JPS58127751A - Stabilized halogen-containing resin composition - Google Patents

Abstract

PURPOSE:To provide a halogen-contg. resin compsn. which has excellent thermal stability and improved toxicity, by adding a metal salt of an org. acid, a partial carboxylic acid ester of a polyhydric alcohol and a salt of a halogen oxyacid to a halogen-contg. resin. CONSTITUTION:A metal salt of an org. acid, a partial carboxylic acid ester of a polyhydric alcohol and a salt of a halogen oxyacid are added to a halogen-contg. resin. Examples of said organic acids suitable for use in the formation of said metal salts include carboxylic acids and phenols. Examples of said metals suitable for use in the formation of said metal salts include GroupIa metals such as Na, K and Li and Group IIa metals such as Zn, Zr and Sn. Examples of said salts of halogen oxyacids include perchlorates of Zn, Al, NH4, K, Ca, Sr, Na, Ba, Mg and Li and bromites of Na, K, Ca and B.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a stabilized halogen-containing resin composition, more specifically, a stabilized halogen-containing resin composition, in which a leading acid metal salt, a carboxylic acid partial ester of a polyhydric alcohol, and a hyhalogen oxyacid salt are added to the halogen-containing resin. The present invention relates to a halogen-containing resin composition.

Halogen-containing resins are susceptible to thermal decomposition (IL-) mainly due to dehydrohalogenation during thermoforming, which leads to deterioration of the mechanical properties (and color tone) of processed products. This will cause significant disadvantage.

In order to avoid such neo-U effects, it is necessary to add one or more types of heat stabilizers to the synthetic resin to suppress deterioration during processing steps.

Conventionally, various organic acid gold 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, such as Ba
/Zn system, CaZZn system, Ba/Ca/Zn system, etc. have been proposed. However, its performance is not sufficient, and various stabilizing agents such as epoxy compounds, polyhydric alcohols,
Organic phosphorus compounds, organic sulfur compounds, phenolic compounds,
Although the use of β-diketone compounds and the like has been proposed, it is still not sufficient and further improvements are needed.

In view of the current situation, the present inventors have conducted various studies and found that (a) at least -fm of a metal salt of an organic acid, (b) at least one kind of 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 type of halogen oxyacid salt.

The present invention will be explained in detail below.

Carbo/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-diterL-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-octylsalicylic acid, oleic acid, elaidic acid, linoleic acid,
Monovalent carboxylic acids such as lylunic acid, thioglycolic acid, mercaptopropionic acid, octylmercaptopropionic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, cepatic acid, Monoesters of dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, aconitic acid, thiodipropionic acid, etc. Examples thereof include monoamide compounds, and di- or triester compounds of trivalent or tetravalent carboxylic acids such as hemimellitic acid, trimellitic acid, merophanic acid, and pyromellitic acid.

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

Further, specific examples of metals constituting the metal salt of the organic acid of component (a) include group Ia metals such as Na5K, :[, i, etc.
Mg.

Group IIa metals such as Ca, Sr, Ba, Zn, Zr,
Examples include Sn.

The amount of the metal salt of the organic acid according to the present invention added is 100% of the resin.
0.01 to 10 parts by weight, preferably 0.01 to 10 parts by weight.
It is 1 to 3 parts by weight.

Examples of polyhydric alcohols having a valence of 5 or more constituting the carboxylic acid partial ester of a polyhydric alcohol as component (b) used in the present invention include trimethylolethane, trimethylolpropane, glycerin, and 2-hydroxymethyl-5-methylbutane. -1,3-diol, 3-methylpentane-1,3,5-triol, tris-(2-hydroxyethyl)in cyanurate, hexane-1,2,
6-) Diol, 2-hydroxymethyl-2-methylbutane-1,3-diol, 2,4-dimethyl-6-hydroxymetherpene-2,4-diol, pentaerythritol, diglycerin, ditrimethylolethane,
Examples include citrimethylolpropane, 2,2°6.6-titramethylolcyclohexanol, dipentaerythritol, inositol, mannitol, sorbitol, 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, 2-ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearin Acid, 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, acetoxybenzoic acid, salicylic acid, p-tert-octylsalicylic acid, oleic acid, elaidic acid, linoleic acid,
Examples include lylunic acid, thioglycolic acid, mercaptopropionic acid, and octylmercaptopropionic acid.

Examples of 2-6 (dfi) multi-flfli carboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 3-
Dihydric carboxylic acids such as methylphthalic acid, 2-methylisophthalic acid, oxyphthalic acid, dioxyphthalic acid, aminophthalic acid, amineterephthalic acid, diaminophthalic acid, 3-chlorophthalic acid, chlorterephthalic acid, hemimellitic acid, trimellitic acid, trimesine Aromatic polycarboxylic acids such as merophane acid, pyromellitic acid, mellitic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, cepatic 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-) dicarboxylic acid, propane-1,2,3-) dicarboxylic acid, butene-1,2,3-) dicarboxylic acid, citric acid, acetyl citric acid, nitrilotriacetic acid, nitrilotripropionic acid, tris(carboxyethyl)in Cyanurate, butane-1,2°3.4-tetracarboxylic acid, pentane-1,3,3°5-tetracarboxylic acid, 1,
1,2,2-ethanetetracarboxylic acid, 1,2,2.3
-propanetetracarboxylic acid, ethylenediaminetetraacetic acid, 5-bicyclo[2,2,1:]butene-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° 7-8.9.14-Tetradecane hexacarboxylic acid and other aliphatic polyhydric carboxylic acids.

