JP2003171518A - Composite stabilizer particle for chlorine-containing polymer and its resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide composite stabilizer particles for chlorine-containing polymers which exhibit an excellent heat stabilizing action compared to not only the conventional granular composite stabilizer for the chlorine-containing polymers but also powdered composite stabilizers, and its production method. <P>SOLUTION: The composite stabilizer particles for the chlorine-containing polymers can be obtained by grinding and mixing a stabilizer having (A) a non-lead-based inorganic stabilizer, (B) an 8-22C fatty acid or fatty acid salt, and (C) a polyhydric alcohol or its ester as the major components in the presence of water, and then subjecting the resulting mixture to spray granulation, and have a particle size of 3-50 μm. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a lead-free chlorine-containing polymer compounding agent and a chlorine-containing resin composition containing the same. More specifically, lead-free inorganic stabilizer, carbon number C
Is composed of fatty acid zinc consisting of 8 to 22 and composite stabilizer particles containing polyhydric alcohol or its ester as a main component,
The present invention relates to a chlorine-containing polymer composite stabilizer particle having excellent dispersibility in a resin, thermal stability and initial colorability, and a chlorine-containing polymer composition containing the same.

[0002]

2. Description of the Related Art Chlorine-containing polymers such as vinyl chloride resins are colored and colored by dehydrochlorination reaction at high temperature.
Degradation occurs, and it is necessary to add a heat stabilizer to prevent this. Further, in order to plasticize and knead the vinyl chloride resin, it is necessary to add a lubricant, a plasticizer and the like.

These compounding agents must be used in the form of fine powders in order to achieve a uniform and uniform dispersion in the resin used. A so-called one-package compounding agent in which several kinds of these compounding agent powders are blended with respect to a chlorine-containing polymer has an advantage that it is not necessary to individually measure each compounding agent component when kneading each compounding ingredient into a resin, The compounding powder has a drawback that it easily scatters during handling and pollutes the working environment and the living environment. In addition, recently, molding is often performed in a high temperature region, and there is a further demand for a nontoxic material which has heat resistance stability during processing and is suitable for work and use.

As a method of granulating a one-package compounding agent for a chlorine-containing polymer in order to prevent the above-mentioned defect of powder scattering, for example, Japanese Patent Publication No. 42-11491 discloses that fatty acid lead is used alone or in a mixture thereof. The same amount or more of inorganic lead-based stabilizers alone or a mixture thereof is added, and mixed by a wet method to form a heavy complex, which is filtered, dried, and then pulverized or granulated, or spray-dried without filtering. It describes a method for producing a compounding agent for vinyl chloride resins, which is characterized in that it is made into a product in the form of small particles.

Further, Japanese Patent Publication No. 48-3701 discloses that
A mixture of a stabilizer powder having a particle size of 40 microns or less that does not melt at the processing temperature of the chlorine-containing resin and a stabilizer that melts at the processing temperature of the chlorine-containing resin is heated and melted, and the molten mixture is in a heated atmosphere. Characterized in that it is dropped onto a rotating disc and thus the centrifugal force of the disc causes the melt to fly from the disc into spherical particles, the size of the particles being substantially 70 to 200 microns, A method of making spherical stabilizers for chlorine-containing resins is described.

Japanese Patent Publication No. Sho 49-15950 discloses a method of melt-spraying a mixed stabilizer of a fusible metal soap and a refractory stabilizer, which is used as a stabilizer for a vinyl chloride-based resin, by first spraying both of them. Is mixed as a powder, then made into a semi-molten pellet, which is melt-extruded by an extruder and supplied to a spray nozzle of a spray granulator or a rotating disk, to supply a raw material in a spray granulation method. Is listed.

Further, Japanese Patent Publication No. 55-20738 discloses a powdery metallic soap which melts at a processing temperature of a vinyl chloride resin below, a powdery stabilizer which does not melt at the processing temperature and a filler if necessary. A composite stabilizer characterized by being mixed by using an ultra-high speed mixer of 1000 rpm or more to form a molten fluid by heat generated by impact and friction, and being sprayed into an air-cooled chamber under pressure to be granulated. Manufacturing methods are described.

