JPH10330567A - Vinyl chloride resin composition for hose - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vinyl chloride resin compsn. which is excellent in heat resistance and weatherability and which, when molded into a hose, is greatly reduced in odor of water passing through it by compounding a vinyl chloride resin with a plasticizer, an alkaline earth metal salt of an org. acid and/or a hydrotalcite compd., a zinc salt of an org. acid, and a phosphite compd. SOLUTION: This compsn. is prepd. by compounding 100 pts.wt. vinyl chloride resin with 10-100 pts.wt. plasticizer, 0.001-10 pts.wt. ingredient comprising an alkaline earth metal salt of an org. acid and/or a hydrotalcite compd., 0.001-10 pts.wt. zinc salt of an org. acid, and 0.001-10 pts.wt. phosphite compd. of the formula (wherein n is 1-3; A is a residue of an alcoholic or phenolic hydroxyl compd. provided when n is 1, then A is R3 ; and R1 to R3 are each a 8C or higher alkyl group or an alkylphenyl group having a 4C or higher alkyl group). An example of the phosphite compd. is tris(2,4-di-tert-butylphenyl) phosphite.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition for hoses, and more particularly to a plasticizer, an organic acid alkaline earth metal salt or a hydrotalcite compound, and an organic acid zinc salt. And a vinyl chloride-based resin composition for hoses which comprises a specific phosphite compound and is excellent in heat resistance, weather resistance and the like.

[0002]

2. Description of the Related Art Vinyl chloride resins are inexpensive, have excellent heat resistance and weather resistance, and can be imparted with flexibility by compounding a plasticizer. For example, they are also used for home hoses.

[0003] A hose using such a vinyl chloride resin (hereinafter also referred to as a "PVC hose") is exposed to high-temperature hot water, even for home use, or exposed to direct sunlight or rain and wind outdoors. Sometimes left in a state,
In order to maintain the durability, high heat resistance and weather resistance are required.

Further, when water is passed through such a PVC hose, an odor remains in the water, which is a problem particularly when the water is used for drinking or cooking, and such measures have been desired. .

Accordingly, an object of the present invention is to provide a vinyl chloride resin composition for hoses which is excellent in heat resistance and weather resistance, and in which the problem of odor during passage of water is remarkably improved.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a plasticizer, an alkaline earth metal organic acid salt or a hydrotalcite compound,
It has been found that the above object can be achieved by adding a zinc salt of an organic acid and a phosphite compound having a specific structure in combination.

The present invention has been made based on the above-mentioned findings, and (a) 10 to 100 parts by weight of at least one kind of a plasticizer, (b) an organic acid salt of an alkaline earth metal, per 100 parts by weight of a vinyl chloride resin. And / or 0.001 to 10 parts by weight of at least one hydrotalcite compound; (c) 0.001 to 10 parts by weight of at least one kind of zinc organic acid;
(d) A vinyl chloride-based hose for a hose comprising at least 0.001 to 10 parts by weight of at least one phosphite compound represented by the general formula (I) of the following [Chemical formula 4] (same as the above [Chemical formula 1]). The present invention provides a resin composition.

[0008]

Embedded image

[0009]

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

Examples of the plasticizer (a) used in the present invention include phthalate plasticizers such as diheptyl phthalate, dioctyl phthalate and diisononyl phthalate, dioctyl adipate, diisononyl adipate and di (butyl diglycol). Adipate plasticizers such as adipate, trimellitate plasticizer, pyromellitate plasticizer, biphenylene polycarboxylate plasticizer, phosphate plasticizer, polyester plasticizer,
Chlorinated paraffin plasticizers and the like can be mentioned.

The amount of the plasticizer is 10 to 100 parts by weight, preferably 30 to 80 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 10 parts by weight, the hose after molding cannot have flexibility, and if it exceeds 100 parts by weight, bleeding may occur or heat resistance and weather resistance may be reduced.

The component (b) used in the present invention is an organic acid salt of an alkaline earth metal and / or a hydrotalcite compound.

The alkaline earth metal organic acid salts include, for example, calcium, barium, magnesium or strontium salts of carboxylic acids, organic phosphoric acids or phenols.

