JPH10168263A - Stabilizer for chlorine-containing polymer and chlorine-containing polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stabilizer for a chlorine-containing polymer which achieves a high thermal stabilizing action with a small amount of blending, and a stabilizer for a chlorine-containing polymer having a drastically improved thermal stability. In addition to having excellent thermal stability, it also has excellent electrical insulation,
Provided is a chlorine-containing polymer composition useful as a wire covering material. SOLUTION: A composite containing microcrystalline calcium silicate having a Ca / Si molar ratio of 0.5 to 2.0 and a polyhydric alcohol at a weight ratio of 20:80 to 80:20; The present invention provides a chlorine-containing polymer stabilizer containing a site or an alkali aluminum composite hydroxide salt in a weight ratio of 5:95 to 95: 5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilizer for a lead-free chlorine-containing polymer and to a stabilized chlorine-containing polymer composition, and more particularly to a heat stabilizing action for a chlorine-containing polymer. To improved stabilizers.

[0002]

2. Description of the Related Art It has long been known that a combination of calcium silicate (calcium silicate) and a hydroxyl group-containing compound is excellent as a heat stabilizer for a chlorine-containing polymer. 52-328
No. 99 describes a stabilizer composition comprising a silicate having a pore volume of 0.5 ml / g or more and an organic compound having a product of hydroxyl group and carbon number of 6 or more contained in the pores. ing.

[0003] Also, JP-A-4-15237 discloses that
It is described that microcrystalline calcium silicate having a specific X-ray diffraction image is a resin compounding agent having excellent heat stabilizing action.

It has long been known that hydrotalcite has a thermal stabilizing effect on chlorine-containing polymers. For example, Japanese Patent Application Laid-Open No. 55-80445 discloses that It is described that 0.01 to 5 parts by weight of hydrotalcite is blended with respect to parts by weight.

It is already known to use a combination of a silicate and hydrotalcite as a stabilizer for a chlorine-containing polymer. Chloric acid group-containing hydrotalcite 0.05 to 10 parts by weight and aluminum or alkaline earth metal silicate 0.001 to 3
Stabilized resin compositions containing parts by weight are described.

JP-A-8-109297 discloses that the molar ratio of hydrotalcite is 0.05 to 10 parts by weight per 100 parts by weight of vinyl chloride resin and the molar ratio of silica to alkaline earth metal oxide is 2.2 to 10 parts by weight. No. 8 describes a vinyl chloride resin composition for covering electric wires containing 0.001 to 3 parts by weight of a silicate of an alkaline earth metal.

[0007]

The stabilizers described in the above proposals are worthy of evaluation in that they exhibit a certain degree of thermal stabilizing action even though they are non-lead-based, but all of them have high thermal stability with a small amount of compounding. There is still room for improvement in achieving the stabilizing effect.

The present inventors have selected microcrystalline calcium silicate having a specific composition and an X-ray diffraction image among calcium silicates, and combined it with hydrotalcite or an alkali aluminum composite hydroxide salt. Sometimes it was found that the thermal stability was significantly improved.

The present inventors have also found that when a composite is formed from the above-mentioned microcrystalline calcium silicate and a polyhydric alcohol and this is combined with hydrotalcite or an alkali aluminum composite hydroxide salt, the thermal stability is further improved. I found something to do.

[0010] That is, an object of the present invention is to provide a chlorine-containing polymer stabilizer having dramatically improved thermal stability.

Another object of the present invention is to provide a chlorine-containing polymer composition which has excellent thermal stability and excellent electrical insulation properties and is useful as a wire covering material.

[0012]

According to the present invention, (A)
General formula (1) CaO.xSiO ₂ .nH ₂ O (1) In the formula, x is a number of 0.5 to 2.0, and n is a number of 2.5 or less. It has a chemical composition and has a spacing of 3.01 to 3.08 angstroms and a spacing of 2.7.
A microcrystalline calcium silicate having an X-ray diffraction image at 8 to 2.82 angstroms and a plane spacing of 1.81 to 1.84 angstroms, and (B) hydrotalcite or an alkali aluminum composite hydroxide salt,
A stabilizer for a chlorine-containing polymer, characterized in that the stabilizer is contained in a weight ratio of 95 to 95: 5.

According to the present invention, (C) general formula (1) CaO.xSiO ₂ .nH ₂ O Ｏ (1) wherein x is a number from 0.5 to 2.0, and n is Having a chemical composition represented by the following, which is not more than 2.5, and having a face spacing of 3.01 to 3.08 angstroms and a face spacing of 2.7.
20: 8 microcrystalline calcium silicate and polyhydric alcohol having an X-ray diffraction image at 8 to 2.82 angstroms and at a spacing of 1.81 to 1.84 angstroms.
A composite containing a weight ratio of 0 to 80:20, and (B)
A stabilizer for chlorine-containing polymer, characterized in that it contains hydrotalcite or an alkali aluminum composite hydroxide salt in a weight ratio of 5:95 to 95: 5.

According to the present invention, there is further provided a chlorine-containing polymer 10.
Per 0 parts by weight, (A) General formula (1) CaO.xSiO ₂ .nH ₂ O (1) where x is a number of 0.5 to 2.0, and n is 2.5 or less. The microcrystalline calcium silicate having a chemical composition represented by the following formula and having a specific surface area in the range of 60 to 200 m ² / g or (C) the microcrystalline calcium silicate and the polyhydric alcohol are mixed in a ratio of 20:80 to 0.2 to 10 parts by weight of a composite containing 80:20 by weight, (B)
A stabilized chlorine-containing polymer composition comprising 0.1 to 10 parts by weight of a hydrotalcite or an alkali aluminum composite hydroxide salt is provided.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, calcium silicate (A) is represented by the following general formula (1): CaO.xSiO ₂ .nH ₂ O (1) wherein x is 0.5 to 2.0. Is a number, and n is a number not greater than 2.5, and has a chemical composition represented by the following formula: 3.01 to 3.08 angstroms, 2.7
A microcrystalline calcium silicate having an X-ray diffraction image at 8 to 2.82 angstroms and an interplanar spacing of 1.81 to 1.84 angstroms is selected.

