JPH11302447A - Stabilizer for chlorine-containing polymer and chlorine-containing polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lead-free stabilizer with improved thermal stability and low temperature heat aging resistance for a chlorine-containing polymer and to obtain a lead-free chlorine-containing polymer composition excellent in thermal stability and low temperature heat aging resistance and useful as a wire- covering material. SOLUTION: There are provided a stabilizer for a chlorine-containing polymer and a resin composition containing the same, the stabilizer comprising(A) a fine crystalline calcium silicate having a chemical composition represented by the formula: CaO.xSiO2 .nH2 O (wherein (x) is a number not less than 0.5 and (n) is a number not more than 2.5) and X-ray diffraction patterns including spacings at 3.01-3.08 Å, 2.78-2.82 Å and 1.81-1.84 Å, or its complex with a polyhydric alcohol and (B) a cyanurate compound, the components (A) and (B) being contained in a wt. ratio of (A) to (B) of 5.0:95.0 to 99.8:0.2.

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 a stabilized chlorine-containing polymer composition, and more particularly to a significantly improved low-temperature heat aging resistance. To a chlorine-containing polymer stabilizer and a chlorine-containing polymer composition.

[0002]

2. Description of the Related Art It has been known for a long time that calcium silicate (calcium silicate) has been used as a compounding agent for resins.
No. 15237 describes that microcrystalline calcium silicate having a specific X-ray diffraction image is a resin compounding agent having excellent heat stabilizing action.

[0003] It is also known that an isocyanurate compound is contained in a chlorine-containing polymer.
No. 74043 discloses tris (2-hydroxyethyl)
A vinyl chloride resin composition containing an isocyanate and an organic acid salt is described.

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 1 part 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 lead-free, but they are still satisfactory with respect to low-temperature heat aging. The desired result has not been obtained.

[0008] That is, the heat resistance which has been a problem in the past with respect to chlorine-containing polymers is the heat resistance at a relatively high temperature of about 180 ° C, and the heat resistance at this high temperature is important as it is. The chlorine-containing polymer is, for example, 10
Even when exposed to a relatively low temperature of about 0 ° C. for a long time, there is a problem of aging. Due to this low-temperature heat aging, the resin tends to be colored or mechanical properties such as elongation tend to be reduced.

The present inventors have selected, among calcium silicates, a microcrystalline calcium silicate having a specific composition and an X-ray diffraction image or a composite of the same and a polyhydric alcohol, and selected the isocyanurate compound. It has been found that when combined with, the thermal stability is remarkably improved, the low-temperature heat aging resistance is also significantly improved, and the initial coloring is small.

[0010] That is, an object of the present invention is to provide a stabilizer for a lead-free chlorine-containing polymer which has remarkably improved thermal stability as well as low-temperature heat aging resistance.

Another object of the present invention is to provide a lead-free chlorine-containing polymer composition which has excellent thermal stability and excellent low-temperature heat aging resistance and is useful as a wire covering material. It is in.

[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 or more, and n is a number of 2.5 or less. With 3.01
To 3.08 angstroms, the spacing between faces 2.78 to 2.82 angstroms, and the spacing between faces 1.81 to 1.
A microcrystalline calcium silicate having an X-ray diffraction image at 84 angstroms or a complex thereof with a polyhydric alcohol, and (B) an isocyanurate compound, and the components (A) and (B) isocyanurate compound are ( A): (B) = 5.0: 95.0 to 99.8: 0.
A stabilizer for a chlorine-containing polymer present in a weight ratio of 2 is provided. According to the present invention, (A) per 100 parts by weight of the chlorine-containing polymer, (A) CaO.xSiO ₂ .nH ₂ O (1) wherein x is a number of 0.5 or more. , N is a number equal to or less than 2.5, and has a specific surface area of 60
0.05 to 10 parts by weight of a microcrystalline calcium silicate in the range of from 200 to 200 m ² / g or a composite containing the microcrystalline calcium silicate and the polyhydric alcohol in a weight ratio of 20:80 to 80:20; B) A chlorine-containing polymer composition having an improved low-temperature heat aging property, comprising 0.01 to 3.0 parts by weight, particularly 0.02 to 1.0 part by weight, of an isocyanurate compound. You. In the stabilizer of the present invention: (A): microcrystalline calcium silicate and (C) hydrotalcite or an alkali-aluminum composite hydroxide salt, (A) :( C) = 0.5: 99.5 to 99.
1. 0: 1.0 weight ratio; (A) The sum of microcrystalline calcium silicate and (B) isocyanurate compound and (D) higher fatty acid zinc are defined as {(A) + (B)} :( D) = 20: 80 to 90: 1.
Similarly, at a weight ratio of 0, the sum of (A) the microcrystalline calcium silicate and (B) the isocyanurate compound and (E)
β-diketone or β-keto acid ester is converted to ｛(A) +
(B)｝: (E) = 35: 65 to 99.9: 0.1 in a weight ratio; (A) The sum of microcrystalline calcium silicate and (B) isocyanurate compound and (F) phenolic antioxidant are {(A) + (B)} :( F) = 35: 65 to 9
It is preferable to further include 9.9: 0.1 by weight. In the chlorine-containing polymer composition of the present invention, per 100 parts by weight of the chlorine-containing polymer: (C) further containing 0.1 to 10.0 parts by weight of hydrotalcite or an alkali-aluminum composite hydroxide salt; (D) 0.1 to 5.0 parts by weight of a higher fatty acid zinc and (E) β-diketone or β-keto acid ester 0.0
2. 1 to 5.0 parts by weight; (F) 0.01 to 5.
It is preferable to further include 0 parts by weight.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, as calcium silicate, (A) general formula (1) CaO.xSiO ₂ .nH ₂ O Ｏ (1) In the formula, x is a number of 0.5 or more, preferably 0.5 to 5.0
, Most preferably a number from 0.5 to 3.0, and n is a number less than or equal to 2.5, and a face-to-face spacing of 3.01 to 3.08 angstroms. , 2.78 to 2.82 angstroms, and the face spacing 1.
Microcrystalline calcium silicate having an X-ray diffraction image at 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. In the present invention, this microcrystalline calcium silicate is selected, and this is mixed with an isocyanurate compound. By combining them, as shown in Tables 5 and 6 described below,
Thermal stability and low-temperature heat aging resistance can be significantly improved.

