JPH01163245A - Halogen-containing thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition outstanding in thermal stability, capable of preventing initial discoloration, discoloration with time, blackening, etc., freefrom development of adhesion of the kneaded product there from on rolls, by incorporating a halogen-contg. thermoplastic resin with a metallic soap, a specific ethylene-vinyl acetate copolymer, etc. CONSTITUTION:The objective composition can be obtained by incorporating (A) 100 pts.wt of a halogen-contg. thermoplastic resin such as polyvinyl chloride resin with (B) 0.1-5 pts.wt. of a metallic soap such as zinc stearate, (C) 0.1-5 pts.wt. of a saponified product prepared by saponification of a vinyl acetate copolymer copolymerized with 20-75mol% of ethylene to effect >=50mol% of saponification degree, (D) 0.05-5 pts.wt. of a compound selected from beta- diketone compounds, organic phosphorous esters and aminocarboxylic acid compounds and (E) 0-5 pts.wt. of either phenol derivative or epoxy compound.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a halogen-containing thermoplastic resin composition that has improved thermal stability, that is, initial discoloration prevention properties, aging discoloration prevention properties, and blackening prevention properties. .

Prior Art Halogen-containing thermoplastic resins, typified by polyvinyl chloride resins, are heated during melt molding to produce a polyene structure due to dehydrochloric acid removal, causing yellowing.

Therefore, in order to improve thermal stability, it is widely practiced to add metal soap as a stabilizer to the resin. In this case, if only metal soap is used as a stabilizer, there is a tendency for so-called metal burns to occur and the resin to turn black over time during long-term melt molding, so polyol (
Usually, stabilizing aids such as pentaerythritol, etc.), organic phosphites (triphenyl phosphite, etc.), and epoxy compounds (bisphenol A type epoxy resin, etc.) are used in combination.

Although it is not intended to improve the thermal stability of a halogen-containing thermoplastic resin, there is Japanese Patent Application Laid-Open No. 60-238345 which shares the same resin components as the present invention.

That is, the publication describes (1) thermoplastic resins (including polyvinyl chloride resins), (2) ethylene-vinyl acetate copolymerized products, and @at least one selected from Groups 1, 2, and 2 of the Periodic Table. salts or oxides containing the elements;
A resin composition consisting of the following is disclosed, and this composition is described as having significantly improved compatibility.

In addition, as a resin component that is common to the present invention, JP-A-52-69955 discloses that a mixture of a vinyl chloride polymer and 10 to 30% by weight of an ethylene/vinyl alcohol copolymer is made of a woody material. A vinyl chloride polymer barrier packaging composition is shown.

Problems to be Solved by the Invention However, in the method of using a metal soap as a stabilizer and a stabilizing aid in combination, when the stabilizing aid is a polyol, the compatibility and dispersibility are insufficient, resulting in roll kneading. Sometimes plate-out (a phenomenon in which a contaminant sticks to the roll) cannot be avoided, and if the stabilizing aid is an organic phosphite, the stabilizing aid will hydrolyze due to moisture absorption, reducing its effectiveness. However, when the stabilizing agent is an epoxy compound, there is a limit in that yellowing and plate-out cannot be sufficiently prevented.

Although the composition described in JP-A-60-238345 is said to have an improvement effect in terms of compatibility, there is still room for improvement in terms of thermal stability.

Although the composition described in JP-A-52-69955 can reduce oxygen permeation while suppressing water vapor permeation, it has poor melt moldability and cannot prevent discoloration, so there is little hope for its practical application. Can not. In addition, this composition contains a large amount of ethylene/vinyl alcohol copolymer, so
The properties of a vinyl chloride polymer alone will change, and its uses will be limited.

The present invention has been made for the purpose of providing a halogen-containing thermoplastic resin composition that has significantly improved thermal stability.

Means for Solving the Problems The halogen-containing thermoplastic resin composition of the present invention contains metal soap (
B) A saponified ethylene-vinyl acetate copolymer (C) having a copolymerization composition of 0.1 to 5 parts by weight, an ethylene content of 20 to 75 mol%, and a degree of saponification of the vinyl acetate portion of 50 mol% or more (C) 0.1 ~5 parts by weight, at least one compound (D) selected from the group consisting of β-diketone compounds, organic phosphites, and aminocarboxylic acid compounds (D) 0.
05 to 5 parts by weight, and 0 to 5 parts by weight of at least one compound (E) selected from the group consisting of phenol derivatives and epoxy compounds.

