JPH01299856A - Stabilized chlorinated resin composition - Google Patents

Abstract

PURPOSE:To obtain a stabilized resin composition excellent in heat stability at high temperature and resistance to deterioration due to prolonged heat buildup at relatively low temperature, by adding an organometal salt compound and a specified normally liquid complex compound to a chlorinated resin. CONSTITUTION:The title composition is obtained by adding an organometal salt compound (A) of Li, Na, K, Mg, Ca, Ba, Zn, Sn, Sb or Ce (e.g., a salt of a carboxylic acid with said metal) and a normally liquid complex compound (B) of a polyalcohol or/and its derivative (e.g., ethylene glycol) with a metal salt formed by treating an aluminum hydroxide/magnesium hydroxide coprecipitation compound [e.g., desirably, a compound of the formula (wherein when n is 1, m is 1.8-3.6, and x is positive number)] are added to a chlorinated resin (e.g., PVC). By the addition of both of components A and B, the resin which is otherwise thermally unstable is converted into a stabilized one having sufficient heat stability at high temperature and has excellent resistance to deterioration due to prolonged heat buildup at relatively low temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a stabilized chlorine-containing resin composition, and more specifically, the present invention relates to a stabilized chlorine-containing resin composition, and more particularly, the chlorine-containing resin contains at least one selected from organic gold scrap salt compounds. In addition to the above, polyhydric alcohol Maku is a metal salt prepared by treating a derivative thereof, a coprecipitable compound with a specific composition ratio of aluminum hydroxide gel and magnesium hydroxide with perchloric acid (hereinafter referred to as "perchloric acid-treated coprecipitable compound"). It has thermal stability at high temperatures and excellent anti-coloring effect against long-term low-temperature heat storage, which is obtained by adding at least one complex compound that is liquid at room temperature. The present invention relates to a stabilized chlorine-containing resin composition characterized by:

[Problems to be solved by conventional technology and inventions] Chlorine-containing resins are inherently thermally unstable resins, and may be susceptible to heating during molding or rising surface temperatures of molded products due to sunlight during use. Secondly, decomposition reactions due to dehydrochlorination are likely to occur mainly within the molecular chain, resulting in deterioration of mechanical properties and color tone of molded products.

In order to prevent these drawbacks of chlorine-containing resins, stabilizers such as various organic acid metal salts, organic tin compounds, epoxy compounds, and organic phosphite esters are added to the chlorine-containing resins singly or in combination. It is necessary to suppress thermal deterioration during molding and use of molded products.

The chlorine-containing resin compositions stabilized by the addition of various conventionally known stabilizers have excellent performance, and by adding plasticizers, etc., molded products that can fully meet the wide variety of quality requirements in the market can be produced. It is an extremely useful material. In recent years, molded products made from such chlorine-containing resin compositions have come to be frequently used for interior parts of vehicles such as automobiles, and the range of use has been expanded for the purpose of reducing the weight of vehicles.

In order to further improve the impact resilience, texture, etc. of molded products for vehicle interior parts made from such chlorine-containing resin compositions, a method is often adopted in which a polyurethane film is bonded to the back surface or injected into the interior. There is. In addition, in recent years, the Notauderslashe molding process, in which powder is integrally molded, has become popular, and thermal stability at very high temperatures of about 220 to 250°C is required. Molded products for vehicle interior parts are required to withstand harsh operating conditions, such as being exposed to heat for long periods of time at relatively low temperatures ranging from 70°C to a maximum of 140°C, depending on the use and purpose. There is. In response to such heat history such as low-temperature heat storage over a long period of time, polyurethane foam Km 4L is
Molded parts for vehicle interior parts made of the chlorine-containing resin composition into which a urethane film has been injected have deteriorated mechanical properties and poor color tone, resulting in significant disadvantages. This decrease in mechanical properties and deterioration of color tone may be caused by amine compounds, imide compounds, or cyan compounds remaining in the polyurethane film used together or by thermal silysis of the polyurethane film. It is presumed that this is caused by the migration of the chlorine-containing resin composition into the base material layer made of the chlorine-containing resin composition, and is further promoted by the heat accumulation of the chlorine-containing resin composition.

Conventionally known stabilizers used for this purpose cannot be said to have a sufficient stabilizing effect on the chlorine-containing resin composition.
Among the organic metal salt compounds, cadmium salts and lead salts in particular have serious toxicity problems, and their use as stabilizers is severely restricted.

