JPS5831105B2 - Stabilizer for chlorine-containing polymers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a chlorine-containing lead sulfate containing tribasic lead sulfate having a novel combination of particle size and crystallographic properties. Regarding stabilizers for coalescence.

Heretofore, basic lead sulfates, such as tribasic lead sulfate, have been widely used as stabilizers in chlorine-containing polymers such as chloride-binyl resin and chlorine-hypolyethylene.

Commercially available tribasic lead sulfate consists of orthorhombic needle-shaped crystals with a major axis of 2 to 8 microns and a minor axis of 0.3 to 1 micron (μ), but it In general, sufficient thermal stability cannot be obtained unless it is used in a relatively large amount, such as 4 to 7% by weight, which is still sufficient for the purpose of reducing the lead content of various chlorine-containing polymers. It was nothing.

The inventors first filled a rotary mill with granules of metallic lead, a liquid medium, and oxygen gas. The rotary mill is rotated under conditions in which the particles of lead metal are exposed in the gas phase above the surface and rub against each other in the liquid medium. We have proposed a new method for producing lead oxide, which consists of separating a dispersion dispersed in a medium and recovering the lead monoxide produced from the dispersion in the form of fine powder (Japanese Patent Application Laid-Open No. 1516975/1983). ).

The new lead oxide obtained by this method has a primary particle size of less than 0.2 microns and a chromic anhydride reaction rate of more than 94%, and is characterized by being extremely fine and easily reactive. are doing.

The present inventors used the above-mentioned wet method lead monoxide as a raw material,
The tribasic lead sulfate obtained by reacting this with sulfuric acid under the specific conditions described below has a novel combination of particle size and crystallographic properties. When lead sulfate is blended with a chlorine-containing polymer, excellent thermal stability, dispersibility, and electrical insulation properties are obtained, and a stabilizer composition in which this ultrafine tribasic lead sulfate is supported on filler carrier particles It has been found that the thermal stabilizing effect is maintained without substantially decreasing despite the reduction in the blending ratio of basic lead sulfate, and furthermore, the transparency of the blended resin composition is significantly improved.

According to the present invention, the wet method consists of tribasic lead sulfate particles obtained by the reaction of acid arsenic and sulfuric acid, and higher fatty acid lead coating the particles, and the coated particles have a particle diameter of 0.2 microns or less. Number average short axis, 1.8? /rnl or less, and in the formula, ■3.2□ is the intensity at a-3, 27A of the X-ray diffraction image, and ■3. .

Provided is a stabilizer for chlorine-containing polymers, characterized in that the X-ray intensity ratio (R) defined by 9 represents the intensity at d-3,09 of an X-ray diffraction image is 7 or more. .

In one embodiment of the present invention, the number average minor axis is 0.2 microns or less, 1.8'? /ml or less, and in the formula, ■3.2□ is the intensity at d=3.27 hole of the X-ray diffraction image, and I3. .

9 represents the intensity of the X-ray diffraction image d3.09 in humans.Tribasic lead sulfate (A) with an X-ray intensity ratio (R) defined as 7 or more is the inorganic filler (B) and A : B=95
: Used as a stabilizer for chlorine-containing polymers in the form of an intimate mixture containing in a weight ratio of 5 to 30 nia.

The ultrafine tribasic lead sulfate used in the present invention is produced using arsenic monooxide as a raw material by the wet method described above.

This raw material ~ acid f arsenic is 8.3 to 9.2 f/cc
True density of primary particle size less than 0.2 microns, wave number approximately 14
It has an infrared absorption peak between 00 and 1410 crrL' and a chromic anhydride reaction rate of 94% or more.

The details of the manufacturing method of this arsenic acid are disclosed in JP-A-52-1516.
It is described in Publication No. 97, so please refer to it.

Furthermore, as the raw material - arsenic acid, arsenic acid is dispersed in water to form an aqueous slurry, and this aqueous slurry is then divided into an upper layer containing a component rich in lead monoxide and a component rich in metallic lead. It can also be produced by a combination of a step of separating the lower layer into a lower layer containing -acid f arsenic and a step of contacting the upper layer aqueous slurry containing the arsenic-rich component with molecular oxygen (
Patent Application No. 52135909).

In the present invention, it is extremely important to use a wet process - lead oxide, which has a fine particle size and high reactivity, in order to produce basic lead sulfate with the combination of particle size and crystallographic properties described above. It is.

As shown in the comparative example below, when the raw material is ordinary lead monoxide obtained by acid-fusing lead zinc oxide produced by the so-called lead powder method at a temperature of 600 to 700°C in an oxygen atmosphere. , the number average minor axis is 2 microns or more, and the bulk specific gravity is 1.
9? Only tribasic lead sulfate in the form of coarse needle-like crystals of /ml or more is produced.

The lead monoxide produced by the wet method described above can be used for the reaction with sulfuric acid as the aqueous slurry obtained, or, if desired, can be subjected to the reaction with sulfuric acid in the form of a cake or dry powder. I can do it.

In addition, arsenic peroxide (PbO2) is often mixed into the arsenic peroxide produced by the wet method in many cases, but in order to improve the hue of the final product, It is desirable to remove it by reduction in advance.

Arsenic peroxide can be reduced by adding an equivalent amount or more of an acid addition salt of hydroxylamine, such as hydroxylamine sulfate, to a lead monoxide slurry by a wet method, and then reacting this addition mixture with sulfuric acid. It can be suitably carried out in a reaction system of arsenic monoate.

The reaction with sulfuric acid is carried out by applying a stoichiometric amount of sulfuric acid to an aqueous slurry of arsenic monoate.

-Acid f arsenic slurry concentration is 5 to 45P/100cc
It is advantageous in terms of handling to keep the range within this range.

It is desirable to add sulfuric acid in the form of an aqueous solution in order to carry out a uniform reaction, and its concentration is preferably in the range of 2.5 to 8 mol/l.

The amount of sulfuric acid varies depending on the basicity of the target basic lead sulfate, but it is 115 mol per 1 mol of Pb0 or 1"; +1
/2 mol.

In the present invention, it is also extremely important that the arsenic slurry is heated within a time period of generally 5 seconds to 40 minutes, particularly 10 seconds to 20 minutes.

The rate of use of sulfuric acid is closely related to the rate of formation of crystal nuclei of basic lead sulfate, and therefore the rate of growth of crystals in the C-axis direction. The growth of the crystals in the C-axis direction becomes incomplete, and the thermal stability and the synergistic effect of the composite with the filler tend to decrease.