Among the components listed in -H to be blended into the halogen-containing thermoplastic resin (A), (B), (C) and (D) are essential components, and (E) is an optional component.

The present invention will be explained in detail below.

A Halogen B A Halogen-containing thermoplastic resin (A) includes polyvinyl chloride resin, polyvinylidene chloride resin, chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene-vinyl acetate copolymer, chlorosulfonated polyethylene. etc. Particularly important are polyvinyl chloride resins, that is, homopolymers of vinyl chloride or copolymers of vinyl chloride and other comonomers.

Gold 1B - As the metal soap (B), Group Ⅰ metal salts such as higher fatty acids, resins, and naphthenic acids are used. Examples of Group Ⅰ metals include magnesium, calcium, strontium, barium, zinc, and cadmium. In particular, zinc, magnesium, calcium and barium salts of higher fatty acids such as stearic acid, lauric acid and ricinoleic acid.

Cadmium salts are important, and zinc salts are especially effective, so it is preferable to use at least a portion of zinc salts of higher fatty acids.Although it is possible to use only one type of the above metal soaps, two or more types can be used in combination. It has a greater stabilizing effect.

Ethylene-vinyl-kenhi C) As the saponified ethylene-vinyl acetate copolymer (C), one having a copolymer composition with an ethylene content of 20 to 75 mol% and a degree of saponification of the vinyl acetate portion of 50 mol% or more is used. It will be done.

If the copolymerization composition deviates from the above range, the effect of improving the thermal stability of the halogen-containing thermoplastic resin (A) will be insufficient. Note that as long as the copolymer composition has the above copolymerization composition, it may also contain a small amount of other comonomers.

Generally, a saponified ethylene-vinyl acetate copolymer is produced by saponifying an ethylene-vinyl acetate copolymer with an alkali catalyst. However, the industrial water and reagents used contain metal salts as impurities, and the saponification catalyst (alkali metal hydroxide) remains as an acetate of the alkali metal even after the reaction. Therefore, these impurities and alkali metal acetate are precipitated from the saponification liquid and are contained in the resin filtered out. Ethylene content of the resin,
The ash content in the saponified ethylene-vinyl acetate copolymer obtained above is usually about 500%, although it cannot be determined in part depending on various factors such as the degree of saponification or saponification conditions.
The alkali metal content is, for example, about 4,000 to 40,000 ppm.

Here, the ash content refers to dry saponified ethylene-vinyl acetate copolymer taken in a platinum evaporating dish, carbonized using an electric heater and gas burner, placed in an electric furnace at 400°C, heated to 700°C, and then heated to 700°C. After complete iodization at 700° C. for 3 hours, it is taken out from the electric furnace, left to cool for 5 minutes, and left in a desiccator for 25 minutes, and the ash content is determined.

Alkali metals are determined by atomic absorption spectrometry using a solution obtained by incinerating a saponified ethylene-vinyl acetate copolymer and dissolving the ash in an acidic aqueous solution of hydrochloric acid under heating in the same manner as in the case of ash content measurement.

In the present invention, it is also possible to use a saponified ethylene-vinyl acetate copolymer (C) having the above-mentioned copolymerization composition obtained by a normal method, but it is possible to use a saponified ethylene-vinyl acetate copolymer (C) having the above-mentioned copolymer composition. Below, preferably 50
ppm or less, more preferably 20 ppm or less,
In addition, it is particularly preferable to use a saponified ethylene-vinyl acetate copolymer having a low ash content and a low alkali metal content and having an alkali metal content of 200 ppm or less, preferably 35 ppm or less, and more preferably 5 ppm or less. The lower the ash content and alkali metal content, the more pronounced the thermal stability effect, especially the initial discoloration prevention effect. It is preferable for the ash content and alkali metal content to be as low as possible within the above ranges, but since there is a limit to refining from an industrial standpoint, the lower limits are about 1 ppm for the ash content and 0.5 ppm for the alkali metal content.
It is about ppm.

