JP3519893B2 - Stabilizer for chlorine-containing polymer and chlorine-containing polymer composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a chlorine-containing polymer stabilizer which is excellent in static and dynamic thermal stability and which is prevented from discoloring due to orientation during molding, and a chlorine-containing polymer containing the stabilizer. It relates to a composition for coalescence.

[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 proposed and widely used.

As a heat stabilizer for a chlorine-containing polymer, tribasic lead sulfate is generally used, and since it is also excellent in heat stability, the heat of an industrial chlorine-containing polymer molded article is improved. Widely used for stabilization.

In order to improve the dispersibility of tribasic lead sulfate in a chlorine-containing polymer, it is often practiced to coat the surface of tribasic lead sulfate particles with higher fatty acid lead. Also,
It is also known to use, as the tribasic lead sulfate, those having various X-ray diffraction images.

Japanese Patent Publication No. Sho 49-15 filed by the applicant
In Japanese Laid-Open Patent Application No. 625 (publication example 1), the formula R = I _3.27 / I _3.09 , where I _3.27 is the intensity of the X-ray diffraction image at d = 3.27 Å, and I _3.09 is the X-ray diffraction image d =. 3.0
It is described that when a chlorine-containing polymer is compounded with microcrystalline tribasic lead sulfate having an X-ray intensity ratio (R) of 6 or less, which is defined by representing the intensity in 9 angstrom, lead elution is suppressed. There is.

Further, Japanese Patent Publication No. 58-31105 (known example 2) discloses that the number average minor axis of 0.2 microns or less, 1.
The tribasic lead sulfate having a bulk density of 8 g / ml or less and the X-ray intensity ratio (R) of 7 or more is a stabilizer for a chlorine-containing polymer having excellent thermal stability and electric insulation. Is described.

Further, in Japanese Patent Publication No. 7-45598 (known example 3), d = 3.27 angstrom and d = 3.
The relative peak intensities of the X-ray diffraction images at 14 angstrom and d = 3.09 angstrom are I _3.27 I
_3.14 and I _3.09 , the following I _3.14 / I _3.27 = 0.45 to 0.75 I _3.09 / I _3.27 = 0.30 to 0.75 and I _3.09 / I _3.14 = 0.90 to 1.50 The use of tribasic lead sulfate having the X-ray diffraction pattern shown as stabilizer for chlorine-containing polymers is described.

[0008]

Although the fine crystalline tribasic lead sulfate used in the above-mentioned known example 1 is a fine crystal, it still has a large particle size of about 1 to 2 μm.
In terms of static and dynamic thermal stability, it was not yet satisfactory.

The tribasic lead sulfate used in Known Example 2 has a minor axis reduced to 0.2 μm or less, and is excellent in thermal stability and electrical insulation, but has an aspect ratio of 3
When the chlorine-containing polymer composition blended with the above flaky crystals is subjected to extrusion molding or injection molding, a molded product has a defect in appearance. That is, in the cross section perpendicular to the resin extrusion direction, a somewhat whitish appearance is exhibited in the middle portion compared to the upper layer portion and the lower layer portion, while in the cross section parallel to the resin extrusion direction, the upper layer portion and The anisotropy in appearance, which is a somewhat blackish appearance in the middle portion compared to the lower layer portion, is recognized. Further, in injection molding, color unevenness occurs in the weld portion due to orientation.

Furthermore, the tribasic lead sulfate used in Known Example 3 has a particle shape close to a cube, and even if the anisotropy in the appearance of the molded body is eliminated, the particle size is still large, In terms of static and dynamic thermal stability, it was not yet satisfactory.

Thus, in the field of stabilizers for chlorine-containing polymers composed of tribasic lead sulfate, both in eliminating the anisotropy of the appearance of the moldings and in improving the static and dynamic thermal stability. Nothing satisfactory is known yet.

Accordingly, an object of the present invention is to eliminate the above-mentioned appearance anisotropy of the molded article and to improve the static and dynamic thermal stability remarkably, and to use a tribasic lead sulfate-based chlorine-containing compound. To provide a stabilizer for coalescence.

