JPH0881604A - Chlorine-containing polymer composition - Google Patents

Abstract

(57) [Summary] [Object] To provide a chlorine-containing polymer composition having a combination of improved amine resistance and thermal stability. [Structure] The following formula Li ₂ Al ₄ (ClO ₄ ) _n (CO ₃ ) _{1-n / 2} (OH)
_{In the 12} · mH ₂ O formula, n is a number of 0.05 to 2 and m is a number of 3 or less. Polymer containing lithium aluminum complex hydroxide perchlorate having a composition represented by
The amount is 0.01 to 10 parts by weight per 00 parts by weight. [Effect] Improving both amine resistance and thermal stability by blending a lithium aluminum complex hydroxide salt in which a part of the carbonate radical is replaced with perchloric acid in a chlorine-containing polymer. I was able to. In addition, this polymer composition has little initial coloring tendency and is excellent in appearance characteristics,
It is particularly useful for soft blending applications.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-stabilized chlorine polymer composition, and more particularly to a chlorine polymer composition having amine resistance.

[0002]

2. Description of the Related Art A chlorine-containing polymer such as a vinyl chloride polymer is liable to be colored or deteriorate in mechanical properties due to a thermal decomposition reaction such as dehydrochlorination during heat molding processing or subsequent heat history. Formulation of stabilizers to prevent is generally required. Japanese Unexamined Patent Application Publication No. Hei.
No. 179052 discloses that the following formula [Al ₂ Li (OH) ₆ ] _n X.mH ₂ 0 (2) where X is an inorganic or organic anion and n is the valence of the anion X. , M is a number of 3 or less. A stabilizer for a resin comprising a lithium aluminum complex hydroxide salt represented by the formula: 0.01 to 10 parts by weight per 100 parts by weight of a chlorine-containing polymer is described. Thermally stabilized chlorine-containing polymer compositions incorporating salts are also described.

[0003]

A chlorine-containing polymer, particularly a soft-blended composition, is used as an overlay sheet for foamed polyurethane and the like for chairs, seats and the like. There is a problem in that they are colored or deteriorated. This is considered to be because unreacted amines used as a chain extender in the production of polyurethane and amines generated by the time-dependent decomposition of polyurethane accelerate the dehydrochlorination reaction of the chlorine-containing polymer. The cause and mechanism of the reaction between the dehydrochlorination reaction by heat and the dehydrochlorination reaction by amines in a chlorine-containing polymer are different, and it is necessary to prevent coloring and deterioration by amines with conventional heat stabilizers. Is generally difficult.

The present inventors have found that the lithium aluminum complex hydroxide salt obtained by substituting a part of the carbonate group with a perchlorate anion has not only a thermal stabilizing effect on a chlorine-containing polymer but also an amine. Action to suppress decomposition and coloring,
That is, they have found that they are also excellent in amine resistance. That is,
An object of the present invention is to provide a chlorine-containing polymer composition having a combination of improved amine resistance and thermal stability.

[0005]

According to the present invention, the following formula Li ₂ Al ₄ (ClO ₄ ) _n (CO ₃ ) _{1-n / 2} (OH) ₁₂ · _m H ₂ O (1) , N is a number of 0.05 to 2, particularly 0.5 to 1.5, and m is a number of 3 or less. Lithium-aluminum composite hydroxide perchlorate having a composition represented by the following is added in an amount of 0.01 to 10 parts by weight, particularly 0.5 to 2 parts by weight, per 100 parts by weight of the chlorine-containing polymer. A chlorine-containing polymer composition is provided.

The present invention is particularly useful for soft-blended chlorine-containing polymer compositions, particularly the following composition general range suitable range chlorine-containing polymer 100 parts by weight (0.01) salt of formula (1) -10 parts by weight 0.5-2 parts by weight Alkaline earth metal component 0.1-10 parts by weight 0.5-3 parts by weight Organic phosphite 0.1-5 parts by weight 0.3-2 parts by weight Plasticizer 5 ~ 100 parts by weight 50 to 70 parts by weight are preferred.