In order to obtain the saponified ethylene-vinyl acetate copolymer (C) having a low ash content and low alkali metal content, a saponified ethylene-vinyl acetate copolymer produced by saponifying an ethylene-vinyl acetate copolymer is used. After thoroughly washing the powder, particles, and pellets with an aqueous solution of an acid, especially a weak acid, to remove ash and salts that cause alkali metals, it is preferable to wash the powder, particles, and pellets with water (
A method is adopted in which acid adhering to the resin is removed by washing with deionized water (the same applies hereafter) and then drying is performed.

Examples of weak acids include acetic acid, propionic acid, glycolic acid, lactic acid, adipic acid, azelaic acid, geltaric acid,
Succinic acid, benzoic acid, isophthalic acid, terephthalic acid, etc. are used. Typically, the pKa at 25°C is 3.
5 or more are useful.

In addition, after performing the treatment with the above-mentioned weak acid, before or after washing with water, dilute strong acids such as oxalic acid, maleic acid, and other organic acids with a pKa of 2.5 or less at 25°C, phosphoric acid, etc.
It is desirable to further treat with an aqueous solution such as sulfuric acid, nitric acid, hydrochloric acid, etc., which makes the alkali metal removal more efficient.

As the compound (D), at least one compound selected from the group consisting of β-diketone compounds, organic phosphate esters, and aminocarboxylic acid compounds is used.

Examples of β-diketone compounds include dibenzoylmethane, benzoylacetone, tribenzoylmethane, diacetylacetobenzene, stearoylacetophenone, valmitoylacetophenone, lauroylacetophenone, p
-methoxy-stearoyl acetophenone, stearoyl benzoylmethane, acetoacetate, acetylacetone, 1,1-diacetylacetone, triacetylmethane, stearoyl acetone, valmitoylacetone,
Lauroylacetone, stearoyl octanone, heptane-2,4-dione, decane-2,4-dione, nonane-2,4-dione-ethyl carbhonate, 8-methylnona-7-nin-2°4-dione, 1- Benzoyloctan-2-one, 2-methyldecane-2-dyne-6,8-dione, methylene-2,2'-bis(cyclohexane-1
,3-dione), 1,4-diphenyl-butane-1,3
-dione, ■-phenyl-2-allyl-1,3-butanedione, benzoylacetaldehyde, 2-methyl-2
Examples include -acetylacetaldehyde, dehydroacetic acid, and dehydroacetate.

Examples of organic phosphates include triarylphosphites such as triphenylphosphite, tris(p-nonylphenylphosphite), monoalkyldiphenylphosphites such as diphenylisooctylphosphite and diphenylisodecylphosphite, and phenyl Examples include alkylaryl phosphites such as dianoCylmonophenyl phosphites such as diisooctyl phosphite and phenyldiisodecyl phosphite, and trialkyl phosphites such as triisioctyl phosphite and tristearyl phosphite.

Examples of aminocarboxylic acid compounds include aminocarboxylic acids such as glycine, alanine, lysine, tryptophan, acetylglutamic acid, acetylphenylalanine, acetylmethionine, pyrrolidonecarboxylic acid, β-aminocrotonic acid, α-aminoacrylic acid, and α-aminoadipic acid. or esterified products thereof. The alcohol components that make up the ester include methanol, ethanol, propatool, impropatool,
Butanol, α-ethylhexanol, octatool,
Inoctatool, monohydric alcohols such as lauryl alcohol and stearyl alcohol, ethylene glycol,
Propylene glycol, 1,3-butanediol, 1.
Examples include polyhydric alcohols such as 4-butanediol, glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, and mannitol.

As the compound (E), at least one compound selected from the group consisting of phenol derivatives and epoxy compounds is used.

Examples of phenol derivatives include 2,5-di-butylhydroquinone, 2,6-di-butyl-p-cresol, 4.4°-thiobis-(6-t-butylphenol), 2.2'-methylene-bis (4-methyl-6-t-
butylphenol), tetrakis-[methylene-3-(
3',5''-di-t-butyl-4'-hydroxyphenyl)propionate comethane, octadecyl-3-(3
', 5°-di-t-butyl-4'-hydroxyphenyl)propionate, 4,4'-thiobis-(6-t-butylphenol), N,N''-hexamethylene-bis(
3,5-di-t-butyl-4-hydroxy-hydrocinnamide) and the like.