Furthermore - it is advantageous for the reaction of the lead oxide slurry with sulfuric acid to be carried out at as low a temperature as possible in order to obtain tribasic lead sulfate with fine particle size characteristics and specific crystallographic properties; In consideration of heat generation due to pressurization of sulfuric acid, the reaction between the two is preferably carried out at a temperature of 80° C. or lower, preferably 40° C. or lower.

The reaction and aging time may be any time as long as it is sufficient to grow the crystals sufficiently, and is generally 10 minutes to 1 hour after mixing the two.
It is sufficient to age the mixed liquid for a long time; aging for a long time will cause the crystals to grow larger.

The reaction can be carried out without a catalyst using the wet method, taking advantage of the easy reactivity of arsenic, but in general, from the viewpoint of the hue of the final product,
It is desirable to add a catalytic amount of a monobasic organic acid such as acetic acid to the arsenic monoacid slurry prior to the reaction.

The amount of catalyst used can be considerably smaller than in the conventional production method of basic lead sulfate, and when acetic acid is selected as the catalyst, -acid f
The amount of acetic acid catalyst used per 100 moles of lead B (PbO) may be 0.25 mol or less, preferably 0.2 mol or less.

The resulting tribasic lead sulfate can be subjected to various post-treatments desirable for stabilizers for chlorine-containing polymers.

For example, forming a coating of higher fatty acid lead on the surface of the basic lead sulfate particles used in the present invention improves dispersibility,
It is also desirable to prevent particles from coagulating together.

This coating process can be performed as follows.

That is, the produced aqueous slurry of basic lead sulfate and a solution or emulsion of ammonium salts, amine salts, etc. of higher fatty acids such as stearic acid, palmitic acid, and lauric acid are mixed at a temperature of 40 to 95°C. , one of the PbO contained in basic sulfate was converted on the spot to lead salt of higher fatty acid.
Hi.

According to such a coating method, fine particles of basic lead sulfate as produced are coated with the metal soap serving as a dispersant without agglomeration, and a stabilizer with extremely excellent dispersibility can be obtained.

Alkali metal salts can also be used as higher fatty acid salts, but in this case a washing operation is required to remove the alkali metal salts from the final product.

The coating amount of the higher fatty acid lead salt is preferably in the range of 0.1 to 24% by weight, particularly 0.5 to 12% by weight, based on basic lead sulfate, from the viewpoint of dispersibility and workability.

The product obtained is separated, dried, loosened if necessary, and used for the purpose of the present invention.

The tribasic lead sulfate used in the present invention can be in the form of a mixture with a basic salt, a dibasic salt, a tetrabasic salt, or the like.

Figure 1 shows the novel tribasic lead sulfate used in the present invention (Example 1).
Fig. 2 is an electron micrograph of tribasic lead sulfate obtained by the conventional method (comparative example is sample number 1B).

As is clear from FIGS. 1 and 2, the tribasic lead sulfate prepared by the conventional method has a number average minor axis of O,S microns or more, and the basic lead sulfate used in the present invention has O,S microns or more.
It has a number average minor axis of 2 microns or less, particularly 0.18 microns or less, and it is understood that the crystals are extremely fine.

Furthermore, basic lead sulfate by the conventional method is 2. (J?/ru1
In accordance with the above bulk specific gravity, the basic lead sulfate used in the present invention has remarkable characteristics due to the fact that the particles are fine and the crystals in the C-axis direction are acicular in development. Small bulk specific gravity, i.e. below 1.1'/rnl, especially L7ff/
It is characterized by having a bulk specific gravity of ml or less.

The attached drawing, Figure 3, shows the tribasic lead sulfate used in the present invention.
A line diffraction diagram is shown.

As is clear from FIG. 3, although the basic lead sulfate used in the present invention has a small number average minor axis of crystal particles of 0.2 microns or less, It is understood that the linear intensity ratio (R) is 7 or more, especially 10 or more, and that although the particles are fine, the crystals in the C-axis direction are clearly developed.

Conventional stabilizers for chlorine-containing polymers made of microcrystalline tribasic lead sulfate include those reacted under conditions that inhibit the growth of tribasic lead sulfate crystals, or ordinary tribasic lead sulfate. Finely pulverized lead sulfate is known
As shown in the X-ray diffraction diagram in Fig. 4, the tribasic lead sulfate species disclosed in Japanese Patent Publication No. 9-15625 has an X-ray intensity ratio (R) of 6 or less, and the crystals are formed in the C-axis direction. It is incompletely developed, or once grown, it is destroyed perpendicular to the growth direction, and in this respect it is clearly distinguished from basic lead sulfate used in the present invention.

The novel ultrafine tribasic lead sulfate of the present invention can be used as a stabilizer with any chlorine-containing polymer, such as vinyl chloride resin, vinylidene chloride resin, 1-hibinyl salt/5-vinylidene salt copolymer, chlorine [hypolyethylene, Chop it into chlorinated vinyl chloride polymer, polychloroprene, etc. and mix it in the amount necessary for stabilization.

The blending amount varies depending on the type of resin and its use, but it is generally 2 to 15 parts by weight, particularly 3 to 10 parts by weight, per 100 parts by weight of resin.

That is, the tribasic lead sulfate of the present invention can achieve sufficient stabilization even when used in a significantly smaller amount than conventional stabilizers.

Furthermore, when this stabilizer is blended with a chlorine-containing polymer,
The electrical insulation properties of the final molded product are significantly superior to those containing conventional basic lead sulfate.

Furthermore, this stabilizer has excellent dispersibility in chlorine-containing polymers.

The ultrafine basic lead sulfate stabilizer of the present invention exhibits unexpected effects when used in intimate admixture with fillers.

Generally, the thermal stabilizing effect of a chlorine-containing polymer depends on the amount of lead-based stabilizer blended, and the heat stabilizing effect decreases in proportion to the decrease in the blended amount.

However, surprisingly, in the present invention, the particulate tribasic lead sulfate (A) and the inorganic filler (B) are mixed in the following manner: A:13=95:
5 to 30 near 0. In particular, a homogeneously mixed stabilizer composition combined in a weight ratio of 95:5 to 50:50 has a heat stabilizing effect even though the amount of basic lead sulfate is substantially low. The decline is virtually unnoticeable.

