JP6905744B2 - A conductive surface-treated powder filler and a resin composition containing the filler. - Google Patents

Description

The present invention relates to a conductive surface-treated powder filler and a resin composition containing the filler, and more particularly, a composition blended in a resin such as rubber, plastic, film, sealant, adhesive, paint, and plastisol. It forms a conductive path in the object, not only has conductivity and antistatic function, but also enables whiteness or transparency, and has the original dispersibility of powder, compatibility with resin, reinforcing property, and flexibility. The present invention relates to a conductive surface-treated powder filler having a weight-reducing function and the like, and a resin composition containing the filler.

Currently, the spread of communication devices such as mobile phones, personal computers, tablet terminals, and printers is remarkable, and they are used in large quantities all over the world and are recognized as indispensable not only in business but also in daily life. .. The touch panels used in these information terminals are indispensable for the presence of materials and raw materials having a conductive function in order to improve operability. Further, the OA rubber roll used in the printer uses a material having a uniform conductive function in order to smoothly print and transfer the paper feedability without impairing the paper feedability. Metal oxide powders such as indium tin oxide (ITO), indium zinc oxide (IZO), silver powder, and zinc oxide doped with copper powder are used as materials and raw materials for exhibiting these conductive functions. .. For example, it was introduced that indium tin oxide and indium zinc oxide are used for the touch panel sensor used as an input switch integrated with the image display device placed in front of the image display device, and that it exhibits long-term durability. (Patent Document 1).
However, indium oxides such as ITO and IZO are raw materials that have a proven track record of exhibiting stable conductive functions, but since they are natural resources called rare earths, there is concern about resource depletion and whether they can be supplied over the long term. I have a problem. The true specific densities of these materials at 23 ° C. and room temperature are ITO (7.1 g / cm ³ ), IZO (6.3 g / cm ³ ), silver powder (5.0 to 10.5), and copper powder (5.0 to 10.5). Since it is very large (5.9), the specific gravity of the resin composition containing these is also large, and as a result, the hardness is also large, which may hinder the flexibility and impact resistance. In addition, its dispersibility and tensile properties are deteriorated and it is very expensive, so that it is restricted from being used for general purposes.

In addition, lead-based solder and the like have been used as adhesive elements on electronic circuit boards, but conductive adhesives using metal powders such as silver powder and silver plating powder have been reported because the material of the substrate is replaced with resin. (Patent Document 2). However, although the conductive function of these metal powders is similar to that of ITO and IZO, silver powders are also relatively expensive and have a high specific density, so they may settle and separate in an adhesive, and fine metal powders may cause human health when inhaled. There is a problem in handling because it may have an adverse effect on.

Further, a conductive rubber roll sponge is used for the purpose of reducing image defects such as toner transfer unevenness, which can be applied to a thermal transfer roller of an image forming apparatus, and carbon black is used as a conductive powder for imparting conductivity. It is used (Patent Document 3). However, although carbon black has a smaller true specific gravity than the conductive metal compound and is advantageous in terms of raw material cost, the raw material color tone of carbon black is black, so that the color tone of the composition such as transparency and whiteness can be obtained. There is a problem that there are restrictions and uneven conductivity occurs depending on the compounding ratio.

Further, in the conductive rubber composition and the resin composition, conductive zinc oxide has a high degree of whiteness and is introduced as a conductive inorganic powder that can be colored (Patent Document 4). However, although there are no restrictions on the color tone, zinc oxide itself has a large specific gravity of 5.4 and tends to be hard as a resin composition, which hinders the weight reduction of information terminals and the impact resistance of the resin composition. In some cases.

In addition, the following general formula (I) is applied to calcium carbonate and silicate minerals.

(Wherein, R ₁ represents a hydrogen atom or a methyl group, M is an alkali metal, ammonium or amine) is introduced conductive inorganic powder, characterized in that surface-treated with a polymer having a structural unit represented by the (Patent Document 5).
However, these conductive inorganic powders are white and have no limitation on colorability and do not have a large true specific gravity. However, those surface-treated with the above-mentioned polymer have a low conductive level and a resin composition. When set to, long-term conductivity and antistatic effect cannot be obtained.

In addition, a composition containing a modified conductive polymer obtained by chemically treating a conductive polymer selected from polyaniline, polythiophene, and polypyrrole with a radical such as an azo compound in a resin imparts stable conductivity with no variation in resistance value. It has been reported that this is allowed (Patent Document 6). However, while these conductive polymers exhibit a conductive function by adopting a so-called percoration structure that forms a conductive path in a state of being continuously bonded to the resin, they have reinforcing properties such as silica and talc. Since the filler is insulating, there is a problem that if even a small amount of these fillers is blended, the conductive path of the conductive polymer is lost and the conductive performance is sharply lowered. Therefore, in order to increase the reinforcing effect without impairing the conductive function, an insulating filler cannot be blended, and a metal oxide powder having a high specific gravity such as ITO, IZO, silver powder, or copper powder is used, or black is used. Since carbon black is blended, the feature of using a conductive polymer is lost. Alternatively, since the composition is limited to a composition that does not contain a reinforcing filler, the characteristics of the conductive polymer are also limited in this case as well.

Japanese Unexamined Patent Publication No. 2012-118814 Japanese Unexamined Patent Publication No. 2015-189860 Japanese Unexamined Patent Publication No. 2012-155263 Japanese Unexamined Patent Publication No. 2004-83314 Japanese Unexamined Patent Publication No. 6-107963 Japanese Unexamined Patent Publication No. 2006-169291

Inorganic powders such as calcium carbonate, calcium compounds typified by calcium phosphate, titanium compounds typified by titanium oxide, magnesium compounds typified by magnesium hydroxide and silicon compounds typified by silica are rubber, plastics, films, etc. It is most often blended in resins such as sealants, adhesives, paints, and plastics, and has many years of experience as a resin composition that exhibits functions such as dispersibility, whiteness, reinforcing properties, and flexibility, and is widely used. Recently, the proportion of acrylic resin balloons, resin beads such as polymethacrylate-based resins, and organic powders such as vinyl chloride powder used for the purpose of reducing the weight of the resin composition and imparting flexibility has become extremely large. ing.
However, these powders are usually insulating, and in order to combine these powders into a resin composition having a conductive function, black carbon black having a conductive function, indium, etc. There is no choice but to use a large amount of conductive substances such as inorganic metal compounds such as tin, silver, copper, zinc, and antimony. Further, a resin composition containing an inorganic powder such as a calcium compound, a titanium compound, a magnesium compound, or a silicon compound, or a resin bead such as an acrylic resin balloon or a polymethacrylate resin, or an organic powder such as vinyl chloride powder is contained. The percoration structure necessary for forming the conductive path cannot be obtained only by blending the conductive substance in the resin composition, the resin composition does not exhibit sufficient conductivity, and the dispersion function is hindered.

In view of such circumstances, the present invention solves at least one of the above-mentioned problems of the prior art, and the powder is contained in a composition blended in a resin such as rubber, plastic, film, sealant, adhesive, paint, and plastisol. It is possible to take a percoration structure that should form a conductive path by dispersing the body, and it not only has conductivity and antistatic function, but also enables whiteness or transparency, and the dispersibility and resin inherent in powder. It is an object of the present invention to provide a conductive surface-treated powder filler having compatibility with, reinforcing property, flexibility, and weight reduction function, and a resin composition containing the filler.

As a result of diligent studies aimed at solving the above problems, the present inventors have conducted diligent studies on the surface of particles of at least one type of powder (A) selected from white-based inorganic powder and white-based organic powder. In the present invention, it has been found that a surface-treated powder having a coating layer of a surface-treated powder (B) having a surface-treating agent containing a π-conjugated conductive polymer and a polyanion solves at least one of the above problems. It came to be completed.

A feature of the present invention for solving the above problems is π-conjugated conductivity on the surface of particles of at least one powder (A) selected from the group consisting of white inorganic powder and white organic powder. A surface treatment powder having a coating layer of a surface treatment agent (B) containing a polymer and a polyanion, which is a conductive surface treatment powder filler characterized by satisfying the following formulas (1) and (2). be.
(1) Dio ≤ 4.3
(2) 0.12 ≤ As ≤ 8.4 [mg / m ² ]
However,
Dio: True specific gravity of surface-treated powder [g / cm ³ ]
As: Amount of surface treatment agent containing π-conjugated conductive polymer and polyanion per unit specific surface area of surface treatment powder calculated by the following formula
As = Tgx / Sw
Tgx: Amount of surface treatment agent containing π-conjugated conductive polymer and polyanion per 1 g of surface treatment powder [mg / g]
Sw: BET specific surface area of surface-treated powder [m ² / g]
Another feature of the present invention is that the surface treatment powder is an aqueous slurry of at least one powder (A) selected from the group consisting of white inorganic powder and white organic powder, and π-conjugated conductivity. It is a conductive surface treatment powder filler obtained by mixing and stirring a dispersion liquid containing a surface treatment agent (B) composed of a polymer and a polyanion.
Another feature of the present invention is a conductive surface-treated powder filler in which the white inorganic powder is at least one selected from the group consisting of calcium compounds, titanium compounds, magnesium compounds, silicon compounds and aluminum compounds. ..
Yet another feature of the present invention is that the white organic powder is at least one selected from the group consisting of acrylic resin, vinyl chloride resin, polystyrene resin, polyethylene resin, polyimide resin, fluororesin, phenol resin and wood powder. It is a seed conductive surface treatment powder filler.
Yet another feature of the present invention is a conductive surface-treated powder filler in which the π-conjugated conductive polymer is at least one selected from the group consisting of polythiophene, polyaniline, polypyrrole and polyfluorene.
Yet another feature of the present invention is a conductive surface-treated powder filler in which the polythiophene is poly (3,4-ethylenedioxythiophene).
Yet another feature of the present invention is a conductive surface-treated powder filler in which the polyanion is at least one selected from the group consisting of polystyrene sulfonic acid, polyvinyl sulfonic acid and polyacrylamide sulfonic acid.
Yet another feature of the present invention is a conductive surface-treated powder filler volume resistivity of not more than 10 ⁸ Ω · cm.
The features of the method for producing the conductive surface-treated powder of the present invention are an aqueous slurry of at least one powder (A) selected from the group consisting of white inorganic powder and white organic powder, and π. A conductive surface treatment powder characterized by surface-treating the particles of the powder (A) by mixing and stirring a dispersion liquid containing a surface treatment agent (B) composed of a conjugated conductive polymer and a polyanion. This is a method for manufacturing body fillers.
Yet another feature of the present invention is a conductive resin composition containing a conductive surface-treated powder filler.
Yet another feature of the present invention is a conductive rubber composition containing a conductive surface-treated powder filler.
Yet another feature of the present invention is a conductive film composition containing a conductive surface-treated powder filler.
Yet another feature of the present invention is a conductive sealing composition containing a conductive surface-treated powder filler.
Yet another feature of the present invention is a conductive adhesive composition containing a conductive surface-treated powder filler.
Yet another feature of the present invention is a conductive coating composition containing a conductive surface-treated powder filler.
Yet another feature of the present invention is a conductive plastisol composition containing a conductive surface-treated powder filler.

