JPH0940830A - Vinyl chloride-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a stabilized vinyl chloride based resin composition which excels in heat stability, resistance to heat discoloration, weathering resistance and light resistance and is useful for architectural members such as window frames, by blending a specific basic zinc phosphite and specific organophosphorus metal salt at a specific proportion to a vinyl chloride-based resin. SOLUTION: This resin composition is obtained by blending (A) 100 pts.wt. of a vinyl chloride-based resin with (B) 0.001-10 pts.wt. of one or more kinds of basic zinc phosphites of formula 1 ((x) is 0.1-20; (y) is 0 or a positive number), and (C) 0.001-10 pts.wt. of one or more kinds of organophosphorus metal salts of formula II or III (R1 and R3 are each a 1-30C alkyl, aryl, arylalkyl, or alkylaryl; R2 is H or R1 O; M is an alkaline earth metal or zinc), and moreover preferably (D) 0.001-10 pts.wt of a hydrotalcite compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a stabilized vinyl chloride resin composition, and more specifically, to the addition of a basic zinc phosphite and an organic phosphorus-containing metal salt, heat resistance and weather resistance are improved. The present invention relates to an excellent vinyl chloride resin composition.

[0002]

2. Description of the Related Art Since the hardness of vinyl chloride resin can be easily adjusted by using a plasticizer, it can be used for agricultural sheets, window frames, and other building materials. It can be used for various purposes up to the intended use.

However, it is known that vinyl chloride resins are difficult to be stable to light and heat, and are liable to be decomposed mainly due to dehydrohalogenation during heat molding and during use of products. . For this reason, various stabilizers such as a metal salt of an organic acid, an organic tin compound, an organic phosphite compound, an epoxy compound, a β-diketone compound, an antioxidant and an ultraviolet absorber are blended to stabilize the vinyl chloride resin. Have been tried to improve.

Further, in recent years, since use of heavy metals such as lead and cadmium has been shunned due to toxicity problems, complex low toxicity stabilizers such as barium-zinc type and calcium-zinc type are used. However, when these stabilizers are used, performances such as heat stability and weather resistance are insufficient.

Among the above-mentioned low-toxicity stabilizers, organic phosphorus-containing metal salts have been proposed to be used in combination with other low-toxicity additives as a weather resistance improver for vinyl chloride resins, but their effects are still present. Is insufficient.

Basic inorganic metal salts such as basic zinc phosphite are also known as stabilizers for vinyl chloride resins. For example, JP-A-51-30850 discloses a basic inorganic metal salt. It has been proposed to use a salt and an organic phosphite compound in combination, and JP-A-54-16555 discloses
JP-A-54-62250 proposes to use a basic inorganic metal salt in combination with a β-diketone compound, and JP-A-4-202451 discloses an organic acid salt of barium and zinc, a hydrous salt. Talcites, organic phosphite compounds and organic acid phosphite compounds, epoxy compounds, phosphorous acid, diphosphorous acid or metal salts thereof,
Although it has been proposed to add titanium dioxide, the effect of improving the weather resistance of all the compositions described in these publications is still insufficient.

Particularly, in the case of a hard vinyl chloride resin composition containing no plasticizer or a semi-rigid vinyl chloride resin composition containing a small amount of plasticizer, it is exposed to high temperature and high pressure during processing, and the thermal stability of the molded product is increased. Alternatively, higher performance is required in terms of weather resistance.

Accordingly, an object of the present invention is to provide a vinyl chloride resin composition having excellent thermal stability and thermal colorability, and particularly excellent stability even in applications where weather resistance is required.

[0009]

Means for Solving the Problems As a result of intensive studies by the present inventors, vinyl chloride obtained by adding a specific basic zinc phosphite and a specific organic phosphorus-containing metal salt to a vinyl chloride resin in combination. It was found that the resin composition can achieve the above object.

The present invention was made on the basis of the above-mentioned findings. 100 parts by weight of a vinyl chloride resin is represented by the following general formula (I) represented by the following [Chemical formula 3] (the same as the above [Chemical formula 1]). At least one basic zinc phosphite to be used 0.001-10
Parts by weight and (b) [Chemical formula 4] below (the same as [Chemical formula 2] above)
The present invention provides a stabilized vinyl chloride resin composition comprising 0.001 to 10 parts by weight of at least one organic phosphorus-containing metal salt represented by the general formula (II) or (III). .

[0011]

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[0012]

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[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the vinyl chloride resin composition of the present invention will be described in detail. Used in the present invention
In the basic zinc phosphite represented by the general formula (I) as the component (a) (hereinafter referred to as “basic zinc phosphite (I)”), in the general formula (I), X is The number is 0.1 to 20, preferably 0.3 to 10. When X is less than 0.1 or exceeds 20, the weather resistance improving effect is insufficient.

