JP2018016790A - Conductive surface-treated powder filler and resin composition containing the filler - Google Patents

Abstract

[PROBLEMS] To form a conductive path in a composition blended with a resin such as rubber, plastic, film, sealing material, adhesive, paint, plastisol, etc., and not only have conductivity and antistatic function, but also whiteness, Alternatively, a conductive surface-treated powder filler capable of transparency and having the dispersibility inherent in the powder, compatibility with the resin, reinforcement, flexibility, and weight reduction function, and a resin containing the filler A composition is provided. A surface treatment agent containing a π-conjugated conductive polymer and a polyanion on the surface of at least one powder (A) selected from the group consisting of a color inorganic powder and a white organic powder. A surface-treated powder having a coating layer of (B), which satisfies the following formulas (1) and (2): (1) Dio ≦ 4.3 (2) 0.12 ≦ As ≦ 8.4 [mg / m 2] Dio: True specific gravity of surface-treated powder [g / cm 3] As: Surface treatment agent amount determined by the following formula As = Tgx / Sw Tgx: amount of surface treatment agent containing π-conjugated conductive polymer and polyanion per gram of surface-treated powder [mg / g] Sw: BET specific surface area of surface-treated powder [m2 / g] Selection diagram] None

Description

  The present invention relates to a conductive surface-treated powder filler and a resin composition comprising the filler, and more specifically, a composition blended with a resin such as rubber, plastic, film, sealing material, adhesive, paint, plastisol and the like. Forms a conductive path in the product, not only has electrical conductivity and antistatic function, but also enables whiteness or transparency, and dispersibility inherent in the powder, compatibility with resin, reinforcement, flexibility The present invention relates to a conductive surface-treated powder filler having a lightening function and the like, and a resin composition containing the filler.

Currently, there is a remarkable spread of communication devices such as mobile phones, personal computers, tablet terminals, printers, etc., 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. . In the touch panel used for these information terminals, the presence of materials and raw materials having a conductive function is indispensable in order to improve operability. The OA rubber roll used in the printer uses materials and raw materials having a uniform conductive function in order to smoothly print and transfer without impairing 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 that exert these conductive functions. . For example, it has been 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 arranged on the front surface of the image display device, and exhibits long-term durability. (Patent Document 1).
However, indium-based oxides such as ITO and IZO are raw materials that have a stable conductive function and have a proven track record. However, since they are natural resources called rare earths, they may be depleted of resources and can be supplied in the long term. I have a problem. The true specific gravity of these materials at room temperature at 23 ° C. is ITO (7.1 g / cm ³ ), IZO (6.3 g / cm ³ ), silver powder (5.0 to 10.5), copper powder ( 5.9), the specific gravity of the resin composition containing them increases, and as a result, the hardness increases and the flexibility and impact resistance may be hindered. In addition, since the dispersibility and tensile properties are lowered and it is very expensive, it is limited to general use.

  In addition, lead-based solder has been used as an adhesive element on electronic circuit boards, but conductive adhesives using metal powders such as silver powder and silver plating powder have been reported by replacing the material of the board with resin. (Patent Document 2). However, the conductive function of these metal powders is close to that of ITO and IZO, but silver powder is also relatively expensive and has a high specific gravity, so it may settle and separate in the adhesive. There is a problem in handling because it may adversely affect

  In addition, a conductive rubber roll sponge is used for the purpose of reducing image defects such as toner transfer unevenness and the like, which can be applied to a thermal transfer roller of an image forming apparatus, but carbon black is used as a conductive powder for imparting conductivity. (Patent Document 3). However, although carbon black has a smaller true specific gravity than conductive metal compounds and is advantageous in terms of raw material cost, since the raw material color of carbon black is black, the color tone of the composition such as transparency and whiteness can be improved. There is a problem in that uneven conductivity is caused by the restrictions or the blending ratio.

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

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

An electrically conductive inorganic powder characterized by being surface-treated with a polymer having a structural unit represented by (wherein R ₁ is a hydrogen atom or a methyl group, M is an alkali metal, ammonium or amine) (Patent Document 5).
However, these conductive inorganic powders are white, have no restrictions on colorability, and do not have a large true specific gravity. However, those treated with the above polymers have a low conductivity level and a resin composition. In this case, long-term conductivity and antistatic effects cannot be obtained.

