosphoric acid or phosphorous acid. When this compound is added and subjected to thermoforming, it reacts with a zinc salt mixed in the vinyl chloride resin composition to form a complex compound, which prevents plate-out, and improves transparency and heat stability. It works effectively to improve sex.

The component (c) comprises a vinyl chloride resin 10
0.0005 to 2 parts by weight, preferably 0.001 to 1 part by weight, is added to 0 parts by weight. 0.0005
If the amount is less than parts by weight, transparency, heat stability, anti-coloring property and anti-plate-out property are not sufficient. If the amount is more than 2 parts by weight, the color in the latter stage is deteriorated and causes adhesion to a molding machine.

The invention according to claim 2 is characterized in that a vinyl chloride resin is
(A) a metal salt compound as described in the first aspect of the present invention;
(B) a β-diketone compound, (c) a polyoxyethylene organic group ether phosphate, and a heat-dissolved product of phosphoric acid or phosphorous acid are added thereto, and for further improving thermal stability, And (d) a thermally stabilized vinyl chloride resin composition further comprising a synthetic hydrotalcite compound as a component and a combination of four components.

The synthetic hydrotalcite compound of the component (d) used in the second aspect of the present invention has a general formula of Mg _X Zn _Y Al _2. (OH) _{2X + 2Y + 4.} (CO ₃ ) _{1 -Z / 2} (ClO ₄ ) _Z · mH ₂ O (2) (where xy and z each represent a number satisfying the condition represented by the following formula, and m represents 0 or an arbitrary number. 0 <
X <10, 0 ≦ y <10, 2 ≦ x + y <20, 0 ≦ z <
As the properties of these compounds, the starting temperature of decrystallization water is about 230 ° C., and the so-called BET specific surface area, which is an adsorption isotherm for multilayer adsorption, is 20 m ² / g or less.
The particle size distribution is preferably less than 1 μm and 92% or more. A typical compound is, for example, Mg ₄ Al ₂ (O
H) ₁₂ CO ₃ .3H ₂ O [hereinafter referred to as (HT-1). ], Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .0-2H ₂ O
[Hereinafter referred to as (HT-2). ], Mg ₃ ZnAl ₂ (O
H) ₁₂ CO ₃ .3H ₂ O [hereinafter referred to as (HT-3). ], Mg ₃ ZnAl ₂ (OH) ₁₂ CO ₃ .0-1H
₂ O [hereinafter referred to as (HT-4). ], Mg ₄ Al ₂ (O
_{H) 12 (CO 3) 1} -X / 2 (ClO 4) · 0~6H 2 O
[Where x = 0.5 to 2.0]. ] [The following (H
T-5). ], Mg ₃ ZnAl ₂ (OH) ₁₂ (C
O ₃ ) _{1-X / 2} (ClO ₄ ) _x · 0-6H ₂ O (wherein,
(X = 0.5 to 2.0). ] [Hereinafter (HT-6)
That. ].

These synthetic hydrotalcite compounds are used in an amount of 0.001 to 100 parts by weight of the vinyl chloride resin.
10 to 10 parts by weight, preferably 0.01 to 5 parts by weight. If the added amount is less than 0.001 part by weight, the prevention of black decomposition (carbonization) during processing and the long-term heat resistance (heat storage) of the obtained molded product are not sufficient. The sex becomes extremely bad.

[0021] Claim 3 specifies the metal of the metal salt compound as a combination of barium-zinc and calcium-zinc. Claim 4 specifies an organic residue that binds to the metal of the metal salt compound. Claim 5 relates to β-
The diketone compound is specified. Further, claim 6 is a general formula) The polyoxyethylene organic group ether phosphate represented by the following formula is specified.

In the present invention, various stabilizing aids and other additives can be used in addition to the above-mentioned stabilizer components. For example, antioxidants such as organic phosphites, hindered phenolic or sulfur-containing alkyl esters, epoxy compounds, perchlorates, organic phosphate compounds, polyhydric alcohols or their esters, ultraviolet absorbers, light stabilizers , An inorganic oxide or an inorganic metal salt compound,
It is an additive such as a surfactant and a lubricant, and these can be appropriately used according to the purpose.