As calcium silicate, many minerals such as zonotolite and tobermorite are known.
In the present invention, the thermal stability of the chlorine-containing polymer can be improved by using microcrystalline calcium silicate having the above-mentioned specific chemical composition and X-ray diffraction image as a main stabilizer. That is, as shown in Comparative Example 3 to be described later, the vinyl chloride resin composition containing zonotolite as a main stabilizer has a blackening time of about 120 minutes at 190 ° C. and a hydrogen chloride capturing time of 300 minutes determined by the Congo Red method. On the other hand, the vinyl chloride resin composition (Example 1) containing the microcrystalline calcium silicate specified in the present invention as a main stabilizer has a blackening time of about 160 minutes or more at 190 ° C. It shows a hydrogen chloride trapping time of 362 minutes as determined by the Congo Red method, and clearly has an excellent thermal stabilizing effect.

Although the microcrystalline calcium silicate used in the present invention is notably useful for improving the thermal stability of a chlorine-containing polymer, it has been found that there is still room for improvement in low-temperature heat aging resistance. Was. That is, when the chlorine-containing polymer composition containing the microcrystalline calcium silicate as a main stabilizer is kept at a temperature of 100 ° C. for one week, the resin composition tends to be colored pink.

However, the microcrystalline calcium silicate and the isocyanurate compound were used in the range of 5.0: 95.0 to 95.0.
When blended in a weight ratio of 9.8: 0.2, particularly preferably in a weight ratio of 15:85 to 99: 1, the coloring tendency is suppressed even when the above temperature is maintained for the above time. .

The low-temperature heat aging of the chlorine-containing polymer is compared with the initial coloring of the chlorine-containing polymer and the general heat resistance. The initial coloring is based on the chlorine-containing polymer containing a stabilizer. Is the processing temperature (generally 150 to 170 ° C)
Coloration after being heat-processed at a temperature, while the heat resistance is such a temperature condition that a dehydrochlorination reaction of the chlorine-containing polymer occurs (generally 1
(80-200 ° C.), whereas low-temperature heat aging is coloring or deterioration occurring at a temperature considerably lower than these temperatures and over a long period of time, and the temperature condition is also the cause. Also seem to be completely different.

In the present invention, the low temperature heat aging resistance is improved by combining the isocyanurate compound with the microcrystalline calcium silicate at a fixed ratio.
It was discovered as a result of numerous experiments,
Although the reason is not in any way binding on the present invention, the pink coloration is based on the formation of a mild polyene structure or even a complex by the interaction of microcrystalline calcium silicate with a chlorine-containing polymer. On the contrary, it is believed that the isocyanurate compound suppresses the formation of these polyene structures or the formation of complexes.

In the present invention, (C) hydrotalcite or alkali alkoxide is added to (A) the microcrystalline calcium silicate or its complex with a polyhydric alcohol.
(A): (C) = 0.
The combination in a weight ratio of 5: 99.5 to 99.0: 1.0 is preferable in order to further improve the heat resistance while keeping the low-temperature heat aging resistance at an excellent level.

Further, in order to suppress the initial coloring tendency of the chlorine-containing polymer composition containing the stabilizer, the total of (A) the microcrystalline calcium silicate and (B) the isocyanurate compound and (D) the higher fatty acid zinc are used. (A) + (B)｝: (D) =
Similarly, at a weight ratio of 20:80 to 90:10, the sum of (A) the microcrystalline calcium silicate and (B) the isocyanurate compound and (E) β-diketone or β-keto acid ester are expressed by Δ (A) + (B )｝: (E) = 35: 65 to 9
It is preferable to further include 9.9: 0.1 by weight.

