JPH0132253B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to stabilizer compositions for molding materials based on polyvinyl chloride or mixed polymers containing vinyl chloride as the main component. When manufacturing molded objects from polyvinyl chloride,
Conventionally, lead compounds, tin compounds, barium compounds, or cadmium compounds have been mainly used as stabilizers. Although these heavy metal stabilizers actually provide very excellent effects, there are several problems with their use, particularly in terms of labor physiology.
For this reason, attempts have been made for some time to replace such heavy metal stabilizers with less hazardous substances; for example, the use of light alkaline earth metal soaps has already been proposed. in this case,
Preferably, calcium soaps are used, optionally with other stabilizers such as zinc stearate, imino compounds and epoxy compounds. The stabilizing effect of this calcium soap system is relatively small compared to heavy metal compounds, and moldings produced using such stabilizer systems often exhibit a dark color and have poor storage stability. Therefore, the scope of use of such stabilizer systems based on calcium soaps is quite limited. DE 2642509 discloses that calcium stearate and/or zinc stearate contain partial esters of pentaerythrite with C ₁₂ -C ₂₂ fatty acids, wax-like hydrocarbons and/or
Stabilizer compositions are described that include C ₁₂ to _{C 22} free fatty acids and the addition of antioxidants. However, the use of such compositions does not provide the same desirable effects as with the use of stabilizer systems based on heavy metal compounds. US Pat. No. 4,000,100 describes the use of so-called inert zeolite A in stabilizer systems for PVC-based resin materials. The knowledge gained from this specification is that the addition of certain water-containing zeolites to the stabilizer system results in improved heat resistance and light resistance due to their synergistic action. Such zeolites include types 3A, 4A and 5A. These are to be used in combination with any inorganic, organometallic or organic stabilizer or stabilizer component. The present invention significantly improves the stability of polyvinyl chloride through the use of a stabilizer system based on calcium soaps and optionally zinc soaps to prevent lead, tin, barium or cadmium compounds. The object of the present invention is to solve the problem of making it possible to produce a light-colored or white polyvinyl chloride molded article having satisfactory storage stability without the use of a polyvinyl chloride molded article. The solution according to the invention to this problem is to achieve the desired objective through the selection and combination of a number of specific components, including the selection of specific sodium alumosilicate of zeolite type. The object of the present invention is to provide a stabilizer composition consisting of: (a) containing 13-25% by weight of bound water and having an anhydrous composition of 0.7-1.1 Na ₂ O.Al; ₄ to 100 parts by weight of a finely divided crystalline synthetic sodium alumosilicate, which is _2O3.1.3 to _2.4SiO2 ; (b) 1 to 30 parts by weight of a calcium salt of a fatty acid having 8 to 22 carbon atoms; (c) 1 to 10 parts by weight of zinc salts of fatty acids having 8 to 22 carbon atoms; (d) polyols having 2 to 6 carbon atoms and 2 to 6 hydroxyl groups and 8 to 22 carbon atoms. 4 to 40 parts by weight of partial esters with fatty acids having on average at least one free polyol hydroxyl group per molecule; (e) thioglycolic acid esters of polyols having 2 to 6 hydroxyl groups; and/or 2 to 200 parts by weight of thioglycolic acid esters of monohydric alcohols having 8 to 22 carbon atoms. The crystalline synthetic sodium alumosilicate described above has an effective average pore size of 4 Å, which is known per se.
NaA type zeolite (therefore this is a zeolite
(also called 4A). Such sodium alumosilicate can be produced by known methods, and in particular the method described in DE 2412837 is suitable. For more detailed properties and production of this sodium alumosilicate, the following documents are cited, for example: West German Patent Publication No. 2651485, West German Patent No. 2651445, West German Patent No. 2651436, West German Patent No.
Publication Specification No. 2651419, Publication Specification No. 2651420, Publication Specification No. 2651437, U.S. Patent No.
