DE3038373A1 - Stabiliser compsn. for chlorine-contg. polymers - comprises mixt. of tri:basic lead sulphate and alkaline earth metal fillers - Google Patents

Abstract

Compsn. comprises a homogeneous mixt. contg. (A) super fine granular tribasic lead sulphate having a number ave. short dia 0.2 mu and a bulk specific gravity 1.8 g/ml and (B) alkaline earth metal fillers in wt. ratio of (A):(B) of 95:5-30:70. (A) is synthesised by reaction of lead monooxide produced by the wet method and sulphuric acid in the presence of water. Pref. the tribasic lead sulphate grains are coated with metal salts of higher fatty acids in aq. slurry in order to improve dispersibility and prevent coagulation. Coating of tribasic lead sulphate is effected by adding an ammonium salt or alkali metal salt of higher fatty acid in amt. 0.1-25wt. % of tribasic lead sulphate to the aq. slurry of tribasic lead sulphate. (B) includes calcium carbonate, calcium silicate, asbestos powder, talc, magnesium oxide, Pref. (B) has a number ave. grain dia. of 50-0.01 mu.

Description

Xorn-shaped stabilizer for chlorine-containing polymers

The invention relates to a granular stabilizer for chlorine-containing Polymers, in terms of the flowability of the particles, the dispersibility or the kneadability with a resin and the migration resistance in combination is excellent, as well as a method for its preparation.

Tribasic lead sulfate and lead salts of higher fatty acids such as lead stearate have been widely used as thermal stabilizers for chlorine-containing polymers, how Vinyl chloride resins are used. Furthermore, a granular composition stabilizer, which consisted of tribasic lead sulfate and such lead salts of higher fatty acids, proposed as a lead-type stabilizer, dusting or scattering is prevented and the dispersibility in the resin is improved.

For example, in Japanese Patent Publication 3554 / Ç6 proposed a method for producing a granular stabilizer, a powder of tribasic lead sulfate homogeneous with a melt of a metal soap, such as lead stearate, is mixed to form a solid solution and the solid solution is formed into granules or small masses. In this procedure it is in order to To get this solid solution, it is necessary to put the metal soap in a relatively large one Amount compared to the amount of powdered stabilizer such as tribasic Lead sulfate, used too. Although a granular stabilizer of this type for a rigid vinyl chloride resin composition can be used, it can be used appropriately cannot be used for a soft vinyl chloride resin composition. If specifically the granular stabilizer is used for a soft vinyl chloride resin composition kneading with the resin is insufficient, as the external lubricity is too great is present and since emigration phenomena such as smearing and blooming continue the metal soap occur and as a result it is practical or very difficult also impossible to use such granular stabilizers for soft vinyl chloride resin compositions apply.

In Japanese Patent Publication 11491/67 is a granular stabilizer described, which by wet mixing tribasic Lead sulfate with the lead salt of a higher fatty acid to form a heavy one Composition material and spray drying and granulation of the composition material was formed.

This method is advantageous as a granular stabilizer can be obtained even if a lead salt of a higher fatty acid in relative small amount compared to the amount of tribasic lead sulfate used will. However, it has been found that this granular stabilizer also works in is still deficient and inadequate from certain points of view.

Is specific even if that by wet mixing tribasic Lead sulphate is a heavy composition material formed with a lead salt of a higher fatty acid assumes a uniform state in an aqueous medium, wherein the respective Parts of the tribasic lead sulphate are coated with the lead salt of the fatty acid, in the granules formed during the spray drying of this composition material the lead salt of the fatty acid distributed in a state where the lead salt of the fatty acid separates and rises to the surfaces of the granules. A granular stabilizer with such a distribution structure inevitably shows poor dispersibility the particles of tribasic lead sulfate in the resin. This inclination will too observed in a cora-shaped stabilizer, which with the addition of an aqueous Solution of a sodium salt of a fatty acid to form a tribasic lead sulfate, which was formed by the reaction of lead oxide with sulfuric acid, so that a coating of the lead salt of the fatty acid formed in situ and the coated tribasic lead sulfate is spray-dried and granulated, as described in Japanese Patent Publication 7537/56.

It is believed that the errors discussed above are the known granular stabilizers are due to the fact that, although the particles of tribasic lead sulfate with a lead salt of a fatty acid are coated, the extent to which the lead salt of the fatty acid binds to the particles of tribasic lead sulfate is very low and that phase separation of the lead salt of the fatty acid through the spray drying granule stage and the subsequent Evaporation of the water applied heat is still favored.

It has now been found that if lead oxide, sulfuric acid and a higher fatty acid in a specific ratio under specific aging conditions are implemented, needle crystals of a new polybasic sulfuric acid / fatty acid lead salt be obtained, wherein the fatty acid component is strongly bound, so that a Phase separation of the fatty acid component under the conditions of spray drying and granulation is not caused and that if these needle crystals the Spray drying granulation are subjected to the rising of the higher fatty acid components to the surfaces of the granules is inhibited and a granular stabilizer for chlorine-containing polymers is obtained in terms of the flowability of the Particles, dispersibility or kneadability with a resin, and migration resistance is excellent in combination.

The main object of the invention is therefore a granular Stabilizer for chlorine-containing polymers, with regard to the flowability of the Particles, dispersibility or kneadability with a resin and the Migration resistance is excellent in combination, as well as in a process for making the same.

Another object of the invention is a granular Stabilizer, which granulates a new polybasic sulfuric acid / fatty acid lead salt comprises wherein the fatty acid component is strongly bound to such an extent that a phase separation of the fatty acid component is not caused, the respective crystalline particles forming the granulate have good binding properties, a good property for promoting dispersion and a good sliding property own.

Another object of the invention is a granular Stabilizer with a homogeneous internal structure, whereby the flowability and Dispersibility by incorporating a small amount of a fatty acid component are greatly improved.

According to the invention, there is a granular stabilizer for chlorine-containing polymer, which comprises porous spherical particles selected from indiscriminately divided needle crystals of a polybasic sulfuric acid / fatty acid lead salt wit a chemical composition of 1 mol of 603, 3.7 to 4.5 mol of PbO and 0.06 up to 1.27 mol of a higher fatty acid are built up and X-ray diffraction peaks at have the distances d of 2.95 i and 3.27 R, in which the fatty acid component in the surfaces of the respective needle crystals practically without phase separation in the Surfaces of spherical particles incorporated or enrolled is.

In the drawings, Fig. 1 is a photograph of a scanning electron microscope of a known granular stabilizer derived from the spray-drying granulation product a tribasic lead sulfate coated with a lead salt of a fatty acid 2 is a photograph of a scanning electron microscope of a granular stabilizer according to the present invention, Fig. 3 shows the X-ray diffraction pattern a common tribasic lead sulfate coated with a lead salt of a fatty acid, 4 shows the X-ray diffraction pattern of a polybasic to be used according to the invention Sulfuric acid / fatty acid lead salt, Fig. 5 is a photograph of a scanning electron microscope of the particles (Sample No. 2-A) consisting of a polybasic sulfuric acid / fatty acid lead salt were granulated in which the amount of the fatty acid component is too small and below of the range prescribed in the present invention, and FIG. 6 is the photograph a scanning electron microscope of a granular stabilizer (sample no. 2-3) according to the invention.

In the context of the detailed description of preferred embodiments is one of the essential characteristic features of the present invention in that it is independent of the usual technical idea of coating the surfaces of tribasic lead sulfate particles with a lead salt of a fatty acid, needle crystals from a polybasic sulfuric acid / fatty acid lead salt with the included therein or contained fatty acid component are granulated into spherical particles.

Fig. 1 is a photograph using a scanning electron microscope of a product, which by prior formation of the particles from tribasic Lead sulphate, coating the surfaces of the particles with a lead salt of a fatty acid and spray drying and granulation of the coated particles was obtained. As As can be seen from FIG. 1, the fatty acid component separates in this product (Lead salt of fatty acid), rise to the surface part of the granulation product on, and in the granulation product with such a distribution structure, as the fatty acid components contained migrate to the surfaces of the granules, the crystalline particles of tribasic lead sulfate close to the interior of the granulation product coagulates and agglomerates and the problem of insufficient dispersion occurs naturally occurs when the granulation product is incorporated into the resin. In contrast one of these is spray drying and granulation of needle crystals polybasic sulfuric acid / fatty acid lead salt formed granulation product with-the fatty acid component included therein, as can be seen from the photograph by means of the Scanning electron microscope according to FIG. 2 can be seen, the tendency of the fatty acid component, to rise to the surfaces of the granules, not to be observed at all and the whole Structure including the interior is homogeneous and Not only does the granulation product show very good dispersibility in the resin the fact that a phase separation of the fatty acid component in the spray drying and granulation stage is not caused, but also the fact that the polybasic Sulfuric acid / fatty acid lead salt has a specific X-ray diffraction pattern, document @@: that in the polybasic sulfuric acid / fatty acid lead salt according to the invention the fatty acid component is fixed or strongly included.