Further, (A) the sum of microcrystalline calcium silicate and (B) isocyanurate compound and (F) a phenolic antioxidant are {(A) + (B)}: (F) = 3
Blending at a ratio of 5:65 to 99.9: 0.1 by weight makes it possible to considerably extend the hydrogen chloride trapping time.

[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 a number of 0.5 or more, but is preferably in the range of 0.5 to 5.0, particularly preferably in the range of 0.5 to 3.0. Also, n is 2.5
The numbers are as follows, but are preferably in the range of 0.5 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 Interplanar spacing (angstrom) Relative intensity 29.2 m 32.0 w 49.3 w In the table, m indicates moderately strong and w indicates weak, respectively. It is clear that the strongest peak is quite 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 a half width (radian) of an interference peak, and λ and θ are the same as in the above formula (3). Where there is a relationship represented by

The half width of the diffraction peak having a plane index of 220 is determined from the X-ray diffraction image of FIG. 1, and the crystallite size is calculated from the half width according to the equation (4).
The crystallite size of 20 is generally constrained in the range of 60 to 120 Angstroms.

The thermal stabilizing action 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.

The microcrystalline calcium silicate used in the present invention generally has a particle size of 40 μm or more at 10% by weight or less and a particle size of 20 μm or less at 50% by weight.
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,
Pore volume of 0.5 ml / g or more, especially 1.0 to 4.0 ml / g, and average particle size of 0.1 to 10 μm 50 to 250 ml / 100 g, especially 80 to 200 ml / 10
It has an oil absorption of 0 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 microcrystalline calcium silicate used in the present invention preferably retains an organic compound having a masking or chelating action on zinc chloride in the pores or on the surface.

As the organic compounding agent for this purpose, polyhydric alcohols are preferable, and suitable examples thereof are as follows. Examples of polyhydric alcohols include ethylene glycol,
Diethylene glycol, triethylene glycol, polyethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, glycerin, diglycerin, pentaerythritol, dipentaerythritol, mannitol, sorbitol, trimethylolpropane, ditrimethylolpropane, tris Examples include isocyanurate and dipentaerythritol adipate.
Pentaerythritol and dipentaerythritol are preferred.

According to a preferred embodiment of the present invention, (C) the form of a composite containing microcrystalline calcium silicate and 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.

[Isocyanurate compound] The isocyanurate compound used in the present invention has the following formula (5)

Embedded image Wherein each of R ₁ , R ₂ and R ₃ is a hydroxyalkyl group.
Preferred is cyanurate, and suitable examples thereof include tris (hydroxyethyl) cyanurate, tris (hydroxypropyl) cyanurate, tris (hydroxybutyl) cyanurate, tris (2,3-dihydroxypropyl) cyanurate, and tris (glycidyl).
Cyanurate and the like.

It is also important that the above-mentioned tris (hydroxyalkyl) cyanurate be used in the above-mentioned ratio, and if it is below the above-mentioned ratio, the low-temperature heat aging resistance is reduced as compared with the case within the range of the present invention. When the amount ratio exceeds the above range, the heat resistance tends to decrease as compared with the case where the ratio is within the range of the present invention.

[Hydrotalcite] Hydrotalcite which can be used in combination with the microcrystalline calcium silicate and isocyanurate compound is a synthetic mineral belonging to aluminum magnesium carbonate hydroxide, and has a general formula (6): M ²⁺ _x M ³⁺ _y (OH) _{2x + 3y-2z} (A ⁺⁺ ) _z · aH ₂ O (6) where 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. Has the chemical composition represented by

Among these composite metal hydroxides, the compound represented by the formula (7) Mg ₆ Al ₂ (OH) ₁₆ (CO ₃ ) .4H ₂ O (7) 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 (8) Mg _4.5 Al ₂ (OH) ₁₃ (CO ₃ ) .3H ₂ O (8) has excellent chlorine ion trapping performance. Are also already known, and can be used as the compounding component of the present invention.

By utilizing 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, a 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 (6),
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] As the alkali-aluminum hydroxide carbonate used in place of the hydrotalcite, lithium aluminum hydroxide carbonate, dawsonite-type sodium
Aluminum hydroxide carbonate or a mixed crystal thereof is exemplified.

(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.

[0046] The lithium aluminum hydroxide carbonate salt is represented by the following formula (9), mAl in _{2 O 3 · nM 2 O ·} X · kH 2 O ‥‥ (9) equation, X is composed mainly of carbonate groups An inorganic anion,
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 Surface spacing d (A) Peak intensity surface index 7.50 to 7.64 large (002) 4.30 to 4.44 small (110) 3.70 to 3.84 large (004) 2.45 -2.58 Medium (006) 2.20-2.30 Small (016) 1.85-2.08 Small (017) 1.40-1.52 Small (330) 1.38-1.48 Small ( 600).