[0007]

In the present invention, as is clear from the composition of the above formula (1), among the lithium aluminum composite hydroxide carbonates,
A part of the carbonate anion substituted with a perchlorate anion is used as a stabilizer. As shown in "Table 1" described later, when the substitution mole number n of the perchlorate anion is lower than 0.05, the amine resistance tends to be worse than that in the range of the present invention. When the number of substitution moles n is higher than 2, the amine stability is satisfactory but the thermal stability tends to decrease. It is particularly preferable that n is in the range of 0.5 to 1.5 in terms of the balance of both characteristics. In the present invention, the complex hydroxide carbonate is used as the original lithium aluminum complex hydroxide salt because the complex hydroxide carbonate is most stably and easily synthesized, and The substance carbonate is effective for thermal stabilization of the chlorine-containing polymer.

The complex hydroxide perchlorate used in the present invention can be obtained by ion-exchange of the complex hydroxide carbonate with a perchlorate anion. In this case, it is especially important in the combination of thermal stability and amine resistance that the number of substitution moles n of perchloric acid does not deviate from the above range.
That is, the carbonate anion in the lithium aluminum complex hydroxide salt is an ion-exchangeable one, but when perchloric acid is added to this system, the perchloric acid naturally has the property as an acid. In addition, it tends to react with lithium and aluminum skeleton in the composite hydroxide to form free lithium perchlorate and aluminum perchlorate as a by-product.

Since these free salts naturally do not contribute to the thermal stability of the chlorine-containing polymer, the thermal stabilizing effect as a whole is reduced. Further, the above-mentioned free salts are deliquescent and have the disadvantage that the stabilizer is coagulated to make it difficult to handle and the compounded chlorine-containing polymer is made hygroscopic. It is extremely significant to suppress the substitution mole number n of the perchlorate anion within the above range in order to suppress this side reaction. In the present invention, it is also important to blend the above lithium aluminum composite hydroxide perchlorate in an amount of 0.01 to 10 parts by weight, particularly 0.5 to 2 parts by weight, based on the chlorine polymer. If the blending amount is less than the above range, the thermal stability and the amine resistance are insufficient, while if it is more than the above range, the chlorine-containing polymer tends to have a marked initial coloring tendency.

The coloring of the chlorine-containing polymer is roughly classified into warm coloring (reddish coloring) and cold coloring (bluish coloring). Carbonate gives a warm-colored initial color to the chlorine-containing polymer, but when ion exchange with perchloric acid is carried out, it shifts to a cold-colored direction, and if the initial coloration as a whole is white or close to it, it becomes a hue. Thus, there is a remarkable advantage that the hue of the compounded resin is remarkably improved. Further, since a complex hydroxide salt having a high degree of perchloric acid substitution has a slightly cold hue, it is preferable to use a warm color stabilizer such as a higher fatty acid alkaline earth metal salt in combination.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The production method and chemical structure of the lithium aluminum complex hydroxide salt which is the source of the perchlorate used in the present invention are described in Clays and Clay Minerals, Vol. 25, 384. ˜391 (1977) and Vol. 30, pages 180-184 (1982). This lithium aluminum complex hydroxide salt (hereinafter L
(AHS may be abbreviated) is said to have incorporated lithium ions into the vacancies of the aluminum hydroxide octahedron layer having a gibbsite structure and incorporated anions (carbonate anions) to supplement the charges. . That is, it is recognized that the lithium ion has the smallest ionic radius among cations, and since it is exceptionally a hexacoordinated ion as a monovalent ion, it enters the above vacancy and has the above structure.

This LAHS is called a hydrotalcite-like compound or lithium hydrotalcite because it has a layered structure and shows a structure and characteristics similar to hydrotalcite such as exhibiting ion-exchangeability with anions. However, hydrotalcite is the one in which a part of magnesium having a brucite structure is isomorphically substituted with aluminum, and thus it is recognized that the two are completely different in chemical composition and structure.

FIG. 1 shows a lithium aluminum complex hydroxide carbonate (hereinafter referred to as LAHS) used as a raw material in the present invention.
2) is an X-ray diffraction pattern of lithium aluminum composite hydroxide perchlorate (hereinafter referred to as LAHPS). The LAHPS of the present invention has a diffraction peak with a surface index [110] at a surface spacing (d) = 4.3 Å to 4.5 Å, and the surface index [002], [004], [0]
06], [008], etc. have diffraction peaks at multiples of 2, which is similar to that of LAHS. L used in the present invention
AHPS is a 5% aqueous suspension, and LAHS shows a pH of about 8 whereas it has a pH of about 4, so it has excellent amine resistance and less tendency to damage the resin.