Specification No. 3112176. During production, the amorphous fine particulate sodium alumosilicate produced by precipitation is
It can be converted to the crystalline state by heating to 200°C. The crystalline sodium alumosilicate is then separated from the remaining aqueous solution by filtration and dried, usually at 50-200 DEG C., to a water content of 13-25% by weight. The crystalline products described, for example, in DE 24 12 837 and also defined by the present invention have a particle size in the range from 0.1 to 50 μm, but preferably from 0.1 to 20 μm. Preference is given to using sodium alumosilicate. The calcium binding capacity of the sodium alumosilicate, determined at 22° C., is at least 50 mg CaO and can be about 200 mg CaO per gram of anhydrous active substance (Aktivsubstanz). This calcium binding ability is the active substance 1
A range of 100 to 200 mg CaO per g is preferable, and usually 150 mg CaO or more. Details of the determination of calcium binding capacity can be found in the above-cited West German Patent No. 2412837.
No. 2, as well as the following description of the preparation of suitable sodium alumosilicates. In a preferred embodiment of the process of the invention, rounded sodium alumosilicate may also be used. For the _production of such zeolites, it is preferable to use _a precipitate with the following molar composition _{: 2.5-6.0Na2O.Al2O3.0.5-5.0SiO2.60-
200H2O} . This precipitate is heated at 70-120℃, preferably at 80℃.
It is advisable to heat at ~95°C for at least 1/2 hour with stirring. The crystalline product can be easily separated by removal of the liquid phase, optionally washed with water and then dried. In the present invention, precipitation and crystallization are performed in the presence of a water-soluble inorganic or organic dispersant.
Water-insoluble particulate sodium alumosilicate can also be used. Preferred water-soluble organic dispersants include surfactants (Tenside), non-surface active aromatic sulfonic acids, and compounds that have the ability to form complexes with calcium. Such dispersants can be introduced into the reaction mixture in any manner before or during the precipitation operation, for example used as a solution or dissolved in an aluminate solution and/or a silicate solution. good. The amount of dispersant should be at least 0.05% by weight, preferably from 0.1 to 5% by weight, based on the total precipitate. For crystallization, the precipitated product is heated at 50-200°C for 1/2-24 hours. Among the many dispersants that are particularly useful are, for example, sodium lauryl ether sulfate, sodium polyacrylate, and 1-hydroxyethane-1,1-
Diphosphonic acid sodium salt may be mentioned. NaA type sodium alumosilicate useful in the present invention has a bound water content of 13 to 25% by weight, with water contents of 18 to 25% by weight being particularly preferred. The calcium and zinc salts of fatty acids used in the present invention are particularly those obtained from fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid and stearic acid. Also,
Salts of individual fatty acids may be used, or salts of fatty acid mixtures obtained from natural fats and oils may be used. Particularly preferred are the calcium and zinc salts of palmitic and stearic acids. The polyol partial ester of component (d) is prepared in a known manner by esterification of a polyol having 2 to 6 carbon atoms and 2 to 6 hydroxyl groups with a fatty acid having 8 to 22 carbon atoms. . At this time, a common esterification catalyst can be used. The mixing ratio of polyol and fatty acid is 1:1 to 1:(n-1) in molar ratio (where n means the number of hydroxyl groups in the polyol). Additionally, these reactive components have hydroxyl numbers between 140 and 580, especially