Specifically, the carboxylic acids 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, arachinic acid, behenic acid, erucic acid, brassic acid and similar acids And a mixture of the above naturally occurring acids such as tallow fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids,
Benzoic acid, pt-butyl benzoic acid, ethyl benzoic acid, isopropyl benzoic acid, toluic acid, xylic acid, salicylic acid, 5-t-octyl salicylic acid, naphthenic acid, cyclohexane carboxylic acid, and the like. Mono- or dioctyl phosphate, mono- or didodecyl phosphate, mono- or di-octadecyl phosphate, mono- or di- (nonylphenyl) phosphoric acid, and the phenols include phenol, cresol, ethyl phenol, cyclohexyl phenol. , Nonylphenol, dodecylphenol and the like.

The organic acid salt of an alkaline earth metal may be any of a normal salt, an acidic salt, a basic salt or an overbased complex.

The above hydrotalcite compound is
It is a double salt compound of carbonic acid and / or perchloric acid between magnesium, an alkali metal and / or zinc and aluminum as represented by the following general formula (IV). Ia _x1 Mg _x2 Zn _x3 Al
_y (OH) _{x1 + 2 (X2 + X3) + 3y-2}・ (CO ₃ ) _{1-z / 2} (ClO ₄ ) _Z・ mH ₂ O (I
V) (wherein Ia represents an alkali metal atom, x1, x
2, x3, y, and z each represent a condition represented by the following formula, and m represents a real number. 0 ≦ x1 ≦ 10, 0 ≦ x2 ≦ 1
0, 0 ≦ x3 ≦ 10, 1 ≦ y ≦ 10, 0 ≦ z ≦ 1, provided that x1 and x2 never become 0 at the same time. )

The hydrotalcite compound may be a natural product or a synthetic product. As a method for synthesizing the above hydrotalcite compound (synthetic product),
JP-B-46-2280, JP-B-50-30039
JP, JP-B-51-29129, JP-B-3-3
Known methods described in, for example, Japanese Patent Publication No. 6839, Japanese Patent Publication No. 4-73457, Japanese Patent Publication No. 7-2858, and Japanese Patent Application Laid-Open No. H8-31284 can be exemplified. Also,
The above hydrotalcite compound can be used without being limited by its crystal structure, crystal particle diameter, and the like.

The above-mentioned hydrotalcite compound has a surface formed of a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic metal sulfonate such as an alkali metal dodecylbenzenesulfonate, Those coated with higher fatty acid amides, higher fatty acid esters or waxes can also be used.

The organic acid salt of the alkaline earth metal and / or
Alternatively, the compounding amount of the hydrotalcite compound 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 not sufficiently exhibited, and if the amount exceeds 10 parts by weight, not only waste but also large coloring occurs.

The zinc organic acid as the component (c) used in the present invention is a zinc salt of a carboxylic acid, an organic phosphoric acid or a phenol, and the carboxylic acid, the organic phosphoric acid or the phenol is exemplified above. Such as
These may be any of normal salts, acidic salts, basic salts or overbased complexes.

The amount of the organic zinc compound is 0.001 to 10 parts by weight, based on 100 parts by weight of the vinyl chloride resin.
Preferably it is 0.01 to 5 parts by weight. The compounding amount is 0.
If the amount is less than 001 parts by weight, the effect is not sufficiently exhibited.
If the amount exceeds 0 parts by weight, blackening occurs during heat history.

In the phosphite compound represented by the above general formula (I) which is the component (d) used in the present invention, in the general formula (I), R ₁ , R ₂ and R ₃ (n = 1 A)
Represents an alkyl group having 8 or more carbon atoms or a phenyl group having at least one alkyl substituent having 4 or more carbon atoms. That is, in the present invention, the terminal of the phosphite compound is esterified with a long-chain alcohol or alkylphenol, thereby improving heat resistance or weather resistance, and further attempts to improve the problem of odor during water passage. However, it is characteristic. Where R ₁ , R ₂
And the alkyl group having 8 or more carbon atoms of R ₃ (A when n = 1) includes, for example, octyl, isooctyl,
2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, triacontyl and the like.Examples of the phenyl group having an alkyl substituent having 4 or more carbon atoms include butyl. Phenyl, tert-butylphenyl, octylphenyl, nonylphenyl, dinonylphenyl, decylphenyl, dodecylphenyl, 2,4-ditertbutyl, 2,6-ditertbutyl-4-methylphenyl, 2-tert-phenyl Butyl-5-methylphenyl and the like. Compounds that can provide A (when n = 2 or 3) include, for example, ethylene glycol, diethylene glycol, 1,
3-propanediol, 1,4-butanediol, 1,
5-pentanediol, 1,6-hexanediol,
1,8-octanediol, 1,9-nonanediol,
1,2-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,2-butanediol , 1,3-butanediol, 1,5-hexanediol, 3-methyl-1,5-
Pentanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-octanediol, 2-methyl-1,8
-Octanediol, glycerin, trimethylolpropane, trimethylolethane, bisphenol A, bisphenol F, bisphenol AD, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and the like. Can be

Accordingly, the phosphite compound represented by the above general formula (I), which is the component (d) used in the present invention, includes, for example, tris (2,4-di-tert-butylphenyl) phosphite. , Tris [2-tert-butyl-4-
(3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, mono (dinonylphenyl) bis (nonylphenyl) phosphite, di (tridecyl) penta Erythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (C _12-15 mixed alkyl) -4,4 '-
n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,
1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite and the like.

The amount of the phosphite compound 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 not sufficiently exhibited, and if the amount is more than 10 parts by weight, not only is useless, but also other properties such as blooming or bleeding are adversely affected.

The vinyl chloride resin used in the present invention is not particularly limited to a polymerization method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. Examples thereof include polyvinyl chloride and chlorinated polyvinyl chloride. , Polyvinyl chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, Vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile 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 nil-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymers, and their blends, or Chlorine-containing resins and other chlorine-free synthetic resins, such as acrylonitrile-
Examples include styrene copolymers, ethylene-vinyl acetate copolymers, ethylene-ethyl (meth) acrylate copolymers, blends with polyesters, block copolymers, graft copolymers, and the like.

The composition of the present invention may further comprise, as a component (e), a compound represented by the following general formula (I),
By using the phosphorus-containing metal salt represented by I) in combination,
It is preferable because a material having more excellent heat resistance and weather resistance can be obtained.

[0027]

Embedded image

In the above formula (II), an alkyl group having 8 or more carbon atoms represented by R ₄ and R ₅ or a carbon atom having 4 carbon atoms
Examples of the phenyl group having an alkyl substituent include the groups exemplified in the above component (d). Examples of the alkaline earth metal represented by M include barium, magnesium, calcium, strontium, and the like.

The phosphorus-containing metal salt represented by the general formula (II) can be prepared, for example, by adding acid phosphite or a mixed acid thereof with a carboxylic acid to an alkaline earth metal and / or zinc oxide or hydroxide. It can be produced by a reaction method, a method of reacting a sodium salt of an acid phosphite or a mixed acid thereof with a carboxylic acid and an alkaline earth metal salt and / or a zinc chloride.

In particular, as the above-mentioned phosphorus-containing metal salt, a carboxylate of alkaline earth metal and / or zinc carboxylate is added to the following general formula (III) of the following [formula 6] (same as the above [formula 3]).
By using a reaction product with acid phosphite represented by the formula (1), heat resistance and weather resistance can be further improved.

[0031]

Embedded image

In obtaining the above reaction product, the reaction temperature is not particularly limited, but is generally 60 to 300 ° C.
Preferably, it is carried out at 80 to 200 ° C. Although the exact structure of the reaction product is not clear, it is presumed that it contains the phosphorus-containing metal salt represented by the general formula (II) because the carboxylic acid ester is replicated.

The above-mentioned phosphorus-containing metal salt can also be formed by adding an acid phosphite to a stabilizer system in which an excess amount of a metal salt of a carboxylic acid is present, followed by heat treatment.

The carboxylic acids 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. Acids, 12-hydroxystearic acid, chlorostearic acid, 12-ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linoleic acid, oleic acid, arachinic acid, behenic acid, erucic acid, brassic acid and similar acids and tallow Fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids and cottonseed oil fatty acids such as naturally occurring acid mixtures,
Benzoic acid, pt-butyl benzoic acid, ethyl benzoic acid, isopropyl benzoic acid, toluic acid, xylic acid, salicylic acid, 5-t-octyl salicylic acid, naphthenic acid, cyclohexane carboxylic acid, etc., and the acid phosphite For example, monooctyl acid phosphite, monodecyl acid phosphite, monododecyl acid phosphite, monotetradecyl acid phosphite, monohexadecyl acid phosphite, monooctadecyl acid phosphite, monoicosyl acid phosphite, mono ( Tert-butylphenyl) acid phosphite, mono (nonylphenyl) acid phosphite and the like.