Although the exact reason for this is unknown, it is thought that among the stabilizer particles, it is the particle surface that is in contact with the chlorine-containing polymer that actually helps in thermal stabilization, and the composite stabilizer of the present invention The effective specific surface area of basic lead sulfate is extremely large, and the particles have a particle shape that makes it difficult for them to coagulate with each other, and furthermore, these fine particles are supported on the surface of the filler, resulting in thermal stabilization. This seems to be due to the fact that the surface area that contributes to this has become significantly larger.

As the inorganic filler, oxides, hydroxides or salts of metals from Group 2 of the periodic table are most preferably used.

Suitable examples include barium oxide, magnesium oxide, hyaluronic hydroxide, hybarium hydroxide, zinc white, calcium carbonate, barium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, basic magnesium carbonate, hydroxide. Examples include magnesium, strontium carbonate, calcium phosphate, calcium silicate, magnesium silicate, barium silicate, etc., but heavy to light calcium carbonate is most preferred.

As the filler, hyaluminum hydroxide, silica powder, Aerosil, various clays, glass powder, hytitanium diacid, etc. can of course be used.

Inorganic fillers may be used alone or in combination of two or more in an amount of at least 3% by weight, particularly 5% by weight or more, based on basic lead sulfate.

The stabilizer of the present invention includes any compounding agents known per se, such as plasticizers (phthalates, phosphates, etc.), metal soaps (lead stearate, calcium stearate, barium stearate, etc.), and lubricants. (fatty acids such as stearic acid, waxes, fats and oils, etc.), stable fusing agents (epoxy compounds, ring phosphate esters, etc.), colorants, modifiers (ABS resin, acrylic resin, etc.) are blended into a powder. Alternatively, it can be made into a granular one-package formulation.

The incorporation of the stabilizers of the invention can be carried out by means known per se, for example by rolling, blending mixer,
Each compounded component is kneaded using a device such as a kneader, a pelletizer, or a mix truder, and then molded into an arbitrary shape such as a pipe, sheet, sheath, or various piping parts using an extruder, injection molding machine, or the like.

The excellent effects of the present invention will be explained in the following examples.

Reference Example 1 In this reference example, a method for producing arsenic acid directly from metal lead grains in a wet process and its arsenic acid will be explained.

The present manufacturing method and lead oxide were carried out in accordance with the method described in the specification of the published patent (Japanese Unexamined Patent Publication No. 151697/1982) invented by the present inventors.

As the raw material metal lead, a metal lead ingot of Fowa Anain, which is called electrolytic lead, was melted and shaped into a spherical bottom with a diameter of about 1 to 6 mm using the principle of melt fracture.

As a device for producing lead oxide directly in water from these metallic lead particles, a stainless steel rotary mill using a wet grinding method described below was selected, and a method of continuous production using this rotary mill was adopted.

This rotary mill for continuous production is a stainless steel tube mill with an inner diameter of 34.5CrL, a length of 130CrIL, an internal volume of approximately 1201cm, and a pressure-resistant container that can withstand 10kg/cr;t gauge pressure. A manhole of approximately 20 CrrL square is provided in the center of the mill to enable cleaning of the interior and charging of raw materials.Of course, the manhole is provided with a lid to withstand a gauge pressure of 10 kg/cm.

Furthermore, as an inlet for the liquid medium, a 1/2-inch stainless steel pipe is connected to one end plate of the tube mill via a rocky joint, and a 3 horsepower diaphragm pump can be used to pressure inject the liquid medium into the tube mill. , On the other hand, as a reaction product slurry discharge port, a 1/2 inch stainless steel pipe was attached to the tube mill end plate on the opposite side of the inlet via a rocky joint similar to the inlet, and was placed in the tube mill. The tip of the pipe is inserted so as to be inserted below the liquid level in the mill, and the reaction product slurry can be discharged from the discharge pipe to the outside of the mill using the internal pressure within the tube mill.

At this time, in order to prevent the solid matter in the tube mill from entering the pipe, the tip of the discharge pipe is provided with stainless steel from the tip of the pipe to the center of the mill.

Furthermore, cooling water is poured outside the tube mill so that the entire tube mill is cooled.

Next, a horse camo was used to rotate this tube mill.
The tube mill is linked with a gear so that it can be driven by a motor.
At the same time, the rotation speed of the tube mill was adjusted to be variable from 20 to 100 revolutions/minute using a continuously variable transmission.

In addition, a liquid cyclone was attached to the tube mill and installed at the end of the discharge port of the tube mill to prevent unreacted substances from transferring into the product if they were mixed into the reaction product slurry. .

Using this continuous wet grinding tube mill, the conditions for producing monoarsenic monoxide directly from metal lead grains are as follows:
200 kg of fresh metal lead grains with a diameter of about 1 to 6 mm formed by the method described above are introduced through the manhole in the center of the tube mill, water is selected as the liquid medium, and the mixture is heated as needed. an acetic acid solution containing acetic acid as a catalyst as indicated in Table 1 is chosen as the liquid medium, and each of these liquid media is maintained at the temperature indicated in Table 1;
If the temperature is low, it is actively cooled to a predetermined temperature, and on the other hand, the tube mill is also poured with water whose temperature has been adjusted to the desired predetermined temperature from the outside to maintain the predetermined temperature.
First, water or acetic acid solution 301 maintained at a predetermined temperature is introduced into the tube mill by rotating at the rotational speed of the zero-turn valve, and the solid-liquid ratio of the raw metal lead particles and the liquid medium is about 6.6. Then, the cooled water or acetic acid solution is injected into the tube mill at a rate of l/min, and in parallel, the same amount of separated liquid corresponding to the amount of liquid injected at the same time is added to the tube mill. The dispersion liquid containing arsenic acid produced was adjusted so that it was discharged and collected from the mill, and the dispersion liquid containing the arsenic acid produced was continuously collected.

In parallel with this, oxygen gas (0□) was filled into the tube mill from an oxygen cylinder, and the internal pressure was adjusted to the internal pressure gauge pressure shown in Table 1. Continuous oxidation reactions were carried out by selecting manufacturing conditions such that the internal pressure was always maintained at a predetermined internal pressure gauge pressure using oxygen gas.

After 30 minutes of the oxidation reaction, the resulting dispersion containing lead oxide is collected, and the unreacted metal lead contained therein is separated and removed using a liquid cyclone. Three types of arsenic dispersions (A-LA2 and A-3
) was produced and recovered.