In recent years, various metal salts of halogen oxyacids, typified by perchloric acid, have been proposed as stabilizers for chlorine-containing resins for this purpose. For example, JP-A-59-184240 and JP-A-61-34042 disclose the use of a metal salt of a halogen oxyacid alone or in combination with a zinc salt of an organic acid and an aluminosilicate having a zeolite crystal structure T-. Showa 6
No. 1-78874 proposes the addition of a metal silicate treated with perchlorate, and Japanese Patent Application Laid-Open No. 62-39652 proposes the combined use of a metal perchlorate and a hindered amine compound for soft applications. However, these metal salts of halogen oxyacids have a coarse crystalline shape;
It has a disadvantage that the dispersibility in the chlorine-containing resin is poor, and the poor dispersibility becomes conspicuous especially when paste-sol molding, etc., which does not include a crosstalk process, is performed. In order to improve this dispersibility, Japanese Patent Application Laid-Open No. 61-231041 2% Publication No. 62-
Publication No. 1622O discloses a complex compound of perchlorate metal salts of sodium, barium, calcium, and magnesium and a polyhydric alcohol or a derivative thereof, which is liquid at room temperature, and some improvement effects have been obtained. . However, as mentioned above, in recent years, with the spread of 4-Udash Island molding, which performs integral molding at a very high temperature of about 220 to 250°C, these liquid complex compounds still have insufficient thermal stability at high temperatures. Furthermore, there is a need for further improvement in preventing heat accumulation and deterioration at relatively low temperatures over long periods of time.

[Means to solve the problem]

As a result of intensive research in view of the current situation, the present inventors have discovered a stabilized chlorine-containing resin composition that has excellent thermal stability at high temperatures and prevention of heat accumulation and deterioration at relatively low temperatures over a long period of time. This invention has been achieved.

That is, the present invention provides a chlorine-containing resin with (&) IJ chicum, sodium, potassium, magnesium, calcium,
At least one selected from organic metal salt compounds of strontium, barium, zinc, tin, antimony, and cerium
A complex compound that is liquid at room temperature, consisting of a polyhydric alcohol or/and its derivative, and a metal salt obtained by treating a coprecipitable compound with a specific composition ratio of aluminum hydroxide gel and magnesium hydroxide with perchloric acid. This is a stabilized chlorine-containing resin composition obtained by adding a combination of at least one or more of the following.

The stabilized chlorine-containing resin composition of the present invention will be explained in detail below.

The organometallic salt compound (a) which is a component of the stabilizing network for chlorine-containing resins in the present invention includes metal salts of organic acids (excluding tin salts) and organotin compounds.

Carboxylic acids, phenols, and the like are useful as the organic acids constituting the metal salts of organic acids.

Examples of carboxylic acids include acetic acid, propionic acid, butyric acid,
Valeric acid, cabroic acid, caprylic acid, neooctanoic acid, 2
-Ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid,
Lumitonic acid, stearic acid, isostearic acid, 2
-Hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, p-t-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-p-f
) v-4-hydroxybenzoic acid, toluic acid, dimethyA
=benzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N,N-tsumethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid% p-j-
Octylsalicylic acid, oleic acid, elaidic acid, linoleic acid, lylunic acid, thioglycolic acid, monocaldic acid such as mercagutopropio 76% octermercabutoglopionic acid, silicic acid, malonic acid, succinic acid, glutaric acid , adipic acid, pimelic acid, superic acid, azelaic acid, sepatic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid , aconitic acid, thiodiglobionic acid and other radicals? Examples include monoesters or monoamide compounds of phosphoric acid, and ditriester or triester compounds of trivalent or tetravalent carboxylic acids such as hemimellitic acid, trimellitic acid, merophanic acid, and pyromellitic acid.

Examples of the above-mentioned phenols include phenol,
Cresol, ethylphenol, dimethylphenol,
Cresol, ethylphenol, dimethylphenol,
isoamylphenol, cyclohexylphenol, t
-butylphenol, phenylphenol, nonylphenol, dinonylphenol, methyl-t-butylphenol, tetramethylphenol, poly(-/-penta)inglobilphenol, diimprovil-m-cresol, butylphenol, isoamylphenol,
inoctylphenol, 2-ethylhexylphenol, t-nonylphenol, decylphenol, t-dodecylphenol, octylphenol, t-octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylglobylphenol, methyl-t-octylphenol, -t-
Examples include nonylphenol and di-t-dodecylphenol.