A 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 not limited to the above, but may be an amorphous or pseudo-boehmite hydrated alumina gel and a 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. Dawsonite-type alkali aluminum hydroxide carbonate) Dawsonite-type alkali aluminum hydroxide carbonate (NAHCS) used in the present invention
Is represented by the following formula (10) mAl in _{2 O 3 · nM 2 O ·} X · kH 2 O ‥‥ (10) equation, X is the anion of an inorganic consisting mainly of carbonic acid radical,
M is an alkali metal or ammonium group mainly composed of sodium or potassium, 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. Has a composition represented by

The dawsonite type crystal structure means 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 suitably 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 and binding to 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 alkali aluminum hydroxide carbonate used in the present invention are generally 0.1 to 10 μm as measured by a laser scattering diffraction method.
In particular, it must have a volume-based median diameter (D ₅₀ ) of 0.1 to 3 μm and an oil absorption (JIS K-5101) of 5
0 to 110 ml / 100 g, BET specific surface area is 30 to 110 m ² / g, and apparent specific gravity (iron cylinder method) is 0.1 to 0.3 g / cm ^3. preferable.

Dawsonite-type alkali aluminum hydroxide carbonates can be converted to respective aluminum hydroxide carbonates by using carbonates of sodium, potassium and ammonium as alkalis. It is manufactured by using sodium, potassium or ammonium carbonate instead of lithium carbonate in the above-mentioned hydrated alumina gel method, but is by no means limited to this.

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

The 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 above (A) microcrystalline calcium silicate and (C) hydrotalcite or alkali-aluminum composite hydroxide The oxide salt is (A) :( C) =
It is preferably used in a weight ratio of 0.5: 99.5 to 99.0: 1.0, and more preferably in a weight ratio of 5:95 to 95: 5.

[Higher Fatty Acid Zinc] In the present invention, in addition to the above components, the sum of the components (A) and (B) and (D)
90:10 to 20:80 weight ratio of higher fatty acid zinc,
In particular, it is preferable to further mix in a weight ratio of 80:20 to 50:50. 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 stearic acid and lauric acid are the most preferred. Fatty acids may of course be mixed fatty acids such as coconut oil fatty acids and palm oil fatty acids.

Further, zinc amino acid can be added to such an extent that the performance of the present invention is not impaired. As the amino acid to be amino acid zinc, glycine, alanine, leucine, isoleucine, serine, threonine, cysteine, cystine, methionine, aspartic acid, glutamic acid, lysine, argin, phenylalanine, tyrosine, histidine, tryptophan, pronin, oxypronin and the like are used. Can also

These fatty acid zinc and amino acid zinc also serve as a lubricant, and are preferably normal salts.

[Β-diketone or β-keto acid ester] In the present invention, (E) β-diketone or β-keto acid ester can be contained in addition to the above-mentioned components. (E) β-diketone or β-diketone and (B) isocyanurate compound
The keto acid ester was converted to {(A) + (B)}: (E) = 99.
It is preferably used in a weight ratio of 9: 0.1 to 35:65, and more preferably in a weight ratio of 95: 5 to 40:60. By using the component (E), initial coloring and zinc burning can be effectively prevented.

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.

[Phenolic Antioxidant] In the present invention, (F) a phenolic antioxidant can be further contained in addition to the above components, and the components (A) + (B) and (F) The inhibitor is {(A) + (B)}: (F) = 9
9.9: 0.1 to 35:65, particularly preferably 95:
It is preferably present in a weight ratio of 5 to 40:60.
This antioxidant is useful for suppressing degradation due to a chain reaction and the like.

As the phenolic antioxidant used in the present invention, both bisphenol type antioxidants and sterically hindered phenolic antioxidants are used. Examples of the phenolic antioxidant include bisphenol A, bisphenol B, bisphenol F, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,
5-di-tert-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) propionic amide], 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-di-tert-butyl-4-
(Hydroxybenzyl) isocyanurate, triethylene glycol bis [(3-tert-butyl-4-hydroxy-
5-methylphenyl) propionate]. These phenolic antioxidants can be used alone or in combination, and may be used in combination with non-phenolic antioxidants.

[Composite Stabilizer] The composite stabilizer of the present invention can be used as a one-pack stabilizer in the form of powder, that is, in the form of 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.

[Chlorine-Containing Polymer Composition] In the low-temperature heat-aging-resistant chlorine-containing polymer composition according to the present invention, (A) microcrystalline calcium silicate or the above microcrystalline calcium silicate is used per 100 parts by weight of chlorine-containing polymer. 0.05 to 10 parts by weight, particularly 0.1 to 5 parts by weight, of a compound containing a polyhydric alcohol in a weight ratio of 20:80 to 80:20 and 0.01 to 3 parts by weight of the isocyanurate compound (B) Parts, especially 0.02 to 1.0 parts by weight.