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 about 100 to 200° C. for several hours using a normal esterification reaction. If these compounds contain at least one hydroxyl group, they will contribute to improving the thermal stability of the composition of the present invention, but those in which all or most of the hydroxyl groups originally present in the polyhydric alcohol are esterified will not be effective. In addition, those with a too low degree of esterification of the hydroxyl group may volatilize or have poor compatibility with resins, resulting in poor modification effects. Furthermore, even polyester-type compounds with an extremely high degree of esterification tend to be poorly compatible with halogen-containing resins and have poor thermal stability and transparency, so it is preferable to adjust the degree of esterification appropriately. The content of hydroxyl groups and the degree of esterification can be easily adjusted by adjusting the molar ratio of 8-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 φ stearate, polyglycerin adipate, bis(trimethylolpropane) adipate, bis(trimethylolethane) itaconate, bis(trimethylolpropane)
・Terephthalate, bis[tris(hydroxyethyl)
Isocyanurate] Adipate, Pentaerythritol φ Monostearate, Bis(Pentaerythritol)
・Terephthalate, bis(pentaerythritol) succinate, pentaerythritol adipate, bis(pentaerythritol) adipate, dipentaerythritol distearate, dipentaerythritol monobenzoate, dipentaerythritol adipate, bis(dipentaerythritol)・Ajibate,
Dipentaerythritol diadibate, bis(dipentaerythritol) terephthalate, bis(dipentaerythritol) terephthalate adipate, bis(dipentaerythritol) sebacate, bis(siventaerythritol) sebacate, Acetate, bis(dipentaerythritol)/phthalate, bis(dipentaerythritol)/isophthalate, bis(dipentaerythritol)/thiodipropionate, bis(
Dipentaerythritol) maleate, bis(dipentaerythritol) maleate, bis(dipentaerythritol) e nitrilotriacetate, tris(dipentaerythritol) trimellitate, tetra(
Dipentaerythritol) pyromellitate, dipentaerythritol monoacetate, dipentaerythritol monooctanoate, ditrimethylolpropane ψ terephthalate, bis(ditrimethylolpropane)
- Examples include terephthalate, tripentaerythritol phthalate, poly (mono-, di-, and tri-mixture) pentaerythritol terephthalate, bis(sorbitol) adipate octanoate, bis(sorbitol) citrate, etc.

The amount of the carboxylic acid partial ester of the polyhydric alcohol according to the present invention added is from 0.005 to 100 parts by weight of the resin.
The amount is 10 parts by weight, preferably 0.01 to 5 parts by weight.

In addition, examples of the (C) component oxychloride used in the present invention include perchlorate (Zn.

Al, NH4, K, Ca, Sr, Na, Ba
, Mg, Li), periodate (ZnXNH4, KN
Na, Ba, Li), chlorate (Zn, ALN
I(4, K, Ca, Sr, Na, Ba, Mg
, Li), bromate (Zn% AI% NH4%
KN Ca, Sr, Na, Ba, Mg, L
i), iodate (Zn, AI, NHII, K, C
a, Sr, Na, Ba%Mg, Li), chlorite (ZnXCa, KN Na, Ba), hypochlorite (Li, Na, KN Ca, Sr,
Bas NI (ll'), bromite (Na, K, C
a, Ba), etc.

Naturally, these may be hydrated salts.

The amount of the above halogen oxyacid added is 10% of the halogen-containing resin.
0 parts by weight. It is 1 to 3 parts by weight of OO, preferably 0.01 to 2 parts by weight of 11-layer.

An excellent synergistic effect is exhibited by further using an organic phosphite compound and/or an epoxy compound in the composition of the present invention.

Organic phosphite compounds that can be used in the present invention include:
Diphenyl tesyl phosphite, triphenyl phosphite, tris-nonylphenyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tributyl phosphite, dilauryl acid phosphite, dibutyl acid phosphite, tris (dinonyl) phenyl) phosphite, trilauryl trithiophosphite, trilauryl phosphite, his(neopentyl glycol)-1,4-cyclohexane dimethyl phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, diphenyl acid phosphite Fight, Tris (
lauryl-2-thioethyl) phosphite, tetratridecyl-1,1,3-)lis(2-methyl-5-tert-butyl 12-14-oxyphenyl)butane diphosphite, tetra(C12-C15 mixture) alkyl) 4,4-isopropylidene diphenyl diposphite, tris(4-oxy-
2,5-di-tert-butylphenyl) phosphite, tris(4-oxy-3,5-di-tert-butylphenyl) phosphite, 2-ethylhexyldiphenyl phosphite, tris(mono-, di-mixed nonylphenyl) phosphite , hydrogenated-4,4-improvylide/diphenol polyphosphite, diphenyl bisC4,4-n-butylidene bis(2-tert-butyl-5-methylphenol)
] Thiogetanol diphosphite, bis(octylphenyl) bis(4,4-n-butylidenebis(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-tertiary)
butyl-5-methylphenol) diphosphite, tris(2,4-di-6-butylphenyl) phosphite,
etc.