It is preferred to use an amount such that 170 to 540 partial esters are formed. The reaction product may be a mixture of different esters, but it is necessary that the acid number be below 15, especially below 8. Preferred polyol components include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, neopentyl glycol, glycerin, Mention may be made of trimethylolethane, trimethylolpropane, pentaerythritol, erythritol, mannite and sorbitol. Particularly important polyol components are those having 3 to 6, especially 3 or 4, hydroxyl groups. Glycerin and pentaerythritol can be used with particular preference within the scope of the invention detailed herein. Preferred fatty acid components include, for example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Also, synthetic fatty acids with the chain lengths mentioned above, such as montanic acid,
Alternatively, unsaturated acids, such as oleic acid and linolenic acid, or substituted fatty acids, especially hydroxylated acids such as 12-hydroxystearic acid, can also be used, but for practical reasons fatty acid mixtures obtained from natural fats and oils are used. There are many things. Of course, component (d) may also be a mixture of the above-mentioned partial esters. Partial esters (having on average 2 to 3 free hydroxyl groups) obtained from polyols having 3 to 6, especially 3 or 4, hydroxyl groups and the aforementioned fatty acids are particularly preferred compounds as component (d). be. As component (e) in embodiments of the invention, thioglycolic acid esters of aliphatic polyols having 2 to 6 hydroxyl groups come into consideration. In particular, these polyols have 2 to 36, especially 2 to 18 carbon atoms. Polyols having 2 to 6 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, Examples include neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, mannite and sorbitol. However, polyols having higher numbers of carbon atoms within the above range are also particularly useful, such as polyols having from 8 to 18 carbon atoms. Particularly preferred polyols in the present invention are those having 2 to 4 hydroxyl groups, especially ethylene glycol, glycerin and/or pentaerythritol. Also particularly useful are α,ω-alkanediols having 8 to 18 carbon atoms, such as 1,10-decanediol, 1,12-dodecanediol and 1,18-octadecanediol. Also useful are diols and polyols, especially those obtained by hydrolysis of long-chain epoxy alkanes. In this case, polyols with vicinal and non-terminally located OH groups, such as octanediol-1,2, decanediol-1,2, tetradecanediol-1,
2. Octadecanediol-1,2, chain length is
_C12 or _C14 , or _C11 - _C14 , _C14 - _C16 ,
Also of interest are mixtures of vicinal alkanediols with C ₁₅ to C ₁₈ and non-terminal OH groups. In the case of thioglycolic acid ester, for example, the polyol is mixed with thioglycolic acid in a molar ratio of 1:1 to 1:n (n
is the number of hydroxyl groups in the polyol) and is obtained by conventional methods. In this case, all hydroxyl groups of the polyol can be esterified with thioglycolic acid. Preferred such thioglycolic esters for use in the present invention are those having an average of at most 3 thioglycolic esters per polyol molecule, especially 1 or at most 2 thioglycolic esters. As component (e), a thioglycolic acid ester of a monohydric alcohol is used, and the alcohol component of this ester is a linear or branched primary or secondary alcohol having 8 to 22 carbon atoms.
or tertiary aliphatic alcohols are used, such as n-octanol, n-dodecanol,
Mention may be made of n-hexanedecanol, n-octadecanol and especially 2-ethylhexanol. In the simplest case, component (e) is polyol thioglycolic acid ester or monohydric alcohol thioglycolic acid ester alone, but these substances can also be used in any combination; in this case, Component (e) forms a mixture. In a preferred embodiment of the process of the present invention, component (d) is a partial ester of a fatty acid having 8 to 22 carbon atoms with pentaerythritol (pentaerythritol:fatty acid molar ratio is 1:1 to 1). :2), further comprising, as component (e), a thioglycolic acid ester of a monohydric alcohol having 8 to 18 carbon atoms; Thioglycolic acid esters or glycerin monothioglycolates are used. The stabilizer composition according to the invention can be easily prepared by mechanically mixing the components in a conventional mixer and is obtained as a free-flowing, non-splatterable product. In addition to polyvinyl chloride, the stabilizer composition of the present invention can also be used to stabilize mixed polymers containing vinyl chloride