JPH0665458A - Chlorine-containing resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition consisting of a chlorine-containing resin, a specific carboxylic acid metallic salt, a polyolpolyketoacid ester and a phenolic antioxidant, etc., free from toxicity and excellent in color protection and thermal stability and useful for films, sheets, etc. CONSTITUTION:The objective composition is obtained by blending (A) 100 pts.wt. chlorine-containing resin such as PVC with (B) preferably 0.1-3 pts.wt. one or two or more kinds of carboxylic acid metallic salts selected from calcium salt, magnesium salt and zinc salt of carboxylic acids such as hexanoic acid, (C) preferably 0.1-2.0 pts.wt. polyolpolyketoacid ester such as ethylene glycol diacetoacetate and (D) a phenolic antioxidant such as 2,6-di-tebutyl-p-cresol or a sulfur-based antioxidant such as thiodipropionic acid dilauryl ester.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chlorine-containing resin composition which is excellent in heat stability and is nontoxic or low in toxicity.

[0002]

2. Description of the Related Art Chlorine-containing resins are excellent in processability, weather resistance, and impart plasticity by the addition of a plasticizer, and are inexpensive. Therefore, chlorine-containing resins can be used in various materials such as films, sheets, tubes, corrugated sheets, and pipes. Widely used in molded products. However, chlorine-containing resins lack heat and light stability, and since the molding processing temperature and thermal decomposition temperature are close to each other, thermal decomposition due to dehydrochlorination during molding is likely to occur, which results in Coloring and deterioration of mechanical strength occur.

The coloring of the chlorine-containing resin by heat is divided into light yellow to brown (initial coloring) that develops in the early stage of heating and dark brown to black (long-term coloring) that develops when heated for a relatively long time. It is generally evaluated and it is necessary to prevent both of these stains. Conventionally, organometallic compounds have been used in order to prevent thermal coloring of chlorine-containing resins, and practical improvements have been made. However, of these organometallic compounds, lead compounds and cadmium compounds are highly toxic and their use is limited.

Among organic metal compounds, calcium soap,
Magnesium soap and zinc soap are non-toxic, but their thermal discoloration prevention performance is not sufficient. Therefore, "Elucidation of Stabilization of Polyvinyl Chloride and Actual Mixing and Effect of Stabilizing Aid" (Showa era)
(Published by Soft Giken Publishing Co., Ltd. on March 15, 1959), a composition aiming at prevention of initial coloring and long-term coloring due to a synergistic effect of the combination of Ca / Zn and Mg / Zn, and a combination thereof. A composition aiming at long-term coloration prevention has been proposed by adding an organic phosphorus compound, an epoxy compound, a polyol compound, a sulfur-containing compound, and a nitrogen-containing compound as a stabilizing aid. However, compositions and stabilizing aids aiming at the synergistic effect of these metal soaps are still insufficient in preventing initial coloration. Then β
-Attempts have been made to improve the initial colorability by adding diketones or acetoacetic acid.

For example, Japanese Examined Patent Publication (Kokoku) No. 55-15498 proposes to improve the thermal stability by using a metal salt of an organic carboxylic acid and a β-diketone compound in combination, and is excellent in the initial coloration preventing property. However, the long-term anti-coloring property is insufficient. In order to improve the long-term coloring, JP-A-61-207466 proposes to use a zinc salt of an organic monocarboxylic acid, a β-diketone compound, and an epoxy group-containing compound polymer in combination, but it is still long-term coloring. Preventability is insufficient.

[0006] Japanese Patent Publication No. Sho 53-20062 proposes to improve the thermal stability by using a tin compound, an organic carboxylic acid metal salt and a keto acid ester in combination. With this formulation, both the initial coloration prevention property and the long-term coloration prevention property are excellent, but the tin-based compound has a problem in terms of toxicity, and its use in general-purpose products is limited.

[0007]

SUMMARY OF THE INVENTION The present invention is to solve the above-mentioned problems and to provide a non-toxic chlorine-containing resin composition which is excellent in both initial coloration prevention property and long-term coloration prevention property. .

[0008]

As a result of intensive studies, the present inventors have added a specific carboxylic acid metal salt, polyol polyketo acid ester, phenol-based antioxidant or sulfur-based antioxidant to a chlorine-containing resin. By doing so, it was found that the initial coloring property and the long-term coloring property can be remarkably improved, and the present invention has been completed.

