JPH0228614B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention provides a stabilized halogen-containing resin composition, more specifically, a halogen-containing resin composition containing hydrotalcites, a specific polyhydric alcohol compound, a zinc organic acid salt, and a group a metal organic acid. The present invention relates to a stabilized halogen-containing resin composition containing a salt. [Problems to be solved by the conventional technology and the invention] When halogen-containing resin is subjected to heat molding,
It is prone to thermal decomposition mainly due to dehydrohalogenation, which causes deterioration of mechanical properties and color tone of processed products, resulting in significant disadvantages. In order to avoid such disadvantages, it is necessary to add one or more kinds of heat stabilizers to the synthetic resin to suppress deterioration during processing steps. Conventionally, various fatty acid metal salts or phenol metal salts have been used for this purpose. As a result, almost satisfactory results were obtained in terms of thermal stability.
However, in recent years, these metal salts, especially cadmium salts, have serious toxicity problems and their use has been severely restricted. For this purpose, various metal salts other than cadmium salts may be used in various combinations, e.g.
Ba/Zn series, Ca/Zn series, Ba/Ca/Zn series, etc. were proposed. However, its performance is not sufficient, and various stabilizing aids such as epoxy compounds, polyhydric alcohols, organic phosphorus compounds, organic sulfur compounds, and β
-The use of diketone compounds, ultraviolet absorbers, etc. has been proposed. In recent years, the use of hydrotalcites having a specific crystal structure as a stabilizer for halogen-containing resins has been proposed (Japanese Unexamined Patent Publication No. 80445/1983). However, hydrotalcites have a neutralizing effect as a stabilizing effect and also have a deoxidizing effect.
Since it accelerates the dehydrochlorination reaction, its use is severely limited. It also has the disadvantage of imparting color to the resin. [Means for Solving the Problems] In view of the current situation, the present inventors have conducted various studies and found that hydrotalcites, specific polyhydric alcohol compounds, zinc organic acid salts, and group a metal organic The present invention was completed by discovering that a significant stabilizing effect can be obtained when an acid salt is used in combination. That is, the present invention blends (a) hydrotalcites, (b) pentaerythritol or dipentaerythritol, (c) zinc organic acid salt, and (d) Group A metal organic acid salt into a halogen-containing resin. The hydrotalcite is a hydrous double salt compound of magnesium and aluminum represented by the following general formula [], and the amount thereof is 0.01 to 10 parts by weight per 100 parts by weight of the halogen-containing resin. parts by weight of the stabilized halogen-containing resin composition. The composition of the present invention will be explained in detail below. The hydrotalcites used in the present invention are hydrous double salt compounds consisting of magnesium and aluminum represented by the following general formula []. Mg _1-x Al _x (OH) ₂ A _x/2・mH ₂ O [] (In the above formula, x is a real number in the range of 0<x≦0.5, A represents CO ₃ or SO ₄ , and m represents a real number.) The above hydrotalcites may be natural products or synthetic products. As a synthesis method, for example, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-
Examples include known methods described in Japanese Patent Publication No. 30039, Japanese Patent Publication No. 51-29129, and the like. Further, in the present invention, it can be used without being restricted by its crystal structure or crystal particle size. In addition, the surface can be coated with higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate, organic sulfonic acid metal salts such as alkali metal todecylbenzenesulfonate, higher fatty acid amides, higher fatty acid esters, waxes, etc. You can also use one coated with. The amount of the hydrotalcite used is 0.01 to 10 parts by weight, particularly preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the halogen-containing resin. The amount of pentaerythritol or dipentaerythritol used in the present invention is 0.01 to 10 parts by weight per 100 parts by weight of the halogen-containing resin.
In particular, it is preferably 0.05 to 3 parts by weight. The organic acid residues in the zinc organic acid salts and group a metal (Mg, Ca, Ba, Sr) organic acid salts used in the present invention include the following carboxylic acid and phenol residues. Examples of carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, neodecanoic acid, 2-ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid,
Lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12
-Hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, P-tert-
Butylbenzoic acid, dimethylhydroxybenzoic acid,
3,5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N,N-dimethylbenzoic acid, acetoxybenzoic acid , monohydric carboxylic acids such as salicylic acid, P-tert-octylsalicylic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, octylmercaptopropionic acid, oxalic acid, malonic acid, succinic acid, Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorphthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid , monoesters or monoamide compounds of divalent carboxylic acids such as aconitic acid and thiodipropionic acid, di- or triester compounds of trivalent or tetravalent carboxylic acids such as hemimellitic acid, trimellitic acid, merophanoic acid, and pyromellitic acid. . In addition, examples of the above phenols include tert-
Butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, isooctylphenol, 2-ethylhexylphenol, tert ―