as a main component, and such mixed polymers can be stabilized by suspension polymerization or bulk polymerization. The K value is 35-80. The polyvinyl chloride materials for molding stabilized with the stabilizer compositions of the invention can be used in particular for the production of tubes and profiles by extrusion processes, and also for the production of hollow packaging bodies. It can be used for manufacturing purposes. The processing properties of moldable polyvinyl chloride materials stabilized with the stabilizer compositions of the present invention can be comparable to the properties of moldable polyvinyl chloride materials stabilized with heavy metal stabilizers, and in particular This is true for initial color tone, initial stability and storage stability. Thus, the stabilizer composition of the present invention is a very valuable alternative to conventional heavy metal stabilizers, and therefore will make a very significant contribution to the development of the field of labor physiology, for example. I can say that there is. Examples of the production of useful sodium alumosilicates are described below. Preparation of Sodium Alumosilicate In a 15 volume reaction vessel, the aluminate solution was mixed with the silicate solution under strong stirring. Stirring was performed at 3000 rpm using a stirrer equipped with a dispersion plate, and both solutions were used at room temperature. An exothermic reaction occurred and sodium alumosilicate was amorphous by X-ray diffraction as the main precipitated product. After 10 minutes of slow stirring, the suspension of the precipitated product was transferred to a crystallization tank and left at 90° C. for 6 hours with stirring (250 revolutions/min) to effect crystallization. Next, the liquid phase is removed by suction from this mixture, and the crystal residue is washed with deionized water so that the pH value of the washed water that flows out is about 10, and then dried. Moisture content was determined after heating the dry product to 800° C. for 1 hour. The sodium alumosilicate obtained after washing to a pH value of about 10, neutralization and drying was then ground in a spherical grinder. Particle size distribution was measured using a sedimentation balance. The calcium binding capacity of alumosilicate was determined by the following method: aqueous solution ( ₁ ) containing 0.594 g of CaCl2 (=
300 mg CaO/=30° dH) (adjusted to pH 10 with dilute NaOH) was mixed with alumosilicate [1 g: as active substance (AS)]. Next, after stirring this suspension vigorously for 15 minutes at a temperature of 22°C (±2°C), the alumosilicate was removed and the residual hardness X of the liquid was measured. From the obtained measured values, calcium binding capacity (mgCaO/gAS) was calculated using the following formula. Measuring calcium binding capacity at temperatures higher than (30-X).10, for example 60°C, generally yields higher values than at 22°C. Manufacturing conditions for sodium alumosilicate A All percentages are by weight. Raw material for precipitation: Aluminate solution (composition: Na ₂ O 17.7%,
Al ₂ O ₃ 15.8%, H ₂ O 66.6%) …2.985Kg Caustic soda …0.15Kg Water …9.420Kg 25.8% sodium silicate solution (composition:
1Na ₂ O・6.0SiO ₂ ) (Fresh one prepared from commercially available water glass and easily alkali-soluble silicic acid)
...2.445Kg Crystallization: 90℃, 6 hours. Drying: 100℃, 24 hours. Composition: 0.9Na ₂ O・1Al ₂ O ₃・2.04SiO ₂・4.3H ₂ O
(=H ₂ O2 1.6%) Crystallinity: Completely crystallized. Calcium binding capacity: 170mgCaO/g active substance. When the particle size distribution was measured by sedimentation analysis, the maximum particle size was 3 to 6μ. This sodium alumosilicate A shows the following interference lines in the X-ray diffraction diagram: d value (measured by Cu-Kα- ray: Å) 12.4 8.6 7.0 4.1 3.68 (+) 3.38 (+) 3.26 (+) 2.96 (+) 2.73 (+) 2.60 (+) Not all of these interference lines will appear in the X-ray diffraction diagram, especially when the alumosilicate is not completely crystallized. Therefore, the most important d values for this type of characterization are indicated with a (+) symbol. Manufacturing conditions for sodium alumosilicate B All percentages are by weight. Raw material for precipitation: Aluminate solution (composition: Na ₂ O 13.2%,