LAHPS used in the present invention is generally a hexagonal plate-like crystal, and the particles show a definite regular particle shape,
The degree of aggregation between particles is extremely low, and the dispersibility in resin is excellent. FIG. 3 is a scanning electron micrograph showing the particle structure of an example of LAHS. The particle size is not particularly limited, but is generally 5 μm or less, and particularly in the range of 0.1 to 3 μm. The LAHS used as a raw material is not limited to this, but the oil absorption (JIS K-5101) is generally in the range of 30 to 70 ml / 100 g, and BE
The T specific surface area is in the range of 1 to 50 m ² / g, and the apparent specific gravity (iron cylinder method) is 0.2 to 0.5 g / cm ^3.
Is in the range.

The carbonate type LAHS can be obtained by reacting a water-soluble lithium salt or lithium hydroxide with a water-soluble aluminum salt in the presence of a water-soluble carbonate and an alkali. Examples of the water-soluble lithium salt include lithium chloride, lithium nitrate, lithium sulfate, lithium carbonate and the like. Examples of the water-soluble aluminum salt include aluminum chloride, aluminum nitrate, aluminum sulfate and the like. Further, sodium carbonate is generally used as the water-soluble carbonate, and sodium hydroxide is generally used as the alkali. Of course, when lithium hydroxide is used, addition of sodium hydroxide may be omitted. Good. Each of these components is preferably used so that the atomic ratio of AL / Li is about 2 and the molar ratio of CO ₃ / Li is 0.5 or more.

PH when all components are added in the reaction
May be added in an amount of 9.5 to 12, particularly 10 to 11.5, and the reaction temperature is preferably in the range of room temperature to 130 ° C. When the reaction temperature is low, the degree of crystallization is low, so it is desirable to carry out the reaction at a temperature of generally 60 ° C. or higher, particularly 80 ° C. or higher. It can also be produced by hydrothermal synthesis using an autoclave or the like, and in a reaction at a high temperature, crystallization proceeds to a high degree, and as a result, the oil absorption amount and the specific surface area tend to decrease and the apparent specific gravity tends to increase. A reaction time of about 5 to 20 hours is generally sufficient, and the reaction can also be carried out in a two-step reaction at a low temperature of 40 ° C. or lower and a high temperature of 80 ° C. or higher.

The as-produced crystals contain about 0.5 to 3 mol (m) of water, which is 300
Partial or complete dehydration can be achieved by heating and drying at a temperature of ℃ or less. The higher fatty acid is added to the reaction mixture produced by the above reaction as an orientation enhancer,
The crystal orientation of LAHS can be improved by aging treatment at the temperature of. The higher fatty acid has 6 to 30 carbon atoms,
In particular, 12 to 20 saturated or unsaturated fatty acids, especially saturated fatty acids are used, and typical examples thereof are stearic acid, palmitic acid, lauric acid, tallow fatty acid, coconut oil fatty acid, palm oil fatty acid and the like. This fatty acid is 0.5 per LAHS
It can be used in an amount of from 1 to 10% by weight, especially from 1 to 5% by weight.

Ion exchange of LAHS to LAHPS
It can be carried out dry or wet using perchloric acid,
It was found that dry type ion exchange treatment is effective for preventing the by-product of free salt. That is, while the LAHS powder is being mixed with a shear stirrer such as a super mixer, an aqueous solution of perchloric acid is dropped or sprinkled, thereby performing ion exchange. Ion exchange proceeds by mixing and stirring, but ion exchange proceeds more easily by drying this mixture. As a perchloric acid aqueous solution, the concentration is generally 50 to 7
A 0% aqueous solution is used, and the amount used is equivalent to the number n of substitutions in the previous period. The mixing and stirring may be performed at room temperature or under heating. Further, the drying may be carried out continuously in the mixer or may be carried out in a dryer separate from the mixer. A suitable drying temperature is about 90 to 120 ° C.

