JPH0415260A - Antistatic transparent resin polymer composition and antistatic agent - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in transparency, heat resistance, migration resistance, weathering resistance and antistatic properties by mixing a polar resin polymer with a specified antistatic agent. CONSTITUTION:A quat. ammonium salt of formula I or II (wherein R1 to R4 are each a monovalent hydrocarbon group provided that at least one of them is 10-24C alkyl; R5 is 8-24C alkyl; and X is an anion) is allowed to react with a perchlorite of formula III (wherein M is an inorganic or organic cation; (m) is 1-3; and (n) is 1-6) at 50-150 deg.C in a molar ratio of (0.8:1) to (1:1.5) in a highly polar solvent (e.g. dioxane) to obtain a quat. ammonium salt/perchlorite complex. A silicate having a content of particles of a secondary particle diameter (as measured by the Coulter counter method) of 5mum or 50% or above, a refractive index of 1.49-1.57, an oil absorption of 80-250ml/100g, a pore volume of 0.1cc/g or above and a BET specific surface area of 100m<2>/g or above and represented by formula IV (wherein M is Ca or Mg; (x) is 1-2; and (n) is 0.3-1.0) is impregnated with the above complex in a weight ratio of 1:(1.5-0.25) to obtain an antistatic agent comprising the complex. 100 pts.wt. polar resin polymer of a dielectric constant of 2.3-4.5 and a volume resistivity of 10<13>-10<17>OMEGA.cm (e.g. PVC) is mixed with 0.5-60 pts.wt. above antistatic agent.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an antistatic transparent resin polymer composition, and more specifically, it has excellent transparency, heat resistance, non-migration properties,
The present invention relates to a polar resin composition having a sustained antistatic function. The invention also relates to antistatic agents used for this purpose.

(Prior technology) i! for resin molded products and resin films. Incorporation of various antistatic agents for the purpose of imparting antistatic properties is widely practiced in various fields.

Antistatic agents are broadly classified into internal antistatic agents and external antistatic agents, each of which has advantages and disadvantages.

Filler-type conductive agents such as conductive carbon black, metal powder, and tin oxide conductive agents have high conductivity and are extremely durable and long-lasting in conductive performance, but they do not contain a large amount in the resin. It must be blended with
There are drawbacks such as the relatively high cost of preventing this, and the strong tendency to color or make the resin molded product opaque.

On the other hand, cationic surfactants, anionic surfactants,
Antistatic agents such as nonionic surfactants are mixed in a small amount with resin and transferred to the surface of the molded product to exhibit antistatic function. It is inevitable that it will bleed out and lose its appearance characteristics (smoothness and surface gloss), and it will also be washed away by contact with water, or it will change in quality due to the action of light and heat, and its antistatic function will be lost. However, it has the disadvantage that the antistatic function is not durable. Furthermore, among surfactant-type antistatic agents, cationic surfactants, which are said to have the best antistatic function, are known to have a tendency to degrade vinyl chloride resins, for example (Japanese Patent Laid-Open No. 48 -65238).

JP-A-61-213231 describes an antistatic agent composition comprising an organic IT antistatic agent and an organic modified clay, and this composition can also form conductive structures in a resin matrix. I have not mentioned it.

From the above, although the conventional IF antistatic agents are excellent, they generally impair the transparency of the resin.

(Problems to be Solved by the Invention) The above prior art imparts conductivity by blending in a resin a combination of organically modified clay, that is, smectite clay incorporating organic cations between the eyebrows, and an organic antistatic agent. However, organically modified clay has a strong tendency to reduce the transparency of resins, and even among polar resins, when mixed with vinyl chloride resin, it not only makes it opaque but also has the disadvantage of significantly discoloring it from purple to black. be.

In addition, the organic IT antistatic agent blended with the organic modified clay tends to bleed out onto the surface of the molded product, although the degree of the antistatic agent varies.

Therefore, an object of the present invention is to provide an antistatic agent for polar resins that does not impair transparency, and which has a non-talk rate of 2.3 to 4.
．． 5 and the specific volume resistivity is 1013 to 10'7ΩC1
It has excellent transparency, heat resistance, bleed-out resistance, water resistance, weather resistance, etc. and lasts for a long time compared to polar resins with 11!
It is an object of the present invention to provide a resin composition having antistatic properties.

