JPS61145241A - Stabilized halogen-containing resin composition - Google Patents

Abstract

PURPOSE:The title composition excellent in stabilizinag effect and mechanical strength and free of coloring, prepared by mixing a halogen-containg resin with an aluminosilicate having a zeolitic crystal structure and a specified dihydropyridine compound. CONSTITUTION:100pts.wt. halogen-containing resing (e.g., PVC) is mixed with 0.01-10pts.wt. aluminosilicate having a special three-dimensional zeolitic crystal structure (e.g., zeolite A, X, Y or P), 0.01-1.5pts.wt. dihydropyridine compound of the formula (wherein R is alkyl, alkenyl or aryl) and, optionally, 0.01-5pts.wt. metal salt of an organic acid (e.g., calcium stearate), a metal inorganic salt (e.g., ZnO) and an organophosphite compound and/or 0.01-10pts.wt. epoxy compound, a phthalate ester plasticizer, an antioxidant, an ultraviolet absorber, etc.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is directed to a stabilized halogen-containing resin composition, specifically, a stabilized halogen-containing resin composition containing an aluminosilicate having a zeolite crystal structure and a specific dihydropyridine compound. The present invention relates to a stabilized halogen-containing resin composition comprising:

[Problems to be solved by the prior art and the invention] Halogen-containing resins tend to undergo thermal decomposition mainly due to dehydrohalogenation during thermoforming processing, and as a result, the mechanical properties of processed products deteriorate. Deterioration of color and deterioration of color tone occur.
This will cause significant disadvantage.

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 metal salts other than cadmium salts are used in various combinations, such as Ba/Zn system, Ca1Z
N series, Ba/Ca/Zn series, etc. were photographed. 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, β-diketone compounds, and ultraviolet absorbers has been proposed.

In recent years, it has been proposed to use aluminosilicate of A-type zeolite crystals as a stabilizer for halogen-containing resins (Japanese Patent Publication No. 5
g-18939).

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.

In addition, 2,6-dimethyl-3,5-dicarbalkoxy-1,4-dihydropyridines were proposed to be used in combination with metal soaps as stabilizers for halogen-containing resins.
It has been proposed in Japanese Patent No. 2065 and Japanese Patent No. 57-22343, and it is stated that the combined use of these is particularly effective in improving initial colorability. However, the stabilizing effect of the above-mentioned dihydropyridines is not much different from that of aminocrotonic acid esters, and is not practically satisfactory.

Measures for Solving Problems c] In view of the current situation, the present inventors have conducted various studies and found that a combination of zeolites and a specific dihydropyridine compound has a remarkable stabilizing effect.
It has been found that the problem of coloration caused by the addition of substances can be solved.

Furthermore, the effect when zeolites and dihydropyridine compounds are used together is significantly greater than when zeolites and aminocrotonic acid esters are used together, indicating that the combined effect of zeolites and dihydropyridine compounds is extremely specific. did.

The present invention has been made based on the above findings, and is a stabilized halogen-containing resin comprising a halogen-containing resin mixed with an aluminosilicate having a zeolite crystal structure and a dihydropyridine compound represented by the following general formula (I). A resin composition is provided.

(In the formula, R represents an alkyl group, an alkenyl group, or an aryl group.) The halogen-containing resin composition of the present invention will be described in detail below.

In the dihydropyridine compound represented by the general formula (T) used in the present invention, examples of the alkyl group represented by R include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tertiary-butyl, amyl, 3
amyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, benzyl, 1-phenylethyl, 2-phenylethyl, α,α-dimethylbenzyl, phenoxyethyl,
Examples of alkenyl groups include butoxyethyl, etc.
Examples include octenyl, decenyl, dodecenyl, octadecenyl, and the like, and examples of the aryl group include phenyl, tolyl, xylyl, tert-butylphenyl, nonylphenyl, and the like.

The amount of the dihydropyridine compound used is 0.001 to 3 parts by weight, particularly 0.001 to 3 parts by weight, based on 100 parts by weight of the halogen-containing resin.
．． It is preferable to set it as 01-1.5 parts by weight.