Further, in Japanese Patent Laid-Open No. 6-254845, a heat stabilizer powder for a chlorine-containing polymer and an organic compounding agent powder having a melting point or softening point lower than that of the heat stabilizer are heat-stabilized. 2 to 60 parts by weight of the organic compounding agent per 100 parts by weight of the agent powder are mixed intimately at a temperature lower than the melting point or softening point of the organic compounding agent, and the mixture is melted or softening point of the organic compounding agent. Heating under the condition that the shearing force does not act on the above temperature, supplying the heated mixture to the inner surface side of the annular perforated plate having a large number of independent through holes,
A granular stabilizer for a chlorine-containing polymer, which comprises contacting a rotating roller on the inner surface side of the perforated plate to fill the mixture in the through hole and extracting a granular material from the outer surface of the through hole. The manufacturing method is described.

[0009]

The stabilizer obtained by the above-mentioned granulation method is a fine particle having a high mechanical strength, which is a dense powder of the metal soap in which the powder stabilizer is dispersed.
Upon kneading with the resin, the powder stabilizer can be dispersed in the resin for the first time as the metal soap is melted and dispersed in the resin. Therefore, unless the kneading operation is continued for a long time in a kneading machine such as a kneader roll or an extruder, satisfactory dispersion in the resin cannot be obtained, and the productivity of the resin molded product and the manufacturing cost are reduced. A flaw is recognized in. In addition, as an organic compounding agent such as metal soap is heated to a high temperature above its melting point for a relatively long time, this organic compounding agent is susceptible to thermal deterioration such as so-called "burning",
This may reduce the original performance of the organic compounding agent.

In addition to the above-mentioned problems, the conventional composite type granular stabilizer for chlorine-containing polymer has a heat stabilizing effect in the original composite stabilizer, which is better than that of the mixed powder, in addition to the above problems. However, there is a problem that it tends to decline. That is, according to the long-term research history of the stabilizer for chlorine-containing polymers by the present inventors, when the components and the composition of the composite stabilizer are the same, the heat stability is highest in the case of the mixed powder, and the granular material is In the case of, there is a tendency to decrease to some extent. Thus, in the field of granular stabilizers for chlorine-containing polymers, the advent of particulate composite stabilizers that have better thermal stability than powdered composite stabilizers is highly desired.

Accordingly, the object of the present invention is, of course, as compared with conventional granular composite stabilizers for chlorine-containing polymers.
Another object of the present invention is to provide a chlorine-containing polymer composite stabilizer particle having an excellent heat-stabilizing effect as compared with a powdered composite stabilizer. Another object of the present invention is to produce a granular stabilizer for a chlorine-containing polymer, which exhibits the above-mentioned excellent heat-stabilizing action and dispersibility in a resin and has a particle size of 3 to 50 μm, in a high yield. Another object of the present invention is to provide a method for producing composite stabilizer particles for a chlorine-containing polymer.

[0012]

According to the present invention, (A)
A lead-free inorganic stabilizer, (B) a fatty acid or fatty acid salt having 8 to 22 carbon atoms, and (C) a stabilizer containing a polyhydric alcohol or its ester as a main component were milled and mixed in the presence of water. Then, there is provided a composite stabilizer particle for a chlorine-containing polymer, which is obtained by spray granulation and has a particle size of 3 to 50 μm. Furthermore, in the stabilizer particles of the present invention: 1. The polyhydric alcohol comprises monopentaerythritol and / or dipentaerythritol; The composite stabilizer particle comprises a core composed of an assembly of lead-free inorganic stabilizer particles and a shell of a monopentaerythritol aggregate which covers the assembly of the lead-free inorganic stabilizer, and has a carbon number C of 8 2. containing a fatty acid or fatty acid salt consisting of The composite stabilizer particles, lead-free inorganic stabilizer particles,
3. An agglomerate composed of dipentaerythritol particles and a plurality of fine spherical particles containing a fatty acid or fatty acid salt having a carbon number of 8 to 22; 4. The lead-free inorganic stabilizer comprises type A zeolite. It is preferred that the fatty acid salt consists of zinc stearate.

