JP2003306323A - Electrical insulation improver and resin composition improved in electrical insulation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrical insulation improver comprising a synthetic amorphous aluminum silicate and having an excellent electrical insulation- improving action compared with a burned clay, and to provide a resin composition containing the above improver and excellent in combination of electrical insulation-improving action, thermal stability and discoloring prevention. <P>SOLUTION: This electrical insulation improver comprises a synthetic amorphous aluminum silicate represented by the formula, Al<SB>2</SB>O<SB>3</SB>-nSiO<SB>2</SB>-mH<SB>2</SB>O (wherein, n is an integer of 3 or more; and m is an integer of 20 or less including 0). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic amorphous aluminum silicate-based electrical insulating property improving agent, and more specifically, an excellent effect of improving electrical insulating property can be obtained with a small blending amount. The present invention relates to an electric insulation improver which is also excellent in heat stabilizing action and anti-coloring property. The present invention also relates to resin compositions having improved electrical insulation.

[0002]

2. Description of the Related Art Synthetic resins or rubbers themselves are remarkably excellent in electrical insulation properties, but in order to process these resins or rubbers, it is indispensable to add a compounding agent such as a plasticizer or a softening agent. However, when these compounding agents are blended, there is a problem that the electrical insulating property is considerably lowered by the addition thereof.

With respect to this problem, in the field of resin or rubber molded products which are required to have electric insulation properties, a baked clay, for the purpose of improving the electric insulation of the resin or rubber,
That is, it has long been practiced to calcine a kaolin group clay mineral and transform it into metakaolin to blend it as an electrical insulation improver.

A kaolin group clay mineral suitable as a raw material for an electrical insulation improver is produced as Georgia kaolin in the United States, but depletion of resources and stable supply are problems, and a synthetic substitute therefor. The appearance of new products is desired, and research on synthetic products that replace them has been conducted for a long time. For example, a calcium silicate-based pigment for improving electrical insulation properties, which is found in JP-B-55-27584, an aluminum hydroxide filler for an electrical insulation agent, which is found in JP-B-59-12605, and JP-A-61-27004.
The modified montmorillonite group clay mineral-based electrical insulating property improver and the like found in the publication of this publication correspond to this.

[0005]

However, none of these synthetic electrical insulating improvers of synthetic products have a performance that is on the right side of the calcined clay, and a drastic improvement in the performance is desired. There is. On the other hand, since calcined clay is derived from natural products, it is unavoidable that there are variations in quality and performance within a certain range, and in addition to being colored, the degree of coloring also differs from lot to lot. There is also the problem of being present.

Accordingly, an object of the present invention is to provide a synthetic amorphous aluminum silicate-based electric insulation improving agent having an excellent electric insulation improving effect as compared with calcined clay. The purpose of the present invention is to provide an electrical insulation improving agent which has an excellent effect of improving the electrical properties, has an excellent effect of improving the electrical insulating property at a high temperature, and also has an excellent thermal stabilizing effect and an anti-coloring property. Another object of the present invention is to contain a synthetic amorphous aluminum silicate-based electric insulation improving agent, and to improve electric insulation.
Another object of the present invention is to provide a resin composition having an excellent combination of thermal stability and anti-coloring property.

[0007]

According to the present invention, the following formula (1) Al ₂ O ₃ .nSiO ₂ .mH ₂ O (1) In the formula, n is a number of 3 or more and m is zero. An electrically insulating improver comprising a synthetic amorphous aluminum silicate having a chemical composition represented by: In the synthetic amorphous aluminum silicate-based electrical insulation improver used in the present invention, 1. The BET specific surface area is in the range of 30 to 700 m ² / g, 2. The synthetic amorphous aluminum silicate has alkali adsorptivity. The acid strength function of synthetic amorphous aluminum silicate is −
3. The acidity in the range of 5.6 to -3.0 is in the range of 0.03 to 0.30 meq / g. 4. In the formula (1), n is in the range of 3 to 100. It is composed of an amorphous gel of aluminum silicate, and has a water content of 1 calculated as the weight loss at 6.110 ° C. × 3 hours.
6. It is in the range of 5% by weight or less, 7. 7. Surface-treated with higher fatty acid calcium, 8. Higher fatty acid calcium is contained in an amount of 0.5 to 30% by weight, The volume-based median diameter is 0.
It is preferable that particles having a particle size of 3 to 20 μm and a particle size of 45 μm or more have a particle size distribution of 10% by volume or less of the whole. According to the present invention, a chlorine-containing polymer is also represented by the following formula (1) Al ₂ O ₃ .nSiO ₂ .mH ₂ O (1) where n is a number of 3 or more and m includes zero. Provided is a resin composition having improved electrical insulation, characterized by comprising a synthetic amorphous aluminum silicate having a chemical composition represented by the following number and a calcium-zinc stabilizer. To be done. In the resin composition of the present invention,
Synthetic amorphous aluminum silicate is a chlorine-containing polymer 100
It is present in an amount of 0.01 to 10 parts by weight per part by weight, the calcium-zinc stabilizer is chlorine-containing polymer 100.
It is preferably present in an amount of 1 to 40 parts by weight per part by weight.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION [Operation] The present invention is based on the discovery that the synthetic amorphous aluminum silicate represented by the general formula (1) can be an excellent electrical insulating property improver. As already pointed out, the cause of the decrease in electrical insulation of synthetic resins and rubbers is the fact that the lubricants and softeners, etc. compounded in this material are the cause of this decrease in electrical insulation. Materials have not yet been pursued, and the search for materials effective for improving electrical insulation was left to trial and error experiments.
When the synthetic amorphous aluminum silicate represented by the general formula (1) is blended with a chlorine-containing polymer, the present inventors can inferior to the calcined clay with a significantly smaller blending amount than the calcined clay. It was found that an effect of improving electric insulation can be obtained.