At this time, the amount of dispersion liquid collected here and the P in the dispersion liquid are
The bO concentration was measured, and the PbO production was determined from this value.

The results are also shown in Table 1. Furthermore, each recovered dispersion liquid was subjected to a solid-liquid separation operation using a centrifugal separator, and each cake obtained was dried under reduced pressure at a low temperature of 50°C to form three types of new ultrafine powders with reactivity. f-arsenic monoate (A-1, A-2, and A-3) rich in light resistance and excellent in light resistance were produced.

Eight physical properties were tested and measured for each of the arsenic acid powders obtained here using the methods described below, and the above measurement results are also shown in Table 1.

Test method: (a) -Acid f Arsenic (PbO) production amount (S'/hr)
Acid (recovered after 30 minutes of arsenic reaction).

Recovery amount of recovered dispersion liquid (1rLl) and monoacid f of the dispersion liquid
From the analytical measurement results of the arsenic (PbO) concentration (P/100 m1), the amount of PbO produced was calculated from the direct absolute amount of arsenic monooxide produced by the oxidation reaction in 30 minutes, and 6
It is expressed in terms of the amount produced in 0 minutes.

The quantitative analysis of -acid f arsenic was conducted in accordance with the method described in JIS K-1456 and by the method described below.

(b) Average particle size (number average) Using a super scope type (JEM-50) electron microscope manufactured by JEOL Ltd., samples were taken using the water paste method using a collodion-carbon vapor deposited film, and the particles were sampled at a magnification of 1000 to 3000 times. , the size of 200 to 300 particles was measured, and the average particle diameter (μ) was determined from the number average of the size of each particle.

(C) Fill a true density pycnometer with benzene solution and fill it with weight (W
) and the temperature (Ti) with the provided thermometer.

Next, pay out the benzene. Predetermined amount of sample (M(P)
), further benzene was added, the mixture was placed in a vacuum desiccator, the pressure was reduced to 3 mmHg using a vacuum pump for 3 hours, the cock was closed, the photographic pump was removed, and the temperature was brought to Ti and left overnight.

Open the cock, take out the pycnometer, fill it with benzene, measure the weight (W') and temperature (Ti), and calculate using the following equation (1).

dS: Sample density d: Specific gravity of benzene in Ti'C (d) Pour 500 ml of water into a beaker with a chromic acid reaction rate of 21, accurately weigh 69.06 P of lead oxide powder as a sample, and slowly The dispersion was poured into the water with good stirring to ensure sufficient dispersion in the water, and then the dispersion was heated to 65°C.

On the other hand, an aqueous solution of chromic anhydride (30,94P
/100ml of water) was slowly added 3 times while stirring.
It was heated for 0 minutes, and then kept at 65°C.
The mixture was stirred and aged for 60 minutes to form lead chromate crystals.

Next, the crystals of lead chromate are filtered through As2 paper and washed with water. The lead chromate thus produced is dried at 110°C, and the amount of chromic acid fixed as lead chromate is removed by drying. Quantitative analysis was performed using the amount (P) of chromic acid (CrO3), and from this result, the amount (P) of fixed chromic acid (Cr03) (
AC) and the amount of chromic acid (CrO3) of the raw material used (P
)(TC), from the following formula (2), RC=AT/T
Cx 100 (%)・・・・・・・・・・・・(2)
The chromic acid reaction rate (RC%) was determined.

(e) X-ray diffraction measurement X-ray self-recording diffractometer manufactured by Rigaku Denki (X-ray generator is Ca
tA2001. The goniometer is a wide-angle Cat
A, 2227, Proportional Counter) was used to measure the sample using the powder measurement method according to the following diffraction conditions.

Diffraction condition target Cu filter
Ni voltage
30KV current 1
5mA count range 1000 cps
High voltage 1450V time constant 1 sec chart speed
1cm/min scanning speed 1°/mir + diffraction angle (2θ)
17°～60.5°Slit width 1°
-1°-0,3 The abbreviations in the table are M: Mashicot type;
L: Lissage type and H: hydrated type of arsenic monoate.

(f) Take 1 gram of light resistance sample on a glass plate of a set of Fever muller,
Vehicle (castor oil 1 ? +D 1 octylpht
Halate' (DOP) 1? ) 0.6
ml and knead thoroughly with a mala to make it homogeneous, transfer it onto a glass plate, add 3.7 ml of permanent lacquer clear, and mix well to make a homogeneous paste. do.

Pour the prepared paste onto art paper, leaving a gap of 0.
Using a 2032 mm film applicator, it is stretched to a uniform thickness on the art paper and air-dried at room temperature to form a hue sheet.

This hue sheet was set at a distance of 36 CrfL from a high-pressure mercury lamp for fading test (manufactured by Tokyo Shibaura Electric (model H-400FT)), and was rotated at a rotation speed of 2 prm for 24 hours.
Irradiate with a mercury lamp for an hour.

The hue of the obtained hue sheet that was irradiated with a mercury lamp and the hue sheet that was not irradiated with a mercury lamp was measured using a color difference meter (Model ND-101D manufactured by Nippon Heavy Industries Ltd.), and the hue was calculated using the following formula (3). △E(
Color difference) is determined and calculated.

Lo, ao, bo: Hue before light irradiation, a, b: Hue after light irradiation (g) Metallic lead content Based on the method described in JIS K-1456 (Lyssage quantitative method), acetic acid insoluble content That is, the metallic lead content was quantified and the content was expressed in (%).

(h) Hiding power In accordance with the method described in JIS K51.04-1964, first test sample 5z by the method described in the light resistance section.
and vehicle (castor oil 10P+DOP10?) 3mA
A paste in the form of a colorless lacquer was prepared by thoroughly kneading the paste, and the hiding power of this paste was measured using a cryptometer, and the hiding power was calculated from the following formula (4).

W: Number of grams of the sample ■ = Number of cc of oil used d: Specific gravity of the sample: Reading of scale with cryptometer constant 1 Amount of change in thickness of wedges arranged in mm L: Nominal line of cryptometer becomes invisible Reference example
2 In this reference example, a method for producing lead oxide using zinc oxide powder (lead powder) as a raw material and lead oxide will be described.

This manufacturing method and arsenic acid are described in the patent specification (Japanese Patent Application No. 52-13590
9) The method described in the specification was followed.

As the lead zinc oxide powder used as a raw material, dark gray-green 1-arsenic oxide powder manufactured by the Shimadzu lead powder method was selected.

