JP3274340B2 - Stabilizer for chlorine-containing polymer, method for producing the same, and chlorine-containing polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilizer for chlorine-containing polymers and a method for producing the same. The present invention relates to a water-prone stabilizer for chlorine-containing polymers and a method for producing the same. The present invention also relates to the effective use of waste clay discharged in the oil and fat refining process as a stabilizer.

[0002]

BACKGROUND OF THE INVENTION Chlorine-containing polymers, such as vinyl chloride resins, undergo dehydrochlorination within their molecular chains when exposed to heat and light,
Decomposition, discoloration, etc. occur. In order to stabilize the vinyl chloride resin against this thermal decomposition, various stabilizers or stabilizer compositions have been conventionally proposed and widely used. Among such stabilizers, it is known to use various siliceous compounds as inorganic ones. For example,
Japanese Patent No. 32899 discloses that a compound containing an organic compounding agent in pores of a silicate such as synthetic calcium silicate is mixed with a chlorine-containing polymer as a heat stabilizer. No. 15237 describes that microcrystalline calcium silicate hydrate is mixed with a chlorine-containing polymer or the like.

[0003]

SUMMARY OF THE INVENTION Silicate particles such as calcium silicate have good pigment properties and are excellent in compounding and dispersing properties in a resin, and react with hydrogen chloride and chloride ions to trap them. However, these silicates are hydrophilic in nature, and have a problem that this tendency is large especially in amorphous or microcrystalline materials having excellent reactivity with hydrogen chloride. That is, these siliceous compounds generally tend to adsorb moisture during storage and tend to release moisture when kneaded with the chlorine-containing polymer to foam the compounded resin composition.

[0004] Silicic compounds are rarely used alone as heat stabilizers, and are generally used in combination with various organic compounding agents. However, silicic compounds are hydrophilic. For this reason, there is also a drawback that it is poorly compatible with hydrophobic organic components such as higher fatty acid salts.

[0005] Furthermore, in the process of refining fats and oils, waste clay containing a relatively large amount of fats and oils is produced as a by-product, and disposal of the waste clay has been a problem. It is considered to be significant in terms of environmental pollution prevention and effective use of resources.

An object of the present invention is to provide a stabilizer for a chlorine-containing polymer which is excellent in compoundability and thermal stability in a chlorine-containing polymer and has a suppressed tendency to condensate, and a method for producing the same. It is another object of the present invention to provide a method of using a clay containing oils and fats as a raw material and effectively reusing it as a stabilizer for a chlorine-containing polymer.

[0007]

According to the present invention, there is provided a siliceous compound selected from the group consisting of silicic acid, silicates and aluminosilicates, and acid-treated products thereof and containing a reactive silicic acid. , A composition containing a fat or oil, and a total amount of the equivalent of KOH required for saponification of the fat or oil and the neutralization amount of reactive silicic acid, which is equal to or more than Group II metal, Group IV metal and / or At least one selected from the group consisting of oxides and hydroxides of a Group V metal is mixed and reacted in the presence of water to form a reactive silicic acid into a Group II metal of the periodic table. A chlorine-containing silicate comprising an oil / fat saponified composite silicate, which is converted into a silicate of a group IV metal and / or a group V metal and the saponified product of the fat / oil is supported on a siliceous compound. A method for preparing a stabilizer for a polymer is provided.

According to the present invention, there is also provided calcium silicate hydrate having a substantially single X-ray diffraction peak at 3.0 to 3.1 angstroms (hereinafter this substance may be abbreviated as CSH-1). And / or 2.8
4 to 2.85, 3.22 to 3.23, 2.97 to 2.98, 1.86 to 1.87, and 4.2 to 4.1
Crystalline lead silicate having a major X-ray diffraction peak at Angstroms (this material may be abbreviated as PbSH hereinafter) and having a substantially single X-ray diffraction peak at 3.05 to 3.15 Angstroms Silicic compound particles mainly composed of calcium lead silicate hydrate (hereinafter, this substance may be abbreviated as PbCSH);
Higher fatty acid calcium salt, higher fatty acid lead salt, glycerin and / or
Alternatively, there is provided a stabilizer for a chlorine-containing polymer, comprising a hydrophobic particle of a composition containing a glycerin derivative.

Further, when the stabilizer is under atmospheric pressure or reduced pressure,
A stabilizer for a chlorine-containing polymer which is heated at 50 ° C to 300 ° C is provided.

[0010]

According to the present invention, there is provided a composition comprising a siliceous compound selected from the group consisting of silicic acid, silicates and aluminosilicates and their acid-treated products and fats and oils, or, if necessary, a zinc compound. And at least one member selected from the group consisting of oxides, hydroxides and reactive salts of Group II metals, Group IV metals and / or Group V metals (hereinafter referred to as Group II metals, etc.) (Hereinafter referred to as oxides) is wet-mixed in the presence of water. The siliceous compound to be used contains a reactive silicic acid, and a Group II metal, a Group IV metal and / or a Group V metal At least one selected from the group consisting of metal oxides, hydroxides and reactive salts is at least the total number of equivalents of KOH required for saponifying fats and oils and equivalents for neutralizing reactive silicic acid. It is important to use in an amount of

When the above composition is wet-mixed with an oxide or hydroxide of a Group II metal, a Group IV metal and / or a Group V metal, the reactive silicic acid in the siliceous compound and the Group II metal are mixed. Metals, oxides of Group IV metals and / or Group V metals, etc. react to form amorphous and Group II metals, Group IV metals and / or Group V metals with large pore volumes. Silicates are formed in the siliceous compound, and fats and oils are saponified with oxides of Group II metals, Group IV metals and / or Group V metals, etc. , Higher fatty acids IV
Group metal salts and / or Group V metal salts of higher fatty acids (hereinafter referred to as
Higher fatty acid group II metal salts, etc.), glycerin and / or
Or a glycerin derivative. Glycerin and glycerin derivatives, such as silicates of Group II metals and the like, and higher fatty acid Group II metal salts, are all stabilizer components for chlorine-containing polymers, and these components act synergistically to be described later. As shown in the examples, a high degree of thermal stability is obtained.

Further, the stabilizer obtained according to the present invention comprises:
Under atmospheric pressure to reduced pressure, 50 ° C to 300 ° C, preferably 1
The use of heat treatment at 00 ° C. to 200 ° C. further improves the condensate prevention property and the heat stabilizing effect.

Prior to the above-mentioned reaction, among oxides of Group II metals and the like, in particular, when a zinc oxide described below is used, it is possible to prevent the chlorine-containing polymer from being initially colored and to be colored during heating. Has a remarkable effect in preventing the Further, the effect of preventing coloring of zinc oxide and the like is particularly remarkable when an alkaline earth metal is used. That is, the alkaline earth metal-based stabilizer is a stabilizer having a tendency to develop a warm color (red) with respect to the chlorine-containing polymer, and a zinc oxide or the like having a tendency to develop a cool color (blue) with the chlorine-containing polymer. By coexisting, a specific coloring tendency is prevented by the complementary action of both. Not only in the stabilizer according to the invention, but also in the stabilizer according to the invention, the zinc component is incorporated into the alkaline earth metal silicate (hereinafter this substance is referred to as Z
It may be abbreviated as CSH-1. ), As compared with the case where the zinc component is separately added, there is an advantage that the heat history in which so-called zinc burning occurs is significantly prolonged.

In the present invention, the reactive silicic acid and the periodic table II
In a system in which a group metal, a group IV metal and / or a group V metal oxide or the like reacts to form a group II metal silicate or the like,
It is also important to perform saponification of fats and oils. That is, since freshly formed silicates such as Group II metals contain macropores and have a high degree of activity,
It exhibits the effect of firmly retaining glycerin and glycerin derivatives, such as higher fatty acid Group II metal salts produced by saponification of oils and fats, in or on the siliceous particles. As an example, in the neutralization of a composition containing a siliceous compound that does not form a silicate such as an amorphous Group II metal, a higher fatty acid Group II metal salt or the like derived from saponification of fats, glycerin and glycerin derivatives Is liberated from the siliceous compound to form a jelly-like mixture as a whole, and it is difficult to make the mixture into a granular material.However, in the present invention, the release of the saponified oil or fat is effectively prevented, and the reaction is prevented. Easy granulation of the mixture.

The wet mixing is advantageously carried out under wet milling and mixing conditions. Milling mixing is a mixing condition under which the fresh surface of the siliceous compound is exposed. Under these mixing conditions, the above-described reactions proceed mechanochemically, and the liberation tendency of the saponified oil and fat products is increased. Is completely prevented, and the reaction mixture can be obtained directly as a powder or as a powder only by slightly drying.

The stabilizer according to the present invention comprises a higher fatty acid fatty acid in the pores (macropores) or on the surface of the siliceous compound particles.
Glycerin and glycerin derivatives, such as Group II metal salts, are uniformly held and fixed, and are characterized in that the composition of each particle is uniform and uniform. For this reason, as shown in an example to be described later, variation in the composition of each particle is extremely small. In addition, since the water-repellent higher fatty acid group II metal salt and the like are uniformly present in the pores and surfaces of the particles, the stabilizer particles of the present invention are hydrophobic in nature, and may be chlorine-containing polymers or other organic compounds. It is very easy to mix with a stabilizer, that is, compounding, and has an advantage of lubricating action that it is easy to dig into and disperse in a resin. In addition, despite the fact that the base of the stabilizer is a metal salt of a group II silicate or the like and contains glycerin, it is quite surprising that
It shows the characteristic that the tendency to absorb moisture is extremely small. That is, the amorphous silicate generally has water of hydration, which is condensed even when the water is removed by drying the water. However, the tendency is remarkably small in the stabilizer according to the present invention.