The conductive surface-treated powder filler of the present invention is a percolation in which a conductive path should be formed by dispersing the filler in a composition blended with a resin such as rubber, plastic, film, sealant, adhesive, paint, or plastisol. It can take a structure. Therefore, it is possible to obtain a conductive resin composition other than black, which not only imparts a conductive function but also has excellent colorability and transparency due to its high whiteness, which is a characteristic of the original powder. can. In addition, the dispersibility is superior to other metal powders containing inorganic metal compounds such as indium, tin, silver, copper, zinc, aluminum, and antimony, and the true specific gravity is small, so the amount of addition is increased. Therefore, it is possible to obtain a resin composition having a sufficient conductive effect, a reinforcing function inherent in the powder, a flexible function such as high elongation of the conductive polymer, and a weight reduction function.

The present invention is a surface treatment agent containing a π-conjugated conductive polymer and a polyanion on the surface of particles of at least one powder (A) selected from the group consisting of white inorganic powder and white organic powder. It is a surface-treated powder having a coating layer of (B), and is a conductive surface-treated powder filler characterized by satisfying the following formulas (1) and (2).
(1) Dio ≤ 4.3
(2) 0.12 ≤ As ≤ 8.4 [mg / m ² ]
However,
Dio: True specific gravity of surface-treated powder [g / cm ³ ]
As: Amount of surface treatment agent containing π-conjugated conductive polymer and polyanion per unit specific surface area of surface treatment powder calculated by the following formula
As = Tgx / Sw
Tgx: Amount of surface treatment agent containing π-conjugated conductive polymer and polyanion per 1 g of surface treatment powder [mg / g]
Sw: BET specific surface area of surface-treated powder [m ² / g]

In the present invention, the white color of the white inorganic powder and the white organic powder as the powder (A) refers to the degree of whiteness normally used in the art, and for example, Nippon Denshoku Co., Ltd. In the L value measured by the color meter ZE-200 manufactured by the manufacturer, it is desirable that the powder is 85 or more and the resin composition is 80 or more.

In the present invention, the true specific gravity Dio of the surface-treated powder having the coating layer of the surface-treating agent (B) on the particle surface of the powder (A) needs to be ^{4.3 g / cm 3 or less.} If the true specific density Dio ^{exceeds 4.3 g / cm 3} , for example, when blended with a resin, the weight of the resin composition becomes large and weight reduction cannot be achieved. Therefore, the amount of addition must be suppressed, and as a result, sufficient. It becomes difficult to obtain a resin composition having a high degree of conductivity. In addition, since the hardness is increased, the flexibility and impact resistance are lowered, and the dispersibility is lowered, so that the tensile properties and the like are also lowered.

The difference between the true specific density of the powder (A) and the true specific gravity of the surface-treated powder having the coating layer of the surface treatment agent (B) is a negligible slight difference and is considered to be substantially the same. It doesn't matter. Therefore, in order to obtain a surface-treated powder having a desired true specific gravity, the powder (A) having the true specific gravity may be selected.

^{Calcium carbonate (true specific density 2.7 g / cm 3} ) is mentioned as a white inorganic powder most often used in resin compositions having a true specific density of 4.3 g / cm ^{3 or less.} Calcium carbonate includes natural calcium carbonate (heavy calcium carbonate) and synthetic calcium carbonate. Natural calcium carbonate is produced directly from sugar crystallized limestone, and can be produced, for example, by mechanically crushing and classifying rough sugar crystallized limestone. Synthetic calcium carbonate is produced by firing calcium oxide in a calcining furnace such as kiln using dense limestone and digesting it with water to make calcium hydroxide. For example, calcium hydroxide is carbonated. It can be produced by reacting with gas. Generally, a product synthesized using dense limestone is a cubic colloidal calcium carbonate, and calcite crystals having a relatively uniform particle shape can be obtained. Further, when the temperature condition of calcium hydroxide is changed, additives such as a magnesium compound, a strontium compound, and a phosphorus compound are added, and this calcium hydroxide is reacted with carbon dioxide gas, aragonite crystals can be obtained from needle-shaped calcium carbonate.

Calcium carbonate can exhibit a conductive function in both natural calcium carbonate and synthetic calcium carbonate. However, in order to stably exert the function of the conductive surface-treated powder filler of the present invention, the powder surface is surface-treated with a surface treatment agent containing a π-conjugated conductive polymer and a polyanion in the resin composition. Synthetic calcium carbonate is more preferable because it is easy to have a structure (percoration structure) in which powders are connected to each other to form a conductive path. Regarding the size of the powder, in the case of colloidal calcium carbonate, the BET specific surface area is preferably ³ to 100 m 2 / g. When the BET specific surface area Sw is ^{less than 3 m 2} / g, the conductive function can be obtained, but the thickening effect and the reinforcing effect of colloidal calcium carbonate tend not to be sufficiently obtained. Further, when the BET specific surface area Sw ^{exceeds 100 m 2} / g, the primary particles tend to aggregate with each other, resulting in poor dispersion in the resin and the inability to fully exhibit the conductive function.

In addition, as another synthetic calcium carbonate, there is aragonite calcium carbonate (true specific density 2.9 g / cm ³ ). The size of the particles is preferably an aragonite acicular crystal having a major axis of about 0.1 to 50 μm, a minor axis of about 0.01 to 5 μm, and an aspect ratio of about 3 to 50. Compared to cubic particles of calcium carbonate, needle-shaped particles tend to have a structure (percolation structure) in which particles are connected to form a conductive path. In terms of BET specific surface area, it is preferably ^{2 to 30 m 2 / g.} When the BET specific surface area Sw is ^{less than 2 m 2} / g, the conductive function can be obtained, but the viscosity increasing and the reinforcing property tend not to be obtained. It also tends to lose the dispersive function that is characteristic of acicular calcium carbonate. Further, when the BET specific surface area Sw ^{exceeds 30 m 2} / g, acicular crystals are aggregated and adsorbed, and the surface treatment agent for imparting conductivity cannot be sufficiently coated to sufficiently perform the conductive function. It tends to be impossible to exert.

Further, as a white inorganic powder of another calcium compound, calcium phosphate (true specific density 3.1 g / cm ³ ) can be mentioned. Calcium phosphate is synthesized by a method called a wet method, a hydrothermal method, and a dry method, and in the case of industrially producing the largest amount, the wet method is used. There are a precipitation method in which phosphoric acid is dropped onto a calcium hydroxide slurry at room temperature to synthesize it, and a hydrolysis method in which calcium hydrogen phosphate dihydrate is reacted with calcium carbonate. It may be calcium phosphate. Further, the obtained calcium phosphate _{may contain hydroxyapatite (Ca 10} (PO ₄ ) ₆ (OH) ₂ ), but the content is preferably less than 10%. Regarding the particle size, the BET specific surface area is 5. when it is preferable .BET specific surface area Sw is less than 5m ² / g ~80m is ² / g, sufficient thixotropy of those conductive features can be obtained, it may be difficult to impart reinforcing properties In addition, when the BET specific surface area Sw ^{exceeds 80 m 2} / g, the amount of surface treatment agent required to coat the surface increases and the strength of the resin composition increases. In some cases, the primary particles may be too low, and the primary particles may aggregate to cause poor dispersion in the resin, making it impossible to exhibit the conductive function.

In addition, there is a silicon compound as another white inorganic powder, and among them, silica (true specific density 1.6 g / cm ³ ) can be mentioned. In particular, the reaction of sodium silicate and sulfuric acid, or the reaction of sodium silicate with salts such as magnesium chloride to generate silicate, and further decomposition with sulfuric acid or carbon dioxide gas to synthesize wet synthetic silica, or vaporization. A dry synthetic silica obtained by burning a mixture of silicon tetrachloride and hydrogen in air at 1600 to 2000 ° C. is preferable. Regarding the particle size, it has become possible to design higher fine particles due to the progress of the above-mentioned manufacturing technology, but it is preferable that the ^{BET specific surface area is 40 to 300 m 2 / g.} If the BET specific surface area Sw is ^{less than 40 m 2} / g, it may be difficult to impart sufficient thixotropy, although the conductive function can be obtained, and the working efficiency of the resin composition may be lowered. Further, when the BET specific surface area Sw ^{exceeds 300 m 2} / g, the amount of the surface treatment agent required for coating the surface may increase and the strength of the resin composition may become too low. Further, the primary particles may aggregate with each other, resulting in poor dispersion in the resin, and the conductive function may not be sufficiently exhibited.

On the other hand, if the surface can be treated with a surface treatment agent containing a π-conjugated conductive polymer and a polyanion, it can be applied to an organic powder. Acrylic resin balloons (true specific density 0.1 to 0.3 g / cm ³ ) can be mentioned as a white organic powder that has a true specific gravity of 4.3 g / cm ^{3 or less and is often used in resin compositions.} By heating microcapsules in which liquid low boiling point hydrocarbons are wrapped in a thermoplastic polymer shell (shell), the polymer shell softens and the liquid hydrocarbons inside change to gas, so the capsules are made under that pressure. Is produced by obtaining expanded particles. Applying this property, heat-expandable microcapsules have been used in various fields in recent years for the purpose of reducing the weight and imparting flexibility of various resin compositions.
The core resin is fine particles of resin such as acrylonitrile resin and polymethyl methacrylate resin, and includes crosslinked type and non-crosslinked type. As for the particle size, the BET specific surface area Sw is preferably ¹ to 10 m 2 / g. If the BET specific surface area Sw is ^{less than 1 m 2} / g, it cannot be measured by the BET specific surface area meter, and it becomes difficult to adjust the amount of the surface treatment agent, and it becomes difficult to obtain the conductive function. Further, if the BET specific surface area Sw ^{exceeds 10 m 2} / g, it becomes difficult to manufacture the resin balloon, and secondary aggregation may occur to cause uneven conductivity.

