JP3153636B2 - Compounding agent for chlorine-containing polymer 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 compounding agent for improving the dimensional stability and thermal stability of a chlorine-containing polymer, and also relates to a chlorine-containing polymer composition having improved physical properties. Related.

[0002]

2. Description of the Related Art A chlorine-containing polymer such as a vinyl chloride resin undergoes an intramolecular dehydrochlorination reaction when exposed to heat, and the generated hydrogen chloride serves as a catalyst to accelerate this reaction, so that a polyene structure is formed. It occurs in the molecule and causes coloration and deterioration of physical properties. In order to prevent this, it has been long practiced to blend various heat stabilizers of inorganic, organic or combination thereof into the chlorine-containing polymer.

It is already known to use various magnesium compounds as one kind of inorganic stabilizers. For example, Japanese Patent Publication No. 53-31500 discloses that magnesium silicate, magnesium carbonate or aluminate is added to colored polyvinyl chloride. It is described that magnesium and an organotin-based stabilizer are blended. Further, Japanese Patent Publication No. 52-32899 proposed by the applicant of the present application discloses a metal silicate having a polyvalent hydroxyl group contained in a porous group II to IV metal silicate, which is made of chlorine. It has been shown to be used as a heat stabilizer for contained polymers.

[0004]

Problems with the Invention The chlorine-containing polymer, particularly the chlorine-containing polymer having a soft composition, has a problem of poor thermal stability, but also has a problem of poor dimensional stability when exposed to heat. This is an important issue. In general, it is a well-known fact that various inorganic fillers are blended in order to improve the dimensional stability of thermoplastics. Then, there is a problem that elongation becomes small and the toughness of the compounded composition is reduced.

The inventors of the present invention have proposed that a homogeneous composition containing a crystalline synthetic layered magnesium phyllosilicate and an excess of magnesium hydroxide or magnesium oxide in which the molar ratio of SiO ₂ / MgO is in a specific range is chlorine-containing. When blended with a polymer, the dimensional stability of the molded product can be significantly improved without reducing the mechanical strength, elongation, and toughness, and the thermal stability of the blended composition is also significantly improved. I found that I got it.

[0006] That is, an object of the present invention is to provide a compounding agent capable of remarkably improving the dimensional stability and the thermal stability of a molded article without deteriorating the mechanical properties of a chlorine-containing polymer. To be. It is another object of the present invention to provide a chlorine-containing polymer composition in which the above-mentioned improvement is achieved by adding a relatively small amount of a magnesium-based inorganic compounding agent.

[0007]

According to the present invention, the molar composition ratio of SiO ₂ / MgO is in the range of 0.25 to 1.33 and the interplanar spacing (angstrom) is provided.
4.5-4.6, 2.5-2.6 and 1.5-1.6
A compounding agent for a chlorine-containing polymer is provided which comprises a homogeneous mixture of a crystalline synthetic layered magnesium phyllosilicate having an X-ray diffraction peak in a range and an excess of magnesium hydroxide or magnesium oxide.

According to the present invention, there is also provided a chlorine-containing polymer
0 parts by weight per the range molar ratio of _SiO 2 / MgO is 0.25 to 1.33 as a whole and a surface interval
(Angstrom) 4.5-4.6, 2.5-2.6
And a homogeneous mixture of a crystalline synthetic layered magnesium phyllosilicate having an X-ray diffraction peak in the range of 1.5 to 1.6 and an excess of magnesium hydroxide or magnesium oxide. A chlorine-containing polymer composition having improved dimensional stability and thermal stability, characterized in that it is blended in an amount of from 20 to 20 parts by weight.

[0009]

The compounding agent for a chlorine-containing polymer of the present invention is characterized by being composed of a homogeneous composition of a crystalline synthetic layered magnesium phyllosilicate and an excess of magnesium hydroxide or magnesium oxide. The crystalline synthetic layered magnesium phyllosilicate has, as described in, for example, Japanese Patent Publication No. 3-51651, a compound represented by the formula

## STR1 ## _{Mg 3 Si 4 O 1 0 (} OH) in ₂ · nH ₂ O type n is a number of 5 or less, in represented by composition, i.e. S
It has a molar composition of iO ₂ /MgO=1.33, and has an interplanar spacing of 4.5 to 4.6, 2.5 to 2.6, and 1.5 to 1.
6 has an X-ray diffraction peak. The compounding agent of the present invention contains an excess of magnesium hydroxide or magnesium oxide in addition to the synthetic layered magnesium phyllosilicate.

