JPH0227376B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilized halogen-containing resin composition, and more particularly to a halogen-containing resin composition obtained by adding an organic acid mixture salt, hydrotalcites, etc., and halogen oxyacid salts to a halogen-containing resin. When halogen-containing resin is heat-molded,
It is prone to thermal decomposition mainly due to dehydrohalogenation, which causes a decrease in the 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 organic acid metal salts and organic tin compounds 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 combinations of metal salts other than cadmium salts are used, such as Ba/Zn salts,
Ca/Zn series, Ba/Ca/Zn series, etc. were proposed. However, its performance is not sufficient, and various stabilizing agents such as epoxy compounds, polyhydric alcohols,
Although the use of organic phosphorus compounds, organic sulfur compounds, phenol compounds, β-diketone compounds, etc. has been proposed, it is still not sufficient and there is a need for further improvements. In recent years, the use of hydrotalcites having a specific crystal structure as a stabilizer for halogen-containing resins has been proposed (Japanese Patent Application Laid-Open No. 80445/1983). However, hydrotalcites have a neutralizing effect as a stabilizing effect and also have a deoxidizing effect and promote the dehydrohalogenation reaction, so their use is severely limited. Hydrotalcites also have the disadvantage of imparting color to the resin. In view of the current situation, the present inventors have conducted various studies and found that (a) at least one metal salt of an organic acid, (b) a hydrotalic compound represented by the following general formula () is added to the halogen-containing resin. At least one type of site, and
(c) The present invention was achieved by discovering that a significant stabilizing effect can be obtained by adding at least one selected from metal salts of halogen oxyacids. Mg _1-x Al _x (OH) ₂ A _x/2・mH ₂ O () (where 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 present invention will be explained in detail below. Carboxylic acids, phenols, and the like are useful as organic acids constituting the metal salt of organic acids used in the present invention. Examples of the above carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid,
Caprylic acid, neooctanoic acid, 2-ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid,
Palmitic acid, isostearic acid, stearic acid, 2-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, P-
tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-ditert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid,
Aminobenzoic acid, N,N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid, P-tert
- Monocarboxylic acids such as 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, aconitic acid, thiodi Examples include monoesters or monoamide compounds of divalent carboxylic acids such as propionic acid, and 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. Further, specific examples of metals constituting metal salts of organic acids include group a metals such as Na, K, and Li, Mg,
Examples include group a metals such as Ca, Sr, and Ba, Zn, Zr, and Sn. The amount of the metal salt of the organic acid according to the present invention added is 0.01 to 10 parts by weight, preferably 0.1 to 3 parts by weight, per 100 parts by weight of the resin. 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 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 disclosed in Japanese Patent Publication No. 30039 and Japanese Patent Publication No. 51-29129. Furthermore, in the present invention, the above-mentioned hydrotalcites can be used without being restricted by their crystal structure or crystal particle size. The surface of the above hydrotalcites is coated with higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate,
Those coated with an organic sulfonic acid metal salt such as an alkali metal salt of dodecylbenzenesulfonic acid, a higher fatty acid amide, a higher fatty acid ester, or a wax can also be used. Therefore, the above-mentioned amount of hydrotalcite added is 0.005 to 100 parts by weight of halogen-containing resin.
5 parts by weight, preferably 0.05 to 2 parts by weight. In addition, examples of the halogen oxyacids used in the present invention include perchlorates (Zn, Al, K,
Ca, Sr, Na, Ba, Mg, Li), periodate (Zn,
K, Na, Ba, Li), chlorate (Zn, Al, K,
Ca, Sr, Na, Ba, Mg, Li), bromate (Zn,
Al, K, Ca, Sr, Na, Ba, Mg, Li), iodate (Zn, Al, K, Ca, Sr, Na, Ba, Mg, Li),
Chlorite (Zn, Ca, K, Na, Ba), hypochlorite (Li, Na, K, Ca, Sr, Ba), bromite (Na, K, Ca, Ba), etc. can give. Naturally, these may contain water. The amount of the halogen oxyacid salt added is 0.001 to 3 parts by weight, preferably 0.01 to 2 parts by weight, per 100 parts by weight of the halogen-containing resin. 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. 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 dilauryl 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 diphosphite, 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
0.01 to 5 parts by weight per 100 parts by weight, preferably
It is 0.1 to 3 parts by weight. 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 fatty acid butyl, 3-(2-xenoxy)-1 ,2
-Epoxypropane, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide,
Examples include 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate. The amount of these epoxy compounds added is 0.01 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the resin.
Parts by weight. The polymer composition of the present invention may contain a phthalate plasticizer or other ester plasticizer, a polyester plasticizer, a phosphate plasticizer, a chlorine plasticizer, or other plasticizer depending on the purpose. Can be used as appropriate. Adding an antioxidant to the polymer composition of the present invention can increase the oxidative deterioration prevention properties of the polymer composition, so 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 polymer composition of the present invention, the photostability can be improved, so it is possible to appropriately select and use these depending on the purpose of use. These include benzophenones, benzotriazoles, salicylates, substituted acrylonitriles, various metal salts or metal chelates,
In particular, nickel or chromium salts or chelates, triazine type, piperidine type, etc. are included. 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 a non-toxic one from among the commonly used metal soaps mentioned above. can get. Others as necessary, such as crosslinking agents, pigments, fillers, foaming agents, antistatic agents, antifogging agents, plate-out prevention agents, surface treatment agents, lubricants, flame retardants, fluorescent agents, antifungal agents, and sterilization agents. agent, metal deactivator, photodegrading agent,
Processing aids, mold release agents, reinforcing agents, etc. can be included. Examples of the halogen-containing polymer used in the present invention include the following. 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 Coalescence, 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, vinyl chloride-acrylic acid ester copolymer, vinyl chloride- Halogen-containing synthetic resins such as maleate ester copolymer, vinyl chloride-methacrylate ester copolymer, vinyl chloride-acrylonitrile copolymer, internally plasticized polyvinyl chloride, and the above halogen-containing resins and polyethylene, polypropylene, polybutene, polyester -α-olefin polymers such as 3-methylbutene or ethylene-
Polyolefins and their copolymers such as vinyl acetate copolymers, ethylene-propylene copolymers, polystyrene, acrylic resins, styrene and other monomers (e.g. maleic anhydride, butadiene,
Examples include copolymers with acrylonitrile (such as acrylonitrile), acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, and blends with methacrylic ester-butadiene-styrene copolymers. The following examples illustrate the effects of the halogen-containing polymer composition according to the present invention, but the present invention is not limited to these examples. Example 1 The following composition was roll-kneaded and then pressed to produce a sheet with a thickness of 1 mm. Using this sheet, initial colorability, transparency, and thermal stability at 190°C were examined. The results are shown in Table 1. <Composition> Polyvinyl chloride resin 100 parts by weight Epoxidized linseed oil 2.0 Zinc stearate 0.5 Barium stearate 1.0 Hydrotalcite compound* 0.2 Oxygen halogen acid salts (Table 1) 0.1 * Hydrotalcite DHT- manufactured by Kyowa Kagaku Co., Ltd.
4A (hereinafter abbreviated as DHT-4A)

