JPH0562131B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a stabilized halogen-containing resin composition, specifically, a halogen-containing resin composition obtained by adding an organic acid zinc salt, zeolites, and halogen oxyacid salts to a halogen-containing resin. relating to things. [Problems to be solved by the prior art and the invention] When halogen-containing resins are subjected to thermoforming processing, they tend to undergo thermal decomposition mainly due to dehydrohalogenation, resulting in a decrease in the mechanical properties of processed products. , resulting in deterioration of color tone and 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 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 the use of various stabilizing aids, such as epoxy compounds, polyhydric alcohols, organic phosphorus compounds, organic sulfur compounds, phenol compounds, and β-diketone compounds, has been proposed. It was still not enough and needed further improvement. In recent years, it has been proposed to use aluminosilicate of type A zeolite crystals as a stabilizer for halogen-containing resins (see Japanese Patent Publication No. 18939/1983). However, the stabilizing effect of zeolites was relatively small and unsatisfactory for practical purposes. Zeolites also have the disadvantage of imparting color to the resin. [Means for Solving the Problems] In view of the current situation, the present inventors have made various studies and found that (a) at least 0.01 to 10% of at least one zinc salt of an organic acid is added to 100 parts by weight of the halogen-containing resin. weight part,
A significant stabilizing effect can be obtained by adding (b) 0.01 to 10 parts by weight of at least one aluminosilicate having a gelite crystal structure and (c) 0.001 to 3 parts by weight of at least one metal salt of a halogen oxyacid. This is what we discovered and arrived at the present invention. The stabilized halogen-containing resin composition of the present invention will be explained in detail below. Carboxylic acids, phenols, and the like are useful as organic acids constituting the organic acid zinc salt 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, citric acid, n-propylbenzoic acid,
Aminobenzoic acid, N,N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid, P-tert
- Monohydric carboxylic 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, zebacic acid, phthalic acid, isophthalic acid, terephthalic acid,
Monoesters or monoamide compounds of divalent carboxylic acids such as oxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, aconitic acid, thiodipropionic acid, hemimellitic acid, trimellitic acid, Examples include di- or triester compounds of trivalent or tetravalent carboxylic acids such as merophanic acid and pyromellitic acid. Further, examples of the above phenols include phenol, cresol, ethylphenol, dimethylphenol, isopropylphenol, cyclohexylphenol, tert-butylphenol, phenylphenol, nonylphenol, dinonylphenol, methyl-tert-butylphenol,
Tetramethylphenol, poly(di-penta)isopropylphenol, diisopropyl-m-cresol, butylphenol, isoamylphenol, isooctylphenol, 2-ethylhexylphenol, tert-nonylphenol, decylphenol, tert-dodecylphenol, tert
-octylphenol, octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, methyl-tert-octylphenol,
Examples include di-tert-nonylphenol and di-tert-dodecylphenol. The amount of the zinc salt of the organic acid added is 0.01 to 10 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the halogen-containing resin. The aluminosilicate having a zeolite crystal structure used in the present invention is an aluminosilicate having a unique three-dimensional zeolite crystal structure,
Typical examples include A-type, A metal-substituted type in which all or a part of is ion-exchanged with Group 3 or Group 3 metal ions can be mentioned. Further, these zeolites may be either hydrated products having water of crystallization (so-called zeolite water) or anhydrous products from which water of crystallization has been removed. The amount of the aluminosilicate added is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the halogen-containing resin. In addition, examples of metal salts of halogen oxyacids used in the present invention include halogen oxyacids such as perchloric acid, periodic acid, chloric acid, bromic acid, iodic acid, chlorous acid, bromous acid, and hypochlorous acid. Oxygen acids Li, Na, K,
Examples include metal salts of Mg, Ca, Sr, Ba, Zn, Al, etc. Among them, perchlorates are preferred, and group a metal (Mg, Ca, Sr, Ba) salts of perchloric acid are particularly preferred. Naturally, these metal salts of halogen oxygen acids may be hydrated salts. The amount of the metal salt of the halogen oxygen acid added is 0.001 to 3 parts by weight, preferably 0.01 to 2 parts by weight, based on 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. Examples of the organic phosphite compounds that can be used in the present invention include diphenyl decyl 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'-tert-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, dimixed nonyphenyl) 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, tetra Tridecyl-4,4'-n-butylidene bis(2-
Examples include tert-butyl-5-methylphenol) diphosphite and tris(2,4-di-tert-butylphenyl) phosphite. 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 fatty acid butyl, 3-(2-xenoxy)-3
(2-xenoxy)-1,2-epoxypropane,
Examples include bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene epoxide, 3,4-epoxycyclohexyl-6-methylepoxycyclohexane carboxylate, and the like. The amount of these epoxy compounds added is preferably 0.01 to 10 parts by weight, particularly 0.5 to 5 parts by weight, based on 100 parts by weight of the halogen-containing resin. The composition of the present invention also includes group a metals (Li, Na, K) or group a metals (Ba, Ca,
Organic acid salts of Mg, Sr) can be used together.
Examples of the organic acids constituting these organic acid salts include those exemplified as the organic acids constituting the zinc salts of organic acids described above. The amount of these organic acid salts added is
The amount is preferably 0.1 to 3 parts by weight per 100 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, and the sulfur-containing 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 a non-toxic one from among the commonly used metal soaps mentioned above. can get. 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, bactericidal agents, 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 with polyethylene, polypropylene, polybutene, poly-3-
α-olefin polymers such as methylbutene or polyolefins such as ethylene-vinyl acetate copolymers, 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. I can do it. 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 formulation was roll-kneaded and then pressed to produce a sheet with a thickness of 1 mm. Regarding this sheet, thermal stability at 190°C, heat aging resistance and light resistance were measured by the following methods. The results are shown in Table 1. <Formulation> Polyvinyl chloride resin 100 parts by weight Di( _C8 - _C12 ) alkyl phthalate 70 Epoxidized soybean oil 3.0 Zinc octylate 0.8 Na-A zeolite 3.0 Oxygen halogen acid salts (Table 1) 0.5 Calcium carbonate 20 Oxidation Titanium 10 Heat aging resistance: Heat aging coloring after 400 hours at 110°C (urethane foam lining) Light resistance: Fade-O-Meter, light discoloration after 600 hours at 83°C (urethane foam lining)