The amount of the phosphorus-containing metal salt is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. When the amount is less than 0.001 part by weight, the effect of use is scarcely observed, and when the amount is more than 10 parts by weight, disadvantages such as a decrease in heat resistance may occur, which is not preferable.

The composition of the present invention may further contain various additives usually used as additives for vinyl chloride resins, for example, polyols, epoxy compounds, β-diketone compounds, phenolic or sulfuric compounds. An antioxidant, an ultraviolet absorber, a hindered amine light stabilizer, an inorganic stabilizer, a filler, and the like can be added.

The polyols include, for example, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentarisritol, polypentaerythritol, pentaerythritol or half-stearic acid ester of dipentarisritol, bis (dipentaerythritol) Adipate, glycerin, tris (2-hydroxyethyl) isocyanurate and the like can be mentioned.

Examples of the epoxy compound include epoxidized animal and vegetable oils such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized tallow oil, epoxidized castor oil, and epoxidized safflower 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, 3 And epoxy compounds such as 1,4-epoxycyclohexylmethylepoxycyclohexanecarboxylate.

Examples of the β-diketone compound include dibenzoylmethane, benzoylacetone, stearoylbenzoylmethane, caproylbenzoylmethane, dehydroacetic acid and the like, and salts of these metals (zinc, copper, cobalt, nickel, etc.). .

Examples of the phenolic antioxidants include 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-p-cresol.
Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-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′-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butyl) Phenyl) butyric acid] glycol ester, 4,
4′-butylidenebis (6-tert-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 dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl and distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecylmercaptopropionate). And β-alkyl mercaptopropionate esters of polyols.

Examples of the ultraviolet absorber include, for example, 2,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis (2-
2- such as hydroxy-4-methoxybenzophenone)
Hydroxybenzophenones; 2- (2-hydroxy-
5-methylphenyl) benzotriazole, 2- (2-
Hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-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-6-benzotriazolylphenol), 2- (2-hydroxy-
2- (3-tert-butyl-5-carboxyphenyl) benzotriazole such as polyethylene glycol ester
(2-hydroxyphenyl) benzotriazoles; 2
-(2-hydroxy-4-hexyloxyphenyl)-
4,6-diphenyl-1,3,5-triazine, 2-
(2-hydroxy-4-octoxyphenyl) -4,6
2- (2-hydroxyphenyl) -1, such as -bis (2,4-dimethylphenyl) -1,3,5-triazine,
3,5-triazines; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4 Benzoates such as -hydroxybenzoate; 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-
Substituted oxanilides such as dodecyl oxanilide; cyanoacrylates such as ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; Metal salts or metal chelates, especially salts or chelates of nickel or chromium, are mentioned.

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, , 2,6,6-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-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
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
And 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 inorganic stabilizers include calcium oxide, calcium hydroxide, calcium silicate, amorphous aluminosilicate, alkali and / or alkaline earth aluminosilicate having a zeolite crystal structure, and powdered silica (silica). ), Sodium perchlorate,
Examples include magnesium perchlorate and barium perchlorate.

Examples of the filler include calcium carbonate, silica, clay, glass beads, mica, sericite, glass flake, asbestos, wollastonite, potassium titanate, PMF, gypsum fiber, zonolite, M
OS, phosphate fiber, glass fiber, carbonate fiber, aramid fiber and the like.

In addition, the composition of the present invention may contain, if necessary, additives usually used for vinyl chloride resins, for example,
Cross-linking agent, antistatic agent, anti-fog agent, plate-out inhibitor,
Surface treatment agents, lubricants, flame retardants, fluorescent agents, fungicides, fungicides,
Metal deactivators, release agents, pigments, processing aids, antioxidants,
A light stabilizer and the like can be blended.