The effects of the stabilizer of the present invention are as follows.
This is shown by an example described later (see the thermal analysis diagram of FIG. 2 and the infrared spectra of FIGS. 4 to 6). That is, FIG. 2 plots the weight change (TG (%)) of the sample when the sample was heated and for about 1000 minutes after the heating. According to FIG. 2, the zinc-calcium-silica composite hydroxide before carrying out the fat-and-oil carrying treatment (sample B described later in the section of Examples)
In the TG curve (curve 1) of -1), the weight loss peak due to moisture evaporation during heating (about 600 to 1000 after the start of measurement)
Minutes) under the same conditions (see curve 3 for temperature conditions)
Example 1 in which the processing for supporting fats and oils obtained by the measurement in
In the TG curve of the stabilizer (curve 2), the peak of weight loss due to water evaporation during heating (about 600 to 100
0 minute), and the comparison between these two peaks indicates that the stabilizer of the present invention is hydrophobic due to the loading of fats and oils, and that it has almost no moisture on the surface or inside. Understand. Further, in FIG. 2, when comparing the change in the TG% value of the curves 1 and 2 after 1000 minutes, the TG value of the curve 1 increases with the passage of time, whereas the TG value of the curve 2 hardly changes. You can read that you did not. From this, in the sample B-1 which has not been subjected to the processing of supporting fats and oils, after a large amount of water loss due to heating, the weight of the sample B-1 is gradually increased by condensing water.
It can be seen that condensate hardly occurs in the stabilizer of Example 1 in which the oil / fat support treatment was performed.

FIG. 4 shows the results obtained by sampling, under various conditions, a stabilizer composed of an oil / fat saponified compound silicate obtained in Example 1 described later, and measuring the infrared absorption spectrum of the sample. It is. According to FIG. 4, the infrared absorption spectrum (spectrum 1) of the air-dried product of the product slurry of Example 1 shows that the absorption derived from the O—H bond of the water molecule is 1580 cm ⁻¹ near 1647 cm ^−1.
It can be confirmed as the shoulder of the absorption peak of ^-1 . On the other hand, an infrared absorption spectrum (spectrum 2) of the air-dried product obtained by removing the moisture by heat treatment is 164.
It can be confirmed that the shoulder around 7 cm ^-1 has disappeared. The infrared absorption spectrum (spectrum 3) obtained by measuring the product of Example 1 after this heat treatment after standing for 7 days at a room temperature and a relative humidity of 75% also shows that the water molecule O—H was around 1647 cm ^−1. No absorption due to bonding was confirmed, and it was confirmed that the stabilizer according to the present invention was difficult to condense.

FIG. 5 shows Example 1 except that no oil or fat was used.
FIGS. 4A and 4B are infrared absorption spectra of an air-dried product of a zinc calcium silica composite hydroxide obtained in the same manner as before but before the heat treatment (spectrum 1) and after the heat treatment (spectrum 2). Hydroxide is poor in water repellency.
^It can be confirmed that the absorption derived from the O—H bond of the water molecule near ⁻¹ has not disappeared. Although not shown in FIG. 5, the sample after the heat treatment was further subjected to 1 hour at room temperature and 75% relative humidity.
The infrared absorption spectrum of the sample left to stand for a week is similar to that of spectrum 1, and it has already been confirmed that the zinc-calcium-silica composite hydroxide not carrying fats and oils is easy to condense.

FIG. 6 is a graph showing the results obtained by performing the same operation as in Example 1 on a zinc calcium silica composite hydroxide (sample B-1) and calcium stearate (about 20% by weight of the slurry air-dried product).
Air-dried powder (spectrum 1) of a homogeneous slurry of the mixture with (a), a powder immediately after heating and drying of the slurry (spectrum 2), and a powder of the same powder left at room temperature under a relative humidity of 75% (spectrum 3). FIG. 4 is an infrared absorption spectrum of calcium stearate (Spectrum 4). In spectrum 3, O- of water molecule around 1647 cm ^-1
As is apparent from the fact that the absorption derived from the H bond can be confirmed, merely mixing the organic silicate with the composite silicate cannot prevent the condensate from condensed, and the effect of the stabilizer according to the present invention is not improved. It turns out that it is not achieved.

As described above, when an oil or fat is supported on the surface of the composite silicate as in the stabilizer of the present invention, a stabilizer composed of a hydrophobic composite silicate can be obtained. Difficult to water. It can be easily understood that the condensate-preventing performance of this stabilizer cannot be obtained by merely using a conventionally known additive of a higher fatty acid salt in the composite silicate.

The stabilizer according to the present invention has an advantage that the higher fatty acid salt is less likely to plate out since the organic component, that is, the higher fatty acid salt is held and fixed on the siliceous particles.

In addition, the stabilizers of the present invention have relatively improved whiteness and offer the advantage that they do not themselves undergo thermal degradation or coloration when processed at high temperatures. This is exactly the same when the used fats and oils are waste fats and oils. That is, in the present invention, it is recognized that the degree of whiteness is improved by converting the reactive silicic acid component in the siliceous compound into an amorphous alkaline earth metal silicate or the like. Further, glycerin is disadvantageous in that it easily undergoes color deterioration at high temperatures, but it is recognized that the stabilizer according to the present invention is stabilized because glycerin coordinates to the group II metal silicate and the like.

According to the most important aspect of the process of the present invention,
Alkaline earth metal silicates are present in the form of calcium silicate hydrate (CSH-1) which has a substantially single X-ray diffraction peak between 3.0 and 3.1 Angstroms. In addition, lead silicate and calcium lead silicate are available from 2.84 to 2.85, 3.22 to 3.23,
2.97 to 2.98, 1.86 to 1.87 and 4.
Crystalline lead silicate (PbSH) with a major X-ray diffraction peak between 2 and 4.1 Angstroms and calcium lead silicate hydrate with a substantially single X-ray diffraction peak between 3.05 and 3.15 Angstroms (P
bCSH). These are particularly excellent in all of the aforementioned characteristics.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION

[Silicic Compound] The silicic compound used as a raw material in the present invention may be any of various silicic acids, silicates, layered silicic acids, aluminosilicates, or acid-treated materials thereof, as long as they contain reactive silicic acid. It can be any of the things. Reactive silicic acid means silicic acid extracted as sodium silicate when reacted with an aqueous NaOH solution. For example, not only amorphous silica but also Hashimoto and
Silica dissolved by the Jackson method (boiled reaction in 0.5N NaOH aqueous solution for 2.5 minutes) and silica dissolved under basic milling conditions such as cristobalite and opal C
T, montmorillonite, chlorite and the like are included in this. The content of the reactive silicic acid content is per silicic compound,
It is preferably at least 10% by weight, particularly preferably at least 30% by weight. The siliceous compound used in the present invention is 10 m ² /
The specific surface area is preferably not less than g.

Examples of the amorphous silica include white carbon, other wet-process amorphous silica, and silica obtained by acid-treating clay minerals such as acid clay, montmorillonite, and flours earth. Is done. This amorphous silica is generally 150 to 400 m
^It has a BET specific surface area of ² / g, and its secondary particle size is preferably in the range of 1 to 10 μm, particularly 1 to 5 μm. The layered silicic acid is obtained by treating magadiite, kenyaite, macatite, islarite, and kanemite with an acid. Examples of the silicate include alkaline earth metal silicates such as magnesium silicate, calcium silicate, barium silicate, and strontium silicate; Group IIb metal salts of silicic acid such as zinc silicate; Group IV metal salt of silicic acid; Group V metal salt of silicic acid such as antimony silicate is used, and those containing the above-mentioned reactive silicic acid are used alone or in combination of two or more. . These silicates may be synthesized by a known wet method or dry method.
As the aluminosilicate, a layered aluminosilicate, in particular, various clay minerals, a tectosilicate, or a zeolite containing the reactive silicic acid described above is used.

Naturally occurring clay minerals such as acid clay,
Most of montmorillonite, bentonite, sepiolite, halloysite and the like contain reactive silica such as amorphous silicic acid and cristobalite, and can be used for the purpose of the present invention. Further, when the clay mineral is acid-treated, the alumina component and other metal components in the clay are eluted and the content of reactive silicic acid (active silicic acid) increases, which is advantageously used for the purpose of the present invention. Can be used. The specific surface area of the clay and the clay-acid-treated product (activated clay) is preferably in the range of 10 to 350 m ² / g.

The acid used may be an inorganic acid or an organic acid without any particular limitation. However, economically, acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid are used. These acids are used in the acid treatment reaction in the form of a diluted aqueous solution.

Naturally obtained zeolites such as mordenite, clinoptilolite, faujasite and the like often contain reactive silicic acid, and these can be advantageously used for the purpose of the present invention. . In addition, crystalline zeolites such as zeolite A, zeolite X, zeolite Y, zeolite P, analcyme, sodalite, etc. can be easily amorphized by acid treatment, and are used for the purpose of the present invention. be able to.

[Oil-and-Fat-Containing Composition] Raw oils and fats are widely present in the natural animal and plant kingdoms and mainly contain esters of fatty acids and glycerin. For example, soybean oil, rapeseed oil, palm oil, palm kernel oil , Cottonseed oil, coconut oil, rice bran oil,
Vegetable oils such as sesame oil, castor oil, linseed oil, olive oil, paulownia oil, camellia oil, peanut oil, kapok oil, cacao oil, wood wax, sunflower oil, corn oil and fish oils such as sardine oil, herring oil, squid oil, saury oil , Liver oil, whale oil, tallow,
Animal fats and oils such as beef tallow, horse oil, lard and sheep fat can be used alone or in combination. In addition, as these used fats and oils, edible waste oil after use as a frying oil for home use or business use, used edible oil from a food processing manufacturer, extracted and recovered oil from an edible fat / oil refiner, silicon oil, etc. can also be used. .

