JPS6330938B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a stabilized chlorine-containing resin composition, and more particularly, to a chlorine-containing resin composition obtained by adding an organic acid metal salt, a carboxylic acid partial ester of a polyhydric alcohol, and a halogen oxyacid salt to a chlorine-containing resin. . Chlorine-containing resins are prone to thermal decomposition, mainly due to dehydrochlorination, when subjected to thermoforming processing, resulting in a decrease in 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 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) at least one carboxylic acid partial ester of a polyhydric alcohol, and ( c) The present invention was achieved by discovering that a significant stabilizing effect can be obtained by adding at least one metal salt of a halogen oxyacid. The present invention will be explained in detail below. Carboxylic acids, phenols, and the like are useful as the organic acids constituting the metal salt of the organic acid as component (a) 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, neodecanoic 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-octyl Monocarboxylic acids such as salicylic 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, thiodipropionic acid monoester or monoamide compounds of dihydric carboxylic acids, such as
Examples include di- or triester compounds of trivalent or tetravalent carboxylic acids such as hemimellitic acid, trimellitic acid, merophonic 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. Specific examples of metals constituting the metal salt of the organic acid as component (a) include group Ia metals such as Na, K, and Li;
Group a metals such as Mg, Ca, Sr, Ba, etc., Zn, Zr, Sn
etc. can be mentioned. 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. Examples of the trihydric or higher polyhydric alcohol constituting the carboxylic acid partial ester of polyhydric alcohol used in the present invention (b) include trimethylolethane, trimethylolpropane, glycerin, and 2-hydroxymethyl-3-methylbutane. ―
1,3-diol, 3-methylpentane-1,
3,5-triol, tris-(2-hydroxyethyl)isocyanurate, hexane-1,2,
6-triol, 2-hydroxymethyl-2-methylbutane-1,3-diol, 2,4-dimethyl-3-hydroxymethylpentane-2,4-diol, pentaerythritol, diglycerin,
Examples include ditrimethylolethane, ditrimethylolpropane, 2,2,6,6-tetramethylolcyclohexanol, dipentaerythritol, inositol, mannitol, sorbitol, and polypentaerythritol. In addition, examples of monovalent carboxylic acids constituting the carboxylic acid partial ester of polyhydric alcohol as component (b) include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, neooctanoic acid, - 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 Acid, N,N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid, P-tert-octylsalicylic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid,
Examples include thioglycolic acid, mercaptopropionic acid, and octylmercaptopropionic acid. Examples of divalent to hexavalent polycarboxylic acids include:
Phthalic acid, isophthalic acid, terephthalic acid, 3-methylphthalic acid, 2-methylisophthalic acid, oxyphthalic acid, dioxyphthalic acid, aminophthalic acid,
Dihydric carboxylic acids such as aminoterephthalic acid, diaminophthalic acid, 3-chlorophthalic acid, and chlorterephthalic acid; aromatic polycarboxylic acids such as hemimellitic acid, trimellitic acid, trimesic acid, merophanoic acid, pyromellitic acid, and mellitic acid; Acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, malic acid, maleic acid, fumaric acid,
Citraconic acid, mesaconic acid, itaconic acid, aconitic acid, thiodipropionic acid, tartaric acid, iminodiacetic acid, butane-1,2,3-tricarboxylic acid, propane-1,2,3-tricarboxylic acid, butene-
1,2,3-tricarboxylic acid, citric acid, acetylcitric acid, nitrilotriacetic acid, nitrilotripropionic acid, tris(carboxyethyl)isocyanurate, butane-1,2,3,4-tetracarboxylic acid, pentane-1,3 , 3,5-tetracarboxylic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,2,2,3-propane tetracarboxylic acid, ethylenediaminetetraacetic acid, 5-bicyclo[2.2.1]heptene-2 ,3-dicarboxylic acid,5-
Bicyclo [2.2.2] octene-2,3-dicarboxylic acid, 7-bicyclo [2.2.2] octene-2,3,
5,6-tetracarboxylic acid, 1,6,8,14-tetradecanetetracarboxylic acid, 1,6,7,8,
Examples include aliphatic polycarboxylic acids such as 9,14-tetradecane hexacarboxylic acid. The carboxylic acid partial ester compound of a polyhydric alcohol used in the present invention is prepared by combining the polyhydric alcohol and the monohydric carboxylic acid or the mixed acid of the polyhydric carboxylic acid or the mixed acid of the polyhydric carboxylic acid and the monohydric carboxylic acid in any ratio. It can be easily obtained by mixing at 100° C. and dehydrating it at about 100 to 200° C. for several hours by a normal esterification reaction. If these compounds contain at least one hydroxyl group, they contribute to improving the thermal stability of the composition of the present invention, but compounds in which all or most of the hydroxyl groups originally possessed by polyhydric alcohols are esterified are not very effective. It has no effect, and those whose hydroxyl group has a too low degree of esterification tend to volatilize or have poor compatibility with resins, resulting in little modification effect. Further, even polyester type compounds having an extremely high degree of esterification have poor compatibility with chlorine-containing resins and tend to have poor thermal stability and transparency, so it is preferable to adjust the degree of esterification as appropriate. The content of hydroxyl groups and the degree of esterification can be easily adjusted by adjusting the molar ratio of polyhydric alcohol and carboxylic acid, reaction temperature, and reaction time. Specific examples of the carboxylic acid partial ester of polyhydric alcohol as component (b) in the present invention include glycerin monooleate, glycerin monostearate, polyglycerin oleate, polyglycerin stearate, polyglycerin adipate, bis (trimethylolpropane) adipate, bis(trimethylolethane) itaconate, bis(trimethylolpropane) terephthalate, bis[tris(hydroxyethyl)isocyanurate] adipate, pentaerythritol monostearate, bis(pentaerythritol) )・terephthalate, bis(pentaerythritol) succinate, pentaerythritol adipate, bis(pentaerythritol) adipate, dipentaerythritol distearate, dipentaerythritol・
Monobenzoate, dipentaerythritol adipate, bis(dipentaerythritol) adipate, dipentaerythritol diadipate, bis(dipentaerythritol) terephthalate, bis(dipentaerythritol) terephthalate adipate, bis(dipentaerythritol)・Sebacate, bis(dipentaerythritol) ・Sebacate ・acetate, bis(dipentaerythritol) ・phthalate, bis(dipentaerythritol) ・isophthalate, bis(dipentaerythritol) ・thiodipropionate, bis(dipentaerythritol) ), maleate, bis(dipentaerythritol), maleate,
Bis(dipentaerythritol) nitrilotriacetate, tris(dipentaerythritol) trimellitate, tetra(dipentaerythritol) pyromellitate, dipentaerythritol monoacetate, dipentaerythritol monooctanoate, ditrimethylolpropane terephthalate, Examples include bis(ditrimethylolpropane) terephthalate, tripentaerythritol phthalate, poly(mono-, di-, and tri-mixture) pentaerythritol terephthalate, bis(sorbitol) adipate octanoate, bis(sorbitol) citrate, and the like. The amount of the carboxylic acid partial ester of polyhydric alcohol according to the present invention added is based on 100 parts by weight of the resin.
The amount is 0.005 to 10 parts by weight, preferably 0.01 to 5 parts by weight. Further, as the halogen oxyacid salts of component (c) used in the present invention, for example, perchlorate (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),
Iodates (Zn, Al, K, Ca, Sr, Na, Ba,
Mg, Li), chlorite (Zn, Ca, K, Na,
Ba), hypochlorite (Li, Na, K, Ca, Sr,
Examples include Ba), bromite (Na, K, Ca, Ba), etc. Naturally, these may be hydrated salts. The amount of halogen oxyacid added above is for chlorine-containing resin.
0.001 to 3 parts by weight per 100 parts by weight, preferably
It is 0.01 to 2 parts by weight. 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)
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 butyl fatty acid, 3-(2-xenoxy)-1 ，
Examples include 2-epoxypropane, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, and 3,4-epoxycyclohexyl-6-methylepoxycyclohexane carboxylate. 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 chlorine-containing polymer, a non-toxic chlorine-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, as necessary, for example, crosslinking agents, pigments, fillers, foaming agents, antistatic agents, 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. Examples of the chlorine-containing polymer used in the present invention include the following. For example, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, 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 Polymer, vinyl chloride-isoprene copolymer, vinyl chloride-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, vinyl chloride
Chlorine-containing synthetic resins such as acrylonitrile copolymers and internally plasticized polyvinyl chloride, and the above chlorine-containing resins and α-olefin polymers such as polyethylene, polypropylene, polybutene, and poly-3-methylbutene, or ethylene-vinyl acetate copolymers; Polyolefins such as ethylene-propylene copolymers and their copolymers, polystyrene, acrylic resins, copolymers of styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene Copolymer, acrylic ester - butadiene-styrene copolymer, methacrylic ester -
Examples include blended products with butadiene-styrene copolymers. The following examples show the effects of the chlorine resin composition according to the present invention, but the present invention is not limited by 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 Barium perchlorate 0.1 Polyhydric alcohols (Table 1) 0.2