The above-mentioned microcrystalline calcium silicate is known as described in the above-mentioned JP-A-4-15237, but in the present invention, this microcrystalline calcium silicate is selected, and is used as hydrotalcite or the like. By combining the above, the thermal stability can be remarkably improved as shown in Examples such as Table 5 described below.

That is, a composition in which 2 parts by weight of hydrotalcite was combined with 100 parts by weight of a vinyl chloride resin in combination with another stabilizing aid (Comparative Example 3) was as shown in Table 6 below. While the blackening time at 190 ° C. for about 100 minutes (the time until black coloration) and the hydrogen chloride trapping time of 264 minutes as determined by the Congo Red method are shown, 0.5 parts by weight of the stabilizer is added. When the zonotrite-type calcium silicate was added (Comparative Example 4), as in the case where calcium silicate was not added, only a blackening time of about 100 minutes and a hydrogen chloride trapping time of 265 minutes were exhibited. On the contrary,
The microcrystalline calcium silicate was added to
The addition of parts by weight (Example 7) increases the blackening time to about 160 minutes and the hydrogen chloride trapping time to 312 minutes, indicating the significance of selecting the microcrystalline calcium silicate according to the present invention. It becomes clear.

In the present invention, the significance of combining microcrystalline calcium silicate with hydrotalcite is also apparent by referring to Table 7 described below. That is, when 0.5 parts by weight of microcrystalline calcium silicate was used in combination with another stabilizing aid (Comparative Example 7),
After 10 minutes of heating at 190 ° C., blackening presumably due to zinc burning occurred, and the hydrogen chloride trapping time was only 11 minutes, while combining 3 parts by weight of hydrotalcite (Example 11). No blackening occurs even after heating at 190 ° C. for 180 minutes, and the hydrogen chloride trapping time is extended to a surprisingly long time of 493 minutes. In addition, compared to the case where hydrotalcite is not blended, the electrical insulation is also improved to an order of magnitude or more higher in view of the value of the volume resistivity, and the chlorine-containing polymer composition containing the stabilizer of the present invention is included. Is useful as a wire covering material.

In the present invention, the microcrystalline calcium silicate and the polyhydric alcohol are used in the form of a composite, for example, by wet co-grinding, so that they are synergistically compared with the case where each is used as a simple mixture. Thermal stability can be improved. For example, as shown in Table 8, when microcrystalline calcium silicate, polyhydric alcohol, and hydrotalcite were simply blended into a vinyl chloride resin (Example 16), the blackening time of this resin composition was about 120.
Minute, while the hydrogen chloride trapping time is only 158 minutes, the microcrystalline calcium silicate and the polyhydric alcohol are preliminarily formed into a complex (Example 14).
The blackening time of the resin composition is about 14
0 minutes and the hydrogen chloride capture time can be extended to 192 minutes.

[Microcrystalline calcium silicate] The microcrystalline calcium silicate used in the present invention has the chemical composition represented by the general formula (1) and the X-ray diffraction image described above. In this general formula, x is 0.5 to 2..
Although it is a number of 0, it is preferably in the range of 0.7 to 1.2. Also, n is a number of 2.5 or less, but 0.5
It is preferably in the range of 1.0 to 1.0.

When the content of silica is large beyond this range, the thermal stability tends to be lower than when the content is within the above range. On the other hand, when the content of silica is small beyond this range, There is a case where the initial coloring tendency is increased as compared with the case where it is within the above range. When the microcrystalline calcium silicate is slightly hydrated, the heat stabilizing activity tends to increase. However, when the hydrated amount is too large, the resin tends to foam, which is not preferable.

FIG. 1 shows an X-ray diffraction image of the microcrystalline calcium silicate used in the present invention. FIG. 2 shows an X-ray diffraction image of zonotolite having a chemical composition similar to that of the microcrystalline calcium silicate. From these comparisons, it is understood that the calcium silicate used in the present invention is a fine crystal.

With respect to the X-ray diffraction image of the microcrystalline calcium silicate used in the present invention, the three strong lines are shown in Table 1 below.

[Table 1] In the table, m indicates moderately strong and w indicates weak, respectively, and it is clear from FIG. 1 that the strongest peak is considerably broad.

In the X-ray diffraction of the crystal, the following Bragg equation (3) nλ = 2dhkl Sinθ ‥‥ (3) In the equation, n is the order, λ is the wavelength of the X-ray, and dhkl
Is the (hkl) plane spacing of the crystal, and θ is the diffraction angle. It is known that an intensity peak appears in the interference, and the difference between the sharpness of the interference peak and the crystal size is known. Also, the following Scherrer equation (4) In the formula, Lhkl is a dimension in a direction perpendicular to the (hkl) plane of the crystal, K is a constant of about 0.9, H is the half width (radian) of the interference peak, and λ and θ are the same as in the above formula (1). Where there is a relationship represented by

From the X-ray diffraction image shown in FIG. 1, the half width of the diffraction peak having a plane index of 040 (plane spacing of 3.01 to 3.08 angstroms) is obtained. From the half width, the above equation (4) is used. When the crystallite size is calculated, the crystallite size with a plane index of 040 is generally suppressed to a range of 60 to 120 °.

The thermal stabilization effect of calcium silicate is manifested through the surface of the crystal. If the size of the crystallite is reduced, the surface area of the crystallite is naturally increased. It is easily understood that it has excellent stabilizing action.