Such metal salts of organic acids may be acidic salts or neutral salts, or basic or overbased salts in which more than the total chemical equivalent of the metal is bound in the compound.

Examples of the metal constituting the metal salt of the organic acid include lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc, zirconium, and cerium.

The above organotin compounds include methylsugnoic acid,
n-butyl stanoic acid, octylstanoic acid,
Dimethyltin oxide, di-n-butyl oxide, di-n-octyltin oxide, dimethyltin sulfide, di-n-butyltin sulfide, di-n-octyltin sulfide, mono-n-butyltin oxide sulfide, methylthiostanoic Acid, % tylthiostanoic l1ff% n-octylthiostanoic acid, di-n-butyltin laurate, di-n-butyltin stearate, di-n-octyltin dioleate, di-n-
Butyltin basic laurate, di-n-butyltin bis(butoxydiethylene glycol malate), di-n-octyltin bis(oleyl maleate), di-n-octyltin bis(stearyl maleate), di-n-octyltin bis (oleyl maleate), di-n-butyltin bis(stearyl maleate), di-n-butyltin bis(benzyl maleate), sea n-octyltin maleate, di-n-octyltin bis(n-butyl maleate) ], di-n-butyltin dimethoxide, di-n-butyltin dilauroxide, di-n-octyltin ethylene glycoxide, pentaerythritol di-n-butyltin oxide condensate, di-n-butyltin bis(lauryl mercapmade) ), dimethyltin bis(stearyl mercaptide), mono-n-butyltin tris(lauryl mercaptide), di-n-butyltin-β-mercagtogropionate, di-n-octyltin-β-mercaptide Gutoprobionate, di-n-butyltin mercaptoacetate, mono-n-butyltin tris(isooctylmercaptoacetate), mono-n-octyltin tris(2-en?/I/hexylmercaptoacetate), di-n -Butyltin bis(isooctylmercaptoacetate), di-n-octyltin bis(2-ethylhexylmercaptoacetate), dimethyltin bis(isooctylmercaptoacetate), dimethyltin bis(
octyl mercaptopropionate], mono-n-
Butyltin tris(in-octylmercaptopropionate), bis[mono-n-butyldi(iso-octoxylic is nilmethylenethio]tin) sulfide, bis[di-n
-butyl mono(isooctoxyl isomethylenethio]tin] sulfide, mono-n-butyl monochlorotin bis(in-octyl mercaptopropionate), mono-n-butyl monochlorotin bis(in-octyl mercaptoacetate), mono-n- Butyl monochlorotin bis(lauryl mercaptide), di-n-butyltin bis(ethyl cellosolve malate), bis(di-n-octyltin laurate) malate, bis(di-n-octyltin n-butyl maleate) malate, bis (G-n-octyltin
- f - malate fumarate, bis(methyltin diisooctylthioglycolate) disulfide, pyx(methyl/dimethyltin mono/diisooctylthioglycolate) disulfide, bis(methyltin diisooctylthioglycolate) Cholate cotrisulfide, bis(n-butyltin diisooctylthioglycolate) trisulfide,
Examples include nylethyltin tris(stearylthioglobionate) where the 2-butoxycar is, nylethyltin sulfide polymer where the 2-butoxycal is nylethyltin sulfide polymer, and bis(2-butoxycal?nylether)tin bis(inoctylthio f j7 :I rate).

When used in the present invention, the organometallic salt compounds of the present invention, particularly the metal salts of organic acids and the organotin compounds, may be used alone or in combination of two or more, and at least It is necessary to use 1 m or more, and the amount added is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of chlorine-containing resin.
There is a 5-view device.

Examples of the polyhydric alcohol and its derivatives (b), which are other stable components for the chlorine-containing resin in the present invention, include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol mono/ethyl ether, and ethylene glycol monoisoamyl ether. , ethylene glycol motsubutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether,
Ethylene glycol monohexyl ether, diethylene glycol, diethylene glycol motumethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisoglobil ether, diethylene glycol monophenyl ether, diethylene glycol monophenyl ether, diethylene glycol dibutyl ether, diethylene glycol acetate, triethylene glycol, triethylene glycol recall monomethyl x
-Flu, triethylene glycol monoethyl ether,
Triethylene glycol motsubutyl ether, tetraethylene glycol, polyethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, glopylene glycol monobutyl ether, diglopylene glycol, diethylene glycol dibutyl ether, diethylene glycol monoethyl ether, diethylene glycol dibutyl ether butyl ether, tripropylene glycol,
Tripropylene glycol monomethyl ether, polypropylene glycol, 1,3-butanediol, 1,4
-butanediol, 1,5-bentanediol, 1,6
-hexanediol, 3-methy/l/-1,5-bentanediol, octylene glycol, glycerin, glycerin heptanoacetate, glycerin diacetate, glycerin monobutyrate, and the like.