In the present invention, in addition to using the above-mentioned siliceous compound and the above-mentioned fats and oils, a mixture of the fats and oils adsorbed on the siliceous compound, for example, fat-and-oil waste discharged in the step of refining fats and oils White clay can also be used. That is, activated clay (acid-treated clay) is widely used for the adsorption (decolorization) of pigments and the like contained in fats and oils, but the waste clay discharged from this purification step accounts for 5 to 60% by weight of the whole. It contains oils and fats, and in the present invention, both clay and the oils and fats contained therein can be effectively used as stabilizer components.

The composition used in the present invention has two components based on two components.
It is preferable to contain the siliceous compound in an amount of from 9 to 99% by weight, especially from 30 to 70% by weight, and from 1 to 98% by weight, especially from 30 to 70% by weight of the fat or oil. That is, when the content of the siliceous compound is lower than the above range, it is difficult to handle as a powder, while when the content is higher than the above range, the performance as a stabilizer decreases.

[Mixing reaction] According to the present invention, the composition comprises the above-mentioned composition, an oxide, a hydroxide and a reactive salt of a Group II metal, a Group IV metal and / or a Group V metal. Mixing with at least one selected from the group in the presence of water,
Let react. In this reaction, the order of addition of the synthetic components is not particularly limited, and it is sufficient that a silicic compound, oils and fats, oxides of Group II metals and the like coexist in the reaction system.

The reactants, ie, siliceous compounds, fats and oils,
Adjusting the mixing ratio of oxides such as Group II metals, etc. to make the reaction conditions the desired ones, or the component composition of the oil / fat saponified composite silicate finally obtained after the mixing reaction is within the desired range After reacting these reactants in a mixed manner,
Further, each of these reactants may be added as appropriate. In this case, the additional reactant can be added irrespective of the feature of the present invention, and the amount is not particularly limited as long as the desired effect of the present invention is exhibited.

As the oxide of the Group II metal, an oxide of an alkaline earth metal and / or zinc is mainly used. As the alkaline earth metal oxide or the like, calcium hydroxide, particularly lime milk, is preferably used, but calcium oxide, magnesium oxide, magnesium hydroxide and the like can also be used. Examples of zinc oxide include zinc acetate, zinc (II) acetylacetonate, zinc benzoate,
Zinc bromide, p-tert-butyl benzoate, basic zinc carbonate, zinc 4-cyclohexylbutyrate, zinc dibenzyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc 2-ethylhexanoate, zinc iodide, Zinc lactate, zinc nitrate, zinc oxide, zinc phenolsulfonate,
Zinc phosphate, zinc pyrithione, zinc salicylate, zinc stearate, zinc sulfate, zinc thiocyanate, zinc metaantimonate, zinc antimony oxide, zinc borate, zinc aluminum oxide, ganite, zinc aluminum phosphate hydrate, zinc aluminum phosphate hydro Oxide hydrate, zinc aluminum silicate, zinalcite, zinc aluminum sulfate hydrate, zinc calcium hydroxide silicate, zinc carbonate, zinc carbonate hydroxide, zinc calcium hydroxide silicate, zinc carbonate hydroxide hydrate, zinc chloride hydrate, zinc Hydrogenf Sulfate hydrate, zinc hydrogen phosphite hydrate, zinc hydroxide, zinc hydroxide hydrate, bismilpite, zinc iodate, lithium zinc iodate, zinc magnesium aluminum silicate hydrate, zinc magnesium phosphate, zinc oxalate, Zinc oxide borate hydrate, zinc oxide phosphate, zinc phosphate, zinc phosphate, zinc silicate, zinc sulfate, zinc sulfate hydroxide, zinc sulfide, zinc titanium oxide, zinc titanium sulfate, zinc titanium sulfide, and the like. In addition, as the Group IV and V oxides, it is preferable to use lead hydroxide (Pb
(OH) ₂ ), lead oxide (PbO), tin oxide (SnO ₂ ,
SnO), antimony oxide (Sb ₂ O ₃ , Sb ₂ O ₄ ,
Sb ₂ O ₅ ) and the like, and more preferably, lead hydroxide, lead oxide and the like.

It is possible to use a combination of at least one or more of these Group II, IV and V metal oxides, hydroxides and reactive salts.

Group II, IV and V metal oxides;
The amount of the hydroxide and / or the reactive salt may be at least the total amount of the equivalent of KOH required for saponification of fats and oils and the neutralization amount of the reactive silicic acid. In particular, under these conditions, when the oxides of the Group II metals and the like are used in an amount of 1.01 to 2000 times by weight of the equivalent of KOH required for saponification of fats and oils, the action and effect of the present invention can be more improved. Effectively demonstrated. In particular, when a zinc oxide or the like is used in order to remarkably exert a coloring prevention effect, the zinc oxide or the like is added in an amount of 0.1 to 0.1% per silicic compound.
It may be used in an amount of 1 to 60% by weight, especially 5 to 30% by weight.

The wet milling reaction is a reaction under the condition that mechanical milling force is applied to amorphous silica or the like. The reaction can be carried out at a temperature as low as possible, generally below 70 ° C., in particular between 15 and 50 ° C., for 3 to 300 hours.

As an example of the production method of the present invention, a raw material of a calcium salt and / or a lead salt is used in a tube mill charged with water and a pulverizing medium in an excess molar amount with respect to silica.
SH-1 or ZCSH-1 and / or PbSH,
PbCSH is reacted and produced under wet milling, and then fats and oils are added, and the hydrolysis reaction is performed under the same milling to produce metal soap and glycerin and glycerin derivatives. Next, the product slurry in the wet-milled state is evaporated to dryness under heating to form a complex, and the product is crushed or classified to obtain the product of the present invention.

The product of the stabilizer thus obtained is
A siliceous compound particle mainly composed of a group II metal salt, a group IV metal salt and / or a group V metal salt of an amorphous or low-crystalline silicic acid; Fatty and oily saponified composite silica comprising hydrophobic particles of a composition containing a group II metal salt, a group IV metal salt and / or a group V metal salt of a higher fatty acid and glycerin and / or a glycerin derivative retained on the surface Consists of acid salts. The saponified fat / silicone composite silicate generally contains 1 to 99% by weight of a siliceous compound based on three components, and a Group II metal salt, a Group IV metal salt and / or a Group V metal salt of a higher fatty acid. Glycerin and / or a derivative thereof is contained in an amount of from 0.02 to 60% by weight as a glycerin content.

The stabilizer of the present invention is, for example, 0.1 to 50 parts by weight, preferably 0.1 to 10 parts by weight, most preferably 0 to 10 parts by weight per 100 parts by weight of a chlorine-containing polymer. When used in an amount of from 0.5 to 2.0 parts by weight, remarkable prevention of foaming and sustained heat resistance are simultaneously exhibited. Specifically, (A) 0.1 to 50 parts by weight of the oil / fat saponified composite silicate of the present invention, (B) zinc oxide, hydroxide and reactivity per 100 parts by weight of the chlorine-containing polymer. 0.1 to 50 parts by weight of at least one selected from the group consisting of salts, (C) 0.1 to 25 parts by weight of alcohols and / or partial esters thereof, and (D)
It is preferable to use a chlorine-containing polymer composition comprising 0.05 to 5 parts by weight of a β-diketone or a β-keto acid ester compound and / or a phosphite compound.

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 polymer, vinyl chloride-isobutylene copolymer, vinyl chloride -Vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-propylene chloride copolymer, vinyl chloride -Vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-acrylate copolymer, vinyl chloride-maleate copolymer, vinyl chloride-methacrylic Acid ester copolymer, vinyl chloride-acrylonitrile copolymer, internal plasticizer Polymers such as vinyl chloride, and these chlorine-containing polymers and polyethylene, polybutene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, polystyrene, acrylic resin, acrylonitrile-butadiene-styrene copolymer, Blends of acrylate-butadiene-styrene copolymers and the like can be given.

The resin composition containing the stabilizer of the present invention may contain various additives known per se, such as non-metallic stabilizers, organotin stabilizers, and basic inorganic acid salts. Agent or stabilizing aid, plasticizer, initial color improver, alcohols and / or partial esters thereof, antioxidant, light stabilizer, nucleating agent, filler, epoxy stabilizer, organic chelator, pigment, antistatic Agents, anti-fogging agents, plate-out preventing agents, flame retardants, lubricants and the like can be added and blended within a range where the stability is not impaired.

Further, an inorganic stabilizer such as a compound containing a perhalogen oxyacid, a hydrotalcite compound, a lithium aluminum composite hydroxide and the like can be added. Specifically, zinc-type hydrotalcite compounds,
A perchloric acid type hydrotalcite compound, a perchloric acid type lithium aluminum composite oxide, and the like can be blended.

More specifically, as the perhalogen oxyacid-containing compound, (1) a perchloric acid-treated hydrotalcite compound described in Japanese Patent Application No. 59-235158, and (2) a perchloric acid-treated lithium aluminum carbonate hydride (3) amorphous silica, alumina, alumina-silica gel structure containing perhalogen oxyacid anions (perchlorate anion, periodate anion, etc.), or anion exchangeability or anion adsorption Inorganic minerals (Japanese Patent Application No. 60-216243, Japanese Patent Application No. 59-2351)
No. 56), (4) metal salts of perchloric acid (the constituent metals include lithium, sodium, potassium, strontium, barium, zinc, cadmium, lead, aluminum, etc.), and (5) perchloric acid treatment Silicates, for example
Perchloric acid-treated products such as calcium silicate, magnesium silicate, barium silicate, zinc silicate, and lead silicate; various silicate clay minerals such as kaolin, bentonite, mica powder, talc, diatomaceous earth, acid clay, activated clay, zeolite Processed products are exemplified.

The organotin compounds include organotin mercaptides, organotin sulfides, organotin mercaptide sulfides, organotin mercaptocarboxylates and organotin carboxylates.