According to the present invention, a homogeneous composition containing the synthetic layered magnesium phyllosilicate and an excess of magnesium hydroxide or magnesium oxide is blended with a chlorine-containing polymer to compare them in the same amount. When blending magnesium phyllosilicate alone, or without reducing the mechanical properties as compared with the case where magnesium hydroxide or magnesium oxide alone is blended, dimensional stability and heat resistance can be significantly improved. .

That is, as shown in the examples described later, when the synthetic layered magnesium phyllosilicate alone or a compound containing an excess of silicic acid is added, the tensile strength is increased but the elongation is decreased as compared with the uncompounded one. However, as a whole, the work of rupture is not improved, and the strength and elongation of the composition containing magnesium hydroxide are almost the same as or slightly improved from those of the composition without magnesium hydroxide. In accordance with the invention comprising a synthetic layered magnesium phyllosilicate and excess magnesium hydroxide or magnesium oxide,
Strength and elongation are also improved compared to those not blended,
It is clear that the work of rupture has also increased considerably.

Further, according to the present invention, those containing a synthetic layered magnesium phyllosilicate and an excess of magnesium hydroxide or magnesium oxide are more than 10 minutes in a heat resistance test at 180 ° C. as compared with those using either alone. It is evident that the blackening time is prolonged, and the dimensional stability test at the same temperature for 30 minutes suppresses the area increase and decrease to 30% or less and the volume increase and decrease to 30% or less.

In the present invention, it is also important that the magnesium silicate combined with magnesium hydroxide or magnesium oxide is a synthetic layered magnesium phyllosilicate. The effect of the invention cannot be obtained. In the present invention, it is also important that the overall molar ratio of SiO ₂ / MgO is in the range of 0.25 to 1.33, particularly 0.3 to 1.0. When it is lower or higher than the above range, the mechanical properties, dimensional stability and thermal stability intended in the present invention cannot be improved.

In the present invention, it is believed that the reason why the above-mentioned improvement is made is that the key lies in the existence of excess magnesium hydroxide or magnesium oxide on the surface or extremely around the synthetic layered magnesium phyllosilicate fine particles.
FIG. 1 is an X-ray diffraction image of the composition used in the present invention,
In addition to the characteristic peak (F) based on the synthetic layered magnesium phyllosilicate, a characteristic absorption peak (M) based on magnesium hydroxide is observed.

In the composition of the present invention, the magnesium hydroxide or magnesium oxide present around the synthetic layered magnesium phyllosilicate promotes the atomization and dispersion of the synthetic phyllosilicate in the chlorine-containing polymer, and It is presumed that it promotes some kind of bonding between the layered magnesium phyllosilicate fine particles and the chlorine-containing polymer. The compounding agent of the present invention is based on 100 parts by weight of the chlorine-containing polymer.
The above properties can be improved by adding a relatively small amount such as 0.5 to 20 parts by weight, particularly 1 to 6 parts by weight.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION

(Homogeneous composition) In the composition used in the present invention, a crystalline layered magnesium phyllosilicate and an excess of magnesium hydroxide or magnesium oxide are present as a homogeneous composition. The homogeneous composition means that the crystalline layered magnesium phyllosilicate and the excess magnesium hydroxide or magnesium oxide are in a physically inseparable state, but are present in a chemically separate state. .

The presence of the magnesium component in the form of crystalline layered magnesium phyllosilicate and magnesium hydroxide or magnesium oxide is confirmed from an X-ray diffraction image as shown in FIG. The crystalline layered magnesium phyllosilicate has an interplanar spacing (angstrom) of 4.5 to 4.5.
It has diffraction peaks at 4.6, 2.5-2.6 and 1.5-1.6, while magnesium hydroxide has an interplanar spacing (angstrom) of 4.7-4.8, 2.36. ~
2.37, 1.79-1.80, 1.57-1.58
And the diffraction peaks at 1.49 to 1.50, the presence of both can be confirmed. The X-ray diffraction peak intensity of the crystalline layered magnesium phyllosilicate naturally changes depending on the degree of crystallization, while the crystallinity of the crystalline layered magnesium phyllosilicate varies. It is difficult to calculate the respective ratios.