Therefore, when these polyhydric alcohols and their derivatives are used in the present invention, they are not used alone, but are combined with aluminum hydroxide gel and magnesium hydroxide in a specific composition ratio. A complex compound produced by reacting a specific amount of a metal salt obtained by treating a precipitable compound (hereinafter referred to as the coprecipitable compound) with perchloric acid, the so-called perchloric acid-treated coprecipitable compound, is used.

In the present invention, the coprecipitable compound to be treated with perchloric acid is prepared by mixing water-soluble aluminum salts, such as aluminum sulfate and magnesium hydroxide, and
Aluminum hydroxide gel and magnesium hydroxide are co-precipitated by maintaining the neutrality around ~7.5, and then nuclear co-precipitable compounds are filtered, washed with water, and centrifugally dehydrated to give a solution of 50-7.
It is an amorphous compound dried at a low temperature of about 0°C and has the general formula mMgo・nAt2O3・xH2O (in the formula n f
1, m is a positive number from 1.8 to 3.6, and X is a positive number). It has been confirmed from differential thermal analysis, infrared absorption spectrum and XIB diffraction analysis that this coprecipitable compound is different from a simple mixture of aluminum hydroxide gel and magnesium hydroxide and from hydrotalcite compounds, and is commercially available. The products are Ky4-Word 3001 Sanalmin (Sanalmin S, S Sanal A) manufactured by Kyowa Chemical Industry Co., Ltd.

SN Sanal A].

The perchloric acid-treated coprecipitable compound used in the present invention can be easily obtained by contacting the coprecipitable compound described above with perchloric acid or an aqueous perchloric acid solution.

The amount of perchloric acid used in the above treatment is preferably less than 1.5 equivalent ratio, more preferably 0.9 to the metal oxide in the coprecipitable compound of aluminum hydroxide dal and magnesium hydroxide. ~1.0 equivalent ratio. Here, the equivalent weight of the metal oxide in the coprecipitable compound subjected to perchloric acid treatment is determined by calculation as the crystal water and adhering water of the coprecipitate compound are not constant. Although it is difficult to confirm, experimentally the coprecipitable compound 1? The consumption amount of 0, IN perchloric acid aqueous solution required for total neutralization (hereinafter referred to as "degree of neutralization")
It can be found from . That is, if the degree of neutralization of the coprecipitable compound is t-Ad/p, then 1 equivalent of the metal oxide in the coprecipitable compound is calculated as follows:
This corresponds to IO moles of perchlorine α.

Concave=AX10-4 (Mole perchloric acid/1000
11 The coprecipitating compound) Therefore, the coprecipitating compound W having a neutralization degree of Am/P, the persalted neic acid aqueous solution W2 of ft-B? When treated with
The equivalence ratio of (W2XBX0
．． 995)/(W, XA).

W XB (11) The amount of perchloric acid actually used. 0.5X1
00 Den W2
is a complex compound as described above, and the reaction ratio of the polyhydric alcohol or its derivative and the perchloric acid-treated coprecipitable compound in such a complex compound is 95:5 to 30.
The weight ratio is 70, preferably 90:10 to 40:60. The complex compound having this specific ratio is a colorless to yellowish brown liquid that is transparent to translucent at room temperature. Although it is difficult to express the general formula of the complex compound clearly because the chemical structure of the nuclear perchloric acid-treated coprecipitable compound itself is unknown, the general formula of the complex compound is 3.2O0 to 3.2O0 based on the results of measuring infrared absorption spectra. Since it exhibits a wide absorption range in the range of 500 G, it is a complex compound with water as a ligand, and is almost the same as the so-called aqua complex compound, in which water is replaced with a polyhydric alcohol or a derivative thereof. It is estimated to be.

When such a complex compound having water as a ligand, that is, an aqua complex compound, is used as a stabilizer for a chlorine-containing resin as in the present invention, it has almost no compatibility with other stabilizer components, and Under the influence of water, other stabilizer components are easily hydrolyzed. Furthermore, when an aqua complex compound is added to a chlorine-containing resin and heat molding is performed, air bubbles are generated in the molded product because the molding temperature is higher than the boiling point of water, resulting in significant defects. When it makes a profit, it flies.