Fig. 3 shows the X-ray diffraction pattern of a conventional one with a lead tribasic lead sulfate coated with a salt of a fatty acid, while FIG X-ray diffraction pattern of the polybasic sulfuric acid / fatty acid lead salt used according to the invention shows.

If FIG. 4 is compared with FIG. 3, it clearly emerges that that the polybasic sulfuric acid / bed acid lead salt used according to the invention at a distance d of 2.95 i has a diffraction peak that points to the polybasic Fatty acid salt is likely to be due. This fact proves that the sulfuric acid component in the lead salt is contained in the form of tribasic lead sulfate and that too the fatty acid component in the lead salt in the form of the basic fatty acid lead salt is included or bound.

From the point of view of dispersibility and flowability of the granular stabilizer it becomes preferred that the X-ray diffraction intensity ratio R corresponds to the following formula: R = 2.95 / I3.2? 7 x x 100 where I2.95 is the intensity of the X-ray diffraction peak at the distance d of 2.95 Å and I3.27 the intensity of the X-ray diffraction peak at the distance d of 3.27 W, in the range of 3 to 30, in particular from 5 to -25.

In order to achieve the above objects, it is important that the present invention Polybasic sulfuric acid / fatty acid lead salt used the following chemical Composition has: Usual range Preferred range 803 1 mole 1 mole PbO 3.7 to 4.5 moles 3.8 to 4.4 moles fatty acid 0.06 to 1.27 moles 0.09 to 1.00 moles if the amount of fatty acid is too small and below the above range, become numerous in the granular product obtained by the spray-drying granulation whiskers on the surfaces of the spherical particles. educated, as can be seen from Fig. 5, which is a photograph by means of a scanning electron microscope of a granular stabilizer according to sample no. 2-A, which is used as a comparative product in the following example 2 was formed, while the flowability of the granulate product is drastically reduced by the presence of these whiskers.

Of course, there is a tendency for such a granulating product of the needle crystal particles to the k glomerierwg before and the dispersibility in the resin is very bad.

This can be easily understood from the fact that in the through Spray-drying granulation using the fatty acid in the invention granulation product formed in the prescribed range is the number of those discussed above beard-like projections is extremely small and the angle of repose is small Reference is made to Fig. 6 which is a photograph of a scanning electron microscope of a granular stabilizer according to Sample No. 2-3, which is shown below Example 2 was formed. If the amount of fatty acid is too large and above the is the range listed above, the external activity is too great, in particular in a resin with a soft composition and disorders such as insufficient Forming and bleeding of the fatty acid component from the molded resin article due to insufficient gelation in the resin kneading and molding steps caused. On the other hand, if the fatty acid component in an amount within the is incorporated in the range of the present invention given above, become good Self-bonding properties, good dispersibility in the resin and a suitable one Slidability in the resin kneading and shaping stages of the granulation product granted because the fatty acid component is included in the needle crystals and the formation or growth of the above-mentioned beard-like projections is inhibited, for which reference is made to FIG. 6, while the flowability of the granulation product is greatly improved.

If the amount of lead oxide component is too small and below the is in the above range, it becomes difficult to remove the fatty acid component to include tightly in the particles of the needle crystals and the thermal stability is sometimes reduced. If the amount of lead oxide component is too large and above of the above range, there will sometimes be discoloration in the formed polybasic sulfuric acid / fatty acid lead salt caused and the obtained Granulation product is not suitable for incorporation into a chlorine-containing polymer.

The polybasic sulfuric acid / fatty acid lead salt used according to the invention is usually used manufactured by a process wherein lead monoxide is mixed with sulfuric acid in an aqueous Medium reacted at a weight ratio PbO / 503 of 92.3 / 7.7 to 91.1 / 8.9 becomes, the higher fatty acid in the form of an ammonium soap to the resulting slurry of polybasic lead sulfate with a fresh one in terms of reactivity Surface area in a weight ratio of PbO / higher fatty acid of 95,424.6 to 73.5 / 26.5 is added and the resulting mixture is aged under such conditions becomes that the specific surface area Rs (cm2 / g) corresponds to the following Formula: Rs = (2γs + 4γL), γs.γL.D where s is the numerical average short diameter of the needle crystals of the polybasic formed Sulfuric acid / fatty acid lead salt, yL the numerical average long diameter of these needle crystals and D is the true density of these needle crystals indicate a value from 1 to 600, in particular 1 to 100, has.

Commercially available black lead can be used as the starting lead monoxide be, d. H. lead monoxide produced by calcining lead suboxide after the lead powder process at a temperature of 450 to 75a ° C in an oxygen-containing Atmosphere, like air.

However, one can achieve the objects of the present invention suitable polybasic sulfuric acid / fatty acid lead salt advantageously using a lead monoxide can be produced by the previously proposed wet process was obtained. As indicated in U.S. Patent 4,117,104, this Wet process granular metallic lead, a liquid medium and oxygen placed in a rotating drum and the drum is rotated under such conditions that the granules of the metallic lead to the oxygen atmosphere above the liquid phase are exposed and that the metallic lead granules frictional contact possess each other in the liquid medium, thereby forming liquid monoxide in the form an aqueous dispersion is obtained. This lead monoxide by the wet process has a true density of 8.3 to 9.2 g / ccm and is made up of such fine particles, which is characterized by a numerical average particle size of less than 0.2 / µm can be reproduced. Furthermore, this lead monoxide is easily reactive, so that the chromic acid anhydride reactivity is at least 94%, even in the absence of a catalyst such as acetic acid. As a result, one is one out of one polybasic lead sulfate made of such lead monoxide whole excellent in terms of reactivity with the fatty acid component.

The reaction between the lead monoxide and the sulfuric acid will performed by pouring sulfuric acid into an aqueous slurry of lead monoxide will.

This reaction can either in the absence of a catalyst or in the presence of a catalyst such as acetic acid or nitric acid. If a lead monoxide by the dry process, which has poor reactivity is used, it is preferred that a catalyst such as acetic acid, In an amount of 0.001 to 1% by weight, in particular 0.005 to 0.9% by weight, based on lead monoxide (PbO) is used, d. H. in an amount up to 0.25 moles, especially up to 0.2 moles for every 100 moles of PbO. Pouring the sulfuric acid can be done in such a short time Time like less than 30 seconds or the sulfuric acid can be finished gradually be poured in the course of 0.5 to 60 minutes. The reaction temperature is not particularly critical, but it is preferred that the reaction be from 15 to 950 C is running.

To, according to the invention, the fatty acid component tightly into the surfaces embed the needle crystals and the fatty acid component strongly to the surfaces To bind the needle crystals, it is important that the implementation between the lead monoxide and the sulfuric acid within the weight ratio given above is carried out.

According to the invention, the fatty acid component is dense in embed the surfaces of the needle crystals and the fatty acid component strong to connect with the surfaces of the needle crystals, it is also important that the higher fatty acid component in the form of an ammonium salt with the polybasic lead sulfate implemented with a fresh surface that is strong in terms of responsiveness will. To avoid this reaction between the polyhasic lead sulphate with a fresh, in terms of reactivity, strong surface and a higher fatty acid ensure that special measures, as listed below, should to be hit.

(1) Sulfuric acid is made into an aqueous slurry of lead monoxide poured and at the point where the pH of the reaction system is in the range of 7.5 to 9.0, the fatty acid is added immediately. The fatty acid will so implemented with the freshly formed fresh polybasic lead sulfate.

(2) Coarse crystals formed from polybasic lead sulfate or. Secondary particles from agglomerated crystals are separated by means of a fine pulverizer, such as a ball mill, a nozzle mill, a vibration mill or a colloid mill, split or split and the finely divided polybasic lead sulfate obtained is reacted with the fatty acid.

In the case of the above lead monoxide by the wet method is used as a starting material, an intermediate product can be obtained, viz polybasic lead sulfate, which is highly reactive with the higher Fatty acid.