The overall molar ratio of SiO ₂ / MgO in the homogeneous composition of the present invention is from 0.25 to 1.33,
In particular, in the range of 0.3 to 1.0, in the present invention, the magnesium component present as crystalline layered magnesium phyllosilicate and the magnesium component present as magnesium hydroxide or magnesium oxide have a difference in reactivity. Utilizing that there is, it is possible to obtain the ratio between the two. That is, the total magnesium content present in the homogeneous composition is leached by reacting the composition with an acid, and its amount can be determined, while the excess magnesium hydroxide or magnesium oxide is As shown in the examples described later, the compound is eluted by reacting with 1 mol of ammonium chloride, so that the amount ratio of the excess magnesium to the total magnesium can be determined by using this. The amount of magnesium hydroxide to magnesium oxide is determined from the excess magnesium content ratio, and the amount of the crystalline layered magnesium phyllosilicate is determined from the remaining amount and the molar ratio of SiO ₂ / MgO.

In the present invention, an excess of magnesium hydroxide or magnesium oxide is contained in the homogeneous composition in an amount of 0.1 to 9%.
It is preferably present at 0% by weight, especially 10-70% by weight. That is, when the amount of excess magnesium hydroxide or the like is less than the above range, the dispersibility of the composition in the polymer is low, and the effect of improving mechanical strength and dimensional stability is small, while the amount is smaller than the above range. If the amount is large, the effect of improving mechanical strength and dimensional stability is also small, and the effect of thermal stabilization is also small.

The crystalline layered magnesium phyllosilicate contained in the composition of the present invention comprises two MgO ₆ octahedral layers.
The basic structure mainly includes a three-layer structure sandwiched by two SiO ₄ tetrahedral layers, and this basic structure is formed by laminating a large number of layers. In that many basic structures including a SiO ₄ tetrahedral layer are stacked, the structure is common to clay minerals, but compared to natural clay minerals,
It has an advantage in that the acidity as a solid acid is low and the chlorine-containing polymer is less likely to be colored.

The homogeneous mixture used in the present invention is 1 to 10 μm , especially 3 to 5 μm , as measured by a Coulter counter.
Although it has a rather large particle size of μm , its BET specific surface area is 100 to 600 m ² / g, particularly 150 to 500 m ² / g.
It is relatively large at m ² / g and has excellent surface activity. The oil absorption is 50 to 100 ml / 100 g , particularly 60 to 90 ml / 100 g , which is in a range suitable for blending with resin.

(Synthesis of Homogeneous Composition)
Amorphous silicic acid and magnesium hydroxide or magnesium oxide or a magnesium compound that becomes magnesium hydroxide under the reaction conditions, crystalline synthetic layered magnesium phyllosilicate is generated, but excess magnesium hydroxide or magnesium oxide remains. It is synthesized by reacting under such conditions. For this purpose, a quantitative ratio of amorphous silicic acid to magnesium hydroxide or the like is such that the molar ratio of SiO ₂ / MgO is in the range of 0.25 to 1.33, especially 0.5 to 1.0. It is important to carry out the reaction under the conditions described above, and the reaction conditions should not be selected so that the entire magnesium component is incorporated into the crystalline synthetic layered magnesium phyllosilicate.

As the raw material for silicic acid, any one may be used as long as it is amorphous. However, those having surface activity are preferred, and commercially available amorphous silicic acid and those obtained by acid treatment of clay minerals can be used. Activated silicic acid is used. This silicic acid material is generally B
Preferably, the ET specific surface area is in the range of 50 to 300 m ² / g. Active silicic acid obtained by acid treatment of a clay mineral is composed of a fine silica thin layer and has a fine structure suitable for synthesizing the layered phyllosilicate having the fine structure described above.

That is, the layered clay mineral is generally based on a two-layer or three-layer structure in which a tetrahedral layer of SiO _{4 and} an octahedral layer of AlO ₆ or the like are combined in a layered manner, and these basic structures are further laminated. Has a structure. When these clay minerals are acid-treated, the octahedral layer of AlO ₆ is extracted as a soluble salt by reaction with the acid, and its crystal structure is substantially destroyed, but the tetrahedral layer of SiO ₄ has a still fine layered structure. In the form of an active silica.