Please refer to the examples described below. FIG. 1 of the accompanying drawings is a semi-logarithmic plot of the relationship between the blending amount of synthetic amorphous aluminum silicate in a chlorine-containing polymer and the volume resistance of the blended chlorine-containing polymer.
For measurement temperature 30 ° C., the volume resistivity of the chlorine-containing polymer of unblended is 2.0 × 10 ^{1 3} Ωcm, calcined clay volume but was blended 0.5 part by weight (sample H-1 below) resistance Is 10.3 × 10 ¹³ Ωcm, whereas the synthetic amorphous aluminum silicate is 0.1 parts by weight, the volume resistance of 5.9 × 10 ¹³ Ωcm is 0.2. A volume resistance of 11.5 × 10 ¹³ Ωcm, and a volume resistance of 0.1.
Volume resistance of 16.2 × 10 ¹³ Ωcm with 3 parts by weight of compound,
The compound of 0.4 parts by weight shows a volume resistance of 19.3 × 10 ¹³ Ωcm, and the compound of 0.5 parts by weight shows a volume resistance of 21.0 × 10 ¹³ Ωcm. That is, when the synthetic amorphous aluminum silicate was used, the compounding amount of 0.2 parts by weight already showed a better effect of improving the electric insulating property than the case of compounding 0.5 part by weight of the calcined clay. This is an unexpected effect of the present invention.

When the measuring temperature is 60 ° C., unblended salt is used.
The volume resistance of the polymer containing element is 0.037 × 10.^ThirteenIn Ωcm
Yes, with 0.5 part by weight of calcined clay (H-1)
Volume resistance of 0.156 × 10^ThirteenEven though it is Ωcm
Then, with a blend of synthetic amorphous aluminum silicate
Is 0.200 × 10 with 0.1 part by weight.^ThirteenΩ cm
Volume resistance, 0.649 × 10 with 0.2 parts by weight^Thirteen
Volume resistance of Ωcm, 1.122 × 1 in 0.3 part by weight
0^ThirteenVolume resistance of Ωcm, 1.33 with 0.4 parts by weight of compounding
2 x 10^ThirteenVolume resistance of Ωcm, with 0.5 parts by weight
1.428 x 10 ^ThirteenIt exhibits a volume resistance of Ωcm.
That is, with the use of synthetic amorphous aluminum silicate, 60
At the high temperature of ℃
Greater effect of improving electrical insulation compared to 0.5 parts by weight
It shows the fruit. In particular, synthetic amorphous aluminum silicate
The system should show excellent electrical insulation at high temperatures.
Is remarkable, which is unexpected according to the present invention.
Is the advantage of.

Further, according to the present invention, the use of synthetic amorphous aluminum silicate as an electric insulation improver can improve the thermal stability of the blended chlorine-containing polymer. The thermal stability of the chlorine-containing polymer can be evaluated in a gear oven heat resistance test by measuring the hue change and blackening time of the chlorine-containing polymer with heating time. 190 ° C with constant type and amount of heat stabilizer
When the gear oven heat resistance test was conducted, the blackening time was 180 minutes without the electrical insulation improver and 180 minutes with the 0.5 parts by weight of the baked clay. As a result, the blackening time was 210 minutes when 0.5 part by weight of synthetic amorphous aluminum silicate was blended, and it was found that the thermal stability was improved by one rank or more (see Table 3).

The synthetic amorphous aluminum silicate used in the present invention is preferably surface-treated with higher fatty acid calcium and higher fatty acid zinc. That is, the synthetic amorphous aluminum silicate surface-treated with these higher fatty acid salts is not only excellent in dispersibility in the chlorine-containing polymer, but also has the effect of improving the electric insulating property in the untreated surface. In comparison, it is significantly superior.

The synthetic amorphous aluminum silicate used in the present invention has a volume-based median diameter of 0.3 to 20 μm and a particle diameter of 45 μm as measured by a laser scattering method.
It is preferable that the particles having the above particle size have a particle size distribution of 10% by volume or less of the whole. That is, the synthetic amorphous aluminum silicate having the particle size characteristics described above is not only excellent in dispersibility in the chlorine-containing polymer, but also has an effect of improving the electric insulating property as compared with the one having a coarse particle size. Is excellent.