According to the invention, the fatty acid component strongly with the surface to connect the needle crystals and prevent the occurrence of phase separation, It is important to have the higher fatty acid in the form of an ammonium salt (soap) the above intermediate is reacted. To the higher fatty acid strongly to bind the surfaces of the above crystalline particles would have to the following two requirements are met. That is, the higher fatty acid must be easily dispersed in the aqueous slurry of the intermediate and the higher fatty acid must be slightly associated with the lead monoxide component in the intermediate get connected. Especially when the higher fatty acid as such is directly in the Reaction system is incorporated, it is very difficult to get the fatty acid with the surfaces of the respective crystalline particles to connect. When the higher fatty acid in In the form of an alkali salt such as the sodium salt, the higher reacts Fatty acid only with the dissolved lead component, usually in the form of a salt an acid used as a catalyst, d. H. the free lead component is from separated from the polybasic lead sulfate. In either of the above two In cases it becomes difficult to distinguish between the intermediate product particles and the fatty acid component to form such a strong bond that no phase separation in the heating granulation stage caused. In contrast, it is believed that if the fatty acid component in the form of the ammonium salt is used, the ammonium salt-easily in the aqueous Medium is emulsified and dispersed and a Graft binding easily between the fatty acid component and that contained in the intermediate product particles Lead oxide component is formed.

According to the invention, natural and synthetic fatty acids can be used as fatty acids Fatty acids, especially those with 8 to 22 carbon atoms, are used, such as B.

Stearic acid, lauric acid, palmitic acid, oleic acid, linoleic acid, Ricinoleic acid, oxo carboxylic acid and neo acids. One by saponification Mixed fatty acids formed by oils and fats can also be used.

It is also important that this is done by adding the smmonium soap of the fatty acid to the slurry formed from the intermediate product is sufficient is aged so that the specific surface area specified above Rs is in the range from 1 to 600 cm2 / g, in particular from 1 to 100 cm2 / g. To the fatty acid to bond uniformly to the surfaces of the intermediate product particles, it is preferred to carry out the aging treatment under certain constant conditions. If however the aging treatment is not carried out under such conditions extreme growth of crystalline particles of polybasic sulfuric acid / Fatty acid lead salt causes and the initially bound fatty acid component is easily expelled from the crystalline particles by this extreme growth, so that phase separation of the fatty acid component is easy at the heating granulation step caused. The occurrence of this disorder is prevented according to the invention, by the aging treatment under such conditions executed becomes that the specific surface area Rs is within the above range lies.

These aging conditions are described below. The aging treatment is carried out with stirring such that homogeneous mixing in the aqueous Medium is ensured and the reaction temperature is within a range from 25 to 850 ° C., in particular from 35 to 750 ° C., is selected and the reaction time is within the range of 20 to 120 minutes, in particular 30 to 90 minutes, is selected, the specific surface area Rs being within that given above Area. The aging treatment can advantageously be carried out under a pulverizing effect a ball mill, a grater or a colloid mill. Furthermore, this pulverizing treatment can be carried out before, during or after the aging treatment are executed.

The polybasic sulfuric acid / fatty acid lead salt obtained in this way is spray-drying granulation as it is in the form of freshly made aqueous slurry or after it has been filtered and washed with water, subjected, whereby porous spherical granules are obtained, which from indiscriminately polybasic sulfuric acid / fatty acid lead salt divided needle crystals are constructed. This granulation can easily be effected by the -aqueous Slurry the lead salt discussed above into a desiccant atmosphere is sprayed through a nozzle, a turntable or a cylindrical rotating nozzle.

It is preferred that the solids concentration in the Slurry 20 to 65% by weight, in particular 35 to 55% by weight. It is preferred that the temperature of the drying atmosphere is adjusted to 100 to 5000 C.

Although the size of the desired porous spherical obtained Granulate varies according to the intended use, it becomes common it is preferred that the particle size be 20 to 1000 μm, in particular 30 to 500 μm, is set. Furthermore, it is preferred that the particle size distribution of the Particle is concentrated within as narrow a range as possible.

According to a preferred embodiment of the present invention becomes CA) the polybasic sulfuric acid / fatty acid lead salt with (B) a filler of alkaline earth p in a weight ratio of (A) / (B) from 95/5 to 30/70 and the resulting mixture is granulated.

It has been found that according to this preferred embodiment Dispersibility of the lead component (A), the flowability of the particles of the. Lead component and the inhibition of the release of the lead from the finished formed Resin article can be improved remarkably. The filler has a specific effect from alkaline earth (B), which acts before granulation, as a solid dispersion medium for dispersing the polybasic sulfuric acid / fatty acid lead salt in the granulation product in the finely-divided state in the resin and the filler of the alkaline earth p (B) exercises furthermore, effects of effectively inhibiting the formation of whiskers during the granulation step and to improve the flowability of the particles the end.

As an alkaline earth filler which can be used in the context of the invention inorganic compounds of alkaline earth metals such as calcium, magnesium, Barium and strontium, for example the carbonates, silicates, sulfates, phosphates, Oxides and hydroxides of these alkaline earth metals are called. As preferred examples are listed light calcium carbonate, heavy calcium carbonate, magnesium carbonate, Calcium silicate, magnesium silicate, titanium calcium surface-treated silica sand, Asbestos powder, talc (basic magnesium illeate), barite (barium sulfate), anhydrous Gypsum, magnesium hydroxide, magnesium oxide, calcium phosphate powder, and mixtures of the two or more of such materials. According to the invention, calcium carbonate becomes special preferred among these fillers. To achieve the objects of the present invention achieve, it is usually preferred that the numerical average particle size of the alkaline earth filler is 0.01 to 70 μm, in particular 0.05 to 50 μm.

Known additives such as stabilizers, modifiers and coloring agents can according to known approaches in the granular stabilizers according to the invention for the chlorine-containing polymers, if necessary, are incorporated.

The granular stabilizer according to the invention is used in an amount from 1 to 10% by weight in the chlorine-containing polymer such as vinyl chloride resin, chlorinated Polyethylene resin, chlorinated polypropylene resin or chlorinated vinyl chloride resin incorporated and the granular stabilizer is valuable for the production of numerous molded objects made of soft resin masses.

According to the invention, a granular stabilizer is thus obtained for chlorine-containing polymers, which comprises porous spherical particles composed of randomly divided needle crystals from a polybasic sulfuric acid / fatty acid lead salt with a chemical composition of 1 mole SO3, 3.7 to 4.5 moles PbO and 0.06 up to 1.27 moles of a higher fatty acid and X-ray diffraction peaks Have distances d of 2.95 i and 3.27 i, the fatty acid component in the Surfaces of the respective needle crystals with practically no phase separation in the surfaces of the spherical particles is embedded or entrapped.

The following examples serve to further illustrate the present Invention.

In the first place for the dry process and the wet process for Production of lead monoxide, which is used as the starting material for the polybasic sulfuric acid / Fatty acid lead salt according to the invention, which is sometimes abbreviated to "TELSS" in the following is used is described with reference to the following two reference examples.

Reference Example 1 The lead monoxide was obtained by the dry method corresponding to that described in Japanese Patent Publication 11801/62 Method made. An electrolytic lead casting became pillars with 2.5 cm in diameter and 2.0 cm in length using a lead forming machine shaped. After this in the experimental report by No. Genzo Shimazu, Journal of Machine Association, Vol. 28, No. 100, pp. 489-516 (1925) Shimazu-type lead powder process, these pillars of metallic lead were used in a rotary mill to form a lead suboxide powder with a dark gray-green Dry powdered paint (so-called lead powder). The lead suboxide powder was obtained, placed in a rotary kiln and introduced with stirring in the presence of Oxygen burned at a temperature of about 630 to about 7200 G. The increase the temperature when the lead suboxide was burned was followed and when no further The increase in temperature when burning was observed more, the product was prompt Discharged into a Edhlkammer and cooled, producing lead oxide in the form of yellow Granules was obtained. Then this yellow granular lead oxide was pulverized and classified according to the gas cyclone process, so that powdery lead monoxide (PbO-DP) with orange color was obtained. This was used to manufacture TBLSS PbO-DP wet pulverized and used to form a slurry with a specific Concentration dispersed and the PbO-DP was used in the form of this slurry (RbO-D »).

Example 2 The lead monoxide after the wet process was after the process described in US Pat. No. 4,117,104. A lead monoxide with a density of 8.3 to 9.2 g / ccm, an average Particle size less than 0.2 µm, an infrared absorption peak at a Wavenumber of 1400 to 1410 cm 1 and an otric acid anhydride reaction ability of at least 94% using the following procedures.