The aluminosilicate having a zeolite crystal structure used in the present invention is an aluminosilicate having a unique three-dimensional zeolite crystal structure, and typical examples include type A,
X-type, Y-type and P-type zeolites, motupunite, analcite, sodalite group aluminosilicate, clinoptilolite, erionite, chabasite, etc., and all or part of the Group 1a metal in these fluminosilicates Examples include metal-substituted types that are ion-exchanged with metal ions of Group Ⅰ or Group Ⅰ. 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 used is 100% of the halogen-containing resin.
0.01 to 10 parts by weight, especially 0.05 parts by weight
It is preferable to set it as 5 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 the metal components of this metal organic acid salt are 1, i,
Na, K, Mg, Ca, Ba, Zn, Sn
, Sr, etc., 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, valmitic acid, isostearic acid, stearic acid, 12-hydroxy Stearic acid, hehenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, P ter
t-Butylbenzoic acid, dimethylhydroxybenzoic acid, 3
゜5-diter t-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid
Acid, N,N-dimethylbenzoic acid, acetoxybenzoic acid, salicylic acid, P-tert-octylsalicylic acid, oleic acid, elaidic acid, linoleic acid, lylunic acid, ricinoleic acid, thioglycolic acid, mercap-1-propionic acid, octylmercapto Monovalent carboxylic acids such as propionic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid, azelaic acid, cehatic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid , monoesters or monoamide compounds of divalent carboxylic acids such as aminophthalic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, aconitic acid, thiodipropionic acid, hemimellitic acid, trimellitic acid, merophonic acid, Examples include di- or triester compounds of trivalent or tetravalent carboxylic acids such as pyromellitic acid.

Examples of the above phenols include tert-butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol,
Octylphenol, phenol, cresol, xylenol, n-butylphenol, isoaminolephenol, ethylphenol, isopropylphenol, isooctylphenol, 2-ethylhexylphenol,
tert-nonylphenol, decylphenol, te
rt-octylphenol, isohexylphenol,
Examples include octadecylphenol, diisobutylphenol, methylpropylphenol, cyamylphenol, methylisohexylphenol, and methyl-tert-octylphenol.

Furthermore, for the composition of the present invention, the above-mentioned metal (Li+
Na, K+ Mg, Ca, Ba, Zn, Sn
, Sr, etc.) can also be suitably used in combination. Examples of inorganic salts of this metal include oxides such as MgO1ZnO, Ca (OH)2, Mg (OH)2, Ba
Examples include hydroxides such as (OH)2, phosphates, phosphites, nitrates, and sulfates.

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.

The above organic phosphite compounds include diphenyldecyl phosphite, triphenyl phosphite, tris-
Nonylphenyl phosphite, tridecyl phosphite, l.lis(2-ethylhexyl) phosphite, tributyl phosphite, 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-thousandoethyl) phosphite, tetratridecyl-1
,1,3-tris(2゛-methyl-5''-tert-butyl-
4”-oxyphenyl)butane diphosphite, tetra(012-CI5 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-ethylhexyldiphenylphosphite, Tris (mono.

Dimixed nonylphenyl) phosphite, hydrogenated = 4.4
°-isopropylidene diphenol polyphosphite,
diphenyl bis[4,4”-n-butylidene bis(2
-tert-butyl-5-methylphenol)] 1,000-ocyethanol diphosphite, bis(octylphenyl) bis[4,4'-n-butylidenebis(2-tert-butyl-5
-methylphenol))-1,6-hexanediol diphosphite, phenyl-4,4°-isopropylidenediphenol pentaerythritol diphosphite,
Phenyl diisodecyl phosphite, tetratridecyl-4,4'-n-butylidene bis(2-tert-butyl-5
-methylphenol) diphosphite, 1 helis (2,
Examples include 4-di-tert-butylphenyl) phosphite.

The amount of these organic phosphite compounds added 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 epoxy compounds 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 flower oil, epoxidized linseed oil fatty acid butyl, 3-(2-xenoxy)-1,2-epoxypropane, bisphenol-
A diglycidyl ether, vinylcyclohexene dieboxide, dicyclopentadiene diepoxide, 3.
Examples include 4-epoxycyclohexyl-6-methyl eboxycyclohexanecarboxylate.

The amount of these epoxy compounds added is 10% of the halogen-containing resin.
0.01 to 10 parts by weight relative to 0 parts by weight,
,.

In particular, it is preferably 0.5 to 5 parts by weight.
i The composition of the present invention may contain a phthalate ester plasticizer, other ester plasticizer, polyester plasticizer, phosphate ester plasticizer, chlorine plasticizer, other plasticizer, etc. as appropriate depending on the use. Can be used.

Adding an antioxidant to the composition of the present invention can increase the oxidative deterioration prevention properties of the composition, so it can be used as appropriate depending on the purpose of use. This antioxidant includes 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. The ultraviolet absorbers include benzophenone type, hensitriazole type, salicylate type, substituted acrylonitrile type, various metal salts or metal chelates, especially nickel or chromium salts or chelates, triazine type, piperidine type, etc.

