JPS60219247A - Novel halogen-containing resin composition - Google Patents

Abstract

PURPOSE:The titled composition having excellent long-term heat stability, made by adding a perchlorate type hydrotalcite compound and zinc glutamate to a halogen-containing resin. CONSTITUTION:To 100pts.wt. halogen-containing resin (e.g. chlorinated PE) are added 0.001-10pts.wt. perchlorate type hydrotalcite compound of the formula (where 0<X<=0.5; m is a positive number), and 0.001-10pts.wt. zinc glutamate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a halogen-containing resin composition with excellent thermal stability.

Halogen-containing resins are inherently thermally unstable.

Heating during molding and the sun during use) 'e Table by Gen + f +
i +7. A decomposition reaction due to dehalogenation reaction occurs within the 9 molecular chains due to an increase in A degree, etc., resulting in 4 colors.

A decrease in mechanical strength is observed. 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. In addition, organic acid zinc salts and organic acid alkaline earth residual salts are used as stabilizers with low toxicity.

Organic tin compounds, nitrogen-containing nonmetallic compounds such as β-aminocrotonic acid esters, polyols, and the like have been used in combination. However, these stabilizers cause coloration during molding, and there has been a strong demand for improvement in long-term thermal stability.

In recent years, attempts have been made to improve long-term thermal stability by adding hydrotalcite compounds to halogen-containing resins, as seen in Japanese Patent Publication No. 5B-46146. However, although these compounds have a greater ability to capture halogen generated by decomposition than halogen-containing resins as a stabilizing effect, they tend to actively extract halogen from the resin.

This had the disadvantage of promoting the formation of holien, resulting in strong coloring. What are the conventional methods used to alleviate this coloration?

Addition of zinc salts of organic acids such as zinc stearate, zinc octoate, etc. While these zinc salts have the effect of improving coloration, they also have the effect of promoting decomposition of resin.
As the amount of added t11- is increased, the coloring caused by the hydrotalcite compound is alleviated, but on the contrary, the time for decomposition and blackening of the halogen-containing resin becomes shorter, and the thermal stability of the halogen-containing resin is reduced. It was still not completely satisfactory.

The present inventors have conducted repeated studies to solve the drawbacks of using a hydrotalcite compound with excellent halogen scavenging ability as described above and a zinc salt of an organic acid in combination as a stabilizer for halogen-containing resin. , the (a+ hydrotalcite compound was ion-exchanged with perchlorate ions) into the halogen-containing resin. By simultaneously adding the perchlorate ion-exchange type hydrotalcite compound and (r+c lead salt of hl glutamic acid), The inventors have completed the present invention by discovering that the 't+'f color caused by polyene formation is significantly alleviated and the thermal stability of JItliJJ is improved. In addition to stability, molded products are subject to thermal deterioration when continuously exposed to a temperature atmosphere of 90° C. to 120° C. (this is called low-temperature aging).

(hereinafter the same) also found a significant improvement effect.

The advantage of the present invention resides in a halogen-containing resin composition containing (a) a hachloric acid ion-exchange type hydrotalcite compound and 0) a zinc salt of glutamic acid as stabilizer components.

The hydrotalcite compound used in the present invention is a hydrous double salt compound of magnesium and aluminum represented by the following general formula (1), and may be a natural product or a synthetic product.

Mg + -X AAx (OH1,2Ax/2 ・m
H2O (1) However, in the formula, 0 (x 0.5. A u C
o, and 1mI''i indicates a positive number.

To obtain a composite of the perchlorate ion type hydrotalcite compound used in the present invention, the hydrotalcite compound is brought into contact with a commercially available aqueous solution of perchloric acid. A (co, which is an anion) in the similar compound is (CAO4)2” K-easy I
It is possible to obtain a composite whose main component is the composition represented by C 匝m G し+下GD(Ill).

ΔLy, 1−xΔgXtoI+1. ((!go41.
- mH2(1(i) However, in formula 1, 0(x(11,5m indicates a positive number.

Two of these are commonly used. EAK bare ion type... called idrotalzite compounds. (The same applies hereinafter) The salivary lead salt of glutamic acid used in the present invention can be prepared by (a) the usual method of adding lead sulfate to sodium glutamate to form a precipitate, or (b) the method of reacting glutamic acid with 1'1141 shunzinc. It can be synthesized and can be expressed by a chemical formula as shown in F corresponding to each production method (a) and (b). These polymers contain glutamine and glutamine (containing 11k...added to Rodan 4i'l fat).

h2 Compared to ordinary zinc salts of organic acids, the decomposition promoting effect of the halogen-containing resin was extremely alleviated.

The halogen-containing resins referred to in the present invention are 9. For example, homopolymers and copolymers obtained by polymerization of vinyl halides, vinylidene halides, etc., and copolymers with compounds capable of copolymerizing these 2. For example, vinyl chloride-ethylene copolymers. Examples include chlorinated polyolefin resins such as chlorinated polyethylene and chlorinated polypropylene.

History of halogen-containing resins and halogen-free resins such as A
The present invention can also be suitably used in polymer blends with BS', MBB, EVA, butanene resins, etc. The amount of the additive of the present invention added to these chlorine-containing resins is 0.001 to 10 parts by weight of zinc salt of perchlorate ion type hydrotalsamic acid per 100 parts by weight of the resin.