In a chlorine-containing polymer composition suitable for heat resistance, 0.1 to 10 parts by weight of (C) hydrotalcite or an alkali-aluminum composite hydroxide salt, especially 100 parts by weight of the chlorine-containing polymer, 0.2 to 5.
0 parts by weight.

In a chlorine-containing polymer composition suitable for initial coloring, 0.1 to 5.0 parts by weight, particularly 0.2 to 2.0 parts by weight, of (D) zinc higher fatty acid is used per 100 parts by weight of chlorine-containing polymer. And (E) 0.01 to 5.0 parts by weight, especially 0.03 to 1.0 part by weight of a β-diketone or β-keto acid ester.

In the chlorine-containing polymer composition suitable for heat resistance, the phenolic antioxidant (E) is used 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. 0 parts 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-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 chlorine-containing polymer composition of the present invention can be blended with a chlorine-containing polymer compounding agent known per se according to 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. , Basic inorganic metal salts,
A well-known resin compounding agent such as perchlorate, epoxy compound, antistatic agent, fatty acid ester and the like can be compounded according to a formulation known per se.

For example, amorphous silica, calcined kaolin, aluminum oxide, aluminum silicate, titanium white, titanium phosphate, zirconium phosphate, etc., may be added in order to improve 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.

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.

Examples of the flame retardant include halogen-based flame retardants, as well as antimony, zircon, molybdenum, aluminum, silica, titanium oxides, hydroxides, and sulfides.
Examples thereof include zinc borate, zinc stannate, zinc hydroxystannate, and metal hydroxide surface-treated products of these zinc compounds.

The basic metal salt is a basic inorganic acid metal salt. The metal component includes Li, Na, K, Mg, Ca,
Sr, Ba, Zn, Ti, Al, Zr, Sn and the like are preferable. As the inorganic acid, phosphoric acid, phosphorous acid, silicic acid, nitric acid,
Examples thereof include nitrous acid, sulfuric acid, sulfurous acid, boric acid, and carbonate. Preferred examples of the basic inorganic acid salt include Mg
(OH) ₂ , Ca (OH) ₂ , Al (OH) ₃ , Ba (O
H) ₃ , MgO, CaO, BaO, Al ₂ O ₃ , SnO ₂ ,
3CaO.Na ₃ PO ₄ , 5CaO.NaHPO ₄ , Mg
O · Mg ₃ (PO ₄ ) ₂ , 3CaO · Ca ₃ (PO ₄ ) ₂ , C
a (OH) ₂ .Ca ₃ (PO ₄ ) ₂ , Ba (OH) ₂ .Ca _{3
(PO 4) 2 · 3H 2} O, Sr (OH 2) · Sr 3 (PO 4)
_{2, Ba0 · Ba 3 (PO} 4) 2, 3Ba (OH 2) · Ba 3
(PO ₄ ) ₂ , ZnO · Zn ₃ (PO ₄ ) ₂ , 2ZnO · B
A3 (PO4) 2, Al2O3.AlPO4,3SnO
・ Sn3 (PO ₄ ) ₂ , Ba (OH ₂ ) ₂・ NaHPH
O ₃ , 5CaO.NaHPHO ₃ , 3Ba (OH) ₂ .K ₂
PHO ₃ , MgO · MgPHO ₃ , 5Mg (OH) ₂ · M
_{gPHO 3, CaO · CaHO 3,} 3CaO (OH) 2 C
aPHO ₃ , Ba (OH) ₂ .CaPHO ₃ , 5CaO.
CaPHO ₃ , BaO.BaPHO ₃ , 2Ba (OH) ₂
・ BaPHO ₃ , 3Ba (OH) ₂・ BaPHO ₃・ 3H ₂
O, ZnO · ZnPHO ₃ , ZnO · 3CaPHO ₃ , T
iO ₂ · Ti (PHO ₃ ) ₂ , Al ₂ O ₃ · Al ₂ (PH
O ₃ ) ₃ , 3ZrO.ZrPHO ₃ , SnO.SnPH
O ₃ , 3SnO.SnPHO ₃ , Mg (OH) ₂ .Mg ₂ S
iO ₄ , 3MgO.MgSiO ₃ , CaO.Ca ₂ Si
O ₄ , 3CaO.Li ₂ SiO ₃ , 3CaO.CaSi ₂ O
₅ , 2Ca (OH) ₂ .Ca ₂ Si ₃ O ₈ , SrO.SrS
iO ₃ , 5BaO.Ba ₂ SiO ₄ , Ba (OH) ₂ .Ba
_{2 SiO 4 · 6H 2 O,} Ba (OH) 2 · BaSiO 3, 3
Ba (OH) .BaSi ₂ O ₅ , 3BaO.Ba ₂ Si
O ₄ , Ba (OH) ₂ .CaSiO ₃ , 2ZnO.ZnS
iO ₃ , ZnO · 3CaSiO ₃ , CaO · Sn ₂ Si
O ₄ , Mg (OH) .Mg (NO ₃ ) ₂ , 3CaO.Ca
(NO ₃ ) ₂ , 2Ca (OH) ₂ .Ca (NO ₂ ) ₂ .5H ₂
O, 3BaO.Ba (NO ₃ ) ₂ , Ba (OH) ₂ .Na ₂
SO ₄ , ZnO · K ₂ SO ₄ , 3CaO · K ₂ SO ₃ , Mg
(OH) ₂ · MgSO ₄ , 5 MgO · MgSO ₃ , 2 Mg
_{O · MgSO 3, MgO · CaSO} 3, 5CaO · CaS
O ₄ , Ca (OH) ₂ · CaSO ₄ , 3CaO · CaS
O ₃ , SrOSrSO ₂ , 3BaO.BaSO ₄ , 3Ba
O.CaSO ₃ , Ba (OH) ₂ .BaSO ₄ , TiO _2.
TI (SO ₄ ) ₂ , Al ₂ O ₃ .Al ₂ (SO ₄ ) ₃ , Al
(OH) ₂ · MgSO ₄ , MgO · Mg ₃ (BO ₄ ) ₂ , C
aO. (BO ₄ ) ₂ , 5Ca (OH) ₂ .Ca ₃ (B
O ₄ ) ₂ , 3CaO · Ca (BO ₂ ) ₂ , 3Ba (OH) ₂
・ Ba ₃ (BO ₄ ) ₂ , 3BaO ・ BaB ₄ H ₇ , 5Ba
(OH) ₂ .Ba (BO ₂ ) ₂ , NaHCO ₃ , Mg (HC
_{O 3) 2, LiHCO 3,} BaCO 3, MgCO 3, ZnC
There are O ₃ and Li ₂ CO ₃ .