Another object of the present invention is to provide a chlorine-containing polymer having a transparent composition among polar resins without impairing its transparency, having no tendency to color, promoting thermal stability, and having excellent properties for the polymer. An object of the present invention is to provide a novel anti-fog agent that can provide anti-fog performance.

(Means for Solving the Problems) According to the present invention, the quaternary ammonium-perchlorate complex has the formula: No-xSiO2.nH,0, where M is a metal element of calcium or magnesium, and is a number from 1 to 2, and n is a number from 0.3 to 1.0. The chemical composition can be expressed as follows, and 50% or more of the particles have a secondary particle diameter of 5 μm or less according to the Coulter-Counter method, and 1. 49-1.57(7) refractive index and 80-25hf/100
g(1) An antistatic agent is provided which comprises a composite supported by a silicate having oil absorption.

According to the present invention, the above composite has a non-call rate of 2.3 to 45 and a volume resistivity of 1013 to 101? Ωc
An antistatic transparent resin polymer composition is provided, which is characterized in that it is blended with a transparent resin polymer of rIi.

Furthermore, according to the present invention, there is provided an antistatic transparent chlorine-containing polymer, which is characterized in that, among the polar resins, the above-mentioned composite is blended with a chlorine-containing polymer together with a non-lead stabilizer and a plasticizer and/or a lubricant. A composition is provided.

(Function) The first characteristic of the antistatic agent used in the present invention is that it contains a quaternary ammonium-perchlorate complex. Fourth
Class ammonium salts are well known as cationic conductive agents, and in the present invention they are used in the form of perchlorate complexes. Although various inorganic anions are known as counter ions (anions) for quaternary ammonium cations, chloride ions are generally used as counter ions.

This is believed to be due to the fact that the conduction mechanism of quaternary ammonium salts is ion conduction due to the movement of counter ions (anions), but chloride ions have a smaller ionic radius than other anions, resulting in a higher ion conduction speed. Seem.

According to the present invention, when a quaternary ammonium salt is used in the form of a perchloric acid complex, the coloring tendency of the chlorine-containing polymer that is observed when quaternary ammonium chloride is blended with the chlorine-containing polymer is effectively eliminated. This is based on the knowledge that

That is, when quaternary ammonium chloride is blended with a chlorine-containing polymer, the polymer develops a purple to black color, and when a perchlorate is blended with a chlorine-containing polymer, the polymer also develops a purple to black color. However, quite unexpectedly, when they are used in the form of complexes, the coloring tendency mentioned above is almost completely eliminated.

In the complex used in the present invention, there are quaternary ammonium ions as cations and perchlorate ions as anions, but in this complex, ion conduction occurs through a completely different conduction mechanism from that of conventional cationic conductive agents. I believe it will be done. That is, the conductive agent of the present invention is
Compared to class ammonium chloride-based conductive agents, it exhibits approximately the same level of conductivity with a significantly smaller amount of ammonium groups, about 20%. This seems to be due to the fact that ionic conductivity is not obtained by movement of anions, which are counterions, but rather by movement of protons within the complex.

Next, the second feature is that this quaternary ammonium-perchlorate complex is retained in the silicate, and among these, in order not to impair the transparency of the resin composition, at least 1.4
It is a silicate with a refractive index of 9 to 1.57.

That is, for example, since the calcium silicate salt in the present invention is an inorganic powder that has surface activity and has voids inside, it can be absorbed into the chlorine-containing polymer while retaining the quaternary ammonium-perchlorate complex. The complex acts to suppress migration of the complex to the surface of the polymer resin. Calcium silicate salts are also themselves excellent heat stabilizers for chlorine-containing polymers, and therefore have a beneficial effect in further eliminating the coloring tendency of chlorine-containing polymers.

Further, from the viewpoint of finely dispersing the composite in the resin polymer, the silicate used is 5 μm or less, preferably 3 μm or less.
It should have an average particle size of less than μm, especially less than 1 μm, and from the point of view of retaining the complex and preventing bleed-out to the surface, 80 rail / 100g
As mentioned above, it is necessary to have an oil absorption amount of 100 ttrll/100g or more, but in order not to impair the transparency of the resin, it is preferable to have an oil absorption amount of 250 mil/100g or less, particularly 200I11β/100g or less.

Further, the electrical conduction mechanism in the resin composition of the present invention is thought to be ionic conduction in which carriers (protons) contained in the composite move through the plasticizer and/or lubricant. This is in good agreement with the fact that as the amount of plasticizer and/or lubricant in the chlorine-containing polymer composition is increased, the volume resistivity decreases with increasing amount, up to a certain extent.