Nonylphenol, decylphenol, tert-octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisohexylphenol, methyl-
Examples include tert-octylphenol. When the composition of the present invention is further combined with an organic phosphite compound and/or an epoxy compound, an excellent synergistic effect is exhibited. Examples of the organic phosphite compounds that can be used in the present invention include diphenyldecyl phosphite, triphenyl phosphite, tris-nonylphenyl phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, tributyl phosphite, and diphenyl phosphite. lauryl acid phosphite, dibutyl acid phosphite, tris(dinonylphenyl) phosphite, trilauryl trithiophosphite, trilauryl phosphite,
Bis(neopentyl glycol)-1,4-cyclohexane dimethyl phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, diphenyl acid phosphite, tris(lauryl-
2-thioethyl) phosphite, tetratridecyl-1,1,3-tris(2'-methyl-5'-tertiary)
Butyl-4'-oxyphenyl)butane diphosphite, tetra( _C12 - _C15 mixed alkyl)4,4'-
Isopropylidene diphenyl diphosphite, tris(4-oxy-2,5-di-tert-butylphenyl) phosphite, tris(4-oxy-3,
5-di-tert-butylphenyl) phosphite, 2
-Ethylhexyl diphenyl phosphite, tris(mono-, di-mixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, diphenyl bis[4,
4'-n-butylidene bis(2-tert-butyl-5-
methylphenol)] thiodiethanol phosphite, bis(octylphenyl) bis[4,
4'-n-butylidene bis(2-tert-butyl-5-
methylphenol)]-1,6-hexanediol diphosphite, phenyl-4,4'-isopropylidene diphenol pentaerythritol diphosphite, phenyl diisodecyl phosphite, tetratridecyl-4,4'-n- Butylidene bis(2-tert-butyl-5-methylphenol)
Examples include diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, and the like. The amount of these organic phosphite compounds added is
It is preferably 0.01 to 5 parts by weight, particularly 0.1 to 3 parts by weight, based on 100 parts by weight of the halogen-containing resin. The above-mentioned epoxy compounds that can be used in the present invention include epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized tallow oil, epoxidized polybutadiene, epoxy methyl stearate, -butyl, ―
2-ethylhexyl, -stearyl, tris(epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized safflower oil, epoxidized linseed oil butyl fatty acid, 3-(2-xenoxy)-
1,2-epoxypropane, bisphenol-A
Diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl-6-methylepoxycyclohexane carboxylate, and the like. The amount of these epoxy compounds added is 0.01 to 10 parts by weight, especially 100 parts by weight of halogen-containing resin.
The amount is preferably 0.5 to 5 parts by weight. Phthalate plasticizers, other ester plasticizers, polyester plasticizers, phosphate plasticizers, chlorine plasticizers, and other plasticizers are used in the composition of the present invention as appropriate depending on the purpose. can. Since adding an antioxidant to the composition of the present invention can increase the anti-oxidative deterioration properties of the composition,
It can be used as appropriate depending on the purpose of use. These antioxidants include phenolic antioxidants, sulfur-containing compounds, and the like. If an ultraviolet absorber is added to the composition of the present invention, the photostability can be improved, so it is possible to select and use these as appropriate depending on the purpose of use. These include benzophenone, benzotriazole, salicylate, substituted acrylonitrile, various metal salts or metal chelates, especially nickel or chromium salts or chelates, triazine, piperidine, and the like. Furthermore, in order to obtain a non-toxic halogen-containing polymer, a non-toxic halogen-containing polymer composition that is non-toxic and has good thermal stability can be obtained by selecting and using a non-toxic metal soap from among the above-mentioned metal soaps. In addition, if necessary, the composition of the present invention may include, for example, a crosslinking agent, a pigment, a filler, a blowing agent, an antistatic agent,
Antifogging agents, plate-out prevention agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, antifungal agents, bactericides, metal deactivators, photodegradants, processing aids, mold release agents, reinforcing agents, etc. can be included. The halogen-containing resin used in the present invention includes:
For example, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, chlorinated rubber, 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, chloride Vinyl-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer Polymers, vinyl chloride-acrylonitrile copolymers, halogen-containing synthetic resins such as internally plasticized polyvinyl chloride, and the above halogen-containing resins and polyethylene, polypropylene, polybutene, poly-3-
α-olefin polymers such as methylbutene or polyolefins such as ethylene-vinyl acetate copolymers and ethylene-propylene copolymers, and their copolymers, polystyrene, acrylic resins, styrene and other monomers (e.g. maleic anhydride) , butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, methacrylic ester-butadiene-styrene copolymers, etc. Can be done. The following examples show the effects of the halogen-containing resin composition of the present invention, but the present invention is not limited to these examples. Example 1 The following composition was roll-kneaded and then press-processed to produce a sheet with a thickness of 1 mm. This sheet was examined for initial colorability, transparency, and thermal stability at 190°C. The results obtained are shown in Table 1. <Composition> Polyvinyl chloride resin 100 parts by weight Dioctyl phthalate 50 Epoxidized linseed oil 1.0 Zinc stearate 0.3 Barium stearate 0.7 Hydrotalcite compound* 0.1 Polyhydric alcohol compound (Table 1) 0.2 *Hydrotalcite manufactured by Kyowa Chemical Co., Ltd. DHT-4A
(hereinafter abbreviated as DHT-4A)