The basic zinc phosphite (I) is not particularly limited in its production method, and may be simply a mixture of zinc oxide and zinc orthophosphite. It may be obtained by the reaction of zinc oxide and phosphorous acid by the method disclosed in JP-A-50-50297.

The particle size of the basic zinc (I) phosphite is not particularly limited, but an average particle size of 100 is preferred.
It is less than or equal to μm, and more preferably less than or equal to 10 μm. By using the basic zinc (I) phosphite in this range, the effect can be more exerted.

The amount of the basic zinc (I) phosphite compounded is 0.00 based on 100 parts by weight of the vinyl chloride resin.
It is 1 to 10 parts by weight, preferably 0.01 to 5 parts by weight. If the amount is less than 0.001 part by weight, the effect is hardly seen, and if it exceeds 10 parts by weight, not only the effect due to the increase in amount is not obtained but also the thermal stability is lowered.

The organic phosphorus-containing metal salt represented by the above general formula (II) or (III) of the component (b) used in the present invention (hereinafter referred to as "organic phosphorus-containing metal salt (II) or (III)"). )
In the general formulas (II) and (III), examples of the alkyl group having 1 to 30 carbon atoms represented by R ₁ and R ₃ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Groups such as dibutyl, tert-butyl, amyl, tert-amyl, hexyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, triacontyl etc. Examples of the arylalkyl group include benzyl, α-methylbenzyl, α, α-
Examples thereof include groups such as dimethylbenzyl, examples of aryl groups include groups such as phenyl, naphthyl, and biphenyl. Examples of alkylaryl groups include groups such as tolyl, xylyl, ethylphenyl, butylphenyl, and tert-butylphenyl. , Octylphenyl, nonylphenyl,
Examples thereof include groups such as dinonylphenyl, decylphenyl and dodecylphenyl, and examples of the alkaline earth metal represented by M include calcium, magnesium and barium.

Accordingly, examples of the above-mentioned organic phosphorus-containing metal salt (II) used in the present invention include the compounds P-1 to P-11 of the following [Chemical formula 5] to [Chemical formula 15]. Examples of the organic phosphorus-containing metal salt (III) include the following [Chemical Formula 1
6] to [Chemical 20] such as compounds P-12 to P-16. In addition, M in each compound represents the above-mentioned alkaline earth metal or zinc.

[0019]

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[0020]

[Chemical 6]

[0021]

[Chemical 7]

[0022]

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[0023]

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[0024]

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[0025]

[Chemical 12]

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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The above-mentioned organic phosphorus-containing metal salt (II) or (III)
The blending amount of is 100 parts by weight of vinyl chloride resin,
The amount is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight. If the blending amount is less than 0.001 part by weight, almost no effect is observed, and if the blending amount exceeds 10 parts by weight, not only the effect due to the increase in amount but also coloring occurs.

The vinyl chloride resin used in the present invention is not particularly limited to its polymerization method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. For example, polyvinyl chloride, chlorinated polyvinyl chloride, Polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, chloride Vinyl-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 Chlorine-containing 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 blended products thereof, or Chlorine-containing resin and other chlorine-free synthetic resin, for example, acrylonitrile-styrene copolymer, ethylene-vinyl acetate copolymer,
Examples include ethylene-ethyl (meth) acrylate copolymers, blends with polyesters and the like, block copolymers, graft copolymers, and the like.

The composition of the present invention may contain a hydrotalcite compound as the component (c) in addition to the components (a) and (b). The composition of the present invention can improve thermal stability and weather resistance by blending the hydrotalcite compound.

As the above-mentioned hydrotalcite compound,
As represented by the general formula (IV) of the following [Chemical Formula 21], a double salt compound composed of magnesium and aluminum, or zinc, magnesium and aluminum is preferably used,
The dehydrated water of crystallization may be used.

[0038]

[Chemical 21]

The hydrotalcite compound may be a natural product or a synthetic product. As a method for synthesizing the above synthetic product, JP-B-46-2280,
JP-B-50-30039, JP-B-51-2912
No. 9, Japanese Patent Publication No. 3-36839, Japanese Patent Publication No. 61-
Known methods described in Japanese Patent No. 174270 can be exemplified. Further, in the present invention, the hydrotalcite compound can be used without being limited by its crystal structure, crystal particle size and the like.