In addition to perchlorate ion-introduced hydrotalcite and alkali aluminum composite hydroxide salts, mention may be made of sodium perchlorate, magnesium perchlorate, calcium perchlorate, barium perchlorate and zinc perchlorate. Can be Also, complexes of these perchlorates and polyhydric alcohols can be used, and preferable polyhydric alcohols include diethylene glycol monomethyl ether, triethylene glycol and propylene glycol monomethyl ether.

Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2'-hydroxy-
5′-methylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-
(2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy3 ', 5'
-Dicumylphenyl) benzotriazole, 2,2'-
2- (2'-hydroxyphenyl) benzotriazoles such as methylenebis (4-tert-octyl-6-benzotriazolyl) phenol.

Examples of the hindered amine compound include 1,2,2,6,6-pentamethyl-4-piperidyl stearate and 2,2,6,6-tetramethyl-4-
Piperidyl benzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide,
1-[(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl- (3,5-di-tert-butyl-4- (Hydroxyphenyl) propionate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetra (2,2,6,6-tetramethyl-4)
-Piperidyl) butanetetracarboxylate, tetra (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (2,2,
6,6-tetramethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, bis (1,2,2
2,6,6-pentamethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate and the like, which are used as a light stabilizer and a heat stabilizer.

Epoxy compounds include epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized tallow oil, epoxidized castor oil, epoxidized safflower oil, and epoxidized linseed oil fatty acid. Butyl, tris-8 epoxypropyl) isocyanurate, 3- (2-xenoxy) -1,2-epoxypropane, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl- 6-methylepoxycyclohexanecarboxylate and the like.

As the antistatic agent used in the present invention, all those generally used for polyolefin films can be applied. Specific examples of antistatic agents include (a) cationic amines such as primary amine salts, tertiary amines, quaternary ammonium compounds, and pyridine derivatives; (ii) sulfated oils, soaps, sulfated Ester oils, sulfated amide oils, sulfate salts of olefins, sulfate salts of fatty alcohols,
Alkyl sulfate ester salt, fatty acid ethyl sulfonate,
Anionic ones such as alkylnaphthalene sulfonate, alkylbenzene sulfonate, succinate sulfonate, phosphate ester salt, (c) partial fatty acid ester of polyhydric alcohol, ethylene oxide adduct of fatty alcohol, fatty acid An ethylene oxide adduct of
An ethylene oxide adduct of a fatty amino or fatty acid amide, an ethylene oxide adduct of an alkyl phenol, an ethylene oxide adduct of an alkyl naphthol,
Nonionic compounds such as ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols and polyethylene glycol, and amphoteric compounds such as (d) carboxylic acid derivatives and imidazoline derivatives can be generally used. Preferred are polyoxyethylene alkylamines, polyoxyethylene alkylamides, fatty acid esters thereof, and fatty acid esters of glycerin.