Organic phosphites include trialkyl phosphites, triaryl phosphites, alkyl aryl phosphites, bisphenol-A-phosphites, polyhydric alcohol phosphites, salicyl phosphites, and organic groups of ester residues. One or more of which are represented by an acid phosphite substituted by a hydrogen atom, such as triphenyl phosphite, triisooctyl phosphite, triisodecyl phosphite, triisotridecyl phosphite, triisodecyl Thiophosphite, tribenzyl phosphite, trisnonylphenyl phosphite, diphenylisooctyl phosphite, diphenylisodecyl phosphite, diphenyltridecyl phosphite,
Diisodecyl pentaerythritol diphosphite, tetraphenyl dipropylene glycol diphosphite,
Poly (dipropylene glycol) phenyl phosphite, trilauryl trithio phosphite, distearyl pentaerythritol diphosphite, tri-2,4-
Di-t-butylphenyl phosphite, 2,4-di-t
- butylphenyl diisodecyl phosphite, tributoxyethyl phosphite, 4,4'-isopropylidene diphenyl alkyl (C ₁₂ -C _l5) diphosphite,
4,4'-isopropylidene dicyclohexyl alkyl (C ₁₂ -C _l5) diphosphite, to heptakis (dipropylene glycol) triphosphite, and the like salicylic octyl phosphite.

Acid phosphites in which one or more of the organic residues in the above phosphite are substituted by a hydrogen atom are also effective, for example, diphenyl acid phosphite, monophenyl acid phosphite, diisooctyl. Acid phosphite, monoisooctyl acid phosphite, ditridecyl acid phosphite, dibenzyl acid phosphite, dinonylphenyl acid phosphite and the like.

Antioxidants include hindered phenols such as alkylated phenols, alkylated phenol esters, alkylene or alkylidene bisphenols, polyalkylated phenol esters, such as butylated hydroxytoluene, 4-hydroxymethyl -2,6-di-t-butylphenol,
4,4'-dihydroxy-2,2'-diphenylpropane, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol) ), Tetrakis [methylene-
3- (3 ', 5',-di-tert-butyl-4'-hydroxyphenyl) propionate] methane. And
Examples of the sulfur-containing alkyl alkanoate include dilauryl thiopropionate and distearyl thiodipropionate.

The epoxy compound is an epoxidized unsaturated oil, an epoxidized unsaturated fatty acid ester, an epoxycyclohexane derivative or an epichlorohydrin derivative. Examples thereof include epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, and epoxidized linseed oil. Safflower oil, epoxidized linseed oil fatty acid butyl, epoxy butyl stearate, alkyl esters such as isooctyl, 2-ethylhexyl, 3- (xenoxy) -1,2-epoxypropane, and di-2-ethylhexyglycyl epoxyhexahydrophthalate , Epoxy polybutadiene, bisphenol-A
-Diglycidyl ether and the like.

Perchlorate is a sodium salt of perchloric acid,
Magnesium salt, calcium salt, barium salt or alkyl ammonium salt. Further, a complex compound composed of these perchlorates and a polyhydric alcohol or a derivative thereof may be used. These compounds are useful as long-term heat (heat storage) aids.

Organic phosphate compounds such as magnesium, calcium, barium or zinc salts of mono-di-mixed isooctyl phosphate, magnesium, calcium, barium or zinc salts of mono-di-mixed isotridecyl phosphate, etc. Useful as stabilizing and processing aids.

Other stabilizing aids are polyhydric alcohols such as mono- and dipentaerythritol, mannitol, sorbitol and trehalose. Ester compounds of the polyhydric alcohol with carboxylic acids, amino acids or rosins, such as stearic acid Pentaerythritol, pentaerythritol adipate, dipentaerythritol adipate, dipentaerythritol pyrrolidonecarboxylate, dipentaerythritol glutamate, wood rosin pentaerythritol, maleic anhydride-modified wood rosin pentaerythritol, and wood rosin glycerol ester.

Incidentally, these ester compounds may be partial ester compounds. Further, an ester compound of β-aminocrotonic acid, which is a nitrogen-containing compound, with 1,3 or 1,4-butanediol, 1,2-dipropylene glycol, thiodiethylene glycol lauryl alcohol, and the like, and tris (hydroxyethyl) isocyanurate And isocyanurate compounds. These improve the thermal stability during processing and the long-term heat resistance (heat storage) of the molded product.

