JPH0135015B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilized halogen-containing resin composition, and more particularly, to a stabilized halogen-containing resin composition comprising a halogen-containing resin mixed with hydrotalcites and a specific polyhydric alcohol compound. be. When halogen-containing resins are subjected to heat molding, they tend to undergo thermal decomposition mainly due to dehydrohalogenation, resulting in deterioration of mechanical properties and color tone of processed products, resulting in significant disadvantages. Maneku. 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 combinations of metal salts other than cadmium salts are used, for example.
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,
The use of β-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 coloring the resin. In view of the current situation, the present inventors have conducted various studies, and as a result, have discovered that a combination of hydrotalcites and a specific polyhydric alcohol compound produces a remarkable stabilizing effect, and has completed the present invention. be. That is, the present invention provides a halogen-containing resin containing (1) hydrotalcites and (2) glycerin, ditrimethylolpropane, mannitol, sorbitol, tris(2-hydroxyethyl)isocyanurate,
trimethylolethane, 3-methylpentane-
A stabilized halogen-containing resin composition comprising a polyhydric alcohol compound selected from the group consisting of 1,3,5-triol, triglycerin, diglycerin, and 2,2,6,6-tetramethylolcyclohexanol. It is something that provides something. 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. 50-30039
For example, the method disclosed in Japanese Patent Publication No. 51-29129 may be used. Further, in the present invention, it can be used without being restricted by its crystal structure or crystal particle size. The surface can also 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 dodecylbenzenesulfonate, higher fatty acids, higher fatty acid esters, or wax. A coated material can also be used. The amount of the hydrotalcite used is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the halogen-containing resin. The amount of the polyhydric alcohol compound used in the present invention is based on 100 parts by weight of the halogen-containing resin.
The amount is 0.01 to 10 parts by weight, preferably 0.05 to 3 parts by weight. It goes without saying that metal organic acid salts (ordinary metal soaps) may be used in combination with the composition of the present invention. Examples of metal components in this case include Li, Na, K, Mg, Ca, Ba, Zn, Sn, and Sr, and organic acid residues 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, crophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, aconitic acid, thiodipropionic acid,
Examples include dihydric carboxylic acids, monoesters, or monoamide compounds such as divalent carboxylic acids, monoesters, or monoamide compounds, and di- or triester compounds of trivalent or tetravalent carboxylic acids such as hemimellitic acid, trimellitic acid, merophanoic acid, pyromellitic acid, and the like. Examples of phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexyfluphenol, phenylphenol, octylphenol, phenol,
Cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol,
Isopropylphenol, isooctylphenol, 2-ethylhexylphenol, tert-nonylphenol, decylphenol, tert-octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol,
Examples include methylisohexylphenol and methyl-t-octylphenol. In addition, the metals (Li, Na, K, Mg, Ca,
Inorganic salts of (Ba, Zn, Sn, Sr, etc.) can also be suitably used in combination, and examples of the inorganic salts of these metals include MgO,
Oxides such as ZnO, Ca(OH) ₂ , Mg(OH) ₂ ,
Examples include hydroxides such as Ba(OH) ₂ , phosphates, phosphites, nitrates, sulfates, and the like. 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 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) diphosphite, tris(2,4-di-tert.
butylphenyl) phosphite, etc. 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. 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 bactericidal agents. , 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 compound was kneaded with a roll 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 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 Kagaku Co., Ltd. DHT−
4A (hereinafter abbreviated as DHT-4A)

【table】

[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 its thermal stability at 190°C,
Initial colorability and elongation after aging at 120℃ for 280 hours,
Tensile strength was measured. The results obtained 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) bisenol A.
Diphosphite 1.0 Calcium stearate 1.0 Zinc stearate 0.5 DHT-4A 0.2 Polyhydric alcohol compounds (Table 2) 0.2

[Table] Example 3 When an organic phosphite compound was used in combination with the composition of the present invention, an even greater stabilizing effect was obtained.
The effects were investigated in the same manner as in Example 1 using the following formulations. The results obtained are shown in Table 3. <Formulation> Polyvinyl chloride resin 100 parts by weight Dioctyl phthalate (DOP) 50 Epoxidized soybean oil 2.0 Zinc octylate 0.5 Calcium stearate 0.5 DHT-4A 0.3 Sorbitol 0.1 Organic phosphite compound (Table 3) 0.1

【table】

Claims (1)

[Claims] 1 Into the halogen-containing resin, (1) hydrotalcites and (2) glycerin, ditrimethylolpropane,
From mannitol, sorbitol, tris(2-hydroxyethyl)isocyanurate, trimethylolethane, 3-methylpentane-1,3,5-triol, triglycerin, diglycerin and 2,2,6,6-tetramethylolcyclohexanol A stabilized halogen-containing resin composition comprising a polyhydric alcohol compound selected from the group consisting of: