JPH0618962B2 - Chlorine-containing resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a chlorine-containing resin composition containing a perchlorate of an amino acid and having excellent coloration-preventing properties and thermal stability.

(B) Problems to be solved by the conventional technology and invention Generally, chlorine-containing resins such as vinyl chloride resin, vinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer resin and chlorinated polyethylene are heated by heat during molding. Significant coloration or decomposition of the resin occurs.

Stabilizers are added to prevent such drawbacks.

However, the stabilizers that have been conventionally used include heavy metals such as cadmium and lead, and have a drawback that they are toxic.

Further, a combination of a low-toxic stabilizer such as a zinc compound of organic acid, an alkaline earth metal salt of organic acid, an organic tin compound, a nitrogen-containing compound such as β-aminocrotonic acid ester and a polyol compound is also used.

However, when these stabilizers having low toxicity are used, coloring of the resin is caused by heating during the molding process, and the thermal stability for a long period of time is inferior.

(C) Means for solving the problem The present inventors, as a result of earnest study to improve the above defects,
By blending perchlorate of amino acid with chlorine-containing resin together with a compound that has been conventionally used as a stabilizer,
The inventors have found that the anti-coloring property is remarkably improved and the long-term thermal stability is also improved, and the present invention has been completed.

That is, the present invention relates to a chlorine-containing resin composition comprising 100 parts by weight of a chlorine-containing resin and preferably 0.001 to 5 parts by weight of an amino acid perchlorate.

Examples of the chlorine-containing resin in the present invention include vinyl chloride resin, vinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer resin, copolymer resin with vinyl chloride and a compound copolymerizable with vinylidene chloride, such as vinyl chloride-ethylene copolymer. Examples include polymerized resins and chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene.

Further, the above-mentioned chlorine-containing resin and chlorine-free resin, for example, a blend resin such as acrylonitrile-butadiene-styrene resin, ethylene-vinyl acetate resin and butadiene resin can be mentioned.

Examples of the amino acid in the present invention include glycine, alanine, valine, leucine, isoleucine, serine, threonine, cystine, cysteine, methionine, lysine, arginine, phenylalanine, tyrosine, histidine, tryptophan, brolin, oxybroline, β-alanine, Examples thereof include aspartic acid, glutamic acid, γ-aminobutyric acid, anthranilic acid and p-aminobenzoic acid.

The amino acid perchlorate in the present invention means perchlorate itself and a mixture of perchlorate and amino acid.

The perchlorate of amino acid can be blended with the chlorine-containing resin not only in the dry state but also in the water-containing state, slurry state and aqueous solution state.

The amino acid perchlorate used in the present invention can be prepared, for example, by adding an aqueous solution of perchloric acid to the amino acid.
It is desirable to prepare by adding 1 to 1 mol.

When a chlorine-containing resin is blended with a perchlorate of an amino acid produced by adding perchloric acid in an amount of more than 1 mol, the chlorine-containing resin composition is inferior in coloring prevention property.

One of the features of the present invention is that an amino acid perchlorate can be added to a chlorine-containing resin in the presence of water.

That is, the water mixed during the preparation of the chlorine-containing resin composition can be removed by high-speed stirring while heating,
In addition, a chlorine-containing resin composition in which each compound is uniformly dispersed is obtained as compared with the case where a perchlorate having no water is compounded.

The amount of amino acid perchlorate to be mixed with the chlorine-containing resin is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the chlorine-containing resin.

When the amount of the amino acid perchlorate compounded is less than 0.001 part by weight, the effect of preventing coloring and heat resistance of the chlorine-containing resin composition is not recognized.

On the other hand, if it exceeds 5 parts by weight, a chlorine-containing resin composition in which each compound is uniformly dispersed cannot be obtained and heat resistance is also impaired.

In the present invention, as the stabilizer to be used together with the perchlorate of amino acid, organic acid zinc salts such as zinc octylate and zinc stearate, organic acid alkali salts such as calcium octylate and stearic acid, magnesium and barium salts, etc. Earth metal salts, organic phosphite compounds such as diphenyldecyl phosphite, polyol compounds such as pentaerythritol and dipentaerythritol, nitrogen-containing compounds such as 1,4-butanediol ester of β-aminocrotonic acid Examples thereof include organotin compounds such as dibutyltin laurate and dioctyltin maleate, metal oxides such as calcium oxide, magnesium oxide and aluminum oxide, and metal hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide.