The microcrystalline calcium silicate used in the present invention is represented by the following formula (2): I _s = tan θ ₂ / tan θ ₁ ‥‥ (2) where θ ₁ is the angle between the perpendicular to the peak at the X-ray diffraction peak at the plane spacing of 3.01 to 3.08 angstroms and the tangent to the narrow angle, and θ ₂ is the perpendicular to the peak at the above-mentioned peak and the wide angle side. It is preferable that the lamination irregularity index (I _s ) defined by an angle formed by a tangent line is 1.75 or more, particularly in the range of 1.8 to 2.0. The microcrystalline calcium silicate used in the present invention is a layered fine crystal as is clear from the X-ray diffraction image described above. The larger the value, the greater the irregularity. The microcrystalline calcium silicate used in the present invention has a large active surface due to irregular lamination, and is excellent in stabilizing the chlorine-containing polymer.

In the microcrystalline calcium silicate used in the present invention, those having a particle size of 40 μm or more are generally 10% by weight or less and those having a particle size of 20 μm or less are 50% or less.
Having a particle size distribution that is at least
It is preferable in terms of uniform dispersion in the chlorine-containing polymer and the effect of heat stabilization. Further, the microcrystalline calcium silicate, in relation to the particle structure, 60 to 200 meters ² / g, a relatively large specific surface area, especially 70 to 150 meters ² / g,
A pore volume of 0.5 ml / g or more, especially 1.0 to 4.0 ml / g, and 50 to 250 ml / 100 g, especially 8
It has an oil absorption of 0 to 200 ml / 100 g.

The microcrystalline calcium silicate can be produced by pulverizing amorphous active silicic acid in lime milk, but is not limited to this production method.

The metal salt of Group 2 of the periodic table of silicic acid used in the present invention is obtained by adding an organic compounding agent which has a masking or chelating action to zinc chloride to the zinc chloride. Alternatively, it is preferable to hold it on the surface.

Examples of the organic compounding agent for this purpose include polyhydric alcohols, phenols, β-keto acid esters and β-keto acid esters.
Diketones are preferred, suitable examples of which are as follows.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, glycerin, diglycerin, pentaerythritol, and dipentaerythritol. Mannitol, sorbitol, trimethylolpropane, ditrimethylolpropane, tris isocyanurate, dipentaerythritol adipate and the like.

Examples of the phenolic antioxidants include bisphenol A, bisphenol B, bisphenol F, 2,6-diphenyl-4-octadecyloxyphenol, and stearyl (3,5-ditert-butyl-4-hydroxyphenyl). ) -Propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], bis [3,3-bis (4 -Hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris ( 2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxylbenzyl) isocyanurate, triethylene glycol Screw [(3-
Tert-butyl-4-hydroxy-5-methylphenyl) propionate].

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

The above-mentioned organic compounding agents are used alone or in combination, and are contained in an amount of 1 to 250% by weight, particularly 10 to 200% by weight, most preferably 100 to 200% by weight, based on the metal salt of Group 2 of the periodic table of silicic acid. It is desirable to have been.

In a preferred embodiment of the present invention, (C) a composite containing microcrystalline calcium silicate and a polyhydric alcohol in a weight ratio of 20:80 to 80:20, particularly 30:70 to 60:40. Used in. The composite can significantly improve the thermal stability of the chlorine-containing polymer,
Prevents initial coloring and zinc burning, and offers the advantage of low migration. This composite is generally obtained by co-grinding a polyhydric alcohol and microcrystalline calcium silicate by a wet method and a dry method.

When the content of the polyhydric alcohol is less than the above range, initial coloring and zinc burning become unsatisfactory, and when the content exceeds the above range, the migration property tends to increase. As the polyhydric alcohol, pentaerythritol and dipentaerythritol are suitable.

[Hydrotalcite] The hydrotalcite used in combination with the microcrystalline calcium silicate is a synthetic mineral belonging to aluminum magnesium carbonate hydroxide, and has the general formula (5): M ²⁺ _x M ³⁺ _y (OH) _{2x + 3y-2z} (A ⁺⁺ ) _z · aH ₂ O (5) In the formula, M ²⁺ is a divalent metal ion such as Mg, and M ³⁺ is A
a trivalent metal ion of l such, A ⁺⁺ is a divalent anion such as CO _3, x, y and z is 8 ≧ x / y ≧ 1/ 4 and z /
x + y is a positive number satisfying 1/20, and a is 0.25 ≦ a / x + y ≦
It is a number that satisfies 1.0. Is used.

Among these composite metal hydroxides, the compound represented by the formula (6) Mg ₆ Al ₂ (OH) ₁₆ (CO ₃ ) .4H ₂ O Ｏ (6) is a natural compound known as hydrotalcite. Minerals and their homologues are described in JP-B-47-32198, filed by Kyowa Chemical Industry Co., Ltd.
JP-B-48-29777 and JP-B-48-29478
It is synthesized by the method described in Japanese Patent Publication No.

These hydrotalcites, in particular, the compound represented by the formula (7) Mg _4.5 Al ₂ (OH) ₁₃ (CO ₃ ) .3H ₂ O (7) has excellent chlorine ion trapping performance. Are also already known, and can be used as the compounding component of the present invention.

By taking advantage of the property that these hydrotalcites are easily ion-exchanged in a state where they are sufficiently dispersed in water, that is, the property that carbonate ions are ion-exchanged with other anions, the perhalogenated oxygen is used. Those into which acid ions have been introduced can also be used.

In the present invention, it is needless to say that ordinary Mg-type hydrotalcite can be used, but zinc-modified hydrotalcite can also be used. As the zinc-modified hydrotalcite, in the general formula (5),
The divalent metal ion of M ²⁺ is a combination of Mg and Zn, and the atomic ratio of Mg: Zn is 9: 1 to 1.
Those having a ratio of 8: 1, especially 3: 1 to 2.5: 1, are excellent in terms of thermal stability and prevention of initial coloring.