Therefore, in order for the antistatic agent of the present invention to be used in transparent resin bodies, it goes without saying that it is necessary that the refractive index of the particles of the antistatic agent is at least close to the refractive index of the resin polymer, and even finer particles are required. It is necessary to linearly disperse the particles. By satisfying these conditions, the antistatic agent of the present invention can improve the above-mentioned ionic conductivity even in resin systems other than vinyl chloride resin systems that require plasticizers, especially in polar resin systems with predetermined electrical properties. By increasing the density of the plasticizer, for example, by increasing the amount of antistatic agent added, or by using a calcium silicate salt as a support for the antistatic agent that has a plasticizer etc. occluded in advance. The fact that the antistatic agent of the present invention can be used for resins that do not require agents and/or lubricants, etc.
This was completely unexpected.

(Preferred Embodiment of the Invention) Complex As the quaternary ammonium salt raw material used in the present invention, any one conventionally known as a cationic conductive agent or a cationic surfactant can be used. Suitable examples include, but are not limited to:

In particular, in the following formula, each of Rl, R2, Rs and R4 is a monovalent hydrocarbon group under the condition that at least one of them is an alkyl group having 10 to 24 carbon atoms, and X is an anion. , quaternary ammonium salt of . For example, halogenated dimethyldialkyl ammonium, dimethyldialkyl ammonium sulfate, halogenated dimethylbenzylalkylammonium, dimethylbenzylalkylammonium sulfate, and derivatives thereof (herein, the alkyl group is one having 10 or more carbon atoms, such as lauryl or stearyl).

A quaternary ammonium salt of the following formula, where R5 is an alkyl group having 8 to 24 carbon atoms. For example, dodecylpyridinium,
Alkylpyridinium chloride like chloride.

As a perchlorate raw material, a salt of the formula % (% formula %), where M is an inorganic or organic cation, m is a number from 1 to 3, and n is a number from 1 to 6, is used. Examples include lithium chlorate, potassium perchlorate, sodium perchlorate, and calcium perchlorate.

The complex used in the present invention can be obtained by reacting the above-mentioned quaternary ammonium salt and perchlorate in a suitable reaction medium under heating. The best results are obtained when the quaternary ammonium salt and the perchlorate are used in equimolar amounts (chemically compatible amounts), but this quantitative ratio can be changed to 0.8:1 depending on demand.
It is also possible to vary within a molar ratio of 1 to 1:5. As the reaction medium, a solvent capable of dissolving both, for example a strong polar solvent such as tetrahydrofuran, dioxane, N,N-dimethylformamide, etc., can also be used.

In this case, a means for removing the solvent is required at some stage for producing the antistatic agent.

The present inventors have discovered that it is possible to react a quaternary ammonium salt with a perchlorate in a plasticizer such as dioctyl phthalate, and that the complex formed by the reaction is a molten liquid in which the complex is uniformly dissolved in the plasticizer. It has been found that the alkaline earth silicate salt described below can be easily retained without requiring a solvent removal operation. The plasticizer is 5 to 500% by weight based on the total amount of quaternary ammonium salt and perchlorate.
The reaction is preferably carried out at a temperature of 50 to 150°C, especially 80 to 100°C. The end of the reaction time can be confirmed by uniformity and transparency.

The complex used in the present invention is generally a solid, and the dimethyl distearyl ammonium
X-ray diffraction image of barchlorate, A in the same figure is an X-ray diffraction image of lithium perchlorate, B in the same figure is an X-ray diffraction image of dimethyldistearylammonium chloride,
Similarly, C in the figure shows an X-ray diffraction image of lithium chloride.

Silicate The silicate used in the present invention has the particle size and oil absorption amount described above. Furthermore, it is necessary to have a refractive index of 1.49 to 1.57, which is close to the refractive index of the resin polymer, in order not to impair the transparency of the resin polymer. Furthermore, this silicate has a concentration of 0.1 cc/g or more, especially 0.2 to 1
It is also necessary to have a pore volume of 5 cc/g and a BET specific surface area of 100 m''/g or more, particularly 150 to 280 m''/g, in order not to impair the retention and transparency of the supported material.