Furthermore, plasticizers such as dioctyl phthalate, fillers such as calcium carbonate, antioxidants, ultraviolet absorbers, pigments, foaming agents, antistatic agents, antifogging agents, surface treatment agents, lubricants, flame retardants and plateout prevention. Agents and the like can be blended as necessary.

(E) Effect of the Invention By adding a perchlorate of an amino acid to a chlorine-containing resin, the color-preventing property of the chlorine-containing resin composition is remarkably improved, and long-term thermal stability is also improved.

Amino acid perchlorates can also be added to chlorine-containing resins in the presence of water, and the chlorine-containing compounds are more uniformly dispersed than when the perchlorates are added in the absence of water. A resin composition is obtained.

(F) Examples Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Example 1 100 parts by weight of vinyl chloride resin, dioctyl phthalate 4
0 parts by weight, barium stearate 1 part by weight, zinc stearate 0.2 parts by weight and glycine perchlorate 0.2 parts by weight [60% perchloric acid aqueous solution per mol of glycine 1
91.1 g of a glycine perchlorate solution to which 6.8 g (0.1 mol) was added was prepared and used in the required amount. The value is 100% converted value excluding water] is charged into a Henschel mixer with a steam jacket and mixed with high speed stirring of 3000 RPM while heating with steam for about 5 minutes, and the temperature of the mixture rises to 110 ° C. Then, the contents were taken out and allowed to cool to room temperature.

Next, 100 g of this uniformly dispersed chlorine-containing resin composition was kneaded at 175 ° C. for 5 minutes using a mixing roll to obtain a thickness of 0.
A 3 mm test sheet was prepared.

The anti-coloring property is obtained by cutting the above sheet into a size of 5 cm × 5 cm and using an overlapping heat press machine at 5 ° C at 180 ° C.
Evaluation was performed by hot pressing for 10 minutes and 15 minutes.
The evaluation values are as follows.

1-2 Black-brown 3-4 Reddish brown 5-6 Yellow 7-8 Slight yellow 9-10 Colorless thermal stability was measured by measuring the blackening time at 180 ° C in a gear oven.

The anti-coloring properties were 9, 7 and 7 in the order of 5 minutes, 10 minutes and 15 minutes.

The thermal stability was 70 minutes.

Examples 2 to 9 Chlorine-containing resin compositions were prepared in the same manner as in Example 1 except that the amino acid perchlorate and the method for preparing the same were changed, and the coloration-preventing property and heat stability were tested. Table 1 shows the preparation conditions and results of the chlorine-containing resin composition.

Comparative Example 1 A chlorine-containing resin composition was prepared in the same manner as in Example 1 except that the perchlorate of amino acid was not added, and the coloration-preventing property and heat stability were tested. The results are shown in Table 1.

Example 10 100 parts by weight of vinyl chloride resin, 30 parts by weight of acrylonitrile-butadiene-styrene resin, 40 parts by weight of dioctyl phthalate, 10 parts by weight of calcium carbonate, 1 part by weight of barium nonylphenate, 0.2 part by weight of zinc octylate and glycine. 0.2 parts by weight of perchlorate (159.1 g of perchlorate solution of glycine prepared by adding 84 g (0.5 mol) of 60% perchloric acid aqueous solution to 1 mol of glycine) was prepared and used in the required amount. The numerical values were the values in 100% conversion excluding water], and a chlorine-containing resin composition was prepared in the same manner as in Example 1 and tested for coloration-preventing property and heat stability. Table 1 shows the preparation conditions and results of the chlorine-containing resin composition.

Examples 11 to 13 Chlorine-containing resin compositions were prepared in the same manner as in Example 10 except that the amino acid perchlorate and the method for preparing the same were changed, and the coloration-preventing property and heat stability were tested. Table 2 shows the preparation conditions and results of the chlorine-containing resin composition.

Comparative Example 2 A chlorine-containing resin composition was prepared in the same manner as in Example 10 except that the amino acid perchlorate was not added, and the anti-coloring property and the heat stability were tested. The results are shown in Table 2.

Comparative Examples 3 to 7 Various stabilizers or the like were added in place of the amino acid perchlorate to 0.2.
A chlorine-containing resin composition was prepared in the same manner as in Example 10 except that the parts by weight were blended, and the coloration-preventing property and heat stability were tested. The results are shown in Table 2.

Claims (1)

[Claims] 1. A chlorine-containing resin composition comprising an amino acid perchlorate compounded therein.