When the synthetic amorphous aluminum silicate used in the present invention is compounded with a chlorine-containing polymer in combination with a calcium-zinc stabilizer, the effect of improving electrical insulation is particularly large, and the thermal stability is also improved. It must be emphasized that it is particularly good. Calcium-zinc stabilizers are more environmentally friendly, harmless, and less expensive than lead stabilizers and organotin stabilizers. The merit of using it in combination with a zinc-based stabilizer is remarkably large.

[Electrical Insulation Improver] In the present invention, the following formula (1) Al ₂ O ₃ .nSiO ₂ .mH ₂ O (1) In the formula, n is 3 or more, and particularly 3 to 100. , M is a number less than or equal to 20 including zero, and a synthetic amorphous aluminum silicate having a chemical composition represented by: is used as an electrical insulation improver.

In the above formula (1), when the number of n (the number of moles of silica per mol of alumina) is below or above the above range, n is within the above range. Therefore, the electrical insulation tends to be deteriorated, and therefore, it is necessary to use one having n within the above range.

FIG. 2 shows an X-ray diffraction image of an example of the synthetic amorphous aluminum silicate used in the present invention. From this FIG. 2, it is understood that this aluminum silicate only has a broad amorphous halo peculiar to the amorphous silicate and does not have a crystal structure. The excellent effect of improving the electrical insulating property in the synthetic amorphous aluminum silicate of the present invention may be due to this amorphous structure.

FIG. 3 shows an infrared absorption spectrum of an example of the synthetic amorphous aluminum silicate used in the present invention.

FIG. 4 shows the results of differential thermogravimetric analysis of an example of the synthetic amorphous aluminum silicate used in the present invention. In FIG. 4, an endothermic peak due to the removal of hydroxyl groups appears at a temperature of around 110 ° C. The one shown in FIG. 4 is in an unsintered state, and in this state, aluminum silicate is present in an amorphous gel state. In the present invention, the synthetic amorphous aluminum silicate can be used in a non-sintered state or in a sintered state. The use of calcined synthetic amorphous aluminum silicate can further improve the electrical insulation. On the other hand, when the synthetic amorphous aluminum silicate is calcined, the thermal stability tends to decrease. Therefore, when thermal stability is required, it is preferable to use an unsintered one or one with a low sintering temperature. Recommended. The firing temperature is 500 ° C or lower, especially 300 ° C
The following is preferable.

The synthetic amorphous aluminum silicate-based electrical insulating property improver used in the present invention preferably has a BET specific surface area of 30 to 700 m ² / g, particularly 30 to 600 m ² / g. Generally, the effect of improving the electrical insulating property of synthetic amorphous aluminum silicate tends to increase as the BET specific surface area increases. In this sense
It is desirable that the specific surface area is large, but if the specific surface area is too large, the aluminum silicate tends to be bulky and the dispersibility in the resin tends to be deteriorated.

The synthetic amorphous aluminum silicate used in the present invention generally has an alkali adsorptivity. As is clear from this fact, the synthetic amorphous aluminum silicate used in the present invention has characteristics as a solid acid.

The characteristics as a solid acid are generally represented by two characteristics, acid strength (H ₀ ) and acidity (acid amount). For example, when a solid acid is neutralized with a base such as n-butylamine, Neutralization is carried out sequentially from the one with high acid strength to the one with low acid strength. At this time, if an indicator corresponding to each acid strength (Hammett indicator) is used for neutralization titration, A cumulative distribution curve of acidity corresponding to acid strength is obtained. The following are used as Hammett indicators. The acidity (milliequivalent / g) of the solid acid determined using the indicator with pka of -3.0 and dicinnamalacetone as the indicator is A ₁
And the acidity (milliequivalent / g) of the solid acid obtained using pka as an indicator of +4.8 and methyl red as an indicator is A ₂ , the acidity A ₁ is the acidity of the highly acidic one (strong acid). On the other hand, A ₃ = A ₂ -A ₁ represents the acidity of the one having a low acid strength (weak acid).

The synthetic amorphous aluminum silicate used in the present invention has a solid acidity (milliequivalent / g) of 0.03 to 0.30 determined by using dicinnamalacetone as an indicator.
Meq / g, especially 0.04 to 0.15 meq / g
And the acidity within the acidity (milli-equivalent / g) of the solid acid determined using methyl red as an indicator is 0.30 meq / g or more, especially 0.33 to 0.60 meq / g
Is within the range of. It is recognized that the synthetic amorphous aluminum silicate of the present invention also has the above-mentioned acidity distribution, which is related to the improvement of electric insulation.

The synthetic amorphous aluminum silicate used in the present invention is preferably surface-treated with higher fatty acid calcium. That is, the synthetic amorphous aluminum silicate surface-treated with higher fatty acid calcium not only has excellent dispersibility in the chlorine-containing polymer, but also has an effect of improving electric insulation as compared with that of untreated surface. And is much better. The higher fatty acid calcium is preferably contained in an amount of 0.5 to 30% by weight. For the surface treatment, a substance other than higher fatty acid calcium, for example, a higher fatty acid other than calcium and a salt thereof, a polyhydric alcohol or a partial ester thereof (dipentaerythritol, etc.) may be used.

