JPH0338299B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a stabilized polyvinyl chloride resin composition. More specifically, the present invention relates to a stabilized composition for polyvinyl chloride resin that has improved color resistance, weather resistance, and transparency. In general, polyvinyl chloride-based resins such as polyvinyl chloride become colored due to heat deterioration during the molding process and weather resistance deterioration mainly due to ultraviolet rays after the product is made.
It is known that it is an excellent product. Therefore, in order to improve these problems, metal salt compounds, epoxy compounds, antioxidants, ultraviolet absorbers, organic phosphite esters, etc. have been used singly or in any combination thereof. Organic phosphorous esters and ultraviolet absorbers are particularly effective in improving weather resistance, but a fully satisfactory product has not yet been obtained. In view of these points, the inventor has conducted extensive studies and found that
The inventors have discovered that hypophosphorous acid and its metal salt compounds have remarkable effects on improving color resistance, weather resistance, and transparency, leading to the present invention. Conventionally, hypophosphite has been used as a stabilizer for ABS resin (Japanese Patent Publication No. 12530/1983), and alkaline earth metal salts of hypophosphite have been used in combination with phosphorus compounds having a specific structure to produce polyolefins, etc. Although it is known that these compounds impart flame retardancy to polyvinyl chloride resins (Japanese Patent Application Laid-Open No. 109940/1989), the fact that these compounds contribute to the stabilization of polyvinyl chloride resins was completely unexpected, and the discovery was surprising. [Structure of the invention] The present invention is based on the general formula [Wherein, M represents hydrogen, a group a metal of the periodic table, a group metal, or alkyltin, and n represents the valence of M. ] This is a composition of a stabilized polyvinyl chloride resin compound, which is obtained by adding one or more kinds of compounds represented by the hypophosphorous acid compound represented by the following to a polyvinyl chloride resin. Among the metals represented by M in the above general formula, group a metals include Li, Na, K, etc.; group metals include Mg,
Ca, Ba, Zn, Cd, etc., and as alkyl tin,
Examples include mono-, di-, and trimethyltin, mono-, di-, and tributyltin, and mono-, di-, and trioctyltin. Representative examples of the compounds used in the present invention are as follows (numbers are shown in the examples below). [Representative compounds] No.1 Hypophosphorous acid No.2 Lithium hypophosphite No.3 Sodium hypophosphite No.4 Potassium hypophosphite No.5 Magnesium hypophosphite No.6 Calcium hypophosphite No.7 Hypophosphite Barium phosphate No.8 Zinc hypophosphite No.9 Cadmium hypophosphite No.10 Dibutyltin hypophosphite No.11 Dioctyltin hypophosphite No.12 Monomethyltin hypophosphite [Polyvinyl chloride resin to be stabilized] The polyvinyl chloride resins to be stabilized in the present invention are as follows. These include polyvinyl chloride and copolymers containing vinyl chloride as a main component and monomers that can be copolymerized therewith, graft polymers, block polymers, and polymer blends containing these as main components. In the present invention, the amount of the compound having the above general formula added is 0.01 to 5.0 parts by weight per 100 parts by weight of the resin. [Examples of substances that can be used in combination] In the present invention, the following compounds can be included together with these compounds as necessary. That is, acidic, neutral, basic group a, group a,
It is an organic acid salt of Group B and Group B, and the organic acids used therein include 2-ethylhexoic acid, neo acid, lauric acid, stearic acid, isostearic acid, hydroxystearic acid, ricinoleic acid, oleic acid, caproic acid, Palmitic acid, 12-hydroxystearic acid, myristic acid, octylic acid, isooctylic acid, phenylstearic acid, or dibasic acids such as maleic acid, malonic acid, sebacic acid, azelaic acid, adipic acid, phthalic acid, and cyclohexanedicarboxylic acid. and carbon number 1 to 18