(1) As the organotin mercaptides,
Dibutyltin bis (lauryl mercaptide), dimethyltin bis (stearyl mercaptide), dioctyltin bis (mercaptoethyl / tall fatty acid fatty acid ester),
Dioctyltin bis (2-mercaptoethylcaprylate), dibutyltinbis (mercaptoethyl / tall fatty acid ester), dimethyltinbis (mercaptoethylstearate), dioctyltinbis (isooctylthioglycolate), dioctyltinbis ( 2-ethylhexylthioglycolate), dioctyltin bis (dodecylthioglycolate), dioctyltin bis (tetradecylthioglycolate), dioctyltin bis (hexadecylthioglycolate), dioctyltin bis (octadecylthioglycolate), dioctyltin bis (C _12-16 mixed alkyl thioglycolate), dibutyltin bis (isooctyl thioglycolate), dimethyltin bis (isooctyl mercaptopropionate), bis (2-mercaptoethyl carbonyl ethyl) tin Diorganotin mercaptides such as bis (isooctylthioglycolate), bis (2-butoxycarbonylethyl) tin bis (butylthioglycolate), monobutyltin tris (laurylmercaptide), monobutylmonochlorotinbis (laurylmel (Captide), monooctyltin tris (2-mercaptoethyl caprylate), monobutyltin tris (mercaptoethyl / tall oil fatty acid ester), monomethyltin tris (mercaptoethyl / tall oil fatty acid ester), monomethyltin tris (mercaptoethyl lau) Monomethyltin tris (mercaptoethyl stearate), monomethyltin tris (mercaptoethyl oleate), monooctyltin tris (isooctylthioglycolate) monooctyltin tris (2-ethylhexyl) Glycolate), monooctyltin tris (dodecylthioglycolate), monooctyltin tris (dodecylthioglycolate), monooctyltin tris (tetradecylthioglycolate), monooctyltin tris (hexadecylthioglycolate), Monooctyltin tris (C _12-16 mixed alkylthioglycolate), monooctyltin tris (octadecylthioglycolate), monobutyltin tris (isooctylthiogrecolate), monobutyltin tris (isooctylmercaptopropionate), monomethyl Tin tris (isooctyl thioglycolate), monomethyltin tris (tetradecyl thioglycolate),
Mono-organic tin mercaptides such as 2-methoxycarbonylethyltin tris (isooctylthioglycolate) and 2-butoxycarbonylethyltin tris (2-ethylhexylthioglycolate) are exemplified.

(2) Examples of the organotin sulfides include methylthiostannoic acid, butylthiostannoic acid,
Octylthiostannoic acid, dimethyltin sulfide, dibutyltin sulfide, dioctyltin sulfide, dicyclohexyltin sulfide, monobutyltin sulfide oxide, 2-methoxycarbonylethyltin sulfide, 2-ethoxycarbonyltin sulfide, 2-butoxycarbonylethyltin Sulfide,
2-isopropoxycarbonylethyltin sulfide,
Bis (2-methoxycarbonylethyl) tin sulfide, bis (2-propoxycarbonylethyl) tin sulfide and the like can be mentioned.

(3) Examples of the organotin mercaptide sulfides include bis [monobutyl di (isooctoxycarbonylmethylenethio) tin] sulfide and bis [dibutylmono (isooctoxycarbonylmethylenethio)
Tin] sulfide, bis [bis (2-methoxycarbonylethyl) tin isooctylthioglycolate] sulfide, bis (methyltin diisooctylthioglycolate)
Disulfide, bis (methyl / dimethyltin mono / diisooctylthioglycolate) disulfide, bis (methyltin diisooctylthioglycolate) trisulfide, bis (butyltin diisooctylthioglycolate) trisulfide, bis [Methyltin di (2-methylcaptoethylcaprylate) sulfide, bis [methyltindi (2-mercaptoethylcaprylate)] disulfide and the like can be mentioned.

(4) Examples of the organotin mercaptocarboxylates include dibutyltin-β-mercaptopropionate, dioctyltin-β-mercaptopropionate, dibutyltin mercaptoacetate, and bis (2-methoxycarbonylethyl) tinthio. (Glycolate) tin thioglycolate, bis (2-methoxycarbonylethyl) tin mercaptopropionate, and the like.

(5) Examples of the organotin carboxylate include octoate, laurate, myristate, palmitate, and sterate of mono or dimethyl tin, mono or dibutyl tin, mono or dioctyl tin or mono or bis (butoxycarbonylethyl) tin. Aliphatic monovalent carboxylate such as isostearate: malate such as malate polymer, butylmalate, benzylmalate, oleylmalate, stearylmalate; and a mixed salt or a basic salt thereof.

Examples of the plasticizer include an ester plasticizer such as a phthalate ester plasticizer and an adipic ester plasticizer, a polyester plasticizer, a phosphate ester plasticizer, a chlorine plasticizer, and a tetrahydrophthalic acid plasticizer. Agents, azelaic acid-based plasticizers, sebacic acid-based plasticizers, stearic acid-based plasticizers, citric acid-based plasticizers, and trimellitic acid-based plasticizers.

Examples of the phthalate plasticizer include dibutyl phthalate, butylhexyl phthalate,
Examples thereof include diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate. Examples of the adipate-based plasticizer include dioctyl adipate, diisononyl adipate, diisodecyl adipate, di (butyldiglycol) adipate, and the like.

Examples of the phosphate ester plasticizer include:
Triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri (butoxyethyl) phosphate, octyl diphenyl phosphate, etc. Is mentioned.

As the polyester plasticizer, for example,
Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,
3-propylene glycol, 1,3-butanediol,
1,4-butanediol, 1,5-hexanediol,
Polyhydric alcohols such as 1,6-hexanediol and neopentyl glycol, and oxalic acid, malonic acid, succinic acid,
Polyesters using glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. No.

Examples of the initial color improver include nitrogen-containing compounds such as β-aminocrotonate, 2-phenylindole, diphenylurea, melamine, dihydropyridine, triazine, and isocyanuric acid derivatives.

Examples of the alcohols and / or their partial esters include pentaerythritol, dipentaerythritol, sorbitol, mannitol, trimethylolpropane, ditrimethylolpropane, pentaerythritol or dipentaerythritol, or their stearic acid partial esters, bis ( Dipentaerythritol) adipate, glycerin, diglycerin, tris (2-hydroxyethyl) isocyanurate, polyethylene glycols, stearyl alcohol and the like.

Examples of the antioxidant include a phenolic antioxidant, a sulfuric antioxidant, and a phosphite antioxidant. Examples of the phenolic antioxidant include 2,6-di-tert-butyl- p-cresol, 2,6-
Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-ditert-butyl-
4-hydroxyphenyl) propionate], 1,6-
Hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2-methylenebis (4-ethyl-6-tert-butyl) Butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butylic acid] glycol ester, 4,4′-butylidenebis (6-tert-butyl-m-cresol), 2,2 '-Ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4-sec-butyl-6-tert-butylphenol), 1,1,3-tris 2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-)
Hydroxybenzyl) isocyanurate, 1,3,5-
Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-
Tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate,
Tetrakis [methylene-3- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionate] methane, 2
-Tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-−２ (3-tert-butyl Butyl-4-hydroxy-5-methylphenyl) propionyloxy {] ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol bis [(3-tert-butyl-4- Hydroxy-5
-Methylphenyl) propionate].

Examples of the sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl and distearyl and β-polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). Alkyl mercaptopropionates can be mentioned.

The phosphite-based antioxidants include:
For example, tris (nonylphenyl) phosphite, tris (2,4-ditertbutylphenyl) phosphite, tris [2-tertbutyl-4- (3-tertbutyl-4-hydroxy-5-methylphenyl) Thio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, monodecyl diphenyl phosphite, mono (dinonyl phenyl) bis (nonyl phenyl) phosphite, Di (tridecyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditertbutylphenyl)
Pentaerythritol diphosphite, bis (2,6-
Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (C _12-15 mixed alkyl)- 4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) Butanetriphosphite, tetrakis (2,4
-Di-tert-butylphenyl) biphenylenediphosphonite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (octyl) phosphite and the like.

The organic phosphite compound also functions as an initial color improver and a heat stabilizer. In the present invention, particularly effective ones include, for example, diphenyldecyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tributyl phosphite, dilauryl acid phosphite, Dibutyl acid phosphite, tris (dinonylphenyl) phosphite, trilauryl thiophosphite, trilauryl phosphite, bis (neopentyl glycol) -1,4-cyclohexanedimethyl phosphite, distearyl pentaerythritol diphosphite, diphenyl Acid phosphite, tetradecyl-1,1,3-tris (2'-methyl-5'-tert-butyl-4'-hydroxyphenyl) butanediphosphite, tetra (C12-C15 mixed alkyl) 4,4'-isopropylidenediphenyl diphosphite, tris (4-hydroxy-2,5-ditert-butylphenyl) phosphite, tris (mono, di-mixed nonylphenyl) phosphite, hydrogenated-4,4 ' -Isopropylidene diphenol polyphosphite, diphenyl bis [4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol)] thiodiethanol diphosphite, bis (octylphenyl) bis [4
4'-n-butylidenebis (2-tert-butyl-5-methylphenol)] thiodiethanol diphosphite, bis (octylphenyl) bis [4,4'-n-butylidenebis (2-tert-butyl-5- Methylphenol)]
-1,6-hexanediol diphosphite, phenyl-4,4'-isopropylidenediphenol pentaerythritol diphosphite, phenyldiisodecylphosphite, tetratridecyl (2-tert-butyl-5-
Methylphenol) diphosphite, tris (2,4-
Di-tert-butylphenyl) phosphite and the like.