That is, the present invention comprises a chlorine-containing resin and (a)
From one or more metal carboxylic acid salts selected from calcium salts, magnesium salts, and zinc salts of carboxylic acids, (b) polyol polyketo acid esters, and (c) phenolic antioxidants or sulfur antioxidants And a chlorine-containing resin composition.

The chlorine-containing resin used in the present invention is, for example, polyvinyl chloride, chlorinated polyvinyl chloride, a copolymer of vinyl chloride and olefin, a copolymer of vinyl chloride and vinyl acetate and the like. The (a) carboxylic acid constituting the calcium salt, magnesium salt, and zinc salt of a carboxylic acid metal salt used in the present invention has 4 to 4 carbon atoms.
24 saturated or unsaturated carboxylic acids, carbocyclic carboxylic acids having 7 to 16 carbon atoms, such as hexanoic acid, octanoic acid,
2-ethylhexanoic acid, decanoic acid, isodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid,
Arachidic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, palmitoleic acid, isostearic acid, 12-hydroxystearic acid, ricinoleic acid, adipic acid, pimelic acid, glutaric acid, azelaic acid, sebacic acid, benzoic acid, toluic acid. , Xylyl acid, ethylbenzoic acid, p
Examples thereof include one or a mixture of two or more of -t-butylbenzoic acid, naphthenic acid, phthalic acid, isophthalic acid, terephthalic acid, cinnamic acid, anisic acid, salicylic acid and the like.

The amount of these metal salts of carboxylic acid added is 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the chlorine-containing resin. The polyol constituting the polyketo acid ester (b) used in the present invention is a compound having two or more hydroxyl groups in the molecule and a compound having two or more ester bonds with a keto acid, such as ethylene glycol diacetate. Acetate, ethylene glycol dibenzoyl acetate, propylene glycol diacetoacetate, propylene glycol dibenzoyl acetate, 1,6-hexanediol diacetoacetate, 1,6-hexanediol dibenzoyl acetate, neopentylene glycol diacetoacetate, glycerin diacetate Acetoacetate, glycerin dibenzoyl acetate, glycerin triacetoacetate, glycerin tribenzoyl acetate, trimethylolpropane triacetoacetate, trimethylolpropane Ribenzoyl acetate, pentaerythritol diacetoacetate, pentaerythritol dibenzoyl acetate, pentaerythritol triacetoacetate, pentaerythritol tribenzoyl acetate, dipentaerythritol diacetoacetate, dipentaerythritol diacetoacetate, dipentaerythritol triacetoacetate, di Pentaerythritol tribenzoyl acetate, dipentaerythritol tetraacetoacetate, dipentaerythritol tetrabenzoyl acetate, dipentaerythritol pentaacetoacetate, dipentaerythritol pentabenzoyl acetate, dipentaerythritol hexaacetoacetate, dipentaerythritol hexabenzoyl acetate, Pentaerythritol tetraacetoacetate-monobenzoyl acetate, Dipentaerythritol tetrabenzoyl acetate-diacetoacetate, Sorbitol diacetoacetate, Sorbitol hexaacetoacetate, Sucrose diacetoacetate, Sucrose octaacetoacetate, Starch polyacetoacetate, Cellulose poly Acetoacetate, polyvinyl alcohol polyacetoacetate, pentaerythritol monobutyrate triacetoacetate, dipentaerythritol distearate tribenzoyl acetate,
Examples thereof include polyacetoacetic acid ester of polyester having a molar ratio of glycerin and maleic anhydride of 1: 1, polyacetoacetic acid ester of alkylene oxide adduct of glycerin, and polyacetoacetic acid ester of alkylene oxide adduct of sucrose monostearate.

These polyol polyketo acid esters are
Although it can be obtained by directly reacting the corresponding polyol with diketene, etc., a monoalcohol monoketo acid ester such as methyl acetoacetate or ethyl benzoylacetate is transesterified with the corresponding polyol to distill off the produced monoalcohol. It can be easily obtained.