In the chlorine-containing polymer of the present invention, (A) a lead-free inorganic stabilizer, (B) a fatty acid or a fatty acid salt having a carbon number of 8 to 22 and ( C) It is obtained by milling and mixing a stabilizer containing a polyhydric alcohol or its ester as a main component in the presence of water and then spray granulating, and the particle size is 3 to 50 μm.
There is provided a chlorine-containing polymer composition containing 0.1 to 10 parts by weight of the chlorine-containing polymer composite stabilizer particles. Furthermore, in the chlorine-containing polymer of the present invention: Per 100 parts by weight of the chlorine-containing polymer, a core composed of an assembly of lead-free inorganic stabilizer particles and a shell of a monopentaerythritol aggregate which covers the assembly of the lead-free inorganic stabilizer, and has a carbon number C 1. 0.1 to 10 parts by weight of chlorine-containing polymer composite stabilizer particles containing a fatty acid or a fatty acid salt of 8 to 22. Per 100 parts by weight of the chlorine-containing polymer, lead-free inorganic stabilizer particles, dipentaerythritol particles and carbon number C
Preferably, 0.1 to 10 parts by weight of chlorine-containing polymer composite stabilizer particles containing an aggregate of a plurality of fine spheres containing 8 to 22 fatty acids or fatty acid salts are contained.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The composite stabilizer particles for a chlorine-containing polymer of the present invention include (A) a lead-free inorganic stabilizer, (B) a fatty acid or a fatty acid salt having 8 to 22 carbon atoms and (C). A stabilizer having polyhydric alcohol or its ester as a main component is milled and mixed in the presence of water and then spray-granulated to obtain a particle size of 3 to 50 μm. is there.

That is, in the method for producing composite stabilizer particles for a chlorine-containing polymer of the present invention, first, (A) a lead-free inorganic stabilizer, and (B) a fatty acid or fatty acid salt having 8 to 22 carbon atoms C. And (C) a stabilizer containing a polyhydric alcohol or its ester as a main component in the presence of water at 10 ° C to 95 ° C,
It is preferably ground and mixed at a temperature of 30 ° C to 80 ° C. Here, it is important to emulsify the component (A), the component (B) and the component (C) to form a mixed layer that is compatible with water. To perform this emulsification smoothly (A)
It is preferable that the lead-free inorganic stabilizer contains an alkali metal such as sodium and potassium.When using a lead-free inorganic stabilizer that does not contain an alkali metal, add an alkali metal during milling and mixing. By doing so, it can be emulsified. Next, a slurry in which the components (A), (B) and (C) are mixed is sprayed and granulated in an atmosphere of 100 ° C. to 300 ° C., preferably 150 ° C. to 250 ° C. to form spherical particles of 3 to 50 μm. Composite particles can be obtained.

As a typical example thereof, type A zeolite is used as the lead-free inorganic stabilizer of the component (A), zinc stearate is used as the component (B), and (1) monopenta is used as the polyhydric alcohol (C). When erythritol was used, from the electron micrograph shown in FIG. 1, a core composed of an aggregate of A-type zeolite particles and
Stabilizer particles are obtained which consist of a shell of monopentaerythritol aggregates covering the aggregates of type zeolite (Example 1 below). (2) Next, when dipentaerythritol is used as the polyhydric alcohol (C), from the electron micrographs shown in FIGS. 2 and 3, a plurality of A-type zeolite particles, dipentaerythritol particles and zinc stearate are contained. An agglomerate composed of the fine spherical particles of is obtained (Example 2 described later). (3) Furthermore, in the case of using monopentaerythritol and dipentaerythritol as the (C) polyhydric alcohol, from the electron micrograph shown in FIG. Stabilizer particles are obtained which consist of a shell of monopentaerythritol aggregates which cover the aggregates (Example 3 below).

In the above case, Na-A is used as the A-type zeolite.
Zinc stearate is preferably used as the fatty acid or the fatty acid salt having a carbon number C of 8 to 22 using a type zeolite. Generally, zinc stearate is water-repellent and is not compatible with water, but when it is made to coexist with Na-A type zeolite, it forms a well-mixed uniform phase with water.
It is considered that this is because a part of zinc stearate reacted with the sodium content of zeolite, was soaped, and was emulsified.