[Alkali aluminum composite hydroxide salt]
Examples of the alkali aluminum hydroxide carbonate used in the present invention include lithium aluminum hydroxide carbonate, dawsonite type sodium aluminum hydroxide carbonate, or a mixed crystal thereof.

(1. Lithium aluminum hydroxide carbonate) Lithium aluminum composite hydroxide carbonate (L
In AHCS, lithium ions enter the vacancies (vacant) of the aluminum hydroxide octahedral layer having a gibbsite structure, and an anion is incorporated to supplement the charge. That is, lithium ions have the smallest ionic radius among cations, and are exceptionally monovalent ions which are hexacoordinated ions, so that they enter the above-mentioned vacancies and have the above structure.

[0045] Lithium aluminum hydroxide carbonate salt used in the present invention has the following formula (8), mAl in _{2 O 3 · nM 2 O ·} X · kH 2 O ‥‥ (8) formula, X is a carbonate groups It is an inorganic anion mainly used,
M is an alkali metal mainly composed of lithium, m is a number of 1.5 to 2.5, n is a number of 0.1 to 1, and k is a number of 0 to 10. Table 2 below

[Table 2] Has an X-ray diffraction image of

The preferred lithium-aluminum composite hydroxide carbonate is represented by the following formula (2): I _s = tan θ ₂ / tan θ ₁ (2) where θ ₁ is a peak in the X-ray diffraction peak at a constant plane spacing. Represents the angle between the perpendicular and the narrow-angle peak tangent, θ ₂
Represents the angle formed by the peak perpendicular to the peak and the tangent to the wide-angle peak at the peak. The stacking irregularity index (I _S ) defined by the following expression is 1.0 or less at the peak of the plane index (016) and the plane index (017) Is 1.0 or less at the peak.

The lithium aluminum hydroxide carbonate used in the present invention has a wave number of 547, 735, 1004, 13
It has an infrared absorption spectrum with large absorption at 75 and 3443 (cm ^-1 ).

The lithium aluminum hydroxide carbonate particles used in the present invention are generally 0.1 to 10 μm, particularly 0.1 to 3 μm, as measured by a laser scattering diffraction method.
m having a volume-based median diameter (D ₅₀ ) of J
0.1 to 0.35 g / measured by IS K6721
cm ^3, in particular having a bulk density of 0.25 to 0.35 g / cm ^3, having a BET specific surface area of 10 to 70m ² / g, it is preferably oil absorption is small and 40 to 70 ml / 100 g.

The lithium aluminum hydroxide carbonate is, of course, not limited to, but amorphous or pseudo-boehmite hydrated alumina gel, lithium carbonate or bicarbonate, In an aqueous medium, alumina (A
A method in which the reaction is carried out under the condition that the concentration as l ₂ O ₃ ) becomes 1 to 5% by weight and the pH at the end of the reaction becomes 7 to 11 (hereinafter sometimes simply referred to as a hydrated alumina gel method).
Or a method of reacting fine particles of gibbsite-type aluminum hydroxide with a lithium salt of carbonate or a combination of a carbonate compound and a lithium compound capable of forming lithium ion and carbonate in the presence of water, that is, a migration method. Manufactured.

(2. Sodium aluminum hydroxide carbonate) Dawsonite type sodium hydroxide used in the present invention
Aluminum hydroxide carbonate salt (NAHCS) is represented by the following formula _{(9) mAl 2 O 3 ·} nM 2 O · X · kH 2 O ‥‥ (9) wherein, X is an anion of an inorganic consisting mainly of carbonate groups Yes,
M is an alkali metal mainly containing sodium, m is a number from 0.5 to 1.5, n is a number from 0.1 to 1, and k is a number from 0 to 3. Having the composition given.

The dawsonite type crystal structure is defined by the following Table 3 in X-ray diffraction using Cu-α.

[Table 3] In the table, VS is very strong, S is strong, m is moderately strong,
"w" indicates an X-ray diffraction image which is substantially the same as that indicating "weak", respectively.

This dawsonite has substantially no weight loss at a temperature of 300 ° C. or less in thermogravimetric analysis, and is suitable for preventing foaming during kneading or molding of a resin. is there.

The sodium-aluminum composite hydroxide carbonate having a dawsonite type crystal structure preferably used in the present invention has a half-width of the peak of the plane index (011) in the Cu-α X-ray diffraction image of 0.4 ° or more. Yes and concentration 5% by weight
Specific resistance is 8000 Ω · cm when used as an aqueous slurry of
It is the following.

In the sodium-aluminum hydroxide carbonate used in the present invention, the fact that the half width of the peak of the plane index (011) is large means that the b-axis direction (fiber axis direction).
This indicates that the crystal size of the crystal is small.

In general, dawsonite is formed by entanglement of a bundle of fine fibers having an extremely large aspect ratio to bind together coarse and thread-like secondary particles.
It can be confirmed that the degree of development of the fiber structure is extremely small, and the secondary particles have a small particle shape with a small degree of aggregation.

Therefore, in relation to the particle shape, general dawsonite has an oil absorption of 70 to 100 ml / 100 g.
Although it is relatively large, the oil absorption of dawsonite preferably used in the present invention is 40 ml / 100 g or more and 70 ml /
Less than 100 g. Furthermore, the former pigment volume concentration is 35%.
Although the following is lower, the latter has a higher characteristic of 40 to 50%.

The particles of the dawsonite-type sodium aluminum hydroxide carbonate used in the present invention are generally 0.1 to 10 μm as measured by a laser scattering diffraction method.
m, especially 0.1 to 3 μm in volume-based median diameter (D ₅₀ ), oil absorption (JIS K-51
01) is in the range of 50 to 110 ml / 100 g,
BET specific surface area is in the range of 30 to 110 m ² / g and apparent specific gravity (iron cylinder method) is 0.1 to 0.3 g
/ Cm ³ is preferably in the range.