The UV absorber used may be a known one represented by a benzotriazole type or a hindered amine type, and the light stabilizer is also a representative of a hindered amine type such as a piperidine compound. Known ones may be used. These are added when it is desired to prevent deterioration and discoloration or chalking (chalking) of the molded article due to sunlight, rainwater and the like.

The inorganic oxide or inorganic metal salt compound is, for example, a metal of sodium, potassium, magnesium, calcium, barium, zinc, aluminum or tin, and an oxide, hydroxide, silicate, Borate, sulfate, phosphite, phosphate, basic carbonate, basic phosphate, stannate, hydroxystannate.

These compounds may be a double salt, an anhydrate or a hydrate having water of crystallization, or may be in the form of a mixture or the like.
Representative of these compounds are, for example, calcium oxide, magnesium oxide, zinc oxide, silicon oxide, aluminum oxide, calcium hydroxide, magnesium hydroxide,
Barium hydroxide, aluminum hydroxide, sodium silicate, calcium silicate, zinc silicate, aluminum silicate, potassium-aluminum silicate (mica), sodium borate, potassium borate, aluminum borate, aluminum sulfate, aluminum sulfate, aluminum sulfate 18 hydrate Product, aluminum sulfate-potassium dodecahydrate, aluminum sulfate-
Sodium dodecahydrate, sodium phosphate, sodium pyrophosphate, magnesium phosphate, calcium phosphate,
Examples include calcium orthophosphate, zinc orthophosphate, zinc stannate, zinc hydroxystannate, A-type zeolites substituted with sodium, calcium, magnesium or zinc, wollastonite, and tobermorites. These additions are suitable for prevention of plate-out, bloom and bleed, addition of printability and flame retardancy, in addition to improvement of thermal stability and weather resistance.

In addition to the above stabilizing aids, the processability is further improved and the antifogging property, antistatic property, printability,
For the purpose of imparting antibacterial properties and the like, a lubricant, a gelling accelerator, a surfactant, an antibacterial and antifungal agent and the like can be appropriately used.

The heat-stabilized vinyl chloride resin composition of the present invention can be converted from hard to soft by increasing or decreasing the amount of a plasticizer, for example, adipate or phthalate, depending on the use of the molded article. Can be obtained over a wide range of molded articles. If necessary, a filler, a pigment, a rust inhibitor, a cross-linking agent, a matting agent, a foaming agent, and other processing aids can be appropriately used in combination.

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

[0037]

The present invention will be described more specifically below with reference to examples and comparative examples. (Synthesis Examples 1 to 4) The synthesis examples described here are for synthesizing the component (c) of the present invention, but are not limited to these examples. Synthesis Example 1 Tridecyl polyoxyethylene (4 to 10) phosphoric acid 80
g and 20 g of phosphoric acid were weighed, stirred at 130 ° C. for 5 minutes, and filtered to obtain a pale yellow oily liquid. Synthesis Example 2 Tridecyl polyoxyethylene (4 to 10) phosphoric acid 80
g and 20 g of phosphorous acid were weighed, stirred at 130 ° C. for 5 minutes, and filtered to obtain a pale yellow oily liquid. Synthesis Example 3 80 g of nonylphenylpolyoxyethylene (5-55) phosphoric acid and 20 g of phosphoric acid were weighed, stirred at 130 ° C. for 5 minutes, and filtered to obtain a pale yellow oily liquid. Synthesis Example 4 80 g of nonylphenylpolyoxyethylene (5-55) phosphoric acid and 20 g of phosphorous acid were weighed, stirred at 130 ° C. for 5 minutes, and filtered to obtain a pale yellow oily liquid.

(Examples 1 to 4, Comparative Examples 1 to 4) A heat-stabilized vinyl chloride resin composition obtained by combining and adding the components (a) to (c) used in the present invention was obtained. The behavior of this product, such as thermal stability, plate-out prevention, and transparency, was examined. The composition and test method are as follows.