Al ₂ O ₃ 8.0%, H ₂ O 78.8%) …7.63Kg Sodium silicate solution (composition: Na ₂ O 8.0
%, SiO ₂ 26.9%, H ₂ O 65.1%) …2.37Kg Raw material mixture ratio (mol): 3.24Na ₂ O: 1.0 Al ₂ O ₃ :
_1.78SiO2 : _70.3H2O . Crystallization: 90°C, 6 hours. Drying: 100℃, 24 hours. Composition of dry product: 0.99Na ₂ O・1.00Al ₂ O ₃・
1.83SiO ₂ 4.0H ₂ O (=H ₂ O20.9%) Crystal type: Cubic with strongly rounded corners. Average particle size: 5.4μ Calcium binding capacity: 172mgCaO/g active substance. Manufacturing conditions for sodium alumosilicate C All percentages are by weight. Raw material for precipitation: Aluminate solution (composition: Na ₂ O 14.5%,
Al ₂ O ₃ 5.4%, H ₂ O 80.1%) …12.15Kg Sodium silicate solution (composition: Na ₂ O 8.0
%, SiO ₂ 26.9%, H ₂ O 65.1%) …237Kg Raw material mixing ratio (mol): 5.0Na ₂ O; 1.0 Al ₂ O ₃ ;
_2.0SiO2 ; _100H2O . Crystallization: 90°C, 1 hour. Drying: The product is washed (PH 10) into a suspension and subjected to thermal spray drying at 295°C (solids content of the suspension is 46%). Composition of dry product: 0.96Na ₂ O・1Al ₂ O ₃・
_1.96SiO2・_4H2O . Crystal type: Cubic with strongly rounded corners. Moisture content 20.5%. Average particle size: 5.4μ. Calcium binding capacity: 172mg/CaO/g active substance. Examples In Examples 1-3, the effectiveness of stabilizer compositions was tested on the "static thermal stability" of rolled membranes. For this test, the moldable polyvinyl chloride material containing the stabilizer composition was rolled on a laboratory rolling mill of size 450 x 220 mm (Fa.Berstorff).
The rolling temperature was 170°C and the rolling speed was 12.5 revolutions per minute in the same direction for 5 minutes, resulting in a thickness of about 0.5 mm.
A test piece was obtained by cutting this into a square with a side length of 10 mm, and the test piece was placed in a drying rack (Heraeus FT420R) with 6 rotary tables at a temperature of 180°C and left for 15 minutes. After that, the test piece was taken out and the change in color tone was observed. The following Tables 2, 4 and 5 summarize the types of stabilizer compositions used, their initial color and the time at which the test was terminated due to intense discoloration (loss of stability). . Example 1 Molding polyvinyl chloride materials A to F having the compositions shown in Table 1 were subjected to tests according to the method described above.

【table】

[Table] Composition A is a moldable polyvinyl chloride material stabilized by the stabilizer composition of the present invention, in particular:
Suitable for manufacturing tubes and profiles by extrusion method.
Compositions B to F are comparative polyvinyl chloride molding materials, in which some components of composition A are omitted;
It is obtained by exchanging something for something else. The test results for "static thermal stability" are shown in Table 2.

【table】

[Table] Example 2 Molding polyvinyl chloride materials G to L having the compositions shown in Table 3 were subjected to tests according to the method described above.

【table】

Table: Composition G is a moldable polyvinyl chloride material stabilized by the stabilizer composition of the invention, which is suitable for the production of packaging materials, in particular for the production of bottles by blow extrusion. There is. Compositions HL are comparative polyvinyl chloride molding materials obtained by removing some components of composition G and replacing them with others. "Static thermal stability" of this group of molding materials
The test results are shown in Table 4.

[Table] Example 3 Polyvinyl chloride suspension (K value 60) ... 100 parts by weight Calcium stearate ... 0.75 parts by weight Zinc stearate ... 0.25 parts by weight Pentaerythritol stearate [Pentaerythritol: stearic acid = 1: 1.5 (molar ratio); OH value 212] …0.3 parts by weight 2-ethylhexylthioglycolate
...0.3 parts by weight Paraffin (melting point, 71°C) ...0.75 parts by weight The following zeolites (n) to (s) were added to polyvinyl chloride material M having the above composition.