The dawsonite-type sodium-aluminum hydroxide carbonate is not limited to this, but in the above-mentioned hydrated alumina gel method, sodium carbonate is used instead of lithium carbonate. It is manufactured by

Further, LAHC can be obtained by combining an amorphous or pseudo-boehmite type hydrated alumina with an alkali salt in combination with sodium carbonate and lithium carbonate.
An alkali-aluminum composite hydroxide carbonate composed of a mixed crystal of S and dawsonite is obtained.

The above LAHCS and dawsonite type N
Of course, AHCS can be blended with the chlorine-containing polymer as it is, but in order to improve the surface characteristics of the composite salt, it is treated with 10% by weight or less, particularly 1 to 6% by weight of a surface treating agent in advance. It is preferable to improve the dispersibility in the resin and to further improve the light transmittance.

Examples of the surface treating agent include silane-based, aluminum-based, titanium-based or zirconium-based coupling agents, higher fatty acids, metal soaps and resin acid soaps, finely powdered amorphous silica and surfactants. Used accordingly. In general, it is preferable to add a higher fatty acid or a surfactant to a reaction mother liquor containing an alkali-aluminum composite hydroxide carbonate, and to carry out the treatment with stirring.

These hydrotalcites or alkali aluminum composite hydroxide salts can be used alone or in combination. The total amount of the components (A), (B) and (C) is 15 parts by weight. To 95
It should be used in parts by weight, but is preferably used in 30 to 90 parts by weight.

[Higher Fatty Acid Zinc] In the present invention, in addition to the above essential components, (D) the higher fatty acid zinc is added in an amount of 5 to 5 parts by weight per 100 parts by weight of the total amount of the components (A) or (C) and the component (B). It is preferred to further add 70 parts by weight, especially 10 to 50 parts by weight. By using the component (D), it becomes possible to effectively prevent the initial coloring of a warm color system.

As the fatty acid to be a zinc salt, a saturated or unsaturated fatty acid having 8 to 22, particularly 8 to 14, and most preferably 8 to 12 carbon atoms, for example, octylic acid, capric acid,
Saturated fatty acids such as undecanoic acid, lauric acid and myristic acid, and unsaturated fatty acids such as lindelic acid, tunic acid, petroselinic acid, oleic acid, linoleic acid, linolenic acid and arachidonic acid are used. Stearic acid, palmitic acid and the like can be used, but lower fatty acids are preferred for preventing zinc burning. In terms of stability, saturated fatty acids are desirable, and lauric acid is the most preferred. Fatty acids may of course be mixed fatty acids such as coconut oil fatty acids and palm oil fatty acids.

These fatty acid salts also function as a lubricant, and are preferably normal salts.

[Phenolic Antioxidant] In the present invention, in addition to the above essential components, (E) a phenolic antioxidant may be used in an amount of 100 parts or more of the above components (A) or (C) and (B). It is preferably used in an amount of 1 to 50 parts by weight, especially 2 to 20 parts by weight per part by weight. This antioxidant is useful for suppressing degradation due to a chain reaction and the like.

As the phenolic antioxidant used in the present invention, any of those exemplified above, bisphenol type antioxidants and sterically hindered phenolic antioxidants can be used. Bisphenol A is particularly preferred. These phenolic antioxidants can be used alone or in combination.

[Β-keto acid ester or β-diketone] In the present invention, (F) β
-The keto acid ester or the β-diketone are compounded in an amount of 0.5 to 30 parts by weight, especially 1 to 15 parts by weight, per 100 parts by weight of the total of the components (A) or (C) and the component (B) be able to. β-keto acid ester or β
-By adding a diketone, the thermal stability is improved and the initial coloring tendency is also improved.

Β-keto acid esters or β-
The diketones are those exemplified above, and they can be used alone or in combination of two or more.

[Composite Stabilizer] The composite stabilizer of the present invention can be used as a one-pack stabilizer in the form of a powder, that is, in the form of a powder, or in the form of granules. For the production of the granular material, a known granulation method such as an extrusion granulation method, a spray granulation method, a rotating disk granulation method, a tumbling granulation method, a compression granulation method and the like can be used. The particle size of the granular material can be arbitrarily adjusted according to the purpose.
It is preferably in the range from μm to 5 mm, especially from 70 μm to 2 mm.

The composite stabilizer of the present invention includes resin compounding agents known per se, for example, colorants, inorganic or organic fillers, antioxidants, lubricants, plasticizers, chelating agents, antibacterial agents, light Stabilizers, flame retardants, impact enhancers and the like can be added.

For example, amorphous silica, calcined kaolin, aluminum oxide, aluminum silicate, titanium white, titanium phosphate, zirconium phosphate, and the like are used for the purpose of improving electrical insulation. It can be blended in an amount of 20 to 1000 parts by weight, particularly 200 to 500 parts by weight, per 100 parts by weight.

[Chlorine-Containing Polymer Composition] In the chlorine-containing polymer composition according to the present invention, (A) the microcrystalline calcium silicate or (C) the microcrystalline calcium silicate and the polyvalent calcium per 100 parts by weight of the chlorine-containing polymer are used. 0.2 to 10 parts by weight, particularly 0.5 to 5 parts by weight, of a compound containing alcohol in a weight ratio of 20:80 to 80:20.
(B) 0.1 to 10 parts by weight, especially 0.2 to 10 parts by weight of hydrotalcite or alkali aluminum composite hydroxide salt
To 0.5 part by weight.