A rotary tube mill made of stainless steel with an inner diameter of 34.5 cm, a length of 130 cm and an internal volume of about 120 liters loaded with 200 kg of metallic lead granules with a diameter of 2 to 7 mm and 30 l of water and oxygen (2 kg / cm2 absolute pressure) were continued into the Tube mill introduced. When turning the tube mill, part of the was wetted with water metallic lead into the gas phase above the water level due to centrifugal force lifted and an ultra-thin layer of water around the lifted metallic lead absorbed oxygen, the granules of metallic lead preserve in water Were brought into frictional contact with each other, thereby obtaining a dispersion, wherein ultrafine particles of lead monoxide in water having a PbO concentration of 335 g / 100 ml were dispersed.

The lead monoxide suspension (PbO-WS) obtained in this way the wet process could or could be used directly as the starting material in the form of a dry powdery product (PbO-WP), which was obtained by subjecting the above slurry to filtration, drying and subjected to pulverization.

Example 1 A stabilizer consisting of porous spherical particles, made from randomly divided needle crystals of a polybasic sulfuric acid / fatty acid lead salt (zELSS) is described in this example.

The TBLSS was made according to the following procedures.

A high speed stirrer 5 out of 60 1 content was filled with 40 l of water and therein were 17.532 kg of powdery Lead monoxide (PbO-DP), produced by the dry process specified above, filled and the charging at high speed for sufficient and homogeneous Dispersion of the lead monoxide in water was stirred and the dispersion was adjusted to 650 C heated. Then 109 cc of an aqueous solution of acetic acid with a concentration of of 2.7 moles per liter added to the dispersion to make up part of the lead monoxide in lead acetate to convict.

Then it became 2702.6. ccm of an aqueous sulfuric acid solution with a A concentration of 7.0 mol per liter was added dropwise to the dispersion in the course of 40 minutes. Aging was then carried out with stirring at 650 ° C. for 60 minutes, see above that a slurry of needle crystals formed from polybasic lead sulfate became.

A stainless steel vessel with a capacity of 10 liters was separated charged with 5 l of water at 700 ° C. and 558 g of stearic acid were in this water solved. Then 24 cm3 of aqueous 7N ammonia were added to the solution and sufficient emulsified with stirring to form an ammonia soap liquor. the the resulting ammonia soap liquor was converted into the polybasic one mentioned above Lead sulfate slurry poured over the course of 10 minutes and the aging reaction was carried out with high speed stirring at 650 G for 20 minutes, so that the stearic acid is incorporated into the crystals of the polybasic lead sulfate and the polybasic sulfuric acid / fatty acid lead salt (TELSS) was formed. The TBLSS slurry thus obtained was sufficiently dispersed and after the coarse granules were removed by sieving, the slurry became granulated into spherical particles with drying in a spray dryer.

A spray tower with a diameter of 2.5 m and a height of 4.6 m was used as the spray drying device and the spray drying was used at a temperature of 300 to 3600 C with a hot air supply speed from 36 to 40 m3 / min and a dilution spray rate of .1 l / min carried out in countercurrent using a turntable.

As a result, a granular product (sample Er. 1-1) became a polybasic one Sulfuric acid / fatty acid lead salt obtained. The water content in the-obtained- spherical TBLSS (1-1) was 0.1%.

The resulting spherical TBLSS was the chemical analysis, the X-ray diffraction of the examination with the scanning electron microscope, the determination of the angle of repose, the determination of the particle size distribution, the Pore volume determination and the determinations of thermal stability, dispersibility, gelling property and migration resistance in the state incorporated in a vinyl chloride resin subject to the test procedures given below. The results obtained are listed in Table I.

Test Method (1) Chemical Analysis: (1-a) Lead Monoxide (PbO): Das The weight of a sample containing about 0.15 g as PbO of the lead component was made weighed exactly and transfer the sample to a separatory funnel with a capacity of 100 ml using 2 ml of a 6N nitric acid and 10 ml of ether and brought the Sample was completely transferred into the separatory funnel by the application of water.

The separatory funnel was closed and shaken and then were 12 ml of a 50% aqueous solution of ammonium acetate are added and the funnel shaken sufficiently to completely dissolve the sample of liquid. then the funnel was left to stand to separate the liquid into a water layer and a layer of ether. The water layer was transferred to an Erleameyer flask with a content of 200 ml, while about 0.5 ml of the water layer was left in the separating funnel. Then were Add 10 ml of water to the separatory funnel and shake the funnel again left to stand In the same manner as before, the water layer was put into the Erlenmeyer flask with about 0.5 ml of the aqueous layer remaining in the flask.

The above operation was repeated three times.

Then the ether layer was applied to the inner wall of the separatory funnel washed with water and finally the water layer was in the Erlenmeyer flask transferred as much as possible. The layers of water collected in this way and the washing liquid in the Erlenmeyer flask containing 200 ml slightly heated until the odor of ether was gone.

The contents of the flask were then left to cool below 400.degree and 5 ml of a 20% aqueous solution of potassium sodium tartrate were added to the 200 ml flask and the flask was shaken. Then 10 ml of an ammoniacal Ammonium chloride buffer solution was added and the flask was shaken sufficiently.

Then 2 ml of a 2% strength solution of potassium cyanide were added and 1 ml of a solution of Eriochrom Black 2 as an indicator was further added. Immediately thereafter, the nitration was carried out using a standard solution of EDTA carried out at a concentration of M / 20 until the color turns from reddish purple changed to sky blue.

The lead content was calculated using the following formula: Lead content (O / o) = where A is the value of Pb or as the Pb content calculation coefficient (= 1.0360) or the value for PbO or as the PbO content calculation coefficient (= 1.1160), B is the titrated amount (ml) of the M / 20-EDTA standard solution , T is the titer value of the M / 20-EDDA standard solution, W is the weight (g) of the sample and 0 is the water content (%) of the sample.

(1-b) Sulfuric acid residue (SO3): A sample containing 0.1 to 0.2 g as SO3 of the sulfuric acid component was accurately weighed out and put into a Beaker with a content of -300 ml was introduced. Then 2 g of sodium chloride, 0.2 g of potassium bromate and 25 ml of hydrochloric acid (1: 1) were added and the mixture was heated gently to decompose and dissolve the sample. Then the solution heated with vigorous heating to blow off the bromine. The solution was cooling Left to a temperature that did not allow the lead chloride to precipitate and an aqueous solution of water hydroxide was added to the solution until the solution was weakly acidic. Then a saturated sodium carbonate aqueous solution became dropwise to the solution using a pipette to form a precipitate of lead carbonate added. Then it became a saturated aqueous solution of sodium carbonate added to adjust the pH to 9-.

The precipitate was removed by filtration using the filter paper No. 3 of Toyo Roshi K.K. recovered and the recovered precipitate became sufficient Washed with water until the presence of sulfuric acid ions was no longer found became. The filtrate and washing liquid were in a beaker with a content of 300 ml brought. Then hydrochloric acid (1: 1) was added to the 300 ml beaker was added dropwise to adjust the pH to about 2 and the solution was heated and cooked to completely rub off the carbon dioxide gas. Then 20 ml a 10% solution of barium chloride into the solution using a pipette was added dropwise to form a precipitate of barium sulfate and then the Aging carried out with heating for 2 to 3 hours.

The precipitate was removed by filtration using the filter paper He. 5C of Toyo Roshi K.K.

The obtained precipitate was washed sufficiently with hot water, until the presence of chlorine ions was no longer detected. The washed one Precipitate was dried together with the filter paper and after the filter paper in a porcelain bowl.

Ashes had been burned, the precipitation was during 8000 a Heated for 40 minutes.

The heated precipitate was then placed in a desiccator and allowed to cool until the weight was constant. The weight was determined and the residual sulfuric acid content was calculated according to the following formula. So content C%) = BaSO4 * (g) x ort3430 Sample (g) z å8sergehalE *: BaS04 (g) = (measured weight - crucible weight-filter paper ash weight) (1-c) fatty acid (R-COOH): The sample (1 to 2 g) was accurately weighed and placed in a beaker with a capacity of 100 ml. The sample was wetted with a small amount of ether and about 25 ml of water was added thereto. Then, 5 ml of 6N nitric acid, 7 ml of 17N acetic acid and 20 ml of 6N aqueous ammonia were added to the mixture, and the mixture was heated to 700 ° C. with stirring to dissolve the sample. The insoluble fatty acid salt and the coagulated fatty acid were recovered using a filter paper, and the recovered solid was transferred to a separatory funnel having a capacity of 100 ml using water. Then 5 ml of 6N nitric acid was added to the solid and the funnel was shaken. Then 20 ml of ether was further added and the funnel was shaken.