Semi-esters of linear or side chain, substituted or unsubstituted, saturated or unsaturated alcohols, alkoxy alcohols, or cycloalkyl, arylalkyl, aryl, alkylaryl having 5 to 18 carbon atoms in total with hydroxy compounds, etc. Substituted and unsubstituted aliphatic carboxylic acids, benzoic acid, methylbenzoic acid, t-butylbenzoic acid, cinnamic acid, salicylic acid, naphthenic acid, pyrrolidone carboxylic acid, acetoacetate and their condensates, benzoylacetone, dibenzoyl Examples include methane, stearoylbenzoylmethane, rosin acid, octylphenol, nonylphenol, and t-butylphenol. Other stabilizers, such as organotin compounds, may also be used in combination. Examples include mono- or dialkyltin fatty acid salts or aromatic acid salts, mono- or dialkyltin maleate salts and polymer salts, mono- or dialkyltin maleate salts, mono- or dialkyltin mono- or dimaleate salts, mono- or di-fatty acid salts, Mono- or dialkyltin mono- or dimaleate salts, mono- or diaromatic acid salts, mono- or dialkyltin mercaptocarboxylic acid salts and polymer salts, mono- or dialkyltin sulfide and polymer salts, mono- or dialkyltin mercaptocarboxylic acid ester salts, mono- or dialkyltin mercaptocarboxylic acid ester salts, mono- or dialkyltin mercaptocarboxylic acid ester salts, or dialkyltin mercaptocarboxylic acid ester mono- or disulfide salt, mono- or dialkyltin mercaptocarboxylic acid ester oxide salt, mono- or dialkyltin mercaptide, mono- or dialkyltin mercaptide, mercapto-acid ester salt, mono- or dialkyltin fatty acid alkyl mercaptide mono Alternatively, there are disulfides, tin compounds described in JP-A-51-44149, and the like. Furthermore, organic non-metallic stabilizers may also be used in combination as long as they do not impede the purpose. Examples of these organic nonmetallic stabilizers include 2-phenylindole,
Diphenylthiourea, cetyl and stearyl β-
Aminocrotonic acid esters, 1,3 and 1,4-
Nitrogen-containing compounds such as butanediol bis β-aminocrotonic acid ester, thiodiethylene glycol bis β-aminocrotonic acid ester, isocyanuric acid and its derivatives such as tris(2-hydroxyethyl) cyanurate, pentaerythritol, mannitol, sorbitol, etc. Hydrolic alcohols, carboxylic acids such as benzoic acid, methylbenzoic acid, glycolic acid, maleic acid, cinnamic acid, p-tert-butylbenzoic acid, crotonic acid, acetoacetate and its condensates, boric acid ester, thiodiglycolic acid ester , malonic acid mono- or diester, benzoylacetone, dibenzoylmethane, stearoylbenzoylmethane, and β-diketones such as dehydroacetic acid. An antioxidant may be used in the composition of the present invention, if necessary.
These antioxidants include phenolic antioxidants including phenol derivatives such as hindered phenols, poly(alkylphenols) bonded via alkylene or alkylidene, and poly(alkylphenols) bonded via sulfur. There are sulfur-containing compounds such as alkanoic acids and their alkyl esters, such as laurylstearyl thiodipropionate and dilauryl thiodipropionate, and triphenylphosphite, tridecylphosphite, and monophenyldidecylphosphite. , tricresyl phosphite, trisnonylphenyl phosphite, triscyclohexyl phenyl phosphite, tris phenyl phenyl phosphite, tris(dipropylene glycol) phosphite, tris(ethoxyethoxyethyl) phosphite, tris[4,4 '-Butylidene bis(2-t-butyl-5
-methylphenol)] phosphite, diphenyl phosphite, mono-2-ethylhexyl phosphite, tetra(tridecyl)-4,4'-isopropylidene diphenyl diphosphite, tetra(phenyl) dipropylene glycol diphosphite, heptakis (nonylphenyl)tetrakis(bisphenol A) pentaphosphite, heptakis(nonylphenyl)tetrakis(bisphenol A) pentaphosphite, heptakis(dipropylene glycol) triphosphite, bis(neopentyl glycol) dipropylene glycol diphosphite, tetrakis (Butoxyethoxyethyl) ethylene glycol diphosphite, bis(cyclohexyl phenyl) bis(phenylethyl) 1,4-dibutanediol diphosphite, didecyl potassium phosphite, zinc di(octyl phosphite), butoxyethoxyethyl calcium phosphate , stearic acid/dilauryl barium phosphite, tricresyl phosphate, trioctyl phosphate, tris(butoxyethyl) phosphate, xylenyl diphenyl phosphate, monolauryl phosphate, lauryloxypolyethoxy phosphate, di-t - Butylphenoxypolyethoxyphosphate, oleyloxypolyethoxydilaurylphosphate, other spiro-type phosphites such as distearylpentaerythritol diphosphite, didecylpentaerythritol diphosphite, diphenylpentaerythritol diphosphite, etc. type phosphite and tris(laurylthio)phosphite, tetrakis(mercaptooctyl)1,6-dimercaptohexylene diphosphite, pentakis(dodecylmercapto)bis(1,6-hexylene dimercapto)triphosphite, 0,0′- There are phosphites and phosphates such as diisopropylthiol phosphate and zinc dibutyldithiophosphate. Weather resistance (light) by adding an ultraviolet absorber to the present invention