Therefore, the complex compound (b), which is a component of the stabilizer for chlorine-containing resins of the present invention, can be used in addition to the organic metal salt compound of the component (&) used in the present invention, as well as other known stabilizers or It also shows good compatibility with stabilizing aids.

The amount of the complex compound added is preferably 0.01 to 10 parts by weight, more preferably 6 parts by weight of O,OS, per 100 parts by weight of the chlorine-containing resin.

Examples of chlorine-containing resins that can be used in the present invention include polyvinyl chloride, polyvinylidene chloride, chlorinated preethylene, chlorinated I-liglobylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, and vinyl chloride-jCC tenone polymer. Combined, vinyl chloride-7'.

Pyrene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-imprene copolymer, vinyl chloride-chlorine propylene chloride copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer,
Vinyl chloride-acrylonitrile copolymer, vinyl chloride-
71 maleic acid esters, vinyl chloride-styrene-
Examples include acrylonitrile terpolymer, hardened vinyl styrene-anhydrous maleic terpolymer, vinyl chloride-vinylidene mide-vinyl acetate terpolymer, and internally plasticized polyvinyl chloride.

In addition, α-′ of the above chlorine-containing resin and polyethylene, polypropylene, polycythene, poly-3-methylbutene, etc.
Olefin polymers, or polyolefins such as ethylene-vinyl acetate copolymers and ethylene-glopyrene copolymers, and copolymers thereof, I-restyrene, acrylic resins,
Styrene-maleic anhydride copolymer, styrene-butadiene copolymer, styrene-acrylonitrile copolymer,
Blends, block copolymers, graft copolymers, etc. with acrylonitrile-butadiene-styrene terpolymer, acrylic ester-butadiene-styrene copolymer, methacrylic ester-butadiene-styrene copolymer, etc. I can do it.

The stabilizer composition of the present invention may be added to the chlorine-containing resin using a conventionally known technique, for example, the resin and each component of the stabilizer may be sequentially added to the chlorine-containing resin using a Henschel mixer. The mixture may be mixed using an emplender, a Banbury mixer, etc., or the stabilizer components may be mixed in advance with the resin using the above-mentioned mixer.

The stabilizer for chlorine-containing resins of the present invention is as described above (&
) and (b), but by using other known stabilizers and/or stabilizing aids, such as organic phosphite compounds and epoxy compounds. , the stabilization of the chlorine-containing resin composition is further improved.

Examples of the organic phosphite compounds that can be used in the present invention include diphenyldecyl phosphite, triphenyl phosphite, trisnonylphenyl phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, and tributyl phosphite. phyto, dilauryl acid phosphite, di-n-butyl acid phosphite, tris(dinonylphenyl) phosphite, trilauryl trithiophosphite, trilauryl phosphite, bis(neopentyl glycol, )-1,
4-cyclohexane dimethyl phosphite, distearyl penquerythritol diphosphite, diphenyl acid phosphite, tris(lauryl-2-thioethyl) phosphite, tetratridecyl-1,1,3-tris(2'-methyl-5'-t-phthyl-4'-oxyphenylcobutane diphosphite, tetra(01□~
C45 mixed alkyl)-4,4'-isoglopylidenezophenyl diphosphite, tris(4-oxy-2,5
-di-t-butylphenyl]phosphite, tris(4
-oxy-3,5-not-butylphenyl) phosphite, 2-ethylhexyldiphenyl phosphite, tris(mono,) mixed nonylphenyl] phosphite, hydrogenated-4,4'-isoglopylidenediphenol Polyphosphite, diphenyl bis[4,4'-n-butylidene bis(2-t-butyl-5-methylphenol)]
Thiogetanol diphosphite, bis(octylphenyl) bis[414'-n-butylidene bis(2-
t-butyl-5-methylphenol) -1,6-
Hexanediol diphosphite, phenyl-4,4'
-Isoglopylidene di phenol/pentaerythritol diphosphite, phenyl diindecyl phosphite, tetratridecyl-4,4'-n-butylidene bis(2-1-7"thi/I/-5-methylphenol diphosphite) Examples include phosphite, tris(2,4-di-t-butylphenyl)phosphite, and the like.