The amount of the polyol polyketo acid ester added is 0.01 to 5.0 parts by weight, preferably 0.1 to 2.0 parts by weight, based on 100 parts by weight of the chlorine-containing resin. The phenol-based antioxidant or sulfur-based antioxidant used in the present invention is an antioxidant that is dispersed or dissolved in a chlorine-containing resin, and a preferable example thereof is 2,6-di-t-butyl-p.
-Cresol, butylated hydroxyanisole, 2,6
-T-butyl-4-ethylphenol, octadecyl
3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, pt-butylphenol, dibutylhydroxytoluene, phenol, resorcin, DL-α-tocopherol, propyl gallate,
Tetrakis- [methylene-3- (3 ', 5'-di-t-
Butyl-4'-hydroxyphenyl) propionate]
Methane, 2,2'-methylene-bis- (4-methyl-6
-T-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-t-butylphenol), 4,
4'-butylidene-bis- (3-methyl-6-t-butylphenol), bisphenol A, 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1, 3,5-trimethyl-2,4,6
-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis [3,3'-bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, Phenolic antioxidants such as vitamin E, α-methylbenzylphenol, butylidenebis (methyl-butylphenol), dilauryl thiodipropionate, stearyl thiodipropionate, 2-mercaptomethylbenzimidazole, nickel dibutyldithiocarbamate, 2- There are sulfur antioxidants such as mercaptobenzimidazole.

In addition, the composition of the present invention includes well-known stabilizing aids such as organic phosphorus compounds, epoxy compounds, polyol compounds, β-diketone compounds, nitrogen-containing compounds and sulfur-containing compounds, and higher fatty acids such as stearic acid, Higher alcohols such as stearyl alcohol, waxes such as paraffin wax, polyethylene wax and montan wax,
Lubricants such as amides such as stearic acid amide, methylenebisstearic acid amide and ethylenebisstearic acid amide, fillers such as calcium hydroxide, calcium carbonate, talc and hydrotalcite, other pigments, antistatic agents,
A processability improver, a flame retardant, an ultraviolet protective agent, etc. can be used as long as the effects of the present invention are not impaired.

[0015]

Since the chlorine-containing resin composition of the present invention is excellent in thermal stability and initial coloration preventing property, it is possible to prevent coloration and deterioration of mechanical strength that occur during molding. Furthermore, since the chlorine-containing resin composition of the present invention is non-toxic,
Can be used in controlled toxicity applications.

[0016]

EXAMPLES The present invention will be specifically described below with reference to examples. [Preparation of sample sheet] 0.5 parts by weight of the polyol polyketo acid ester shown in Tables 1 to 3 and Table 1 and antioxidant
A chlorine-containing resin composition consisting of 0.2 parts by weight was kneaded at 170 ° C. for 3 minutes using a hot roll having a diameter of 9 inches to prepare a sheet having a thickness of 1 mm.

[Thermal stability evaluation method] A sample sheet of 5 × 5
It was cut into cm and heated in a gear oven at 180 ° C.
To evaluate the initial colorability, the color tone of the sample sheet after 15 minutes of heating was examined. To evaluate the long-term colorability, the time until the sample sheet became black was measured. <Compound 1> (Invention Examples No. 1 to 14 and Comparative Examples No. 17 to 21) Polyvinyl chloride resin (Daiichi PVC Sales Co., Ltd., 103EP) 100 parts by weight Calcium stearate salt 0.5 〃 Zinc stearate salt 0.5 〃 Epoxidized soybean oil 1.0 〃 Polyethylene wax (Hi-Wax 220, Mitsui Petrochemical Industry Co., Ltd.) 0.5 〃 <Compound 2> (Invention example No.15) Polyvinyl chloride resin (Daiichi PVC Sales Co., Ltd., 103EP) 100 parts by weight Calcium stearate 0.3 〃 Magnesium stearate 0.2 〃 Zinc stearate 0.5 〃 Epoxidized soybean oil 1.0 〃 Polyethylene wax (Hi-Wax 220) 0.5 〃 <Compound 3> (Example of the present invention) No.16) Polyvinyl chloride resin (Daiichi PVC Sales Co., Ltd., 103EP) 100 parts by weight zinc stearate 0.5 〃 Epoxidized soybean oil 1.0 〃 Polyethylene wax (Mitsui Petrochemical Co., Ltd. Hi-Wax 220) 0.5 〃 Evaluation The results are shown in Table 1.

[0018]

[Table 1]

* 1 Nippon Ciba Geigy Co., Ltd. trade name, Tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane * 1 Nippon Ciba Geigy Co., Ltd. product Name, octadecyl
3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate The chlorine-containing resin composition of the present invention is excellent in both initial coloration prevention property and long-term coloration prevention property.

Claims (1)

[Claims] 1. A chlorine-containing resin, one or more metal carboxylates selected from calcium salts, magnesium salts and zinc salts of (a) carboxylic acids, (b) polyol polyketo acid esters and (c) phenols. A chlorine-containing resin composition comprising a system-based antioxidant or a sulfur-based antioxidant.