JP2003160707A - Polyvinyl chloride-based resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyvinyl chloride-based composition having excellent thermal stability and weatherability without using heavy metal-based stabilizers, and suitably usable for applications requiring high weatherability such as construction materials completely free from plasticizers. <P>SOLUTION: This polyvinyl chloride-based resin composition comprises (a) 0 to 40 pts.wt. of a plasticizer, (b) 0.001 to 10 pts.wt. of at least an organic acid alkaline earth metal salt, (c) 0.001 to 10 pts.wt. of at least one organic acid zinc salt, (d) 0.001 to 10 pts.wt. of at least a basic zinc phosphate expressed by formula (I): xZnO.ZnPO<SB>4</SB>.yH<SB>2</SB>O (wherein x denotes 0.1 to 20 and y denotes 0 or a positive number), and (e) at least a hydrotalcite compound expressed by formula (II): Mg<SB>x1</SB>Zn<SB>x2</SB>Al<SB>2</SB>.(OH)<SB>2x1+2x2+4</SB>.(CO<SB>8</SB>)<SB>1-y1/2</SB>(ClO<SB>4</SB>)<SB>y1</SB>.mH<SB>2</SB>O (wherein x1, x2 and y1 are each a number satisfying conditions expressed by inequalities: 0≤x2/x1<10, 2≤x1+x2<20, 0≤y1≤2, m denotes 0 or an arbitrary positive number). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition, and more specifically, by adding an organic acid alkaline earth metal salt, an organic acid zinc salt, a basic zinc phosphate and a hydrotalcite compound together. , A hard or semi-rigid vinyl chloride resin composition having excellent heat resistance and weather resistance and containing no heavy metal.

[0002]

2. Description of the Related Art Vinyl chloride resins can be used for various purposes because their hardness can be easily adjusted by using a plasticizer. A semi-rigid vinyl chloride resin composition containing no agent or containing a small amount of a plasticizer is widely used for building materials because of its excellent rigidity.

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. Therefore, various stabilizers such as metal salts of organic acids, organic tin compounds, organic phosphite compounds, epoxy compounds, β-diketone compounds, antioxidants, and ultraviolet absorbers are blended to stabilize vinyl chloride resins. Are being tried to improve.

In recent years, since the use of heavy metals such as lead and cadmium has been shunned due to toxicity problems, barium-zinc composite stabilizers tend to be used, and more recently barium is also a heavy metal. Therefore, it is desired to replace the calcium-zinc-based or calcium-magnesium-zinc-based composite system with a low toxicity with a stabilizer, but when these stabilizers are used, thermal stability,
Performance such as weather resistance is completely insufficient.

Basic inorganic metal salts such as basic zinc phosphate are also known as stabilizers for vinyl chloride resins. For example, JP-A-51-30850 discloses a basic inorganic metal salt and an organic salt. It has been proposed to use a phosphite compound in combination, and JP-A-54-16555 and JP-A-5-55555 have been proposed.
Japanese Patent Application Laid-Open No. 4-62250 proposes to use a basic inorganic metal salt and a β-diketone compound in combination, but in these combinations, the effect of improving weather resistance is still insufficient.

Further, in Japanese Patent Application Laid-Open No. 4-202451, organic acid salts of barium and zinc, hydrotalcites, organic phosphite compounds and organic acid phosphite compounds, epoxy compounds, phosphorous acid, diphosphorous acid. Alternatively, it has been proposed to add these metal salts and titanium dioxide, and JP-A-9-67489 discloses an organic acid calcium salt, an organic acid zinc salt, a basic phosphite and a hydrotalcite compound. Although it has been proposed to add them, the effect of improving the weather resistance was still insufficient in these combinations.

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.

Therefore, an object of the present invention is to show excellent heat stability and weather resistance without using a heavy metal stabilizer.
It is an object of the present invention to provide a vinyl chloride resin composition that can be suitably used even in applications requiring a high degree of weather resistance such as building materials applications that do not use plasticizers at all.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that vinyl chloride resins contain organic acid alkaline earth metal salts, organic acid zinc salts, specific basic zinc phosphates and hydrodesalts. By adding the talcite compound together,
The inventors have found that the above objects can be achieved and have reached the present invention.