Examples of the light stabilizer include hindered amine light stabilizers, for example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6
-Pentamethyl-4-piperidyl stearate, 2,
2,6,6-tetramethyl-4-piperidylbenzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-di-tert-butyl- 4-hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4piperidyl- (3,5-ditert-butyl-4-hydroxyphenyl) propionate, bis (2,2,6,6 -Tetramethyl-4-piperidyl) sebacate, bis (1,2,2
2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4) -Hydroxybenzyl) malonate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl)
Hexamethylenediamine, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetra (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis ( 2,2,6,6-tetramethyl-4-piperidyl) ・
Di (tridecyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) butanetecarboxylate,
3,9-bis [1,1-dimethyl-2- {tris (2,
2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy {ethyl]-
2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2, -tris (1,2,2,6,6-pentamethyl-4- Piperidyloxycarbonyloxy) butylcarbonyloxy {ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,5,8,12-tetrakis [4,6-bis} N- (2 , 2,6,6-Tetramethyl-4-piperidyl) butylamino {-1,3,5-triazin-2-yl] -1,5,8,12-tetraazadodecane, 1- (2-hydroxyethyl ) -2,2,6
6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro-s-triazine / N, N'-bis (2,2,6,6
-Tetramethyl-4-piperidyl) hexamethylenediamine condensate and N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine / dibromoethane condensate.

Examples of the nucleating agent include aluminum-p-tert-butylbenzoate, dibenzylidene sorbitol, bis (4-methylbenzylidene) sorbitol, bis (4
-Tert-butylphenyl) phosphate sodium salt,
2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate sodium salt.

Epoxy compounds are used not only as stabilizers but also as plasticizers, such as epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tung oil, and epoxidized tall oil fatty acid. Esters, epoxidized tallow oil, epoxidized castor oil, epoxidized safflower oil, epoxidized linseed oil fatty acid ester (epoxidized linseed oil fatty acid butyl, etc.), epoxidized stearic acid ester (methyl epoxy stearate,-
Butyl, 2-ethylhexyl or -stearyl), tris (epoxypropyl) isocyanurate,
3- (2-xenoxy) -1,2-epoxypropane,
Epoxidized polybutadiene, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl-6-methylepoxycyclohexanecarboxylate and the like can be mentioned.

Examples of the β-diketone compound include dehydroacetic acid, 1,3-cyclohexadione, methylenebis-1,
3-cyclohexadione, 2-benzyl-1,3-cyclohexadione, acetyltetralone, palmitoyltetralone, stearoyltetralone, benzoyltetralone, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, 2-acetyl-1, 3-cyclohexadione, benzoyl-p-chlorobenzoylmethane,
Bis (4-methylbenzoyl) methane, bis (2-hydroxybenzoyl) methane, benzoylacetone, tribenzoylmethane, diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, lauroylbenzoylmethane, dibenzoylmethane, bis (4-chloro Benzoyl) methane, bis (methylene-3,4-dioxybenzoyl) methane, bis (methylene-3,4-dioxybenzoyl) methane, benzoylacetylphenylmethane, stearoyl (4-methoxybenzoyl) methane, butanoylacetone, Distearoylmethane, bis (4-chlorobenzoyl) methane, bis (methylene-3,4-dioxybenzoyl) methane, bis (methylene-3,4-dioxybenzoyl)
Methane, benzoylacetylphenylmethane, stearoyl (4-methoxybenzoyl) methane, butanoylacetone, distearoylmethane, acetylacetone, stearoylacetone, bis (cyclohexanoyl) methane, dibivaloylmethane, and the like, and metal salts thereof are also included. It is equally useful.

Examples of the β-keto acid ester include ethyl acetoacetate such as methyl acetoacetate, ethyl acetoacetate and propyl acetoacetate, and propionyl acetate such as methyl propionyl acetate and ethyl propionyl acetate.
Examples thereof include benzoyl acetate such as methyl benzoyl acetate and butyl benzoyl acetate, and the most preferable one is acetoacetate.

As the lubricant, (a) a hydrocarbon type such as fluid, natural or synthetic paraffin, microwax, polyethylene wax, chlorinated polyethylene wax and the like; (ii) a fatty acid type such as stearic acid and lauric acid; (C) stearic acid amide, valmitic acid amide,
Fatty acid monoamides or bisamides, such as oleic amide, esylamide, methylenebisstearamide, ethylenebisstearamide, etc .; (d) Esters such as butyl stearate, hydrogenated castor oil, ethylene glycol monostearate , Those based on alcohols such as (e) cetyl alcohol, stearyl alcohol,
(F) Metal soaps such as lead stearate and calcium stearate and (g) mixed systems thereof are generally used, and fatty acid monoamides or bisamides are particularly preferred.

[0068]

EXAMPLES In the following examples, measurement of raw materials and products was performed by the following method. (1) X-ray Diffraction It was measured with Cu-Kα using a Gaugerflex RAD-1B system manufactured by Rigaku Corporation. Target Cu filter Curved crystal graphite monochromator Detector Scintillation counter Voltage 40KV Current 30mA Count full scale 700c / s Smoothing point 25 Scanning speed 1 ° / min Step sampling 0.02 ° Slit DS1 ° RS0.15mm SS1 ° Irradiation angle 6 ° Especially , CSH-1 and ZC which are reaction products of the present invention
The production of SH-1 was determined by the decrease or disappearance of the diffraction peaks of Ca (OH) ₂ or ZnO and the generation of a diffraction peak substantially single detected at 3.0 to 3.1 angstroms.

(2) Infrared absorption spectrum Using a TGS sensor of FTIR8000 manufactured by JASCO Corporation
The absorbance of the transmitted light was measured. The sample was made of KBr powder.
Hard molding and reference of KBr wafer without sample
And measured in an air atmosphere with a relative humidity of 45%. Special
In addition, the presence of fats and oils in the reaction system
1750 ~ 1717cm^-1Absorption of
It was determined by In addition, gold which is a hydrolysis product of fats and oils
The genus soap is formed by anti-symmetric stretching vibration of carboxyl group.
10-1550cm^-1And symmetric stretching vibrations 1240-13
00cm ^-1The determination was made by detecting the absorption peak.

(3) Differential thermal analysis and measurement of condensate rate SSC-5200TG-DTA system manufactured by Seiko Denshi Kogyo. Using the standard substance α-A1 ₂ O ₃ , the rehydration of the reaction product after the heat dehydration was measured. First, about 20mg of sample
Was heated to about 190 ° C. at a heating rate of 20 ° C./min, held for 30 minutes, allowed to cool naturally, and the amount of condensate 25 hours after cooling was measured. Dehydration loss due to heating (TG reading; wt%) = A TG reading after 25 hours (wt%) = B Condensate rate (%) C = 100 (AB) / A Condensate amount (per 100 g of heated sample) G / 100 g) D =
It is defined as 100AC / (100-A).

(4) Liquid chromatography High performance liquid chromatography manufactured by Shimadzu Corporation, Chromatopack CR4A column, Shodex GPC KF
A saponification product was identified by a differential refractometer using a solvent extract obtained by 801 Soxhlet as a sample.

(5) Chemical analysis The chemical analysis was carried out in accordance with the lime chemical analysis method of JIS R9011.

(6) Number average particle size Scanning electron microscope WET-S manufactured by Akashi Beam Technology
Using EM (WS-250), the average particle diameter was obtained by arithmetically averaging the particle diameter (μm) in the selected area image.

(7) Apparent specific gravity Measured according to JIS K-6220.

(8) Specific surface area Polarographic micro-meridics manufactured by Shimadzu Corporation
The measurement was performed using an autopore 9220.

(9) Water absorption After heating and evaporating to dryness, the sample was allowed to cool in a silica gel desiccator, and then placed in a desiccator of a saturated aqueous potassium chloride solution at 25 ° C., and kept at a relative humidity of 85% for 48 hours. %] Was measured.

(10) Oil absorption The oil absorption was measured in accordance with JIS K-5101-19.

(11) X-ray Fluorescence Analysis Metals, Zn, Ca and Si in the product were identified by SEA2001L manufactured by Seiko Denshi Kogyo.

(Calcium-silica composite hydroxide [CSH
Preparation of -1]) A 15 L magnetic ball mill (inner diameter 25 cm, length 30 cm) filled with 5 L of grinding media composed of alumina balls having a diameter of 10 to 20 mm was charged with 2 L of ion-exchanged water and silica having an average particle diameter of 5.0 μm. Acidic compounds (55% by weight of amorphous silica, 39% by weight of crystalline silica, specific surface area 1)
20m ² /g)127.7g, calcium hydroxide (Ca
(OH) ₂ content: 99.9%), and the mill was rotated at room temperature for 60 hours at a rotation speed of 60 rpm for 60 hours in the presence of unreacted calcium hydroxide to obtain a calcium-silica composite hydroxide having a pH of 12.5 to 13.0. A slurry was obtained (Sample A-
1). Identification was by X-ray diffraction. It is shown in FIG.

(Zinc calcium silica composite hydroxide [Z
Preparation of CSH-1] A magnetic ball mill (inner diameter 25 cm, length 30 cm) filled with 5 L of pulverizing medium composed of alumina balls having a diameter of 10 to 20 mm was charged with 2 L of ion-exchanged water and having an average particle diameter of 5.0 μm. 127.7 g of a siliceous compound (55% by weight of amorphous silica, 39% by weight of crystalline silica, specific surface area: 120 m ² / g), 190 g of calcium hydroxide [Ca (OH) ₂ content: 99.9%], and zinc oxide (ZnO content: 99.9%) 31 g was charged, and the mill was rotated at room temperature for 60 hours at a rotation speed of 60 rpm to obtain a zinc calcium silica composite hydroxide having a pH of 12.5 to 13.0 in the presence of unreacted calcium hydroxide. A slurry was obtained (Sample B
-1). Identification was by X-ray diffraction. It is shown in FIG.

(Preparation of Lead Silicate [PbSH]) A magnetic ball mill (inner diameter 25 cm, length 30 cm) having a capacity of 15 L filled with 5 L of pulverizing medium composed of spherical alumina balls having a diameter of 10 to 20 mm was charged with 2 L of ion-exchanged water and lead oxide PbO. 5
10.4 g, 80.4 g of a siliceous compound having an average particle size of 5.0 μm (amorphous silica: 85.8%, specific surface area: 180 m ² )
Was added, and the mill was rotated at room temperature for 60 hours at a rotation speed of 60 rpm. The obtained slurry was transferred to a 5 L beaker, and heated and stirred for 3 hours to obtain a white slurry (Sample C-1). The obtained sample was identified by X-ray diffraction. The X-ray diffraction spectrum is shown in FIG.