The higher fatty acid calcium has a carbon number of 1
0 to 22, especially 14 to 18 saturated or unsaturated fatty acids, for example, saturated fatty acids such as capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, linderic acid, tzunic acid. ,
Calcium salts of unsaturated fatty acids such as petroselinic acid, oleic acid, linoleic acid, linolenic acid and arachidonic acid are used. Among them, calcium stearate is preferable. The fatty acids may of course be mixed fatty acids such as beef tallow fatty acid, coconut oil fatty acid and palm oil fatty acid.

The synthetic amorphous aluminum silicate used in the present invention has a volume-based median diameter of 0.3 to 20 μm and a particle diameter of 45 μm as measured by a laser scattering method.
It is preferable that the particles having the above particle size have a particle size distribution of 10% by volume or less of the whole. FIG. 5 is a particle size distribution curve of an example of the synthetic amorphous aluminum silicate used in the present invention. That is, the synthetic amorphous aluminum silicate having the particle size characteristics described above is not only excellent in dispersibility in the chlorine-containing polymer, but also has an effect of improving the electric insulating property as compared with the one having a coarse particle size. Is excellent.

[Chlorine-Containing Polymer Composition] The resin composition of the present invention comprises a chlorine-containing polymer represented by the following formula (1) Al ₂ O ₃ .nSiO ₂ .mH ₂ O (1) where n is 3 The above number, m is a number of 20 or less including zero, characterized by containing a synthetic amorphous aluminum silicate having a chemical composition represented by: and a calcium-zinc stabilizer. However, this resin composition is characterized in that the electric insulation is remarkably improved and the thermal stability is remarkably improved.

As the synthetic amorphous aluminum silicate,
The ones already pointed out are used.

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, 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 ternary copolymer Coal, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, chlorinated vinyl-
Propylene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, Vinyl chloride-acrylonitrile copolymers, polymers such as internally plasticized polyvinyl chloride, and chlorine-containing polymers thereof and polyethylene, polypropylene, polybutene, poly-3
-Α-olefin polymers such as methylbutene or ethylene-vinyl acetate copolymers, polyolefins such as ethylene-propylene copolymers and copolymers thereof, polystyrene, acrylic resins, styrene and other monomers (for example, anhydrous Copolymer with maleic acid, butadiene, acrylonitrile, etc., acrylonitrile-butadiene-styrene copolymer, acrylic ester-butadiene-styrene copolymer, methacrylic ester-butadiene-
Examples thereof include blended products with a styrene copolymer.

As the calcium-zinc stabilizer, any known stabilizer can be used. This stabilizer is an inorganic stabilizer which does not melt at the processing temperature of the chlorine-containing polymer, or a chlorine-containing polymer. It may be used as an organic stabilizer that melts at the processing temperature. At least a part of the calcium-zinc stabilizer is preferably an inorganic stabilizer. Suitable examples of the former inorganic stabilizer are as follows.

1. Zeolite stabilizer Synthetic zeolite such as zeolite A, zeolite X and zeolite Y or a metal ion (calcium, zinc ion) exchange treated product of an acid-treated product thereof.

2. Layered metal hydroxide stabilizer 2-1. Zinc-modified hydrotalcite-based stabilizer General formula M ²⁺ _x M ³⁺ _y (OH) _{2x + 3y-2z} (A ²⁻ ) _z · aH ₂ O (2) In the formula, M ²⁺ is a divalent metal ion such as Zn. ^Yes , M ³⁺
Is a trivalent metal ion such as Al, A ²⁻ is a divalent anion such as CO ₃ , and x, y and z are 8 ≧ x / y ≧ 1/4.
And z / x + y> 1/20 are positive numbers and a is 0.25 ≦
It is a number that satisfies a / x + y ≤ 1.0. A composite metal hydroxide having As the zinc-modified hydrotalcite, in the general formula (2), the M ²⁺ divalent metal ion is a combination of Mg and Zn, and the atomic ratio of Mg: Zn is 9: 1 to 1.8. : 1, especially 3: 1 to 2.
Those in the range of 5: 1 are excellent in thermal stability and prevention of initial coloration.

2-2. Microcrystalline calcium silicate In the present invention, as calcium silicate, (A) CaO.xSiO ₂ .nH ₂ O (3) In the formula, x is a number of 0.5 to 2.0. And n is a number of 2.5 or less, and has a chemical composition represented by the following formula, and has a surface spacing of 3.01 to 3.08 angstrom and a surface spacing of 2.7.
A complex of microcrystalline calcium silicate or a polyhydric alcohol thereof or a partial ester thereof having an X-ray diffraction pattern at a surface spacing of 8 to 2.82 angstroms and a surface spacing of 1.81 to 1.84 angstroms is used. This microcrystalline calcium silicate is also excellent in thermal stability and prevention of initial coloration.