The fatty acid esters also include partial esters, such as n-butyl stearate, hydrogenated rosin methyl ester, dibutyl sebacate <n-butyl>, dioctyl sebacate <2-ethylhexyl and n-octyl) glycerin fatty acid ester, Pentaerythritol tetrastearate, polyethylene glycol fatty acid ester,
Polyethylene glycol distearate, polyethylene glycol dilaurate, polyethylene glycol dioleate, polyethylene glycol coconut fatty acid diester, polyethylene glycol tall oil fatty acid diester, ethanediol montanic acid diester, 1,3 butanediol montanic acid diester, diethylene glycol stearic acid diester, propylene Glycol fatty acid diester, triglyceride wax, hydrogenated edible fat, glycerin ester of 12-hydroxystearic acid, spar acetyl wax, montan wax, carnauba wax, beeswax, wood wax, monohydric fatty acid alcohol and fatty acid saturated acid ester, <Example: curing Whale oil lauryl stearate, stearyl stearate>, lanolin, polyethylene wax, Propylene wax, polyethylene oxide wax, acid-modified polyolefin waxes, epoxy-modified polyethylene wax, petroleum wax and the like.

[0091]

The present invention is further described in the following examples. The measurement in the examples was performed by the following method. (1) Gear oven heat resistance The kneaded and molded PVC sheet was heated to 190 ° C in an oven, and the degree of coloring at each time was evaluated on a 1 to 6 scale. Colorless 2. Pale yellow 3. Yellow 4. Yellow-brown Reddish brown 6. Blackening (2) Thermal stability (CR) It was measured by a hydrogen chloride scavenging test at 180 ° C by the Congo red method according to JIS-K-6723. (3) Low-temperature heat aging test The compositions having the compositions shown in Tables 5 and 6 were kneaded with a roll mill at a temperature of 160 ° C. for 5 minutes, a uniform 1 mm-thick vinyl chloride sheet was taken out after a certain number of days, and the coloring state was visually observed. It was observed and judged. The coloring degree of the sheet was evaluated in the following four stages, and the evaluation criteria are shown below.

(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 (Ca 0 min 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 a fine powder calcium silica composite hydroxide (CSH-1) having a SiO 2 / CaO molar ratio of 1.25. The SiO2 / CaO molar ratio is 2.5
Powdered calcium silica composite hydroxide (C
SH-2) was obtained. Table 4 shows the physical properties.

(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 (Ca 0%, 6%), 24.2 g of activated silicic acid powder having an average particle diameter 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.

[0094]

[Table 4]

(Examples 1 to 5, Comparative Examples 1 to 3) The compounds shown in Table 5 were kneaded with a kneading roll at 160 ° C. for 5 minutes to prepare a sheet having a thickness of about 1 mm. A test piece was prepared from the sheet, and the heat resistance, heat stability, and low temperature heat aging of the gear oven were measured. The results are shown in Table 5. Soft blending Number of blending parts PVC (TK-1300: manufactured by Shin-Etsu Chemical Co., Ltd.) 100 DINP (diisononyl phthalate) 50 Zinc stearate 0.5 β-diketone 0.1 Phenolic antioxidant 0.1 Each sample (Table 5)

(Examples 6 to 12, Comparative Examples 4 to 6) The compounds shown in Table 6 were kneaded with a kneading roll at 160 ° C. for 5 minutes.
A sheet of constant thickness was created. A test piece was prepared from the sheet, and the heat resistance, heat stability, and low-temperature heat aging of the gear oven were measured. The results are shown in Table 6. Hard compounding compounding number of parts PVC (TK-1300: Shin-Etsu Chemical Co., Ltd.) 100 zinc stearate 1.0 β-diketone 0.1 fatty acid ester wax 0.5 phenolic antioxidant 0.1 each sample (Table 6)

[0097]

[Table 5]

[0098]

[Table 6]

[0099]

According to the present invention, among calcium silicates, a microcrystalline calcium silicate having a specific composition and an X-ray diffraction image or a compound of the same and a polyhydric alcohol is selected and isocyanate is used. By combining it with a nullate compound and using it as a stabilizer for a chlorine-containing polymer, the thermal stability of the chlorine-containing polymer can be significantly improved, and the low-temperature heat aging resistance can also be significantly improved.
The chlorine-containing polymer composition according to the present invention is particularly useful as a wire covering material.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction image of microcrystalline calcium silicate used in the present invention.

FIG. 2 is an X-ray diffraction image of zonotlite having a chemical composition close to that of the microcrystalline calcium silicate of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08K 3:34 5: 3477 5: 053 3:26 3:12 5: 098 5:07 5:13) (72) Inventor Abe Nagaichi 4-1-1, Nihonbashi Muromachi, Chuo-ku, Tokyo Mizusawa Chemical Industry Co., Ltd. (72) Inventor Kenetsu Ogasawara 4058 Nakatsu, Aikawa-cho, Aiko-gun, Kanagawa Prefecture Shinagawa Chemical Co., Ltd. (72) Inventor Hitoshi Yajima Kanagawa Prefecture 4058 Nakatsu, Aikawa-cho, Aiko-gun Shinagawa Chemical Co., Ltd.

