JPS6234063B2 - - 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 stabilized by the combined addition of an organic acid metal salt and a ketoacetate compound of a specific polyhydric alcohol. Chlorine-containing resins tend to undergo thermal decomposition mainly due to dehydrochlorination during hot molding, resulting in deterioration of mechanical properties and color tone of processed products, resulting in significant disadvantages. Various stabilizers have been used to eliminate such disadvantages, but all of the stabilizers conventionally used had certain drawbacks and were not fully satisfactory in practice. Metal salts such as group or group metal carboxylates and phenol salts are used as basic thermal stabilizers in most formulations, but it is extremely difficult to stabilize chlorinated resins with these alone. Therefore, the combined use of various auxiliary agents is essential. As these auxiliaries, organic phosphite compounds, epoxy compounds, polyhydric alcohols, amine compounds, keto acid compounds, etc. are used.
Among these compounds, keto acid compounds are effective in improving initial coloration and are preferred stabilizers, but the conventionally used keto acid compounds are highly volatile and have little effect on improving long-term thermal stability, making them difficult to put into practical use. It was not good enough. Furthermore, polyhydric alcohols are effective in improving initial coloration and long-term thermal stability, but these effects are insufficient and often have a negative effect on transparency and plate-out properties, making them insufficient for practical use. It was hot. As a result of intensive studies in view of the current situation, the present invention, etc. has been developed based on the results of a chlorine-containing resin containing (a) at least one organic acid metal salt, and (b) at least a ketoacetate compound of polytrimethylolalkane or polypentaerythritol. It was discovered that a chlorine-containing resin composition with effectively improved initial coloring properties, long-term thermal stability, thermal coloring properties, etc., can be obtained without deteriorating transparency and plate-out property by adding one type of chlorine-containing resin composition in combination. We have arrived at the present invention. The chlorine-containing resin composition of the present invention will be explained in detail below. The metal components constituting the organic acid metal salt used in the present invention include Li, Na, K, Mg, Ca,
Examples include Ba, Sr, Zn, Al, Sb, Zr, etc., and examples of 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, neoacid, 2-ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid. Acid, palmitic acid, isostearic acid, stearic acid, 1/2-
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-dimethylaminobenzoic acid, salicylic acid, Monohydric carboxylic acids such as 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, superric acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, aconitic acid , thiodipropionic acid, hemimellitic acid, trimellitic acid, merophanoic acid, pyromellitic acid, mellitic acid, and other polyvalent carboxylic acids or partial ester compounds of polyvalent carboxylic acids. Examples of 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,
Examples include methylisohexylphenol and methyl-t-octylphenol. The amount of organic acid metal salt added in the present invention is
Preferably 0.01 to 10 parts by weight per 100 parts by weight
It is 0.05 to 5 parts by weight. In addition, examples of the polytrimethylolalkane constituting the polytrimethylolalkane or the ketoacetic acid ester of polypentaerythritol include ditrimethylolethane, ditrimethylolpropane,
Examples of polypentaerythritol include dipentaerythritol, tripentaerythritol, and tetrapentaerythritol, and examples of the ketoacetic acid component include acetoacetic acid. , propionyl acetate, α-hexylacetoacetate, α-octylacetoacetate, lauroyl acetate, stearoyl acetate, benzoyl acetate,
Examples include trimethylbenzoylacetic acid, cyclohexanoylacetic acid, and tetrahydrofurfurylcarbonylacetic acid. Further, in the ester compound, all of the hydroxyl groups of the alcohol may be esterified, or some of them may remain unesterified. In the present invention, the amount of the polytrimethylolalkane or polypentaerythritol ketoacetate compound added is 0.001 to 100 parts by weight of the resin.
5 parts by weight, preferably 0.01 to 3 parts by weight. The ketoacetate compound of polytrimethylolalkane or polypentaerythritol used in the present invention can be easily synthesized, for example, by transesterification of the polyhydric alcohol with a ketoacetate or reaction of the polyhydric alcohol with diketene. be able to. Next, the manufacturing method will be explained using specific synthesis examples, but the present invention is not limited by these synthesis examples. Synthesis example: Take 25.4 g (0.1 mol) of dipentaerythritol and 23.2 g (0.2 mol) of methyl acetoacetate,
The reaction was carried out at 140 to 150°C for 3 hours while distilling off the methanol produced. Since the theoretical amount of methanol was produced, the reaction was stopped, and after cooling, a pale yellow viscous liquid product was obtained. This liquid solidified into a gel by standing. The product was a mixture consisting mainly of acetoacetic diester of dipentaerythritol. Similarly, by changing the amount of methyl acetoacetate, tetraester (n ²⁵ _D = 1.4860), hexaester (n ^2
5 _D
= 1.4908) was obtained as a pale yellow viscous liquid. 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, trisnonylphenyl 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, tetra(C _12-15 mixed alkyl) 4,4'-isopropylidene diphenyl diphosphite, bis(2-cyclohexyl phenyl) acid phosphite, bis(2,4-di-tertiary) butyl phenyl) acid phosphite, bis(2,4-di-tert-butylphenyl) cyclohexyl phosphite, di(tridecyl) di(2-cyclohexyl phenyl) hydrogenated bisphenol A diphosphite, butoxyethoxyethyl diphenyl Phosphite, 2-ethylhexyl diphenyl phosphite, tris(mono-, di-mixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, phenyl-4,4'-isopropylidene diphenol penta Erythritol diphosphite, phenyl diisodecyl phosphite,
Examples include tris(2,4-di-tert-butylphenyl) phosphite. 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 light stabilizer can be improved, so it is possible to appropriately select and use these 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 chlorine-containing polymer, a non-toxic chlorine-containing polymer composition which is non-toxic and has good thermal stability can be obtained by selecting and using a non-toxic one among the organic acid metal salts mentioned above. Others as necessary, such as plasticizers, crosslinking agents, etc.
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-ethylene copolymer, vinyl chloride -isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-ethylene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride- Isobrene 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, chloride Chlorine-containing synthetic resins such as vinyl-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, internally plasticized polyvinyl chloride, and α- Olefin polymers 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 copolymer, acrylic ester-butadiene-
Examples include blended products with styrene copolymers and methacrylic acid ester-butadiene-styrene copolymers. The following examples illustrate the effects of the chlorine-containing polymer composition according to the present invention, but the present invention is not limited by these examples. Example 1 In order to examine the effects of the composition of the present invention, a sheet with a thickness of 1 mm was prepared using a kneading roll according to the following formulation, and a thermal stability test at 190°C, an initial coloring and transparency test, and a sheet at 190°C were performed. A thermal coloring test after 30 minutes and a plate-out property test were conducted. The results are shown in Table-1. The initial colorability and thermal colorability are the yellowness (%) measured using a Hunter colorimeter, and the plate-out value is the yellowness measured using a Hunter colorimeter.
Shown in ppm. <Composition> Polyvinyl chloride 100 parts by weight Dioctyl phthalate 50 Epoxidized soybean oil 3.0 Zinc stearate 0.3 Calcium stearate 1.0 Stearic acid 0.3 Trisnonyl phenyl phosphite 0.5 Sample 0.3