  In addition, a composition containing a modified conductive polymer obtained by chemically treating a conductive polymer selected from polyaniline, polythiophene, or polypyrrole with a radical such as an azo compound in a resin provides stable conductivity with no variation in resistance. (Patent Document 6). However, these conductive polymers exhibit a conductive function by taking a so-called percolation structure that forms a conductive path in a state of being continuously bonded in the resin, whereas they have reinforcing properties such as silica and talc. Since the filler is insulative, there is a problem that when these fillers are blended even in a small amount, the conductive path of the conductive polymer is lost and the conductive performance is rapidly lowered. Therefore, in order to improve 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, copper powder or the like is used. Since carbon black is blended, the characteristics using the conductive polymer are lost. Or since it will be limited to the composition which does not mix | blend a reinforcing filler, the characteristic of a conductive polymer is also limited in this case.

JP 2012-118814 A Japanese Patent Laying-Open No. 2015-189860 JP 2012-155263 A JP 2004-83614 A JP-A-6-107963 JP 2006-169291 A

Inorganic powders such as calcium carbonate, calcium phosphate typified by calcium phosphate, titanium compound typified by titanium oxide, magnesium compound typified by magnesium hydroxide, and silicon compound typified by silica are rubber, plastic, film, It has been used for many years as a resin composition that is blended most in resins such as sealing materials, adhesives, paints, and plastisols and that exhibits functions such as dispersibility, whiteness, reinforcement, and flexibility. Recently, an acrylic resin balloon, resin beads such as polymethacrylate resins, and organic powders such as vinyl chloride powder are used in an extremely large proportion for reducing the weight of the resin composition or imparting flexibility. ing.
However, these powders are usually insulating, and in order to blend these powders into a resin composition having a conductive function, black carbon black having a conductive function, indium, There is no choice but to deal with a large amount of conductive materials such as inorganic metal compounds such as tin, silver, copper, zinc and antimony. Also, resin compositions containing inorganic powders such as calcium compounds, titanium compounds, magnesium compounds and silicon compounds, or resin beads such as acrylic resin balloons and polymethacrylate resins, and organic powders such as vinyl chloride powders. If only a conductive substance is added to the resin composition, a percolation structure necessary for forming a conductive path cannot be obtained, and sufficient conductivity is not exhibited, and the dispersion function is hindered.

  In view of such circumstances, the present invention solves at least one of the problems of the prior art, and the powder is contained in a composition blended with a resin such as rubber, plastic, film, sealing material, adhesive, paint, plastisol and the like. Percolation structure that should form a conductive path by dispersing the body, not only has conductivity and antistatic function, but also allows whiteness or transparency, and the dispersibility inherent in the powder, resin It is intended to provide a conductive surface-treated powder filler having compatibility, reinforcing properties, flexibility, and weight reduction function, and a resin composition containing the filler.

  As a result of intensive studies aimed at solving the above-mentioned problems, the present inventors have determined that the surface of particles of at least one powder (A) selected from a white inorganic powder and a white organic powder. Further, the present invention has found that a surface-treated powder having a coating layer of a surface-treated powder (B) having a surface treatment agent containing a π-conjugated conductive polymer and a polyanion solves at least one of the above problems. It came to be completed.

The feature of the present invention for solving the above problems is that the surface of at least one powder (A) selected from the group consisting of a white inorganic powder and a white organic powder has a π-conjugated conductivity. A surface-treated powder having a coating layer of a surface-treating agent (B) containing a polymer and a polyanion, which satisfies the following formulas (1) and (2): is there.
(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 the surface-treated powder obtained by the following formula
As = Tgx / Sw
Tgx: amount of surface treatment agent containing π-conjugated conductive polymer and polyanion per gram of surface-treated powder [mg / g]
Sw: BET specific surface area of the surface-treated powder [m ² / g]
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. .
Still another feature of the present invention is that the white organic powder is at least one selected from the group consisting of an acrylic resin, a vinyl chloride resin, a polystyrene resin, a polyethylene resin, a polyimide resin, a fluororesin, a phenol resin, and a woody powder. It is a conductive surface-treated powder filler that is a seed.
Still another feature of the present invention is the conductive surface-treated powder filler, wherein 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).
Still another feature of the present invention is the conductive surface-treated powder filler, wherein the polyanion is at least one selected from the group consisting of polystyrene sulfonic acid, polyvinyl sulfonic acid, and polyacrylamide sulfonic acid.
Still another feature of the present invention is a conductive surface-treated powder filler having a volume resistivity of 10 ⁸ Ω · cm or less.
The method for producing the conductive surface-treated powder of the present invention is characterized in that an aqueous slurry of at least one powder (A) selected from the group consisting of a white inorganic powder and a white organic powder, and π Conductive surface-treated powder characterized in that the particles of the powder (A) are surface-treated by mixing and stirring a conjugated conductive polymer and a dispersion containing a surface treatment agent (B) comprising a polyanion. It is a manufacturing method of body filler.
Still another feature of the present invention is a conductive resin composition containing a conductive surface-treated powder filler.
Still another feature of the present invention is a conductive rubber composition containing a conductive surface-treated powder filler.
Still another feature of the present invention is a conductive film composition containing a conductive surface-treated powder filler.
Still another feature of the present invention is a conductive sealing material composition containing a conductive surface-treated powder filler.
Still another feature of the present invention is a conductive adhesive composition containing a conductive surface-treated powder filler.
Still 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 comprising a conductive surface-treated powder filler.