Formulation Polyvinyl chloride (degree of polymerization 1300) 100 parts by weight diisononyl adipate 40 エ ポ キ シ epoxidized soybean oil 10 〃 isostearic acid 0.3 ポ リ polyglycerin oleate 1.0 〃 sorbitan monolaurate 2.0 〃 benzoic acid Calcium 0.1 亜 鉛 Zinc oleate 0.1 亜 鉛 Zinc ricinoleate 0.1 〃 * Components (a) to (d) Described in Table 1 * The components (a) to (d) above are the compounds shown below. is there. (A-1): overbased oleate carbonate complex of calcium (b-1): stearoylbenzoylmethane (c-1): component of Synthesis Example 1 (c-2): component of Synthesis Example 2 (d-1) : HT-2 (trade name: Alkamizer-2, manufactured by Kyowa Chemical Industry Co., Ltd.) Test 1 The above composition was kneaded with a kneading roll heated to 185 ° C. for 5 minutes to form a uniform sheet having a thickness of 0.5 mm. And a portion was taken from this sheet. This was used as the original sheet. The sheet on the roll surface was continuously kneaded for another 15 minutes. In this rolling test, coloring of the sheet due to thermal aging, plate-out (corresponding to eye rejection during extrusion molding), lubricity, and the like were examined. The results are shown in Table 1.

The judgment of coloring was shown by the following numerical values.
5 is uncolored, 4 is slightly yellow, 3 is yellow, 2 is yellow-brown, and 1 is red-brown. Next, the plate-out judgment was indicated by the following numerical values. 5 is not dirty at all, 4 is slightly dirty,
3 is a little dirty, 2 is dirty, 1 is severely dirty.
The determination of the lubricity was indicated by the following numerical values. 5 is very good, 4 is good, 3 is slightly bad, 2 is bad, and 1 is very bad. If these values are 4 or more, there is no problem in industrial implementation. Test 2 The above-mentioned original sheet was pressed at 185 ° C. for 5
The plate was pressed for 3 minutes (150 kg / cm ² ) to produce a plate having a thickness of 3 mm. The transparency of this plate was examined. The results are shown in Table 1. The judgment of transparency was indicated by the following numerical values. 5 is very good, 4 is good, 3 is slightly bad, 2 is bad, and 1 is very bad. In addition, if this numerical value is 4 or more, there is no problem in industrial implementation. Test 3 Further, a strip-shaped test piece was prepared from the original sheet, and the strip-shaped test piece was subjected to a gear oven aging test machine heated to 190 ° C.
The time until coloring and black decomposition due to thermal deterioration was examined. The results are shown in Table 1. The judgment of coloring was indicated by the following numerical values. 5 is uncolored, 4 is slightly yellow, 3 is yellow, 2 is yellow-brown, and 1 is red-brown. If this value is 4 or more after 30 minutes, there is no problem in industrial practice. In addition, the time until black separation was displayed in minutes. If this value is 80 minutes or more,
There is no hindrance in industrial implementation.

[0041]

[Table 1]

As is clear from Table 1, for the comparative example,
According to the present invention, excellent results are obtained in all respects of coloring, plate-out (in the case of extrusion molding, it is equivalent to eye filing deposited on a die or a screw portion), lubricity, transparency, and black decomposition time. Is shown. (Examples 5 to 8, Comparative Examples 5 to 8) A heat-stabilized vinyl chloride resin composition obtained by adding the components (a) to (d) used in the present invention in combination was obtained. Here, a semi-rigid film containing a small amount of a plasticizer was used. Behaviors such as thermal stability, plate-out prevention, and transparency were examined. The test method and test conditions were the same as in Tests 1 to 3 above. The results are shown in Table 2. Compounding polyvinyl chloride (degree of polymerization 1050) 100 parts by weight diisooctyl phthalate 20 〃 epoxidized soybean oil 3 バ barium stearate 0.5 亜 鉛 zinc 12-hydroxystearate 0.2 ｐ zinc pt-butyl benzoate 0 .2 {Diphenylisooctyl phosphite 0.6} * Components (a) to (d) Described in Table 2 * The components (a) to (d) are compounds shown below. (A-2): overbased oleate carbonate complex of barium (b-2): dibenzoylmethane (c-3): component of Synthesis Example 3 (c-4): component of Synthesis Example 4 (d-2) : HT-5 (trade name: Alkamizer-5, manufactured by Kyowa Chemical Industry Co., Ltd.)