[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 the thermal stability at 120°C and 190°C and the elongation after aging at 120°C for 382 hours were determined. 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 Barium perchlorate 0.2 Poly Alcohols (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 a heat aging test at 175°C was conducted. The results are shown in Table 3. <Composition> Polyvinyl chloride resin 100 parts by weight Dioctyl phthalate 50 Epoxidized soybean oil 1.0 Nonylphenol barium salt 1.0 Zinc neodecanoate 0.5 Bis(dipentaerythritol) adipate
0.3 Oxygen halogen acid 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. <Composition> Polyvinyl chloride resin 100 parts by weight Dioctyl phthalate 50 Epoxidized soybean oil 1.0 Zinc octylate 0.5 Barium stearate 0.5 Bis(dipentaerythritol) adipate
0.2 Barium perchlorate 0.05 Organic phosphite compounds (Table 4)
0.2

【table】

[Table] Example 5 In order to investigate the effect of using the composition of the present invention together with other positioning aids, 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. <Composition> Polyvinyl chloride resin 100 parts by weight Epoxidized soybean oil 5 Magnesium stearate 0.2 Calcium stearate 0.5 Zinc stearate 0.5 Bis(dipentaerythritol) adipate
0.1 Barium perchlorate 0.1 Other stabilizing aids (Table 5) (Table 5)

【table】

Claims (1)

[Claims] 1 Stable product made by adding (a) at least one metal salt of an organic acid, (b) at least one carboxylic acid partial ester of a polyhydric alcohol, and (c) at least one metal salt of a halogen oxygen acid to a chlorine-containing resin. chlorine-containing resin composition.