In addition, (A) a lead-free inorganic stabilizer, (B) a fatty acid or fatty acid salt having a carbon number of 8 to 22 and (C) a stabilizer containing a polyhydric alcohol or its ester as a main component are water. By milling and mixing (wet pulverization) in the presence of, the components (A) and (C) are finely divided, and the component (B) intervenes therein. Thereby, composite stabilizer particles having good dispersibility and thermal stability when blended with the chlorine-containing polymer can be obtained.

Generally, a slurry obtained by milling treatment such as wet milling is filtered and dried, and it is very hard to mill. However, in the present invention, a particulate stabilizer is obtained by spray granulation after milling and mixing, and the pulverization step is not always necessary. Further, since the stabilizer of the present invention is in the form of particles, it does not generate dust and is excellent in handling.

(A) Lead-free inorganic stabilizer, (B) carbon number C of 8 to 2 of the chlorine-containing polymer composite stabilizer particles of the present invention.
Although the respective components of the fatty acid or fatty acid salt consisting of 2 and (C) polyhydric alcohol or its ester are well known, the thermal stability is improved by combining these three components, and further these three components ( A) component is 30 to 60
By compounding the components in an amount of 5 to 30% by weight of the component (B) and 30 to 60% by weight of the component (C), thermal stability and dispersibility are unexpectedly improved.

When a metal aluminosilicate such as zeolite is used as the (A) lead-free inorganic stabilizer used in the present invention, it has extended thermal stability and sustained hydrogen chloride scavenging ability, but has a warm initial coloration. Have a tendency. In order to neutralize and reduce this initial coloring tendency, it is preferable to use a stabilizer having a cold initial coloring, especially a zinc compound, and (B) a fatty acid having 8 to 22 carbon atoms or a fatty acid. A zinc salt is used. Next, the polyhydric alcohol (C) or its ester is blended with the components (A) and (B) to further extend the thermal stability, further maintain the hydrogen chloride scavenging property, and further delay the occurrence of zinc burning. Can be made. In the present invention, the particles of zeolite are finely pulverized by performing a milling treatment such as wet pulverization, and as shown in Example 11 described later, the thermal stability is further improved as compared with Comparative Example 2 in which zeolite is simply mixed. And the use of a zinc compound also has the advantage that zinc burning can be significantly delayed.

The milling treatment can be carried out using a milling mixer known per se. For example, a vibrating ball mill, a rotary ball mill or the like can be used alone or in combination, but it is not limited to the exemplified ones.

Further, (A) a lead-free inorganic stabilizer and (B) a carbon number C of 8 to 2 per 100 parts by weight of the chlorine-containing polymer.
It is obtained by milling and mixing a fatty acid or fatty acid salt consisting of 2 and a stabilizer (C) whose main component is a polyhydric alcohol or its ester in the presence of water, and then spray granulating. 0.1 to 10 parts by weight of chlorine-containing polymer composite stabilizer particles, characterized in that they are 3 to 50 μm.
A second characteristic is that the chlorine-containing polymer composition preferably contains 0.2 to 5 parts by weight.

(A) Lead-free inorganic stabilizer: (A) of the present invention
As the lead-free inorganic stabilizer, aluminosilicate metal salts such as zeolite, calcium silicate, magnesium hydroxide,
Magnesium carbonate, basic magnesium carbonate, aluminum hydroxide, magnesium silicate, synthetic layered magnesium silicate, talc, hydrotalcite, alkali aluminum complex hydroxide salt, alkali aluminum complex hydroxide carbonate salt, complex metal polybasic Examples thereof include salts, and these may be used alone or in combination of two or more. Type A zeolite is preferably used.

[Aluminosilicate Metal Salt] Examples of the aluminosilicate metal salt include layered aluminosilicates, particularly various clay minerals, tectosilicates and zeolites. Zeolites are not limited to natural and synthetic, for example,
A-type, X-type, Y-type, Pc-type, L-type zeolite, etc., analcime, chabazite, mordenite, erionite, clinoptilolite are used, and naturally Ca, Zn, Mg, Sn,
Those ion-exchanged with ions such as Ti and Pb can also be used. Generally, the cation exchange capacity of A-type zeolite is 400
~ 550 meq / 100g, about 370 meq / 10 for Y-type zeolite
0g, about 470 meq / 100g in X type Zeolaoto. In particular, type A zeolite, preferably Na-A type zeolite, is used.