Epoxy compounds include epoxidized animal and vegetable oils such as epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, and epoxidized tallow oil, epoxidized methyl stearate,
Epoxidized fatty acid esters such as epoxidized butyl stearate, epoxidized alicyclic compounds such as epoxidized butyl tetrahydrophthalate, epoxidized octyl tetrahydrophthalate, glycidyl ethers such as bisphenol A diglycidyl ether, glycidyl methacrylate and its polymers; Examples include epoxy polymer compounds such as glycidyl ester compounds, epoxidized polybutadiene, and epoxidized acrylonitrile-butadiene rubber.

The ratio of each component to 100 parts by weight of the halogen-containing thermoplastic resin (A) is: Metal soap (B) 0.1 to 5 parts by weight Saponified ethylene-vinyl acetate copolymer (C) 0.1 to 5 parts by weight 5 parts by weight Compound (D) 0.05 to 5 parts by weight Compound (E) 0 to 5 parts by weight. A particularly preferable range is metal soap (B)
0.5 to 4 parts by weight Saponified ethylene-vinyl acetate copolymer (C) 0.2 to 4 parts by weight Compound (D) 0.1 to 3 parts by weight Compound (E) 0.01 to 4 parts by weight .

If any of the (B), (C), (D) components, or in some cases the (E) component is missing, or the ratio of these components to the (A) component is out of the above tolerance range, the desired heat The effect of improving stability cannot be achieved sufficiently.

Although the effects of the present invention can be sufficiently obtained by blending only components (B), (C), and (D), the heat stabilizing effect is further improved by using component (E) in combination. is practically preferable.

Characteristics 1 The halogen-containing thermoplastic resin composition of the present invention may further contain plasticizers, dyes and pigments, fillers, lubricants, antistatic agents, surfactants, kerating agents, reinforcing materials, foaming agents, anti-foaming agents, etc. Known additives for halogen-containing thermoplastic resins such as impact improvers (ethylene-vinyl acetate copolymer, acrylic copolymer, ABS resin, MBS resin, etc.) can be blended.

In addition, other antioxidants, ultraviolet absorbers, stabilizing aids (polyols, general 2 MxAly(OH) zx+37-z
z(E)z* aH2,0[M: Mg, Ca, Z
n, E: (103, HPO3, X.

y and 2 are positive numbers, a is O or a positive number, etc.) may be used in combination, and other thermoplastic resins may also be blended as long as they do not impair the spirit of the present invention. You can also.

The combination of plasticizers is particularly useful, and phthalate esters,
Plasticizers such as aliphatic dibasic acid esters, trimellitic acid esters, phosphoric acid esters, fatty acid esters, epoxy plasticizers, polyester plasticizers, and chlorinated paraffin are harmful to halogen-containing thermoplastic resin (A). Any amount can be added.

Examples of melt molding methods include calendar molding method, extrusion molding method,
Injection molding method, blow molding method, etc. can be adopted.

Effects and Effects of the Invention In the present invention, by blending metal soap (B), saponified ethylene-vinyl acetate copolymer (C), compound (D), and compound (E) in specific proportions, halogen-containing heat The thermal stability (initial discoloration prevention property, aging discoloration prevention property, and blackening prevention property) of the plastic resin (A) can be significantly improved. In this case, the metal stone* (B) plays the role of a stabilizer,
The saponified ethylene-vinyl acetate copolymer (C), compound (D) and compound (E) are considered to play the role of stabilizing aids.

With this composition, plate-out is not observed even during calender molding, and even in the case of extrusion molding, long-run molding is possible, and discoloration of the resulting molded product is effectively suppressed.

Therefore, the present invention greatly contributes to the industry of molding halogen-containing thermoplastic resins such as polyvinyl chloride resins.

Example Next, the composition of the present invention will be further explained with reference to Examples.

In the following, "parts" and "%" are expressed on a weight basis unless otherwise specified. All water used was deionized water.