Molding materials N to S were obtained by adding 1 part by weight to 100 parts by weight: (n) Inactive synthetic Na-zeolite (NaA
type). _Na2O : _{Al2O3 : SiO2} =0.99:1:1.83 Moisture content, 20.9%; average particle size, 5.4μ. (o) Inactive synthetic Na-zeolite (NaX
type). _Na2O : _Al2O3 : _SiO2 = 1 _: 1:2.4-2.6. (p) Inactive synthetic Na-zeolite (NaY
type). _Na2O : _{Al2O3 : SiO2} =1:1:4.3. (q) Inactive synthetic K-zeolite (KA type). _{K2O : Al2O3} : _SiO2 =1:1:2. (r) Inactive synthetic Ca-zeolite (CaA type) = produced by subjecting (n) to ion exchange with calcium chloride. (s) Inactive synthetic sodium alumosilicate. Amorphous _{Na2O : Al2O3} : _SiO2 =1:1:2. Composition N is a polyvinyl chloride material stabilized by the stabilizer composition of the present invention. Compositions M and O-S are comparative polyvinyl chloride materials in which the sodium alumosilicate (n) of Composition N was removed or replaced. These polyvinyl chloride molding materials were subjected to a "static thermal stability" test according to the method described above. The results obtained are shown in Table 5. Table 5

[Table] Example 4 Polyvinyl chloride suspension (K
Value 65) 100 parts by weight of a stabilizer mixture with the following composition:
A polyvinyl chloride material for molding was obtained by mixing with 4.65 parts by weight: inactive synthetic Na-zeolite (NaA type)
( _Na2O : _Al2O3 : _{SiO2 =} 0.99:1:1.83; _H2O
=20.9%) ...20 parts by weight Calcium stearate ...10 parts by weight Zinc stearate ...3 parts by weight Pentaerythritostearic acid partial ester (molar ratio, 1:1.5; OH value 212) ...3 parts by weight 2-ethylhexylthioglyco rate
...3 parts by weight Paraffin (melting point, 71° C.) ...7.5 parts by weight This polyvinyl chloride material for molding was processed using a commercially available double helix extruder CM55 [manufactured by Cincinnati Milacron (Vienna)]. The performance of this extruder is as follows: Helix diameter: 55/110mm Effective length: 1050mm Arrangement: conical/serrated Direction of rotation: upwardly moving away from each other in the counter-running direction. Processing was performed under the following conditions: wall thickness 5.3 mm, outer diameter
A 110mm PVC pipe was manufactured: Cylinder: 185/170/135℃ Inlet: 140℃ Head: 190/190℃ Nozzle: 200℃ Perforator: 190℃ Core: 140℃ Motor rotation speed: 2000 rotations /min Spiral rotation speed: 35 revolutions/min Motor load: 42-45% (the helix was sufficiently filled with the raw material) Production volume: 157 Kg/hr The obtained tube was white to caramel colored. Example 5 A stabilizer mixture was prepared with the following composition: Inactive synthetic Na-zeolite (NaA type)
( _Na2O : _Al2O3 : _{SiO2 =} 0.99:1:1.83; _H2O
=20.9% by weight) ...10 parts by weight Calcium stearate ...2 parts by weight Zinc octoate ...4 parts by weight Pentaerythritostearate (molar ratio, 1:1.5; OH value 212) ...20 parts by weight 2-ethylhexylthioglyco rate