[Calcium silicate] Examples of calcium silicate include tobermorite and xonotlite, among which microcrystalline calcium silicate is preferable.

Microcrystalline calcium silicates are generally 4
It has a particle size distribution such that particles having a particle size of 0 μm or more are 10% by weight or less of the whole particles and particles having a particle size of 20 μm or less are 50% by weight or more of the entire particles. It is preferable in terms of dispersion and heat stabilization effect. Also,
This microcrystalline calcium silicate has a particle size of 60 to 200 m ² / g, especially 70 to 1 in relation to the above-mentioned grain structure.
Relatively large specific surface area of 50 m ² / g, 0.5 ml /
g or more, especially 1.0 to 4.0 ml / g pore volume, and 50 to 250 ml / 100 g, especially 80 to 200
It has an oil absorption of ml / 100 g.

The microcrystalline calcium silicate can be produced by pulverizing amorphous activated silicic acid in lime milk, but of course the production method is not limited to this.

[Hydrotalcite] Hydrotalcite is a synthetic mineral belonging to aluminum magnesium carbonate hydroxide and has the general formula (1) M ² _x M ³ _y (OH) _{2x + 3y-2z} (A ^2- ) _z. aH ₂ O (1) In the formula, M ² is a divalent metal ion such as Mg, M ³ is a trivalent metal ion such as Al, and A ²⁻ is a divalent metal ion such as CO _3.
It is a valent anion, x, y and z are positive numbers satisfying 8 ≧ x / y ≧ 1/4 and z / (x + y)> 1/20, and a is 0.25 ≦ a /
It is a number that satisfies (x + y) ≦ 1.0. A complex metal hydroxide having is used.

Among these complex metal hydroxides, the compound represented by the formula (2) Mg ₆ Al ₂ (OH) ₁₆ (CO ₃ ) .4H ₂ O (2) is a natural compound known as hydrotalcite. Minerals, and these minerals and their homologues are related to Kyowa Chemical Industry Co., Ltd.
JP-B-48-29477 and JP-B-48-29478
It is synthesized by the method described in the publication.

These hydrotalcites, particularly the compound represented by the formula (3) Mg _4.5 Al ₂ (OH) ₁₃ (CO ₃ ) .3H ₂ O (3), are excellent in chlorine ion scavenging performance. It is already known that this is present, and this can also be used as (D) of the present invention.

By utilizing the property that these hydrotalcites are easily ion-exchanged in a state where they are sufficiently dispersed in water, that is, carbonate ion is ion-exchanged with other anion, the perhalogen oxygen is utilized. What introduced the acid ion can also be used.

[Lithium / aluminum hydroxide carbonate] Lithium / aluminum composite hydroxide carbonate (LA
HCS) is said to have lithium ions penetrating into vacancies of an aluminum hydroxide octahedron layer having a gibbsite structure and an anion incorporated therein to supplement the charge. That is, it is recognized that the lithium ion has the smallest ionic radius among the cations, and since it is exceptionally a hexacoordinate ion as a monovalent ion, it enters the above vacancy and has the above structure.

[0034] Inorganic Lithium aluminum hydroxide carbonate salt is represented by the following formula _(4), mAl in _{2 O 3 · nM 2 O ·} X · kH 2 O ‥‥ (4) equation, X is composed mainly of carbonate groups Is an anion of
M is an alkali metal mainly composed of lithium, m is a number of 1.5 to 2.5, n is a number of 0.1 to 1, and k is a number of 0 to 10. Has a composition that is

The lithium aluminum hydroxide carbonate particles have a volume-based median diameter (D ₅₀ ) of generally 0.1 to 10 μm, particularly 0.1 to 3 μm, as measured by a laser scattering diffraction method. What is JIS K6
0.1 to 0.35 g / cm ³ , measured at 721,
In particular, it is preferable to have a bulk density of 0.25 to 0.35 g / cm ³ , to have a BET specific surface area of 10 to 70 m ² / g, and to have a small oil absorption of 40 to 70 ml / 100 g.