【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 about this sheet,
Thermal stability at 120°C and 190°C, and elongation after aging at 120°C for 400 hours were 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 ( _{C12-15 mixed} alkyl) bisphenol A diphosphite 1.0 Barium stearate 0.4 Zinc laurate 0.4 Na-A type zeolite 2.0 Halogen Oxygen salts (Table 2) 0.2

【table】

[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 was measured at 175°C. The result is the third
Shown in the table. <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 Na-A type zeolite 2.0 Halogen oxyacid salts (Table 3) 0.1

[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 Na-A zeolite 1.0 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. The thermal stability of this sheet at 180°C was measured. 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 Na-A zeolite 1.0 Ba perchlorate 0.1 Other stabilizing aids (Table 5) (Table 5) )

【table】

[Table] Example 6 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 was measured at 190°C. The result is the 6th
Shown in the table. <Composition> Polyvinyl chloride resin 100 parts by weight Zinc stearate 0.5 Barium stearate 0.5 Zeolites (Table 6) 1.0 Ba perchlorate 0.1

[Table] Example 7 The following formulations were mixed in a Henschel mixer to prepare a powder compound. This powder compound was made into a thickness of 3 mm and gelled for 4 minutes in a gear oven at 230°C to produce a sheet with a thickness of 1.8 mm. Regarding this sheet, the thermal stability (190° C.), heat aging resistance, and light resistance were measured in the same manner as in Example 1. The results are shown in Table 7. <Composition> Polyvinyl chloride resin 90 parts by weight Polyvinyl chloride resin for paste 10 Di( _C10-12 ) alkyl phthalate 70 Epoxidized soybean oil 5 Titanium dioxide 10 Zinc octylate _0.8 Na-A type zeolite 3 Halogen oxyacid salts ( Table 7) 0.5

【table】

Claims (1)

[Claims] 1 100 parts by weight of halogen-containing resin, (a) 0.01 to 10 parts by weight of at least one zinc salt of an organic acid, (b) 0.01 to 10 parts by weight of at least one aluminosilicate having a zeolite crystal structure, and (c) halogen A stabilized halogen-containing resin composition comprising 0.001 to 3 parts by weight of at least one metal salt of an oxyacid.