As a saponified ethylene-vinyl acetate copolymer (C),
I prepared the following:

(C-O) 1000 parts of a 40% methanol solution of an ethylene-vinyl acetate copolymer with an ethylene content of 44 mol% was charged into a pressure-resistant reactor and heated to 110°C while stirring [7]. Next, 40 parts of a 6% methanol solution of sodium hydroxide and 2,500 parts of methanol were continuously charged, and a saponification reaction was carried out for 2.5 hours while distilling by-product methyl acetate and excess methanol from the system. A saponified ethylene-vinyl acetate copolymer with a degree of saponification of the vinyl portion of 99.5 mol% was obtained.

While adding 450 parts of 30% water-containing methanol to the saponified liquid, excess methanol was distilled off, resulting in a resin concentration of 39%.
A water/methanol (composition ratio 3/7) solution was prepared.

The water/methanol mixture of the saponified ethylene-vinyl acetate copolymer at a liquid temperature of 50"C was passed through a nozzle with a hole diameter of 4 mm at a rate of 1-51/hr to water/methanol (maintained at 5C). Mixing ratio 9/1) Coagulation liquid tank (width 100
It was extruded into a strand with a length of 4000 mm and a depth of 100 mm. After coagulation, the strand is passed through a take-up roller (linear speed 2 m/win) attached to the end of the coagulation tank and cut with a cutter to form a white, porous material with a diameter of 4 mm and a length of 4 mm. Got a beret.

The ash content of this saponified ethylene-vinyl acetate copolymer pellet is 7,400 ppm, and the sodium metal content is 48
00 ppm.

This saponified ethylene-vinyl acetate copolymer (C-O
).

(C-1) Next, a washing operation (weak acid washing) in which 100 parts of the above pellets (C-0) was immersed in 300 parts of a 0.3% acetic acid aqueous solution and stirred at 30°C for 1 hour was repeated twice. Then, after filtering the slurry, the obtained pellets were poured with 300% water again.
After repeating the washing operation (washing with water) three times, the slurry was stirred at 30° C. for 1 hour, and then dried.

The ash content of the saponified ethylene-vinyl acetate copolymer pellet after the above washing operation is 6 ppm, and the sodium metal content is 2.
．． It was 7 ppm.

This saponified ethylene-vinyl acetate copolymer (C-1
).

(C-2) Also, prior to the water washing in (C-1) above, a washing operation (strong acid Washing) was performed once, and then the same water washing operation as in the case of producing (C-1) was repeated three times, followed by drying.

The resulting saponified ethylene-vinyl acetate copolymer pellets had an ash content of 1 Oppm and a sodium metal content of 1.
It was 4 ppm.

This saponified ethylene-vinyl acetate copolymer (C-2
).

(C-3) The above pellets (C-0) were washed according to the manufacturing method of (C-1), but by reducing the number of washings at that time,
Ash content 4 i ppm, sodium metal content 26 ppm
Saponified ethylene-vinyl acetate copolymer pellets of m were obtained. This is referred to as (C-3).

(C-4) L pellets (c-o) were washed according to the production method of (C-1), but by lowering the acetic acid aqueous solution concentration in weak acid washing, the ash content was 240 pp, sodium, lium metal. Saponified ethylene-vinyl acetate copolymer pellets containing 170 ppm of i were obtained. This is referred to as (C-4).

(C-5) Ethylene-vinyl acetate copolymer particles obtained by suspension polymerization (ethylene content 71 mol%, water content 11.0%) 112
4 parts were added to a mixed solution of 1950 parts of methanol, 925 parts of water, 182 parts of sodium hydroxide, and 38 parts of acetone, and the mixture was stirred at 30°C for 3 hours and then at 35°C for 3 hours before being saponified to obtain a saponified slurry. was filtered using a centrifuge.

100 parts of the obtained saponified particles were added to 300 parts of a 1% acetic acid aqueous solution.
The washing operation (weak acid washing) of mixing the slurry with 100% of the sample to form a slurry and stirring at 30°C for 1 hour was repeated twice.

Then, after filtering the slurry, the obtained particles were reduced to 0.5%.
A cleaning operation (strong acid cleaning) of immersing the sample in 300 parts of an aqueous phosphoric acid solution and stirring at 30° C. for 1 hour was performed once.