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

The blending amount of the above-mentioned hydrotalcite compound is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
Parts by weight. If the blending amount is less than 0.001 part by weight, the effect is scarcely seen, and if it exceeds 10 parts by weight, the effect is not improved and there is a possibility that performance may be deteriorated such as deterioration in coloring property, which is not preferable. .

The vinyl chloride resin composition of the present invention is particularly effective for hard or semi-rigid applications such as those requiring high temperature and high pressure during processing. Can be used. Here, the rigid vinyl chloride resin composition means that no plasticizer component is blended at all, and the semi-rigid vinyl chloride resin composition means that the blending amount of the plasticizer is 40 parts by weight or less.

Further, the composition of the present invention contains the metal (Li, Na, K, Ca, B) of carboxylic acid or phenol.
a, Mg, Sr, Zn, Cd, Sn, Cs, Al, organic Sn) salts can be added. Examples of the carboxylic acid forming the metal salt of the carboxylic acid include, for example, caproic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid. ,
Isostearic acid, 12-hydroxystearic acid, chlorostearic acid, 12-ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linoleic acid, oleic acid, arachidic acid, behenic acid, erucic acid, brassic acid and similar acids, and Naturally occurring mixtures of the above acids such as tallow fatty acid, coconut oil fatty acid, tung oil fatty acid, soybean oil fatty acid and cottonseed oil fatty acid, benzoic acid, p-tert-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluic acid, Examples thereof include xylyl acid, salicylic acid, 5-tertiary octyl salicylic acid, naphthenic acid, and cyclohexanecarboxylic acid.
Examples thereof include ethylphenol, cyclohexylphenol, nonylphenol, dodecylphenol and the like.

The addition amount of the above-mentioned metal salt of carboxylic acid or phenol is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of vinyl chloride resin.

The composition of the present invention further contains various additives which are usually used as additives for vinyl chloride resins, such as polyols, organic phosphite compounds, phenolic or sulfur antioxidants. It is also possible to add an epoxy compound, a plasticizer, an ultraviolet absorber, a hindered amine light stabilizer and the like.

Examples of the above-mentioned polyols include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, polypentaerythritol, pentaerythritol or stearic acid half ester of dipentaerythritol, and bis (dipentaerythritol). Examples include adipate, glycerin, tris (2-hydroxyethyl) isocyanurate.

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

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,
4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenylacid phosphite,
2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, diphenyldecyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tri (2-ethylhexyl) phosphite, tridecyl phosphite, tridecyl phosphite Lauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite,
Bis (neopentyl glycol) / 1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite,
Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, phenyl-4,4 '
- isopropylidenediphenol · pentaerythritol diphosphite, tetra (C ₁₂ ~ ₁₅ mixed alkyl) -
4,4'-isopropylidenediphenyl diphosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis (octylphenyl) bis [4,4'-n-butylidenebis (2-tert-butyl) -5
-Methylphenol)] ・ 1,6-hexanediol ・
Diphosphite, tetratridecyl-4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4) -Hydroxyphenyl) butane triphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-1
0-oxide and the like.

The amount of the organic phosphite compound added is
It is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol,
2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-
Di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylenebis [(3,5-di-tert-butyl-4
-Hydroxyphenyl) propionate], 4,4'-
Thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl-4-)
(Hydroxyphenoxy) -s-triazine, 2,2′-
Methylene bis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butylic acid] glycol ester, 4,4′-butylidenebis (6-tert-butyl Butyl-m
-Cresol), 2,2′-ethylidenebis (4,6-
Di-tert-butylphenol), 1,1,3-tris (2-
Methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-
Hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6
-Dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-
Di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4)
-Hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-
4-hydroxyphenyl) propionyloxyethyl]
Isocyanurate, tetrakis [methylene-3- (3,
5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6-
(2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5 , 5] undecane-bis [β-
(3-tert-butyl-4-hydroxy-5-butylphenyl) propionate] and triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

Examples of the sulfur-based antioxidants include dilauryl thiodipropionate, dimyristyl,
Examples thereof include dialkylthiodipropionates such as myristyl stearyl and distearyl esters, and β-alkylmercaptopropionic acid esters of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate).

Examples of the epoxy compound include epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, and epoxidized safflower oil. Animal and vegetable oil, epoxidized methyl stearate, -butyl,
2-ethylhexyl, -stearyl ester, epoxidized polybutadiene, tris (epoxypropyl) isocyanurate, epoxidized tall oil fatty acid ester, epoxidized linseed oil fatty acid ester, bisphenol A diglycidyl ether, vinylcyclohexene diepoxide, dicyclohexene diepoxide Examples include epoxy compounds such as 3,4-epoxycyclohexylmethylepoxycyclohexanecarboxylate.