That is, the present invention is based on the vinyl chloride resin 100.
(A) 0 to 40 parts by weight of a plasticizer, and (b) at least one kind of organic acid alkaline earth metal salt 0.001 to 100 parts by weight.
10 parts by weight, (c) at least one kind of organic acid zinc salt.
001 to 10 parts by weight, (d) at least one kind of basic zinc phosphate represented by the following general formula (I) 0.001 to 10
Parts by weight, and (e) at least one kind of hydrotalcite compound represented by the following general formula (II) 0.001 to 10
It is intended to provide a vinyl chloride-based resin composition containing 1 part by weight.

[0011]

[Chemical 3]

[0012]

[Chemical 4]

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The vinyl chloride resin composition of the present invention will be described in detail below.

Examples of the plasticizer which is the component (a) used in the present invention include phthalate plasticizers such as diheptyl phthalate, dioctyl phthalate and diisononyl phthalate, dioctyl adipate, diisononyl adipate, di (butyl diglycol) adipate. Adipate plasticizers such as, phosphate plasticizers such as tricresyl phosphate, polyester plasticizers, chlorinated paraffin plasticizers, trimellitate plasticizers, pyromellitate plasticizers, biphenyl tetracarboxylate plasticizers, etc. To be

The blending amount of the above plasticizer is 0 to 40 parts by weight, preferably 0, to 100 parts by weight of the vinyl chloride resin.
~ 30 parts by weight. Here, if the blending amount exceeds 40 parts by weight, the rigidity decreases.

Examples of the alkaline earth metal constituting the component (b) of the organic acid alkaline earth metal salt used in the present invention include magnesium, calcium, barium, etc., and the organic acid alkaline earth metal salt is constituted. Examples of the organic acid used include carboxylic acid, organic phosphoric acid, and phenols. The organic acid alkaline earth metal salt may be any of an acidic salt, a basic salt or an overbased salt.

Examples of the carboxylic acid include 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. Acids, 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 tallow. Naturally occurring mixtures of the above acids such as fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids, benzoic acid, p-tert-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid, toluic acid, xylyl. Acid, salicylic acid, 5-tertiary octylsali Le acid, naphthenic acid, and cyclohexane carboxylic acid. Examples of the above organic phosphoric acid, mono- or dioctyl phosphate, mono- or Jidodeshirurin acid, mono- or di-octadecyl phosphoric acid, mono- or di -
Examples thereof include (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, phosphonic acid stearyl ester, and the like, and the phenols include phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol, dodecylphenol, and the like.

The amount of the organic acid alkaline earth metal salt 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 blending amount is less than 0.001 part by weight, thermal stability is insufficient, and if it exceeds 10 parts by weight, coloring is large,
It causes a plate out.

The organic acid constituting the component (c) of the organic acid zinc salt used in the present invention is the same as the organic acid exemplified as the component (b) of the organic acid alkaline earth metal salt. There are things. The organic acid zinc salt may be an acid salt, a basic salt or an overbased salt.

The amount of the organic acid zinc salt is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 0.001 part by weight, the effect of improving the coloring property, weather resistance and the like is insufficient, and if it exceeds 10 parts by weight, the thermal stability is lowered.

In the basic zinc phosphate represented by the above general formula (I) which is the component (d) used in the present invention, x represents 0.1 to 20 in the general formula (I), and is preferable. Represents 0.3 to 10. When x is less than 0.1 or 2
If it exceeds 0, the weather resistance improving effect is insufficient.
Further, y represents 0 or a positive number.

The compositional formula of the basic zinc phosphate is represented by the general formula (I), and the method for producing the basic zinc phosphate is not particularly limited, and it is simply zinc oxide and orthophosphoric acid. It may be a mixture with zinc.

The average particle size of the basic zinc phosphate is not particularly limited, but is preferably 100.
It is less than or equal to μm, and more preferably less than or equal to 10 μm. The effect can be more exerted by using the one having the average particle diameter within the above range.

The amount of the basic zinc phosphate compounded is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. 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 hydrotalcite compound which is the component (e) used in the present invention is a double salt compound composed of magnesium and aluminum, or zinc, magnesium and aluminum, as represented by the following general formula (II). It is preferable that the water of crystallization be dehydrated.