Claims (17)

[Claims] (A) General formula (1) CaO.xSiO ₂ .nH ₂ O ‥‥ (1) where x is a number of 0.5 or more and n is a number of 2.5 or less. , And a plane spacing of 3.01
To 3.08 angstroms, the spacing between faces 2.78 to 2.82 angstroms, and the spacing between faces 1.81 to 1.
A microcrystalline calcium silicate having an X-ray diffraction image at 84 angstroms or a complex thereof with a polyhydric alcohol, and (B) an isocyanurate compound, and the components (A) and (B) isocyanurate compound are ( A): (B) = 5.0: 95.0 to 99.8: 0.
A stabilizer for chlorine-containing polymers present in a weight ratio of 2. 2. 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 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. 2. The stabilizer for a chlorine-containing polymer according to claim 1, wherein the lamination irregularity index (I _s ) defined by an angle formed by a tangent is 1.75 or more. 3. The microcrystalline calcium silicate has a specific surface area of 60 to 200 m ² / g, 50 to 250 ml / 10.
3. The stabilizer for a chlorine-containing polymer according to claim 1, which has an oil absorption of 0 g and an average particle size of 0.1 to 10 [mu] m. 4. The chlorine-containing weight according to claim 1, wherein said composite is a composite containing microcrystalline calcium silicate and polyhydric alcohol in a weight ratio of 20:80 to 80:20. Stabilizer for coalescence. 5. The composite according to claim 1, wherein the composite of microcrystalline calcium silicate and polyhydric alcohol is obtained by co-grinding microcrystalline calcium silicate and polyhydric alcohol by wet and dry methods. The stabilizer for a chlorine-containing polymer according to any one of the above. 6. The stabilizer for a chlorine-containing polymer according to claim 1, wherein the polyhydric alcohol is pentaerythritol or dipentaerythritol. 7. The stabilizer for a chlorine-containing polymer according to claim 1, wherein the isocyanurate compound is tris (hydroxyalkyl) isocyanurate. 8. The composition further comprising (C) hydrotalcite or an alkali-aluminum composite hydroxide salt, wherein the components (A) and (C) hydrotalcite or alkali
(A): (C) = 0.
The stabilizer for a chlorine-containing polymer according to any one of claims 1 to 7, wherein the stabilizer is present in a weight ratio of 5: 99.5 to 99.0: 1.0. 9. The stabilizer for chlorine-containing polymers according to claim 8, wherein the hydrotalcite is a zinc-modified hydrotalcite. 10. The stabilizer for chlorine-containing polymers according to claim 8, wherein the alkali-aluminum composite hydroxide salt is a lithium-aluminum composite hydroxide carbonate. 11. The stabilizer for a chlorine-containing polymer according to claim 8, wherein the alkali-aluminum composite hydroxide salt is a dawsonite-type alkali-aluminum composite hydroxide carbonate. 12. (D) higher fatty acid zinc and (E) β-
The diketone or β-keto acid ester is further contained, and the sum of the components (A) and (B) and (D) the higher fatty acid zinc are {(A) + (B)} :( D) = 20: 80 to 90 : 1
0, and the sum of the components (A) and (B) and (E) β-diketone or β-keto acid ester are {(A) + (B)}: (E) = 35.0. : 65.0 to 99.9: 0.1 in a weight ratio of 1 to 11.
The stabilizer for a chlorine-containing polymer according to any one of the above. 13. (F) A phenolic antioxidant is further contained, and the sum of the components (A) and (B) and the (F) phenolic antioxidant are {(A) + (B)} :( F ) = 35:
2. The composition according to claim 1, wherein the weight ratio is 65 to 99.9: 0.1.
13. The stabilizer for a chlorine-containing polymer according to any one of items 1 to 12. 14. 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 or more, and n is a number of 2.5 or less. Has a chemical composition and a specific surface area of 60
0.05 to 10.0 parts by weight of microcrystalline calcium silicate in the range of from 200 to 200 m ² / g, or a composite containing the microcrystalline calcium silicate and the polyhydric alcohol in a weight ratio of 20:80 to 80:20; And (B) a chlorine-containing polymer composition having an improved low-temperature heat aging property, comprising 0.01 to 3.0 parts by weight of an isocyanurate compound. 15. Per 100 parts by weight of the chlorine-containing polymer,
The chlorine-containing polymer composition according to claim 14, further comprising (C) 0.1 to 10.0 parts by weight of a hydrotalcite or an alkali-aluminum composite hydroxide salt. 16. 0.1 to 5.0 parts by weight of zinc (D) higher fatty acid and 0.01 of (E) β-diketone or β-keto acid ester per 100 parts by weight of chlorine-containing polymer.
The chlorine-containing polymer composition according to claim 14 or 15, further comprising from 5.0 to 5.0 parts by weight. 17. The chlorine-containing polymer composition according to claim 14, further comprising (F) 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.