As the clay mineral, a smectite-group clay mineral, for example, a so-called montmorillonite-group clay mineral such as acid clay, bentonite, sub-bentonite, and flource earth; Is preferably used. Clay minerals other than the above, for example, kaolin group clay minerals such as kaolin and halloysite, and chain clay minerals such as attapulgite, sepiolite, and palygorskite can be used. The acid treatment of the clay mineral requires an acid treatment to the extent that the alumina component constituting the clay mineral is completely removed.
The acid treatment conditions can be in accordance with the conditions known per se. For example, as the acid, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid are used, and it is preferable to use a mineral acid such as sulfuric acid.

The method of contacting the clay mineral with the acid may be of any type, for example, a slurry activation method in which the clay and the acid are contacted in a slurry state, and a granular activation method in which the granulated clay and the acid are brought into solid-liquid contact. For example, a dry activation method in which a mixture of clay and an acid is allowed to react in a dry manner (in a granular material), and then by-product salts are extracted may be employed. The particle size of the acid-treated clay is desirably as fine as possible, and those having a particle size of 5 μm or less account for 20% by weight or more, especially 30% by weight or more, and a particle size of 20% or more.
It is preferred that the particle size is adjusted to be smaller than 30% by weight, especially smaller than 10% by weight, of a particle having a size larger than μm and used for the reaction.

As the magnesium raw material, a compound such as an oxide or hydroxide of magnesium or a basic magnesium carbonate capable of forming the oxide or hydroxide under the reaction conditions can be used. Although various magnesium salts can be decomposed into magnesium hydroxide in situ for the reaction, in order to produce the magnesium phyllosilicate according to the present invention, it is possible to mix various water-soluble salts into the reaction system. Should be avoided as far as possible. Magnesium oxides and hydroxides are suitable raw materials.

The aqueous slurry containing the silica and magnesium components having the above molar ratio is subjected to a wet treatment under grinding conditions using a ball mill or the like to obtain an aqueous slurry in which both components are uniform. In the present invention, it is particularly important that the wet milling reaction is performed before the following heat treatment, and the milling process varies depending on the mill capacity, milling conditions, and the like. It is necessary to subject the 5 to 30% by weight aqueous slurry to a trituration reaction for 3 to 30 hours. Then, the primary reactants are stirred under non-pressurized conditions,
By performing a heat treatment at 50 ° C. or more, preferably 80 to 95 ° C., for at least 2 hours or more, preferably 5 to 12 hours, a composition comprising magnesium phyllosilicate and excess magnesium hydroxide can be obtained.

The composition of the present invention has a composition of SiO ₂ / M
It is characterized in that an unreacted excess magnesium component is uniformly contained within a range that does not impair the essence of the layered structure of the layered magnesium phyllosilicate having a molar ratio of gO of 1.33. As described above, in the present invention, before performing the heat treatment, a sufficient aqueous milling treatment is performed to form a uniform aqueous slurry, and then the non-pressurized hydrothermal treatment at 100 ° C. or less is performed. The purpose is achieved.

The product is subjected to post-treatments such as washing with water, drying, pulverization and classification if necessary to obtain a product. The compounding agent comprising the homogeneous composition of the present invention includes various stabilizers, plasticizers, lubricants, organic chelating agents, anti-plateout agents, release agents, antistatic agents, antifogging agents, ultraviolet absorbers, Organic components such as an inhibitor, an insect repellent, an insect repellent, a bactericide, a fragrance, and a coloring agent can also be used together. Furthermore, this compounding agent includes various metal soaps including the aforementioned various organic components,
Surface treatment can also be performed in advance with waxes, resins, surfactants, various coupling agents, and the like. The organic component used for loading and surface treatment is 0.5 to 1 per compounding agent.
It is preferably in the range of 0% by weight, particularly 2 to 8% by weight.

(Use) The compounding agent of the present invention may be, for example, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene,
Chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride -Vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride- Chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylate copolymer, vinyl chloride-maleate copolymer, vinyl chloride-methacrylate copolymer , Vinyl chloride-acrylonitrile copolymer, internal plasticized polyvinyl chloride, etc. Body, and these chlorine-containing polymer and polyethylene, polypropylene, polybutene, poly -3
Α-olefin polymers such as methylbutene or polyolefins such as ethylene-vinyl acetate copolymer and ethylene-propylene copolymer and copolymers thereof, polystyrene, acrylic resin, styrene and other monomers (for example, maleic anhydride , Butadiene, acrylonitrile, etc.)
And acrylonitrile-butadiene-styrene copolymers, acrylate-butadiene-styrene copolymers, blends with methacrylate-butadiene-styrene copolymers, and the like.