(Preparation of Calcium Lead Silicate Hydrate [PbCSH]) A magnetic ball mill (inner diameter 25 cm, length 30 cm) having a capacity of 15 L filled with 5 L of grinding media composed of spherical alumina balls of 10 to 20 mm was charged with 2 L of ion-exchanged water. 513.6 g of lead oxide PbO and a siliceous compound having an average particle size of 5.0 μm (amorphous silica 85.8)
%, Specific surface area 180 m ² ) 80.4 g and purity 99.9
% Of calcium hydroxide, and the same procedure as in the preparation of Sample C-1 was performed to obtain a white slurry of calcium-lead composite hydroxide (Sample D-1). The obtained sample was identified by X-ray diffraction. Fig. 3 shows the X-ray diffraction spectrum.
Shown in

Example 1 80 g of rapeseed oil having a saponification value of 173 was added to the slurry of Sample B-1.
The hydrolysis reaction of the fat and oil and the reaction of the zinc calcium silica composite oxide were continued under grinding at 0 rpm for 15 hours, and the saponification reaction of the fat and oil was terminated in the presence of unreacted calcium hydroxide. The end of the saponification reaction was analyzed by analyzing the infrared spectrum. Further, 51.3 g of activated silicic acid powder having an average particle diameter of 5.0 μm was added, and the mill was rotated for 5 hours.
50 g of dried product was obtained. According to chemical analysis and thermal analysis, the product was found to be zinc calcium silica composite hydroxide; 354 g,
Saponified product: 96 g. This oil and fat saponified compound Z
The measured values of the physical properties of CSH-1 (sample H-1) are shown in Table 1, various performances when incorporated into hard and soft PVC formulations are shown in Tables 2 and 3, and the change of TG (%) with time is shown. FIG.
Shown in

(Example 2) Saponification value 19 as raw material fat
Except for using 80 g of soybean oil of No. 4, the same operation and the same identification method as in Example 1 were performed to obtain a fat / saponified compound ZCSH-1. Such a fat saponified compound ZCSH-1 (sample H-
Table 1 shows the physical properties of 2), and Tables 2 and 3 show various properties when incorporated into the hard and soft PVC compounds.

Example 3 Saponification value of 18 as raw material fat
Except for using 80 g of rice bran oil of No. 5, the same operation and identification as in Example 1 were performed to obtain a fat / saponified compound ZCSH-1. Such an oil / saponified compound ZCSH-1 (sample H-3)
Are shown in Table 1, and various properties when incorporated into hard and soft PVC formulations are shown in Tables 2 and 3.

Example 4 Saponification value of 20 as raw material fat
Except for using 80 g of palm oil of No. 3, the same operation and identification as in Example 1 yielded a fat / saponified compound ZCSH-1. Such a fat saponified compound ZCSH-1 (sample H-
Table 1 shows the physical properties of 4), and Tables 2 and 3 show various properties when incorporated into the hard and soft PVC compounds.

Example 5 Saponification value 19 as raw material fat
Except that fish oil No. 0 was used, the same operation and identification as in Example 1 yielded a fat / saponified compound ZCSH-1. Table 1 shows the physical properties of the oil / saponified compound composite ZCHS-1 (sample H-5).

(Example 6) Saponification value 21 as raw material fat
Except for using 80 g of beef tallow of Example 4, an oil / fat saponified compound ZCSH-1 was obtained by the same reaction operation and identification as in Example 1. Such an oil / saponified compound ZCSH-1 (sample H-6)
Are shown in Table 1, and various properties when incorporated into hard and soft PVC formulations are shown in Tables 2 and 3.

Example 7 An oil / saponified compound ZCSH-1 (sample H-7) was obtained in the same manner as in Example 1, except that the oil / fat material was changed to 10 g of rapeseed oil having a saponification value of 173. . The physical properties of this product are shown in Table 1
Tables 2 and 3 show various performances when incorporated into the C composition.

(Example 8) 300 g of rapeseed oil having a saponification value of 173 and calcium hydroxide (purity: 99.9%)
The same raw materials as in Example 1 except that 258.5 g was used,
By the operation, a saponified oil / fat compound ZCSH-1 was obtained. This product (Sample H-8) has the physical properties, hard and soft PVC
Tables 2 and 3 show various performances when incorporated in the composition.

(Example 9) Activated clay after decolorizing rapeseed oil comprising 40.0% by weight of rapeseed oil (saponification value 150) and 60.0% by weight of activated clay (SiO _2: 77.0% by weight) 200 g of waste clay (the content of reactive silicic acid is 67.5% by weight in waste clay) and calcium hydroxide (purity 99.
(9%) 176.4 g and 2 L of ion-exchanged water in Example 1
And the milling reaction was continued at 60 rpm for 65 hours to obtain a uniform slurry having a pH of 12.6.
In addition to this, activated silica powder having an average particle diameter of 5.0 μm was added.
5 g (water content: 10%, purity: 94.6% by weight) was added, and the ball mill was further rotated for 15 hours to obtain a uniform slurry having a pH of 11.8.
5 g of a dried product were obtained. From the analysis results, the product (sample H-
9) is an active clay component-containing casium silica composite hydroxide; 362.4 g, a saponified product; 88.1 g;
Table 2 and Table 3 show the physical properties and various properties when incorporated into the hard and soft PVC formulations.

(Example 10) Activated clay after decolorization treatment of beef tallow comprising 39.4% by weight of tallow (saponification value 214) content and 60.6% by weight of activated clay (74.8% by weight of SiO ₂ ) The same ball mill as in Example 1 was charged with 200 g of tallow refined waste clay (the content of reactive silicic acid was 63.4% by weight in waste clay), 148 g of calcium hydroxide (purity 99.9%), and 2 L of ion-exchanged water. The milling reaction was continued at 60 rpm for 65 hours to obtain a uniform slurry having a pH of 12.8. Activated silica powder 4 having an average particle size of 5.0 μm was added to this slurry.
8.0 g (water 10%, purity 94.6% by weight) was added, and the ball mill was further rotated for 15 hours to obtain a uniform slurry of pH 12.1. Thereafter, the same procedure as in Example 9 was performed. According to the analysis results, the product (Sample H-10) was composed of 297.6 g of activated silica-containing calcium-silica composite hydroxide and 90.2 g of saponified product. Tables 2 and 3 show various performances in the case of being incorporated in the.

(Example 11) Acid clay (SiO ₂ 70.30) mainly containing montmorillonite which is an aluminosilicate.
150 g, 166.5 g of calcium hydroxide having a purity of 99.9%, and 80 g of soybean oil having a saponification value of 194 were put into a ball mill as in Example 1 together with 2 L of ion-exchanged water, and rotated at 60 rpm for 60 hours. , Average particle size 5.0
69.3 g of active silicic acid powder (water 10%) of μm was added, and the ball mill was further rotated for 15 hours to obtain a uniform slurry of pH 12.1. According to the analysis results, the product (sample H-11) was composed of 370.0 g of a calcium-silica composite hydroxide containing an acid clay component, and 90.6 g of a saponified product.
Tables 2 and 3 show various performances when incorporated into the VC compound.

(Example 12) 4 which is an aluminosilicate
The zeolite A was immersed in 6N hydrochloric acid for 24 hours, washed thoroughly with water, and dried and pulverized to obtain an activated silicic acid powder having an average particle diameter of 15.0 μm, a specific surface area of 280 m ² / g and a purity of 94.3%. 127.3 g of this activated silicic acid powder and a saponification value of 20
Example 3 was carried out in the same manner as in Example 1 except that 100 g of palm oil of No. 3 was used. According to the analysis results, the product (sample H-12) was composed of 360 g of zinc-calcium-silica composite hydroxide and 100.3 g of saponified product. Table 1 shows the physical properties, various properties when incorporated into hard and soft PVC formulations. Table 2 and Table 3
It was shown to.

Example 13 128 g of activated silicic acid powder having an average particle diameter of 5.0 μm (water content: 10%, SiO ₂ purity: 9)
6.5%), 99.9% pure calcium hydroxide 19
3.1 g, 10 g of fish oil having a saponification value of 190 and 2 L of ion-exchanged water were charged into the same ball mill as in Example 1 and reacted under grinding at a rotation speed of 60 rpm for 60 hours. The mixture was charged in a ball mill and reacted under grinding for 24 hours to neutralize excess alkali. Calcium-silica composite hydroxide: 367.1 g, saponification value: 10.6 g
(Sample H-13) was obtained, and the physical properties thereof were shown in Table 1.
Tables 2 and 3 show various performances when incorporated into hard and soft PVC formulations.

Example 14 180 g of activated silica powder having an average particle diameter of 5.0 μm (water content: 10%, SiO ₂ purity: 9)
6.5%), 99.9% pure calcium hydroxide 19
3.1 g, 148.3 g of zinc oxide having a purity of 99.0%, 20 g of fish oil having a saponification value of 190, and 2 L of ion-exchanged water were charged into the same ball mill as in Example 1, and the rotation speed was 60 rpm.
After reaction for 60 hours under milling, an additional 20 g of activated silicic acid powder was again charged into a ball mill, and reacted under grinding for 24 hours to neutralize excess alkali, and 593 g of zinc calcium silica composite hydroxide; 23.9 g of a composite product (Sample H-14) was obtained, and its physical properties are shown in Table 1, and various properties when incorporated into hard and soft PVC compounds are shown in Tables 2 and 3.
It was shown to.