…4 parts by weight adipic acid/pentaerythritol/stearate (molar ratio, 6:7:16; OH-value approx. 2; acid value, approx. 10) …10 parts by weight epoxidized soybean oil (epoxy value, 6.3)
80 parts by weight 92 parts by weight of polyvinyl chloride suspension (K value 60), 8 parts by weight of methacrylate-butadiene-styrene resin, and 7 parts by weight of the above stabilizer mixture were mixed in a high-speed mixer to form a fluid solution. A dry blend composition was obtained. This composition was processed in a conventional blow extruder (cylinder diameter 40 mm, specific helix length 20 D) to produce bottles with a capacity of about 290 ml. Under certain processing conditions, bottles with smooth and shiny surfaces, good transparency and high impact resistance were obtained. Example 6 A stabilizer mixture was prepared with the following composition: Inactive synthetic Na-zeolite (NaA type)
( _Na2O : _Al2O3 : _{SiO2 =} 0.99:1:1.83; _H2O
=20% by weight) ...10 parts by weight Calcium stearate ...6 parts by weight Zinc stearate ...5 parts by weight Pentaerythritostearate (molar ratio, 1:1.5) ...24 parts by weight 2-ethylhexylthioglycolate
…6 parts by weight Adipic acid/pentaerythritate/stearate (mole ratio, 6:7:16; OH value: approx. 2; acid value, approx. 10) …10 parts by weight α-phenylindole …3 parts by weight epoxide Chemicalized soybean oil (epoxy value 6.3)
...40 parts by weight 100 parts by weight of a polyvinyl chloride suspension (K value 60) and 7.35 parts by weight of the above stabilizer mixture were mixed in a high-speed mixer to obtain a polyvinyl chloride material for molding.
This was rolled using a laboratory rolling mill with a size of 450 x 220 mm (manufactured by Berschuttorf) at a rolling temperature of 170°C and a rolling temperature of 12.5 mm.
A translucent film with a thickness of about 0.5 mm was obtained by rolling in a conventional manner in the same direction at a rolling rotation speed of 1/min. This film had a smooth and shiny surface. Example 7 Polyvinyl chloride suspension (K value
65) 100 parts by weight of a stabilizer mixture of the following composition 4.65
A polyvinyl chloride material for molding was obtained by mixing with parts by weight: Inactive synthetic Na-zeolite (NaA type)
( _Na2O : _Al2O3 : _{SiO2 =} 0.99:1:1.83; _H2O
=20.9%) ...20 parts by weight Calcium stearate ...10 parts by weight Zinc stearate ...3 parts by weight Glycerin stearic acid partial ester (molar ratio, 1:1.5) ...2 parts by weight Trimethylolpropane ...1 part by weight Ethylene glycol monothioglyco rate
...3 parts by weight Paraffin (melting point, 71°C) ...7.5 parts by weight This polyvinyl chloride material for molding was molded using a commercially available double helix extruder CM55 [manufactured by Cincinnati Milacron (Vienna)]. The performance of this extruder is as follows: Helix diameter: 55/110mm Effective length: 1050mm Arrangement: conical/serrated Direction of rotation: upwardly moving away from each other in the counter-running direction. The molding process was performed under the following conditions, with a wall thickness of 5.3 mm.