The obtained LAHPS can be used as a heat stabilizer as it is, but if desired, a free salt produced as a by-product can be removed by extraction treatment with an aqueous solution containing water-alcohol and a surfactant. The obtained LAHPS can be used as a heat stabilizer as it is, but for example, fatty acids such as stearic acid, palmitic acid and lauric acid, metal soaps such as calcium salts, zinc salts, magnesium salts and barium salts of fatty acids, and silane coupling. Stabilization by surface treatment with coating agents such as agents, aluminum-based coupling agents, titanium-based coupling agents, zirconium-based coupling agents, various waxes, various unmodified or modified resins (such as rosin and petroleum resins) It can be used as an agent. These coating agents can be added to LA.
It is preferably used in an amount of 5 to 10% by weight, especially 1 to 5% by weight.

Further, as the inorganic auxiliary agent, Aerosil,
Hydrophobicized fine particles of silica such as Aerosil, silicates such as calcium silicate and magnesium silicate, metal oxides such as calcia, magnesia and titania, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, and calcium carbonate It is also possible to use LAHPS as a blend or mabushi with regular particles comprising a metal carbonate, a type A or P type synthetic zeolite, and an acid-treated product thereof or a metal ion exchange product thereof.

(Resin Composition) According to the present invention, LAHP is added to 100 parts by weight of the chlorine-containing polymer to be stabilized.
S is generally 0.01 to 10 parts by weight, especially 0.5 to 2
It is preferable to use it in an amount of part by weight.

Examples of the chlorine-containing polymer include polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene,
Chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, chlorinated Vinyl-vinylidene chloride copolymer, vinyl chloride-styrene-
Maleic anhydride terpolymer, vinyl chloride-styrene-
Acrylonitrile copolymer, vinyl chloride-butadiene copolymer, chlorinated vinyl-propylene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-
Maleic acid ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, polymers such as internally plasticized polyvinyl chloride, and these chlorine-containing polymers and polyethylene, polypropylene polybutene, poly Polyolefins such as α-olefin polymers such as -3-methylbutene or ethylene-vinyl acetate copolymers, ethylene-propylene copolymers and the like, polystyrenes, acrylic resins, styrene and other monomers ( For example, maleic anhydride, butadiene,
Acrylonitrile etc.), acrylonitrile-butadiene-styrene copolymer, acrylic acid ester-butadiene-styrene copolymer, methacrylic acid ester-butadiene-styrene copolymer, and blended products.

In the present invention, it is preferable to use an alkaline earth metal salt-based stabilizer composed of an alkaline earth metal salt of a higher fatty acid or an alkaline earth metal silicate together with a magnesium salt as the alkaline earth metal salt. Calcium salt and barium salt are used alone or in combination. The higher fatty acids may be those exemplified above. Suitable examples of silicate-based stabilizers are described in Japanese Patent Publication No. 52-32899, which is the present applicant's application. These alkaline earth metal components are preferably used in an amount of 0.1 to 10 parts by weight, particularly 0.5 to 3 parts by weight, based on 100 parts by weight of the chlorine-containing polymer. A zinc stabilizer such as a higher fatty acid zinc salt or glycine zinc may also be used in combination with the alkaline earth metal stabilizer. Further, in order to further improve the hue of the blended resin, it is possible to blend other organic stabilizers or stabilizing aids, such as polyhydric alcohols, phenols, phosphite,
A stabilizer such as a phosphonite type, a phosphonic acid derivative type, or a β-diketone type can be added. Among these, organic phosphite stabilizers are particularly effective in improving the hue.