The amount of the organic phosphite compound added is preferably 0.01 to 5 parts by weight per 100 parts by weight of the chlorine-containing resin.
The above-mentioned epoxy compounds that can be used in the present invention include epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxidized flower oil, and niboxidized flower oil. Butyl linseed oil fatty acid, epoxidized fish oil, epoxidized tallow oil, epoxidized tall oil fatty acid ester, epoxidized polybutadiene, methyl epoxy stearate, butyl epoxy stearate, 2-ethylhexyl epoxy stearate, stearyl epoxy stearate, tris(
Epoxyglobil] isocyanurate, 3-(2-xenoxy)-1,2-eboxygropa/, bisphenol A diglycidyl ether, vinylcyclohexene diepoxide, dicycloink diene diepoxide, 3
#4-Epoxycyclohexyl-6-methylnipoxycyclohexanecarboxylate etc. The amount of the above epoxy compound added is 1 ooi of the chlorine-containing resin.
The amount is preferably from 0.01 to 10 parts by weight, and more preferably from 0.2 to 5 parts by weight.

The composition of the present invention may also contain the following stabilizing aids.

For example, initial coloring inhibitors include β-diketone compounds such as dibenzoylmethane, benzoylacetone, stearoylbenzoylmethane, and dehydroacetic acid, and complex compounds thereof with barium, calcium, zinc, and the like.

tel inorganic metal salt compounds including lithium, sodium, potassium, magnesium, calcium, stronticum,
Hydroxides, oxides, carbonates or basic inorganic salts of metals selected from the group consisting of barium, aluminium, silicon, zinc and tin, such as phosphoric acid, phosphorous acid, silicic acid,
Nitric acid, nitrous acid, sulfuric acid, nitrite, chloric acid, perchlorate, and mixtures or double salts of the above gold and k salts, such as zeolites, hydrotalcites, alum, etc. I can list them all.

Also, polyhydric alcohol compounds such as interaerythritol, diintererythritol, mannitol, sorbitol or these polyhydric alcohols and aliphatic polyhydric carbs? Ester compound with phosphoric acid and amino acid, nitrogen-containing non-gold 1
System stabilizers such as β-amictronic acid alkyl ester salts, α-phenylindole, N,N'-diphenylthiourea, phenol-based, sulfur-containing, phosphorus-containing or amine-based antioxidants, benzophenone-based, Light stabilizers such as benzotriazole-based, salicylate-based, substituted acrylonitrile-based, nickel or chromium salts or chelates, triazine-based, piperidine-based, etc. can also be used as appropriate depending on the purpose.

The composition of the present invention further includes a phthalate ester plasticizer, a 7-dipate ester plasticizer, a trimellitate ester plasticizer or other ester plasticizer, a polyester plasticizer, a phosphate ester plasticizer, Chlorinated plasticizers, such as chlorinated base roughin, and other plasticizers can also be used as appropriate depending on the purpose.

In addition, if necessary, the composition of the present invention may include, for example, a lubricant, a processing aid, a filler, a pigment, a blowing agent, a crosslinking agent, an antistatic agent,
Anti-fog agent, plate-out prevention agent, surface treatment agent, gift cutting,
Antifungal agents, mold release agents, reinforcing agents, etc. can be included.

〔Example〕

Next, the present invention 1r: will be specifically explained with examples, but the present invention is not limited thereto. Note that %it in the examples is based on weight.

Synthesis Example 1 (Synthesis of perchloric acid-treated coprecipitable compound) 2, 5
A coprecipitable compound of aluminum hydroxide dull and magnesium hydroxide represented by MgO"At2O3"xH2O (trade name S Sanal A: manufactured by Kyowa Chemical Industry, neutralization degree 285 Go/1
, MgO26%, α2O328chi) 100? To, 60-
477.47 g of an aqueous perchloric acid solution was gradually added while stirring at room temperature, and the mixture was mixed for 2 hours at 50° C. or lower to obtain a slurry. Perchlorine e! was used for the metal α-ide in the coprecipitable compound. The amounts were 1.0 equivalent ratio. then 100
℃ under reduced pressure conditions to obtain 350 fi' of a perchloric acid-treated coprecipitable compound powder (hereinafter referred to as treated metal salt A).

Hereinafter, by the same synthesis method, the treated metal salt B shown in Table 1
and C were obtained.