[Table] Example 2 A sheet with a thickness of 1 mm was prepared in the same manner as in Example 1 using the following formulation, and about this sheet,
Thermal stability at 190℃, initial colorability, and at 120℃
Elongation and tensile strength were measured after 280 hours of deterioration. The results obtained are shown in Table 2. <Formulation> Polyvinyl chloride resin 50 parts by weight ABS resin 50 NBR 10 Epoxidized soybean oil 10 Tetra (C _12-15 mixed alkyl) bisphenol A diphosphite 1.0 Calcium stearate 1.0 Zinc stearate 0.5 DHT-4A 0.2 Polyhydric alcohol compound (Table 2) 0.2

[Table] Example 3 A sheet with a thickness of 1 mm was prepared in the same manner as in Example 1 using the following formulation, and for this sheet,
Thermal stability and initial coloration at 190°C were measured.
The results obtained are shown in Table 3. <Formulation> Polyvinyl chloride resin 100 parts by weight Zinc stearate 0.5 Barium stearate 0.5 Dibutyltin malate polymer 0.2 Dipentaerythritol 0.3 Hydrotalcite compound (Table 3) 0.1

[Table] Example 4 In order to investigate the effect of using other stabilizing aids in combination with the composition of the present invention, a sheet with a thickness of 1 mm was prepared in the same manner as in Example 1 using the following formulation. The thermal stability of this sheet at 180°C was measured. The results obtained are shown in Table 4. <Formulation> Polyvinyl chloride resin 100 parts by weight Epoxidized soybean oil 5 Magnesium stearate 0.2 Calcium stearate 0.5 Zinc stearate 0.5 Mg _0.75 Al _0.25 (OH) ₂ (CO ₃ ) _0.125 0.63H ₂ O 0.1 Dipentaerythritol 0.1 Others stable Chemical aids (Table 4) (Table 4)

【table】

Claims (1)

[Claims] 1. A halogen-containing resin containing (a) hydrotalcites, (b) pentaerythritol or dipentaerythritol, (c) zinc organic acid salt, and (d) Group A metal organic acid salt. The composition comprises a composition in which the above-mentioned hydrotalcite is a hydrous double salt compound consisting of magnesium and aluminum represented by the following general formula [], and the amount thereof is equal to the above-mentioned halogen-containing resin.
A stabilized halogen-containing resin composition in an amount of 0.01 to 10 parts by weight per 100 parts by weight. Mg _1-x Al _x (OH) ₂ A _x/2・mH ₂ O [] (In the above formula, x is a real number in the range of 0<x≦0.5, A represents CO ₃ or SO ₄ , and m indicates a real number.)