Examples of the organic phosphites include various ones, for example, triphenyl phosphite; diphenyl phosphite; didecyl phenyl phosphite; tridecyl phosphite: trioctyl phosphite; tridodecyl phosphite; Octadecyl phosphite: trinonyl phenyl phosphite; tridodecyl trithiophosphite; distearyl pentaerythritol diphosphite; 4,4'-butylidene bis (3-methyl-6-t-butylphenyl ditridecyl)
Phosphite; tris (2,4di-t-butylphenyl) phosphite; bis (2,4di-t-butylphenyl) pentaerythritol diphosphite, and others having an alkyl group having 12 to 15 carbon atoms , 4'-isopropylidene diphenyl tetraalkyl diphosphite and the like. These organic phosphites are preferably used in an amount of 0.1 to 5 parts by weight, particularly 0.3 to 2 parts by weight, based on 100 parts by weight of the chlorine-containing polymer. Further, a plasticizer may be added to the chlorine-containing polymer composition of the present invention. As such a plasticizer,
Although any known per se can be used, a suitable example thereof is as follows.

1. Phthalic acid ester: diethyl phthalate, di-n-butyl phthalate, di-i-phthalate
Butyl, dihexyl phthalate, di-i-butyl phthalate, dioctyl phthalate (DOP) [including n-octyl, 2-ethylhexyl, isooctyl (oxo)], di-i-heptyl-i-nonyl phthalate, phthalic acid Acid di-n-octyl-n-decyl, didecyl phthalate [including n-decyl and i-decyl], butylbenzyl phthalate, diphenyl phthalate, cyclohexyl phthalate, dimethylcyclohexyl phthalate, dimethoxyethyl phthalate , Diptoxyethyl phthalate, ethylphthalylethyl glycolate, butylphthalylbutyl glycolate. 2. Aliphatic dibasic acid ester: di-i-butyl adipate, octyl adipate [including 2-ethylhexyl and n-octyl], didecyl adipate [i-decyl, n
-Including decyl], di (n-octyl-n-adipate)
Decyl), dibenzyl adipate, di (n-sebacate)
Butyl), dioctyl sebacate [including 2-ethylhexyl and n-octyl], a-n-hexyl azelate and dioctyl azelate [including 2-ethylhexyl].

3. Phosphate ester: diphenyl phosphate-
2-ethylhexyl,

4. Hydroxy polycarboxylic acid ester:
Diethyl tartrate, acetyl triethyl citrate, acetyl tributyl citrate, acetyl-2-ethylhexyl citrate, monoisopropyl citrate, tributyl citrate, mono-di-tristeryl citrate.

5. Fatty acid ester: methyl acetylricinoleate, ethyl palmitate, ethyl stearate,
-N-Butyl stearate, amyl stearate, cyclohexyl stearate, butyl oleate, hydrogenated rosin methyl ester.

6. Polyhydric alcohol ester: glycerin triacetate, glycerin tripropionate, glycerin tributyrate, glycerin triheptanoate triethylene glycol dicaprylate, triethylene glycol dicaprate, pentanediol diyne butyrate.

7. Epoxy plasticizer: epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized safflower oil, epoxidized linseed oil fatty acid butyl,
Epoxy octyl stearate [including i-octyl and 2-ethylhexyl], 3- (2-xenoxy) -1,
2-epoxy propane.

8. Polyester plasticizer: poly (diethylene glycol, terbene maleic anhydride adduct) ester, poly (propylene glycol, adipic acid) ester, poly (1,3-butanediol, adipic acid) ester, poly (propylene glycol, sebacic acid) Ester, poly (1,3-butanediol, sebacic acid)
Ester Poly (propylene glycol, phthalic acid) ester,
Poly (1,3 butanediol, phthalic acid) ester,
Poly (ethylene glycol, adipic acid) ester, poly (1,6-hexanediol, adibic acid) ester, acetylated poly (butanediol, adipic acid) ester [butanediol is 1,3- and 1,4-type] .

9. Other: alkylsulfonic acids (C ₁₂ ~
C _20), phenol esters, alkyl sulfonic acids (C
₁₂ -C _20), hydrogenated polybutene, p-tert-butylphenyl salicylate, cresol esters, chlorinated paraffins.

The above-mentioned plasticizer is a chlorine-containing polymer 100.
It is preferably used in an amount of 5 to 100 parts by weight, especially 50 to 70 parts by weight.