The Shimadzu lead powder method employs a method of producing lead powder by dry-pulverizing pre-shaped metal lead particles from the same electrolytic lead as selected in Reference Example 1 in a rotary mill. Arsenic acid powder was recovered.

The recovered arsenic acid f arsenic powder was analyzed and measured according to the method for measuring the metallic lead component described below. The impurity iron (Fe203) was 5ppm, and the copper content (Fe203) was 5ppm.
CuO) to 0. The "bulk" of the powder was 0.72 ml/7.

Incidentally, when measuring the "bulk" of the powder, the reciprocal of the value measured by the bulk specific gravity measurement method described later was taken and expressed in ml/g.

The arsenic acid powder is prepared into an aqueous slurry using water prior to entering the oxidation step.

At this time, the concentration of suboxide f arsenic component in the aqueous slurry was 20
Adjust to a concentration of 100 ml.

Next, a liquid cyclone applying centrifugal force classification is used to classify and separate the coarse metallic lead powder contained in the raw material lead zinc oxide powder and the coarse particles of suboxide f arsenic powder. An aqueous slurry of lead powder was prepared.

The liquid cyclone used in this S was a stainless steel liquid cyclone with a diameter of 55 mm, a conical apex angle of 20 degrees, an inlet of 8 mm, a downstream nozzle of 6 mm, and a discharge pressure of 1.8 ky/crA.

The composition of the aqueous slurry of homogeneous lead zinc oxide whose coarse particles were classified and separated using this liquid cyclone is 12.4 P/100ml as a solid content, and the amount of metallic lead in this solid content is 12.4 P/100ml. was 10.5% by weight.

As a contact method for this homogenized aqueous slurry of lead zinc oxide and molecular oxygen, a contact method mainly using an aeration method was adopted. , we adopted a bench scale device with a single-fluid nozzle installed at the top of a circular stainless steel tower with a height of 2 m and a diameter of 0.6 m, and an aqueous slurry of zinc oxide was sprayed into the tower from the nozzle. The aqueous slurry that was oxidized by the spray was recovered from the conical part provided at the bottom of the tower by making efficient contact with oxygen in the air.

Then, in order to increase the oxidation efficiency of the aqueous slurry in contact with oxygen by this spraying, a height of 1 m and a diameter of ° 0.6 was installed after the lower conical part of the contact tower with the above aeration method.
A bubble column equipped with an atomizer was attached to disperse air from the bottom of a mφ stainless steel tank into the liquid in the tank by bubbling.

After introducing the aqueous slurry recovered from the contact tower into this bubble column and filling it, air is finely dispersed in the aqueous slurry using an atomizer installed inside the bubble column, and the above aeration ensures sufficient contact with oxygen. This provided sufficient time for the acid reaction of the oxygen-entrained aqueous slurry to be completed and completed effective oxidation.

In addition, after the aeration type contact tower attached to this bubble column, unreacted suboxide (liquid similar to that used in preparing the aqueous slurry of homogeneous suboxide f arsenic described above for separation and classification of the arsenic component) Cyclone included.

This liquid cyclone was used to classify and separate the unoxidized lead zinc oxide component remaining in the aqueous slurry after the acid milling process.

The manufacturing conditions in the above manufacturing process were carried out under two types of conditions shown in Table 2, and two types of -acid (arsenic dispersion liquids (sample numbers B-1 and B-2) were recovered.

In addition, the amount of monoacid [arsenic] recovered in this S is expressed as the amount of metal lead (
The lead component present in the aqueous slurry of zinc oxide powder added to the oxidation process in terms of Pb) is determined by the recovery rate (%) of arsenic monooxide relative to the metallic lead content (Pb), and the result is calculated as follows. 2
They are also shown in the table.

Next, various physical properties of the lead monoxide slurry recovered here were measured, including its average particle size, composition of the metallic lead component of arsenic acid, chromic acid reaction rate, X-ray diffraction hue, and light resistance. The results are also shown in Table 3.

In addition, in the above-mentioned physical property measurement, the composition of the metallic lead component and the like of the arsenic acid was analyzed by the following method.

Composition of metal components, etc. of arsenic acid: The composition was analyzed in accordance with the method described in JIS K1456 (Litharge quantitative method).

In this specification, aqueous slurries are often used as row samples, but unless otherwise specified, all compositions are expressed in weight percent on a dry matter basis.

(1) Arsenic acid 1 (PbO) Weigh the sample accurately, measure the moisture content, and after converting the moisture content, (
If the sample was a powder, it was moistened with water beforehand.

) Add 6N acetic acid, heat, dissolve, and then cool.
Adjust the pH of the sample solution to 5.0 with aqueous ammonia and buffer.
After adjusting the concentration to 0 to 5.5, titration was performed with a 1/100 molar EDTA (disodium ethylenediaminetetraacetic acid) solution using xynol orange as an indicator.
- The content (%) of acid (arsenic (PbO)) was determined on a dry matter basis.

(2) Komyotan (Pb304) After sampling in the same manner as in the case of -lead oxide in (1) above, the sample was dissolved in 6N acetic acid and sodium acetate, and then a certain amount of 1/10N thiosulfuric acid was added. A sodium solution was added, and after a certain period of time, back titration was performed with a 1/10N iodine solution using the starch solution as an indicator to determine the content (%) of Pb3o4 on a dry matter basis.

(3) Metallic lead (Pb) After sampling in the same manner as in the case of -acid arsenic in 1) above, 6N acetic acid was added and dissolved by heating, and at the same time, a small amount of 1 molar hydroxylamine hydrochloride was added. , dissolve the lead peroxide f arsenide present in the sample, then divide it into one piece of paper, wash it with warm water, and wash it until no lead component is detected in the washing solution, then divide the above one piece of paper into one piece of paper. Transfer the residue to an Erlenmeyer flask, and dissolve the metal lead on the paper with 6N nitric acid and 3
After dissolving with 2 to 3 drops of 0% hydrogen peroxide solution and adjusting the pH to 5 using aqueous ammonia and sodium acetate,
The content (%) of metallic lead (Pb) was determined on a dry matter basis by titration with a 17,100 molar EDT A solution using xylenol orange as an indicator.

(4) Impurities (Fe, Cu) After sampling in the same manner as in the case of -lead oxide in 1) above, add nitric acid and hydrogen peroxide to dissolve it, and repeat evaporation to dryness. Fe (iron) and Cu (copper) were quantified in accordance with KO120 "General Rules for Atomic Absorption Spectrometry", and their content (%) was determined on a dry matter basis.