[0013]

According to the present invention, in a chlorine-containing polymer stabilizer comprising tribasic lead sulfate and a higher fatty acid lead coating the tribasic lead sulfate, the tribasic lead sulfate is d =
When the relative peak intensities of the X-ray diffraction images at 3.27 angstrom, d = 3.14 angstrom and d = 3.09 angstrom are I _3.27 I _3.14 and I _3.09 , the following I _3.14 / I _3.27 = 0.20 is obtained. 0.44 I _3.09 / I _3.27 = 0.10 to 0.29 and I _3.09 / I _3.14 = 0.50 to 0.85 X-ray diffraction images, and the volume-based median diameter is 0.5. A stabilizer for a chlorine-containing polymer is provided which is composed of tribasic lead sulfate having an aspect ratio in the range of 1.0 to 0.8 μm and an aspect ratio in the range of 1.0 to 1.5.

In the tribasic lead sulfate used in the present invention, when the 25% particle size in the volume-based cumulative particle size distribution is D25 and the 75% particle size is D75, the particle size uniformity defined by D25 / D75 is 3. It is preferably 0 or less.

Also according to the invention, the chlorine-containing polymer 10
A chlorine-containing polymer composition comprising 0.1 to 100 parts by weight of a stabilizer consisting of tribasic lead sulfate and higher fatty acid lead covering the same per 0 parts by weight, wherein the tribasic lead sulfate is d = 3.27 Angstrom, d = 3.1
The relative peak intensities of the X-ray diffraction images at 4 Å and d = 3.09 Å were _calculated as I _3.27 I _3.14.
And I _3.09 , the following I _3.14 / I _3.27 = 0.20 to 0.44 I _3.09 / I _3.27 = 0.10 to 0.29 and I _3.09 / I _3.14 = 0.50 to 0.85 A tribasic lead sulfate having a volume-based median diameter of 0.5 to 0.8 μm and an aspect ratio of 1.0 to 1.5. A featured chlorine-containing polymer composition for extrusion is provided.

Further in accordance with the present invention, the chlorine containing polymer 10
A chlorine-containing polymer composition comprising 0.1 to 100 parts by weight of a stabilizer consisting of tribasic lead sulfate and higher fatty acid lead covering the same per 0 parts by weight, wherein the tribasic lead sulfate is d = 3.27 Angstrom, d = 3.1
The relative peak intensities of the X-ray diffraction images at 4 Å and d = 3.09 Å were _calculated as I _3.27 I _3.14.
And I _3.09 , the following I _3.14 / I _3.27 = 0.20 to 0.44 I _3.09 / I _3.27 = 0.10 to 0.29 and I _3.09 / I _3.14 = 0.50 to 0.85 A tribasic lead sulfate having a volume-based median diameter of 0.5 to 0.8 μm and an aspect ratio of 1.0 to 1.5. A featured chlorine-containing polymer composition for injection molding is provided.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The stabilizer for a chlorine-containing polymer used in the present invention comprises tribasic lead sulfate and higher fatty acid lead coating the same, and the tribasic lead sulfate used has the above-mentioned relative peak. Having an X-ray diffraction image represented by an intensity ratio, having a volume-based median diameter in a fine range of 0.5 to 0.8 μm, and having an aspect ratio of 1.0 to 1.5, which is close to a cube. Is characterized by having.

The tribasic lead sulfate used as a stabilizer in the present invention has a fine volume-based median diameter of 0.5 to 0.8 μm and an aspect ratio of 1.0 to 1.5, which is close to a cubic shape. It is characterized by showing the particle shape. Due to this characteristic, the stabilizer of the present invention, when blended with a chlorine-containing polymer and used for applications such as profile extrusion molding and injection molding,
It does not cause whitening or color unevenness due to the orientation of tribasic lead sulfate particles, and it not only excels in the appearance characteristics and internal structure uniformity of molded products, but also in dynamic thermal stability and static thermal stability. Is also excellent, and this fact will become clear by referring to the examples and comparative examples described later.

The tribasic lead sulfate particles (commercially available) produced by an ordinary method have crystals developed in the b-axis direction, and b / a
The aspect ratio defined by is generally in the range of 2 to 10, and the volume-based median diameter is about 1.5 to 5 μm, which is considerably large. A chlorine-containing polymer composition containing this stabilizer is The particles tend to be oriented.