Example 15 15.3 g of activated silica powder having an average particle diameter of 5.0 μm (water content: 10%, SiO ₂ purity: 9)
6.5%), 99.9% pure calcium hydroxide.
8 g and 1.5 L of ion-exchanged water were put in the same ball mill as in Example 1, and rotated at 60 rpm for 20 hours while grinding. Next, 200 g of rapeseed oil having a saponification value of 173 was added, and the mixture was rotated for 50 hours under grinding at a rotation speed of 60 rpm to complete the saponification reaction. Further, 20.1 g of activated silicic acid powder was charged into the ball mill again, followed by grinding for 24 hours. Reaction under crushing to neutralize excess alkali, calcium silica composite hydroxide; 6
3.2 g, saponified product: 235.4 g of a composite product (sample H-15) was obtained, and its physical properties are shown in Table 1, and various properties when incorporated into hard and soft PVC formulations are shown in Tables 2 and 3.
It was shown to.

(Comparative Example 1) 4A zeolite (sample HT
Table 1 shows the powder physical properties of -1), and Tables 2 and 3 show various performances when the powder physical properties were incorporated into hard and soft PVC compounds.

Comparative Example 2 Table 1 shows the powder properties of the activated clay (sample HT-2), and Tables 2 and 3 show various properties when it was incorporated into hard and soft PVC compounds.

Comparative Example 3 Calcium Silicate CSH-1
Table 1 shows the powder properties of (Sample HT-3).
Tables 2 and 3 show various performances when incorporated into the VC compound.

Comparative Example 4 400 g of type 4A zeolite,
200 g of calcium stearate and glycerin 58
g into a 10L super mixer manufactured by Kawada Manufacturing Co., Ltd.
Table 2 shows the various performances when incorporated in the sample HT-4 hard and soft PVC blend mixed for 3 minutes at a rotation speed of 00 rpm.
And Table 3.

(Comparative Example 5) 400 g of activated clay, 200 g of calcium stearate and 58 g of glycerin were charged into a 10 L super mixer manufactured by Kawada Seisakusho at 800 rpm.
Tables 2 and 3 show various properties of the sample HT-5 mixed at a rotation speed of m for 3 minutes when incorporated into a hard and soft PVC compound.

Comparative Example 6 Calcium silicate (CSH-
1) Various performances when 1600 g, 300 g of calcium stearate, and 170 g of glycerin were charged into a 10 L super mixer manufactured by Kawada Seisakusho and mixed at a rotation speed of 800 rpm for 3 minutes into a hard and soft PVC compound of sample HT-6 were mixed. And Table 3.

Comparative Example 7 Calcium silicate (CSH-
1) 1600 g and calcium stearate 300 g were charged into a 10 L super mixer manufactured by Kawada Seisakusho and 800 r
Tables 2 and 3 show various performances of the sample HT-7 mixed at a rotation speed of pm for 3 minutes when incorporated into the hard and soft PVC formulations.

(Example 16) 32 g of beef tallow having a saponification value of 214 was added to the slurry of sample C-1, and the mixture was stirred at room temperature for 60 rpm.
ending the saponification reaction of fats and oils under grinding for 20 hours at pm
The slurry was evaporated to dryness to obtain 622 g of a dried product. The completion of the saponification reaction was determined by analyzing the infrared spectrum.
Table 4 shows the physical properties of the obtained oil / fat saponified compound PbSH (sample H-16), and Tables 5 and 6 show various properties when incorporated into hard and soft PVC compounds.

Example 17 420 g of beef tallow having a saponification value of 214 and 179 g of PbO were added to the slurry of sample C-1, and the mixture was ground at room temperature for 20 hours at 60 rpm. The reaction was terminated, and the slurry was evaporated to dryness to obtain 1205 g of a dried product. The completion of the saponification reaction was determined by analyzing the infrared spectrum. Table 4 shows the physical properties of the obtained oil / fat saponified compound PbSH (sample H-17), and Tables 5 and 6 show various properties when incorporated into hard and soft PVC compounds.

(Example 18) 32 g of beef tallow having a saponification value of 214 was added to the slurry of Sample D-1, and the mixture was stirred at room temperature for 60 rpm.
ending the saponification reaction of fats and oils under grinding for 20 hours at pm
The slurry was evaporated to dryness to obtain 625 g of a dried product. The completion of the saponification reaction was determined by analyzing the infrared spectrum.
Obtained oil / fat saponified compound PbCSH (sample H-18)
Are shown in Table 4, and various properties when incorporated into hard and soft PVC formulations are shown in Tables 5 and 6.

(Comparative Example 8) The powder properties of tribasic lead sulfate (manufactured by Mizusawa Chemical Co., Stavinex Tc, sample HT-8) are shown in Table 4, and various properties when incorporated into hard and soft PVC formulations The results are shown in Tables 5 and 6.

(Comparative Example 9) The powder properties of lead stearate (manufactured by Mizusawa Chemical Co., Ltd., Stavinex NC18, sample HT-9) are shown in Table 4, and various properties when incorporated into hard and soft PVC compounds are shown in Table 5. And Table 6.

Comparative Example 10 Dibasic lead stearate (manufactured by Mizusawa Chemical Co., Ltd., Stabinex C18, sample HT-1)
Table 4 shows the physical properties of the powder of No. 0), and Tables 5 and 6 show the various properties when incorporated into the hard and soft PVC compounds.

(Comparative Example 11) The powder properties of dibasic lead phosphite (Stabinex D, manufactured by Mizusawa Chemical Co., Ltd., sample HT-11) are shown in Table 4, and various properties when incorporated into hard and soft PVC formulations. The performance is shown in Tables 5 and 6.

(Comparative Example 12) The powder properties of lead silicate (manufactured by Mizusawa Chemical Co., Stavinex S, sample HT-12) are shown in Table 4, and various properties when incorporated into hard and soft PVC compounds are shown in Table 5. And Table 6.

(Examples 19 to 26, Comparative Examples 13 to 16)
A predetermined amount (unit: PHR) of a vinyl chloride resin (average degree of polymerization 1050) shown in Table 7 and a saponified oil / fat silicate A
(Example 10, sample H-10), oil / fat saponified compound silicate B (example 2, sample H-2), zinc stearate (manufactured by Mizusawa Chemical, Stavinex NT-Z1), dipentaerythritol (Koei Chemical) Made, dipentaerythritol 30
0), dibenzoylmethane (manufactured by Rhone-Poulenc, Rohde Astab 83), diphenyltridecyl phosphite (manufactured by BorgWarner, XR1518), polyethylene wax (manufactured by Mitsui Petrochemical, Hiwax220MP), hydrotalcite (manufactured by Kyowa Chemical, DHT-4A) and zeolite 4A (Mizukalizer DS, manufactured by Mizusawa Chemical Co., Ltd.) were supplied to a Henschel mixer and uniformly mixed to obtain a vinyl chloride resin composition. The obtained polyvinyl chloride resin composition was molded by a hard polyvinyl chloride molding method described below, and evaluated by a hard polyvinyl chloride evaluation method described below. The results are shown in Table 7.

(Evaluation with Rigid Polyvinyl Chloride) A rigid polyvinyl chloride sheet was prepared by the following methods such as blending and molding, and an evaluation test was conducted. The results obtained for the samples of each of the above examples are shown in the following table. (Formulation 1; applied to samples of Examples 1 to 15 and Comparative Examples 1 to 7) 100 parts by weight of vinyl chloride resin (polymerization degree 1050) 0.5 parts by weight of zinc stearate 0.5 parts by weight of dipentaerythritol adipate Dibenzoylmethane 0.05 parts by weight Polyethylene wax 0.1 parts by weight Sample 2.0 parts by weight (Formulation 2; applied to samples of Examples 16 to 18 and Comparative Examples 8 to 12) Vinyl chloride resin (degree of polymerization 1050) 100 Parts by weight Stearic acid 0.3 parts by weight Polyethylene wax 0.2 parts by weight 2,2-bis (4'-oxyphenyl) propane 0.1 parts by weight Sample 2.0 parts by weight

(Molding method)
Roll mill kneading was performed at 0 ° C. for 6 minutes to prepare a uniform mixture having a thickness of 0.4 mm.
It was heated at 0 kg / cm ² for 5 minutes under pressure to produce a hard vinyl chloride plate having a thickness of 1 mm.

(Test Method) (1) Thermal Stability Duration A 0.4 mm-thick sample plate is hung on a gear-type heat aging tester adjusted to 190 ° C., taken out every 10 minutes, and its coloring degree is visually judged. Then, the time until it was dispersed to dark brown was measured. (2) Foamability Place a 2.5 mm thick sample plate on a stainless steel plate and
After heating for 30 minutes in a gear-type heat aging tester adjusted to 0 ° C., unevenness of the sample plate surface due to foaming was visually determined. (3) Transparency Using a 1001DP color difference meter manufactured by Nippon Denshoku Industries, thickness 0.5
The white light transmittance of the sample sheet of mm was measured. (4) Shallby impact test Shardby impact test method for hard plastics JISK
7111. (5) Dispersibility A sample plate having a thickness of 0.2 mm is placed on a sample stage of an optical microscope.
The particle size distribution of the sample particles dispersed in the sheet within the microscope field of view at a magnification of 60 times when the sample transmitted light is viewed vertically is visually determined. (6) Gelation properties Using Toyo Seiki Labo Plastomill Model; 30R150, 1
At 80 ° C., 40 rpm, a resin amount of 60 g, and 2.4 g of a sample were charged, and the gelation characteristics of each sample were measured. (7) Plate-out property Use Toyo Seiki Labo Plastomill Model;
At 80 ° C., 40 rpm, a resin amount of 60 g, and 2.4 g of a sample were charged, the plate-out property of each sample at the end of gelation was visually determined. The evaluation was performed according to the following criteria. ◎: No plate out ○: With plate out ●: Large plate out

(Evaluation with Soft Polyvinyl Chloride) A soft polyvinyl chloride sheet was prepared by the following blending and molding techniques, and an evaluation test was conducted. For the samples in each of the above examples,
The results obtained are shown in the table below. (Formulation 3; applied to samples of Examples 1 to 15 and Comparative Examples 1 to 7) 100 parts by weight of vinyl chloride resin (degree of polymerization 1050) 50 parts by weight of dioctyl phthalate 0.5 part by weight of zinc stearate 0.25 part by weight of dipentaerythritol 0.25 Parts by weight Bisphenol A 0.1 parts by weight Dibenzoylmethane 0.05 parts by weight Sample 2.5 parts by weight (Formulation 4; applied to samples of Examples 16 to 18 and Comparative Examples 8 to 12) Vinyl chloride resin (degree of polymerization 1050) 100 parts by weight Dioctyl phthalate 50 parts by weight Polyethylene wax 0.2 part by weight 2,2-bis (4'-oxyphenyl) propane 0.1 part by weight Sample 2.0 parts by weight

(Molding method)
Roll mill kneading was performed at 0 ° C. for 6 minutes to prepare a uniform admixture having a thickness of 0.4 mm.
It was heated under pressure of 0 kg / cm ² for 5 minutes to produce a soft vinyl chloride sheet having a thickness of 1 mm.