The preferred composition of the composition of the present invention is such that 100 parts by weight of the vinyl chloride resin is mixed with the component (a) 10
To 100 parts by weight, 0.001 to 10 parts by weight of the component (b), 0.001 to 10 parts by weight of the component (c), 0.001 to 10 parts by weight of the component (d) and 0 for the component (e). .00
It is a composition comprising 1 to 10 parts by weight.

Further, a more preferable composition of the composition of the present invention is such that 100 parts by weight of the vinyl chloride resin is mixed with
30-80 parts by weight of component (a), 0.01-5 parts of component (b)
Parts by weight, 0.01 to 5 parts by weight of the component (c), 0.01 to 5 parts by weight of the component (d), and 0.01 to 5 parts by weight of the component (e).
It is a composition comprising parts by weight.

The composition of the present invention is prepared according to a conventional method using the above components. Then, the obtained composition of the present invention is further formed into a hose for domestic use or the like by a usual forming method.

The composition of the present invention is excellent in heat resistance and weather resistance, has a remarkably improved odor problem when passing water, and can provide an excellent hose. The effects of the invention are further exhibited.

[0051]

Next, the present invention will be described with reference to examples.
The present invention is not limited by the following examples.

Example 1 The following formulation was kneaded on a roll at 175 ° C. and 20 rpm for 6 minutes, and then pressed at 180 ° C. for 5 minutes to form a 1 mm thick sheet, and the yellowness of the sheet was measured. The color difference from the sheet pressed for 30 minutes under the same conditions was determined. Further, a test piece was prepared from this sheet, heated in a gear oven at 190 ° C., and the time until blackening was measured to evaluate the thermal stability.

In addition, outdoor exposure of test pieces (Urawa City, Saitama Prefecture)
And sampled after 6 and 12 months,
The surface condition was observed and the weather resistance was evaluated. The evaluation criteria for the weather resistance are 1 to 10 in 1 to 10, and 1 represents a state where there is no change, and a state where browning or dirt is large with an increase in the numerical value.

Further, 30 cm of a test specimen of 10 cm × 10 cm was placed in a 100 cc sample bottle with a lid filled with tap water.
After adding the test piece, the test piece was removed and the odor was confirmed. At that time, 1 (no odor) to 16 subjects was 10 to 10
(A strong odor) was evaluated on a 10-point scale, and the average value was taken.

The results are shown in Table 1 below.

(Combination) parts by weight polyvinyl chloride resin (degree of polymerization 1300) 100 di-2-ethylhexyl phthalate 60 epoxidized soybean oil 2 zinc stearate 0.7 barium oleate 0.3 barium nonyl phenyl acid phosphite ( Ba-P) ^{* 1} 0.2 Alkamizer 1 ^{* 2} 0.5 Test compound (see [Table 1] below) 0.7

[0057]

Embedded image

* 2: Kyowa Chemical Co., Ltd. hydrotalcite Composition formula: Mg ₄ Al ₂ (OH) ₁₂ CO ₃ .3H ₂ O

[0059]

[Table 1]

Next, the barium used in Example 2 was
A production example of a zinc-based phosphorus-containing metal salt will be described.

Production Example 1 350 parts by weight of barium oleate, 77 parts by weight of zinc benzoate and 200 parts by weight of a hydrocarbon-alcohol mixed solvent were charged, the system was made uniform while the temperature was raised, and bis (nonylphenyl) acid phosphite was further added. 365 parts by weight were charged and subjected to a heat treatment at 100 ° C. to produce a barium-zinc phosphorus-containing metal salt (BZP-1).

Production Example 2 A barium-zinc phosphorus-containing material was produced in the same manner as in Production Example 1 except that 365 parts by weight of bis (nonylphenyl) acid phosphite used in Production Example 1 was replaced with 175 parts by weight of diphenyl acid phosphite. A metal salt (BZP-2) was produced.

Example 2 The same test as in Example 1 was conducted with the following formulation. The results are shown in Table 2 below.