Example 1 In this example, a lead compound, which is a heat stabilizer for vinyl chloride resin, will be explained using a new arsenic acid produced by a wet method.

New raw materials - As lead oxide, some of sample numbers A-1, B-1 and B-2 produced in Reference Examples 1 and 2 were prepared into powder by dehydrating and drying the arsenic slurry at low temperature. (Arsenic was selected, and then water was added to the lead oxide powder to adjust the slurry concentration to a PbO content of 140?/e. Three types of partially oxidized lead slurry were selected.

A tribasic lead sulfate powder in the form of fine particles for use as a stabilizer was produced using the slurry of the novel arsenic acid f as a raw material by the following method.

In addition, in this specification, "tribasic lead sulfate" is referred to as rTB.
It may be expressed below using the abbreviation LJ.

The above new acid 1 arsenic slurry 655771. Pour 1 of each into 21 beakers and heat to 40°C while stirring with a glass blade.

Next, 10 ml of a 3% solution of hydroxylamine sulfate was mixed well to reduce the arsenic peroxide partially present in the lead oxide slurry, resulting in a concentration of 3.861 mol/ml.
l of sulfuric acid (H2SO4) solution 26.14 TIll to 10
The mixture was quickly added within seconds and stirred, and after 30 minutes, the mixture was heated to 65 to 70° C. on a heater and reacted and aged in that state for 60 minutes to prepare microcrystalline TBL base slurries.

At this time, the slurry 1,1-pH was 8.2.

Separately, 1.44 granular stearic acid in a 200ml beaker?
and ammonia water with a concentration of 0.736 mol/l2.
Ammonia soap is prepared by taking 08 ml and 50111 ml of water, stirring vigorously with a glass rod, and heating to 90°C to completely emulsify.

This ammonia soap suspension was applied to the above TBL base slurry to disperse it well, and heated and aged for 60 minutes while maintaining the temperature at 65 to 70°C. Too much TBL is separated,
The cake was dried in a constant temperature dryer at 90° C. for one day and night, and then ground in an atomizer to produce three types of fine particle white TBL powder (sample numbers 1-1.1-2 and 1-3).

Each of the TBL powders produced here was tested for each test item according to the test method described below, and the results are also shown in Table 5.

In this example, in the tests (thermal stability, insulation, etc.) using PVC resin, the sample stabilizer was resin],
It was tested by mixing 5 parts by weight of each into 0 parts by weight.

(1) Number average short diameter Using an electron microscope in accordance with the method described in the section (b) Average particle diameter (number average) of Test 1 test method of the reference example described above,
Sampled using the grease-paste method, and then
i-000 to 20000x magnification, 200 to 3
The major axis and minor axis of 00 particles were actually measured, and the number average minor axis (μ) was determined from the number average of the measured values of the major axis and minor axis of each particle.

(2) Bulk specific gravity specific volume tester that performs drop impact 30 times at 15 rotations per minute
Pour the sample little by little into a calibrated test tube of Ishiyama Specific Volume Tester (Ishiyama Specific Volume Tester, manufactured by Ishiyama Kagaku), tap the bottom of the test tube, and repeat this until the sample almost matches the 20 m1 mark.

This was placed in the above test tube and rotated at 300 rpm for 20 minutes at 60 rpm.
Perform a fall impact 0 times.

After that, remove the graduated test tube and read the volume vml, then take out the content sample on a medicine wrapper, weigh its weight Wg, and from this, the bulk specific gravity of the sample (D ) ('?/ml>
(3) X-ray intensity ratio (R) Based on the method described in (e) X-ray diffraction measurement section of the test method of the reference example mentioned above, except that the diffraction conditions are
Diffraction angle 27.26° (planar spacing (n=
1) equivalent to d=3.27A and 28.89° (d=
The areas of the peaks with X-ray diffraction intensities I3.2□ and I3.09 were determined from the height and half-width of both peaks of 3.09 people, respectively, and the ratio ■3.2□/■3. .

9 (=R) was determined, and this R was used to define the X-ray intensity ratio R.

(4) Add 50 parts by weight of DOP (manufactured by Kyowa Hakko) to 100 parts by weight of heat-stable vinyl chloride resin (Vinicron 4000M manufactured by Mitsui Toatsu), and further add the specified weight part of the sample lead compound stabilizer to ensure sufficient homogeneity. The mixture was kneaded for 7 minutes at 160°C using a 3.5-inch kneading roll, and then taken out as a sheet with a thickness of about 0.5 mm.

Three of these sheets were stacked at 165℃ and weighed 100 kg.
/c77L Press for 7 minutes to prepare a soft sheet approximately 11n7rt thick.

Next, the sheet prepared here is approximately 3×10 CrrL
The sample pieces were cut into corners, placed on a stainless steel plate coated with silicone oil, placed in a gear oven kept at 190°C, and a sheet of this sample piece was placed on a stainless steel plate coated with silicone oil. The time (minutes) it took for the material to turn black due to thermal decomposition was measured, and the longer it took to turn black, the better the thermal stability.

(5) Plasticity kneading resistance tester (Plasticorder manufactured by Prabender Co., Ltd.
60CC for PLASTI-CORDER) P151 type)
Attach the attached roll mixer, weigh out 5.0 parts of each stabilizer sample to 100 parts of salt f vinyl resin (Zeon 103EP), mix them, charge 551 from the mixture into the above mixer, and heat at 200°C. , rotation speed 35r, p
The plasticity state of the resin mixture due to kneading under the temperature conditions at this time is measured over time, and the cross-wire resistance that occurs at that time is recorded as torque (kym) on a chart, and the torque of the cross-wire resistance is the maximum. The time when it became plastic f
The time required for this time is taken as the plasticization time (gel f
The maximum torque at this time (τ
max) (kg・m).

Note that if the blend of resin and stabilizer is too slippery, the plasticization (gelling) time will be long and the maximum torque will be low.

On the other hand, if the compound has low slipperiness, the plasticization time will be short (and the maximum torque will be high).

In particular, in the case of soft formulations, plasticizers are added, so during actual molding processing, the data from this plasticcorder shows that gelation due to plasticization of the resin is less likely to occur, making it difficult to manufacture the desired molded product. be.

(6) Insulating properties (volume resistivity) JIS K67 JIS K67 lead compound stabilizer vinyl resin press soft sheet made in the same manner as in (4) above.
Volume resistivity (
Ω-cIrL) was determined.