In order to make the above-mentioned ordinary tribasic lead sulfate into fine particles, wet milling with a ball mill or the like can be considered, but the tribasic lead sulfate wet-milled in this way has a volume-based median diameter of 0. The particle size is similar to that of tribasic lead sulfate before pulverization, and the aspect ratio is still in the order of 2 to 5, and the particles are oriented during molding. Tend to do.

On the other hand, as a tribasic lead sulfate having an aspect ratio in the range of 1 to 1.5, Japanese Examined Patent Publication No. 7-45598.
Japanese Patent Laid-Open No. 63-137937 discloses that the particles have a volume-based median diameter of 2 to 1
It is on the order of 0 μm and thermal stability is still insufficient.

The inventors of the present invention added the granular higher fatty acid lead to the tribasic lead sulfate produced by an ordinary method, and performed impact pulverization in a dry process until the grain size was brought to the above-mentioned grain size characteristics. It was found that a tribasic lead sulfate having an X-ray diffraction image which has an unprecedented X-ray diffraction ratio can be obtained.

The tribasic lead sulfate particles used in the present invention and the conventional tribasic lead sulfate particles are compared in terms of X-ray diffraction image, volume-based median diameter, aspect ratio and particle size uniformity. It becomes as follows.

The sample names in the table mean the following. A: Tribasic lead sulfate particles used in the present invention, B: Tribasic lead sulfate (sample No. 1) described as a commercial product in FIG. 1 of JP-B-49-15625, C: JP-B-49-15625. 1 of the publication, a tribasic lead sulfate described as a commercially available wet-ground product (Sample No.
2), D: Tribasic lead sulfate described as Example 2 in FIG. 1 of JP-B-49-15625 (Sample No. 12, reaction of lead monoxide with sulfuric acid was performed at a low temperature of 40 ° C.) , E: Tribasic lead sulfate (Sample (A)) described as in Table 1 of Japanese Patent Publication No. 7-45598 in accordance with a common synthesis method, F: Higher fatty acid in Table 1 of Japanese Patent Publication No. 7-45598, Tribasic lead sulfate (Sample (B)) described by the synthesis method in the presence of, etc., G: described in Table 1 of Japanese Examined Patent Publication No. 7-45598 as the synthesis method in the presence of fine particle silica. Tribasic lead sulfate (sample (C)).

[0025]

[Table 1] ABCD EF G X-ray diffraction image I _3.14 / I _3.27 0.20-0.44 0.5 0.59 0.72 0.2 0.42 0.56 I _3.09 / I _3.27 0.10-0.29 0.08 0.3 0.55 0.06 0.14 0.61 I _3.09 / I _3.14 0.55- 0.74 0.16 0.48 0.77 0.30 0.33 1.09 Volume-based media 0.5 -0.8 2.8 1.0 0.9 2.0 1.1 4.9 Anne diameter Aspect ratio 1.0 -1.5 2-10 2-5 2-10 2-10 2-5 1-1.5 Grain size uniformity -3.0 8.1 5.9 4.4 6.1 5.5 2.2

According to the results shown in Table 1 above, the tribasic lead sulfate used in the present invention has not been known so far in the X-ray diffraction image, and the volume-based median diameter and aspect ratio defined in the present invention are There is nothing satisfying both of the above, and it is peculiar in that the particle size uniformity defined by D25 / D75 is 3.0 or less.

[Tribasic Lead Sulfate and Process for Producing the Same] The tribasic lead sulfate used in the present invention is a needle-shaped particle-shaped tribase described as a commercial product in Table 1 of Japanese Patent Publication No. 49-15625. Soluble lead sulfate in the presence of granular higher fatty acid lead,
Obtained by subjecting to impact crushing.

Conventionally, tribasic lead sulfate coated with higher fatty acid lead is prepared by adding ammonium fatty acid soap of higher fatty acid to an aqueous reaction mixture containing the produced tribasic lead sulfate. It was produced by forming higher fatty acid lead in situ on the surface of the particles.

On the other hand, in the present invention, tribasic lead sulfate is subjected to dry impact pulverization, and granular higher fatty acid lead is made to coexist during the impact pulverization. This impact pulverization exerts a mechanochemical effect on the tribasic lead sulfate particles, and the higher fatty acid lead present in the form of particles is not only coated on the surface of the tribasic lead sulfate particles by grinding and mixing. Nonetheless, it is believed to act to prevent the tribasic lead sulfate particles from crushing into high aspect ratio particles.