Examples of the plasticizers include phthalate plasticizers such as diheptyl phthalate, dioctyl phthalate and diisononyl phthalate, adipate plasticizers such as dioctyl adipate, diisononyl adipate, di (butyl diglycol) adipate, and tritate. Examples include phosphate plasticizers such as cresyl phosphate, polyester plasticizers, chlorinated paraffin plasticizers, trimellitate plasticizers, pyromellitate plasticizers, and biphenyl tetracarboxylate plasticizers.

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

Examples of the hindered amine light stabilizer include, for example, 2,2,6,6-tetramethyl-4-
Piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6
-Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) sebacate, tetrakis (2,2,
6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetrakis (1,2,2,6,6-
Pentamethyl-4-piperidyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) di (tridecyl) -1,2,3,4
-Butanetetracarboxylate, bis (1,2,2,
6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,
2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6
-Tetraethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6
-Tetramethyl-4-piperidylamino) hexane /
2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6- Trioctylamino-s-triazine polycondensate,
1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl]- 1,
5,8,12-tetraazadodecane, 1,5,8,12
-Tetrakis [2,4-bis (N-butyl-N- (1,
2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12
-Tetraazadodecane, 1,6,11-tris [2,4
-Bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6
-Ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,
Hindered amine compounds such as 6-pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane.

Further, to the composition of the present invention, a stabilizing aid usually used for vinyl chloride resins can be added. Examples of the stabilizing aid include diphenylthiourea, anilinodithiotriazine, melamine, benzoic acid,
Examples thereof include cinnamic acid, p-tert-butylbenzoic acid, dehydroacetic acid (metal salt), dibenzoylmethane, stearoylbenzoylmethane, hydrotalcite, zeolite and perchlorate.

In the composition of the present invention, other additives which are usually used in vinyl chloride resins, such as a cross-linking agent, a foaming agent, an antistatic agent, an antifogging agent and a plate-out preventing agent, are added to the composition of the present invention. Agents, surface treatment agents, lubricants, flame retardants, antifogging agents, fluorescent agents, antifungal agents, bactericides, metal deactivators, release agents, pigments, processing aids, antioxidants, light stabilizers, etc. can do.

The composition of the present invention can be used irrespective of the processing method of the vinyl chloride resin,
For example, calendar processing, roll processing, extrusion processing,
It can be suitably used for melt casting, pressure molding, paste processing, powder molding and the like.

The composition of the present invention is used for building materials such as wall materials, floor materials, window frames, and wallpaper; interior materials for automobiles; covering materials for electric wires;
Agricultural materials such as tunnels; food packaging materials such as wraps and trays; paints; can be suitably used as miscellaneous goods such as leather, sheets, hoses and toys.

[0060]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples.

Example 1 Using the following composition, calendering was performed at 196 ° C. to prepare a 0.5 mm sheet. This was laminated and pressed at 180 ° C. to form a 1 mm press sheet, which was put in a gear oven at 190 ° C. and the blackening time (minutes) (thermal stability) was measured.

Further, in order to evaluate the weather resistance, the above press sheet was subjected to UV tester (60 mW / cm ² , 45 ° C., Li
ght / Dew / Rest = 6h / 3h / 2h, 40%
RH), after 50 hours, 100 hours and 200
The surface condition after the elapse of time was visually evaluated. Evaluation is 1 to 1
It is represented by 0, and 1 represents that the browning is large with the increase of the value without any change.

The results are shown in Table 1 below.

(Composition) Parts by weight Polyvinyl chloride resin (Geon 103EP) 100 Titanium oxide (rutile type) 6 Calcium carbonate 3 MBS resin 5 Acrylic processing aid 0.5 Oxidized polyethylene wax 0.5 Glycerin monostearate 0. 4 Calcium stearate 1.5 Zinc stearate 1.0 Test compound (see Table 1 below) 0.3 Hydrotalcite-1 ^{* 1} 1.2 Dipentaerythritol 0.3 Stearyl (3,5-ditertiary) butyl-4-hydroxy-0.2) propionate dibenzoylmethane 0.1 tribasic phosphite zinc _{(3ZnO · ZnPHO 3 · 2H 2} O) 0.2 * 1: Mg 3 ZnAl 2 (OH) 12 CO 3・ 3H ₂ O

[0065]

[Table 1]

In the table, compounds P-1 to P-16 are the compounds shown in [Chemical formula 5] to [Chemical formula 20] (hereinafter the same).

Example 2 A press sheet was prepared in the same manner as in Example 1 using the following formulation, and the same test as in Example 1 was conducted. The results are shown in Table 2 below.