If at this point the nitric acid layer was cloudy or a insoluble substance at the interface between the nitric acid layer and the Ether layer was present, ether or a solution of ammonium acetate was added and the judge was shaken.

Then the nitric acid layer was removed and the remaining ether layer was washed with 20 ml of water while shaking. The water layer was carefully removed and the ether layer was placed in a horizontal 40 mm weighing bottle, which had been dried and weighed in a thermostatic dryer kept at 60 + 5 ° C. Then, 10 ml of ether was put into the separating funnel, and the funnel was shaken to wash the inner wall of the separating funnel, and the washing liquid was also added to the above weighing bottle. The weighing bottle was left to stand for the evaporation of the ether and the weighing bottle was dried in a thermostatic dryer kept at 60 + 50 ° C., placed in an Exsi1 ^ 92tor, left to cool and then weighed. The fatty acid content was calculated using the following formula: weighed weight (g) - weight Fatty acid - the weighing bottle (g) x 100 content (40) sample (g) z9 - water content 100 (id) Water (E20): About 1 g of the sample was accurately weighed and placed in a 40 mm horizontal weighing bottle and was dried for 4 hours in a thermostatic dryer kept at 105 + OC so that the weight did not change any further. The water content was calculated using the following formula: Sample weight (g) - sample Water content (%) according to the Crocknuni: (g) x 100 Sample weight g) The chemical composition was determined by calculations on the basis of the contents of the respective components determined in this way.

Each value given in brackets below is included in the specification the chemical composition gives the number of moles of PbO or stearic acid (St-H) per mole of SO3.

(2) X-ray diffraction determination: The sample was subjected to X-ray diffraction determination according to the powder determination method under the following conditions using an automatic X-ray diffraction device from Rigaku Denki K.K. subjected to an X-ray generator Catalog No. 2001, a wide-angle goniometer Contains Catalog No. 2227 and a proportional counter.

Diffraction conditions: Protective material: Cu filter: Ni Voltage: 30 KV Current: 15 mA Counting range: 2000 c.p.s.

High voltage: 1450 V Time constant: 1 second Card speed: 1 cm / min Scanning speed: 1 ° / min Diffraction angle (20): 10 to 60 ° Slit width: 1 ° -0.31-1 °.

The areas of the diffraction intensity I3,27 and the diffraction intensity I2.95 were made from the heights and half-widths of the two peaks at the diffraction angles of 25.5 ° (d = 3.27 i) and 30.00 (d 2.95) on that in the above-mentioned X-ray diffraction determination method obtained map and the ratio I3.27 / I2.95 (= R) was calculated and the obtained value R was defined as the X-ray diffraction intensity ratio R.

(3) Scanning electron microscope examination: A scanning electron microscope Model JSM-U3 from Nippon Denshi K.K. was used.

The sample was slurried in isopropylene and placed on a mesh screen collected. After vacuum evaporation deposition performed in an ion vacuum deposition apparatus was carried out, the sample was placed in the sample chamber of the scanning electron microscope brought.

Then the degassing was carried out in a vacuum and the electron beams were rested.

The images of the particles were obtained while the magnification was kept in the range of 100x to 3000x magnification and after the Focusing the photographs were taken.

(4) Numerical average particle size (long diameter and short diameter): Sampling was carried out on a vacuum-deposited Collodion carbon membrane using the water paste method and application an electron microscope of the Super Scope type (JEM-50) from Nippon Denshi K.K.), the sizes (long diameter and short diameter) from 50 to 200 particles at magnifications from 1000 to 10 000 were measured and the numerical average Particle size from the numerical average long or short diameter Czun) of the measured values was determined.

(5) Angle of repose (flowability): A chemical glass funnel with a mouthpiece diameter of 100 mm was attached so that the upper end of the Funnel was at a height of 100 mm from the horizontal surface. The sample powder was dropped onto a paper lying on the horizontal surface, whereupon two concentric circles with diameters of 50 mm and 100 mm were drawn, namely through the fixed funnel to the center of the circle with a diameter of 50 mm drawn on the paper. When the bottom of the through the funnel Fallen cone of the sample powder full the circle with a diameter of 100 mm, the dropping of the sample powder was stopped. The height X (mm) of the cone was measured and the angle of repose (4) was obtained from the following formula calculated: tan Q = The smaller the value X, the better the flowability of the Powder sample. Usually, if the value o is less than 200, it becomes a blockage or bridging is not caused when the sample is taken from a storage tank such as a Funnel is discharged and a good flow is obtained.

(6) Thermal stability: To 100 parts by weight of a vinyl chloride resin (Viniclone 4000M from Mitsui Toatsu K.E.) was added 50 parts of DOP (dioctyl phthalate from Eyowa-Hakko K.K.) and a certain one narrow (parts by weight) of the stabilizer lead compound sample was added and the mixture was mixed sufficiently to become a homogeneous mass result. The cup was heated to 1600 C for 7 minutes by means of a roller from Kneaded 8.9 cm (3.5 inches) to form a sheet about 0.5 mm thick. Then three of the sheets thus formed were stacked and at 1650 C under 100 kg / cm2 for 7 minutes to form a soft arch pressed to a thickness of about 1 mm. The arch was made into rectangular test pieces cut with a size of about 3 cm x about 10 cm.

The test pieces were placed on a plate coated with silicone oil made of stainless steel and placed in a gear furnace held at 190 ° C set. The time (minutes) required for the sample pieces to be blackened thermal decomposition was measured. If a longer time is required for blackening is, it means better thermal stability.

(7) Plasticizer property: An auxiliary roll mixer with a content von 60 @@@ was tested on a kneading resistance tester (Plasti-Corder model P151 from. Brabender Co.) and 55 g of one by mixing 100 parts of vinyl chloride resin (Geon 103EP from Japanese Geon K.E.) with 5.0 parts of the stabilizer sample Mass were placed in the mixer and at a temperature of 2000 C and one Speed of 35 rpm. kneaded. The plasticizer state of the above Resin mixture kneading conditions were measured at certain intervals and the kneading resistance obtained was recorded as torque (came) on a card. The place where the kneading resistance torque is the maximum value reached was defined as the plasticization point. The one to achieve this plasticizing point required time was referred to as plasticizing time Tp (gel time) (minutes) and the maximum torque ymax (kg.m) at this point was read from the map.

If the lubricity of a resin stabilizer compound is too high, the plasticizing time (gel time) is long and the maximum torque is low. On the other hand, if the lubricity of a resin stabilizer composition is low, the plasticizing time is short and the maximum torque is high. In the case of one soft mass, since a plasticizer is incorporated, the gelation by the Plasticization of the resin is less easily caused in actual operation than can be expected on the basis of the values obtained by the method given above would and it often happens that the production of the desired molded article becomes impossible.

(8) Dispersibility: 2.0 g of a homogeneous mixture of 100 parts a commercially available vinyl chloride resin (Sumilit SX-11F from Sumitomo Kagaku E.K.) and 0.05 part of Russ (Seast II from Tokai Denkyoku K.K.). using weighed on a balance (sensitivity 0.1 g) and placed in a beaker with a content of 100 ml and 12 g of DOP (product of Kyowa Rakko K.E.) was added and 1 g of the sample was then added. The contents of the beaker were placed on double kneading rollers (Friction ratio 1.25) with a surface temperature of ~ 1600 C and a diameter of 8.9 cm (3.5 inches) with the Content has not been significantly mixed.

After kneading for 10 minutes, the mass became deducted in the form of a black sheet with a thickness of 0.2 mm. The number the small white spots with a diameter of 0.1 to 0.2 mm, the middle white spots with a diameter of 0.2 to 0.3 mm and the large white one Spots larger than 0.3 mm in diameter appearing in the black sheet of film formed when the sample was not sufficiently dispersed counted on a square area of 100 mm x 100 mm. If the total number If these white spots are large, the dispersibility is judged to be not good and when these white spots are not observed, the dispersibility becomes judged to be good.