According to the invention, the resin 100 to be stabilized
In general, 0.01 to 20 parts by weight of the compounding agent of the present invention is blended with respect to parts by weight. The amount is, of course, properly selected within the above range according to the type of the resin. In one preferred embodiment of the present invention, the chlorine-containing polymer per 100 parts by weight of the polymer,
It is preferable to mix and use 0.5 to 10 parts by weight, particularly 1 to 6 parts by weight.

As the heat stabilizer, any conventionally known lead-free stabilizer can be used. In this case, 0.01 to 10 parts by weight of a metal soap based on 100 parts by weight of the chlorine-containing polymer is used. Stabilizer or 0.01 to 10 parts by weight of β
-Diketone or β-keto acid ester can be used in combination. Examples of the metal soap include fatty acids such as stearic acid, palmitic acid, and lauric acid, and metal soaps such as calcium salts, zinc salts, magnesium salts, and barium salts of fatty acids.

As the metal soaps, those exemplified above can be used. As the β-diketone or β-keto acid ester, those conventionally known for this use, for example, 1,3-cyclohexadione, methylenebis-1,1 3-cyclohexadione, 2-benzyl-1,3-cyclohexadione,
Acetyltetralone, palmitoyltetralone, stearoyltetralone, benzoyltetralone, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, 2-acetyl-1,3-cyclohexanedione, benzoyl-p-chlorobenzoylmethane, bis (4-methyl Benzoyl) methane, bis (2-hydroxybenzoyl) methane, benzoylacetone, tribenzoylmethane, diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, lauroylbenzoylmethane, dibenzoylmethane, bis (4
-Chlorobenzoyl) methane, bis (methylene-3,4)
-Dioxybenzoyl) methane, butanoylacetone,
Distearoylmethane, acetylacetone, stearoylacetone, bis (cyclohexanoyl) -methane, dipivaloylmethane, and the like can be used.

Further, examples of the non-lead-based stabilizer include zeolite-based, hydrotalcite-based, inorganic porous systems containing perchloric acid, lithium-aluminum composite hydroxide-based and tin-based stabilizers. Can be used.

[0036]

【Example】

Embodiment 1 FIG. The method for preparing the compounding agent for chlorine-containing polymer according to the present invention will be described below. (Preparation of compounding agent and Properties) SiO ₂ / MgO molar ratio =
As the silica raw material, an average particle diameter of 3
Commercially available white carbon (Shionogi Seiyaku Carplex # 80, SiO ₂ min 95%) 100 g reagent magnesium hydroxide [mu] m (Mg (OH) ₂ content of 97%) 380
g Further, 4313 g of distilled water was added, and the mixture was ground with a 15 L ball mill for 5 hours to obtain an aqueous slurry having a solid content of 10%.
The aqueous slurry was reacted at 90 ° C. for 10 hours under stirring at 500 rpm. Then, after filtering and washing,
After drying at 10 ° C, pulverization and classification, a compounding agent fine powder of the present invention was obtained. This sample was designated as Sample No. Let it be 1. Next, the following physical properties were measured, and the results are shown in Table 1.

(Measurement Method) (1) X-ray Diffraction Using a RAD-IB system manufactured by Rigaku Corporation,
It was measured by u-Kα. Target Cu filter Curved crystal graphite monochromator Detector SC voltage 40KVP Current 20mA Count full scale 7000c / s Smoothing point 25 Scanning speed 1 ° / min Step sampling 0.02 ° Slit DS1 ° RS0.15mmSS1 ° Monochromator RS0.80mm Illumination angle 6 °

(2) Average Particle Size The average particle size was determined using a laser diffraction particle size analyzer LS130 particle size distribution analyzer manufactured by Coulter Counter Co., Ltd. (3) Apparent specific gravity Measured in accordance with JIS K-6220. (4) Oil absorption The oil absorption was measured according to JIS K-5101-19. (5) Specific surface area Carlopmba's Sortpmatic Series
It was measured by the BET method using s1800. (6) Chemical analysis In conformity with the chemical analysis method for rocks of JIS M8855,
The molar ratio of SiO ₂ / MgO was measured.