The tribasic lead sulfate used as a raw material preferably has a volume-based median diameter of 1 to 5 μm and an aspect ratio of 2 to 5.

The fatty acid to be the lead salt is a saturated or unsaturated fatty acid having 8 to 22 carbon atoms, particularly 8 to 14 carbon atoms, and most preferably 8 to 12 carbon atoms, for example, octylic acid, capric acid, undecanoic acid, lauric acid, myristin. Saturated fatty acids such as acids, unsaturated fatty acids such as linderic acid, tudzuic acid, petroselinic acid, oleic acid, linoleic acid, linolenic acid and arachidonic acid are used. Although stearic acid, palmitic acid, etc. can be used, a lower fatty acid is preferable for preventing zinc burning. In terms of stability, saturated fatty acids are desirable, and lauric acid is the most preferable. The fatty acids may of course be mixed fatty acids such as coconut oil fatty acids and palm oil fatty acids. These fatty acid leads also serve as a lubricant and are preferably normal salts.

The amount of higher fatty acid lead relative to tribasic lead sulfate is in the range of 0.1 to 20 parts by weight, especially 0.5 to 10 parts by weight, of higher fatty acid lead per 100 parts by weight of tribasic lead sulfate. preferable. When the amount of the higher fatty acid lead is less than the above range, it tends to be difficult to form tribasic lead sulfate satisfying the conditions of the present invention, and the dispersion in the resin tends to decrease. The stability also tends to decrease slightly. On the other hand, when the amount of the higher fatty acid lead exceeds the above range, the impact pulverizability is lowered and the slipperiness tends to be excessive.

The impact crushing can be carried out by using an apparatus known per se, for example, jaw crusher, hammer mill, pulperizer, edge runner, supermicron mill, roll mill, jet mill, fine victory mill, roller mill, dyno mill, aquamizer. , Raymond mill, feather mill, palverizer, atomizer, cutter mill, dispamill, pin mill and the like.

[Stabilizer] The stabilizer of the present invention may be used in the form of powder or granules, that is, in the form of powder, or in the form of granules, either as a single stabilizer or as a one-pack composite stabilizer. it can. Granules known per se such as extrusion molding granulation method, spray granulation method, rotary disk granulation method, tumbling granulation method and compression granulation method can be used for the production of the granular material. The particle size of the granular material can be arbitrarily adjusted according to the purpose. Generally, the particle size is 50 μm to 5 mm, especially 70 μm to 2 mm.
It is preferable that it is in the range of.

The composite stabilizer of the present invention includes the compounding agents known per se for the resin, for example, stabilizing aid, colorant, inorganic or organic filler, antioxidant, chelating agent, lubricant, plasticizer, An antibacterial agent, a light stabilizer, an impact enhancer, a flame retardant, an electrical insulation improver and the like can be added.

As the stabilizing aid, an inorganic or organic stabilizing aid can be used. As the inorganic stabilizing aid, a lead-based stabilizer other than tribasic lead sulfate, aerosil,
Hydrophobicized fine particles of silica such as Aerosil, silicates such as calcium silicate and magnesium silicate, metal oxides such as calcia, magnesia and titania, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, and calcium carbonate Shaped particles composed of metal carbonate, A-type, P-type synthetic zeolite and its acid-treated product or its metal ion exchange product, alumina, attapal guide, kaolin, carbon black, graphite, finely divided silicic acid, diatomaceous earth,
Stabilizing aids such as magnesium oxide and hydrotalcite can be used.

As the organic stabilizing aid, there can be used lead soap salts of higher fatty acids, organic tin stabilizers, metal soaps such as zinc salts, calcium salts, magnesium salts and barium salts.

The impact strengthening agent is, for example, 30 to 40%.
Chlorinated polyethylene containing chlorine, copolymer rubber mainly composed of acrylic acid ester, and methyl methacrylate,
Examples thereof include multicomponent resins obtained by graft-polymerizing monomers such as styrene and acrylonitrile, acrylonitrile / butadiene / styrene resins, metal methacrylate / butadiene / styrene resins, and vinyl acetate / ethylene copolymer resins.