(9) Transparency: Pressed soft sheets made in the same way as described in (8) above, were on black Paper arranged. If the black color of the black below the arch As the paper could be seen through the sheet, the density became the black Color examined. If the black color of the paper is transparent or practical was observed transparently, the transparency was judged to be good and with the Mark t indicated. When the black color of the paper is observed somewhat opaque the transparency was judged to be sufficient and marked with O specified. If the black color of the paper was seen whitish and opaque, was the Transparency judged as bad and marked X denotes. If the density of the apparent black color was high, it was Opacity poor and the transparency of the sheet was excellent. That is, the Light transmission properties of the vinyl chloride resin were determined by the Resin incorporated stabilizer sample not damaged. Usually favored, if the stabilizer does not damage the light transmission properties of a base resin, the stabilizer, the coloring effect achieved when a pigment or the like is incorporated the color of the resin in the given tone and the amount of pigment or the like, which is necessary to achieve the desired tone can be reduced.

(10) Migration resistance (bleeding test): The migration resistance was made according to the Watchung-Red method, which is commonly used as a bleeding test method is determined. A mass with batch A listed below was found at 1500 C for 10 minutes using the above kneading rollers of 8.9 cm (3.5 inches) kneaded sufficiently cleaned. Immediately afterwards was a mass with the batch B given below in the same way kneaded the same kneading rollers. The one obtained from batch B when the mass was kneaded Sheet using the kneading rollers shortly after the mass has been kneaded with the batch A was at 1600 C for 5 minutes to form an arc with a thickness of 1 mm pressed. The red color of the watchung red transferred to the kneading rollers the mass of approach A and from there on the arch with the crowd The color transferred from the batch B from the kneading rollers became corresponding to the density the tint with Watchung Red. For this determination, a previous watch was made Red to the mass from batch B in ten different amounts of 0.0005 g (0.5 mg) to 0.05 g (50 mg) (per 1000 parts of PVC) each added and 10 sheets of different red color densities were produced and used as calibration sheets for Determination of color density used. The extent of the red color became specific in the test sheets produced by the above process with the strength of compared to red color of these oak arches and migration caused by bleeding by Watchung Red was determined based on the amount of migration (mg) which was determined by comparing the color density of Watchung Red above. When the migration amount (mg) of Watchung Red is large, the bleeding is considerable and the migration resistance is poor. In this case, blooming becomes one white powder on the molded article obtained and the surface gets wet and sticky, causing considerable disruption. In contrast indicates a small amount of migration (mg) of Watchung Red that the resin mass has excellent migration resistance.

Compositions (parts by weight for the bleeding test 'Bnsatz'A approach B Vinyl chloride resin (Viniclon 4000 M) 100 100 DOP 50 40 Watchung Red 1 0 sample stabilizer 2 0 Titanium Oxide 0 2 Dib utyl tin aur at 0 2 (11) pore volume (ccm / g): Mercury was under a pressure of up to 1000 kg / cm2 in pores with a size from rX5 to 75 000 i by a mercury porosimeter (model AG-65 from Carlo-Erba Co., Italy) and the total volume of the pores with a diameter of 75 to 75,000 i became the volume of the mercury filled into the pores and the pore volume per unit area (ccm / g) is calculated from this total volume.

(12) Particle size distribution: That by spray drying granulation method The granular stabilizer produced was passed through Tyler standard sieves of 43 µm (325 mesh), 74 µm (200 mesh), 140 µm (100 mesh) and 355 µm (42 mesh) and the particle size distribution is expressed as proportions (% by weight) of the respective fractions specified.

Comparative Example 1 A comparative product (a) which only produced by homogeneously mixing tribasic lead sulfate with lead stearate had been, and. a comparative product (b), which by coating the surfaces of tribasic lead sulfate crystals made with lead stearate described in this comparative example.

Comparative product (a): tribasic lead sulfate (TBL) became homogeneous mixed with lead stearate by the following procedures.

A TBL slurry was prepared according to that disclosed in Japanese Patent Publication 1149/67 described method produced. For this purpose, 8.162 kg of powder Lead monoxide (PbO-DP) in a vessel equipped with a high-speed stirrer with a content of 60 liters, which was filled with 10 1 of water, introduced and the high-speed stirring became sufficient for 10 minutes homogeneous dispersion of the powder was carried out and the dispersion was increased to 650 C heated. Then 50.8 cc of an acetic acid solution with a concentration of 2.7 mol / liter was added as a catalyst and 1306 ccm of sulfuric acid with a Concentration of 7 mol / liter was added to the lead monoxide slurry during one A period of 40 minutes was added dropwise and the aging was carried out with stirring at 65 ° C for 60 minutes to form a slurry of needle crystals of tribasic Lead sulfate carried out (sample Er. TBL-H1).

Separately, 3.5 l of warm water of 700 g was poured into a beaker stainless steel with a content of 10 1 was charged and 419 g of stearic acid were charged added and dissolved with heating. Then there was 24.0 cc of all 7N aqueous ammonia dropped into the solution, and the mixture was stirred and emulsified homogeneously, so that the ammonia soap liquor was obtained. 725 cc were separated Lead nutide slurry (PbO-DS) with a concentration of 680 g / l, 1 l of water and 14.2 cc of acetic acid at a concentration of 2.7 mol / liter in a high-speed stirrer equipped vessel made of stainless steel with a content of 10 1 introduced and the mixture was kept at 700 C. The above Ammonia soap liquid was added to this lead monoid slurry and the reaction was under Agitation was carried out to form the lead stearate slurry.

The lead stearate slurry thus obtained became the above slurry TBI, -H1 added so that the amount of lead stearate 9% by weight based on the TBL in the TBL-H1 slurry. The two slurries were mixed with stirring and immediately afterwards the mixture was in spray dried in the same manner as in Example 1. This made the mixture granulated into spherical particles, which were dried, thereby obtaining a granulated product (Sample H-1) obtained from a mixture of TBL crystals with lead stearate was built.

Comparative product (b): The surfaces of the crystals of tribasic Lead sulfate was mixed with lead stearate in the following manner after that in Japanese Patent publication 7537/56 coated process described.

Crystals of TBL (Sample No. TBL-H1) obtained according to the above Procedure. to the. Preparation of the comparative product (a) were prepared used as tribasic lead sulfate crystals. Into a tribasic slurry Lead sulfate TBL-H1 with a concentration of 79.2% were 9.029% 1 aqueous sodium stearate solution was incorporated therein and the mixture was allowed to stir for 20 minutes for coating treatment touched. Then the slurry was using Washed water and filtered and the cake turned into a homogeneous slurry processed at a concentration of 48.2 s. The slurry became one Spray drying device guided and spherical particles with drying granulated in the same manner as in Example 1, whereby a granulated product (sample H-2) was obtained, which contained TBL-Ilristalle, whose surfaces with lead stearate were coated.

The properties of the two granulation products obtained were determined and tested according to the test procedures given in Example 1, the values listed in Table I was obtained.

From the results of the products of Example 1 and of Tests carried out in Comparative Example 1, the following can be seen. Of the granular stabilizer according to the invention, which by initially taking place Formation of crystals of a tribasic sulfuric acid / fatty acid lead salt and granulating the crystals into spherical particles by the spray drying method is made up of porous spherical particles made from random divided needle crystals are built up, as from the photograph of the scanning electron microscope can be seen. From the values of the pore volume it can be seen that the comparison products have larger pores than the product according to the invention. In the comparison product (b) the phase of the stearic acid component is separated and. the stearic acid component is mainly present in the outer parts of the spherical particles and, though the angle of repose of this comparative product is small and less than 700 what the Indicating fluidity on handling, this product was versus the product of the present invention in terms of dispersibility in a resin inferior when mixed and kneaded with the resin. Furthermore, the thermal stability of the comparison products very poor and due to the poor Compatibility of the stearic acid component with the resin is the amount of migration from Watchung Red in the large-scale products æuAd is consequently the migration resistance bad if the comparison is based on the amount of equals tangled in the mass incorporated stearic acid takes place. In contrast to this is the migration amount from Watchung Red very low for the product according to this one. Invention. It it is believed that this reduction in migration to training of the polybasic sulfuric acid / fatty acid lead salt. From the The above can be easily understood that if the fatty acid component is sufficient in the lead sulfate crystals during the aging stage to produce the polybasic one Sulfuric acid / fatty acid lead salt is incorporated and the aging reaction product is granulated by the spray drying process, spherical particles are obtained that are easy to use. and which have good dispersibility, when the granular stabilizer thus formed is incorporated into a resin and is kneaded. - Table I sample no.