The amount of these organic phosphite compounds added is 0.01 to 5 parts by weight, preferably 1 to 3 parts by weight per 100 parts by weight of the resin.
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(epoxyprobyl) in cyanurate, epoxidized castor oil, epoxidized flower oil, epoxidized linseed oil butyl fatty acid, 3-(2-xenoxy)-1,2-epoxypropane, bisphenol- Examples include A dicrycidyl ether, vinylcyclohexene dieboxide, dicyclopentadiene dieboxide, and 6,4-epoxycyclohexyl-6-methylepoxycyclohexane carboxylate.

The amount of these epoxy compounds added is 0.01 to 1 part by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the resin.

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 benzophenone, benzotriazole, salicylate, substituted acrylonitrile, various metal salts or metal chelates, especially nickel or chromium salts or chelates, triazine, piperidine, and the like.

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 soaps, a halogen-containing polymer composition that is non-toxic and has good thermal stability can be obtained.

Other items may be added as necessary, such as cross-linking, pigments, fillers, foaming agents, antistatic agents, antifogging agents, plate-out anti-corrosion, surface treatment agents, lubricants, flame retardants, fluorescent abrasions, anti-fungal agents, and anti-mold agents. Cocooning agents, metal deactivators, photodegradants, processing aids, mold release agents, reinforcing agents, and the like can be included.

Examples of the halogen-containing polymer used in the present invention include the following. 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-hynylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride ternary copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, 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, chloride Halogen-containing synthetic resins such as vinyl-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, and internally plasticized polyvinyl chloride, and alpha- Olefin polymers or polyolefins such as ethylene-vinyl acetate copolymers and ethylene-propylene copolymers, and their copolymers, polystyrene, acrylic resins, styrene and other polymers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.) ), acrylonitrile-butadiene-styrene copolymer, acrylic ester-butadiene-styrene copolymer, methacrylic ester-butadiene-
Examples include blended products with styrene copolymers.

The following examples show the effects of the halogen-containing resin composition according to 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 11III+. Using this sheet, initial colorability, transparency, and thermal stability at 190°C were examined. The results are shown in Table 1.

Blend> 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 19 - Example 2 Using the following formulation, a sheet with a thickness of 1 was prepared in the same manner as in Example 1, and heated at 120°C. Thermal stability at 190°C and elongation after aging at 120°C for 382 hours were measured. The results are shown in Table 2.

Blend> Polyvinyl chloride resin 50 parts by weight A
BS resin 5ONBR10 Epoxidized dog bean oil 10 tetra(0
12-□5 mixed alkyl) 1.0 Bisphenol A-diphosphite barium stearate 1.0 Zinc laurate 0.5 Barium perchlorate 0.2 Polyhydric alcohols (Table 2) 0.2 20- Implementation Example 3 A series of thick sheets were prepared in the same manner as in Example 1 using the following formulations and subjected to heat aging testing at 175°C. The results are shown in Table 3.

<Blend> Polyvinyl chloride resin 100 Parts by weight Dioctyl phthalate 50 Epoxidized soybean oil 1.0 Nonylphenol barium salt 1.0 Zinc neodecanoate 0.5 Halogen oxyacid (Table 3) 0.1 Table 3 231 Example 4 When an organic phosphite compound was used in combination with the composition of the present invention, an even greater 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.

Blend> 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)・0.2 Barium adipate perchlorate 0. 05 Organic phosphite compound (Table 4) 0.224 - Table 4 Example 5 In order to investigate the effect of using other stabilizing aids in combination with the composition of the present invention, the following formulation was used. A sheet with a thickness of one inch was prepared in the same manner as in Example 1, and a thermal stability test at 180°C was conducted. The results are shown in Table 5.

Blend> Polyvinyl chloride resin 100 parts by weight Epoxidized dog bean oil 5 Magnesium stearate 0.2 Calcium stearate 0.5 Zinc stearate 0.5 Barium perchlorate
0.1 Other stabilizing aids (Table 5)
(Table 5) Table 5 Patent Applicant Adeca Argus Chemical Co., Ltd.

Claims (1)

[Claims] A stabilized product obtained by adding (a) at least one metal salt of an organic acid, (b) at least one carboxylic V partial ester of a polyhydric alcohol, and (c) at least one halogen oxyacid to a halogen-containing resin. A resin composition containing norogen.