[0034]

The present invention will be described in the following examples. The measuring method of each item in the present invention was as follows. (Measurement Method) (1) X-ray Diffraction Using a RAD-IB system manufactured by Rigaku Denki Co., Ltd., C
It was measured by u-Kα. Target Cu filter Curved crystal graphite monochromator Detector sc Voltage 40KVP current 20mA Count full scale 700c / s Smoothing point 25 Scanning speed 2 ° / min Step sampling 0.02 ° Slit DS1 ° RS 0.15mm SS1 ° Illumination angle 6 °

(2) Apparent specific gravity It was measured according to JIS K-6220. (3) Oil absorption amount It was measured according to JISK-5101-19. (4) Specific surface area Sorptpmatic Series manufactured by Carlo Erba
s 1800 was used and measured by the BET method. Particle size by SEM (5) Representative particles were selected from the photographic images obtained with a scanning electron microscope (S-570 manufactured by Hitachi), and the diameter of the particle image was measured using a scale and shown as a temporary particle diameter. . (6) Molding method The above blended composition was roll-milled at a temperature of 150 ° C. for 7 minutes to prepare a uniform mixture having a thickness of 0.5 mm, and then a temperature of 160 ° C., a pressure of 150 kg / cm ² , and a pressure of 5 minutes. It heated and produced the soft vinyl chloride sheet of thickness 1mm.

(Synthesis Method of Lithium-Aluminum Composite Hydroxide Perchlorate) 1 mol of a lithium-aluminum composite hydroxide salt (hereinafter abbreviated as LAHS), a synthetic product manufactured by Mizusawa Chemical Co., was suspended in ion-exchanged water. Then, add 70% aqueous solution of perchloric acid as HClO ₄ at room temperature to 0.0
1 mol was gradually added dropwise and stirred until generation of carbon dioxide gas by ion exchange with LAHS carbonate was stopped, and then the obtained slurry was filtered, dried and pulverized to obtain a sample (No.
1). In the same manner as described below, the ion exchanger sample No.
2 to No. 5 was prepared. Sample No. Ion exchange mole number 1 0.01 2 0.5 3 1.0 4 1.5 5 2.0

Example 1 A sample of LAHPS prepared above was blended with a polyvinyl chloride resin in the following blending ratio, and then a vinyl chloride sheet was prepared, and the thermal stability and amine resistance of the vinyl chloride sheet were examined. It was The basic composition and test method are as follows. Blending polyvinyl chloride resin 100 parts by weight of di (C ₉ ~ ₁₁ alkyl) phthalate 70 epoxidized soybean oil 3 barium stearate 0.5 zinc stearate 0.2 diphenyl tridecyl phosphite 0.4 Sample 0.5 or 1. 0

(Method for preparing test vinyl chloride sheet, thermal stability test, amine resistance test method)
The sheet was kneaded at 0 ° C. and then pressed to form a sheet having a heat of 1 mm. This sheet was measured for thermal stability in a 190 ° C. gear oven. Also, the above sheet was immersed in a 5% solution of pentamethyldiethylenetriamine for 10 minutes, and the solution was wiped off and subjected to a low temperature heat aging test in a 120 ° C gear oven to measure amine resistance. The results are shown in Table 1.
In addition, the degree of coloring of thermal stability and amine resistance was expressed in five levels. 1. Colorless 2. Pale yellow 3. Yellow 4. Reddish brown (yellowish brown) 5. Black (brown)

(Comparative Example 1) In Example 1, the sample L
AHPS was not used at all (Comparative Example 1-1), or 0.5 part by weight of LAHS (Comparative Example 1-2) was used instead of the sample LAHPS, or 1.0 part by weight of Alkamizer 5 (Kyowa Chemical Industry Co., Ltd.). A vinyl chloride sheet was prepared in the same manner as in Example 1 except that perchloric acid type hydrotalcite manufactured by Co., Ltd. (Comparative Example 1-3) was used, and the same experiment was conducted for each sheet. It shows in Table 1.

[0040]

[Table 1]

(Example 2) In order to examine the effect of the initial coloring preventing agent on the vinyl chloride sheet, except for the zinc stearate compounded in Example 1, the thermal stability and amine resistance in that case were examined. The thermal stability test and the amine resistance test were performed in the same manner as in Example 1. The results are shown in Table 2.