As the flame retardant, not to mention halogen flame retardants,
Examples include antimony, zircon, molybdenum, aluminum, silica, titanium oxides, hydroxides, and sulfides, zinc borate, zinc stannate, zinc hydroxystannate, and metal hydroxide surface-treated products of these zinc compounds. To be

Examples of the electrical insulation improver include amorphous silica, calcined kaolin, aluminum oxide, aluminum silicate, titanium white, titanium phosphate, zirconium phosphate, etc., in an amount of 20 to 1000 parts by weight, especially 100 parts by weight of the resin. It can be added in an amount of 200 to 500 parts by weight.

These stabilizing aids can be used alone or in combination of two or more. The stabilizing aid is preferably used in an amount of 0.1 to 200 parts by weight, particularly 0.5 to 100 parts by weight, per 100 parts by weight of tribasic lead sulfate.

As the antioxidant, examples of the phenolic antioxidant include bisphenol A, bisphenol B, bisphenol F and 2,6-diphenyl-4-.
Octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-Di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl)]
Propionic acid amide], bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 1,1,3-tris (2-methyl-4-hydroxy-5-second Tributylphenyl) butane, 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, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-
Methylphenyl) propionate] and the like.

The phenolic antioxidant is added in an amount of 0.01 to 5 parts by weight, especially 0.1% by weight per 100 parts by weight of the tribasic lead sulfate.
It is preferably used in an amount of 05 to 2 parts by weight. This antioxidant is useful for suppressing degradation and the like due to chain reaction.

As the chelating agent, polyhydric alcohol,
β-keto acid esters or β-diketones are preferred, suitable examples of which are as follows.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, glycerin, diglycerin, pentaerythritol and dipentaerythritol. Etc. can be mentioned.

Examples of the β-diketone or β-keto acid ester include 1,3-cyclohexadione, methylenebis-1,3-cyclohexadione, 2-benzyl-
1,3-cyclohexadione, acetyltetralone, palmitoyltetralone, stearoyltetralone, benzoyltetralone, 2-acetylcyclohexanone, 2
-Benzoylcyclohexanone, 2-acetyl-1,3
-Cyclohexanedione, bis (benzoyl) methane,
Benzoyl-p-chlorobenzoylmethane, bis (4-
Methylbenzoyl) methane, bis (2-hydroxybenzoyl) methane, benzoylacetone, tribenzoylmethane, diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, lauroylbenzoylmethane, dibenzoylmethane, bis (4-chlorobenzoyl) methane, Bis (methylene-
3,4-dioxybenzoyl) methane, benzoylacetylphenylmethane, stearoyl (4-methoxybenzoyl) methane, butanoylacetone, distearoylmethane, acetylacetone, stearoylacetone, bis (cyclohexanoyl) -methane and dipivaloyl. Methane or the like can be used.

These chelating agents can be added in an amount of 0.5 to 20 parts by weight, particularly 1 to 10 parts by weight, per 100 parts by weight of tribasic lead sulfate.

[Chlorine-Containing Polymer Composition] The stabilizer of the present invention contains 0.1 to 100 parts by weight, especially 0.5 to 10 parts by weight of tribasic lead sulfate per 100 parts by weight of the chlorine-containing polymer. It is good to mix in the amount. When the amount is less than the above range, satisfactory thermal stability cannot be obtained. On the other hand, when the amount is more than the above range, there is no particular advantage and it is economically disadvantageous.

Examples of the chlorine-containing polymer include polyvinyl chloride, polyvinylidene chloride, chlorinated polyvinyl 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 ternary copolymer Coal, 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 copolymers, polymers such as internally plasticized polyvinyl chloride, and chlorine-containing polymers thereof and polyethylene, polypropylene, polybutene, poly-3
-Α-olefin polymers such as methylbutene or ethylene-vinyl acetate copolymers, polyolefins such as ethylene-propylene copolymers and copolymers thereof, polystyrene, acrylic resins, styrene and other monomers (for example, anhydrous Copolymer with maleic acid, butadiene, acrylonitrile, etc., acrylonitrile-butadiene-styrene copolymer, acrylic ester-butadiene-styrene copolymer, methacrylic ester-butadiene-
Examples thereof include blended products with a styrene copolymer.