1-1 H-1 H-2 chemical analysis (%) PbO 86.55 86.60 86.42 (4.26 mol) (4.25 mol) (4.28 mol) SO3 7.28 7.31 7.23 St-H 4.17 4.19 4.21 (0.16 mol) (0.16 mol) (0.16 mol) tip area (cm²) in X-ray diffraction d = 3.27 Å 2.13 2.20 2.11 d = 2.95 Å 0.099 0 0 Scanning electron microscope photograph Fig. 2 Fig. 1 - Angle of rest (°) 27.5 22.5 33.0 Thermal stability (minutes) 253 208 188 Plasticizing properties maximum torque (kg.m) 4.7 4.2 4.1 plasticizing time (minutes) 3.3 3.5 3.6 dispersibility (Number of white spots) 5 numerous numerous Migration resistance (mg) 1.0 20.0 40.0 Transparency 0 0 0 pore volume (ccm / g) 0.652 0.815 0.823 Tabel I (continued) Sample No.

1-1 H-1 H-2 particle size distribution (%) 43 to 74 µm 50 20 46 74 up to 140 µm 40 59 38 140 to 350 µm 10 21 16 Example 2 In this Examples are spherical TBLSS granulation products of different compositions using black lead after the wet process as the starting material and stearic acid as a typical case of a higher fatty acid and incorporation of stearic acid into the needle crystals manufactured.

The slurry of the black lead using the wet process (PbO-WS) with a PbO concentration of 335 g / l, which is specified after that in Reference Example 2 Procedure established was used. The respective starting materials were used in the amounts shown in Table II. The slurry of Black lead after the Nåss process was heated to about 400 C and 20 g of a crystalline Powder of hydroxylamine sulfate was added to the slurry with stirring. The mixture was aged for 10 minutes and a certain amount of 710N sulfuric acid was poured into the mixture over about 5 minutes. The mixture was at 400 C for 25 minutes to form crystals of polybasic lead sulfate stirred and a certain amount of ammonium stearate soap liquid, which according to the in the procedure given in Example 1 was added and the stearic acid incorporation reaction was carried out at 50 ° C. with stirring for 25 minutes executed. The TBLSS slurry obtained was passed through a turntable in hot air sprayed in the same manner as in Example 1. This made spherical granules products (Sample No. 2-1 to 2-7) with different amounts of built-in stearic acid manufactured.

For comparison, granular products were made in the same way as prepared above, however, the incorporated amount of stearic acid is so small -: (less than 0.06 moles per mole of SO3) (sample no. 2-A) or stearic acid at all was not added (Sample 1Gr. 2-B).

The spherical TELSS granulation products obtained thereby became tested according to the procedure described in Example 1. The results obtained are listed in Table III.

From the results of Table III, the following can be seen. Palls the built-in amount of stearic acid too little and less than 0.06 moles each Is mole 803, or stearic acid is not added at all, is the angle of repose of the spherical TBLSS granulation product obtained and the flowability is drastically reduced. This can also be seen when FIGS. 5 and 6 together be compared. Namely, if the amount of stearic acid is small, they become whiskers Projections are formed on the surfaces of the spherical granules.

From this it can be seen that good results are obtained when the stearic acid the crystals in an amount of at least 0.06 moles per mole of SO3 is incorporated according to the present invention. If, however, the built-in amount the stearic acid becomes too large, the migration resistance is reduced.

If black lead is used as the starting material after the wet process is, the reaction is terminated in the absence of a catalyst, although the presence a catalyst is absolutely necessary, if one is common calcined Metallic lead is used as the starting material.

Therefore, the mother liquor remaining after the recovery of TBLSS can can be reused as a reaction medium, so that the problem of waste water treatment can be effectively solved to prevent environmental pollution.

Table II Sample - Amount of Amount of Amount of No. Metabolic acid. Sulfuric acid Stearic acid (kg as PbO) (g as S03) (g as H-St) 2-1 1.74 146 68 2-2 1.71 144 102 2-3 1.64 138 171 2-4 1.57 131 258 2-5 1.49 124 347 2-6 1.41 117 436 2-7 1.67 135 149 2-A 1.76 147 147 (comparison) 2-B 1.78 149 149 (comparison) Tabel III sample no.

2-1 2-2 2-3 2-4 2-5 Chemical Analysis (%) (moles) PbO 86.60 85.28 82.21 78.31 74.36 (4.25) (4.26) (4.27) (4.28) (4.29) SO3 7.32 7.18 6.90 6.56 6.21 St-H 3.40 5.11 8.56 12.92 17.33 (0.130) (0.200) (0.394) (0.554) (0.785) X-ray diffraction tip area (cm²) d = 3.27 Å 2.13 2.12 2.12 2.10 2.10 d = 2.95 Å 0.100 0.098 0.098 0.098 0.096 Thermal stability (minutes) 250 250 240 240 240 Dispersibility (number of white spots) 8 5 5 5 2 Transparency # # # # # Plasticizing property, plasticizing time (Minutes) 3.6 3.5 3.4 3.4 3.2 maximum torque (kg.m) 4.7 4.5 4.5 4.2 4.1 migration resistance (mg) 1.0 1.0 5.0 10.0 20.0 Angle of repose (°) 27.5 26.0 25.5 24.0 23.0 pore volume (ccm / g) 0.655 0.635 0.620 0.610 0.605 Particle size distribution (%) 43 to 74 µm 50 52 56 54 53 74 to 140 µm 42 40 40 44 43 140 to 350 µm 8 8 4 2 4 Tabel III (continued) Sample No.

2-6 2-7 2-A 2-B (comparison) (comparison) chemical analysis (%) (mol) PbO 70.35 83.57 88.10 89.21 (4.30) (4.45) (4.30) (4.30) SO3 5.86 6.73 7.34 7.44 St-H 21.81 7.43 1.25 0 (1.046) (0.310) (0.048) -X-ray diffraction tip area (cm²) d = 3.27 Å 2.09 2.11 2.10 2.12 d = 2.95 Å 0.095 0.097 0 0 Thermal stability (Minutes) 235 240 210 210 Dispersibility (number of white spots) 0 5 numerous numerous transparency # # # # plasticizing property plasticizing time (minutes) 3.0 3.4 3.5 3.6 maximum torque (kg.m) 4.1 4.4 4.2 4.2 migration resistance (mg) 25.0 2.0 35.0 1.0 angle of repose (°) 21.0 25.5 36.0 38.0 pore volume (ccm / g) 0.580 0.625 0.817 0.855 Particle size distribution (%) 43 to 74 µm 56 55 52 48 74 to 140 µm 42 40 40 44 140 to 350 µm 2 5 8 8 Example 3 In this For example, an alkaline earth filler was homogeneously and intimately incorporated into the crystals a polybasic sulfuric acid / fatty acid lead salt mixed in and the mixture granulated into spherical particles.

As a polybasic sulfuric acid / fatty acid salt for the crystal slurry TBLSS (sample no. 2-2), made from black lead by the wet process according to Example 2, selected and used.

Among the chemicals available on the market, the following became thirteen Fillers selected and used from alkaline earth: light calcium carbonate, heavy Calcium carbonate, anhydrous calcium sulfate, finely divided gypsum hemihydrate, anhydrous Calcium sulfite, calcium silicate, magnesium carbonate, basic magnesium carbonate, strontium carbonate, Barium carbonate, barium sulfate, calcium phosphite and calcium aluminate. Furthermore, was a commercially available non-toxic stabilizer made up of calcium silicate (CASH of Mizusawa Kagaku Kogyr K.K.) is used as a filler. Any filler was used after it was pulverized and sieved so that the particle size was less than 10 µm.

The TBLSS slurry (2-2) became homogeneous and intimate with the above inorganic filler mixed in the following manner.

The inorganic filler was specified in Table IV Quantities (%, based on the mixture) to the TBLSS slurry, which had been kept at about 400 C, was added and the mixture at high speed stirred for 15 minutes. Then the mixed homogeneous slurry was through a colloid mill driven at high speed led to pulverization and the mixture became spherical particles with heating in the spray dryer granulated in the same manner as in Example 1. This made granular stabilizers (Samples No. 3-1 to 3-24), which consisted of homogeneous TBLSS filler mixtures, manufactured.

If the particle size distribution was determined, it was found that each product 50 to 55% particles with a size of 43 to 74 µm, 35 to 40% particles with a size of 74 to 140 µm and 5 to 10% particles with a The spherical granulate stabilizers obtained in this way contained from 140 to 350 μm in size were tested according to the procedure of Example 1. The results obtained are listed in Table IV.

For comparison, the calcium carbonate chosen as the filler was not previously mixed into the TBLSS but it was mixed in when. the TBLSS was added to the resin (Sample No. 3-A). Also in this comparison test were the examinations carried out in the same way. The results obtained are included in Table IV.