【table】

[Table] Example 2 Using the following formulation, a sheet with a thickness of 1 mm was prepared in the same manner as in Example 1, and the thermal stability at 120°C and 190°C, and the results after aging at 120°C for 382 hours. Elongation was measured. The results are shown in Table 2. <Composition> 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 Barium stearate 1.0 Zinc laurate 0.5 DHT-4A 0.2 Halogen oxygen acid Salts (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 a heat aging test at 175°C was conducted. The results are shown in Table 3. <Formulation> Polyvinyl chloride resin 100 parts by weight Dioctyl phthalate 50 Epoxidized soybean oil 1.0 Ba-nonyl phenolate 1.0 Zn-neodecanoate 0.5 DHT-4A 0.3 Halogen oxyacid salts (Table 3) 0.1

【table】

[Table] Example 4 When an organic phosphite compound was used in combination with the composition of the present invention, a further stabilizing effect was obtained.
The effects were investigated in the same manner as in Example 1 using the following formulations. The results are shown in Table 4. <Formulation> Polyvinyl chloride resin 100 parts by weight Dioctyl phthalate 50 Epoxidized soybean oil 1.0 Zinc octylate 0.5 Barium stearate 0.5 DHT-4A 0.3 Ba perchlorate 0.05 Organic phosphite compound (Table 4) 0.1

[Table] Example 5 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. 180
A thermal stability test at ℃ was conducted. The results are shown in Table 5. <Formulation> Polyvinyl chloride resin 100 parts by weight Epoxidized soybean oil 5 Magnesium stearate 0.2 Calcium stearate 0.5 Zinc stearate 0.5 DHT-4A 0.1 Ba perchlorate 0.1 Other stabilizing agents (Table 5) (Table 5) )

【table】

【table】

Claims (1)

[Scope of Claims] 1. A halogen-containing resin containing (a) at least one metal salt of an organic acid, (b) at least one hydrotalcite represented by the following general formula (), and (c) At least one selected from metal salts of halogen oxyacids
A stabilized halogen-containing resin composition comprising added seeds. Mg _1-x Al _x (OH) ₂ A _x/2・mH ₂ O () (where 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. )