Examples of the chlorine-containing polymer include polyvinyl chloride, polyvinylidene chloride, chlorinated polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, and vinyl chloride Ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer Copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, chlorinated vinyl-
Propylene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylate copolymer, vinyl chloride-maleate copolymer, vinyl chloride-methacrylate copolymer, Polymers such as vinyl chloride-acrylonitrile copolymer and internally plasticized polyvinyl chloride, and these chlorine-containing polymers and polyethylene, polypropylene, polybutene, and poly-3
Polyolefins such as α-olefin polymers such as -methylbutene or ethylene-vinyl acetate copolymers, ethylene-propylene copolymers and copolymers thereof, polystyrene, acrylic resins, styrene and other monomers (for example, anhydrous With maleic acid, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymer, acrylate-butadiene-styrene copolymer, methacrylate-butadiene-
Blends with styrene copolymers can be mentioned.

The stabilizer of the present invention is useful for heat stabilization of the above-mentioned chlorine-containing polymer, but the type of the stabilizer to be used can be selected according to the type of the chlorine-containing polymer. For example, when the chlorine-containing polymer is a vinyl chloride resin, the component (B) is preferably hydrotalcite, and when the chlorine-containing polymer is a chlorinated vinyl chloride resin, the component (B) is used. Is preferably an alkali aluminum composite hydroxide salt.

In the composition of the present invention, 0.1 to 5.0 parts by weight, particularly 0.2 to 2.0 parts by weight, of the zinc (D) higher fatty acid is preferably added per 100 parts by weight of the chlorine-containing polymer. It is preferred that the phenolic antioxidant (E) be incorporated in an amount of 0.01 to 5.0 parts by weight, particularly 0.05 to 2.0 parts by weight, per 100 parts by weight of the chlorine-containing polymer. Furthermore, when the hydrotalcite is a zinc-modified hydrotalcite, (F) β-diketone or β-keto acid ester is added in an amount of 0.0 per 100 parts by weight of the chlorine-containing polymer.
It is preferred that the amount be 1 to 5.0 parts by weight, particularly 0.03 to 1.0 part by weight.

The chlorine-containing polymer composition of the present invention can be blended with a chlorine-containing polymer compounding agent known per se in accordance with a formulation known per se. For example, the composition of the present invention includes a plasticizer, a lubricant, a filler, a coloring agent, a weathering stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, an antistatic agent, a reinforcing agent, a modifying resin or rubber. , Etc. can be blended according to a formulation known per se.

Examples of the plasticizer include an ester plasticizer such as a phthalate ester plasticizer and an adipic ester plasticizer, a polyester plasticizer, a phosphate ester plasticizer, a chlorine plasticizer, and a tetrahydrophthalic acid plasticizer. Agent, azelaic acid plasticizer, sebacic acid plasticizer, stearic acid plasticizer, citric acid plasticizer, trimellitic acid plasticizer,
And pyromellitic acid plasticizers.

Examples of the lubricant include (a) hydrocarbon-based lubricants such as fluid, natural or synthetic paraffin, microwax, polyethylene wax, and chlorinated polyethylene wax; (b) fatty acid-based lubricants such as stearic acid and lauric acid; (C) stearic acid amide, valmitic acid amide,
Fatty acid monoamides or bisamides such as oleic acid amide, esylic acid amide, methylenebisstearamide, ethylenebisstearamide, etc .; (d) butyl stearate, hydrogenated castor oil, ester such as ethylene glycol monostearate , Those based on alcohols such as (e) cetyl alcohol, stearyl alcohol,
(F) Metal soaps such as lead stearate and calcium stearate and (g) mixed systems thereof are generally used.

As the impact enhancer, for example, 30 to 40%
Chlorinated polyethylene containing chlorine, methyl methacrylate to copolymer rubber mainly composed of acrylic acid ester,
Examples include a multi-component resin obtained by graft polymerization of a monomer such as styrene and acrylonitrile, acrylonitrile / butadiene / styrene resin, metal methacrylate / butadiene / styrene resin, and vinyl acetate / ethylene copolymer resin.

As the flame retardant, not only halogen-based flame retardants, but also
Magnesium, antimony, zirconium, molybdenum, aluminum, silica, titanium oxides, hydroxides and sulfides, zinc borate, zinc stannate, zinc hydroxy stannate, metal hydroxide surface treated products of these zinc compounds, etc. Is mentioned.

[0082]

EXAMPLES The present invention will be described with reference to the following examples, but the present invention is not limited to the following examples. The measurement in the examples was performed by the following method. (1) Evaluation of Initial Coloring The color of the sheet pieces was visually determined after 190 minutes at 190 ° C. in a gear oven, and the results are shown below. 1 2 3 4 Colorless Light yellow Yellow Red (2) Gear oven heat resistance Heat the kneaded molded PVC sheet to 190 ° C in an oven, measure the time (minutes) until it turns black, and heat resistance of the sheet Was evaluated. (3) Thermal stability (HT) According to the JIS-K-6723 method, it was measured by a hydrogen chloride scavenging test at 180 ° C. by the Congo Red method. (4) Volume resistivity Using ADVANTEST R8340, applied voltage 5
The volume resistivity was measured at 00V.

(Synthesis Example 1) An example of a method for synthesizing microcrystalline calcium silicate used in the examples of the present invention will be specifically described. Lime milk slurry (CaO content 6%) 498.8 g
And 42.8 g of activated silicic acid powder having an average particle size of 5 μm were placed in a magnetic pot mill and subjected to a grinding reaction for 54 hours to obtain a slurry having a pH of 10. This was filtered, washed with water, dried at 110 ° C., and then pulverized with a small sample mill to obtain fine powdered calcium silica composite hydroxide (CSH). The physical properties are shown in Table 4.