(7) Determination of Excess Magnesium Oxide Approximately 5 g of a sample dried at 110 ° C. for 3 hours was weighed in a 100 ml beaker, and 50 ml of a 1N ammonium chloride aqueous solution adjusted to pH 7 was added. Stirred for 24 hours. Separate the solution with a centrifuge,
5 ml of the supernatant was collected. The pH of the supernatant was adjusted to pH 10 with an ammonium chloride-ammonium buffer solution.
Titration was carried out with 05MEDTA, and soluble magnesium oxide was quantified from the titer.

Embodiment 2 FIG. SiO ₂ / MgO molar ratio = 0.
The raw material of silica was a commercial white carbon having an average particle size of 3 μm (Carplex # manufactured by Shionogi Pharmaceutical Co., Ltd.)
80, SiO ₂ min 95%) 100 g reagent magnesium hydroxide (Mg (OH) ₂ content 97%) 172.9g further distilled water 2444.9g added and triturated for 4 hours at 15L ball mill, 10% of Sample No. 1 of Example 1 was obtained except that an aqueous slurry was obtained. The same operation as in Example 1 was performed to obtain a fine magnesium silicate powder (Sample No. 2). Table 1 shows the physical properties.

Embodiment 3 FIG. SiO_Two / MgO molar ratio = 1.
00, the average particle diameter is 3 μm as a silica raw material.
Commercially available white carbon (Shionogi Pharmaceutical Carplex
# 80, SiO _Two 95%) 100g and reagent hydroxide mug
Nesium (Mg (OH)_Two Content: 97%) 95.2 g
1745.8 g of distilled water was added to the mixture, and the mixture was added using a 15 L ball mill.
Milled for 3 hours to obtain an aqueous slurry with a solid content of 10%
Is the sample No. of Example 1. Perform the same operation as Step 1
A bright compounding agent fine powder (sample No. 3) was obtained. Table 1 shows
Physical properties were shown.

Embodiment 4 FIG. SiO ₂ / MgO molar ratio = 1.
As a raw material for silica, an average diameter of 3
Commercially available white carbon (Shionogi Seiyaku Carplex # 80, SiO ₂ min 95%) 100 g reagent magnesium hydroxide [mu] m (Mg (OH) ₂ content 97%) 71.
1532.4 g of distilled water was further added, and the mixture was milled in a 15 L ball mill for 2 hours to obtain an aqueous slurry having a solid content of 10%. The same operation as in Example 1 was performed to obtain a fine powder of the compounding agent of the present invention (Sample No. 4). Table 1 shows the physical properties.

Embodiment 5 FIG. Cracked acid clay from Kushibiki-cho, Yamagata Prefecture (35% water), 34% sulfuric acid in 250g
Then, the mixture was heated at 85 ° C. for 24 hours to perform an acid treatment. Thereafter, the mixture was filtered and washed with water to obtain a cake. The cake
After drying at 10 ° C., the mixture was pulverized to obtain fine white powdered active silicic acid mainly composed of silicic acid having an SiO ₂ content of 92.7%. This sample is referred to as silica source A. Next, the SiO ₂ / MgO molar ratio =
100 g of silica source A and reagent magnesium hydroxide (Mg (OH) ₂ content 97%) so as to be 1.00.
Example 1 except that 87.2 g and 1727.5 g of distilled water were further added.
Sample No. The same operation as in Example 1 was performed to obtain a compounding agent fine powder of the present invention (Sample No. 5). Table 1 shows the physical properties.

Comparative Example 1 SiO ₂ / MgO molar ratio = 0.
As the silica raw material, the average particle diameter is 3 μm so as to be 10.
In addition the commercially available white carbon (Shionogi Seiyaku Carplex # 80, SiO ₂ min 95%) 100 g reagent magnesium hydroxide (Mg (OH) ₂ content of 97%) 951 g of distilled water 9459g, 5 at 15L ball mill
Milling for an hour resulted in an aqueous slurry with 10% solids. The aqueous slurry was stirred at 90 ° C. under 500 rpm for 10 minutes.
A time reaction was performed. After filtration and washing with water,
After drying at ℃ and pulverization and classification, a fine powder comprising magnesium silicate and magnesium hydroxide was obtained. This sample is called sample N
o. H-1. Table 1 shows the physical properties.