This silicate may be a so-called normal salt, a basic salt, or an acidic salt, but generally it has the formula % formula % where M is a metal element such as calcium or magnesium, X is a number from 1 to 2, and n It is preferable that the silicate has a structure with a number of 0.3 to 1.0. Generally, it is preferable that this silicate is substantially amorphous in terms of X-ray diffraction from the knowledge that it is microcrystalline. , as long as it has the above-mentioned properties,
It may have a crystalline structure in terms of line diffraction.

This silicate is, for example, a calcium silicate salt, in which a fine aqueous dispersion of calcium hydroxide is mixed with silica hydrosyl, hydrogel, xerogel, or other amorphous silica. It is produced by reacting so as to obtain. Suitable calcium silicate salts are obtained by reacting layered silica (active silicic acid) obtained by acid treatment of clay minerals as a silica source with the above aqueous slurry of calcium hydroxide, but fine hydroxide The slurry is obtained by lime emulsification of quicklime under wet grinding.

This silicate has a refractive index similar to that of the resin used in the present invention and has excellent oil absorption.

In the case of magnesium silicate salts, activated silica is preferably added to an aqueous dispersion of fine magnesium hydroxide or basic magnesium carbonate under normal pressure or hydrothermal conditions so as to obtain the above-mentioned silicate. By reacting with , it is possible to produce a magnesium silicate salt having a refractive index and oil absorption properties that suit the present invention.

Legacy 1 According to the invention, the silicate powder retains the complex. The ratio of silicate to complex varies depending on the oil absorption amount of the silicate, etc., but is generally 1+1.5 to 1:0.2.
5. It is particularly desirable to use both in a weight ratio of 1:0.5 to 1:1.

In producing the composite, the silicate powder may be mixed under heating if necessary, and the melt or solution of the complex may be dropped or sprayed thereinto to continue mixing. When a solvent is used, the solvent may be distilled off, and when the above-mentioned plasticizer is used, the mixed system may be directly cooled.

According to the present invention, a free-flowing powder in which the complex is retained in silicate particles is obtained, which can be used as an antistatic agent in a transparent formulation in chlorine-containing polymers and other polar resins. Just use it.

In addition, these composite particles are loaded with organic components such as plasticizers, lubricants, antifogging agents, ultraviolet absorbers, antioxidants, insect repellents, insect repellents, antibacterial agents, fragrances, colorants, and medicinal ingredients. It can also be used as Furthermore, the surfaces of these composite particles, including those carrying the various organic components mentioned above, are coated with fatty acids, resin acids, various metal soaps, derivatives such as amides and esters, and various coupling agents. It can also be surface treated. The organic components used for support and surface treatment are 5 to 10% by weight, in particular 0.5% by weight, based on the silicate particles.
The content is preferably in the range of 5 to 3% by weight.

゛Bright polar resin heavy delta body assembly The antistatic agent of the present invention is made of resin polymer 100! 0 per part
．． It is preferably used in an amount of 5 to 60 parts by weight, preferably 1 to 10 parts by weight, most preferably 2.0 to 5.0 parts by weight. When the amount is less than the above range, the volume resistivity cannot be sufficiently lowered and the antistatic property is deteriorated, and when it is more than the above range, it tends to be disadvantageous in terms of resin hue and mechanical strength.

IF of the present invention! Based on the knowledge that the inhibitor effectively imparts antistatic properties to the resin, among the so-called polar resins, CII has a specific electric constant of 2.3 to 4.5 and a volume resistivity of 10'3 to 10''Ω CII. Preferably, such polar resins include polyvinyl chloride; conjugated polyvinyl chloride; polyvinyl acetate; polyacrylonitrile; polyvinylidene chloride; polyvinylidene fluoride; polyoxymethylene: ethylene-vinyl acetate copolymer. Coalescence; polymethyl methacrylate; polyethyl methacrylate; polybutyl methacrylate: polyoctyl methacrylate; polyethylene terephthalate: polyamide such as nylon 66 and nylon 610; 4,6-polyurethane; triacetylcellulose, epoxy: phenol formaldehyde resin, etc. The refractive index of these resins is 1.49 to 1.54.
It is within the range of

In the above-mentioned chlorine-containing polymer, a lead-free stabilizer is preferable from the viewpoint of transparent formulation, and any known metal soap-based or tin-based stabilizer is used, especially methyltin mercaptide, butyltin mercaptide, octyl. Tin mercaptide, butyltin laurate, octyltin laurate, butyltin maleate, octyltin maleate, dioctyltin maleate polymer, dibutyltin maleate ester, dibutyltin maleate laurate, dibutyltin mercaptopropionate, epoxy octyltin Examples include mercaptite. These lead-free stabilizers are used in amounts of 0.5 to 10 parts by weight, especially 2 to 5 parts by weight, per 100 parts by weight of the chlorine-containing polymer.
Blend in parts by weight.