The chlorine-containing polymer composition of the present invention can be blended with a chlorine-containing polymer compounding agent known per se in accordance with a formulation known per se. For example, the composition of the present invention includes a plasticizer, a lubricant, a filler, a colorant, a weather resistance stabilizer, an antiaging agent, a light stabilizer, an ultraviolet absorber, an antistatic agent, a modifying resin or rubber, and the like. Known resin compounding agents can be compounded according to a formulation known per se.

Examples of the plasticizer include ester plasticizers such as phthalic acid ester plasticizers and adipic acid ester plasticizers, polyester plasticizers, phosphoric acid ester plasticizers, chlorine plasticizers, tetrahydrophthalic acid plasticizers. Agent, azelaic acid plasticizer, sebacic acid plasticizer, stearic acid plasticizer, citric acid plasticizer, trimellitic acid plasticizer,
Examples include pyromellitic acid plasticizers.

As the lubricant, (a) hydrocarbon type such as fluid, natural or synthetic paraffin, microwax, polyethylene wax, chlorinated polyethylene wax and the like, (b) fatty acid type such as stearic acid and lauric acid, (C) Stearic acid amide, Balmitic acid amide,
Fatty acid monoamides or bisamides such as oleic acid amide, esyl acid amide, methylene bis stearamide, ethylene bis stearamide, etc., (di) butyl stearate, hydrogenated castor oil, ester type ethylene glycol monostearate, etc. Those of alcohol type 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.

The stabilized chlorine-containing polymer composition according to the present invention is useful as an extrusion molding resin composition or an injection molding resin composition for producing various molded articles, and tribasic sulfuric acid in the molded article is used. It is effective in eliminating the anisotropy of appearance due to the orientation of lead particles.

[0054]

The present invention will be described in the following examples, but the present invention is not limited to the following examples. The measurement in the examples was performed by the following method. (1) X-ray diffraction measurement Rigaku Denki Co., Ltd. RAD-IB system
It was measured by u-Kα. Target Cu filter Curved crystal graphite monochromator Detector SC Voltage 40KVP Current 20mA Count full scale 700c / s Smoothing point 25 Scanning speed 1 ° / min Step sampling 0.02 ° Slit DS1 ° RS0.15mm SS1 ° Illumination angle 6 ° (2 ) Average particle size measurement The average particle size (median size; μm) was measured using a laser diffraction particle size analyzer (Coulter R LS130) manufactured by Coulter Counter. (3) Gear oven heat resistance: static heat stability test The kneaded and molded PVC sheet was heated to 190 ° C. in an oven, and the time (minutes) until deterioration and coloring was measured to evaluate the heat resistance of the sheet. . (4) Plast heat resistance: dynamic heat stability test The plast heat resistance time until decomposition was measured with a Labo Plast mill manufactured by Toyo Seiki Seisakusho. <Test conditions> Laboplast mill model 20R200 Roller mixer model R-60H Capacity about 60cc Blade shape Roller type blade rotation ratio 2: 3 (L: R) Temperature 190 ° C Rotation speed 40rpm PVC filling amount 63g <Compound A> Vinyl chloride resin (Polymerization degree 800) 100 parts by weight Barium stearate 0.3 parts by weight Stearic acid 0.3 parts by weight Pigment 0.5 parts by weight Sample 3.0 parts by weight (5) Orientation test during extrusion molding Extrusion processing was performed to prepare a polyvinyl chloride hard plate having a thickness of 4 mm. This plate was cut, and the presence or absence of hue change on the cut surface in the thickness direction was observed to confirm the orientation of the tribasic lead sulfate. (In the case of a material having a strong orientation, discoloration due to the orientation is remarkably observed in the cut surface, particularly in the central portion of the cut surface. Parts by weight Lead stearate 1 part by weight Pigment 0.3 parts by weight Sample 4.0 parts by weight The evaluation criteria are as follows: 1: No discoloration of cut surface is observed, 2: Discoloration of cut surface is slight 3: Discoloration of the cut surface can be clearly identified (6) Orientation test during injection molding Toshiba Machine Co., Ltd. visually observed color unevenness due to the orientation of the welded part of the molded product. <Test conditions> Injection molding machine model IS100F-5A Mold 75mm (wall thickness) Single socket temperature NH.H3 185 ℃, H1.H2 195 ℃ Measurement value 160mm Suckback 2.0m
m screw 100 rpm, back pressure 10 Kg / cm ² <Compound C> The same evaluation criteria as in Formula A were as follows. 1: No unevenness in the color of the weld was observed. 2: Color unevenness in the weld part can be discerned slightly. 3: Color unevenness in the welded portion can be clearly identified.