The lithium-aluminum hydroxide carbonate is not limited to this, of course, but an amorphous or pseudo-boehmite hydrated alumina gel and a lithium carbonate or bicarbonate may be used. In an aqueous medium, alumina (A
The method of reacting under the conditions that the concentration as l ₂ O ₃ ) becomes 1 to 5% by weight and the pH at the end of the reaction becomes 7 to 11 (hereinafter sometimes simply referred to as hydrated alumina gel method)
Alternatively, a method of reacting fine particles of gibbsite type aluminum hydroxide with a lithium salt of carbonic acid or a combination of a lithium compound capable of forming a carbonate ion and a lithium ion and a carbonate in the presence of water, that is, a migration method. Manufactured.

Further, examples of the alkali aluminum hydroxide carbonate used in the present invention include dawsonite type sodium aluminum hydroxide carbonate, which may be used alone or in combination with lithium aluminum hydroxide carbonate. It can also be used in the form of crystals.

(B) Fatty acid or fatty acid salt having 8 to 22 carbon atoms: (B) Fatty acid or fatty acid salt having 8 to 22 carbon atoms of the present invention, particularly saturated or unsaturated fatty acid having 14 to 18 carbon atoms Examples of the metal soap include alkali metal salts such as sodium salt and potassium salt; calcium salt,
Alkaline earth metal salts such as magnesium salt and barium salt,
Zinc salt or the like is used. These may be used alone or in combination of two or more, and among them, zinc salt is preferable. As the fatty acid of the metal soap, for example, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, saturated fatty acids such as arachidic acid, linderic acid, tsuzuic acid, petroselinic acid, oleic acid, linoleic acid. Unsaturated fatty acids such as acids, linolenic acid and arachidonic acid are used. Of these, stearic acid is preferable. The fatty acids may of course be mixed fatty acids such as beef tallow fatty acid, coconut oil fatty acid and palm oil fatty acid.

[0039] In particular, zinc salts are preferable, and metal salts of aluminosilicates such as the above-mentioned zeolites, and lead-free inorganic stabilizers such as calcium silicate are generally used as the zinc salt. Although it has scavenging properties, it has a warm-colored initial coloring tendency, so in order to neutralize and mitigate this initial coloring tendency, it has a cold-colored initial coloring tendency. This is because stabilizer particles can be obtained. When a compound other than a zinc salt is used, coloring can be suppressed by adding a zinc compound and / or a perchlorate compound at the time of compounding the resin.

(C) Polyhydric alcohol or its ester:
Examples of the (C) polyhydric alcohol or ester thereof of the present invention include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, glycerin, diglycerin, Examples thereof include dipentaerythritol, mannitol, sorbitol, trimethylolpropane, ditrimethylolpropane, tris isocyanurate, monopentaerythritol, and dipentaerythritol adipate. Preferably,
Monopentaerythritol and dipentaerythritol are used. The polyhydric alcohols or esters thereof may be used alone or in combination of at least one selected from them.

Other compounding agent: The chlorine-containing polymer composition of the present invention may be compounded with a compounding agent for chlorine-containing polymer known per se in accordance with a formulation known per se.
For example, the compositions of the present invention include plasticizers, lubricants, fillers,
Colorants, weather resistance stabilizers, anti-aging agents, light stabilizers, UV absorbers, antistatic agents, flame retardants, impact toughening agents, modifying resins and rubbers, basic inorganic metal salts, perchlorates, epoxy compounds. , Known antistatic agents, fatty acid esters, known stabilizers such as tin-based agents, and known resin compounding agents such as antibacterial agents, colorants, chelating agents, antioxidants, etc. can be added according to a method known per se. Further, in order to prevent initial coloring and zinc burning, β-diketone, β-keto acid ester, perchloric acid, perchlorate or dihydropyridine derivative can be further added.

[Chlorine-Containing Polymer Composition] Examples of the chlorine-containing polymer include polyvinyl chloride, polyvinylidene chloride, chlorinated polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-acetic acid. Vinyl copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-
Vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, chlorinated vinyl-propylene chloride copolymer, vinyl chloride -Vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, Polymers such as internally plasticized polyvinyl chloride, and these chlorine-containing polymers and α-olefin polymers such as polyethylene, polypropylene, polybutene, poly-3-methylbutene or ethylene-vinyl acetate copolymers, ethylene-propylene copolymers Polymers such as polyolefins and their copolymers, polymers Styrene, acrylic resin, copolymer of styrene and other monomer (for example, maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymer, acrylic ester-butadiene-styrene copolymer, methacryl Examples thereof include blends with acid ester-butadiene-styrene copolymer.