The white inorganic powder and the white organic powder having a true specific density of 4.3 g / cm ³ or less are not limited to those described above. Other white inorganic powders include magnesium hydroxide (true specific gravity 2.4), magnesium carbonate (about 2.9), basic magnesium carbonate (about 2.9), and talc (2.7) as magnesium compounds. ), As silicic acid compounds, quartz powder (2.2), siliceous stone powder (3.2), fine powder silicic acid (1.2), fine powder calcium silicate (2.9), sericite (2.7), mica (2.8-3.2), bentonite (2.6), neferin cynicite (2.6), sepiolite (2.3), wallastnite (2.9), zonotolite (3.0), titanium Potassium acid (3.3 to 3.6), glass fiber (2.1 to 2.6), silas balloon (0.2 to 1.5), fly ash barrun (0.7), glass balloon (0. 2), silica beads, glass beads (2.5) as aluminum compounds, finely divided aluminum silicate (2.6), kaolin clay (2.6), talc (2.7) aluminum hydroxide (2.4), alumina beads (3.6), examples of the titanium compound include titanium oxide (3.8 to 4.3) and potassium titanate (3.3 to 3.4). ^{The unit g / cm 3} is omitted for the true specific gravity in parentheses.

Other white organic powders include phenolic resins (true specific gravity 1.2-2.1) such as bisphenol A, bisphenol F, bisphenol M, bisxinol P, bisphenylhydroxyphenylmethane, polytetrafluoroethylene, and polyfluoride. Fluororesin such as vinylidene, polychlorotrifluoroethylene, polyvinyl chloride, perfluoroalkoxyfluorine (1.6 to 2.2), polystyrene resin (1.1), low density polyethylene, high density polyethylene, polyethylene such as polyethylene terephthalate Resin (0.99 to 1.05), vinyl chloride resin (1.0 to 1.4) such as polyvinyl chloride and polyvinylidene chloride, aromatic polyimide and pyromellitic acid anhydride and 4,4'-diaminodiphenyl ether. Polyimide resin (1.42) such as a polymer with, cellulose powder (1.3 to 1.6), pulp powder (1.1 to 1.6), wood powder (1.0 or less) as a wood-based material. , Walnut powder (1.0 or less), cork powder (1.0 or less), starch (1.6), ebonyite powder (1.2), lignin (1.3 to 1.6) and the like. ^{The unit g / cm 3} is omitted for the true specific gravity in parentheses.

The BET specific surface area Sw is a value measured by the BET method based on the nitrogen adsorption method of surface-treated calcium carbonate, and is measured by the following method.
[Sample preparation method]
A 300 mg sample is charged in a glass cell, pretreated at 200 ° C. for 10 minutes while conducting nitrogen, and then cooled at room temperature to prepare a measurement sample.
[Measurement method of BET specific surface area]
Measured by the one-point method with a BET specific surface area meter (Macsorb HMmodel-1210, manufactured by Mountech).

The specific gravity of the powder is indicated by the true specific gravity or the bulk specific gravity, and the true specific gravity defined here is the weight per volume of the solid itself excluding the surface pores and internal voids. In the case of natural resource materials, the numerical values introduced in the Chemical Handbook may be used as a guide, but the measured value of particle density by the gas volume method is defined as the true specific gravity.
[Measurement method of particle density (true specific gravity) by gas volumetric method]
The powder weighed with an electronic balance is set in a dry automatic densitometer (Accupic II 1340 10CC manufactured by Shimadzu Corporation), and the volume of the powder is measured using helium gas in accordance with JIS M 8717. The true specific gravity value is defined as the weighing value ÷ the volume value of the powder.

On the surface of the particles of at least one powder (A) selected from the group consisting of the white inorganic powder and the white organic powder, a surface treatment agent containing a π-conjugated conductive polymer and a polyanion is applied to the surface. It is treated (surface-coated) to obtain a conductive surface-treated powder filler having a coating layer of the surface-treating agent (B) on the surface of the particles of the powder (A). There are two types of surface treatment: a dry method in which the surface treatment is performed in the powder state, and a wet treatment in which the surface treatment is performed in the form of an aqueous slurry or in a phthalic acid-based, alcohol-based, naphthenic, or aromatic organic solvent. , Any surface treatment method may be used. Since the surface treatment agent containing the π-conjugated conductive polymer and the polyanion is preferably used as a dispersion liquid, preferably an aqueous dispersion liquid, the powder has a surface in a water-soluble state such as an aqueous slurry or an alcohol-based organic solvent. The wet method of performing the treatment is preferable, and there is an effect of imparting a more conductive function. In the case of the dry method, the treatment equipment includes a method in which the powder is fluidly stirred with a Henshell mixer or the like and a surface treatment agent containing a π-conjugated conductive polymer and a polyanion is added while applying heat. In the case of, a method of performing surface treatment by mixing and stirring using a tank equipped with a stirring device for flowing the slurry can be mentioned.
The conductive surface-treated powder filler of the present invention is a π-conjugated system on the surface of at least one type of powder surface (A) particles selected from the group consisting of these white inorganic powders and white organic powders. A conductive surface treatment powder that is surface-treated (surface-coated) with a surface treatment agent (B) containing a conductive polymer and a polyanion, and has a coating layer of the surface treatment agent (B) on the surface of the particles of the powder (A). The body. Further, the conductive surface-treated powder filler of the present invention comprises two or more types of inorganic powder surfaces, two or more types of organic powder surfaces, or particles of each powder in which inorganic powder and organic powder coexist. The surface is surface-treated (surface-coated) with a surface treatment agent (B) containing a π-conjugated conductive polymer and a polyanion, and the surface treatment agent (B) is applied to the surface of two or more kinds of powder (A) particles. It may be a conductive surface-treated powder having a coating layer of.

The π-conjugated conductive polymer refers to an organic polymer whose main chain is composed of a π-conjugated system, for example, polythiophene, polypyrrole, polyacetylene, polyphenylene, polyphenylene vinylene, polyaniline, polythiophene vinylene, polyfluorene, and their co-weights. Coalescence etc. can be mentioned. These may be used alone or in combination of two or more as required. Of these, polythiophene, polypyrrole, polyaniline, and polyfluorene are preferable because of their conductive stability. Further, polythiophene is preferable from the viewpoint of ease of surface treatment and whiteness after surface treatment.

Examples of polythiophene include poly (3,4-ethylenedioxythiophene), poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), and poly (3-butylthiophene). 3-hexylthiophene), poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3-octylthiophene) Bromothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene), poly (3,4-dibutylthiophene) 3-methoxythiophene), poly (3-ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxythiophene), poly (3-octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3-octadecylthiophene), poly (3,4-dihydrooxythiophene), poly (3,4-dimethoxythiophene), poly (3, 4-diethoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxythiophene), poly (3,4-diheptyloxythiophene), poly (3,4-dioctyloxythiophene) ), Poly (3,4-didecyloxythiophene), Poly (3,4-didodecyloxythiophene), Poly (3,4-propylene dioxythiophene), Poly (3,4-butendioxythiophene), Poly (3-methyl-4-methoxythiophene), poly (3-methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethyl) Thiophene), poly (3-methyl-4-carboxybutylthiophene) can be mentioned. These may be used alone or in combination of two or more as required.
Of these, poly (3,4-ethylenedioxythiophene) is most preferable in terms of conductive function, heat resistance, whiteness, and transparency.

Examples of polypyrrole include poly (N) methylpyrrole, poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-propylpyrrole), poly (3-butylpyrrole), and poly (3-octylpyrrole). , Poly (3-decylpyrrole), Poly (3-dodecylpyrrole), Poly (3-carboxypyrrole), Poly (3,4-dimethylpyrrole), Poly (3,4-dibutylpyrrole), Poly (3-Methylpyro) 4-carboxypyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-methyl-4-hexyl) Oxypyrrole) can be mentioned. These may be used alone or in combination of two or more as required.

Examples of polyaniline include poly (2-methylaniline), poly (2-ethylaniline), and poly (3-isobutylaniline). These may be used alone or in combination of two or more as required.

Examples of polyfluorene include poly [9,9-di- (2-ethylhexyl) -9-fluorene-2,7-vinylene] and poly [9,9-bis- (2-ethylhexyl) -9-fluorene-2, 7-diyl], poly [9,9-di (3', 7'-dimethyloctyl) fluorene-2,7-ylene ethynylene], poly [9,9-di (2'-ethylhexyl) fluorene-2,7- Irene ethynylene], poly [9,9-dihexyl-2,7-fluorene-alt-9-phenyl3,6-carbazole] and the like. These may be used alone or in combination of two or more as required.

Even if the particle surface of the white inorganic powder or the white organic powder is surface-treated only with the above-mentioned π-conjugated conductive polymer, the particle surface of the white inorganic powder or the white organic powder is insufficient. It becomes a processed state, and the conductive function tends to vary. Therefore, in order to contain a polyanion and function as a dopant agent for a π-conjugated conductive polymer, it is important to prepare a dispersion liquid in order to perform surface treatment and to improve the conductive function.

Polyanions include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyacrylamide sulfonic acid, polymethacrylsulfonic acid, polyisoprenesulfonic acid, polysulfoethylmethacrylate, polymetallicyloxybenzenesulfonic acid, polyvinylcarboxylic acid, polystyrenecarboxylic acid, and polyallylcarboxylic acid. Acids and the like can be mentioned. These may be a single polymer or two or more kinds of copolymers, but the polyanion containing a sulfonic acid group improves the surface treatment and the conductive function. Most preferable to.
In the present invention, as described above, the dispersion liquid containing the π-conjugated conductive polymer and the polyanion exerts the most conductive function, but the ratio of the amount of the polyanion to the total weight of the conductive polymer and the polyanion is usually set. It is 30 to 95% by weight.