Example 1 Commercially available litharge (lead monoxide)
Water was added to the powder to prepare a slurry of 140 g / L, 800 mL of this slurry was placed in a 2 L beaker, and 2 mL of 1.5N acetic acid was added with stirring to adjust the slurry temperature to 35
The temperature was adjusted to ˜45 ° C., and then 41.7 mL of 6N sulfuric acid was added over 1 minute with vigorous stirring. While maintaining the slurry temperature at 60 to 65 ° C., stirring and aging for 90 minutes,
A white slurry of tribasic lead sulfate was further washed with water, filtered, and dried at 110 ° C. to obtain a powder of tribasic lead sulfate (Sample A).

Next, 3.5 g of lead stearate granular product
Was added, and the mixture was uniformly mixed and pulverized with a jet mill until the volume average median diameter became 0.7 μm, and the surface of the tribasic lead sulfate powder was coated with lead stearate. Sample (A-1)
Got D = 3.27Å, d = in the X-ray diffraction image of the surface-treated tribasic lead sulfate obtained by grinding and mixing.
The following relative peak intensities of 3.14Å and d = 3.09Å
It is shown in Table 1 described above. Further, the volume-based median diameter (see FIG. 2), the aspect ratio (see FIG. 1), and the particle size uniformity were measured and shown in Table 1 above.

Example 2 Sample A-manufactured in Example 1
The composition A composition 1 of Example 1 was tested for plast heat resistance and injection moldability, and the same composition was kneaded at 160 ° C. for 5 minutes to prepare a sheet having a thickness of 0.5 mm. This sheet was subjected to a gear oven heat resistance test. It was Further, an extrusion test was conducted on the compound B composition, and the results are shown in Table 2.

(Comparative Examples 1 to 7) The same measurement was performed except that the sample A-1 of Example 2 was changed to the following samples B to G. The results are shown in Table 2.

B: Commercially available tribasic lead sulfate having a particle size of 2 to
The needle-like crystal product having a diameter of 10 μm, the median diameter, the aspect ratio, and the uniformity of the particle size were measured and shown in Table 1. C: B tribasic lead sulfate was wet pulverized using a pot mill and pulverized to have a particle size of 1 to 2 μm. The median diameter, aspect ratio and particle size uniformity of the pulverized product were shown in Table 1 above. D: 177.9 g of commercially available lead monoxide was placed in a 3 liter beaker, 1200 ml of water was added, and the mixture was heated to 40 ° C. for 6.4.
After adding 1.53 ml of N-acetic acid, about 65 ml of 3N sulfuric acid3
Gradually inject for 0 minutes to obtain a suspension of tribasic lead sulfate having a pH of 7.5, and further add a sodium stearate aqueous solution corresponding to 3% of dibasic lead stearate to the surface of tribasic lead sulfate. Apply processing. After filtering and drying, pulverizing to obtain Sample D, which has a median diameter, an aspect ratio,
The particle size uniformity was measured and is shown in Table 1 above. E: Lead trisulfate whose reaction temperature was changed to 80 ° C. by the production method of D. The median diameter, the aspect ratio, and the degree of particle size uniformity were measured, and F: scale-like tribasic lead sulfate shown in Table 1 above. The median diameter, the aspect ratio, and the uniformity of the particle size were measured and shown in Table 1 above. G: Tribasic lead sulfate synthesized in the presence of fine particle silica. The median diameter, the aspect ratio, and the uniformity of the particle size were measured and shown in Table 1 above.

[0060]

[Table 2]                     A-1 B C D E F G   Gear oven resistance 100 80 90 90 80 90 70   Fever   190 ℃ Degradation time (min)   Plast heat resistance 22.0 18.9 20.8 21.2 19.5 20.8 18.5   Heat resistance (min)   Extrusion molding 1 3 2 2 3 2 1   (Whitening of cross section)   Injection molding 1 3 1 2 3 1 1   (Welding color unevenness)

[0061]

The present invention has a unique X-ray diffraction image,
Moreover, by using a tribasic lead sulfate having a particle shape close to a cube with an aspect ratio of 1.0 to 1.5, which is fine as a volume-based median diameter of 0.5 to 0.8 μm, as a stabilizer component, When blended with chlorine-containing polymer and used for applications such as profile extrusion molding and injection molding, whitening and color unevenness due to the orientation of tribasic lead sulfate particles do not occur, and the appearance characteristics and internal properties of the molded product It has excellent tissue homogeneity as well as excellent dynamic thermal stability and static thermal stability.