As a plasticizer, any one known as a plasticizer for chlorine-containing polymers, such as phthalate ester, aliphatic dibasic acid ester, phosphoric acid ester, hydroxy polycarboxylic acid ester, monofatty acid ester, polyhydric alcohol ester , epoxy plasticizers, and polyester plasticizers are used. As the lubricant, various waxes such as petroleum wax, polyethylene wax, polypropylene wax, fatty acids or their conductors, animal and vegetable waxes, etc. are used. Plasticizer is 10 to 1 per 100 polymerized parts of resin.
00 parts by weight, especially in an amount of 20 to 60 parts by weight, the lubricant is 0.00 parts by weight.
It is preferably used in an amount of 5 to 3.0 parts by weight, a total of 10 to 100 parts by weight, particularly 25 to 70 parts by weight.

Since these transparent resin polymers endowed with antistatic ability are transparent, they also have high pigment coloring properties, so they can be used for tapes, flooring sheets, wall sheets, emblems, antifouling sheets,
Widely used for various purposes such as desk mats, disaster prevention sheets, and stretched films.

This antistatic agent can also be used by adding it to paints, lacquers, varnishes, etc.

(Effects of the Invention) According to the present invention, by using a complex in which a specific silicate holds a 'tS quaternary ammonium-perchlorate complex as an antistatic agent, polar While eliminating coloration and deterioration without impairing the transparency of the resin polymer, excellent heat resistance, bleed-out resistance, water resistance, weather resistance, and sustained charging performance were obtained.

Example 1 Quaternary ammonium salt constituting the antistatic agent of the present invention
The method for producing a silicate that retains a perchlorate complex and the resulting composite (antistatic agent) will be described below.

Production method of silicates Samples Ne1A-1 to NoA-6 (calcium silicate salts) Commercially available sodium silicate was poured into sulfuric acid as a silicate raw material, and the pH was maintained at 2 to 5 throughout the pouring period. After the reaction, the silicic acid gel obtained by filtration and water washing and quicklime as a calcium raw material were mixed in a ball mill at a molar ratio of 1:1.0 to 1:1.8 based on CaO:5i02. After a 60-hour wet milling reaction, the reaction product slurry was stirred in a stainless steel container at a temperature of 20 to 70°C, and then dried at 100 to 115°C to the extent that physically adsorbed water was removed. Grind and classify samples NaA-1 to No.
A-6 was prepared, and the physical properties of each of the obtained silicates were measured by the methods shown below, and the results are shown in Table 1.

Note that for samples NoA-2 and A-3, layered silica (activated silicic acid) obtained by acid-treating acid clay, which is a clay mineral, was used as the silica source.

Sample NoA-7 (magnesium silicate salt) The silicic acid raw material is an acidic clay acid-treated product produced in Nakajo-cho, Kitakanbara-gun, Niigata Prefecture, and S
M in an aqueous slurry of activated silicic acid with an iO□ content of 98.5%.
Commercially available magnesium hydroxide with an average particle size of 1.5 pm was added so that the molar ratio of gO:SiO□ was 3=4, and 120
The product obtained by hydrothermal treatment at 130 to 130° C. for 2 hours was similarly dried at 100 to 115° C., then crushed and classified to prepare sample NoA-7, and the results are shown in Table 1.

(1) Using a refractometer to measure the refractive index in advance, measure a solvent with a known refractive index (α-
Bromnaphthalene, kerosene). Then La
According to Rsen's oil immersion method, sample powder Img was taken on a slide glass, one drop of a solvent with a known refractive index was added, a cover glass was placed on the slide, and the movement of the Becke line was observed using an optical microscope. Observe and find out.

When you immerse the powder in a liquid and observe the transmitted light using a polarizing microscope, the boundary between the powder and the liquid appears to shine brightly. This is called the Betzke line (Backs). At this time, when the tube of the microscope is moved up and down, this Becke line moves. When the tube is lowered, the bright line moves inside the particles and the particles appear brighter.
If the bright line moves outwards when the tube is raised and the particles appear darker, this is because the liquid has a higher refractive index than the powder. The opposite phenomenon is observed when the refractive index of the powder is higher. having a refractive index greater than that of a powder when measured with a suitable liquid;
If the smaller one is selected, the refractive index of the powder can be determined as the intermediate value between the refractive indexes of these two types of liquids.