The feature of the conductive surface treatment powder filler of the present invention is that the surface is treated with a surface treatment agent containing a π-conjugated conductive polymer and a polyanion, but calcium carbonate is within a range that does not impair the conductive function. The surface treatment may be performed in combination with a general surface treatment agent used for the surface treatment of other powders. Examples of general surface treatment agents include saturated fatty acids, unsaturated fatty acids, alicyclic carboxylic acids, resin acids and the like, and examples of these derivatives include sodium salts, potassium salts, ammonium salts and amine salts.

As the saturated fatty acid, a saturated fatty acid having 6 to 31 carbon atoms is preferable, the number of carbon atoms is 8 to 26, and the number of carbon atoms is 9 to 21. Specific examples of saturated fatty acids include butyric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, alignic acid, behenic acid, lignoceric acid, cerotic acid, and montane. Examples include acid and melissic acid. Among these, it is preferable to use palmitic acid, stearic acid and lauric acid in combination.

Unsaturated fatty acids are fatty acids that have a double bond in the molecule and are synthesized, for example, by the dehydration reaction of saturated fatty acids. As the unsaturated fatty acid, an unsaturated fatty acid having 6 to 31 carbon atoms is preferable, an unsaturated fatty acid having 8 to 26 carbon atoms is more preferable, and an unsaturated fatty acid having 9 to 21 carbon atoms is more preferable. Specific examples of unsaturated fatty acids include obscilic acid, carrolleic acid, undecylene acid, lindelic acid, tsuzuic acid, fizeteric acid, moristrenic acid, palmitreic acid, petroceric acid, oleic acid, ellaic acid, asclebic acid, and buxene. Examples thereof include acids, gadrainic acids, gondonic acids, setreic acids, erucic acids, brushzic acids, serachorene acids, ximenic acids, lumecic acids, sorbic acids and linoleic acids. Among these, oleic acid, erucic acid and linoleic acid are preferable.

Further, a fatty acid derived from an animal raw material such as beef tallow or lard, or a fatty acid derived from a plant raw material such as palm or palm, which is a mixture of these, may be used as long as the conductive function is not impaired.
Further, to the extent that it does not interfere with the present invention, alicyclic carboxylic acid typified by naphthenic acid, abietic acid, pimaric acid, palastolic acid, resin acid typified by neoavietic acid, and their disproportionate rosin and water. A modified rosin typified by a rosin, a dimer rosin, a trimeric rosin, and a sulfonic acid typified by alkylbenzene sulfonic acid may be used.
The acid and its salt, which are the above-mentioned general surface treatment agents, are used alone or in combination of two or more, if necessary.

Further, in the present invention, the amount As of the surface treatment agent per unit specific surface area of the conductive surface treatment powder filler having the coating layer of the surface treatment agent (B) containing the π-conjugated conductive polymer and the polyanion is 0. It is 12 to 8.4 mg / m ² . If the amount of the surface treatment agent As is ^{less than 0.12 mg / m 2} , there is a possibility that an untreated surface may be present, the conductive function may be impaired, and the dispersibility may be hindered. Further, when the amount of the surface treatment agent As ^{exceeds 8.4 mg / m 2} , the amount of the surface treatment agent becomes excessive, and although the conductive effect can be obtained, the economic burden becomes large and the dispersibility is hindered. Or, the whiteness may be reduced. The preferable range of the surface treatment agent amount As is 0.24 to 3.6 mg / m ² , and a more preferable range is 0.36 to 2.4 mg / m ² .

When the powder is surface-treated with a surface treatment agent containing a π-conjugated conductive polymer and a polyanion per unit specific surface area, a surface treatment containing the π-conjugated conductive polymer and a polyanion per 1 g of the surface-treated powder. It is determined by the dosage As [mg / m ² ] = Tgx / Sw.
Tgx: Amount of surface treatment agent containing π-conjugated conductive polymer and polyanion per 1 g of surface treatment powder [mg / g]
Sw: BET specific surface area of surface-treated powder [m ² / g].
The Tgx is determined by the heat loss [mg / g] per 1 g of the surface-treated powder at 200 ° C. to 500 ° C.
[Measurement method of heat loss]
Using a thermal analyzer (ThermoPlusEVOII, manufactured by Rigaku), 30 mg of surface-treated inorganic powder was collected in a sample pan (made of platinum) with a diameter of 5 mm and a depth of 5 mm, and the temperature was raised from room temperature to 510 ° C at a temperature rise rate of 15 ° C / min. The heat loss at 200 ° C. to 500 ° C. when the temperature is raised is measured, and the heat loss (mg / g) per 1 g of the surface-treated powder is determined.
When the organic powder is surface-treated with a surface treatment agent containing a π-conjugated conductive polymer and a polyanion, the ratio cannot be determined by the method for measuring heat loss. Therefore, the inorganic powder surface-treated with the same amount of the above-mentioned surface treatment agent. The heat loss of the body was defined as the amount of the surface treatment agent for the organic powder. Further, when used in combination with a surface treatment agent such as fatty acid, fatty acid derivative, resin acid, resin acid derivative, sulfonic acid, etc., as long as the conductive function is not impaired, the surface treatment agent containing a π-conjugated conductive polymer and a polyanion. A conductive powder that was surface-treated independently was prepared separately, and the combined use ratio was calculated based on the difference in heat loss.

The conductive surface-treated powder filler of the present invention is blended with rubber or resin to form various conductive rubber or resin compositions.
The conductive rubber composition of the present invention uses rubber materials such as ethylene propylene diene rubber (EPDM), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), and epichlorohydrin rubber (CO, ECO, GECO). You can give things. Of these, acrylonitrile butadiene rubber and epichlorohydrin rubber used for conductive rubber rollers can obtain stable conductivity as rubber components, but colloidal calcium carbonate blended for the purpose of adjusting the hardness of the composition is insulating. Therefore, the conductivity tends to decrease, and printing unevenness due to pressure sensitivity may occur. By blending the π-conjugated conductive polymer of the present invention and the conductive surface-treated powder filler surface-treated with a surface-treating agent containing a polyanion, the hardness of the composition is low and the composition is more stable while maintaining flexibility. It becomes a rubber composition which can obtain the said conductivity. In addition, the conductive rubber composition includes, if necessary, processing aids such as zinc stearate, vulcanization accelerators such as zinc oxide, vulcanization accelerators such as thiazole and thiuram, process oils, polyesters, etc. A plasticizer such as phthalic acid, a diluent, and a filler such as carbon black can be added. Further, if an ionic conductive agent that imparts conductivity such as sodium perchlorate, lithium perchlorate, stearyltrimethylammonium chloride, modified aliphatic dimethylethylammonium etosulfate, and stearyltetraethylammonium is blended, the conductivity is further improved. The conductive rubber composition obtained can be obtained.

The conductive film composition of the present invention includes general-purpose resins typified by acrylic resin (PMMA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polybutadiene (PBD), polyethylene terephthalate (PET), and polyacetal. (POM), polyamide (PA), polycarbonate (PC), modified polyphenylene ether (PPE), polybutylene terephthalate (PBT), ultrahigh molecular weight polyethylene (UHPE), polysulfone (PSF), polyether sulfone (PES), polyphenylene. Engineering plastics such as sulfide (PPS), polyarylate (PAR), polyetheretherketone (PEEK), polyimide (PI), polyetherimide (PEI), fluororesin (FR), liquid crystal polymer (LCP), phenol, Urea, melamine, alkyd, unsaturated polyester, epoxy, polyesteramide, polyether ester, polyvinyl chloride, and resins which are copolymers containing these as main components are used. General inorganic powders and organic powders are blended with these resins to improve dispersibility, film reinforcing effect, and reflectance. By blending the conductive surface-treated powder filler of the present invention, these resins are blended. A film composition that not only maintains dispersibility, reinforcing effect of film, and reflectance, but also has higher conductivity, more stable conductivity, and flexibility is obtained. The conductive film composition is usually blended with pigments, antioxidants, antistatic agents, plasticizers, etc. to improve the processability, flexibility, durability, and heat resistance of the film. By blending the conductive surface-treated powder filler of the present invention, these functional effects can be further enhanced.

The conductive sealant composition and adhesive composition of the present invention include silicone, modified silicone, acrylic silicone, silicone modified epoxy, silylated urethane, polyisobutylene, cyanoacrylate and the like at the ends of silanol groups or reactive silyl groups. Resins having a crosslinkable silicon group, polyurethane resins, polysulfide resins, acrylic resins, epoxy resins and the like are used. In particular, a resin having a crosslinkable silicon group is used as an alternative material for soldering a printed substrate by blending a metal powder such as silver powder or copper powder to exert a conductive function. By blending the conductive surface-treated powder filler of the present invention, it is possible to impart flexibility as compared with the composition containing silver powder and copper powder, and it is more stable without blending silver powder and copper powder. It can exert its conductive function. Further, in these resin compositions, silicone oil, plasticizers such as phthalic acid, and high boiling point solvents such as isoparaffin and naphthene are used, and the conductive surface treatment powder filler of the present invention is blended. As a result, the amount of the plasticizer and the amount of the high boiling point solvent can be reduced, and the bleeding of the liquid component can be suppressed, so that a more stable conductive effect can be obtained. Further, in the conductive sealant composition and the adhesive composition, pigments, ultraviolet absorbers, antioxidants, catalysts and the like are usually used as sealants, adhesive processability, flexibility, reaction speed, durability and heat resistance. However, by blending the conductive surface treatment powder filler of the present invention, these conductive sealant compositions and adhesive compositions are lightweight and adhere without increasing the specific gravity. The strength can also be improved.

As the conductive coating composition of the present invention, acrylic resin, polyester resin, epoxy resin, polyamide resin, polyethylene resin, polypropylene resin, acrylic silicone resin, acrylic urethane resin, polyurethane resin and the like are used. Further, these paint resin compositions include silicone oil, phthalic acid-based plasticizers, isoparaffin-based and naphthen-based high-boiling solvents, methanol, ethanol, acetone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide and the like. An organic solvent alone or a mixture, and water can be used. By blending the surface-treated conductive surface-treated powder filler of the present invention with these resin compositions for paints, the strength of the coating film can be improved and stable conductivity can be imparted.