(Combination) parts by weight polyvinyl chloride resin (degree of polymerization 1300) 100 di-2-ethylhexyl phthalate 60 epoxidized soybean oil 2 zinc stearate 0.2 barium-zinc based phosphorus-containing metal salt (BZP-1) 1.2 Barium oleate 0.3 Dibenzoylmethane 0.1 2,5-Ditert-butyl-4-hydroxyphenylstearate 0.1 2-Hydroxy-4-n-octylbenzophenone 0.2 Test compound (see below) (See [Table 2]) 0.7

[0065]

[Table 2]

Production Example 3 350 parts by weight of barium oleate and 200 parts by weight of a hydrocarbon-alcohol mixed solvent were charged, the system was made uniform while raising the temperature, and 97 parts by weight of bis (nonylphenyl) acid phosphite were further charged. A heat treatment was carried out at ℃ to produce a barium-based phosphorus-containing metal salt (BP-1).

Preparation Example 4 Preparation Example 3 was repeated except that 97 parts by weight of bis (nonylphenyl) acid phosphite used in Preparation Example 3 was replaced by 92 parts by weight of bis (2,4-di-t-butylphenyl) acid phosphite. In the same manner as in Example 3, a barium-based phosphorus-containing metal salt (BP-2) was produced.

Production Example 5 A barium-based phosphorus-containing metal was produced in the same manner as in Production Example 3, except that 97 parts by weight of bis (nonylphenyl) acid phosphite used in Production Example 3 was replaced with 72 parts by weight of didecyl acid phosphite. A salt (BP-3) was produced.

Production Example 6 A barium-based phosphorus-containing metal salt was prepared in the same manner as in Production Example 3 except that 97 parts by weight of bis (nonylphenyl) acid phosphite used in Production Example 3 was replaced with 47 parts by weight of diphenyl acid phosphite. (BP-4) was produced.

Example 3 The same test as in Example 1 was conducted with the following formulation. The results are shown in Table 3 below.

(Combination) parts by weight polyvinyl chloride resin (degree of polymerization 1300) 100 di-2-ethylhexyl phthalate 60 epoxidized soybean oil 2 zinc stearate 0.7 barium oleate 0.2 dibenzoylmethane 0.1 2 , 5-Ditert-butyl-4-hydroxyphenylstearate 0.1 2-hydroxy-4-n-octylbenzophenone 0.2 Tris (nonylphenylphosphite) 0.7 Test compound (see Table 3 below) 1.0

[0072]

[Table 3]

As is clear from the examples, the weather resistance was improved by using an organic acid salt and / or hydrotalcite compound of an alkaline earth metal, an organic acid zinc and a specific phosphite compound in combination with a vinyl chloride resin. It exhibits excellent heat resistance and also has an improved odor. The effect can be further improved by using a specific phosphorus-containing metal salt in combination.

On the other hand, when a phosphite compound such as triphenyl phosphite was used instead of the specific phosphite compound according to the present invention (Comparative Examples 1-2, 1-3, 2-2,
According to 2-3), both heat resistance and weather resistance are insufficient, and the odor is strong.

[0075]

Industrial Applicability The vinyl chloride resin composition for hoses of the present invention has excellent heat resistance and weather resistance, has significantly improved odor during passage of water, and can provide excellent hoses.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08K 5:56) (C08K 13/02 3:26 5:00 5: 524) (72) Inventor Masaru Nagahama Shirahata, Urawa-shi, Saitama 5-2-1-3 Asahi Denka Kogyo Co., Ltd.

Claims (4)

[Claims] (1) 100 parts by weight of a vinyl chloride resin, (a)
10 to 100 parts by weight of at least one kind of plasticizer, (b) 0.001 to 10 parts by weight of at least one kind of organic acid salt of alkaline earth metal and / or hydrotalcite compound,
(c) 0.001 to 10 parts by weight of at least one kind of zinc organic acid and (d) 0.001 to 10 parts by weight of at least one kind of a phosphite compound represented by the following general formula (I): A vinyl chloride resin composition for hoses comprising: Embedded image 2. The method according to claim 1, wherein (e) is a compound of the following general formula (II):
At least one of the phosphorus-containing metal salts represented by 0.001 to
The vinyl chloride resin composition for a hose according to claim 1, which is blended with 10 parts by weight. Embedded image 3. The phosphorus-containing metal salt as the component (e) is a carboxylate and / or zinc carboxylate of an alkaline earth metal and an acid represented by the following general formula (III): 3. The vinyl chloride resin composition for a hose according to claim 2, which is obtained by reacting with a phosphite. Embedded image 4. The vinyl chloride resin composition for hoses according to claim 1, which is used for water.