The chlorine-containing polymer composition of the present invention can be molded and processed by various molding methods such as extrusion molding, injection molding, compression molding, inflation, calendering, coating after mixing or mixing by a known method. You can Further, in the oxygen-free molding method of the present invention, coloring can be prevented by carrying out in an atmosphere that does not come into contact with air as much as possible or further in an inert gas atmosphere.

[0044]

The present invention will be described in more detail by the following examples. The test method was as follows.

(Measurement Method) (1) Average Particle Size Representative particles were selected from the photographic images obtained by a scanning electron microscope (S-570 manufactured by Hitachi), and the particle size was measured.

(2) Gear Oven Heat Resistance Test (Static Thermal Stability) (For Hardness) The composition shown in the following Formulation 1 was kneaded by a roll mill at a temperature of 160 ° C. for 3 minutes to give a uniform hard vinyl chloride having a thickness of 1 mm. A sheet was prepared, and then the test piece was placed in a gear oven set at 185 ° C., and the blackening time was measured. (Compound 1) Vinyl chloride resin (degree of polymerization = 1050) 100 parts Compound sample (see table) 2.7 parts

(3) Gear Oven Heat Resistance Test (Static Thermal Stability) (For Softness) The composition shown in Formula 2 below was kneaded with a roll mill at a temperature of 150 ° C. for 5 minutes to give a uniform soft vinyl chloride film having a thickness of 1 mm. A sheet was prepared, and then the test piece was placed in a gear oven set at 185 ° C., and the blackening time was measured. (Compound 2) Vinyl chloride resin (degree of polymerization = 1050) 100 parts Di-2-ethylhexyl phthalate 50 parts Compound sample (see table) 2.7 parts

(4) Thermal stability test (HT chlorine scavenging ability) JIS. K. According to 6723, the soft vinyl chloride sheet of the above-mentioned formulation 2 was cut into 1 mm × 1 mm, and a test tube equipped with Congo red paper was filled with 2 g of the sample chip, 180
After heating to ℃, the hydrogen chloride desorption time by the thermal decomposition of vinyl chloride was measured.

As the lead-free inorganic stabilizer used in the examples,
The following items were used. [Aluminosilicate metal salt] 4A zeolite (Mizukalyzer DS manufactured by Mizusawa Chemical Co., Ltd.) Average particle size: 2.15 μm [Calcium silicate] Microcrystalline calcium silicate (manufactured by Mizusawa Chemical Co., Ltd.) Chemical composition: CaO.1.25SiO ₂ 0.58H ₂ O average particle diameter: 4 μm

(Examples 1 to 5) Water was added to each substance in the proportions shown in Table 1 and the mixture was ground and mixed at 50 ° C., and then spray granulated to obtain composite stabilizer particles. In addition, each sample is shown in Table 1.
The sample name is as shown in. In addition, SE of sample S-1
The M photograph is shown in FIG. 1, and the SEM photograph of the sample S-2 is shown in FIGS.
4 shows the SEM photograph of Sample S-3, respectively.

[0051]

[Table 1]

(Examples 6 to 10, Comparative Example 1) The ingredients were blended in the proportions shown in Table 2, and the gear oven heat resistance test (for hard) was measured. The results are shown in Table 2.

[0053]

[Table 2]

(Examples 11 to 13, Comparative Examples 2 to 4) Table 3
The mixture was blended in the ratio shown in, and the gear oven heat resistance test (for softness) and the chlorine capturing ability were measured. The results are shown in Table 3.

[0055]

[Table 3]

[0056]

According to the present invention, (A) a lead-free inorganic stabilizer, (B) a fatty acid or fatty acid salt having a carbon number of 8 to 22 and (C) a polyhydric alcohol or its ester are main components. The stabilizer is obtained by milling and mixing in the presence of water and then spray granulating, and the particle size is 3 to 50 μm.
It has succeeded in producing composite stabilizer particles for a chlorine-containing polymer. In addition, by blending the composite stabilizer particles with a chlorine-containing polymer resin, not only compared with conventional granular chlorine-containing polymer composite stabilizers, but also excellent as compared with powder composite stabilizers. It also showed a heat stabilizing effect. Further, according to the present invention, the above-mentioned granular stabilizer for chlorine-containing polymer can be produced in a high yield.