(2) Median diameter The median diameter was measured under the following conditions using a coal tar counter (manufactured by Coal Tar Electronics, Inc., USA) model TA-If. Sample approx. 0. ! +g in a 200ml beaker, add about 150 raI of pure water, and incubate with ultrasonic (UL)
TRASONICCLEANERB-220) from 60
Disperse for 90 seconds.

Add several drops of the above dispersion to 150 ml of electrolytic solution (ISOTON If) using a dropper, and measure the particle size distribution using a coal tar counter. However, the aperture tubes were used differently in the following measurement particle size ranges.

Apatcher tube 50μ measurement particle meter range 1 to 20μ Apatcher tube 100μ measurement particle meter range 2 to 40μ The median diameter was determined by reading the 50% diameter of the cumulative particle size distribution diagram.

(3) Oil absorption measured by JIS 5101 pigment test method. The sample amount is 0.5g.

(4) Constants Magnesium and silica components were quantified, and based on the calcium and magnesium elements, the perilla strength and the molar ratio of water molecules were calculated and used as constants.

Preparation sample No. of quaternary ammonium salt-chlorate complex
B-1 750 mJ of tetrahydrofuran in a 111 Ersinmeyer flask! Lithium perchlorate monohydrate 11.
6 g of the solution was dissolved at room temperature, and then 55 g of dimethyl distearyl ammonium chloride was added, and the mixture was refluxed at 70 t while stirring with a magnetic stirrer until the reaction product became a homogeneous melt.

Tetrahydrofuran was then distilled off under reduced pressure at 60-70°C to produce a clear melt. The product was a cheese-like solid at room temperature.

Sample NoB-2 5 g of sodium perchlorate was added to 100 g of di-2←ethylhexyl phthalate and dissolved under heating at 120°C.

Next, 22 g of trimethyl monostearyl ammonium chloride was added thereto, and the reaction was carried out at a temperature of 90 to 100° C. until the reaction system became homogeneous and transparent.

The obtained reaction product exhibits the same shape as sample NoB-1 at room temperature, and can be said to be a complex similar to sample NoB-1 from its X-ray diffraction diagram and infrared absorption spectrum.

Preparation of antistatic agent) The antistatic agent of the present invention was prepared using the silicate (sample A) and complex (sample B) prepared as described above in the following manner.

Capacity 101 in which a predetermined amount of sample B powder was heated to 100°C
into a stirring transfer mixer, then add a 80 to 90° C. melt of sample B corresponding to 30 to 80% of the oil absorption of sample A under transfer, and then cool to room temperature while transferring;
Powdered antistatic agents of samples N0C-1 to C-8 were obtained.

Comparative Example 1 (Sample NaCH-1) A part of the aqueous slurry obtained as a silicate by the grinding reaction using a ball mill in Sample NoA-2 of Example 1 was placed in a beaker 11 and heated at 95°C for 2 hours with stirring. An antistatic agent was prepared in the same manner as in Example 1 except that the silicate obtained by the treatment was used.

Comparative Example 2 (Sample N0cH-z) An antistatic agent using commercially available aurastonite-type calcium silicate as the silicate.

Comparative Example 3 (Sample NoCH-3) An antistatic agent using 1 ml tobermorite-type calcium silicate prepared by the method described below as a silicate.

Quartz powder with an average particle size of 2 μm and E ash milk prepared in the same manner as that used in Example 1 were placed in a No. 11 autoclave so that the molar ratio was 1 + 1.2 based on CaO:SiO2, and the mixture was heated at 180°C. Hydrothermal treatment was performed for 16 hours, and after the reaction was completed, fine powder silicate was prepared in the same manner as in Example 1. As a result of X-ray diffraction, the obtained silicate was found to be 11A
It was Tobermorite.

Comparative Example 4 (Sample P & ocH-4) Mole ratio of CaO:SiO□ to silicate is 1:2.2
An antistatic agent using calcium silicate obtained in the same manner as Sample NoA-1 of Example 1 except that.