Comparative Example 2 SiO ₂ / MgO molar ratio = 2.
00, the average particle diameter is 3 μm as a silica raw material.
Commercial white carbon (Shionogi Seiyaku Carplex # 80, SiO ₂ min 95%) 100 g reagent magnesium hydroxide (Mg (OH) ₂ content of 97%) 47.6 g
Further, 1317 g of distilled water was added, and 1
The same operation as in Comparative Example 1 was performed except that an aqueous slurry having a solid content of 10% was obtained by milling for an hour to obtain a fine magnesium silicate powder. This sample was designated as Sample No. H-2. Table 1 shows the physical properties.

Comparative Example 3 Commercially available white carbon having an average particle diameter of 3 μm (Carplex # 80, S
(IO ₂ min 95%) 300 g and distilled water 2667 g were added,
Milling was performed for 1 hour in a 15 L ball mill to obtain an aqueous slurry having a solid content of 10%. Then, after filtration and washing with water, 110 ° C
After crushing and classification, fine silica powder was obtained. This sample was designated as Sample No. H-3. Table 1 shows the physical properties.

Comparative Example 4 Reagent magnesium hydroxide (Mg
(OH) ₂ content 97%) 300 g and distilled water 2667 g
And milled in a 15 L ball mill for 2 hours to obtain a solid content of 1
A 0% aqueous slurry was obtained. After filtration and washing with water,
After drying at 110 ° C, pulverization and classification, a fine powder of magnesium hydroxide was obtained. This sample was designated as Sample No. H-4. Table 1 shows the physical properties.

Comparative Example 5 Reagent magnesium hydroxide (Mg
(OH) ₂ content 97%) 200g and reagent talc 200
g Further, 3600 g of distilled water was added, and the mixture was ground with a 15 L ball mill for 5 hours to obtain an aqueous slurry having a solid content of 10%. Thereafter, the mixture was filtered and washed with water, dried at 110 ° C., pulverized and classified to obtain a mixed fine powder of magnesium hydroxide and talc. This sample was designated as Sample No. H-5. Table 1 shows the physical properties.

[0049]

[Table 1]

Application Example 1 In this application example, the heat stability effect and the dimensional stability effect when the chlorine-containing polymer compounding agent of the present invention is added to a chlorine-containing resin will be described. (Evaluation with soft vinyl chloride sheet)

In order to confirm the effect of the resin stabilizer of the present invention on the thermal stabilization of vinyl chloride, a soft vinyl chloride sheet was prepared by the following blending and molding techniques, and an evaluation test was conducted. Formulation Vinyl chloride resin (degree of polymerization: 1050) 100 parts by weight Dioctyl phthalate 50 parts by weight Calcium-zinc stabilizer 2.0 parts by weight Dibenzoylmethane 0.1 parts by weight Dihydroxydiphenylpropane 0.2 parts by weight Sample 2 parts by weight

(Molding method)
Roll mill kneading at 7 ° C. for 7 minutes to prepare a uniform mixture having a thickness of 0.5 mm.
It was heated under pressure of 0 kg / cm ² for 5 minutes to prepare a soft vinyl chloride sheet having a thickness of 1 mm.

(Test method) (1) Thermal stability According to JIS K 6723, a sample sheet was 1 mm ×
The test tube was cut into 1 mm, filled with 2 g of a sample chip in a test tube equipped with Congo Red paper, heated to 180 ° C., and the HCl desorption time due to thermal decomposition of vinyl chloride was measured. (2) Dimensional stability by heating in a constant-temperature dryer A sheet kneaded with a roll and press-molded was cut into 30 × 30 mm, and the area and volume were measured to obtain test pieces. The test piece was heated at 185 ° C. for 30 minutes, allowed to cool, the area and volume were measured, and the area and volume increase / decrease rate was calculated from the following equation. Area and volume change ratio (%) = A / B × 100 A: the area before heating (cm ²⁾ and volume ^{(cm 3) B: 185 ℃} , area after heating for 30 min (cm ²⁾ and volume (cm ³ (3) Tensile strength Measured according to JIS 7113.

(Evaluation with Soft Vinyl Chloride Plate) Table 2 shows the results obtained.

[0055]

[Table 2]

(Evaluation with Hard Vinyl Chloride Plate) As in the case of the above-mentioned soft vinyl chloride sheet, in order to confirm the reinforcing effect on vinyl chloride, the impact resistance effect and the bending resistance effect of the chlorine-containing polymer compounding agent of the present invention. Then, a rigid vinyl chloride plate was prepared by the following methods such as blending and molding, and an evaluation test was performed.