That is, after the mixed wire press sheet prepared by the above method was left in a steady state in a desiccator for at least 24 hours, 30 copies of this sheet test piece were kept at a constant temperature in a constant temperature bath at 2°C, and then ultra-super insulating Meter ((Model 5M-10 manufactured by Toa Denpa Kogyo ■)
The volume resistivity (Ω-crrL) was determined and the sheet thickness etc. were corrected to obtain the volume resistivity.

(7) Dispersibility To evaluate dispersibility, 0.05 part of carbon black (Sheath) H (manufactured by Tokai Electrode) was homogeneously mixed with 100 parts of a commercially available vinyl chloride resin (Sumiritsu SX-11F (manufactured by Sumitomo Chemical))2 Weigh sample 1' into a 100TLl beaker using a top balance (Akudo 0.11), add DOP (manufactured by Kyowa Hakko) 121, and then sample 1'? Add.

Without mixing the contents of this beaker too much,
The black film was dropped onto a 3.5-inch diameter double roll (friction ratio 1.25) with a surface temperature of 160°C, kneaded for 10 minutes, and then taken out as a 0.2 mm thick sheet. 0, 1 to 0.
2mm small white spot, 0.2-0.3mm medium white spot and 0
．． The number of white spots of 3 mm or more was counted, and the larger the number of white spots, the poorer the dispersion, and the case where no white spots were observed was considered good.

(8) Light resistance A vinyl chloride resin pressed soft sheet containing the lead compound stabilizer sample of this experiment prepared by the method described in (1) was treated in the same manner as in (f) Light resistance described in Reference Example (1). The press sheet was irradiated with a mercury lamp for 3 hours using a high-pressure mercury lamp for a fading test, and the change in hue at that time was determined as ΔE (color difference) using a color difference meter.

The smaller the color difference, that is, ΔE, the better the light resistance.

(9) Transparency Place pressed soft sheets prepared in the same manner as in (4) above on black paper, and observe the black density when the black of the underlying black paper is visible through the sheet. did.

As a result, when the black color under the bulrush was observed as transparent or almost transparent, it was marked with "◎", and when the black color was slightly opaque, it was marked with ``○'', and the black color under the bulrush became whitish and opaque. Objects are indicated with an “x” mark.

At this time, the darker the black density appears, the lower the hiding power is and the more transparent the sheet is. In other words, when the light transmittance is not impaired, the pigments that are added when coloring the resin are generally carved into the purpose and work effectively to obtain the desired hue. This shows that only a small amount of dye is required.

As a comparative example, TBL was manufactured by the lead powder firing method manufactured by Suikagaku Kagaku Kogyo ■, which is commercially available and is industrially manufactured and used, and TBL was manufactured by the same manufacturing method as described above using surge powder as a raw material. (Sample No. 1-A) was selected for comparison.

In other words, it is manufactured by lead powder firing method or surge (PbO)
The average particle size (μ) of the powder was determined according to the test method described above.
, true density ('?/CC), chromic acid reaction rate (RC%),
X-ray diffraction, light resistance (ΔE), and metallic lead content (%) were determined.

The results are shown in Table 4.

Manufactured by this lead powder firing method, or by adding pure water to surge powder, 140? The slurry concentration was adjusted to a slurry concentration of /l, and only 655 ml of this litharge slurry was used to dissolve litharge using a known method (for example, the method described in the example of the specification of Japanese Patent Publication No. 49-15625). Without adding acetic acid as a catalyst, pour into a beaker of 21 liters and warm to 40° C. with stirring, then add 1 liter of a 3% solution of hydroxylamine sulfate.

After using it and stirring it well, the concentration was 3.861 mo.
Quickly add 26.14 ml of 1/l sulfuric acid solution over 10 seconds, stir, and after 30 minutes, heat to 65 mL on a heater.
The mixture was heated to ~70°C, and reacted and aged for 60 minutes in that state to prepare a TBL base slurry using litharge as a raw material by a lead powder firing method.

The slurry pH at this time was 8.2 tare.

Next, as in Example 1, using ammonium stearate soap, stearic acid coated TBL powder (
Sample number 1-A) was produced.

The TBL manufactured here and the commercially available TBL (manufactured by Suikagaku Kogyo ■, trade name StabinexTc) (sample number 1-B) were also tested in the same manner as above, and the results are shown in Table 5. Also displayed.

As a result of the above, ultrafine crystalline TBL manufactured using a new ultrafine resurge powder produced by a wet method as a raw material is different from TBL manufactured using a large particle diameter resurge powder synthesized by a conventional lead powder sintering method as a raw material. When compared with commercially available TBL, its crystal particle size is thin and small, especially in its short axis, at 115 or less.The surface area of this example is theoretically compared (calculated) based on the particle size per unit weight. It is understood that the fine TBL according to the present invention has 4 to 10 times more surface area per unit weight.

In other words, when these TBLs are blended into vinyl chloride resin as a heat stabilizer, even if the same weight number of TBL is blended, if the TBL is fine, the contact area with the vinyl chloride resin is 4.
It shows that there are ~10 times more.

As can be seen from the results in Table 5, this is understood to be excellent in terms of various physical properties such as thermal stability and heat resistance.

In addition, TBL synthesized by the calcination method, produced by a wet method using Sarge as a raw material, or produced in the same way as Sarge without using acetic acid as a catalyst can be understood from the chromic acid reaction rate of the raw material Lysurge. The reaction rate is poor, and even if the reaction with sulfuric acid is carried out under sufficient reaction conditions, the reaction does not proceed completely**, resulting in a pink color with a Lissage color. It is understood that in this respect as well, it has lost its usefulness as a stabilizer.

Example 2 In this example, another embodiment of producing fine particles of tribasic lead sulfate using a novel arsenic acid produced by a wet method will be described.

The new acid [arsenic slurry is made from sample number A-1 selected in Example 1 and has a PbO concentration of 186? /l
A partially arsenic slurry prepared in the following manner was selected.

2,465 ml of the above new lead oxide slurry') was placed in a beaker 51, and heated to 40°C and stirred well, 15 rnl of a 10% by weight solution of hydroxylamine sulfate was added.
is added to reduce the arsenic peroxide partially present in this arsenic acid slurry.