[0026]

[Chemical 5]

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.
No. 3, Japanese Patent Publication No. 3-36839, Japanese Patent Publication No. 61-1
Known methods described in Japanese Patent No. 74270 can be exemplified. Further, the hydrotalcite compound can be used without being limited by its crystal structure, crystal particle size and the like.

In the present invention, the surface of the hydrotalcite compound is a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an oleic acid alkali metal salt, or an organic sulfone such as dodecylbenzene sulfonic acid alkali metal salt. Those coated with an acid metal salt, higher fatty acid amide, higher fatty acid ester, wax or the like can also be used.

The amount of the above-mentioned hydrotalcite compound added 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 blending amount is less than 0.001 part by weight, the effect is hardly seen, and if it exceeds 10 parts by weight, the effect is not enhanced and the performance such as deterioration of the coloring property is caused.

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, vinyl chloride Chlorine-containing resins such as le-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 other Synthetic resin not containing chlorine, for example, acrylonitrile-styrene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl (meth) acrylate copolymer, blended product with polyester, block copolymer, graft copolymer Examples include coalescing.

The composition of the present invention may also contain other non-heavy metal (Li, Na, K, Al) salts of organic acids and the like. Examples of the organic acid that constitutes the organic acid salt include the same as those exemplified in the above (b) Organic acid alkaline earth metal salt. Further, the organic acid metal salt,
It may be an acid salt, a basic salt or an overbased salt.

The content of the non-heavy metal salt is preferably 0.001 to 1 with respect to 100 parts by weight of the vinyl chloride resin.
0 parts by weight.

Further, the composition of the present invention usually further comprises
Various additives used as additives for vinyl chloride resins, for example, organic phosphite compounds, phenolic or sulfur antioxidants, epoxy compounds, ultraviolet absorbers, hindered amine light stabilizers, foaming agents, etc. It can also be blended.

Examples of the above organic phosphite compound include, for example, 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-ditertiarybutylphenyl) octylphosphite, diphenyldecylphosphite, phenyldiisodecylphosphite, tributylphosphite, tri (2-ethylhexyl) phosphite, tridecylphosphite, tridecylphosphite Lauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite,
Bis (neopentyl glycol) -1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite,
Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, phenyl-4,4 ′
- isopropylidenediphenol · pentaerythritol diphosphite, tetra (C ₁₂ ~ ₁₅ mixed alkyl) -
4,4'-isopropylidene diphenyl diphosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis (octylphenyl) .bis [4,4'-n-butylidene bis (2-tertiary butyl) -5
-Methylphenol)]-1,6-hexanediol-
Diphosphite, tetratridecyl-4,4'-butylidene bis (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 can be mentioned.

Examples of the above-mentioned phenolic antioxidant include 2,6-di-tert-butyl-p-cresol and 2,6-
Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylenebis [ (3,5-Ditert-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'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butyl) Phenyl) butyric acid] glycol ester, 4,
4'-butylidene bis (6-tert-butyl-m-cresol), 2,2'-ethylidene bis (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, 1,3,3 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) bropionyloxyethyl] 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], triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

Examples of the sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecylmercaptopropionate). And β-alkyl mercaptopropionic acid esters of polyols and the like.

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, epoxidized safflower oil, and other epoxidized animal and vegetable oils. , 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,
Epoxy compounds such as dicyclohexene diepoxide and 3,4-epoxycyclohexylmethylepoxycyclohexanecarboxylate can be used. Further, when an epoxy compound such as epoxidized soybean oil used as a plasticizer is used here, the rigidity is lowered. Therefore, 25 parts by weight together with the plasticizer is added to 100 parts by weight of the vinyl chloride resin. It cannot be used in excess of parts.

Examples of the ultraviolet absorber include 2,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis (2-
2-hydroxybenzophenones such as (hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5)
-Methylphenyl) benzotriazole, 2- (2-hydroxy-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-tertiary octyl-6-benzotriazolyl) phenol, 2- (2-hydroxy-
2-tert-butyl-5-carboxyphenyl) benzotriazole such as polyethylene glycol ester
(2-Hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, hexadecyl-
Benzoates such as 3,5-di-tert-butyl-4-hydroxybenzoate; Substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide; Ethyl-α -Cyano-β, β-
Examples thereof include cyanoacrylates such as diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

Examples of the hindered amine light stabilizers 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, bis (2,2
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-di-tert-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
-Tertiary octylamino-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-triazin-6-ylamino] undecane, 1,6,11-tris [2,4
Examples thereof include hindered amine compounds such as -bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane.