(Composition) Parts by weight Polyvinyl chloride resin (Geon 103EP) 100 Titanium oxide (rutile type) 6 Calcium carbonate 3 Acrylic graft polymer 5 Acrylic processing aid 0.5 Oxidized polyethylene wax 0.5 Glycerin monostearate 0 .4 Calcium stearate 1.5 Zinc stearate 1.0 P-8-Zinc salt 0.15 P-13-Zinc salt 0.15 Hydrotalcite-1 1.2 Dipentaerythritol 0.3 Stearyl (3,5 -Di-tert-butyl-4-hydroxy 0.3 phenyl) propionate dibenzoylmethane 0.1 inorganic metal salt (see Table 2 below) 0.2

[0069]

[Table 2]

Example 3 A press sheet was prepared in the same manner as in Example 1 using the following formulation, and the same test as in Example 1 was conducted. However,
The accelerated weather resistance test was measured only for 50 hours and 100 hours. The results are shown in Table 3 below.

(Combined) parts by weight polyvinyl chloride resin (Geon 103EP) 100 dioctyl 2-ethylhexanol 30 barium stearate 0.6 zinc stearate 0.5 dibenzoylmethane 0.2 P-8-zinc salt 0.1 P-13-zinc salt 0.1 hydrotalcite ^-2 * 2 2.0 tetra (C ₁₂ ~ ₁₅ mixed alkyl) -4,4' Isopuropiri 0.3 den diphenyl phosphite inorganic metal salt (below Table 3 ]) 0.2 * 2: Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ · 3.5H ₂ O

[0072]

[Table 3]

Example 4 Using the following formulation, calendering was performed at 190 ° C. to prepare a 0.1 mm film. This film was set on an exposure table facing south at 45 degrees and the deterioration state (weather resistance) with time was observed. The evaluation of the weather resistance was conducted by a five-level evaluation by visual inspection according to the evaluation criteria shown below, and the results are shown in [Table 4] below. .

(Evaluation criteria of weather resistance) 1: No change in appearance 2: Slightly brown part is seen. 3: Black-brown spots are seen. 4: Large blackish-brown spots are seen and there is a break. 5: A tear is seen on the entire surface.

(Combined) parts by weight polyvinyl chloride resin (manufactured by Shin-Etsu Chemical: TK-1300) 100 dioctyl phthalate 47 tricresyl phosphate 5 sorbitan mon palmitate 2 methylenebisamide 0.5 octyl diphenyl phosphite 0.8 Barium stearate 0.5 Zinc stearate 0.2 Bisphenol A type epoxy resin 2 Organic phosphorus-containing zinc salt (see Table 4 below) 0.3 Surflon S-145 0.1 (perfluoroalkyl EO adduct manufactured by Asahi Glass) ) Hydrotalcite-2 5 tribasic zinc phosphite 0.1

[0076]

[Table 4]

From the results of the above [Table 1] to [Table 4], the following is clear. Vinyl chloride-based resin, organic phosphorus-containing metal salts or basic zinc phosphite even when used alone respectively, although some weather resistance improvement effect is shown, but still insufficient (Comparative Examples 1-1, 1-4 , 2-1,3-1,4-1,4-2
). Further, when acidic or neutral zinc phosphite or a basic phosphite of another metal species is used, the weather resistance improving effect is insufficient (Comparative Examples 2-3 to 2-6).

On the other hand, when the vinyl chloride resin is blended with the organic phosphorus-containing metal salt (I) and the basic zinc phosphite (II) or (III), excellent weather resistance is improved. Shows effects (Examples 1-1 to 1-11, 2-1 to 2-4, 3-1 to 3-
4, 4-1 to 4-8).

[0079]

EFFECTS OF THE INVENTION The vinyl chloride resin composition of the present invention (claim 1) is required to have excellent heat stability and heat colorability, and high weather resistance for construction materials such as window frames or agricultural materials. It can be preferably used for applications. Further, the vinyl chloride resin composition of the present invention (claim 2) has further improved thermal stability and light resistance.

Claims (2)

[Claims] (1) 100 parts by weight of a vinyl chloride resin, (a)
0.001 to 10 parts by weight of at least one basic zinc phosphite represented by the following general formula (I)
(b) At least one of the organic phosphorus-containing metal salts represented by the general formula (II) or (III) of the following [Chemical Formula 2] 0.001-10
A stabilized vinyl chloride-based resin composition containing 1 part by weight. Embedded image Embedded image 2. The vinyl chloride resin composition according to claim 1, which further comprises 0.00.1 to 10 parts by weight of the hydrotalcite compound (c).