(Synthesis Example 2) An example of a method for synthesizing a milled mixture of microcrystalline calcium silicate and a polyhydric alcohol used in Examples of the present invention will be specifically described. 285 g of lime milk slurry (CaO content: 6%), 24.2 g of activated silicic acid powder having an average particle size of 5 microns and 40 g of dipentaerythritol were put into a magnetic pot mill, and a grinding reaction was carried out for 54 hours.
10 slurries were obtained. After filtration and washing with water, 110 ° C
And then pulverized with a small sample mill to obtain a polyhydric alcohol-coated fine powdered calcium silica composite hydroxide (C
ASH) is shown in Table 4 below.

[0085]

[Table 4]

(Examples 1 to 5, Comparative Examples 1 and 2) A composition having the following composition was kneaded with a kneading roll at 150 ° C. for 7 minutes to prepare a 0.5 mm thick sheet. A test piece was prepared from the sheet, and initial coloring, heat resistance in a gear oven, heat stability, and volume resistivity were measured. The results are shown in Table 5. Blending parts by weight Polyvinyl chloride resin (degree of polymerization = 1050) 100 Dioctyl phthalate 50 Samples Table below (the blending amount in the table is parts by weight)

[0087]

[Table 5] * Alkamizer 4: Zinc-modified hydrotalcite (Kyowa Chemical Industry Co., Ltd.)

(Examples 6 to 8, Comparative Examples 3 to 6) A composition having the following composition was kneaded with a kneading roll at 150 ° C for 7 minutes to prepare a sheet having a thickness of 0.5 mm. A test piece was prepared from the sheet, and the initial coloring, the heat resistance of the carbon opener, the thermal stability, and the volume resistivity were measured. The results are shown in Table 6. Formulation Parts by weight Polyvinyl chloride resin (degree of polymerization = 1050) 100 Dioctyl phthalate 50 Zinc stearate 0.4 Bisphenol A 0.1 Dibenzoylmethane 0.1 Alkamizer 4 2.0 Sample Parts by weight)

[0089]

[Table 6]

(Examples 9 to 13, Comparative Examples 7 and 8) A composition having the following composition was kneaded with a kneading roll at 150 ° C. for 7 minutes to form a 0.5 mm thick sheet. The heat resistance, heat stability, and volume resistivity of the prepared gear oven were measured, and the results are shown in Table 7. Compounding parts by weight Polyvinyl chloride resin (degree of polymerization = 1050) 100 Dioctyl phthalate 50 Zinc stearate 0.4 Bisphenol A 0.1 Dibenzoylmethane 0.1 CSH 0.5 Sample The following table (the compounding amount in the table is parts by weight )

[0091]

[Table 7]

(Examples 14 to 17, Comparative Examples 9 and 10) A composition having the following composition was kneaded with a kneading roll at 150 ° C. for 7 minutes to form a sheet having a thickness of 0.5 mm. The heat resistance, heat stability, and volume resistivity of the prepared gear oven were measured, and the results are shown in Table 8. Formulation Parts by weight Polyvinyl chloride resin (degree of polymerization = 1050) 100 Dioctyl phthalate 50 Zinc stearate 0.8 Bisphenol A 0.1 Dibenzoylmethane 0.1 Alkamizer 4 0.5 Sample Parts by weight)

[0093]

[Table 8]

(Examples 18 to 20, Comparative Example 11) Dipentaerythritol in Synthesis Example 2 was changed to mannitol,
Dry milled and mixed polyhydric alcohol-coated fine powdered calcium silica composite particles (CASH-M) were obtained. Similarly, dipentaerythritol in Synthesis Example 2 was changed to dipentaerythritol adipate, and polyhydric alcohol-coated fine powder calcium silica composite particles (CASH-S) were obtained by dry milling and mixing. A composition having the following composition was kneaded with a kneading roll at 150 ° C. for 7 minutes to form a sheet having a thickness of 0.5 mm. A test piece was prepared from the sheet, and the heat resistance, heat stability, and volume resistivity of a gear oven were measured. Table 9 shows the results. Formulation Parts by weight Polyvinyl chloride resin (degree of polymerization = 1050) 100 Dioctyl phthalate 50 Zinc stearate 0.5 Bisphenol A 0.1 Dibenzoylmethane 0.01 Alkamizer 4 1.0 Sample Parts by weight)

[0095]

[Table 9]

(Examples 21 to 24, Comparative Example 12) A composition having the following composition was kneaded with a kneading roll at 150 ° C. for 7 minutes to prepare a sheet having a thickness of 0.5 mm. A test piece was prepared from the sheet. Gear oven heat resistance, heat stability, and volume resistivity were measured. The results are shown in Table 10. Mixing parts by weight Chlorinated PVC resin (chlorine content 67%) 100 Dioctyl phthalate 50 Zinc stearate 0.4 Bisphenol A 0.1 Dibenzoylmethane 0.05 Sample The following table (the mixing amount in the table is parts by weight)

[0097]

[Table 10]

[0098]

According to the present invention, among calcium silicates, microcrystalline calcium silicate having a specific composition and an X-ray diffraction image is selected, and this is mixed with hydrotalcite or an alkali aluminum composite hydroxide salt. By combining them, it is possible to provide a chlorine-containing polymer composition in which the thermal stability is remarkably improved, the electrical insulation properties are improved, and the initial coloring tendency is also improved.

When a composite is formed from the above-mentioned microcrystalline calcium silicate and a polyhydric alcohol, and this is combined with hydrotalcite or an alkali aluminum composite hydroxide salt, thermal stability and initial coloring prevention are further improved. Can be improved.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction image of microcrystalline calcium silicate of Synthesis Example 1.

FIG. 2 is an X-ray diffraction image of zonotolite.

FIG. 3 illustrates how to obtain θ ₁ and θ ₂ for calculating a stacking irregularity index (Is).