Examples of the foaming agent include azo foaming agents such as azodicarbonamide, azobisisobutylnitrile, diazoaminobenzene, diethylazodicarboxylate, diisopropylazodicarboxylate and azobis (hexahydrobenzonitrile). Nitroso-based foaming agents such as N, N'-dinitropentamethylenetetramine, N, N'-dimethyl-N, N'-dinitroterephthalamine, benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, 3,3'-disulfone hydrazide phenyl Hydras such as sulfone, toluenedisulfonylhydrazone, thiobis (benzenesulfonylhydrazide), toluenesulfonyldiazide, toluenesulfonylsemicarbazide, p, p'-bis (benzenesulfonylhydrazide) ether -Based foaming agents, carbazide-based foaming agents such as p-toluenesulfonyl semicarbazide and 4,4'-oxybenz (sulfonyl semicarbazide), triazine-based foaming agents such as trihydrazinotriazine and 1,3-bis (o-biphenyltriazine) Is mentioned.

Further, the vinyl chloride resin composition of the present invention may contain a stabilizing aid usually used for vinyl chloride resins. Examples of the stabilizing aid include, for example,
Diphenylthiourea, anilinodithiotriazine, melamine, benzoic acid, cinnamic acid, p-tert-butylbenzoic acid,
Examples thereof include dehydroacetic acid (metal salt), dibenzoylmethane, stearoylbenzoylmethane, zeolite, perchlorate and the like.

In addition, if necessary, the vinyl chloride resin composition of the present invention may contain additives such as a crosslinking agent, an antistatic agent, an antifogging agent and a plate-out preventing agent, which are usually used in vinyl chloride resins. Agents, surface treatment agents, lubricants, flame retardants, antifog agents, fluorescent agents, antifungal agents, bactericides, metal deactivators, release agents,
Pigments, processing aids, antioxidants, light stabilizers and the like can be added.

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

The vinyl chloride resin composition of the present invention is used for building materials such as wall materials, floor materials, window frames, wallpaper, automobile interior materials, electric wire coating materials, agricultural materials, food packaging materials, paints, hoses, It can be suitably used as a miscellaneous goods such as a pipe, a sheet, a toy, etc., but it is particularly preferably used as a coating agent for a decorative board.

The decorative plate is a general term for a printed decorative plate, a decorative gypsum board, a vinyl chloride decorative plate, a vinyl chloride steel plate, and a vinyl chloride incombustible plate. The printed decorative board is obtained by printing thin paper or the like and laminating it on a support made of plywood, particle board or the like. Decorative plaster board, PVC decorative board,
A vinyl chloride metal plate, a vinyl chloride non-combustible plate, etc. are obtained by coating a vinyl chloride resin sheet on a support made of gypsum board, particle board, plywood, metal plate, concrete plate, or the like.

Examples of the metal plate used here include a steel plate, a stainless steel plate, an aluminum plate, and the like. These are plated with zinc, aluminum, or the like, chromate treatment, pickling, mechanical polishing treatment, phosphorus. It may be acid-treated.

The decorative board obtained by using the vinyl chloride resin composition of the present invention can be subjected to printing, embossing, etc., and can increase the surface hardness and improve smoothness and depth. For this purpose, an acrylic or silicone surface coating layer may be provided.

A vinyl chloride-coated plate obtained by using the vinyl chloride resin composition of the present invention is a building interior / exterior material, a refrigerator,
It can be used for household appliances such as washing machines and electric stoves, vending machines, office equipment, metal products such as furniture including food display cases.

[0049]

EXAMPLES Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention.

Example 1 The following formulation was calendered at 190 ° C. to prepare a 0.5 mm sheet. This is laminated and pressed at 180 ° C,
A 1 mm press sheet was prepared and placed in a gear oven at 190 ° C. to measure the blackening time (heat stability: HS; minutes).

Further, in order to evaluate the weather resistance, the above-mentioned press sheet was subjected to UV tester (60 mW / cm ² , 45 ° C., L
light / Dew / Rest = 6h / 3h / 2h, 40
% RH) and 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.