3. Calcium and zinc hydroxides, basic salts and silicates Hydroxides such as calcium hydroxide and zinc hydroxide. Formula (oxide standard) MO · qMX _{z / m} (4) In the formula, M is calcium or zinc, X is an inorganic acidic oxide anion or an organic anion, and m is a valence of the anion X, A basic salt having a composition represented by the following: q is a number of 0.1 to 10, particularly 0.5 to 5. In particular, basic calcium carbonate, basic zinc carbonate, basic calcium stearate, basic zinc stearate, basic calcium palmitate and the like. Formula (oxide standard) MO · kSiO ₂ (5) In the formula, M represents an alkaline earth metal or zinc, and k is 0.
A silicate having a composition represented by the number 1 to 10, in particular 0.5 to 5.

Suitable examples of the latter organic heat stabilizer are as follows. 4. Metal soap stabilizers Calcium salts and zinc salts of higher fatty acids such as stearic acid, lauric acid and palmitic acid.

These inorganic or organic stabilizers may be used alone or in combination of two or more. At least a part of the stabilizer is preferably an inorganic stabilizer in order to prevent excessive lubricity due to the incorporation of metal soap. The stabilizer used in the present invention is not limited to the calcium-zinc stabilizer. That is, other metal-based stabilizers such as magnesium-based, barium-based, and strontium-based stabilizers can be appropriately combined and used.

The above calcium-zinc stabilizer is
It can be used in combination with any stabilizing aid known per se. As such a stabilizing aid, polyhydric alcohols, phenols, β-keto acid esters or β-diketones are preferable, and suitable examples thereof 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, dipentaerythritol. , Mannitol, sorbitol, trimethylolpropane, ditrimethylolpropane, tris isocyanurate, dipentaerythritol adipate and the like.

Examples of phenolic antioxidants include bisphenol A, bisphenol B, bisphenol F, 2,6-diphenyl-4-octadecyloxyphenol, and 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 acid 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-ditert-butyl-4-hdoxybenzyl) isocyanurate, triethylene glycol Screw [(3-
Tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.

Examples of the β-diketone or β-keto acid ester include 1,3-cyclohexadione, methylenebis-1,3-cyclohexadione and 2-benzyl-
1,3-cyclohexadione, acetyltetralone, palmitoyltetralone, stearoyltetralone, benzoyltetralone, 2-acetylcyclohexanone, 2
-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.

In the resin composition of the present invention, the synthetic amorphous aluminum silicate is used in an amount of 0.01 to 10 parts by weight, particularly 0.05 to 5 parts by weight, based on 100 parts by weight of the chlorine-containing polymer. Good. If the amount of synthetic amorphous aluminum silicate is less than the above range, a satisfactory effect as an electrical insulating property improver is not exhibited. On the other hand, if the amount of the synthetic amorphous aluminum silicate is too much for the chlorine-containing polymer, the action as the electrical insulation improver cannot be added, which is disadvantageous in terms of cost.

In the resin composition of the present invention, the calcium-zinc stabilizer is preferably used in an amount of 1 to 40 parts by weight, particularly 1 to 15 parts by weight, based on 100 parts by weight of the chlorine-containing polymer. When the amount of the calcium-zinc stabilizer is less than the above range, a satisfactory heat stabilizing effect is not exhibited. On the other hand, if the calcium-zinc stabilizer is too much for the chlorine-containing polymer, the effect as a heat stabilizer is not added, which is disadvantageous in terms of cost.

[0043]

The present invention will be further described with reference to the following examples. The test method used in the examples was as follows.

(1) Chemical analysis JIS. M. It was measured according to 8855.

(2) X-ray Diffraction It was measured with Cu-Kα using a Geiger flex RAD-IB system manufactured by Rigaku Denki Co., Ltd. Target Cu filter Curved crystal graphite monochromator Detector SC Voltage 40KVP Current 20mA Count full scale 700c / s Smoothing point 25 Scanning speed 1 ° / min Step sampling 0.02 ° Slit DS1 ° RS0.15mm SS1 ° Illumination angle 6 °

(3) Infrared absorption spectrum analysis (IR) Fourier transform infrared spectrophotometer FT / IR- manufactured by JASCO Corporation
It measured using 610. The measurement sample is KBr 200mg,
1 mg of powder was added, and it was made with a tablet press.

(4) Thermal analysis The measurement sample was prepared by previously treating the sample with ethyl alcohol to remove the surface treatment agent and drying it at 110 ° C. using a constant temperature dryer. Next, TAS100-TG manufactured by Rigaku Co., Ltd.
It was measured using an 8110 thermal analysis system. As the measurement conditions, α-Al ₂ O ₃ was used as the standard substance, and the heating rate was 10 ° C. /
Minutes and atmosphere were air, and the weight loss was measured.

(5) Specific surface area ASAP2010 manufactured by Micromeritics was used to measure the nitrogen adsorption isotherm. The specific surface area was determined by integrating the total pore volume with a specific pressure of 0.2 or less.

