JPS6272741A - Chlorine-containing resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having remarkably excellent discoloration resistance and long-term thermal stability, by compounding an amino acid perchlorate to a base resin. CONSTITUTION:(A) 100pts.wt. of a chlorine-containing resin is compounded with (B) 0.001-5pts.wt. of an amino acid perchlorate produced preferably by adding 0.1-1mol of perchloric acid to 1mol of an amino acid.

Description

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

(b) Problems to be solved by the prior art and the invention In general, chlorine-containing resins, such as vinyl chloride resin, vinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer resin, and chlorinated polyethylene, etc., are heated during molding. Significant discoloration and decomposition of the resin occur.

To prevent such drawbacks, stabilizers are added.

However, conventionally used stabilizers contain heavy metals such as cadmium and lead, and have the disadvantage of being toxic.

Also used are combinations of less toxic stabilizers such as organic acid zinc salts, organic acid alkaline earth metal salts, organotin compounds, nitrogen-containing compounds such as β-aminocrotonic acid esters, and polyol compounds.

However, the use of such low-toxicity stabilizers causes coloring of the resin due to heating during molding and poor long-term thermal stability, so improvements in these have been strongly desired.

(c) Means for solving the problems - As a result of intensive studies in order to improve the above-mentioned drawbacks, the present inventors discovered that amino acid perchlorate was used together with a compound conventionally used as a stabilizer in a chlorinated resin. The present inventors have completed the present invention by discovering that the coloration prevention property and long-term thermal stability can be significantly improved by blending the compound into a polyester.

That is, the present invention relates to a chlorine-containing resin composition characterized in that an amino acid perchlorate is preferably blended in an amount of 0.001 to 5 parts by weight per 100 parts by weight of the chlorine-containing resin.

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 of vinyl chloride and a compound copolymerizable with vinylidene chloride, such as vinyl chloride-ethylene copolymer resin. Examples include polymer resins and chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene.

Furthermore, blend resins of the above-mentioned chlorine-containing resins and chlorine-free resins, such as acrylonitrile-butadiene-styrene resins, ethylene-vinyl acetate resins, and butadiene resins, may also be mentioned.

In addition, examples of amino acids in the present invention include glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, cysteine, methionine,
Lysine, arginine, phenylalanine, tyrosine, histidine, tryptophan, proline, oxyproline, β-alanine, aspartic acid, glutamic acid, γ-
Examples include aminobutyric acid, anthranilic acid and p-aminobenzoic acid.

Amino acid perchlorate in the present invention refers to perchlorate itself and a mixture of perchlorate and amino acid.

Furthermore, the amino acid perchlorate can be blended into the chlorine-containing resin not only in a dry state but also in a wet state, a slurry state, and an aqueous solution state.

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

If a perchlorate of an amino acid produced by adding more than 1 mole of perchloric acid is blended into a chlorine-containing resin, the coloring prevention properties of the chlorine-containing resin composition will be poor.

One of the features of the present invention is that perchlorate of an amino acid can be blended into a chlorinated resin in the presence of moisture.

That is, water mixed in during the preparation of the chlorine-containing resin composition can be removed by stirring at high speed while heating.
In addition, a chlorine-containing resin composition in which each compound is more uniformly dispersed than when water-free perchlorate is blended can be obtained.

The amount of amino acid perchlorate added to the chlorine-containing resin is preferably 0.001 to 5 parts by weight per 100 parts by weight of the chlorine-containing resin.

If the amount of the amino acid perchlorate is less than 0.001 part by weight, no effect on the coloring prevention properties and heat resistance of the chlorine-containing resin composition will be observed.

Moreover, 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, stabilizers used with perchlorates of amino acids include organic acid zinc salts such as zinc octylate and zinc stearate, and organic acid alkali salts such as calcium, magnesium and barium salts of octylate and stearate. 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 , organic tin compounds such as diptyltin 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 plate-out prevention agents. Agents and the like can also be added as necessary.

(E) Effects of the Invention By blending a perchlorate of an amino acid into a chlorine-containing resin, the coloring prevention properties of the chlorine-containing resin composition are significantly improved, and the long-term thermal stability is also improved.

Amino acid perchlorates can also be blended into chlorine-containing resins in the presence of moisture, making each formulation more uniformly dispersed chlorine-containing resin than when perchlorates are blended in the absence of moisture. A resin composition is obtained.

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

Example 1 100 parts by weight of vinyl chloride resin, 4 parts of dioctyl phthalate
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 16 parts per mole of glycine]
．． 91.1 g of a perchlorate solution of glycine to which 8 g (0.1 mol) was added was prepared and used in the required amount. [Values are calculated as 100% excluding water] were put into a Henschel mixer with a steam jacket and mixed for about 5 minutes at high speed stirring at 3000 R, P, M while heating with steam. When the temperature rose to 110°C, 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 for 5 minutes at 175°C using a mixing roll until the thickness was 0.
A test sheet for three cranes was prepared.

The coloring prevention property was determined by cutting the above sheet into 5Ω x 5cm pieces, stacking them together using a heat press machine, and heating them at 180°C for 5cm.
For evaluation, heat pressing was performed for 10 minutes, 10 minutes, and 15 minutes.

The evaluation values are as follows.

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

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

Moreover, 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 perchlorate of the amino acid and the method of preparation thereof were changed, and tests for anti-coloration properties and thermal stability were conducted.

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 no amino acid perchlorate was added, and tests for anti-coloring properties and thermal stability were conducted. The results are shown in Table 1.

Example 10 100 parts by weight of vinyl chloride resin, 30 parts by weight of arcrylonitrile-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 parts by weight of zinc octylate. and 0.2 parts by weight of glycine perchlorate [glycine 1
159.1 g of a glycine perchlorate solution to which 84 g (0.5 mol) of a 60% aqueous perchloric acid solution was added per mole was prepared and used in the required amount. A chlorine-containing resin composition was prepared in the same manner as in Example 1, using the values calculated on a 100% basis excluding moisture, and was tested for anti-coloring properties and thermal 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 perchlorate of the amino acid and the method of preparation thereof were changed, and tests for anti-coloring properties and thermal stability were conducted. 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 no amino acid perchlorate was blended, and tests for anti-coloring properties and thermal stability were conducted. The results are shown in Table 2.

Comparative Examples 3 to 7 Various stabilizers etc. were used in place of amino acid perchlorate at 0.2
A chlorine-containing resin composition was prepared in the same manner as in Example 10, except that it was blended in parts by weight, and the coloring prevention property and thermal stability were tested. The results are shown in Table 2.

Claims (1)

[Claims] A chlorine-containing resin composition characterized by containing an amino acid perchlorate.