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/00 C08K 5/00 5/07 5/07 5/098 5/098 5/13 5/13

Claims (19)

[Claims] (A) General formula (1) CaO.xSiO ₂ .nH ₂ O Ｏ (1) wherein x is a number of 0.5 to 2.0, and n is 2.5 or less. Having a chemical composition represented by the following formula, and having a face spacing of 3.01 to 3.08 angstroms, and a face spacing of 2.7.
A microcrystalline calcium silicate having an X-ray diffraction image at 8 to 2.82 angstroms and a plane spacing of 1.81 to 1.84 angstroms, and (B) hydrotalcite or an alkali aluminum composite hydroxide salt,
A stabilizer for a chlorine-containing polymer, which is contained in a weight ratio of 95 to 95: 5. (C) General formula (1) CaO.xSiO ₂ .nH ₂ O Ｏ (1) where x is a number of 0.5 to 2.0, and n is 2.5 or less. Having a chemical composition represented by the following formula, and having a face spacing of 3.01 to 3.08 angstroms, and a face spacing of 2.7.
20: 8 microcrystalline calcium silicate and polyhydric alcohol having an X-ray diffraction image at 8 to 2.82 angstroms and at a spacing of 1.81 to 1.84 angstroms.
A composite containing a weight ratio of 0 to 80:20, and (B)
A stabilizer for a chlorine-containing polymer, comprising hydrotalcite or an alkali aluminum composite hydroxide salt in a weight ratio of 5:95 to 95: 5. 3. The microcrystalline calcium silicate is represented by the following formula (2): I _s = tan θ ₂ / tan θ ₁ ‥‥ (2) where θ ₁ is the angle between the perpendicular to the peak at the X-ray diffraction peak at an interplanar spacing of 3.01 to 3.08 angstroms and the tangent to the narrow angle, and θ ₂ is the perpendicular to the peak at the above-mentioned peak and the wide angle side. chlorine-containing polymerization-body stabilizer according to claim 1 or 2, wherein indicating the angle, in being defined laminated irregularities index (I _S) is 1.75 or more formed by the tangent line. 4. The microcrystalline calcium silicate has a specific surface area of 60 to 200 m ² / g, a pore volume of 0.5 ml / g or more, an oil absorption of 50 to 250 ml / 100 g, and an average particle size of 0.1 to 10 μm. The stabilizer for a chlorine-containing polymer according to any one of claims 1 to 3, which has: 5. The composite (C) of microcrystalline calcium silicate and polyhydric alcohol is obtained by co-grinding microcrystalline calcium silicate and polyhydric alcohol by wet and dry methods. Or the stabilizer for chlorine-containing polymers according to 3. 6. The polyhydric alcohol is pentaerythritol or dipentaerythritol.
4. The stabilizer for a chlorine-containing polymer according to item 1. 7. The component (A) or (C) and the component (B)
The chlorine-containing polymer stabilizer according to any one of claims 1 to 6, further comprising 5 to 70 parts by weight of (D) a higher fatty acid zinc per 100 parts by weight of the total amount of the components. 8. The component (A) or (C) and (B)
The stabilizer for a chlorine-containing polymer according to any one of claims 1 to 7, further comprising 1 to 50 parts by weight of (E) a phenolic antioxidant per 100 parts by weight of the total amount of the components. 9. The stabilizer for a chlorine-containing polymer according to claim 1, wherein the hydrotalcite is a zinc-modified hydrotalcite. 10. The composition according to claim 1, further comprising 0.5 to 30 parts by weight of (F) β-diketone or β-keto acid ester per 100 parts by weight of the total amount of component (A) or (C) and component (B). Item 10. The chlorine-containing polymer stabilizer according to Item 9. 11. The stabilizer for a chlorine-containing polymer according to claim 1, wherein the alkali aluminum composite hydroxide salt is a lithium aluminum composite hydroxide carbonate. 12. The stabilizer for chlorine-containing polymers according to claim 1, wherein the alkali aluminum composite hydroxide salt is a dawsonite-type sodium aluminum composite hydroxide carbonate. 13. Per 100 parts by weight of the chlorine-containing polymer,
(A) General formula (1) CaO.xSiO ₂ .nH ₂ O ‥‥ (1) In the formula, x is a number of 0.5 to 2.0, and n is a number of 2.5 or less. The microcrystalline calcium silicate having the chemical composition represented and having a specific surface area in the range of 60 to 200 m ² / g, or (C) the microcrystalline calcium silicate and the polyhydric alcohol in a weight ratio of 20:80 to 80:20. Characterized in that it contains 0.2 to 10 parts by weight of a compound containing 0.1 to 10 parts by weight of (B) hydrotalcite or an alkali aluminum complex hydroxide salt. Polymer composition. 14. The chlorine-containing polymer composition according to claim 13, wherein the chlorine-containing polymer is a vinyl chloride resin, and the component (B) is hydrotalcite. 15. The chlorine-containing polymer composition according to claim 13, wherein the chlorine-containing polymer is a chlorinated vinyl chloride resin, and the component (B) is an alkali aluminum composite hydroxide salt. 16. The chlorine-containing polymer composition according to claim 13, further comprising (D) 0.1 to 0.5 parts by weight of a higher fatty acid zinc per 100 parts by weight of the chlorine-containing polymer. 17. The chlorine-containing polymer composition according to claim 13, further comprising (E) a phenolic antioxidant in an amount of 0.01 to 5.0 parts by weight per 100 parts by weight of the chlorine-containing polymer. Stuff. 18. The stabilizer for a chlorine-containing polymer according to claim 13, wherein the hydrotalcite is a zinc-modified hydrotalcite. 19. The amount of (F) β-diketone or β-keto acid ester per 100 parts by weight of chlorine-containing polymer is 0.0
19. The chlorine-containing polymer composition according to claim 18, further comprising 1 to 5.0 parts by weight.