(6) A solution obtained by adding potassium hydroxide (KOH) to di-propylene glycol so that the alkali adsorptive concentration becomes 0.4% is obtained at 95 ° C.
After adjusting to 1, the sample was added at 1% and the KOH adsorption capacity (meq / g) after 30 minutes was determined.

(7) Method for Measuring Acid Strength n-Butylamine [Reference: "Catalyst" Vol. 11, No6,
P210-216 (1969)].

(8) Water content The water content was defined as the weight loss of the sample before and after drying at 110 ° C. for 3 hours.

(9) Particle size measurement The average particle size was measured using a Particle Size Analyzer Model LS230 manufactured by Coulter.

(10) Gear Oven Heat Resistance Test (Static Thermal Stability) The resin composition was kneaded with a roll mill at a temperature of 150 ° C. for 5 minutes to prepare a uniform soft vinyl chloride sheet having a thickness of about 1 mm, and then 190 The test piece was placed in a gear oven set to ° C, and the blackening time was measured.

(11) Thermal stability test (HT chlorine scavenging ability) JIS. K. According to 6723, a soft vinyl chloride sheet is cut into 1.0 mm x 1.0 mm, a test tube equipped with Congo red paper is filled with 2 g of sample chips, heated to 190 ° C, and hydrogen chloride is generated by thermal decomposition of vinyl chloride. The desorption time was measured.

(12) Electric insulation (VR) A soft vinyl chloride sheet is put at 160 ° C. and a pressure of 150 kg / c.
m ² for 5 minutes under pressure and heat to form a sheet having a thickness of 1 mm as a test piece. According to 6723, the volume resistivity of the sample sheet at 30 ° C. or 60 ° C. was measured.

In the evaluation of the resin containing the insulating property improving agent, the composition other than the insulating property improving agent is as follows. The vinyl chloride resin used in each table is from a different manufacturer.

(Examples 1 to 3, Comparative Example 1) Silica sol and aluminum sulfate solution were mixed and coprecipitated by adjusting the pH to 3 at room temperature and atmospheric pressure. This was aged at 60 ° C. for 4 hours, washed with water and dried to obtain amorphous aluminum silicate (referred to as S-1). Next, a part of the sample was pulverized with an atomizer or a jet mill to obtain a sample. The atomizer crushed product is referred to as sample S-2, and the jet mill crushed product is referred to as sample S-3. Physical properties were measured for each, and the results are shown in Table 1. Further, the X-ray diffraction of the sample S-3 is shown in FIG. 2, the infrared absorption spectrum is shown in FIG. 3, the result of the differential thermogravimetric analysis is shown in FIG. 4, and the particle size distribution curve is shown in FIG. Further, each sample was blended with a resin and evaluated (basic blending was 1). The results are shown in Table 2. Comparative Example 1
Is the measurement result when no electrical insulation improver was blended (blank).

(Examples 4 to 5) Calcium stearate was added to Sample S-1 in an amount of 10% based on the weight of S-1 and mixed to perform surface treatment. Further, the sample was subjected to atomizer pulverization (S-4) and jet mill pulverization (S-5) to obtain a sample. Each sample was blended with the resin and evaluated (basic formulation was 1). The results are shown in Table 2.

Examples 6 to 7 Calcium stearate was added to sample S-1 in an amount of 20% based on the weight of S-1 and mixed to perform surface treatment. Further, the sample was subjected to atomizer crushing (S-6) and jet mill crushing (S-7) to obtain a sample. Each sample was blended with the resin and evaluated (basic formulation was 1). The results are shown in Table 2.

(Examples 8 to 9) Calcium stearate was added to the sample S-1 in an amount of 30% with respect to the weight of S-1 and mixed to perform surface treatment. Further, the sample was subjected to atomizer crushing (S-8) and jet mill crushing (S-9) to obtain a sample. Each sample was blended with the resin and evaluated (basic formulation was 1). The results are shown in Table 2.

[0061]

[Table 1]

[0062]

[Table 2]

(Examples 10 to 14) Sample S-7 was blended with the resin in the proportion shown in Table 3 and evaluated (basic blending was 1). The results are shown in Table 3.

(Comparative Examples 2 to 5) The basic composition was 1, and the composition was evaluated by compounding it with the resin as follows. Comparative Example 2 is the measurement result when the electrical insulation improver was not blended (blank). Comparative Examples 3 to 5 were evaluated by adding 0.5 parts by weight of each of the following samples. H-1: calcined clay 1 (Satenton SP-33; SiO ₂ / Al
₂ O ₃ molar ratio = 2) H-2: Calcined clay 2 (Insulite MC manufactured by Mizusawa Chemical Co., Ltd.)
-100) H-3: Amorphous silica (Carplex # 80D) The results are shown in Table 3. Moreover, the graph which plotted the result of Examples 10-14 and Comparative Examples 2-3 is shown in FIG. As a result, the comparative sample had a particularly low electrical insulating property (VR) at 60 ° C.