Formulation Vinyl chloride resin (degree of polymerization: 1050) 100 parts by weight Calcium-zinc-based stabilizer 1.2 parts by weight Polyhydric alcohol-based stabilizer 0.3 parts by weight Hydrocarbon-based lubricant 0.8 parts by weight Dibenzoylmethane 0.06 parts by weight Dihydroxydiphenylpropane 0.06 parts by weight Sample 2 and 5 parts by weight

(Molding method)
Roll mill kneading at 7 ° C. for 7 minutes to prepare a uniform mixture having a thickness of 0.6 mm.
It was heated under pressure of 0 kg / cm ² for 5 minutes to prepare a hard vinyl chloride plate having a thickness of 2 mm.

(Test Method) (1) Tensile Strength and Elongation Measured in accordance with JIS 6745. (2) Impact test Measured according to JIS 7111. (3) Bending test Measured in accordance with JIS 7203. (4) Work Breakage From the tensile strength and elongation measured according to JIS 6745, the work breakage was calculated by the following formula. Breaking work = tensile strength x elongation Table 3 shows the obtained test results.

[0060]

[Table 3]

From the results shown in Tables 2 and 3, when the chlorine-containing polymer compounding agent of the present invention is added to soft and hard vinyl chlorides, it exhibits an excellent heat stabilizing effect and an excellent reinforcing effect and size. It is understood that it exerts a stability effect.

[0062]

According to the present invention, SiO 2_Two / Mo of MgO
Component ratio in the range of 0.25 to 1.33.
After the aqueous slurry is subjected to wet milling,
By hydrothermal treatment at a temperature of 0 ° C. or less, SiO 2_Two 
Having a molar composition of 1.33 / MgO molar ratio
Synthetic layered magnesium phyllosilicate and SiO as a whole
_Two / MgO molar ratio in the range of 0.25 to 1.33
Excess magnesium hydroxide or magnesium oxide
A composition comprising:

By blending this composition with a chlorine-containing polymer, the chlorine-containing polymer molded product can be produced more in comparison with the case where the synthetic layered magnesium phyllosilicate alone, magnesium hydroxide alone or both are simply blended. The dimensional stability and the heat resistance were able to be significantly improved without lowering the mechanical properties. The effect of the present invention was not obtained with talc or sepiolite except that the magnesium silicate combined with magnesium hydroxide was other than the synthetic layered magnesium phyllosilicate according to the present invention.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction spectrum of the compounding agent for chlorine-containing polymer obtained in Example 1 of the present invention, which is obtained by using a Cu-Ka line, wherein (F) indicates a layered magnesium phyllosilicate;
The mark (M) indicates the diffraction line peak of magnesium oxide.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ identification code FI C08L 23/28 C08L 23/28 (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 27/04-27/08 C08K 3/22 C08K 3/34-3/36 C08K 9/02 C08K 9/08 C08L 23/28

Claims (4)

(57) [Claims] An overall SiO ₂ / MgO molar composition ratio in the range of 0.25 to 1.33 and a plane spacing
(Angstrom) 4.5-4.6, 2.5-2.6
And a homogeneous mixture of a crystalline synthetic layered magnesium phyllosilicate having an X-ray diffraction peak in the range of 1.5 to 1.6 and an excess of magnesium hydroxide or magnesium oxide. Compounding agent for contained polymer. 2. The combination according to claim 1, which has a BET specific surface area of 100 to 600 m ² / g and an oil absorption of 50 to 100 ml / 100 g. 3. A volume-based median diameter of 0.5 to 10
The resin compounding agent according to claim 1, which is in a range of µm. 4. The total molar composition of SiO ₂ / MgO is in the range of 0.25 to 1.33 per 100 parts by weight of chlorine-containing polymer, and the interplanar spacing (angstrom)
4.5-4.6, 2.5-2.6 and 1.5-1.6
A compounding agent comprising a homogeneous mixture of a crystalline synthetic layered magnesium phyllosilicate having an X-ray diffraction peak in the range and an excess of magnesium hydroxide or magnesium oxide in an amount of 0.5 to 20 parts by weight. A chlorine-containing polymer composition having improved dimensional stability and thermal stability.