Subsequently, after filtering the slurry, the obtained particles were further mixed with 300 parts of water to form a slurry, and the washing operation (washing with water) of stirring at 30°C for 1 hour was repeated three times, and then vacuum-dried at room temperature. .

The degree of saponification of the obtained saponified ethylene-vinyl acetate copolymer particles was 61.2 mol%, the ash content was 15 ppm, and the sodium metal content was 4.0 ppm.

This saponified ethylene-vinyl acetate copolymer (C-5
).

In addition, the ash content and sodium metal were determined in accordance with the following.

<Ash content> Approximately 80 g of the dried sample was accurately weighed, and approximately 10 g of it was placed in a platinum evaporation dish with constant weight, and carbonized with an electric heater. After carbonization, approximately Log samples were added and the same operation was repeated. Finally, I heated it with a gas burner and baked it until there was no smoke.

The platinum evaporation dish was placed in an electric furnace at about 400°C, most of it covered with a magnetic crucible lid, and the temperature was gradually raised to 700°C. After being held at 700°C for 3 hours to completely incinerate, it was taken out from the electric furnace, allowed to cool for 5 minutes, and then left in a desiccator for 25 minutes, and the ash content was accurately weighed.

<Sodium metal> Approximately Log of the dried sample was accurately weighed, placed in a platinum crucible, and incinerated in the same manner as above. 2m of special grade hydrochloric acid in a platinum crucible
1 and pure water were added and heated with an electric heater to dissolve.

The above solution was poured into a 501 volumetric flask with pure water, and pure water was added roughly up to the marked line to prepare a sample for atomic absorption spectrometry.

Atomic absorbance was measured using a separately prepared standard solution (sodium metal 1 ppm, hydrochloric acid 0.5N) as a control solution.
The amount of sodium metal was determined from the ratio of absorbance. The measurement conditions are as follows.

Apparatus: Hitachi Model 180-30 Atomic Absorption/Flame Spectrophotometer Wavelength: 589.0 nm Flame: Acetylene-Air Ratio "LX" The following compound (D) was prepared.

(D-1): Dehydroacetic acid (D-2) Nistearoylbenzoylmethane (D-3)
Nidibenzoylmethane (D-4) Nidiphenylisodecyl phosphite (
D-5) Nidiphenyl octyl phosphite (D-6): Triphenyl phosphite (D-7
): l, 4-butanediol bis(β-aminocrotonate) (D-8): stearyl β-aminocrotonate (
D-9) Niacetylglutamic acid 1 Tachimiko compound (E) was prepared as follows.

(E-1): Tetrakis[methylene-3-(3°.

5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane (Irganox 1010 from Ciba Geigy) (E
-2): N,N'-hexamethylene-bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide) (Irganox 109B from Ciba Geigy) (E
-3): Octadecyl-3-(3',5'-di-t-butyl-4°-hydroxyphenyl)propionate (Irganox 107ft from Ciba Geigy) (
E-4): Bisphenol A diglycidyl ether (E-5): Epoxidized soybean oil (E-6): Epoxidized linseed oil Examples 1 to 6, Comparative Examples 1 to 12 Polyvinyl chloride (A ) 100 parts dioctyl phthalate (plasticizer) 20 parts calcium stearate (B) 1 part zinc stearate (B)
) 1 part saponified ethylene-vinyl acetate copolymer (C) described below
Compound (D) described below Compound (E) described later After premixing the following, roll kneading was performed at 170°C for 5 minutes using a 6"φ x 12" roll to obtain a sheet with a thickness of 0.5 mm. Ta.

A test piece of 50 x 60 mm was cut out from the obtained sheet.
It was placed in a gear oven at 180°C and left to examine its thermal stability.