[Brief description of drawings]

FIG. 1 shows the tribasic lead sulfate used in the present invention (Sample A-
It is an electron micrograph which shows the particle structure of 1).

FIG. 2: Tribasic lead sulfate used in the present invention (Sample A-
It is a graph which shows the particle size distribution of 1).

FIG. 3: Tribasic lead sulfate used in the present invention (Sample A-
It is an X-ray diffraction image of 1).

Front page continuation (72) Inventor Kazuto Sugai 4-1-21, Nihombashi Muromachi, Chuo-ku, Tokyo Mizusawa Chemical Industry Co., Ltd. (56) Reference JP-A-63-137937 (JP, A) JP-A-1 -110548 (JP, A) JP-A-4-92817 (JP, A) JP-A-6-80822 (JP, A) JP-A-62-87237 (JP, A) (58) Fields investigated (Int.Cl) . ⁷ , DB name) C08L 27/04-27/08

Claims (4)

(57) [Claims] 1. A stabilizer for a chlorine-containing polymer comprising tribasic lead sulfate and a higher fatty acid lead coating the tribasic lead sulfate, wherein the tribasic lead sulfate is d = 3.27 angstrom, d =
The relative peak intensities of the X-ray diffraction images at 3.14 Å and d = 3.09 Å were _calculated as I _3.27.
Assuming I _3.14 and I _3.09 , the following I _3.14 / I _3.27 = 0.20 to 0.44 I _3.09 / I _3.27 = 0.10 to 0.29 and I _3.09 / I _3.14 = 0.50 to 0.85 X-ray diffraction image represented by, consisting of tribasic lead sulfate having a volume-based median diameter of 0.5 to 0.8 μm and an aspect ratio of 1.0 to 1.5. A stabilizer for a chlorine-containing polymer, which is characterized in that 2. When the 25% particle size in the volume-based cumulative particle size distribution is D25 and the 75% particle size is D75, D25
The stabilizer for chlorine-containing polymers according to claim 1, wherein the particle size uniformity defined by / D75 is 3.0 or less. 3. A chlorine-containing polymer composition containing 0.1 to 100 parts by weight of a stabilizer consisting of tribasic lead sulfate and higher fatty acid lead coating the same as 100 parts by weight of the chlorine-containing polymer. , The tribasic lead sulfate has d = 3.
Assuming that the relative peak intensities of the X-ray diffraction images at 27 Å, d = 3.14 Å and d = 3.09 Å are I _3.27 I _3.14 and I _3.09 , the following I _3.14 / I _3.27 = 0.20-0. 44 I _3.09 / I _3.27 = 0.10 to 0.29 and I _3.09 / I _3.14 = 0.50 to 0.85, and the volume-based median diameter is 0.5 to 0. A chlorine-containing polymer composition for extrusion molding, which comprises tribasic lead sulfate having an aspect ratio of 1.0 to 1.5 in the range of 0.8 μm. 4. A chlorine-containing polymer composition comprising 0.1 to 100 parts by weight of a stabilizer consisting of tribasic lead sulfate and higher fatty acid lead covering the same, per 100 parts by weight of the chlorine-containing polymer. , The tribasic lead sulfate has d = 3.
Assuming that the relative peak intensities of the X-ray diffraction images at 27 Å, d = 3.14 Å and d = 3.09 Å are I _3.27 I _3.14 and I _3.09 , the following I _3.14 / I _3.27 = 0.20-0. 44 I _3.09 / I _3.27 = 0.10 to 0.29 and I _3.09 / I _3.14 = 0.50 to 0.85, and the volume-based median diameter is 0.5 to 0. A chlorine-containing polymer composition for injection molding, characterized in that it comprises tribasic lead sulfate having an aspect ratio of 1.0 to 1.5 in the range of 0.8 μm.