Comparative example 5 (sample NoC)! -5) Antistatic agent using magnesium silicate prepared in the same manner as sample NaA-7 except that commercially available basic magnesium carbonate was used as a magnesium source and hydrothermally treated at 150° C. for 3 hours.

Example 2 The antistatic agent of the present invention obtained in Example 1 was blended with a chlorine-containing polymer composition using a non-lead stabilizer to prepare a polyvinyl chloride sheet with a thickness of 1 mm.

Next, the initial coloring, heat resistance, bleed-out resistance, anti-static property, and transparency were evaluated using the measurement methods shown below, and the results were evaluated. It is shown in the J2 table.

PVC resin sheet (compound) Nippon Vinyl 4000M PVC resin (1”-1
500) 100 parts by weight Mizusawa Chemical Co., Ltd. Stabinex NL-120 (Mg-Zn metal soap) 1.
5 Nitto Kasei TVS #8831 (Butyltin mercaptite) 1.5 Nitto Kasei TVS #8813 (Octyltin malate polymer) 0.5 Plasticizer DOP 50 Sample (antistatic agent) ~2.0 Add the above compounding agent to 3 The mixture was kneaded using a .5-inch roll for 5 minutes at 150°C, and then pressed at 180°C and 160 kg/crn for 5 minutes to form a sheet with a thickness of 1.0 cm.

1 square diagonal (5) Thermal stability The above sample sheet was cut into approximately 3 x 10 pieces and kept under that temperature condition in a gear oven kept at 185°C until the sheet became colored due to thermal deterioration. Thermal stability was indicated at a time of . Moreover, in particular, the retention time up to 15 minutes was evaluated as initial coloring.

(6) Bleed-out resistance The test sheet was kept in an atmosphere of 70° C. and 90% relative temperature for 7 days, and then the bleed-out resistance of the sheet surface was visually evaluated according to the following criteria.

◎No nib bleed out Δ: Slight bleed out A sample sheet of Omm was left in an atmosphere at 25°C and 50% relative temperature for 24 hours, and the volume resistivity [Ωca+] of the sheet was measured in accordance with JIS K 1723 to evaluate antistatic properties.

(8) A brand sheet containing no transparent antistatic agent sample and a test sheet were visually compared and judged based on the following criteria.

Transparency: 20 to ○OO○ Opacity:
%, blended with ethylene vinyl acetate copolymer with a melt index of 150 g/win, 3.5 inch roll, 11
Knead at 0°C for 5 minutes, press at 160°C for 5 minutes,
A sheet with a thickness of 2■■ was prepared, and the results are shown in Table *3.

Table 3

[Brief explanation of drawings]

Figure 1 is an X-ray diffraction diagram, and A, B, CD, and E in the figure are lithium perchlorate, dimethyl distearyl ammonium chloride, lithium chloride, and a synthetic complex (sample N), respectively.
oB-1) and a synthetic complex (sample NoB-2). Mizusawa Chemical Industry Co., Ltd. Ri Patent Attorney Ikuo Suzuki

Claims (4)

[Claims] (1) The quaternary ammonium salt-perchlorate complex has the formula: MO・xSiO_2・nH_2O In the formula, M is a metal element such as calcium or magnesium, x is a number from 1 to 2, and n is from 0.3 to A chemical composition that can be expressed as a number of 1.0, and 50% or more of particles with a secondary particle diameter of 5 μm or less according to the Coulter Counter method, and 1.49
Refractive index of 1.57 and 80-250ml/100g
An antistatic transparent resin polymer composition, characterized in that a composite supported by a silicate having an oil absorption of (2) The polar resin polymer has a specific dielectric constant of 2.3 to 4.5 and a specific volume resistivity of 10^1^3 to 10^1^7 Ωcm. antistatic transparent resin polymer composition. (3) the polar resin polymer is a chlorine-containing polymer,
The antistatic transparent resin polymer composition according to claim 1, characterized in that it is blended with a non-lead stabilizer, a plasticizer and/or a lubricant. (4) The quaternary ammonium salt-perchlorate complex has the formula: MO・xSiO_2・nH_2O In the formula, M is a metal element such as calcium or magnesium, x is a number from 1 to 2, and n is from 0.3 to A chemical composition that can be expressed as a number of 1.0, and 50% or more of particles with a secondary particle diameter of 5 μm or less according to the Coulter Counter method, and 1.49
Refractive index of 1.57 and 80-250ml/100g
1. An antistatic agent comprising a complex supported by a silicate having an oil absorption amount of .