【table】

[Table] Example 2 A sheet was prepared using the following formulation, and a thermal stability test at 190°C, an initial coloring test, and a thermal coloring test at 190°C for 30 minutes were conducted. The results are shown in Table-2. <Composition> Polyvinyl chloride 100 parts by weight Zinc-stearate 0.5 Calcium-stearate 1.0 Epoxidized soybean oil 3.0 Octyl diphenyl phosphite 1.0 Stearic acid 0.3 Sample 0.5

【table】

[Table] Example 3 In order to examine the effects of the present invention on polymer blends, sheets were prepared using the following formulation and tests were conducted on thermal stability at 175°C, initial colorability, and thermal colorability after 60 minutes at 175°C. Summer. The results are shown in Table-3. <Composition> Polyvinyl chloride 100 parts by weight Acrylonitrile-butadiene-styrene copolymer resin 10 Dioctyl phthalate 10 Zinc octoate 0.4 Calcium benzoate 1.0 Tetra( _C12-15 alkyl) bisphenol A diphosphite 1.0 Stearic acid 0.5 Sample 0.3

[Table] Example 4 In order to examine the effect of the composition of the present invention on a base sol, a test was conducted using the following formulation. After thoroughly stirring and mixing each compound to make it homogeneous, 5 mm
After degassing with Hg for 1 hour, it was coated on a ferro plate to a thickness of 1 mm and gelled at 190°C for 5 minutes to prepare a test piece. This test piece was subjected to a thermal stability test at 175°C, an initial coloring test, and a thermal coloring test at 175°C for 30 minutes. The results are shown in Table-4. <Composition> Polyvinyl chloride 100 parts by weight Dioctyl phthalate 80 Epoxidized linseed oil 2.0 Zinc laurate 0.6 Barium-12-OH-stearate 1.2 Sample 0.1

[Table] Example 5 The composition of the present invention further contains an epoxy compound and/or
Alternatively, excellent effects can be achieved by using a phosphite compound in combination. A test similar to Example 1 was conducted using the following formulation. The results are shown in Table-5. <Composition> Polyvinyl chloride 100 parts by weight Dioctyl phthalate 50 Zinc-p-tert-butyl benzoate 0.5 Barium stearate 0.7 Stearic acid 0.3 Dipentaerythritol diacetoacetate
0.2 Epoxy compounds or phosphite compounds (Table-
5)

【table】

Claims (1)

[Claims] 1. A stabilized chlorine-containing resin composition obtained by adding (a) at least one organic acid metal salt, and (b) at least one ketoacetate compound of polytrimethylolalkane or polypentaerythritol to a chlorine-containing resin. thing.