The results are shown in Table 1. The thermal stability was evaluated on the following 9 scales.

l: Colorless 2: Slight pink or slightly yellow 3: Slight orange
4: Light pink 5: Light orange 6: Yellow-orange 7: Orange
8: Black spot 9: Black Example 1 (C) component: (C-1) 0.5 part (D) component:
(D-1) 0.3 parts Example 2 (C) component: (C-1) 0.5 parts (D) component:
(D-4) 0.3 parts Example 3 (C) component: (C-1) 0.5 parts (D) component:
(D-7) 0.3 parts Example 4 (C) component: (C-1) 0.5 parts CD) component:
(D-1) 0.3 parts (E) component: (E-1
) 0.1 part Example 5 (C) component: (C-1) 0.5 part (D) component:
(D-4) 0.3 parts (E) component: (E-2
) 0.1 part Example 6 (C) component: (C-1) 0.5 part (D) component:
(D-7) 0.3 parts (E) component: (E-3
) 0.1 part Comparative Example 1 Component (C): Not blended (D) Component: Not blended (E) Component: Not blended Comparative Example 2 Component (C): (C-0) 0.5 part ( D) Ingredients:
Not blended (E) component: Not blended Comparative example 3 (C) component + (C-1) O', 5 parts (D) component: Not blended (E) component: Not blended Comparative example 4 (C ) Component: Not blended (D) component: (D-1) 0.3 parts (E) component:
Comparative Example 5 (Not blended) Component (C): Not blended (D) component: (D-4) 0.3 parts (E) component:
Comparative Example 6 (Not blended) Component (C): Not blended (D) component: (D-7) 0.3 parts (E) component:
Comparative Example 7 (Not blended) Component (C): Not blended (D) component: (D-1) 0.3 parts (E) component:
(E-1) 0.1 part Comparative Example 8 (C) component: Not blended (D) component: (D-4) 0.3 part (E) component:
(E-2) 0.1 part Comparative Example 9 (C) component: Not blended (D) component: (D-7) 0.3 part (E) component:
(E-3) 0.1 part Comparative Example 10 (C) component: (C-1) 0.5 part (D) component:
Not blended (E) component: (E-1) 0.1 part Comparative Example 11 (C) component: (C-1) 0.5 part (D) component: Not blended (E) component: (E- 2) 0.1 part Comparative Example 12 (C) component: (C-1) 0.5 part (D) component:
Not blended (E) component: (E-3) 0.1 part Examples 7 to 1
2 Sheets were obtained in the same manner as in Examples 1 to 6, except that the composition was changed as follows, and the thermal stability was examined.

Polyvinyl chloride (A) with a degree of polymerization of 800 100 parts Dioctyl phthalate (plasticizer) 20 parts Barium stearate (B) 1 part Zinc laurate (B)
1 part Saponified ethylene-vinyl acetate copolymer (C) described below
Compound (D) described below Compound (E) described later
It is also shown in the table. Note that the thermal stability was evaluated on a 9-level scale in the same manner as above.

Example 7 Component (C): (C-2) 1.0 part Component (D):
(D-2) 0.4 part (E) component: (E-1
) 0.2 part Example 8 (C) component: (C-3) 1.0 part CD) component:
(D-5) 0.4 part (E) component: (E-1
) 0.2 parts Example 9 Component (C): (C-4) 1.0 part (D) component:
(D-8) 0.4 part (E) component: (E-1
) 0.2 parts Example 10 (C) component: (C-2) 1.5 parts (D) component:
(D-3) 0.5 part (E) component: (E-4
) 0.5 parts Example 11 (C) component: (C-3) 1.5 parts (D) component:
(D-8) 0.5 part (E) component: (E-5)
3.0 parts Example 12 Component (C): (C-5) 2.5 parts Component (D):
(D-9) 0.5 part (E) component: (E-6
) 3.0 parts Example 13 Vinylidene chloride-methyl acrylate copolymer (methyl acrylate content 7 mol %) 100 parts dioctyl phthalate (plasticizer) 20 parts calcium stearate (B) 1 part zinc stearate (B)
2 parts saponified ethylene-vinyl acetate copolymer (C-1) 1 part (D-7) 0
．． A composition consisting of 3 parts (E-1) and 1 part was extrusion molded, resulting in a thickness of 0.5 mm.
A thermal stability test was conducted on the sheet at a gear oven temperature of 170°C.

In addition, in the above, the extrusion molding conditions were as follows.

Extruder: 40+s layer φ Screw: L/D 23, compression ratio 3.2 Cylinder maximum temperature: 170°C Head temperature: 170°C, die temperature = 170°C The results are also shown in Table 1.