[0043]

[Table 2]

As is clear from Table 2, according to the present invention, in comparison with the comparative examples, coloring, plate-out (in the case of calendering, mixing, calendering, cooling or take-up rolls and the like, The results show excellent results in all respects, such as the phenomenon of depositing materials, lubricity, transparency, and black separation time.

[0045]

As described in Examples, the heat-stabilized vinyl chloride resin composition of the present invention has good heat stability, especially initial coloration, without generating plate-out or impairing lubricity. Black decomposition and deterioration of the transparency of the molded product can be prevented, and workability and commercial value can be significantly increased.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5: 138 5: 521) F-term (Reference) 4J002 BD041 BD051 BD061 BD071 BD081 BD181 BN031 BN081 BN171 BN201 BP031 CH052 DE289 DH038 DH048 EE047 EG026 EG036 EG046 EG056 EG076 EG106 EJ066 EJ076 EW049 FD030 FD062 FD066 FD067 FD068 FD069 FD070 FD130

Claims (6)

[Claims] 1. 100 parts by weight of a vinyl chloride resin,
(A) 0.1 to 5 parts by weight of at least one metal salt compound of a carboxylic acid or an alkylphenol, and (b) β-
0.0005 to 3 parts by weight of at least one diketone compound, and (c) the following general formula: (Wherein R is alkyl, aryl, alkylaryl,
Represents an arylalkyl, alkenyl, cycloalkyl, alkylene or acyl group; n represents 4-55; x represents 1 or 2; ) Is added to the polyoxyethylene organic group ether phosphate represented by the formula (1) and added with phosphoric acid or phosphorous acid. A thermally stabilized vinyl chloride resin composition comprising: 2. 100 parts by weight of a vinyl chloride resin,
(A) 0.1 to 5 parts by weight of at least one metal salt compound of a carboxylic acid or an alkylphenol, and (b) β-
0.0005 to 3 parts by weight of at least one diketone compound; (Wherein R is alkyl, aryl, alkylaryl,
Represents an arylalkyl, alkenyl, cycloalkyl, alkylene or acyl group; n represents 4-55; x represents 1 or 2; ), At least one of 0.0005 to 2 parts by weight of a heated melt obtained by adding phosphoric acid or phosphorous acid to the polyoxyethylene organic group ether phosphoric acid ester and heating; formula _{Mg X Zn Y Al 2 · (} OH) 2X + 2Y + 4 · (CO 3) 1-Z / 2 (ClO 4) Z · mH 2 O (2) ( wherein, x.y and z are each A number that satisfies the condition represented by the following formula is shown, and m represents 0 or an arbitrary number.
0 <X <10, 0 ≦ y <10, 2 ≦ x + y <20, 0 ≦
at least one compound represented by the formula z <2) 0.001
A heat-stabilized vinyl chloride-based resin composition containing a combination of the heat-curable vinyl chloride resin composition with a total of 10 to 10 parts by weight. 3. The method according to claim 1, wherein the metal of the metal salt compound of carboxylic acid or alkylphenol is barium-zinc, calcium-
3. The thermally stabilized vinyl chloride resin composition according to claim 1, which is a combination of zinc or calcium-magnesium-zinc. 4. The metal salt compound according to claim 1, wherein the metal salt compound is a combination of a barium or calcium overbased carboxylate carbonate complex or an overbased alkyl phenolate carbonate complex with zinc carboxylate. And a thermally stabilized vinyl chloride resin composition. 5. The method according to claim 1, wherein the β-diketone compound is any one of dibenzoylmethane, palmitoylbenzoylmethane, and stearoylbenzoylmethane.
3. The thermally stabilized vinyl chloride resin composition according to item 1. 6. General formula (Wherein R is alkyl, aryl, alkylaryl,
Represents an arylalkyl, alkenyl, cycloalkyl, alkylene or acyl group; n represents 4-55; x represents 1 or 2; The polyoxyethylene organic group ether phosphate represented by the formula (1) is either tridecyl polyoxyethylene (4 to 10) phosphoric acid or nonylphenyl polyoxyethylene (5 to 55) phosphoric acid. 3. The thermally stabilized vinyl chloride resin composition according to 2.