[0042]

[Table 2]

The compounding polyvinyl chloride resin 100 parts by weight of di (C ₉ ~ ₁₁ alkyl) phthalate 70 epoxidized soybean oil 3 barium stearate 0.5 diphenyl tridecyl phosphite 0.4 Samples 0.5 or 1.0

(Comparative Example 2) In Example 2, L of the sample
AHPS was not used at all, and 1.0 part by weight of Alkamizer 5 was used in place of LAHPS of (Comparative Example 2-1) or sample.
(Comparative Example 2-3) was used to prepare a vinyl chloride sheet in exactly the same manner as in Example 2 and the same experiment was performed. Table 2 shows the results. Furthermore, the results of experiments conducted on the vinyl chloride sheet prepared in Comparative Example 1-1 are shown in Comparative Example 2-
2 is shown in Table 2.

Example 3 In order to confirm the combined effect of the stabilizer comprising LAHPS and glycine zinc according to the present invention, a vinyl chloride sheet having the following composition was prepared and an experiment was conducted. Table 3 shows the results. Blending polyvinyl chloride resin 100 parts by weight of di (C ₉ ~ ₁₁ alkyl) phthalate 50 glycine - zinc 1.4 Zinc stearate 0.6 Samples 0.5 or 1.0

(Comparative Example 3) In Example 3, L of the sample
AHPS was not used at all (Comparative Example 3-1), or L
1.0 parts by weight of LAHS instead of AHPS (Comparative Example 3
-2) or 1.0 part by weight of Alcamizer 5 (Comparative Example 3)
A vinyl chloride sheet was prepared in the same manner as in Example 3 except that -3) was used, and the same experiment was performed. The results are shown in Table 3.
Shown in

[0047]

[Table 3]

Example 4 In order to confirm the combined effect of LAHPS according to the present invention and another stabilizer, a vinyl chloride sheet having the following composition was prepared and the same test was conducted. The results are shown in Table 4. Alanine as a blending polyvinyl resin 100 parts by weight of di (C ₉ ~ ₁₁ Aruoru) chloride phthalate 50 Zinc stearate 0.6 LAHPS (sample No.3) 1.0 Sample (Other stabilizers) 1.4 other stabilizers Zinc, zinc glutamate (Ajinomoto Planerizer ST-Z300) or Alcamizer 5 was used.

[0049]

[Table 4]

[0050]

INDUSTRIAL APPLICABILITY According to the present invention, lithium-aluminum complex hydroxide salt in which a part of the carbonate group is replaced with perchloric acid is blended with a chlorine-containing polymer to obtain amine resistance and thermal stability. It was possible to improve both sex. Further, this polymer composition has a small initial coloring tendency and is excellent in appearance characteristics, and is particularly useful for applications of soft blending.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction spectrum of a lithium aluminum composite hydroxide carbonate (LAHS) used as a raw material in the present invention.

FIG. 2 is an X-ray diffraction spectrum of the lithium aluminum composite hydroxide perchlorate (LAHPS) obtained in the present invention.

FIG. 3 is a scanning electron microscope photograph at a magnification of 30,000 showing a particle structure of lithium aluminum composite hydroxide carbonate (LAHS) which is a raw material of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area C08L 101/04 KAF

Claims (3)

[Claims] 1. The following formula Li ₂ Al ₄ (ClO ₄ ) _n (CO ₃ ) _{1-n / 2} (OH) ₁₂ · mH ₂ O (1) In the formula, n is a number from 0.05 to 2. Yes, m is a number of 3 or less. Polymer containing lithium aluminum complex hydroxide perchlorate having a composition represented by
A stabilized chlorine-containing polymer composition comprising 0.01 to 10 parts by weight per 100 parts by weight. 2. In the formula (1), n is 0.5 to 1.5.
2. The composition of claim 1, wherein 3. A group consisting of 100 parts by weight of a chlorine-containing polymer, 0.01 to 10 parts by weight of the lithium aluminum complex hydroxide perchlorate, zinc of a higher fatty acid alkaline earth metal and alkaline earth metal silicate. The composition according to claim 1, which comprises 0.1 to 10 parts by weight of an alkaline earth metal component selected from the above, 0.1 to 5 parts by weight of organic phosphites, and 5 to 100 parts by weight of a plasticizer.