As the conductive plastisol composition of the present invention, an acrylic resin, a vinyl chloride resin, a polyester resin, a polyurethane resin and the like are used. Among them, vinyl chloride resin is used as a main resin for plastisols such as undercoats and body sealers for automobiles. In addition, usually, these are filled with quicklime, talc, clay, mica, wet silica, dry silica, colloidal calcium carbonate, heavy calcium carbonate, glass balloon, acrylic resin balloon, diatomaceous earth and other fillers, and phthalic acid-based plasticizers. , Isoparaffin-based, naphthen-based and other high-boiling solvents are used as additives. These plastisol compositions do not have a conductive function and are insulating. However, by blending the conductive surface-treated powder filler of the present invention, the adhesiveness to the electrodeposition plate of an automobile is improved and the slip resistance is improved. Can be significantly improved and the antistatic effect required for automobile applications can be imparted.

Examples and comparative examples are shown below, and the present invention will be described in more detail, but these are not intended to limit the present invention.
In the following description, regarding various characteristics and physical properties, in addition to the measured values, four-step judgment results by ◎, ○, △, and × are shown for reference, but these are relative to the point of getting tired. It is only a guideline and is not bound by these.

The whiteness and volume resistivity of the conductive surface-treated powder filler were measured according to the following methods.
[Whiteness]
10 g of the filler was weighed in a 100 ml poly cup, and 10 g of the plasticizer DINP (diisononyl phthalate) was weighed, and this was stirred with a planetary defoaming stirrer manufactured by Kurabou Co., Ltd. for 60 seconds. The obtained powder paste was measured with an L value indicating whiteness with a color meter ZE-2000 manufactured by Nippon Denshoku Co., Ltd.
(Criteria for whiteness)
⊚; 95 or more ○; 90 or more to less than 95 Δ; 85 or more to less than 90 ×; less than 85

[Volume resistivity]
The powder was molded by applying a pressure of 100 MPa (1020 kgf / cm ² ) with a hand press to prepare a powder molded product having a diameter of 10 mm. The volume resistivity of the obtained molded product was measured with an impedance / gain phase analyzer 4194A manufactured by Hewlett-Packard Company.
(Criteria for volume resistivity)
◎; 1 × 10 ³ Ω ・ cm or more to ^{less than 1 × 10 5} Ω ・ cm ○; 1 × 10 ⁵ Ω ・ cm or more to 1 × 10 ⁷ Ω ・ cm or less △; 1 × 10 ⁷ Ω ・ cm or more to 1 × 10 ⁸ Ω ・ cm or less ×; 1 × 10 ⁸ Ω ・ cm or more

[Preparation of conductive surface-treated powder filler]
Example 1
2800 g of a 7 wt% concentration colloidal calcium carbonate aqueous slurry adjusted to a BET specific surface area of 7 m ² / g by reacting calcium hydroxide with carbon dioxide was put into a 10 L tank, and poly (3,4-ethylenedioxythiophene) 0. 200 g of a dispersion (manufactured by Sigma Aldrich) prepared at a mixing ratio of 5 wt% and 0.7 wt% polystyrene sulfonic acid, that is, 2.4 g of a solid conductive material component was added and stirred by a motor with metal blades for 30 minutes. The obtained surface-treated colloidal calcium carbonate slurry is dehydrated, dried at 105 ° C. for 4 hours, and pulverized to have a true specific gravity of 2.6, a BET specific surface area of 6.8 ^{m 2} / g, and a treatment amount of 12.00 mg / g. A colloidal calcium carbonate filler was prepared.

Example 2
2800 g of 7 wt% calcium carbonate water slurry adjusted to a BET specific surface area of 7 m ² / g was put into a 10 L tank, and 0.5 wt% of poly (3,4-ethylenedioxythiophene) and 0.7 wt% of polystyrene sulfonic acid were added. 200 g of a dispersion liquid (manufactured by Sigma Aldrich Co., Ltd.), that is, 2.4 g of a conductive material component, was added and stirred by a motor with metal blades for 30 minutes. The obtained surface-treated aragonite calcium carbonate slurry is dehydrated, dried at 105 ° C. for 4 hours, and pulverized to have a true specific density of 2.8, a BET specific surface area of 6.8 ^{m 2} / g, and a treatment amount of 12.00 mg / g. An aragonite calcium carbonate filler was prepared.

Example 3
All except changing the dispersion prepared in Example 1 at a mixing ratio of 0.5 wt% of poly (3,4-ethylenedioxythiophene) and 0.7 wt% of polystyrene sulfonic acid to 15 g (0.18 g of the same solid). A conductive colloidal calcium carbonate filler having a true specific density of 2.6, a BET specific surface area of 6.9 ^{m 2} / g, and a treatment amount of 0.90 mg / g was prepared in the same manner as in Example 1.

Example 4
In the colloidal calcium carbonate of Example 1, 35.1 g of a dispersion prepared by mixing 0.5 wt% of poly (3,4-ethylenedioxythiophene) and 0.7 wt% of polystyrene sulfonic acid was prepared, that is, the conductive material component was 0. A conductive colloidal calcium carbonate filler having a true specific gravity of 2.6, a BET specific surface area of 6.9 ^{m 2} / g, and a treatment amount of 2.14 mg / g was prepared in the same manner as in Example 1 except that the amount was changed to 421 g.

Example 5
All except changing the dispersion prepared in Example 1 at a mixing ratio of 0.5 wt% of poly (3,4-ethylenedioxythiophene) and 0.7 wt% of polystyrene sulfonic acid to 334 g, that is, 4.0 g of the conductive material component. A conductive colloidal calcium carbonate filler having a true specific gravity of 2.6, a BET specific surface area of 6.8 ^{m 2} / g, and a treatment amount of 20.40 mg / g was prepared in the same manner as in Example 1.

Example 6
All except changing the dispersion prepared in Example 1 at a mixing ratio of 0.5 wt% of poly (3,4-ethylenedioxythiophene) and 0.7 wt% of polystyrene sulfonic acid to 884 g, that is, 10.6 g of the conductive material component. A conductive colloidal calcium carbonate filler having a true specific gravity of 2.6, a BET specific surface area of 6.5 m ² / g, and a treatment amount of 54.00 mg / g was prepared in the same manner as in Example 1.

Example 7
In the colloidal calcium carbonate of Example 1, all the dispersions (manufactured by Sigma Aldrich) prepared to 0.5 wt% of polypyrrole-block-poly (caprolactam) were changed to 480 g, that is, 2.4 g of the conductive material component. A conductive colloidal calcium carbonate filler having a true specific density of 2.6, a BET specific surface area of 6.8 ^{m 2} / g, and a treatment amount of 12.00 mg / g was prepared in the same manner as in the above.

Example 8
A dispersion prepared in 1.2 wt% of poly [9,9-bis- (2-ethylhexyl) -9H fluorene-2,7-diyl] in the colloidal calcium carbonate of Example 1 (THF solvent, manufactured by Sigma Ordrich). Is 200 g, that is, a conductive colloid having a true specific gravity of 2.6, a BET specific surface area of 6.8 ^{m 2} / g, and a treatment amount of 12.00 mg / g in the same manner as in Example 1 except that the conductive material component is changed to 2.4 g. A calcium carbonate filler was prepared.

Example 9
In Example 1, colloidal calcium carbonate was changed to 2000 g of talc powder (Nanotalc FG-15 manufactured by Nippon Tarku Co., Ltd.) adjusted to a ^{BET specific surface area of 18 m 2 / g, and poly (3,4-ethylenedioxythiophene) 0.} .The dispersion prepared at a mixing ratio of 5 wt% and 0.7 wt% polystyrene sulfonic acid was added to 5000 g, that is, 60 g of the conductive material component, and the 10 L mixer was changed to a Henschel mixer and stirred at 110 ° C. for 60 minutes to perform a dry treatment. rice field. Then, it was transferred to a metal bucket and dried at 110 ° C. for 4 hours. The obtained powder was pulverized to prepare a conductive talc filler having a true specific density of 2.6, a BET specific surface area of 17.8 m ² / g, and a treatment amount of 30.00 mg / g.

Example 10
In Example 1, the colloidal calcium carbonate was changed to 2000 g of titanium oxide powder (TITONE A-110 manufactured by Sakai Chemical Industry Co., Ltd.) having a BET specific surface area of 10 m ^{2 / g, and poly (3,4-ethylenedioxythiophene) was used.} ) The dispersion prepared at a mixing ratio of 0.5 wt% and 0.7 wt% polystyrene sulfonic acid was added to 2860 g, that is, 34.3 g of the conductive material component, and the 10 L mixer was changed to a Henschel mixer and stirred at 110 ° C. for 60 minutes. Dry treatment was performed. Then, it was transferred to a metal bucket and dried at 110 ° C. for 4 hours. The obtained powder was pulverized to prepare a conductive titanium oxide filler having a true specific density of 3.9, a BET specific surface area of 9.8 m ² / g, and a treatment amount of 17.00 mg.

Example 11
In Example 1, the colloidal calcium carbonate was changed to 200 g of an acrylonitrile resin balloon (Microsphere FN-80SDE manufactured by Matsumoto Yushi Seiyaku Kogyo Co., Ltd.) adjusted to a ^{BET specific surface area of 3 m 2 / g, and poly (3,4-ethylene).} The dispersion prepared at a mixing ratio of 0.5 wt% of dioxythiophene) and 0.7 wt% of polystyrene sulfonic acid was added to 86 g, that is, 1.03 g of the conductive material component, and the 10 L mixer was changed to a Henschel mixer for 30 minutes at 110 ° C. The mixture was stirred, dried, and dried. The obtained powder was not pulverized, and a conductive acrylic resin balloon filler having a true specific density of 0.1, a BET specific surface area of 2.8 m ² / g, and a treatment amount of 5.00 mg was prepared.