(Combination) Parts by weight Polyvinyl chloride resin (Geon 103EP) 100 Titanium oxide (rutile type) 0.2 Calcium carbonate 2 Carbon black 0.01 MBS resin 5 Calcium stearate 0.4 Zinc stearate 1.2 Dipenta erythritol 0.4 stearyl (3,5-di-tert-butyl-4-hydroxy-0.2) propionate dibenzoylmethane 0.2 tribasic zinc phosphate _{(3ZnO / ZnPHO 4 · 2H 2} O) 0.2 test Compound (See [Table 1] below) 0.5

[0054]

[Table 1]

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.

(Compounding) Parts by Weight Polyvinyl Chloride Resin (Geon 103EP) 100 Titanium Oxide (Rutile Type) 0.2 Calcium Carbonate 2 Carbon Black 0.01 MBS Resin 5 Calcium Stearate 0.4 Zinc Stearate 1.2 Dipentaerythritol 0.4 Stearyl (3,5-di-tert-butyl-4-hydroxy 0.2 phenyl) propionate Dibenzoylmethane 0.2 Inorganic metal salt (see [Table 2] below) 0.2 Mg ₄ Al ₂ (OH) ₁₂ (CO ₃ ) _0.4 (ClO ₄ ) _0.6 / 3H ₂ O 0.5

[0057]

[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. The results are shown in [Table 3] below.

(Compounding) Parts by weight Polyvinyl chloride resin (Geon 103EP) 100 Di (2-ethylhexyl) phthalate 20 Epoxidized soybean oil 2 MBS resin 5 Calcium stearate 0.3 Zinc stearate 1.2 Stearyl (3,5-di) Tert-Butyl-4-hydroxy 0.2 phenyl) propionate 2- (2-hydroxy-5-methylphenyl) 0.1 benzotriazole stearoylbenzoylmethane 0.2 inorganic metal salt (see Table 3 below) 0.2 Mg _4.5 Al ₂ (OH) ₁₃ CO ₃・ 3.5H ₂ O 0.3

[0060]

[Table 3]

From the results of the above [Table 1] to [Table 3], the following is clear. In a vinyl chloride resin that does not use a plasticizer at all, or uses a small amount and does not use a heavy metal stabilizer, in the case where a hydrotalcite compound is not used even when using a basic zinc phosphate, Its thermal stability is not sufficient at all, and even if a hydrotalcite compound is used, if an acidic or neutral zinc phosphate or a basic phosphate of another metal species is used, the weather resistance improving effect Is insufficient. Further, when a hydrotalcite compound and a basic zinc phosphite are combined, the effect of improving the weather resistance is improved, but the heat resistance is lowered.

On the other hand, in the vinyl chloride resin containing no plasticizer or a small amount of the plasticizer, organic acid calcium salt, organic acid zinc salt, basic zinc phosphite of the above general formula (I) are used. , And the vinyl chloride resin composition in which the hydrotalcite compound represented by the general formula (II) is used in combination exhibits extremely excellent improving effects on thermal stability and weather resistance.

[0063]

EFFECTS OF THE INVENTION The vinyl chloride resin composition of the present invention exhibits excellent heat stability and weather resistance without using a heavy metal stabilizer, and has a high weather resistance such as a construction material application in which no plasticizer is used. It can be suitably used even in applications where sex is required. The vinyl chloride resin composition of the present invention is more excellent in heat resistance.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J002 AE042 BD031 CF002 DE289                       DH049 EG037 EG048 EG077                       EG078 EH096 EH146 EW046                       EW047 EW048 FD022 FD026                       GL01

Claims (2)

[Claims] 1. To 100 parts by weight of vinyl chloride resin,
(A) 0 to 40 parts by weight of a plasticizer, (b) 0.001 to 10 parts by weight of at least one kind of organic acid alkaline earth metal salt,
(C) At least one kind of organic acid zinc salt 0.001-10
Parts by weight, (d) 0.001 to 10 parts by weight of at least one basic zinc phosphate represented by the following general formula (I), and
(E) A vinyl chloride resin composition comprising 0.001 to 10 parts by weight of at least one hydrotalcite compound represented by the following general formula (II). [Chemical 1] [Chemical 2] 2. The vinyl chloride resin composition according to claim 1, which is used for a decorative board.