Then, a sulfuric acid solution with a concentration of 7.37 mol/IE 67.
25 ml was added within the predetermined time shown in Table 6, and then aged under stirring at the predetermined temperature and for the predetermined time shown in Table 6 to prepare 10 types of fine TBL crystal slurries.

These TBLs were then coated with stearic acid in the following manner.

That is, in a separate 300 Tnl beaker, granular stearic acid 7
．． Add 250rrLl of water and heat to 80°C.

While stirring vigorously in a glass frame, the concentration was 0.736 mol/l.
Add 10.4 ml of ammonia water and milk the mixture completely to prepare an ammonia soap solution.

This ammonia soap solution is poured into the base slurry of each TBL above, dispersed well, and the temperature is adjusted to 65-7.
The TBL slurry coated with stearic acid was recovered by heat aging for 40 minutes while maintaining the temperature at 0°C, and then the recovered cake was dried by one-pass separation, and then transferred to an atomizer.
, to produce 10 types of fine particle white TBL powder (sample number 2-1...2-10).

Each of the TBL powders produced herein was tested according to the method described in Example 1, and the results are also shown in Table 6.

As a result of the above, when new lead oxide manufactured by wet method is used as a raw material, even if the TBL manufacturing conditions are slightly changed, TBL with fine particles can be suitably manufactured, and it has good thermal stability and heat resistance. It is understood that it has excellent stability and dilutability.

Example 3 In this example, a stabilizer in which ultrafine tribasic lead sulfate crystals and calcium carbonate powder are homogeneously mixed will be described.

As the ultrafine TBL crystals, a slurry of fine TBL coated with stearic acid of Sample No. 1-1, which was produced using a new litharge as a raw material by a wet method according to the method described in Example 1, was selected.

As the inorganic filler, heavy calcium carbonate purified from a commercially available reagent was selected.

In addition, in this specification, "heavy calcium carbonate" is referred to as "heavy calcium carbonate".
It may be indicated below with the abbreviation ``Main Cal''.

The main cal powders were added to this TBL slurry at the respective compounding ratios shown in Table 7, stirred well to obtain a slurry with a homogeneous composition, dried, and homogeneously powdered using an atomizer. Seven types of stabilizers (sample numbers 3-1, 3-7) were prepared.

Regarding the two stabilizers prepared here, which are intimately mixed together,
The physical properties of each were measured in the same manner as in Example 1, and the results are shown in Table 7.

As a comparative example, the same commercially available TBL (sample number 1-B) selected in the comparative example of Example 1 was mixed with the main cal powder in a slurry in the same manner as above, and a comparative example stabilizer (sample number 3-B) was mixed with the main cal powder in a slurry.
B), and as a comparative example ※※ (3-C), an amount of commercially available TBL (1- Regarding the case where B) was blended with the resin, various physical properties were measured in the same manner as above, and the results are also shown in Table 7.

As a result of the above, compared with the case of Comparative Example (2-A) and Comparative Example (1-B) shown in Table 5 (i.e., commercially available TBL), the ultrafine crystals synthesized using the new litharge as a raw material T
, when the main flame cal is intimately mixed in the BL, unlike the case where the main flame cal is mixed in the conventional large crystal TBL, it shows a high thermal stability effect, and improves insulation and dispersion properties. Moreover, the TBL of the present invention is an ultra-fine TBL, so it has a large specific surface area per unit weight, and compared to commercially available TBL, calcium carbonate is a good dispersion medium. Therefore, it seems that the fineness is more effective and has a significant effect on physical properties such as thermal stability.

In addition, in order to further clarify the present invention, T is added to the resin.
When BL and charcoal were not mixed in advance and were mixed together at the time of resin kneading, results were obtained that were inferior in thermal stability etc. than when they were mixed in advance (sample number 3-4).

Example 4 In this example, a stabilizer in which various inorganic fillers are intimately mixed in advance with ultrafine crystalline tribasic lead sulfate will be described.

As the ultrafine TBL crystals, a slurry of fine TBL coated with sample number 1-1 prepared by the method described in Example 1 and coated with stearic acid was selected.

Examples of inorganic fillers include light calcium carbonate, anhydrous calcium sulfate, anhydrous calcium sulfite, calcium silicate, magnesium carbonate, basic magnesium carbonate, strontium carbonate, barium carbonate, barium sulfate, calcium phosphite, and silicate. We selected 18 types of acid zinc, zinc oxide, calcium phosphate, boehmite-type alumina, finely powdered silicic acid, metakaolin powder, aluminum silicate powder, and finely powdered aluminosilicate soda (gelalite). Powder sized to a particle size of 1 to 5 μm was used.

Into the TBL (1-1) slurry, each of the above inorganic fillers was selected so that the blending ratio of TBL: filler was 60 = 40, and mixed homogeneously in the same manner as in Example 3 to form a stabilizer. Powder (sample numbers 4-1, 4-18)
And so.

Next, various physical properties were measured in the same manner as in Example 1, and the results are also shown in Table 8.

As a result of the above, each of the sized inorganic fillers was cut into ultrafine TBLs as in Example 3 and acted as a dispersion medium, repelling the mutual effect, and effectively dissolving into PVC. It is well understood that it can be used as a heat stabilizer.

[Brief explanation of drawings]

Figure 1 is an electron micrograph of the novel tribasic lead sulfate used in the present invention, Figure 2 is an electron micrograph of the tribasic lead sulfate obtained by the conventional method, and Figure 3 is an electron micrograph of the novel tribasic lead sulfate used in the present invention. This is an X-ray diffraction diagram of tribasic lead sulfate.
It is an X-ray diffraction diagram of tribasic lead sulfate of Publication No.-15625.

Claims (1)

[Claims] 1. Wet method - consisting of tribasic lead sulfate particles obtained by the reaction of acid fls lead and sulfuric acid and higher fatty acid lead coating the particles, the coated particles having a particle size of O.2 microns or less. Number average short axis, L8? /ml or less, and has the formula % formula % where I3.27 represents the intensity at d=3.27A of the X-ray diffraction image, and I3. OQ is d-3,0 of the X-ray diffraction image
1. A stabilizer for chlorine-containing polymers, characterized in that the X-ray intensity ratio (R), defined as the intensity in 9 people, is 7 or more. 2 Higher fatty acid lead is 0.1 to 25 equivalent to tribasic lead sulfate.
The stabilizer of claim 1 present in an amount of % by weight. 3. The stabilizer according to claim 1, which has an X-ray diffraction image that is substantially the same as the X-ray diffraction image shown in FIG.