Example 12
In Example 1, the colloidal calcium carbonate was changed to 2000 g of a polytetrafluoroethylene resin (microdisperse 200 manufactured by Technochemical Co., Ltd.) having a BET specific surface area of 10 m ^{2 / g, and poly (3,4-ethylenedioxy) was used.} The dispersion prepared at a mixing ratio of 0.5 wt% of thiophene) and 0.7 wt% of polystyrene sulfonic acid was added to 2860 g, that is, 34.3 g of the conductive material component, and the 10 L mixer was changed to a Henschel mixer and stirred at 110 ° C. for 60 minutes. , Dry processing was performed. Then, it was transferred to a metal bucket and dried at 110 ° C. for 4 hours. The obtained powder was not pulverized to prepare a conductive Teflon (registered trademark) filler having a true specific density of 2.0, a BET specific surface area of 9.8 m ² / g, and a treatment amount of 17.00 mg.

Example 13
Poly (3,4-ethylenedioxy) was added to 140 g of a wet synthetic silica water slurry having a BET specific surface area of 100 m ^{2 / g and adjusted to a BET specific surface area of 100 m 2 / g.} 140 g of a dispersion (manufactured by Sigma Ordrich) prepared at a mixing ratio of 0.5 wt% of thiophene) and 0.7 wt% of polystyrene sulfonic acid, that is, 1.68 g of a conductive material component was added and circulated and stirred for 30 minutes. The obtained silica slurry was dehydrated, dried at 105 ° C. for 4 hours, and pulverized to ^{prepare a conductive silica filler having a true specific density of 1.6, a BET specific surface area of 95.0 m 2} / g, and a treatment amount of 170.00 mg.

Example 14
In the silica of Example 13, the dispersion prepared at a mixing ratio of 0.5 wt% of poly (3,4-ethylenedioxythiophene) and 0.7 wt% of polystyrene sulfonic acid is changed to 10 g, that is, 0.12 g of the conductive material component. A conductive silica filler having a true specific gravity of 1.6, a BET specific surface area of 98.0 m ² / g, and a treatment amount of 12.00 mg was prepared in the same manner as in Example 9 except for the above.

Example 15
In the silica of Example 13, the dispersion prepared at a mixing ratio of 0.5 wt% of poly (3,4-ethylenedioxythiophene) and 0.7 wt% of polystyrene sulfonic acid is changed to 620 g, that is, 7.44 g of the conductive material component. A conductive silica filler having a true specific gravity of 1.6, a BET specific surface area of 90.0 ^{m 2} / g, and a treatment amount of 750.00 mg / g was prepared in the same manner as in Example 9 except for the above.

Example 16
In Example 1, the colloidal calcium carbonate was changed to 2000 g of titanium oxide powder (R-38L manufactured by Sakai Chemical Industry Co., Ltd.) adjusted to a ^{BET specific surface area of 5 m 2 / g, and poly (3,4-ethylenedioxythiophene) was used.} The dispersion prepared at a mixing ratio of 0.5 wt% and 0.7 wt% polystyrene sulfonic acid was added to 1430 g, that is, 17.2 g of the conductive material component, and the 10 L mixer was changed to a Henschel mixer and stirred at 110 ° C. for 30 minutes, and dried. Treatment and drying were performed. The obtained powder was pulverized to prepare a conductive titanium oxide powder having a true specific density of 4.3, a BET specific surface area of 4.8 m ² / g, and a treatment amount of 9.00 mg / g.

Example 17
All except changing the dispersion prepared in Example 1 at a mixing ratio of 0.06 wt% of poly (3,4-ethylenedioxythiophene) and 1.14 wt% of polystyrene sulfonic acid to 200 g (2.4 g of the same solid). A conductive colloidal calcium carbonate powder having a true specific density of 2.6, a BET specific surface area of 6.8 ^{m 2} / g, and a treatment amount of 12.00 mg / g was prepared in the same manner as in Example 1.

Comparative Example 1
In the colloidal calcium carbonate of Example 1, 12.6 g of a dispersion prepared by mixing 0.5 wt% of poly (3,4-ethylenedioxythiophene) and 0.7 wt% of polystyrene sulfonic acid was prepared, that is, the conductive material component was 0. ^{A conductive colloidal calcium carbonate filler having a true specific gravity of 2.6, a BET specific surface area of 6.9 m 2} / g, and a treatment amount of 0.77 mg / g was prepared in the same manner as in Example 1 except that the amount was changed to 15 g.

Comparative Example 2
In the colloidal calcium carbonate of Example 1, a dispersion prepared at a mixing ratio of 0.5 wt% of poly (3,4-ethylenedioxythiophene) and 0.7 wt% of polystyrene sulfonic acid was added to 1000 g (12.0 g of the same solid). A conductive colloidal calcium carbonate filler having a true specific gravity of 2.6, a BET specific surface area of 6.9 ^{m 2} / g, and a treatment amount of 60.00 mg / g was prepared in the same manner as in Example 1 except for the modification.

Comparative Example 3
The colloidal calcium carbonate of Example 1 was changed to 2000 g of zinc oxide (first grade manufactured by HakusuiTech Co., Ltd.) adjusted to a BET specific surface area of 10, 0.5 wt% of poly (3,4-ethylenedioxythiophene) and polystyrene sulfone. The dispersion prepared at a mixing ratio of 0.7 wt% acid was added to 2860 g, that is, 34.32 g of the conductive material component, and the 10 L mixer was changed to a Henschel mixer and stirred at 110 ° C. for 30 minutes for dry treatment and drying. The obtained powder was not pulverized to prepare a conductive zinc oxide filler having a true specific density of 5.6, a BET specific surface area of 9.8 m ² / g, and a treatment amount of 17.20 mg / g.

Comparative Example 4
The colloidal calcium carbonate of Example 1 was changed to 2000 g of barium sulfate (precipitated barium sulfate 110 manufactured by Sakai Chemical Industry Co., Ltd.) adjusted to a BET specific surface area of 5, and poly (3,4-ethylenedioxythiophene) 0. The dispersion prepared at a mixing ratio of 5 wt% and 0.7 wt% polystyrene sulfonic acid was added to 1430 g, that is, 17.16 g of the conductive material component, and the 10 L mixer was changed to a Henschel mixer and stirred at 110 ° C. for 60 minutes for dry treatment. went. Then, it was transferred to a metal bucket and dried at 110 ° C. for 4 hours. The obtained powder was not pulverized to prepare a conductive barium sulfate filler having a true specific density of 4.6, a BET specific surface area of 4.8 m ² / g, and a treatment amount of 8.58 mg / g.

Comparative Example 5
In Example 1, 200 g of a dispersion prepared at a mixing ratio of 0.5 wt% of poly (3,4-ethylenedioxythiophene) and 0.7 wt% of polystyrene sulfonic acid was prepared with 1.2% of a sodium beef fatty acid aqueous solution, that is, a conductive material. In the same manner as in Example 1, the true specific gravity was 2.6, the BET specific surface area was 9.8 m ² / g, and the treatment amount was 12.24 mg / g, except that the component was changed to 0 and the beef fatty acid sodium solid component was changed to 2.4 g. A colloidal calcium carbonate filler was prepared.

Comparative Example 6
In the silica of Example 13, the dispersion prepared at a mixing ratio of 0.5 wt% of poly (3,4-ethylenedioxythiophene) and 0.7 wt% of polystyrene sulfonic acid is changed to 9 g, that is, 0.108 g of the conductive material component. A conductive silica filler having a true specific gravity of 1.6, a BET specific surface area of 98.0 m ² / g, and a treatment amount of 11.00 mg / g was prepared in the same manner as in Example 6 except for the above.

Comparative Example 7
In the silica of Example 13, the dispersion prepared at a mixing ratio of 0.5 wt% of poly (3,4-ethylenedioxythiophene) and 0.7 wt% of polystyrene sulfonic acid is changed to 630 g, that is, 7.56 g of the conductive material component. A conductive silica filler having a true specific gravity of 1.6, a BET specific surface area of 90.0 ^{m 2} / g, and a treatment amount of 770.00 mg / g was prepared in the same manner as in Example 6 except for the above.

Comparative Example 8
In the silica of Example 13, 0.5 wt% of poly (3,4-ethylenedioxythiophene) and 0.7 wt% of polystyrene sulfonic acid are mixed in a wet synthetic silica water slurry having a BET specific surface area of 100 and a concentration of 7 wt%. ^{A true specific gravity of 1.6, a BET specific surface area of 98.0 m 2} / g, and an untreated silica filler were applied in the same manner as in Example 9 except that the dispersion prepared in proportion was not added and changed to an untreated state. Made.

Comparative Example 9
In the colloidal calcium carbonate of Example 1, the dispersion prepared at a mixing ratio of 1.2 wt% of poly (3,4-ethylenedioxythiophene) and 0 wt% of polystyrene sulfonic acid is changed to 200 g (2.4 g of the same solid). A conductive colloidal calcium carbonate powder having a true specific gravity of 2.6, a BET specific surface area of 6.8 ^{m 2} / g, and a treatment amount of 12.00 mg / g was prepared in the same manner as in Example 1 except for the above.

Comparative Example 10
In the colloidal calcium carbonate of Example 1, the dispersion prepared by mixing 0 wt% of poly (3,4-ethylenedioxythiophene) and 1.2 wt% of polystyrene sulfonic acid is changed to 200 g (2.4 g of the same solid). A conductive colloidal calcium carbonate powder having a true specific gravity of 2.6, a BET specific surface area of 6.8 ^{m 2} / g, and a treatment amount of 12.00 mg / g was prepared in the same manner as in Example 1 except for the above.

Table 1 shows the characteristics of the fillers obtained in Examples 1 to 17 and Comparative Examples 1 to 10.

Examples 18-34, Comparative Examples 1-20
[Conductive rubber composition]
The fillers obtained in Examples 1 to 17 and Comparative Examples 1 to 10 are kneaded using an open roll (manufactured by Kansai Roll Co., Ltd.) under 60 ° C. temperature conditions with the formulations shown below and the formulations shown in Table 2. A dust compound was prepared.
(Mixing)
Epichlorohydrin Rubber Daiso EPION-301 100 parts by weight Variable amounts of fillers in Examples 1 to 17 and Comparative Examples 1 to 10 *
Vulcanizing agent Hosoi Chemical Sulfur powder 2 parts by weight Vulcanization accelerator Ouchi Shinko Kagaku Noxeller M 1 part by weight Vulcanization accelerator Auxiliary Ouchi Shinko Kagaku Noxela TET 1 part by weight Stearic acid Kao Stearate Sakura 1 part by weight Zinc oxide Huxitec Oxidation 2 types of zinc, 5 parts by weight * Adjusted to an appropriate amount to make a compound according to the particle size of the filler.