A polyvinyl chloride pipe with an outer diameter of 110 mm was manufactured: Cylinder: 185/170/135°C Inlet: 140°C Head: 190/190°C Nozzle: 200°C Perforator: 190°C Core: 140°C Motor rotation speed: 2000 revolutions/min Helical rotation speed: 35 revolutions/min Motor load: 42-45% (the helical portion was sufficiently filled with the raw material) Production volume: 157 Kg/hr The obtained tube was white to caramel colored. Example 8 A stabilizer mixture was prepared with the following composition: Inactive synthetic Na-zeolite (NaA type)
( _Na2O : _Al2O3 : _{SiO2 =} 0.99:1:1.83; _H2O
=20.9% by weight) ...10 parts by weight Calcium stearate ...2 parts by weight Zinc octoate ...4 parts by weight Glycerin di-12-hydroxystearate
…20 parts by weight Decanediol-1,10-bis-thioglycolate …4 parts by weight Adipic acid-pentaerythritol-stearate (mole ratio, 6:7:16; OH value: approx. 2; acid value, approx. 10) …10 parts by weight epoxidized soybean oil (epoxy value 6.3)
...80 parts by weight 92 parts by weight of polyvinyl chloride suspension (K value 60), 8 parts by weight of methacrylate-butadiene-styrene resin, and 7 parts by weight of the above stabilizer mixture were mixed in a high-speed mixer to obtain fluidity. A dry blend composition was obtained. This composition was molded using a conventional blow press (cylinder diameter: 40 mm, specific helix length: 20 D) to produce a bottle with a capacity of about 290 ml. Under certain processing conditions, bottles with smooth and shiny surfaces, good transparency and high impact resistance were obtained. Example 9 A stabilizer mixture was prepared with the following composition: Inactive synthetic Na-zeolite (NaA type)
( _Na2O : _Al2O3 : _{SiO2 =} 0.99:1:1.83; _H2O
=20% by weight)...10 parts by weight Calcium stearate 6 parts by weight Zinc stearate...5 parts by weight Trimethylolpropane laurate (molar ratio,
1:1.5)...24 parts by weight n-octadecylthioglycolate...6 parts by weight adipic acid-pentaerythritol-stearate (mole ratio, 6:7:16:OH value approx. 2; acid value, approx. 10) ...10 parts by weight α-phenylindole ...3 parts by weight Epoxidized soybean oil (epoxy value 6.3)
...40 parts by weight 100 parts by weight of a polyvinyl chloride suspension (K value 60) and 7.35 parts by weight of the above stabilizer mixture were mixed in a high-speed mixer to obtain a polyvinyl chloride material for molding.
This was rolled in a conventional manner in the same direction using a 450 x 220 mm laboratory rolling mill (manufactured by Berschtorff) at a rolling temperature of 170°C and a rolling speed of 12.5 revolutions/min to a thickness of approximately 0.5 mm. A translucent film was obtained.
This film had a smooth and shiny surface.

Claims (1)

[Scope of Claims] 1 (a) Fine particle crystallinity containing 13 to 25% by weight of bound water and having an anhydrous composition of 0.7 to 1.1Na ₂ O・Al ₂ O ₃・1.3 to 2.4SiO ₂ 4 to 100 parts by weight of synthetic sodium alumosilicate (b) 1 to 30 parts by weight of calcium salts of fatty acids with 8 to 22 carbon atoms (c) 1 to 10 parts of zinc salts of fatty acids with 8 to 22 carbon atoms Part by weight (d) Partial esters of polyols having 2 to 6 carbon atoms and 2 to 6 hydroxyl groups and fatty acids having 8 to 22 carbon atoms (on average at least one polyol hydroxyl group per molecule) and (e) 2 to 200 parts by weight of thioglycolic esters of polyols having 2 to 6 hydroxyl groups and/or thioglycolic esters of monohydric alcohols having 8 to 22 carbon atoms. A stabilizer composition for polyvinyl chloride materials for molding, comprising: 2. The stabilizer composition according to item 1, wherein component (a) has a particle size of 0.1 to 20μ. 3. The stabilizer composition according to item 1 or 2, wherein component (a) is bound water-bearing zeolite 4A containing 18 to 25% by weight of water. 4 Component (d) has a hydroxyl value of 140 to 580, especially 170
540 and an acid value of 15 or less, especially 8 or less. 5. The stabilizer according to any one of items 1 to 4, wherein component (e) is a thioglycolate of an aliphatic straight-chain or branched monoalcohol and/or a mono- and/or di-thioglycolate of a polyol. Composition. 6 pentaerythritate partial ester of a fatty acid in which component (d) has 8 to 22 carbon atoms (molar ratio; pentaerythrite:fatty acid = 1:1 to 1:2),
Component (e) is a thioglycolic acid ester of a monohydric alcohol having 8 to 18 carbon atoms, a monothioglycolic acid ester of an aliphatic diol having 2 to 6 carbon atoms, or a glycerin monothioglycolate. The stabilizer composition according to any one of items 1 to 5.