Since they can improve properties, they are used alone or in combination as appropriate depending on the purpose of use. These include benzophenones, benzotriazoles, salicylates,
These include cyanoacrylates, hindered amines, metal chelates, especially nickel and chromium salts. Also, phthalate ester plasticizers or other ester plasticizers or polyester plasticizers, phosphate ester plasticizers, chlorine plasticizers,
Other plasticizers and also epoxy compounds, such as epoxidized soybean oil, epoxidized vegetable oils such as epoxidized linseed oil, butyl epoxy stearate, octyl epoxy stearate, 2-ethylhexyl tall oil fatty acid ester, epoxy stearyl epoxy stearate, epoxy Epoxy compounds such as epoxidized esters such as dioctyl tetrahydrophthalate, distearyl cyclohexanedicarboxylate, and epoxy resins such as a polycondensate of 4,4'-isopropylidene diphenol and epichlorohydrin may also be used as necessary. Can be used in combination. Others as required Calcium carbonate, calcium oxide, calcium hydroxide, zinc oxide, zinc hydroxide, zinc carbonate, zinc sulfide, magnesium carbonate, magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, alumina, silicic anhydride , sodium silicate, magnesium silicate, calcium silicate, zeolite, hydrotalcite, activated clay, talc, clay, red iron, aspest, antimony trioxide and other fillers, fluorescent agents, fungicide, plate-out Anti-fogging agents, cross-linking agents, lubricants, surfactants, reinforcing agents, processing aids, mold release agents, viscosity-lowering agents, etc. can be included in the polyvinyl chloride resin composition of the present invention. . [Examples and Effects] Next, the effects of the halogen-containing resin stabilizing composition according to the present invention will be shown by Examples. The results of the tests used in the examples are shown using the following symbols to indicate the stages.

[Table] Example 1 In order to examine the stabilizing effect of the compound used in the present invention on polyvinyl chloride resin, the following formulation was kneaded with two rolls at 170°C for 10 minutes and a plate-out test was conducted. In addition, the coloring resistance and transparency of this sheet were compared. The results are shown in Table-1. Formula (parts by weight) Polyvinyl chloride resin 100 Dioctyl phthalate 50 Epoxidized soybean oil 2.0 Calcium stearate 0.4 Zinc stearate 0.4 Didecyl monophenyl phosphite 0.5 Additives Table 1 The above formulation contains known stabilizers. .

[Table] Example 2 In order to examine the stabilizing effect of the compound used in the present invention on polyvinyl chloride resin, a film with a thickness of 0.2 mm was made by kneading it with two rolls at 180°C for 10 minutes with the following formulation. . This film is 180
The samples were pressed at −100 Kg/cm ² for 3 minutes to compare color resistance and transparency. This film was also exposed outdoors for one year to compare its weather resistance. The results are shown in Table-2. Composition (parts by weight) Polyvinyl chloride resin 100 Dioctyl phthalate 40 Tricresyl phosphate 5 Epoxy resin 2 Sorbitan monopalmitate 1.5 Ethylene bisstearoylamide 0.3 Octyl diphenyl phosphite 0.5 Diphenyl phosphite 0.1 Barium stearate 0.4 Zinc stearate 0.4 Additives Table 2 The above formulation contains known stabilizers.

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Claims (1)

[Scope of Claims] 1. A polyvinyl chloride resin stabilizing composition comprising a polyvinyl chloride resin containing one or more hypophosphorous compounds represented by the following general formula. general formula [Wherein, M represents hydrogen, a group a metal of the periodic table, a group metal, or alkyltin, and n represents the valence of M. ]