The obtained compound was formed into a rubber sheet having a thickness of 2 mm, and the following measurements were carried out under environmental conditions of a temperature of 23 ° C. and a humidity of 50%.
[Whiteness, rigidity, elongation at break, resistivity]
The color value of the composition was measured with a color meter ZE-2000 manufactured by Nippon Denshoku Co., Ltd., and the L value was taken as the measured value of whiteness. In addition, the hardness value after a load of 1000 g was measured with a hardness tester (Type C manufactured by Ascar Co., Ltd.). Further, it was punched with dumbbell No. 3 and subjected to a tensile test (tensile speed 200 mm / min.) Conforming to JIS K 6253, and the elongation at break was measured.
Further, the obtained compound was made into a rubber sheet-like size having a width of 120 mm, a length of 100 mm and a thickness of 2 mm, allowed to stand in a humidity condition of 23 ° C. × 50% for 3 hours, and composed with a resist meter 4339B manufactured by Agilent. The volume resistivity of the object was measured.

(Criteria for whiteness)
⊚; 90 or more ○; 85 or more to less than 90 Δ; 80 or more to less than 85 ×; less than 80 (hardness value judgment standard)
⊚; 40 or more and less than 50 ○; 30 or more and less than 40 Δ; 20 or more and less than 30 ×; less than 20, 70 or more
(Criteria for determining elongation at break)
⊚; 300% or more ○; 200% or more to less than 300% Δ; 100% or more to less than 200% ×; less than 100% (criteria for volume resistivity)
◎; 1 × 10 ³ Ω ・ cm or more to ^{less than 1 × 10 5} Ω ・ cm ○; 1 × 10 ⁵ Ω ・ cm or more to 1 × 10 ⁷ Ω ・ cm or less △; 1 × 10 ⁷ Ω ・ cm or more to 1 × 10 ^{Less than 10} Ω ・ cm ×; 1 × 10 ¹⁰ Ω ・ cm or more

From the measurement results in Table 2, by blending the conductive surface-treated powder filler of the present invention, a white conductive rubber composition can be obtained, and the original hardness value and breaking elongation of the rubber composition can be determined. It can be seen that the conductivity is maintained without lowering.

Examples 35-51, Comparative Examples 21-30
[Conductive film composition]
A white polyethylene resin film was prepared by using the fillers obtained in Examples 1 to 17 and Comparative Examples 1 to 10 as shown below.
(Mixing)
Polyethylene resin 100 parts by weight of Japanese polypenco Filling materials of Examples 1 to 10, 12, 16, 17, Comparative Examples 1 to 5, 9, and 10 50 parts by weight Filling material of Example 11 5 parts by weight Examples 13 to 15, Comparative Example 6 Filler of ~ 8 6 parts by weight Add the filler to polyethylene resin in a Henshell mixer, disperse and stir for 30 minutes, and then use a kneading extruder (Laboplast Mill 2D25W type; manufactured by Toyo Seiki Co., Ltd.) at 130 ° C. Granulated with and made into pellets. The obtained pellets are dried at 110 ° C. for 1 hour, and then the pellets are extruded into a film from a T-type die using a film extruder (Laboplast Mill D2025 type; manufactured by Toyo Seiki Co., Ltd.) at 30 ° C. A non-stretched film was obtained by cooling and solidifying with a cooling drum. Then, the unstretched film was stretched 3.3 times in the extrusion direction with a tenter stretching machine, further heated to 120 ° C. and stretched 3 times in the lateral direction to obtain a film composition having a thickness of 180 μm.

The following physical characteristics of the obtained film were measured or evaluated.
[Whiteness, dispersibility, volume resistivity, reflectance, tensile properties]
Whiteness: The whiteness of the film was measured with a color meter ZE-2000 manufactured by Nippon Denshoku Co., Ltd., and the L value indicating the whiteness was measured.
Dispersity: Dispersity was evaluated by the number of agglomerates and fish eyes due to coarse particles in a film of 300 mm × 300 mm.
Volume resistivity: A film having a thickness of 180 μm and a width of 150 mm × a length of 100 mm was allowed to stand under a humidity condition of 23 ° C. × 50% for 3 hours or more, and the volume resistivity was measured with a resist meter 4339B manufactured by Agilent.
Reflectance: Using an ultraviolet-visible spectrophotometer (UV3101PC, manufactured by Shimadzu Corporation), measure the wavelength range of reflectance of 0.30 to 0.80 μm when barium sulfate white plate is taken as 100%, and obtain a reflectance of 0.45 μm. It was used as a representative value.
Tensile properties: Based on the tensile properties of JIS Z 1702 polyethylene film, 500 mm / min. The breaking strength and breaking elongation rate when pulled at the speed of 1 were measured.

(Criteria for determining whiteness)
⊚; 90 or more ○; 85 or more and less than 90 Δ; 80 or more and less than 85 ×; less than 80 (dispersion criterion)
⊚; 0 aggregates and coarse particles ○; 1 or 2 aggregates and coarse particles Δ; 3 or 4 aggregates and coarse particles ×; 5 or more aggregates and coarse particles (volume resistivity) Criteria for determining the rate)
◎; 1 × 10 ⁴ Ω ・ cm or more to ^{less than 1 × 10 6} Ω ・ cm ○; 1 × 10 ⁶ Ω ・ cm or more to 1 × 10 ⁸ Ω ・ cm or less △; 1 × 10 ⁸ Ω ・ cm or more to 1 × 10 ^{Less than 10} Ω ・ cm ×; 1 × 10 ¹⁰ Ω ・ cm or more (Reflectance criterion)
⊚; 96% or more ○; 93% or more to less than 96% Δ; 90% or more to less than 93% ×; less than 90% (criteria for determining tensile properties)
(1) Breaking strength ⊚; 40 MPa or more ○; 30 MPa or more and less than 40 MPa Δ; 20 MPa or more and less than 30 MPa ×; less than 20 MPa (2) Breaking elongation ◎; 350% or more ○; 250% or more and less than 350% Δ; 150% or more 250 Less than% ×; less than 150%

The measurement results are shown in Table 3.

From the measurement results in Table 3, by blending the conductive surface-treated powder filler of the present invention, the original whiteness and reflectance of the film composition can be maintained without impairing the conductivity and dispersibility. Furthermore, it can be seen that the breaking strength and breaking elongation rate also have sufficient performance.

Examples 52 to 68, Comparative Examples 31 to 40
[Conductive sealant composition]
A modified silicone sealant was prepared by using the fillers obtained in Examples 1 to 17 and Comparative Examples 1 to 10 with the formulations shown below and the formulations shown in Table 4.
(Mixing)
Modified Silicone Polymer Co., Ltd. Kaneka MS Polymer S-203 100 parts by weight Amido Wax Itoh Oil Chemicals Co., Ltd. ASA-T-1800 Fluent *
Fillant variables of Examples 1 to 17 and Comparative Examples 1 to 10 *
Heavy Calcium Carbonate Maruo Calcium Super S Fluent *
Plasticizer J-PLUS DINP 60 parts by weight dehydrating agent Shin-Etsu Chemical Industry KBM-1003 6 parts by weight tin catalyst Nitto Kasei Neostan U-220H 2 parts by weight Adhesive imparting agent Shin-Etsu Chemical Industry KBM-603 2 parts by weight * Amido wax, filler , And heavy calcium carbonate were appropriately varied according to the type.

The filler, heavy calcium carbonate, and amido wax were dried or melted at 110 ° C. for 3 hours, and then put into a 5 L Dalton mixer (manufactured by Dalton Co., Ltd.) together with the modified silicone polymer, and the mixture was stirred under reduced pressure. Next, a plasticizer, a dehydrating agent catalyst, and an adhesive-imparting agent were added and stirred in the same manner to prepare a modified silicone sealant. The obtained sealant was filled in a 320 ml cartridge, sealed and stored.

The following physical properties of the obtained sealant were measured.
[Viscosity, whiteness, tensile properties, volume resistivity]
Viscosity: The obtained sealant was projected from the cartridge and filled in a 100 ml PP cup. Rotor No. B type viscometer (manufactured by Tokimec Co., Ltd.). 1 rpm viscosity and 10 rpm viscosity were measured using 7. At the same time, the TI value (1 rpm viscosity / 10 rpm viscosity), which is a measure of workability, was measured.
Whiteness: The obtained sealant was measured for whiteness with a color meter ZE-2000 manufactured by Nippon Denshoku Co., Ltd., and the L value indicating the whiteness was measured.
Tensile properties: The obtained sealant was filled into a sheet having a thickness of 2 mm, a width of 20 mm, and a length of 100 mm, cured at 23 ° C for 14 days + 35 ° C for 14 days, punched into a No. 3 dumbbell, and conformed to JIS K 6253. The tensile properties were measured.
Volume resistivity: The obtained sealant was filled into a sheet having a thickness of 2 mm, a width of 120 mm and a length of 100 mm, and cured at 23 ° C × 14 days + 35 ° C × 14 days under 23 ° C × 50% humidity conditions for 3 hours or more. After allowing to stand, the volume resistivity of the composition was measured with a resist meter 4339B manufactured by Agent.
(Criteria for determining viscosity)
⊚; 1 rpm viscosity value / 10 rpm viscosity value = 6.5 or more ○; 6.0 or more to less than 6.5 △; 5.0 or more to less than 6.0 ×; 5.0 or less (whiteness judgment) standard)
⊚; 90 or more ○; 85 or more to less than 90 Δ; 80 or more to less than 85 ×; less than 80 (criteria for determining tensile characteristics)
(1) 50% tensile stress (stress when the distance between marked lines is 20 mm and is pulled to 30 mm)
◎; less than ^{0.15N / mm 2 ○; 0.15N /} mm 2 or more 0.25 N / mm lower than ² △; 0.25N / mm ² or more 0.35 N / mm ² less ×; 0.35N / mm ² or more (2) Break elongation rate ⊚; 400% or more ○; 350% or more and less than 400% Δ; 300% or more and less than 350% ×; less than 300% (judgment standard for volume resistance)
◎; 1 × 10 ⁴ Ω ・ cm or more to ^{less than 1 × 10 6} Ω ・ cm ○; 1 × 10 ⁶ Ω ・ cm or more to 1 × 10 ⁸ Ω ・ cm or less △; 1 × 10 ⁸ Ω ・ cm or more to 1 × 10 ^{Less than 10} Ω ・ cm ×; 1 × 10 ¹⁰ Ω ・ cm or more

The measurement results are shown in Table 4.