Synthesis Example 2 (Synthesis of a complex compound of a polyhydric alcohol or its derivative and a perchloric acid-treated coprecipitable compound) Diethylene glycol 7-methyl ether 3001 was heated with stirring and the treatment obtained in Synthesis Example 1 was carried out at a temperature of 60°C. Gold monosalt A2O0Sl' was added little by little and dispersed in the diethylene glycol monomethyl ether.Then, the gold was gradually heated in the system and reacted at 100°C for 1 hour with constant stirring to obtain a transparent liquid. Heat to temperature 1
After the completion of the 0 reaction in which the water in the system was distilled off at 10°C under a reduced pressure of 150 wHg for 1 hour, a total of 4821 complex compounds (hereinafter referred to as "complex compound A") consisting of a pale yellow transparent liquid were prepared. Nine points. Such complex compound A has a reaction ratio of diethylene glycol monomethyl ether and a perchloric acid-treated coprecipitable compound of 62:38 by weight, and a reaction ratio of 1.0 at 25°C.
It exhibited a viscosity of 50 cps.

Further, as a result of measuring the complex compound A using an infrared absorption spectrum, it showed a wide absorption in the range of 3.2O0 to 3.500 cm-'.

Synthesis Example 3 (Synthesis of a complex compound of a polyhydric alcohol or its derivative and a perchloric acid-treated coprecipitable compound) Ethylene glycol motuptyl ether 42O? and the treated metal salt Al 50P obtained in Synthesis Example 1 above, and synthesized based on the same synthesis method as Synthesis Example 2 to obtain a complex compound (hereinafter referred to as "complex compound B") consisting of a total of 5541 pale yellow transparent liquids. Such complex compound B has a reaction ratio of ethylene glycol motsubutyl ether and a perchloric acid-treated coprecipitable compound of 75.
:25 weight ratio, has a viscosity of 60 cps at 25°C, and as a result of measuring the infrared absorption spectrum,
It showed a broad absorption between 3,2O0 and 3,500 cm-'.

Synthesis Example 4 (Synthesis of a complex compound of a polyhydric alcohol or its derivative and a perchloric acid-treated coprecipitable compound) Synthesis Example 1 using diethylene glycol mottyl ether 373P as a polyhydric alcohol or its derivative and Afl.
Using the treated metal salt A1005F obtained in Synthesis Example 2, 462? A complex compound consisting of a pale yellow transparent liquid (hereinafter referred to as "complex compound C") was obtained.The reaction ratio of the complex compound ch diethylene glycol moptyl ether and the coprecipitable compound treated with perchloric acid was 80:2O by weight. ratio, 130 cp at 25°C
It has a viscosity of 1.5 s, and as a result of measuring its infrared absorption spectrum, it showed a wide absorption range between 3.2O0 and 3.500crIK.

Synthesis Example 5 (Synthesis of a complex compound of a polyhydric alcohol or its derivative and a perchloric acid-treated coprecipitable compound) Diethylene glycol monomethyl ether 370 S' was obtained in Synthesis Example 1 as a polyhydric alcohol or its derivative. Synthesis example 2 using treated metal salt B100?
Synthesize based on the same synthesis method as 460? A complex compound (hereinafter referred to as "complex compound D") consisting of a pale yellow transparent liquid was obtained.The reaction ratio of such complex compound DH diethylene glycol monomethyl ether to perchloric acid treated coprecipitable compound was 80:2O weight ratio. and 55 c at 25°C
It has a viscosity of ps, and as a result of measuring its infrared absorption spectrum, it showed a wide absorption range between 3,2O0 and 3,500t:m.

Synthesis Example 6 [Synthesis of a complex compound of polyhydric alcohol-A/or its derivative and a perchloric acid-treated coprecipitable compound] Diethylene glycol moptyl ether 375 f obtained in Synthesis Example 1 above as a polyhydric alcohol or its derivative Synthesis was performed using the treated metal salt ciooy according to the same synthesis method as in Synthesis Example 2, and 465? A complex compound 1 (hereinafter referred to as "complex compound E") consisting of a pale yellow transparent liquid was obtained. The reaction ratio of the complex compound Etl/F L/glycol monobutyl ether and the coprecipitable compound treated with perchloric acid is 80=2O weight ratio, and the viscosity at 25°C is 14
As a result of measuring the infrared absorption spectrum at 5 epl, it showed a wide absorption range between 3.2O0 and 3,500 cm.

Example 1 The following formulation was mixed with a 6-inch test roll adjusted to 1180°C for 5 minutes to form a uniform sheet of thickness o, s m.
Created. The heat stability of this sheet at 190° C. was measured using a Gear aging tester, and the heat aging coloration property after 400 hours at 120° C. was measured using a Gear aging tester in order to expose the sheet to heat storage at a relatively low temperature for a long time.