In order to obtain a more non-toxic halogen-containing polymer,
If a non-toxic one is selected from among the above-mentioned commonly used metal soaps, a halogen-containing polymer composition that is non-toxic and has good thermal stability can be obtained.

If necessary, the composition of the present invention may include, for example, a crosslinking agent, a pigment, a filler, a foaming agent, an antistatic agent, an antifogging agent, an antiplate-out agent, a surface treatment agent, a lubricant, a flame retardant, and a fluorescent agent. ,
Antifungal agents, bactericidal agents, metal deactivators, photodegradants, processing aids, mold release agents, reinforcing agents, and the like can be included.

Examples of the halogen-containing resin used in the present invention include:
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 combination, 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-
Halogen-containing synthetic resins such as Li coffi (acrylic acid ester), vinyl chloride-maleic ester copolymer, vinyl chloride-methacrylic ester copolymer, vinyl chloride-acrylonitrile copolymer, internally plasticized polyvinyl chloride, and α of the above halogen-containing resin and polyethylene, polypropylene, polybutene, poly-3-methylbutene, etc.
- Olefin polymers or polyolefins such as ethylene-vinyl acetate copolymers, ethylene-propylene copolymers and their copolymers, polystyrene, acrylic resins, styrene and other monomers such as maleic anhydride, butadiene, acrylonitrile etc.), acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, and methacrylic ester-butadiene-styrene copolymers.

The following examples show the effects of the halogen-containing resin composition of the present invention, but the present invention is not limited by these examples.

Example 1 The following formulation was roll-kneaded and then pressed to create a sheet 1 with a thickness of 1 mm. About this sheet
Initial colorability, transparency and thermal stability at 175°C were investigated. The results obtained are shown in Table 1.

<Formulation> Polyvinyl chloride resin 100 parts by weight Epoxidized soybean oil 3.0 Na-A type zeolite l-0.5 Zinc stearate 0.2 Non-metallic stabilizer (see Table 1) 0.2 Table 1 Examples 2 Similar to Example 1 using the following formulation to obtain a thickness of lll1.
175℃ for this sheet.
Thermal stability and initial colorability were investigated. The results obtained are shown in Table 2.

<Composition> Polyvinyl chloride resin 100 parts by weight Epoxidized soybean oil 3.0 Na-A zeolite 0.3 Calcium stearate 0.5 Zinc stearate
0.5 Nonmetallic stabilizer (see Table 2) 0.2 Table 2 Example 3 A sheet with a thickness of 1 mm was prepared in the same manner as in Example 1 using the following formulation. Thermal stability and initial coloration at ℃ were investigated. The results obtained are shown in Table 3.

<Composition> Polyvinyl chloride resin 100 parts by weight Epoxidized soybean oil 3.0 Calcium stearate 0.2 Zinc stearate
0.22.6-dimethyl-3,5-dicarborouryloxo1,4-dihydropyridine
0.2 Tetra (C12-15 mixed alkyl) Bisphenol A diphosphite 0.5 Zeolites (see Table 3) 0.2 Table 3 Example 4 Thickness was measured as in Example 1 using the following formulation: A sheet with a diameter of 1 mm was prepared, and the thermal stability and initial colorability of this sheet at 175° C. were examined. The results obtained are shown in Table 4.

<Composition> Polyvinyl chloride resin 100 parts by weight Dioctyl phthalate 50 Epoxidized soybean oil 3.0 Calcium stearate
0.2 Zinc stearate
0.2Na-A type zeolite
0.2 Nonmetallic stabilizer (see Table 4) 0.2 Table 4 Example 5 A 1 mm thick sheet was prepared in the same manner as in Example 1 using the following formulation, and the sheet was heated at 190°C. Thermal stability and initial colorability were investigated. The results obtained are shown in Table 5.

<Composition> Polyvinyl chloride resin 100 parts by weight ABS
Resin 5ONBR10 Epoxidized soybean oil 10 Octyl diphenyl phosphite 1.0 Barium stearate 0.4 Zinc laurate
0,4Na-A type zeolite
0.6 Non-metallic stabilizer (see Table 5) 0.2 Table 5

Claims (1)

[Scope of Claims] A stabilized halogen-containing resin composition comprising a halogen-containing resin mixed with an aluminosilicate having a zeolite crystal structure and a dihydropyridine compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents an alkyl group, an alkenyl group, or an aryl group.)