Comparative Examples 13 to 15 Example 13 was changed as follows. Results first
It is also shown in the table.

Comparative Example 13 Component (C): Not blended Component (D): (D-7) 0.3 parts Component (E):
(E-1) 0.1 part Comparative Example 14 (C) component: (C-1) 1.0 part CD) component:
Not blended (E) component: (E-1) 0.1 part Comparative Example 15 (C) component: (C-1) 1.0 part (D) component:
(D-7) 0.3 parts Component (E): Not blended Example 14 Chlorinated polyethylene (chlorine content 40%) 100 parts Dioctyl phthalate (plasticizer) 20 parts Triazine vulcanizing agent 1 part Mercaptobenzothiazole system Vulcanization accelerator 2 parts Calcium stearate (B) 1 part Zinc stearate (B) 2 parts Saponified ethylene-vinyl acetate copolymer (C-2)
Part 1 CD-1)
0.3 parts (E-5)
The composition consisting of 3 parts was molded (roll kneading: 14,000.5 minutes, vulcanization: 160° C., 20 minutes) to obtain a sheet with a thickness of 1 mm.

The sheet was subjected to a thermal stability test at a gear oven temperature of 170°C.

The results are also shown in Table 1.

Comparative Examples 16 to 18 Example 14 was changed as follows. Results first
It is also shown in the table.

Comparative Example 16 Component (C): Not blended Component (D): (D-1) 0.3 parts Component (E):
(E-5) 3.0 parts Comparative Example 17 (C) component: (C-2) 1.0 parts (D) component:
Not blended (E) component: (E-5) 3.0 parts Comparative Example 18 (C) component: (C-2) 1.0 parts (D) component,
(D-1) 0.3 parts (E) Component: Not blended Procedural amendment (voluntary) June 1, 1988 Patent application No. 323328, filed in 1988 2, Title of invention Halogen-containing thermoplastic resin composition 3. Relationship with the case of the person making the amendment Patent Applicant Address 9-6 Nozaki-cho, Kita-ku, Osaka Name (410) Nippon Gosei Kagaku Kogyo Co., Ltd. Representative No. 1) Katsuya 4, Agent 533-6, Contents of the amendment (1) On page 38 of the specification of the present application, the number "7" in the 100th minute section of the patent application of Example 4 is corrected to ['9J].

(2) Delete "6" from the elapsed time of 120 minutes in Example 13, Comparative Examples 13-15, Example 14, and Comparative Examples 16-18 on page 39.

that's all

Claims (1)

[Claims] 1. Metal soap (B) 0.1 to 5 parts by weight, ethylene content 2 to 100 parts by weight of halogen-containing thermoplastic resin (A)
0 to 75 mol%, degree of saponification of vinyl acetate part 50 mol%
At least 0.1 to 5 parts by weight of a saponified ethylene-vinyl acetate copolymer (C) having the above copolymerization composition, a β-diketone compound, an organic phosphite, and an aminocarboxylic acid compound. One type of compound (D
) 0.05 to 5 parts by weight, and at least one selected from the group consisting of phenol derivatives and epoxy compounds.
A halogen-containing thermoplastic resin composition containing 0 to 5 parts by weight of a seed compound (E). 2. The composition according to claim 1, wherein the halogen-containing thermoplastic resin (A) is a polyvinyl chloride resin. 3. The composition according to claim 1, wherein at least a part of the metal soap (B) is a zinc-based metal soap. 4. A saponified ethylene-vinyl acetate copolymer (C) having a copolymerization composition with an ethylene content of 20 to 75 mol% and a degree of saponification of the vinyl acetate portion of 50 mol% or more has an ash content of 3.
The composition according to claim 1, which is a saponified ethylene-vinyl acetate copolymer having a low ash content and a low alkali metal content of 00 ppm or less and an alkali metal content of 200 ppm or less. 5. Claim 4, wherein the saponified ethylene-vinyl acetate copolymer with low ash and low alkali metal has an ash content of 50 ppm or less and an alkali metal content of 35 ppm or less.
Compositions as described in Section. 6. The composition according to claim 4, wherein the saponified ethylene-vinyl acetate copolymer with low ash and low alkali metal has an ash content of 20 ppm or less and an alkali metal content of 5 ppm or less.