(Test Method) (1) Thermal Stability Duration A sample plate having a thickness of 0.4 mm was placed on a Teflon plate, and 185
It was put into a gear-type heat aging tester adjusted to ° C., taken out every 15 minutes, and its coloring degree was visually judged, and the time until it was decomposed into black was measured. (2) Thermal stability According to JIS K6723, a sample sheet is 1 mm x 1 m
m, and a test tube equipped with Congo red paper was filled with 2 g of the sample chip, heated to 180 ° C., and the hydrogen chloride desorption time due to the thermal decomposition of vinyl chloride was measured. (3) Electric Insulation The volume resistivity of the sample sheet at 30 ° C. was measured in accordance with JIS K6723. (4) Transparency Using a 1001DP color difference meter manufactured by Nippon Denshoku Industries, thickness 1.0
The white light transmittance of the sample sheet of mm was measured.

[0120]

[Table 1]

[0121]

[Table 2]

[0122]

[Table 3]

[0123]

[Table 4]

[0124]

[Table 5]

[0125]

[Table 6]

[0126]

[Table 7]

[0127]

According to the production method of the present invention, a saponified oil, a siliceous compound and a compound of the Periodic Table II having a PVC heat stabilizing effect can be obtained.
An oxide of a group metal, a group IV metal and / or a group V metal,
At least one selected from the group consisting of hydroxides and reactive salts, reacts competitively under aqueous milling conditions,
The desired stabilizer can be formed. Further, under basic water-based grinding conditions, the frequency of contact between fats and oils and water increases, and the hydrolysis rate of the fats and oils increases as compared with a normal stirring system.
Furthermore, according to the process of the present invention, waste clay and crude oils and fats can be used, and various metal soaps having various molecular weights and degrees of unsaturation can be produced directly from the oils and fats at a low cost and used as a PVC stabilizer. There is. Glycerin and low-molecular-weight metal soap as saponification products of fats and oils are viscous liquids themselves, but calcium silicate with a high specific surface area.
As a result of being chemically and physically adsorbed to the siliceous compound particles mainly composed of hydrates, etc., it becomes in the same form as a stable solid powder, and at the same time, absorbs moisture such as calcium silicate and hydrate which causes foaming of PVC. Also improves complex water. The stabilizer of the present invention is transparent, spontaneous lubrication, non-foaming,
It is also excellent as a highly heat-resistant non-toxic stabilizer for PVC.

[Brief description of the drawings]

FIG. 1 shows a calcium-silica composite hydroxide (CS).
H-1 shows the X-ray diffraction spectra of sample A-1), zinc calcium silica composite hydroxide (ZCSH-1: sample B-1) and calcium hydroxide as a comparison.

FIG. 2 is a graph showing the heating condensate curve (curve 2) of the stabilizer composed of the fat / oil saponified composite silicate of Example 1 of the present invention, the heat condensing curve (curve 1) of the sample B-1 powder, and The change (curve 3) is shown.

FIG. 3: Lead silicate (PbSH; sample C-1), calcium lead silicate hydrate (PbCSH; sample D-)
1) and an X-ray diffraction spectrum of lead oxide PbO are shown for comparison.

FIG. 4 shows an infrared absorption spectrum of each sample. Spectrum 1: air-dried product of the product slurry of Example 1 Spectrum 2: product of Example 1 immediately after heating Spectrum 3: dried product of Example 1, heated to room temperature 7
Product of Example 1 after 7 days at 5% relative humidity

FIG. 5 shows an infrared absorption spectrum of each sample. Spectrum 1: Air-dried product of a composite silicate slurry obtained in the same manner as in Example 1 except that no fats and oils were used. Spectrum 2: Immediately after the air-dried product was heated and cooled.

FIG. 6 shows an infrared absorption spectrum of each sample. Spectrum 1: Sample B-1 by the same operation as in Example 1.
-Dried powder of a uniform slurry of a mixture of urea and calcium stearate (adding about 20% by weight of the air-dried slurry) Spectrum 2: Powder immediately after heating and drying the slurry Spectrum 3: Seven days after the same powder at room temperature and 75% relative humidity Spectra 4: Calcium stearate

──────────────────────────────────────────────────続 き Continuing on the front page (72) Hiroshi Sawada 4-1-21, Nihonbashi Muromachi, Chuo-ku, Tokyo Inside Mizusawa Chemical Industry Co., Ltd. (72) Seiji Wakagi 4-1-1, Nihonbashi Muromachi, Chuo-ku, Tokyo No. Mizusawa Chemical Industry Co., Ltd. (72) Satoru Ota 4-1-1, Nihonbashi Muromachi, Chuo-ku, Tokyo Mizusawa Chemical Industry Co., Ltd. No. Mizusawa Chemical Industry Co., Ltd. (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 27/06 C01B 33/20-33/46

Claims (18)

(57) [Claims] 1. A composition comprising a siliceous compound selected from the group consisting of silicic acid, silicates and aluminosilicates and their acid-treated products and containing a reactive silicic acid, and a fat or oil. , Oxides and hydroxides of metals of Group II, IV and / or V of the Periodic Table which are equal to or greater than the sum of the equivalent of KOH required for saponification of fats and oils and the amount of neutralization of reactive silicic acid And reacting with at least one selected from the group consisting of substances in the presence of water to form a reactive silicic acid
An oil / fat saponified composite silicate, which is converted into a silicate of a group IV metal, a group IV metal, and / or a group V metal, and a saponified product of the fat / oil is supported on a siliceous compound. A method for producing a stabilizer for chlorine-containing polymers, comprising: 2. The method according to claim 1, wherein the siliceous compound contains at least 10% by weight of reactive silicic acid. 3. The method according to claim 1, wherein the siliceous compound has a specific surface area of 10 m ² / g or more. 4. The method according to claim 1, wherein said composition is a composition containing 2 to 99% by weight of a siliceous compound and 1 to 98% by weight of fats and oils based on two components. 5. The method according to claim 1, wherein the composition is waste clay discharged in a fat / oil refining step. 6. The group II metal is an alkaline earth metal and / or
2. The method according to claim 1, wherein the method is zinc. 7. The method according to claim 6, wherein the alkaline earth metal is calcium. 8. The method according to claim 1, wherein the Group IV metal is lead. 9. At least one selected from the group consisting of oxides and hydroxides of a Group II metal, a Group IV metal and / or a Group V metal , and an equivalent of KOH required for saponification of fats and oils. 2. The method according to claim 1, wherein the method is used in an amount of 1.01 to 2000 times by weight. 10. The composition according to claim 1, wherein the composition contains at least one selected from the group consisting of zinc oxides and hydroxides in an amount of 0.1 to 60% by weight based on the siliceous compound. Manufacturing method. 11. The method according to claim 1, wherein the wet mixing is attrition mixing. 12. A siliceous compound particle mainly composed of an amorphous or low-crystalline silicic acid group II metal salt, group IV metal salt and / or group V metal salt of the periodic table; Hydrophobicity of a composition containing a group II metal salt, a group IV metal salt and / or a group V metal salt of a higher fatty acid and glycerin and / or a glycerin derivative retained on pores or surfaces of a siliceous compound A stabilizer for a chlorine-containing polymer comprising an oil / fat saponified compound silicate characterized by comprising particles. 13. A silicic compound in an amount of 1 to 99% by weight based on three components, a metal salt of Group II metal of the Periodic Table of higher fatty acids, and a Group IV metal salt.
13. The chlorine-containing polymer stable material according to claim 12, comprising 0.4 to 97% by weight of a Group V metal salt and / or Group V metal salt and 0.02 to 60% by weight of glycerin and / or a derivative thereof as a glycerin component. Agent. 14. The stabilizer for a chlorine-containing polymer according to claim 12, wherein the Group II metal salt is an alkaline earth metal salt and / or a zinc salt. 15. The stabilizer for chlorine-containing polymers according to claim 12, wherein the Group IV metal salt is a lead salt. 16. The stabilizer for a chlorine-containing polymer according to claim 14, wherein the alkaline earth metal salt is a calcium salt. 17. The method according to claim 17, wherein the stabilizer is at atmospheric pressure or under reduced pressure.
13. Heat-treated at a temperature of 300C to 300C.
The stabilizer for a chlorine-containing polymer according to the above. 18. Per 100 parts by weight of the chlorine-containing polymer,
(A) The fat / saponified compound silicate of claim 12 is 0.1%
To 50 parts by weight, (B) 0.1 to 50 parts by weight of zinc oxide and hydroxide, (C) 0.1 to 25 parts by weight of alcohols and / or partial esters thereof, and (D)
A chlorine-containing polymer composition comprising 0.05 to 5 parts by weight of a β-diketone or a β-keto acid ester compound and / or a phosphite compound.