Zinc salts of organic acids such as stearic acid, octyl, benzoic acid, and oleic acid are included in the compositions of the invention.

The combined use of zinc salts of acyhinic acid, phenol, tert-butylphenol, nonylphenol, etc. should be avoided, as these zinc salts accelerate the decomposition and blackening time of the 7if4 fat composition, as mentioned above. , and other known substances that are commonly used as stabilizer components, do not reduce the effects of the present invention in any way.

These commonly used stabilizers include organic acid salts, organic phosphite compounds, antioxidants, and ultraviolet absorbers.
], gold-enzyme oxide, gold-water impregnated.

Polyols, nitrogen-containing nonmetallic compounds, ebogishi compounds, and patent application No. 57-19564 filed by the same applicant.
6 g + + 2 hydride/l/site compound is calcined to reduce water content in the crystal structure to 50
Examples include firing-treated products of hydrotalcite compounds that have been desensitized within the range of ~200 tons ili:%.

Furthermore, plasticizers, pigments, and fillers as necessary.

Foaming agent, antistatic agent, antifogging agent, plate-out prevention agent 9
There is no problem in adding surface treatment, lubricant, flame retardant, etc. to the formulation.

Next, examples of synthesis of filtered chlorate ion type hydrotalcite compounds and zinc salt of glutamate acid will be shown below. In the synthesis, one unit of Alcamizer 1 (hereinafter referred to as Alcamizer 1 and Lower) manufactured by Kyowa Chemical Industry Co., Ltd. was used as an iJA compound. Alcamizer 1 has the general formula (1) above.

”Lll-x A,il!x(OH)2Ax/2-m
H2O (11x=0.555. A=CO,, m=0.
5 and 41), and substituting these into (11) gives I axis 0.6.67 A, g 0.555 fOH12 (
C,031j, 1.1665・0.5 H2O.

If each coefficient is multiplied by 6, it can be expressed by the chemical formula Mp;, A], tOH], 2(co, l.3H20, which is 1 mole of Alkamizer-1.

becomes 4691.

Synthesis Example 1 An aqueous perchloric acid solution corresponding to 2 moles of perchloric acid was gradually added to 1 mole of Alkamizer 1) with stirring, and thoroughly mixed. When the generation of carbon dioxide gas was completed]1'j stirring was stopped to obtain a wet powder composite. This was dried at 50°C under reduced pressure for 60 minutes, and 1'
,, 1'.

Synthesis Example 2 One mole of Alkamizer (1q') was gradually added to an aqueous solution of 17 moles of perchloric acid with stirring, and the mixture was thoroughly mixed until the generation of carbon dioxide gas had ceased. fc nonionic surfactant e, 1 to improve mixing
if-added. Filter the compound.

? Tonzai was changed to ``Inui'', and ii゛I'i song use'' was changed to Nangle Notification 2.

Synthesis example glutamic acid 111 superlead Jiil'L (
Combination of a) + jy example - 2 moles of glutamic acid, 1 mole of zinc sulfate and 1 mole of zinc sulfate are stirred in water, 8[] to 8
The reaction was carried out at 5°C. It was cooled to near Q'C and the resulting precipitate was filtered and dried. This is a sample for evaluation (a)
And so.

Synthesis ψj14 Synthesis example L of zinc salt of glutamic acid (b)
- 1 mole of glutamic acid and 1 mole of th'r cIi zinc in a flask with 1 noflux while stirring.

The reaction was carried out at 95°C to iooo°C. After cooling, it was dried under reduced pressure to obtain a planned horn pull (L+).

This will be explained in detail below using examples.

1^J, The degree of coloring in Examples was expressed using the following numerical values.

Example 1 In order to see the effect of the chlorine-containing resin composition according to the present invention, the following formulation was rolled to a thickness of 0.5 mm using a mixed wire roll.
A test sheet of 11111 was created. Thermal stability at 180°C using a gear aging tester.

Low temperature aging properties at 120°C were investigated. Moreover, it was expressed by the time of 1 coloring property. The coloration property is expressed by the degree of coloration of the test piece at 20, 40, and 60 minutes of removal using a gear aging tester, and is expressed as fC0fJ! :i Crystal aging resistance was also expressed as a numerical value of the degree of coloration for each sample taken out. In addition, for comparison, the same tests were conducted using Alkamizer 1 and 11F lead stearate as well as the sample No. 6, and the results are also shown in the second column. "Bonka Vinyl 100 Jui Tsujibe 1) OF
40 #Barium Stearley) 0.5 ll Practical HM Example 2 When a known substance, which is usually used as a stable edge component, was used in combination with the composition of the present invention, a further improvement effect was obtained. The effect of the combined stabilizer was investigated in the same manner as in Practical HM Example 1 using the formulation shown below. The results are shown in the second layer.

Composition Polyvinyl chloride 1 q, "0 Car j, itr flea l5A13s 30 # DOP 50 N Barium nonyl phenate o5 〃 Perchlorate ion type hydroglutamic acid zinc salt Ifis (Table 2) 04 I Concomitant stabilizer ( Table 2, [1,5'

Claims (1)

[Claims] Halogen-containing resin VC (a) perchlorate ion type hydrotalcite compound at 0001 to 10 TJ (iij k
lI and (h) zinc salt of glutamic acid at 0.0 D 1
A novel halogen-containing resin composition characterized in that 6≦~10 parts by weight are added at the same time.