From the results listed in Table IV it is easy to see that spherical particles made of homogeneous Mixing a polybasic Sulfur acid / fatty acid lead salt with various inorganic substances an angle of repose suitable for handling, better dispersibility than that only spherical particles built up from TBLSS and good thermal Show stability even when the amount of TBLSS incorporated in the resin is small is. These benefits become even more apparent when testing the results with the products compared according to the invention with the test results of the comparative product will.

Table IV Robe No. Filler Amount of Thermal Dispersing Transparent Resting filler Stability availabil- ity reference angle (%) (minutes) (number of white- (°) stains) 3-1 Light calcium carbonate 25 230 0 # 28.0 3-2 Heavy calcium carbonate 5 240 0 # 29.5 3-3 as well 10 240 0 29.0 # 3-4 as well 20 240 0 27.0 # 3-5 as well 30 200 0 27.0 # 3-6 also 50 140 0 27.0 3-7 also 70 80 0 # 26.0 3-8 anhydrous Calcium sulfate 20 230 0 # 28.0 3-9 Gypsum hemihydrate 20 240 0 # 28.0 3-10 Anhydrous Calcium sulfate 20 240 0 # 28.0 3-11 calcium silicate 20 240 0 # 28.0 3-12 magnesium carbonate 20 220 0 # 28.0 3-13 Basic Magnesium Carbonate 20 220 0 # 28.0 3-14 Strontium Carbonate 20 220 0 # 28.0 3-15 barium carbonate 20 230 0 # 28.0 3-16 barium sulfate 20 220 0 # 28.0 3-17 calcium phosphite 22 240 0 # 28.0 3-18 calcium phosphate 20 240 0 28.0 # 3-19 Calcium aluminate 20 220 0 # 29.0 # Table IV (continued) Sample No. Filler Amount of thermal dispersing, transparent, resting filler. Stability availability angle (%) (minutes) (number of white (°) spots) 3-20 CASH 10 240 0 # 27.0 3-21 CASH 20 240 0 # 26.0 3-22 CASH 25 240 0 # 26.0 3-23 CASH 30 220 0 # 25.0 3-24 CASH 40 200 0 # 24.0 3-A Heavy Calcium Carbonate 30 180 numerous # - To be even clearer that through homogeneous and intimate preceding Mixing TBLSS with. to show the effect achieved by the alkaline earth filler, the amount of lead leached out when a molded article was determined from a Resin composition containing the cora-shaped stabilizer according to the invention in water was immersed using the procedure described below. The results obtained are shown in Table V.

The through homogeneous and intimate mixing of heavy calcium carbonate with the TBLSS suspension and spray drying and granulation of the mixture Granular stabilizer obtained in the spray dryer (sample No. 3-4) was chosen as a sample.

The amount of leached lead was determined by the following procedure certainly.

(13) Amount of Leached Lead Component: The test was carried out after Standard method for determining the leached lead from a vinyl chloride existing city water pipe carried out.

A test sheet was made from a rigid mass.

For this purpose, 3 parts by weight of the stabilizer sample were added to 100 parts by weight a vinyl chloride resin (Viniclon 4000Ibi from Mitsui Toatsu E.K.) was added and the mixture mixed sufficiently to form a homogeneous mixture.

The mixture was stirred at 1600 ° C. for 5 minutes using the for "thermal stability" in Example 1 described kneading rollers kneaded, and a sheet 0.4-0.5 mm thick was obtained. then three of the sheets produced in this way were stacked on top of one another and at 170 + 20 C under 100 kg / cm2 for 7 minutes to form a stiff arch pressed to a thickness of about 1 mm.

The sheet was made into square test pieces with a size of 8 cm X 8 cm cut and the adhering to the surfaces of the sample pieces Substances were mixed using dry cotton gauze and the Sample pieces were kept in a thermostatic tank kept at 100 + 30 C for 5 minutes heated. The soaked specimens were placed on a toughened glass tube with a diameter of about 30 mm (graduated cylinder with 100 ml content) to form a cylindrical Molded article wound.

The extraction of the lead component was carried out in the following manner.

Deionized water was distilled and condensed and a Commercial chlorine solution was added so that the effective chlorine concentration was about 2 ppl. Then the pH was adjusted to 7 + 0.05 using sodium carbonate. set. The resulting solution was used as an extraction solvent. The above molded article was treated with tap water (city tap water in an amount of about 2 1 / min) for 30 minutes and washed with the above listed extraction solvent rinsed. A clogged cylinder was disconnected made of tempered glass for extraction, which has an inner diameter of 60 mm and a height of 150 mm, filled with 246 ml of the extraction solvent and inserting the molded article into the cylinder.

The cylinder was sealed and in one at 25 + 10 for 24 hours C held thermostat tank left to stand.

After the above extraction treatment, the Pb content in Extraction solvent determined by the known dithizone method. The Pb concentration in the extraction solvent is given in units of ppm.

For comparison, the product in which calcium carbonate was not incorporated was used (Sample No. 3-B) to which the granular TBLSS stabilizer (Sample No. 1-1) according to Example 1, and that by incorporating calcium carbonate at the stage of adding the above TELSS No. 1-1 to the PVC resin without previous Admixture of the calcium carbonate (sample No. 3-C) in the same manner as above Procedure tested. The results obtained are shown in Table V.

Table V Stabilizer Amount of Grain - Theoretical amount of out sample No. shaped stabilizer - amount of TBL dissolved lead lizer (PHR) in PVC (PHR) (ppm) 3-5 5 3.5 0.026 3-A 5 5 0.080 3-B 3.5 3.5 0.055 3-C 5 3.5 0.050 the end From the above test results, it is readily apparent that if calcium carbonate is intimately mixed beforehand with TBLSS, the leaching of lead from the obtained Molded article can be effectively controlled. It's from the values in the table Obviously, if calcium carbonate is not previously mixed with BBSS but it is incorporated when the TBLSS is added to the PVC resin, the effect of combating the leaching of the lead component is hardly improved, for which reference is made to the results of Sample No. 3-B. The reason for this appearance is not entirely clear, however, it is believed that, as stated above, the alkaline earth filler incorporated in the homogeneously mixed state as solid dispersion medium acts and a function for fine division and dispersion of the UBBSS particles in the chlorine-containing polymer. Therefore it is assumed that the TBLSS is in a highly finely divided state in the chlorine-containing polymer is dispersed, the absolute amount of that on the surface of the molded article exposed TBLSS is reduced and the amount of lead leached out accordingly is decreased. The from a molded article made of a chlorine-containing polymer, in which the TBLSS was incorporated, the released lead component should be in the Forming stage be lead chloride formed. It is believed that the intimately in The TBLSS blended and incorporated filler from alkaline earth p a function the decomposition of this lead chloride into insoluble substances and no puncture to dissolve the lead chloride.

Claims (5)

Claims 1. Granular stabilizer for chlorine-containing polymers, characterized in that it consists of spherical particles which are random divided Hadell crystals of a polybasic sulfuric acid / fatty acid lead salt with a chemical composition of 1 Nol SO3, 3.7 to 4.5 mol PbO and 0.06 up to 1.27 Nol of a higher fatty acid and with X-ray diffraction peaks at distances d of 2.95 Å and 3.27 Å, with the fatty acid component in the surfaces of the respective needle crystals practically without phase separation in the surfaces of the spherical particles is included or incorporated. 2. Granular stabilizer according to claim 1, characterized in that that the porous spherical particles have an alkaline earth filler in such Amount included that the weight ratio (A) / (B) of (A) the polybasic sulfuric acid / fatty acid lead salt to (B) the alkaline earth filler ranges from 95/5 to 30/70. 3. Granular stabilizer according to claim 1, characterized in that that the polybasic sulfuric acid / fatty acid lead salt has an X-ray diffraction intensity ratio R has from 3 to 30, the X-ray diffraction intensity ratio R being given by the the following formula is reproduced: R = [I2.95 / I3.27] x 100 wherein 12 95 is the intensity of the X-ray diffraction peak at a distance d of 2.95 Å and I3.27 mean the intensity of the X-ray diffraction peak at a distance d of 3.27 Å. 4. Granular stabilizer according to claim 1, characterized in that that the polybasic sulfuric acid / fatty acid lead salt has a chemical composition from 1 mole SO3, 3.8 to 4.4 moles PbO and 0.09 to 1.00 moles fatty acid. 5. Spine-shaped stabilizer according to claim 1 to 4, characterized in that that it is made by mixing (A) the polybasic sulfuric acid / fatty acid lead salt with (B) the alkaline earth filler in a weight ratio (,) / (B) of 95/5 to 30/70.