[0065]

[Table 3]

(Examples 15 to 18, Comparative Examples 6 to 7) Sample S-7 and the isocyanurate compound were blended in the proportions shown in Table 4 and evaluated (basic blending was 1). The results are shown in Table 4. In addition, Comparative Example 6 is a measurement result when the electrical insulation improving agent is not blended (blank).

[0067]

[Table 4]

(Examples 19 to 23, Comparative Example 8) An aqueous solution of sodium silicate and an aqueous solution of aluminum hydroxide were mixed with SiO ₂ / Al ₂ O.
_As shown in Table 5, the ₃ molar ratio was mixed, coprecipitated, and aged at 60 ° C. for 4 hours to obtain amorphous aluminum silicate. 0.5 part by weight of the obtained sample was blended with a resin for evaluation (basic formulation was 1). The results are shown in Table 5. Comparative Example 8
Is the measurement result when no electrical insulation improver was blended (blank).

[0069]

[Table 5]

(Examples 24 to 29, Comparative Example 9) Sample S-
5% of each surface treatment agent shown in Table 6 was added to 1 and mixed, and surface treatment was performed. 0.5 part by weight of the obtained sample was blended with a resin for evaluation (basic formulation was 1). The results are shown in Table 6. Comparative Example 9
Is the measurement result when no electrical insulation improver was blended (blank).

[0071]

[Table 6]

In the following resin evaluation, the basic composition other than the insulation improver is as follows. The vinyl chloride resin used was made by a different manufacturer from each table.

(Examples 30 to 36, Comparative Example 10) Sample S
-7 and calcined clay (Insulite MC manufactured by Mizusawa Chemical Co., Ltd.-
400) was blended in the ratio shown in Table 5 and evaluated (basic blending was 2). The results are shown in Table 7. Comparative Example 1
0 is the measurement result when the electrical insulation improver was not blended (blank).

[0074]

[Table 7]

(Examples 37 to 40, Comparative Example 11) Sample S
-3 was heat-treated at temperatures of 110, 150, 300, and 500 ° C. for 1 hour, respectively. Each of the obtained samples had a value of 0.
5 parts by weight of each was mixed with the resin and evaluated (basic composition was 2). The results are shown in Table 8. In addition, Comparative Example 1 is a measurement result when the electrical insulation improving agent is not blended (blank).

[0076]

[Table 8]

(Example 41) In Example 1, SiO ₂ /
Amorphous aluminum silicate was obtained by performing synthesis in the same manner as in Example 1 except that the Al ₂ O ₃ molar ratio was adjusted.
-10). Physical properties were measured and the results are shown in Table 1.
Further, the sample was blended with 0.5 part by weight of resin and evaluated (basic blending was 2). The results are shown in Table 9.

Example 42 In Example 1, SiO ₂ /
Amorphous aluminum silicate was obtained by performing synthesis in the same manner as in Example 1 except that the Al ₂ O ₃ molar ratio was adjusted.
-11). Physical properties were measured and the results are shown in Table 1.
Further, the sample was blended with 0.5 part by weight of resin and evaluated (basic blending was 2). The results are shown in Table 9.

(Example 43) As raw materials, JIS products of sodium silicate (SiO ₂ 22.5%, Na ₂ O 7.2%, SG 1.295 / 15 ° C) and 45% sulfuric acid (SG 1.352 / 15 ° C) were used. Using a device capable of instantaneous contact, sodium silicate is supplied at a rate of 7.5 l / min and sulfuric acid at a rate of 2.0 l / min to the device to form an acidic silica sol. 14.0 kg of this silica sol was added to an aluminum sulfate solution (Al ₂ O ₃ 7.6% SG
(1. 302/25 ° C.) 13.5 kg was poured and mixed to generate silica-alumina sol, which was allowed to stand for 24 hours for aging. After aging, it was treated with aqueous ammonia to obtain silica-alumina gel. Subsequently, this gel was washed with pure water, then ion-exchanged with a 4.5% ammonium chloride solution, and washed again with pure water. The washed silica-alumina gel was hydrothermally treated at 120 ° C. for 3 hours and then dried at 140 ° C. to recover the dried silica-alumina gel. The dried silica-alumina gel was pulverized with a jet mill to prepare powdered silica-alumina (referred to as sample S-12). Physical properties were measured and the results are shown in Table 1. Further, the sample was blended with 0.5 part by weight of resin and evaluated (basic blending was 2). The results are shown in Table 9
Shown in.

(Example 44) 0.147 based on SiO ₂
A commercially available sodium silicate solution (solution A) having a concentration of g / ml and a gibbsite type aluminum hydroxide powder (Hijilite H-32 manufactured by Showa Denko) having an average particle diameter of 8 μm as (SP), and SiO _{2 in} solution A. Using a two-fluid nozzle, a sodium silicate solution containing SiO ₂ : SP = 85: 15 by weight and a 10% sulfuric acid solution are instantly released into the mixed atmosphere and dropped into the water in the receiving tank. The mixture was aged at room temperature in the range of pH 8 to 10, prepared by a sol-gel reaction, and ground to obtain amorphous aluminum silicate (referred to as sample S-13). Physical properties were measured and the results are shown in Table 1. Further, the sample was blended with 0.5 part by weight of resin and evaluated (basic blending was 2). The results are shown in Table 9.