[Brief description of drawings]

FIG. 1 is a SEM photograph of the composite stabilizer particles for a chlorine-containing polymer according to the present invention, obtained in Example 1 (magnification: 2000
Times).

FIG. 2 is an SEM photograph of the composite stabilizer particles for a chlorine-containing polymer according to the present invention, obtained in Example 2 (magnification: 2000
Times).

FIG. 3 is an SEM photograph of the composite stabilizer particles for a chlorine-containing polymer according to the present invention obtained in Example 2 (magnification: 10000).
Times).

FIG. 4 is a SEM photograph (magnification: 2000) of the chlorine-containing polymer composite stabilizer particles of the present invention obtained in Example 3.
Times).

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09K 15/06 B01J 13/02 Z (72) Inventor Kazunori Sakao 1-13-6 Nihombashi Muromachi, Chuo-ku, Tokyo Issue Mizusawa Chemical Co., Ltd. F term (reference) 4G004 EA00 4G005 AA01 BA14 DA18X DC18Y DC26Y EA06 4H025 AA01 AA14 4J002 AC121 BB241 BD041 BD051 BD061 BD071 BD101 BD181 BF021 BH021 DJ006 FB086 FB236 FB246 FD20

Claims (9)

[Claims] 1. (A) a lead-free inorganic stabilizer, (B) a fatty acid or fatty acid salt having 8 to 22 carbon atoms, and (C)
Chlorine characterized in that it is obtained by milling and mixing a stabilizer containing polyhydric alcohol or its ester as a main component in the presence of water and then spray granulating, and the particle size is 3 to 50 μm. Composite stabilizer particles for polymers containing. 2. The composite stabilizer particle for a chlorine-containing polymer according to claim 1, wherein the polyhydric alcohol is composed of monopentaerythritol and / or dipentaerythritol. 3. The composite stabilizer particle comprises a core composed of an assembly of lead-free inorganic stabilizer particles and a shell of a monopentaerythritol aggregate which covers the assembly of lead-free inorganic stabilizer particles, and The composite stabilizer particle for a chlorine-containing polymer according to claim 2, which contains a fatty acid or a fatty acid salt having a carbon number C of 8 to 22. 4. The composite stabilizer particle comprises a lead-free inorganic stabilizer particle, a plurality of fine spherical particles containing dipentaerythritol particles and a fatty acid or fatty acid salt having a carbon number of 8 to 22. The composite stabilizer particles for a chlorine-containing polymer according to claim 2, which are aggregates. 5. The composite stabilizer particles for a chlorine-containing polymer according to claim 1, wherein the lead-free inorganic stabilizer comprises an A-type zeolite. 6. The composite stabilizer particles for a chlorine-containing polymer according to claim 1, wherein the fatty acid salt comprises zinc stearate. 7. Per 100 parts by weight of the chlorine-containing polymer,
(A) a lead-free inorganic stabilizer, (B) a fatty acid or fatty acid salt having a carbon number of 8 to 22 and (C) a stabilizer containing a polyhydric alcohol or its ester as a main component are abraded in the presence of water. 0.1 to 10 parts by weight of chlorine-containing polymer composite stabilizer particles obtained by crushing and mixing and then spray granulation, wherein the particle size is 3 to 50 μm. Chlorine-containing polymer composition. 8. A core comprising an aggregate of lead-free inorganic stabilizer particles and a shell of a monopentaerythritol aggregate covering the aggregate of lead-free inorganic stabilizer per 100 parts by weight of a chlorine-containing polymer. And a chlorine-containing polymer composition containing 0.1 to 10 parts by weight of composite stabilizer particles for a chlorine-containing polymer containing a fatty acid or a fatty acid salt having a carbon number of 8 to 22. 9. From 100 parts by weight of a chlorine-containing polymer, lead-free inorganic stabilizer particles, dipentaerythritol particles, and a plurality of fine spherical bodies containing a fatty acid or a fatty acid salt having a carbon number of 8 to 22. A chlorine-containing polymer composition comprising 0.1 to 10 parts by weight of the composite stabilizer particles for a chlorine-containing polymer containing the agglomerate.