JPS5833891B2 - Method for producing stabilizer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a stabilizer for chlorine-containing polymers that has an excellent combination of suppressed lead elution, thermal stability, transparency and dispersibility.

Tribasic lead sulfate, which is widely used as a heat stabilizer for chlorine-containing polymers such as vinyl chloride resin and chlorinated polyethylene, is made from litharge, which is obtained by baking zinc oxide in an oxygen atmosphere. It is generally produced by reaction with sulfuric acid in the presence of an acetic acid catalyst.

Such known tribasic lead sulfate generally has a number average minor axis of 0.3 to 1 micron (-1 number average major axis of 2 to 8 μm).
It consists of relatively coarse particles in the range of .

Tribasic lead sulfate with a large particle size has the advantage of not impairing the transparency of the blended vinyl chloride resin composition, but its thermal stability against vinyl chloride resin is still sufficiently satisfactory. However, it also has the disadvantage of being relatively difficult to disperse into the resin.

That is, the thermal stabilizing effect of tribasic lead sulfate on vinyl chloride resin is ultimately carried out through the contact interface between the resin and the lead-based stabilizer particles, and therefore, the lead-based stabilizer particles enter the resin phase. If the dispersed particle size of the polyvinyl chloride resin is large, the ability and performance of trapping hydrogen chloride generated during thermal decomposition of vinyl chloride resin cannot be sufficiently enhanced.

When ultrafine particulate tribasic lead sulfate is used in a chlorine-containing polymer, the thermal stability of the chlorine-containing polymer can be significantly improved, and the dispersibility in the polymer can also be improved. However, tribasic lead sulfate with a fine particle size has a large hiding power, and the resulting blended resin composition becomes opaque, and in the case of a colored blended resin composition,
The disadvantage is that much larger amounts of colored pigment are required to achieve the same level of coloration.

The present inventors used higher fatty acid lead-coated particles of ultrafine thirteen basic lead sulfate having a number average minor axis of 0.2 microns or less and a bulk specific gravity of 1.8 i 7 ml or less as tribasic lead sulfate. When using a composition prepared by wet-mixing selected material and an alkaline earth metal filler in a fixed quantitative ratio, remarkable improvements in thermal stability, transparency and dispersibility can be obtained. It has been found that the amount of lead bath released is significantly suppressed when molded from a blended resin.

In other words, the stabilizer composition according to the present invention has a significantly lower thermal resistance than conventional tribasic lead sulfate or ultrafine tribasic lead sulfate when compared with the same lead content in a chlorine-containing polymer. Stability can be improved, and as a result, the amount of lead added to the chlorine-containing polymer can be reduced, making it possible to lower the manufacturing cost.

Furthermore, when the stabilizer composition according to the present invention is blended with a chlorine-containing polymer, it produces a resin composition with significantly superior transparency and dispersibility compared to a composition containing ultrafine 13 basic lead sulfate alone. Moreover, the advantage is achieved that this improvement in transparency and dispersibility is accompanied by a marked reduction in lead elution and an improvement in thermal stability.

According to the present invention, higher fatty acid lead-coated particles (4) of ultrafine thirteen basic lead sulfate having a number average minor axis of 0.2 microns or less and a bulk specific gravity of 1.8 g/ml or less and an alkaline earth metal A method for producing a stabilizer composition for a chlorine-containing polymer is provided, which comprises wet-mixing a filler (B) and a filler A:B at a weight ratio of 95:5 to 30:70.

In the present invention, tribasic lead sulfate has a number average short axis of 0.2 microns or less, particularly 0.1 microns or less,
L8g/rnl or less, especially 1.7g/ml! It is important to select ultrafine 13 basic lead sulfate having the following bulk specific gravity:

Tribasic lead sulfate, which is commonly used as a stabilizer for chlorine-containing polymers, has a number average minor axis larger than 0.2μ and a diameter of 1.8μ. p/rn
1, and even if alkaline earth metal fillers such as calcium carbonate are added to this material, these fillers merely act as fillers, and the final composition is The thermal stability of the resin composition simply tends to decrease as the proportion of tribasic lead sulfate decreases.

In contrast, according to the present invention, when an alkaline earth filler is wet-mixed intimately with ultrafine thirteen basic lead sulfate having the above-mentioned characteristics, the thermal stability is significantly improved. Unforeseen benefits were achieved from the formulation,
Furthermore, the poor transparency often observed when ultrafine 13 basic lead sulfate is blended is significantly improved, and its dispersibility in the resin is also significantly improved.

Although the exact reason for this is unknown, the inventors of the present invention assume that it is due to the following effect.

That is, even though the primary particle size of the ultrafine 13 basic lead sulfate used in the present invention is extremely small, they are dispersed in the chlorine-containing polymer in the form of secondary particles that are aggregated and coarsened to some extent. It seems that there are.

On the other hand, when ultrafine 13 basic lead sulfate is mixed with an alkaline earth metal filler, this filler acts as a solid dispersion medium for the lead salt particles, and the chlorine-containing polymer contains lead. It is recognized that it acts to atomize and disperse salt particles.

Thus, with the stabilizer compositions of the present invention, increased contact interface between the lead salt particles and the chlorine-containing polymer provides increased thermal stability, as well as improved transparency and dispersibility. I can believe it.

The ultrafine 13-basic lead sulfate used in the present invention is produced by the wet method proposed by the present inventors - lead oxide, that is, JP-A-52-151.
8.3 to 9.2 g/cc disclosed in Publication No. 697
It can be produced using lead monoxide as a raw material, which has an infrared absorption peak at a wave number of 1400 to 1410CrfL-' with an average particle size of 0.2μ or less, and a chromic anhydride reaction efficiency of 94 or more.

This - lead oxide is produced by filling a rotary mill with granules of metallic lead, a liquid medium and oxygen such that at least a portion of the granules of metallic lead moistened with the liquid medium is above the level of the liquid medium. A dispersion liquid in which ultrafine particles of lead monoxide are dispersed in the liquid medium by rotating the rotary mill under conditions in which the particles of metallic lead rub against each other in the liquid medium while being located in the gas phase. It is characterized by extremely fine secondary particle diameter, excellent reactivity, and no heating history.

In producing tribasic lead sulfate, the above-mentioned lead monoxide and sulfuric acid are reacted in the presence of water.

In this case, the above-mentioned wet method - lead oxide has a fine particle size and is highly reactive, so the reaction proceeds even without a catalyst. Small amounts can also be added to the reaction system.

This wet method - tribasic lead sulfate produced from lead oxide is
In addition to the above-mentioned physical properties, the following formula % formula % In the formula, ■3.2□ represents the intensity of the X-ray diffraction image for d=3.27 person, and I3. .

, has the crystallographic property that the X-ray intensity ratio (R) defined by d = 3.09 of the X-ray diffraction image, which represents the intensity in a person, is 7 or more, especially 9 or more. It is suitable for the above-mentioned purpose to have such crystallographic properties.

A lead salt of a higher fatty acid formed in an aqueous slurry of tribasic lead sulfate to improve the dispersibility of tribasic lead sulfate and to prevent the growth of tribasic lead sulfate particles and mutual coagulation of the particles. It is generally advantageous to coat the particles.

The amount of fatty acid lead is between o, i and 2 per tribasic lead sulfate.
The amount may vary from 1 to 21 weight φ, in particular 5 weight φ.

This coating treatment is carried out, for example, by adding ammonium salts or alkali metal salts of higher fatty acids to an aqueous slurry of tribasic lead sulfate containing a stoichiometric amount of lead monoxide corresponding to the higher fatty acids to be added, and then coating on the spot. That is, this can be easily achieved by forming a fatty acid metal salt on the surface of tribasic lead sulfate particles.

The ultrafine 13 basic lead sulfate that can be used in the present invention can also be produced by other methods.

That is, when reacting salt monoxide (PbO) with sulfuric acid by a commercially available calcination method, the amount of catalyst such as acetic acid used is lower than that in the conventional method, generally 0.3 mol or less per 40 mol of Pb, and especially The amount is preferably 0.25 mol or less,
Precautions 1) Keep the reaction temperature as low as possible, e.g., 40°C or lower; (11) - Mix lead oxide and lead sulfate as quickly as possible, e.g. within 40 seconds; (iii)
It can be produced by using at least one condition such as adding a crystal growth inhibitor such as a surfactant or silica sol to the reaction system.

This method is similar to the method for producing ultrafine 13 basic lead sulfate disclosed in Japanese Patent Publication No. 49-15625, but differs in the following points.

That is, in any of the methods disclosed in the examples of this publication,
The amount of catalyst used is considerably larger than 0.3 mol per 40 mol of Pb0, and although the tribasic lead sulfate crystals produced are fine in particle size, their number average minor axis is 0.2 microns. The X-ray intensity ratio (2) mentioned above is 7.
is smaller than

On the other hand, tribasic lead sulfate obtained by the above method is
The number average minor axis is smaller, and the X-ray intensity ratio (B) is also 7 or more.

Of course, the tribasic lead sulfate used in the present invention is not limited to the method described above, but may be obtained by any other method as long as it has the characteristics described above, such as coarse crystalline tribasic lead sulfate. Dry or wet pulverize, sieve if necessary, and obtain the above-mentioned average particle diameter, bulk specific gravity and
It is possible to use particles whose particle size has been adjusted to have a linear intensity ratio (I()).

In the present invention, the alkaline earth metal filler includes:
Any filler consisting of inorganic compounds such as carbonates, silicates, sulfates, phosphates, oxides, and hydroxides containing alkaline earth metals such as calcium, magnesium, barium, and strontium as components can be used. be done.

Suitable examples thereof are light to heavy calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium surface treated silica sand, asbestos powder, talc (basic magnesium silicate), pallite (barium sulfate). , anhydrite, magnesium hydroxide, magnesium oxide, calcium phosphate powder, or a combination of two or more of these.

In the present invention, calcium carbonate is the most preferred among these.

It is advantageous for the purposes of the present invention that these alkaline earth metal fillers generally have a number average particle size in the range of 50 to 0.01μ, particularly 30 to 0.05μ.

In the present invention, among various fillers, it is important to use alkaline earth metal fillers from the viewpoints of thermal stability, transparency, and dispersibility.

That is, when a silica-based or alumina-based filler is added to a chlorine-containing polymer in combination with the tribasic sulfate,
There is a tendency to initially color the blended resin composition, furthermore, a synergistic improvement in thermal stability cannot be expected by the combination of the two, and transparency and dispersibility are also lower than when using the composition of the present invention. Tend.

In the present invention, the ultrafine thirteen basic sulfate (4) and the alkaline earth metal filler (B) are mixed in a weight ratio of A:B=95:5 to 30, particularly 95:5 to 50:50. Combining in ratios is also important for purposes of the present invention.

If the amount of the alkaline earth metal filler CB) is less than the above range, it will improve the dispersibility of the ultrafine 13 basic lead sulfate in the chlorine-containing polymer and reduce the transparency of the final composition. On the other hand, if the amount of alkaline earth metal filler (B) exceeds the above range,
The synergistic effect of the thermal stabilizing action becomes small, and the overall thermal stabilizing effect becomes unsatisfactory.

In the present invention, the presence of the tribasic lead sulfate having the above-mentioned characteristics and the alkaline earth metal filler in the form of a homogeneous mixture is also extremely important in terms of dispersibility and suppression of lead elution. It is.

That is, as shown in Table 1 of Example 1, which will be described later, the ultrafine 13-basic lead sulfate specified in the present invention has a considerably lower lead elution property than the commercially available coarse-grained 13-basic lead sulfate. As shown, even if this material and an alkaline earth metal filler are simply blended into a chlorine-containing polymer, there is almost no improvement in lead elution (sample numbers 1-F and 1-A). (see contrast).

On the other hand, if the ultrafine 13-basic lead sulfate and the alkaline earth metal filler are homogeneously mixed in advance and incorporated into the chlorine-containing polymer in this form, the amount of lead leached into the molded product will be significant. (See sample number 1-1).

Although the exact reason for this is unknown, it is presumed to be as follows.

As already mentioned above, the alkaline earth metal filler in the form of an intimate admixture acts as a solid dispersion medium and serves to atomize and disperse the tribasic lead sulfate particles in the chlorine-containing polymer. It is recognized that

Therefore, it is thought that the more atomized and dispersed tribasic lead sulfate is in the chlorine-containing polymer, the more the absolute amount of tribasic lead sulfate exposed on the surface of the molded product will decrease, and the amount of lead eluted will decrease. .

In addition, lead elution from chlorine-containing polymer molded products containing tribasic lead sulfate seems to be due to the elution of lead chloride generated during processing, but The alkaline earth metal filler blended into
It is thought that rather than eluting lead chloride, it decomposes it into insoluble forms.

The unexpected effects of the compositions of the invention can thus be explained.

Various means can be employed to intimately mix the tribasic lead sulfate and the alkaline earth metal filler.

For example, tribasic lead sulfate and alkaline earth metal filler can be mixed wet or dry.

As liquid medium for wet mixing, an aqueous medium can advantageously be used, but if desired, organic liquids such as methanol, toluene, butane, etc. can also be used.

Most advantageously, the alkaline earth metal filler is added to the aqueous slurry of tribasic lead sulfate produced in the synthesis process and intimately mixed in an aqueous slat.

This achieves the most uniform mixing of tribasic lead sulfate and alkaline earth metal filler.

The wet mixture is processed as necessary and dried to form a product.

When dry mixing tribasic lead sulfate and alkaline earth metal filler, in order to enable homogeneous dispersion of both,
It is preferable to carry out the mixing under crushing or crushing conditions in a crusher such as an atomizer or a ball mill.

The stabilizer composition of the present invention can be incorporated into the chlorine-containing polymer in the form of so-called powder or granules.

Of course, this composition can also be used as a so-called one-package formulation by adding metal soap, lubricant, stabilizing agent, modifier, coloring agent, etc., if necessary.

The stabilizer composition of the present invention can be applied to a chlorine-containing polymer such as vinyl chloride resin, chlorinated polyethylene, chlorinated polypropylene, chlorinated vinyl chloride resin, etc., in an amount of 2 to 15 weight φ, particularly 3 to 10 weight φ. It can be used in applications to obtain heat-stabilized resin molded products, coating films, etc. with excellent transparency.

The invention is illustrated by the following example.

Example 1 In this example, a stabilizer composition consisting of ultrafine crystalline tribasic lead sulfate and an alkaline earth oxyacid filler had a thermal stabilizing effect despite its low lead content. It will be explained that in terms of transparency and dispersibility, it exhibits an effect equal to or higher than that of commercially available tribasic lead sulfate.

In addition, in this specification, "tribasic lead sulfate" is referred to as "TB
The abbreviation "L" will be used below.

For the ultrafine crystal TBL used in this example, an ultrafine condensation device slurry manufactured under the following conditions was selected, and a commercially available heavy calcium carbonate (manufactured by Spar 81 Maruo Calcium ■) was used as the alkaline earth metal filler. After classifying and completely removing coarse particles, select heavy calcium carbonate powder that has been sized to a size of 1 to 4 microns, mix the two in a wet method in a predetermined ratio using a high-speed stirring mixer, then dry and pulverize. New stabilizer compositions were prepared respectively.

. For the production of ultrafine crystalline tribasic sulfate (TBL-1), litharge (pbo) powder 275 is produced using a commercially available calcination method.
Take 51 g of 2N acetic acid in a beaker, add 1800 ml of water, be careful not to raise the temperature above 40℃, and add 1 liter of 2N acetic acid.
．． After adding 48-, 1011 rL of 6N sulfuric acid was poured into it while stirring for about 10 seconds, and then aged at that temperature for 10 minutes with stirring to obtain an aqueous suspension slurry of ultrafine crystals of TBL, and further, stearic acid 2. 1g, caustic soda 0
．． Add a sodium stearate aqueous solution prepared with 3.9 and 5011 L of water to the above TBL slurry under stirring,
The microcrystals were subjected to surface treatment and then washed with water.

The microcrystalline TBL-1 slurry thus obtained was dried if necessary and tested for the following test items to confirm its physical properties, and the results are also shown in Table 1.

Test method for physical properties: (a) Number average particle diameter and number average short diameter using a JEOL Superscope type (JEM50) electron microscope,
Sampling was carried out using the water paste method on a collodion-carbon vapor deposited film, and 2
The size of 00 to 300 particles was measured, and the average particle diameter was calculated from the number average of the size of each particle.

The major axis and minor axis of the particles at this time were actually measured, and the number average major axis or minor axis (Oki) was determined from the number average of the measured values of the major axis and minor axis of each particle.

(b) While placing a small amount of the sample into a graduated test tube of a specific volume tester (manufactured by 6 Yama Kagaku, 6 mountain type specific volume tester) that performs drop impact at 15 revolutions and 30 revolutions per minute, the bottom of the test tube is gently touched. Strike,
Repeat this and add the sample until it almost lines up with the 20- mark line.

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

Thereafter, the graduated test tube is removed, the volume (■-) is read, and the content sample is then taken out onto a medicine wrapper paper, its weight Wg is measured, and the bulk specific gravity (D) l/7d) of the sample is calculated using the following formula.

-V (c) X-ray intensity ratio (R) X-ray self-recording diffractometer (X-ray generator Cat
A 2001. The goniometer is a wide-angle CatA22.
The sample was measured by the powder measurement method using a 27-proportional counter) according to the following diffraction conditions.

Diffraction conditions: Target Cu Filter Ni Voltage 30KV Current 15mA Count range 2000 cps High voltage
1450V Time Constant 1 sec Chart Speed 1cfrL/Blood Scanning Speed 1°/71uIL Diffraction Angle (2)
23°~35° slit width 1
°-0, 3-1 ° Diffraction angles on the chart measured by the above method 27, 26 ° (Spacing (n = 1) d =
3.27 people) and 28.89° (d=3.09
Determine the area of the peaks with X-ray diffraction intensities I3.27 and I3.09 from the height and half-width of both peaks of human), respectively.
Find the ratio I3,27/I3.09 (=R), and calculate this R
The X-ray intensity ratio R was defined as follows.

Next, the sized calcium carbonate was added to the prepared ultrafine crystal TBL-1 slurry under stirring so that the weight ratio of TBL:calcium carbonate was 70:30, and the mixture was thoroughly mixed. After being dispersed, it was overdried and pulverized with an atomizer to obtain a stabilizer composition (sample number 1-1) consisting of microcrystalline TBL-1-calcium carbonate.

The stabilizer composition obtained here was tested for thermal stability, insulation (volume resistivity), dispersibility, and transparency (hiding power), and the results are shown in Table 1.

Test method: (a) Add 50 parts by weight of DOP Kuwahakusatsu to 100 parts by weight of heat-stable vinyl chloride resin (Vinicron 4000M, manufactured by Mitsui Toatsu). The mixture was mixed thoroughly and homogeneously, then kneaded for 7 minutes at 160°C using a 3.5-inch kneading roll, and then taken out as a sheet of about 0.5 mm.

These sheets are stacked in three layers, 165℃, 100kg/f
A soft sheet having a thickness of about 1 nm was prepared by pressing for 17 minutes.

The sheet prepared here was cut into approximately 3 x 10 α squares to form test pieces.The test pieces were arranged on a stainless steel plate coated with silicone oil, and this was placed in a gear kept at 190°C. The sheet pieces were placed in an oven and the time it took for the sheet pieces to turn black due to thermal decomposition (8) was measured, and the longer the time it took to turn black, the better the thermal stability.

(b) Insulating properties (volume specific resistance) Volume specific resistance (!2-crI' L) was obtained.

That is, after the kneaded 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 brought to a constant temperature in a constant temperature bath at 2°C, and then (Model 5M-10 manufactured by Toa Denpa Kogyo ■), the volume resistivity (, Q-CfrL) was determined, and the volume resistivity was determined by correcting the sheet thickness, etc.

(c) Dispersibility To evaluate the dispersibility, 100 parts of a commercially available vinyl chloride resin (Sumirit 5X-11F, manufactured by Sumitomo Chemical) was homogeneously mixed with 0.05 part of carbon black (manufactured by GIST H Tokai Electrode). Weigh the sample into a 100-yard beaker using a top balance (weight 0.1 g), add 12 g of DOP (manufactured by Kyowa Hakko), and then add 1 g of the desired sample.

Without mixing the contents of this beaker too much,
The black film sheet was dropped onto a 3.5-inch diameter double kneading roll (friction ratio 1.25) with a surface temperature of 160°C, kneaded for 10 minutes, and then taken out as a sheet with a thickness of 0.211 rIL. Top 100mX 100mm
0, 1 to 1, which occurs when a sample that is saturated within the corner is not dispersed.
Small white spots of 0.2 mrrt, medium white spots of 0.2 to Q, 31 part m, and white spots of 0.3 or more are counted, and the root dispersion with a large number of white spots is considered to be poor, and white spots are recognized. Cases in which no results were reported were considered good.

(d) Transparency Pressed flexible sheets prepared in the same manner as in section (a) above were placed on black paper, and the density of the black color when the black of the underlying black paper was visible through the sheet was observed. .

As a result, "◎" indicates when the black color at the bottom is observed as it is or almost transparent, and "○" indicates when the black color is slightly opaque. Objects are indicated with an “x” mark.

At this time, the darker the black density appears, the lower the hiding power is, indicating that the sheet is transparent, and the stabilizer composition of the sample added to the sheet impairs the light transmittance of the vinyl chloride resin. This shows that there is no
In other words, when light transmittance is not impaired, the dyes added when it is desired to color the resin generally work effectively for that purpose, and a small amount of the dye is required to obtain the desired hue. ing.

In addition, in order to clarify the present invention, as comparative examples, the following five stabilizer composition samples (sample numbers 1-A...1-E) were also treated with PVC in the same manner as above. A test was conducted when the compound was blended with the following, and the results are also shown in Table 1.

The sample of Comparative Example 1-A was TBL-1 prepared by the above method.
selected ultrafine crystalline tribasic lead sulfate powder.

The sample of Comparative Example 1-B was a commercially available tribasic lead sulfate (“Stapinex TcJ” manufactured by Suikagaku Kagaku Kogyo ■) (sample number T
BL-M) powder was selected.

In the sample of Comparative Example 1-C, TBL-M powder was selected in place of TBL-1 in the stabilizer part of the stabilizer composition containing the heavy calcium carbonate described above in this example.
A slurry of TBL-M with a concentration of 500 g/l was prepared in the same way as in the case of TBL-1 slurry, and then heavy calcium carbonate was added to the weight ratio of 70:30 and mixed thoroughly. A stabilizer composition (1C) consisting of TBL-M-calcium carbonate was obtained in the same manner as above.

The sample of Comparative Example 1-D was prepared in accordance with the method described in (2-3) of Example 2 of the specification of Japanese Patent Publication No. 15625/1983.

Fine TBL crystal powder (TBL-S) was made into synthetic leather.

That is, lysazage (p bo ) powder 177 produced by a commercially available calcination method.
．． 9g was placed in a 31 beaker, 1200 liters of water was added, heated to 40°C, 1.53ml of 6.4N acetic acid was added, and about 65TLl of 3N sulfuric acid was added in a short period of 10 seconds under high-speed stirring. A slurry of fine but thick tribasic lead sulfate crystals (TBL-8) was prepared by aging for 30 minutes under the same conditions under high-speed stirring, and then this TBL-8 was added to the slurry. Stearic acid corresponding to 1.5% was added as an aqueous solution of sodium stearate for surface treatment, followed by filtration and drying to prepare a fine powder of Ohno's TBL-8.

For the sample of Comparative Example 1-E, heavy calcium carbonate was added to the slurry of TBL-8 in the same manner as in this example so that the amount ratio was 70:30, and the mixture was homogeneously mixed. Thereafter, a stabilizer composition (1-E) consisting of TBL-8-calcium carbonate was obtained in the same manner as above.

In the sample of Comparative Example 1-F, TBL-1 and calcium carbonate were not intimately mixed in advance in the case of sample number 1-1 of this example, and TBL-1 and calcium carbonate were mixed at the time of cross-mixing with PvC. Each was weighed and mixed.

The amount of lead elution was measured as follows.

(e) Amount of lead elution This was based on the lead elution test method for vinyl chloride pipes for water service.

The test sheet was prepared by hard compounding using the following method: adding 3 parts by weight of a stabilizer sample to 100 parts by weight of vinyl chloride resin (Vinicron 4000M, manufactured by Mitsui Toatsu), mixing thoroughly homogeneously, and then determining the thermal stability. After kneading at 160°C for 5 minutes using the kneading roll described in Section 1, to form a sheet with a thickness of 0.4 to 0.5 plate; stack the sheets in three layers and heat at 170±2°C.
, 100kg/Cr? L. Press for 7 minutes to prepare a hard sheet about 1 inch thick.

Next, the sheet created under the above conditions is 8crfL x 8c
IrL was cut into strips, wiped with dry gauze to remove any deposits on the surface, heated in a constant temperature bath kept at 100±3°C for 5 minutes, softened, and placed in a hard glass tube (10
Wrap it around a 0ml graduated cylinder and form it into a cylindrical shape.

The extraction conditions for lead are as follows: As the extractant solvent, commercially available chlorinated water is added to water that has been further distilled from ion-exchanged water.
The effective chlorine concentration was approximately 2 ppm, and the pH was adjusted to 7 using soda carbonate.
Selecting water adjusted to ±0.05, first, the formed sheet described above was washed with running water (Suido Hontsuri 21/1ni!L) for 30 minutes, and further rinsed with the extractant prepared earlier.
Hard glass stopper cylinder for extraction 60mm (inner diameter) x
A 150 dish (height) is filled with 246M extractant, the molded sheet is immersed and sealed, and left in a constant temperature bath at 25±1°C for 24 hours.

Next, the extract after the above-mentioned extraction was quantified according to a known method for quantifying Pb using the dithizone method, and the concentration of Pb in the extract was expressed in ppm in terms of Pb.

As a result of the above, the stabilizer composition (1-l) of the present invention obtained by homogeneously wet-mixing calcium carbonate as a filler with ultrafine crystalline tribasic lead sulfate as in this example was found to be suitable for PVC. When blended, although only 3.5 parts of TBL was blended, it showed a higher thermal stability effect compared to the comparative example,
Moreover, it has good insulation properties and shows very good dispersibility, and in the past, when fine crystals were mixed with PVC resin, it was necessary to add a large amount of coloring pigments or dyes to achieve the desired hue. The drawback of not being able to obtain this has also been resolved.

Comparing this with comparative examples, we find that TBLs with a small specific surface area per unit g, that is, fine and obese TBLs (e.g. TBL-8), and TBLs with large crystals.
(For example, TBL-M), even if calcium carbonate is blended, it only shows thermal stability in an amount equivalent to the amount of TBL, and a mutual effect with calcium carbonate has not been found. Furthermore, it can be seen that the dispersibility is poor and the transparency is generally poor.

That is, in the case of the ultrafine crystalline TBL of the present invention, since the TBL is sufficiently fine, calcium carbonate acts as a dispersion medium for the sufficiently fine TBL, and the sufficiently effective dispersion into the resin is achieved, thereby improving thermal stability and other properties. It is thought that this will bring mutually good results to various physical properties.

Furthermore, it is understood that the amount of lead leached into the water after the resin molding is extremely small due to the mutual effect caused by the homogeneous mixing with calcium carbonate in advance.

Example 2 In this example, stabilizer compositions prepared by varying the addition ratio of calcium carbonate to ultrafine crystal TBL will be described.

As the ultrafine crystal TBL, the ultrafine crystal TBL (TBL-1) prepared by the method described in Example 1 was selected.

As the calcium carbonate, the same heavy calcium carbonate (abbreviated as Charcoal) used in Example 1 was used.

The blending ratio (weight ratio) of the above ultrafine crystal TBL and calcium carbonate is 95:5, 90:10, 80:20, 60:
40, 40: 60, 30 near 0 and 10: 7 of 90
I chose a variety of combinations.

These blended compositions were heated to T by a high-speed stirring mixer.
Mix homogeneously in the BL-1 slurry, and further homogenize the dried product with an atomizer to obtain each stabilizer composition (sample number 2-1,...
...2-7).

Next, these stabilizer compositions were tested and measured for thermal stability, electrical insulation properties, and sheet transparency in the same manner as in Example 1.
The results are shown in Table 2.

As a comparative example, the microcrystal TBL-1 used in this example
Only an amount corresponding to the amount of TBL in the stabilizer composition was blended with the PVC resin, and various physical property tests were conducted in the same manner, and the results are also shown in Table 2.

In addition, in order to further clarify the present invention, a case where TBL-1 and Charcoal were mixed into the vinyl chloride resin at the time of kneading and blending into the resin without pre-mixing (Sample No. 2-G) ) was also subjected to physical property tests.

As a result, a composition in which calcium carbonate, which is a filler, is homogeneously mixed in advance with ultrafine crystal TBL at a blending ratio of 95 = 5 to 30 nia 0, can be blended into the resin. It is understood that the mutual effects of the two are significantly repelled by the thermal stability, insulation properties, and dispersibility when

This will be better understood when comparing the case where both are simply mixed together or the case where only TBL is blended alone with respect to the resin as a comparative example.

Example 3 This example describes a stabilizer composition in which calcium carbonate is intimately mixed with ultrafine crystal TBL obtained using a novel lead oxide produced by a wet method.

Ultrafine crystal TBL (TBL-3) is disclosed in Japanese Patent Application Laid-Open No. 52-151.
Wet method manufactured according to the following method described in Publication No. 697 - Manufactured by the following method using lead oxide.

As the calcium carbonate, the same heavy calcium carbonate used in Example 1 was selected.

The blending ratio of the above TBL-3 and calcium carbonate is 75
Two formulations were chosen: :25 and 60:40.

These blended compositions were heated to T by a high-speed stirring mixer.
They were mixed homogeneously in a BL-3 slurry, and the dried product was further homogenized into powder using an atomizer to obtain each stabilizer composition (sample number 3-1.3-2).

These stabilizer compositions were then prepared in the same manner as in Example 1.
A PHR compound was prepared into a vinyl chloride sheet, and its thermal stability, electrical insulation properties, and sheet transparency were tested and measured.

Manufacturing method of raw material lead oxide by wet method: 200 pieces of metallic lead granules with a diameter of 2 to 7 mm! 9 is placed in a rotary stainless steel tube mill (inner diameter 34.4 (1771, length 130 crfL1 internal volume approximately 1207), filled with water 301 and oxygen (2 kg absolute pressure), and by rotating this tube mill, water is removed. A part of the metallic lead moistened with water is held down by centrifugal force in the gas phase above the water surface, and the ultra-thin layer of water around the metallic lead absorbs oxygen, and the granules of metallic lead are suspended in the water. When the particles rub against each other, a dispersion of ultrafine lead monoxide particles dispersed in water is obtained.

Wet method - lead oxide slurry IJ - (
PbO-WS) can be used as it is as a raw material for lead compounds, or it can be filtered, dried and ground to form a dry powder product (Pbo-WP).
It can also be used as

Manufacturing method of ultrafine crystal TBL (TBL-3): The wet method lead monoxide slurry obtained by the above method was adjusted to a PbO concentration of 140 g/l, and this lead oxide slurry IJ-655TLl was prepared. Pour the mixture into a beaker 21 and heat it to 40°C while stirring with a glass blade.

Then 10TrLl of 3φ solution of hydroxylamine sulfate
and stir well - After ringing some of the lead peroxide present in the lead oxide slurry, the concentration was 3.861 mol.
/l sulfuric acid (H2SO4) solution 26.1411Ll to 1
Add quickly for 0 seconds, stir, and after 30 minutes,
The mixture was heated to 65 to 70°C on a heater and reacted and aged for 60 minutes to prepare base slurries of tribasic lead sulfate.

The slurry pH at this time was 8.2.

Separately in a 200rrLl beaker granular stearic acid 1.4
4g and ammonia water 2 with a concentration of 0.736 mol/l
．． Take 0811Ll and 50TLl of water, stir vigorously with a glass rod, and heat to 90°C to completely emulsify to prepare ammonia soap.

This ammonia soap suspension was poured into the above tribasic lead sulfate base slurry and dispersed well at 65-70°C.
The cake was heated for 60 minutes at a constant temperature of 90℃, coated with stearic acid, and the tribasic lead sulfate coated with stearic acid was separated by filtration. After drying the cake in a constant temperature dryer at 90℃ overnight, - to produce ultrafine crystalline tribasic lead sulfate powder (TBL-3).

Each of the tribasic lead sulfate powders produced herein was tested for number average minor axis, number average major axis, bulk specific gravity, and X-ray intensity ratio according to the test method shown in Example 1, and these results were They are also shown in Table 3.

As a comparative example, a sample was prepared in the same manner as in this example using only ultrafine crystal TBL (TBL-3) that does not contain calcium carbonate.
A test was conducted when blended with vinyl chloride, and the results are also shown in Table 3.

As a result of the above, it was understood that a stabilizer composition made by homogeneously blending calcium carbonate with ultrafine crystalline TBL prepared using wet litharge as a raw material exhibits superior synergistic effects in various physical properties compared to the TBL standard. Ru.

Example 4 In this example, a stabilizer composition in which various alkaline earth metal fillers are intimately mixed with ultrafine crystal TBL will be described.

The ultrafine crystal TBL obtained in Example 3 (T
BL-3), and as alkaline earth metal fillers, commercially available reagents such as light calcium carbonate, anhydrous calcium sulfate, anhydrous calcium sulfite, calcium silicate, magnesium carbonate, strontium carbonate, barium carbonate, barium sulfate, and The particles were classified using nine types of barium phosphate to completely remove coarse particles, and powders sized to a size of 1 to 4 microns were selected.

The above TBL-3 and the above filler were homogeneously mixed at a ratio of 3:2 in the same manner as in Example 2, and a homogeneous stabilizer composition (sample number 4-1...・・・・・・
...4-9).

These stabilizer compositions were then treated with 5P in the same manner as in Example 1.
A PVC sheet was prepared by HR blending, and its thermal stability, electrical insulation properties, and sheet transparency were tested and measured, and the results are shown in Table 4.

As a result of the above, the stabilizer composition of the present invention, which is obtained by homogeneously mixing various alkaline earth fillers with ultrafine crystal TBL, has the same properties as when heavy calcium carbonate is used as the filler. It is understood that they exhibit excellent mutual effects in various physical properties.

Claims (1)

[Claims] Higher fatty acid lead-coated particles (4) of ultrafine tribasic lead sulfate having a number average minor axis of 10.2 microns or less and a bulk specific gravity of 1.897 or less and alkaline earth metal-based filling Agent (B)
A method for producing a stabilizer composition for a chlorine-containing polymer, which comprises wet-mixing A:B intimately at a weight ratio of 95:5 to 30 nia. 2 Ultrafine tribasic lead sulfate has the formula % Formula % In the formula, I3,27 is the intensity of the X-ray diffraction image d = 3.27 in a person, and I 3.09 is the intensity of the X-ray diffraction image d = 3
．． The method according to claim 1, wherein the tribasic lead sulfate has an X-ray intensity ratio (R) defined as 7 or more, each representing the intensity in humans. 3. The manufacturing method according to claim 1, wherein ultrafine particles of tribasic lead sulfate are coated with higher fatty acid lead having a weight φ of 0.1 to 25. 4. The manufacturing method according to claim 1, wherein the alkaline earth metal filler is calcium carbonate. 5. The method according to claim 1, wherein the alkaline earth metal filler is an alkaline earth metal silicate.