(Comparative Examples 12 to 15) The basic composition was 2, and the composition was evaluated by combining it with the resin as follows. Comparative Example 12 is
It is a result of measurement without blending the electrical insulation improver (blank). Comparative Examples 13 to 15 were each evaluated by adding the following samples to 0.5 part by weight of resin. H-1: calcined clay 1 (Satinton SP-33) H-4: calcined clay 3 (Insulite MC manufactured by Mizusawa Chemical Co., Ltd.
-400) H-5: Calcined clay 4 (Translink 77 made by Tsuchiya Kaolin)

[0082]

[Table 9]

[0083]

According to the present invention, a synthetic amorphous aluminum silicate having a specific chemical composition is blended with a chlorine-containing polymer as an electrical insulation improving agent, so that the blending amount thereof is smaller than that of calcined clay. , The excellent effect of improving the electric insulating property is obtained, and also the effect of improving the electric insulating property at high temperature is excellent,
Further, the advantage of being excellent in heat stabilizing action and anti-coloring property is achieved. In addition, this synthetic amorphous aluminum silicate-based electrical insulation improver is said to be most excellent in combination with the calcium-zinc stabilizer, in terms of the electrical insulation-enhancing action, thermal stability, and anti-coloring property. There are advantages.

[Brief description of drawings]

FIG. 1 is a graph plotting the relationship between the blending amount of synthetic amorphous aluminum silicate to a chlorine-containing polymer and the volume resistance of the blended chlorine-containing polymer.

FIG. 2 shows an X-ray diffraction image of an example of synthetic amorphous aluminum silicate used in the present invention.

FIG. 3 shows an infrared absorption spectrum of an example of synthetic amorphous aluminum silicate used in the present invention.

FIG. 4 shows the results of differential thermogravimetric analysis of an example of synthetic amorphous aluminum silicate used in the present invention.

FIG. 5 is a particle size distribution curve of an example of synthetic amorphous aluminum silicate used in the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01B 3/44 H01B 3/44 BF term (reference) 4G073 BA57 BA63 BD03 BD07 BD20 CE01 FA01 GA01 GA11 GA12 UB12 4J002 BD041 BD051 BD061 BD071 BD081 BD101 BD181 DE146 DE287 DJ006 DJ007 FB236 FD030 FD037 FD070 GQ01 5G305 AA14 AB01 AB24 AB40 BA15 CA03 CA37 CC12 CD04

Claims (13)

[Claims] During 1. A formula _{(1) Al 2 O 3 ·} nSiO 2 · mH 2 O ‥ (1) formula, n is the number of 3 or more, m is a number of 20 or less, including zero, in An electrical insulation improver comprising a synthetic amorphous aluminum silicate having a chemical composition shown. 2. BET of synthetic amorphous aluminum silicate
The electrical insulating property improver according to claim 1, having a specific surface area of 30 to 700 m ² / g. 3. The synthetic amorphous aluminum silicate having an alkali adsorbing property.
Alternatively, the electrical insulation improving agent described in 2. 4. The acidity of the synthetic amorphous aluminum silicate in the range of -5.6 to -3.0 is 0.0.
The electrical insulation improver according to any one of claims 1 to 3, which is in the range of 3 to 0.30 meq / g. 5. In the formula (1), n is 3 to 10.
It is in the range of 0, The electrical insulation improving agent in any one of Claim 1 thru | or 4 characterized by the above-mentioned. 6. The electrical insulation improving agent according to claim 1, which is made of an amorphous gel of aluminum silicate. 7. The electrical insulation improver according to claim 1, wherein the amount of water determined as the weight loss at 110 ° C. for 3 hours is in the range of 15% by weight or less. 8. The electrical insulation improver according to claim 1, which is surface-treated with higher fatty acid calcium. 9. The higher fatty acid calcium is 0.5 to 30.
9. It is contained in an amount of% by weight.
The electrical insulation improver described in 1. 10. The volume-based median diameter is 0.3 to 20 μm and the particle diameter is 45 μm as measured by a laser scattering method.
The electrical insulation improver according to any one of claims 1 to 9, wherein particles having a particle size of m or more have a particle size distribution of 10% by volume or less based on the whole. 11. A chlorine-containing polymer, the following formula (1) Al ₂ O ₃ .nSiO ₂ .mH ₂ O (1), wherein n is a number of 3 or more and m is 20 or less including zero. A resin composition having improved electrical insulation, comprising a synthetic amorphous aluminum silicate having a chemical composition represented by the formula: and a calcium-zinc stabilizer. 12. The resin composition according to claim 11, wherein the synthetic amorphous aluminum silicate is present in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the chlorine-containing polymer. 13. The resin composition according to claim 11, wherein the calcium-zinc stabilizer is present in an amount of 1 to 40 parts by weight per 100 parts by weight of the chlorine-containing polymer.