From Table 4, by blending the conductive surface-treated powder filler of the present invention, a sealing material having excellent conductivity can be obtained, and the sealing material composition is maintained without impairing low modulus and high elongation performance. It can be seen that the original whiteness and tensile properties of the object are maintained.

Examples 69-85, Comparative Examples 41-50
[Preparation of conductive plastisol composition]
The fillers obtained in Examples 1 to 17 and Comparative Examples 1 to 10 were used to prepare a vinyl chloride resin-based plastisol with the formulations shown below and the formulations shown in Table 5.
[Mixing]
PVC paste resin PCH-22 Kaneka Corporation 250 parts by weight Polyamide Co., Ltd. Henkel 15 parts by weight DINP Co., Ltd. J-Plus 250 parts by weight Tarpen 37 parts by weight Quick lime Wako Pure Chemical Industries, Ltd. 15 parts by weight Examples 1 to 17 , Variable amount of filler in Comparative Examples 1 to 10 *
Heavy Calcium Carbonate Super S (manufactured by Maruo Calcium Co., Ltd.) Fluent Disparon # 309 Fluent * The filler was variable as shown in Table 5 because the effect of imparting viscosity differs depending on the type and particle size.

Each compounding agent is put into a 5L universal mixing stirrer (manufactured by Dalton) and kneaded for 3 minutes. Once the lid is opened and the compounding agent adhering to the wall surface is scraped off, the mixture is kneaded again in a vacuum atmosphere for 10 minutes. The kneaded sol was defoamed with a planetary defoaming kneader (manufactured by Kurabo Industries Ltd./KK-500) under kneading conditions 5-5-18 to prepare a vinyl chloride resin-based plastisol.
In the kneading condition "ab-c", a indicates a revolution condition, b indicates a rotation condition, and c indicates a time, which means c × 10 seconds.

The following physical characteristics of the obtained plastisol were measured.
[Viscosity, whiteness, slip resistance, dispersibility, volume resistivity]
Viscosity: The obtained plastisol was filled in a 100 ml PP cup, and a BH type viscometer (manufactured by Tokimec Co., Ltd.) rotor No. 2 rpm viscosity and 20 rpm viscosity were measured using 7. At the same time, the TI value (2 rpm viscosity / 20 rpm viscosity), which is a measure of workability, was measured.
Whiteness: The obtained plastisol was measured for whiteness with a color meter ZE-2000 manufactured by Nippon Denshoku Co., Ltd., and the L value indicating the whiteness was measured.
Slip resistance: The obtained plastisol is packed in a 100 ml PP cup, allowed to stand at 23 ° C for 3 days, applied to a 130 mm × 60 mm adherend on a 12 mm semicircular bead with a length of 100 mm, and then at 23 ° C. After 30 minutes of standing vertically, the distance that the sol slipped off was measured with a ruler.
Dispersity; Measured by the following method.
Put each compounding agent and a filler under compaction conditions into a 5L universal mixing stirrer (manufactured by Dalton), knead for 3 minutes, open the lid once, scrape off the compounding agent adhering to the wall surface, and then vacuum atmosphere again. Knead under for 10 minutes. The sol after kneading was defoamed with a planetary defoaming kneader (manufactured by Kurabo Industries Ltd./KK-500) under kneading conditions 5-5-18 to prepare a vinyl chloride sol for measuring dispersibility.
Dispersity was measured by spreading a vinyl chloride sol for measuring dispersibility thinly on a glass plate with a spatula so as to have a length of 5 cm or more, a width of 5 cm or more, and a thickness of 1 mm or less.
Volume resistivity: The obtained plastisol was filled into a sheet having a thickness of 2 mm, a width of 120 mm and a length of 100 mm, and allowed to stand in a humidity condition of 23 ° C. x 50% for 3 hours or more. The volume resistivity of the composition was measured.

(Criteria for determining viscosity)
Judgment was made according to the Ti value of 2 rpm viscosity / 20 rpm viscosity according to the following criteria.
⊚: 6.0 or more ○: 5.5 or more and less than 6.0 Δ: 5.0 or more and less than 5.5 ×: less than 5.0 (whiteness criterion)
⊚: 90 or more ○: 85 or more and less than 90 Δ: 80 or more and less than 85 ×: less than 80 (slip resistance criterion)
◯: 0 mm
Δ: More than 0 mm and less than 10 mm ×: 10 mm or more (Criteria for determining dispersibility)
The number of grains of 0.5 mm or more per 5 cm square on the surface of the vinyl chloride coated on the glass plate was counted.
◯: 0 grains of 0.5 mm or more Δ: 1 or 2 grains of 0.5 mm or more ×: 3 or more grains of 0.5 mm or more (criteria for volume resistivity)
◎; 1 × 10 ⁴ Ω ・ cm or more to ^{less than 1 × 10 6} Ω ・ cm ○; 1 × 10 ⁶ Ω ・ cm or more to 1 × 10 ⁸ Ω ・ cm or less △; 1 × 10 ⁸ Ω ・ cm or more to 1 × 10 ^{Less than 10} Ω ・ cm ×; 1 × 10 ¹⁰ Ω ・ cm or more

The measurement results are shown in Table 5.

From the measurement results in Table 5, by blending the conductive surface-treated powder filler of the present invention, a plastisol composition having excellent conductivity can be obtained, and the plastisol without impairing the dispersibility and slip resistance function is not impaired. It can be seen that the original whiteness of the composition is maintained.

The conductive surface-treated powder filler of the present invention is a percolation in which a conductive path should be formed by dispersing the filler in a composition blended with a resin such as rubber, plastic, film, sealant, adhesive, paint, or plastisol. It can take a structure.
Therefore, the conductive surface-treated powder filler of the present invention not only imparts a conductive function, but also has excellent whiteness, which is a characteristic of the original powder, and thus has excellent colorability, enables transparency, and is black. A conductive resin composition other than the system can be obtained.
In addition, it has excellent dispersibility compared to other metal powders containing inorganic metal compounds such as indium, tin, silver, copper, zinc, aluminum, and antimony, and has a small true specific gravity, so the amount added is relatively small. However, it is possible to obtain a resin composition having a conductive effect, a reinforcing function inherent in the powder, a flexible function such as high elongation of the conductive polymer, and a weight reduction function.

Claims (16)

A surface treatment agent (B) containing a π-conjugated conductive polymer and a polyanion on the surface of particles of at least one powder (A) selected from the group consisting of white inorganic powder and white organic powder. A conductive surface-treated powder filler having a coating layer, which satisfies the following formulas (1) and (2).
(1) Dio ≤ 4.3
(2) 0.12 ≤ As ≤ 8.4 [mg / m ² ]
However,
Dio: True specific gravity of surface-treated powder [g / cm ³ ]
As: Amount of surface treatment agent containing π-conjugated conductive polymer and polyanion per unit specific surface area of surface treatment powder calculated by the following formula
As = Tgx / Sw
Tgx: Amount of surface treatment agent containing π-conjugated conductive polymer and polyanion per 1 g of surface treatment powder [mg / g]
Sw: BET specific surface area of surface-treated powder [m ² / g] A surface treatment agent consisting of an aqueous slurry of at least one powder (A) selected from the group consisting of a white inorganic powder and a white organic powder, a π-conjugated conductive polymer, and a polyanion. The conductive surface-treated powder filler according to claim 1, wherein the dispersion liquid containing (B) is mixed and stirred. The conductive surface-treated powder filler according to claim 1 or 2, wherein the white inorganic powder is at least one selected from the group consisting of a calcium compound, a titanium compound, a magnesium compound, a silicon compound and an aluminum compound. Claims 1 to 3 wherein the white organic powder is at least one selected from the group consisting of acrylic resin, vinyl chloride resin, polystyrene resin, polyethylene resin, polyimide resin, fluororesin, phenol resin and woody powder. The conductive surface-treated powder filler according to any one of the items. The conductive surface-treated powder filler according to any one of claims 1 to 4, wherein the π-conjugated conductive polymer is at least one selected from the group consisting of polythiophene, polyaniline, polypyrrole and polyfluorene. The conductive surface-treated powder filler according to claim 5 , wherein the polythiophene is poly (3,4-ethylenedioxythiophene). The conductive surface-treated powder filler according to any one of claims 1 to 6 , wherein the polyanion is at least one selected from the group consisting of polystyrene sulfonic acid, polyvinyl sulfonic acid and polyacrylamide sulfonic acid. Conductive surface treated powder filler according to any one of claims 1 to 7 volume resistivity of not more than 10 ⁸ Ω · cm. Contains an aqueous slurry of at least one powder (A) selected from the group consisting of white inorganic powder and white organic powder, and a surface treatment agent (B) composed of a π-conjugated conductive polymer and a polyanion. The production of the conductive surface-treated powder filler according to any one of claims 1 to 8 , wherein the particles of the powder (A) are surface-treated by mixing and stirring with the dispersion liquid. Method. A conductive resin composition containing the conductive surface-treated powder filler according to any one of claims 1 to 8. A conductive rubber composition containing the conductive surface-treated powder filler according to any one of claims 1 to 8. A conductive film composition containing the conductive surface-treated powder filler according to any one of claims 1 to 8. A conductive sealing material composition containing the conductive surface-treated powder filler according to any one of claims 1 to 8. A conductive adhesive composition containing the conductive surface-treated powder filler according to any one of claims 1 to 8. A conductive coating composition containing the conductive surface-treated powder filler according to any one of claims 1 to 8. A conductive plastisol composition containing the conductive surface-treated powder filler according to any one of claims 1 to 8.