The degree of coloration of the sheet during heating was evaluated using the following reference values. The results are shown in Table 2. O (Colorability) 1: No coloration 6: Yellowish brown 2: Slightly yellow 7: Brown 3: Slightly yellow 8: Dark brown 4: Pale yellow 9 Partial black decomposition (zinc burning) 5: Yellow 10: Black decomposition (formulation) NBR (Nippon Zeon Hiker 1042) 1
0 /F antimony trioxide 3
1 Zinc stearate 0.6# Barium stearate 0.5# Barium neodecanoate 0.5# Sample (Table 2) Example 2 Same as Example 1 using the following chlorine-containing resin formulation. A sheet with a thickness of 0.51 mm was prepared.Then, a polyurethane film was injected into this sheet, and the bonded composite molded product was exposed to heat storage at a relatively low temperature for a long period of time. Gear aging test by Iso at 12O℃, 40
The heat aging colorability after 0 hours was measured and evaluated using the same reference values as in Example 1.

The results are shown in Table 3.

(Formulation: chlorine-containing resin composition) Calcium carbonate (Nitto Funkasha fiNs-100)
2O 1 stearin moromi zinc
0.5 Zinc 2-ethylhexylate
0.3〃Barium stearate
0.5# barium neodecanoate 0
．． 8# Sample (Table 3) (Formulation: ?Liurethane) The above (N composition) was thoroughly mixed using a hand mixer at room temperature, and then the diisocyanate (IS) was gradually added while stirring. The polyurethane preparation solution was thoroughly mixed at room temperature.
．． The mixture was injected and foamed onto a 5-layer chlorine-containing resin sheet to a thickness of 20 mm to obtain a composite product consisting of a chlorine-containing resin composition and a polyurethane film.◎/G'7-' Example 3 A sheeter was prepared using the following chlorine-containing resin (-Stosol compound).

That is, the following blended composition was thoroughly mixed at room temperature with stirring using a hand mixer, and then degassed under reduced pressure to remove the mixed air, and the resulting base sol compound was mixed to a thickness of 1 mm. The sol was coated on a flat stainless steel plate so that the sol was coated on a flat stainless steel plate, and then heated for 2 minutes in a dryer at a temperature of 200°C to completely glue the sol, thereby obtaining a mulch sheet.

(Composition) Zinc 2-ethylhexylate 0.
51 barium neodecanoate 1. O
#Sample (Table 4) Next, a polyurethane adjustment solution was prepared in the same manner as in Example 2, and the polyurethane adjustment solution was injected onto the glued sheet so that the thickness was 2t)el. The mixture was foamed to obtain a molded composite consisting of a chlorine-containing resin composition and a polyurethane film. A test piece was taken from the molded product of the composite, and the heat aging coloration property was measured in exactly the same manner as in Example 2 after 400 hours at 120°C. Table 4 shows the results of evaluating the colorability in the same manner as in Example 1.

/ /7 7・″ 等）'””−' 7・″ /″ [Effects of the Invention] As is clear from the above examples, the present invention particularly provides a polyhydric alcohol or its derivative, aluminum hydroxide gel, and hydroxide. A complex compound of a coprecipitable compound of magnesium with a specific composition ratio and a metal salt treated with perchloric acid, which is liquid at room temperature, is uniformly dispersed in the chlorine-containing resin composition and is compared over a long period of time. Excellent in preventing heat storage aging at extremely low temperatures.This effect is particularly noticeable in chlorine-containing resin paste sol compounds.Since the complex compound is liquid, it has excellent uniform dispersibility, and heat aging resistance is maintained at 120°C for 400 hours. No zinc burning phenomenon was observed even after conducting the sex test.

Claims (2)

[Claims] (1) In the chlorine-containing resin, (a) lithium, sodium,
At least one selected from organometallic salt compounds of potassium, magnesium, calcium, strontium, barium, zinc, zirconium, tin, antimony, and cerium.
and (b) at least one of a complex compound which is liquid at room temperature, and (b) a polyhydric alcohol or/and its derivative, and a metal salt obtained by treating a coprecipitable compound of aluminum hydroxide gel and magnesium hydroxide with perchloric acid. A stabilized chlorine-containing resin composition containing at least one species. (2) A coprecipitable compound of aluminum hydroxide gel and magnesium hydroxide has the general formula: mMgO-nAl_2O_3・xH_2O (where n is 1, m is a positive number from 1.8 to 3.6, and x is a positive number Claim No. 1 is a coprecipitable compound represented by
) The stabilized chlorine-containing resin composition described in item 2.