  The conductive surface-treated powder filler of the present invention is a percolation that forms a conductive path by dispersing the filler in a composition blended with a resin such as rubber, plastic, film, sealing material, adhesive, paint, and plastisol. Can take structure. Therefore, in addition to imparting a conductive function, the whiteness that is a characteristic of the original powder is high, so that it is excellent in colorability, enables transparency, and obtains a conductive resin composition other than black. it can. Compared to other metal powders containing inorganic metal compounds such as indium, tin, silver, copper, zinc, aluminum, antimony, etc., it is superior in dispersibility and has a low true specific gravity. Therefore, a sufficient conductive effect can be obtained, and a resin composition having a reinforcing function inherent in the powder, a flexible function such as high elongation of the conductive polymer, and a weight reducing function can be obtained.

The present invention relates to a surface treatment agent containing a π-conjugated conductive polymer and a polyanion on the surface of at least one powder (A) selected from the group consisting of a white inorganic powder and a white organic powder. It is a surface-treated powder having a coating layer of (B), 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 the surface-treated powder obtained by the following formula
As = Tgx / Sw
Tgx: amount of surface treatment agent containing π-conjugated conductive polymer and polyanion per gram of surface-treated powder [mg / g]
Sw: BET specific surface area of the surface-treated powder [m ² / g]

  In the present invention, the white inorganic powder and the white organic powder as the powder (A) refer to the degree of whiteness normally used in this field. For example, Nippon Denshoku Co., Ltd. The L value measured with a color meter ZE-200 is preferably 85 or more for the powder and 80 or more for the resin composition.

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

  Note that the difference between the true specific gravity of the powder (A) and the true specific gravity of the surface-treated powder having the coating layer of the surface-treating agent (B) is a negligible difference and is substantially the same. Don't hesitate. 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 gravity: 2.7 g / cm ³ ) is an example of a white inorganic powder having a true specific gravity of 4.3 g / cm ³ or less and most frequently used in a resin composition. Calcium carbonate includes natural calcium carbonate (heavy calcium carbonate) and synthetic calcium carbonate. Natural calcium carbonate is produced directly from sugar crystalline limestone, and can be produced, for example, by mechanically crushing and classifying raw sugar crystalline limestone. Synthetic calcium carbonate is manufactured after calcining in a kiln or other firing furnace using dense limestone to form calcium oxide and digesting with water to form calcium hydroxide. For example, calcium hydroxide is carbonated. It can be produced by reacting with a gas. In general, what is synthesized using dense limestone is a cubic colloidal calcium carbonate, and a calcite crystal having a relatively uniform particle shape can be obtained. Further, by changing the temperature condition of calcium hydroxide and adding additives such as magnesium compound, strontium compound and phosphorus compound and reacting this calcium hydroxide with carbon dioxide, aragonite crystals can be obtained with acicular calcium carbonate.

Calcium carbonate can exert a conductive function in both natural calcium carbonate and synthetic calcium carbonate. However, in order for the conductive surface-treated powder filler of the present invention to function stably, the surface of the powder is 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 can easily have a structure (percolation 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, a conductive function can be obtained, but there is a tendency that the thickening effect and the reinforcing effect of colloidal calcium carbonate cannot be obtained sufficiently. On the other hand, if the BET specific surface area Sw exceeds 100 m ² / g, the primary particles agglomerate, resulting in poor dispersion in the resin, and the conductive function tends not to be sufficiently exhibited.

Another synthetic calcium carbonate is aragonite calcium carbonate (true specific gravity 2.9 g / cm ³ ). The size of the particles is preferably an aragonite needle 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 calcium carbonate, acicular particles tend to have a structure (percolation structure) in which particles are connected to form a conductive path (percolation structure). In terms of the 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, a conductive function is obtained, but there is a tendency that thickening and reinforcing properties cannot be obtained. In addition, there is a tendency to lose the dispersive function that is characteristic of acicular calcium carbonate. In addition, when the BET specific surface area Sw exceeds 30 m ² / g, the needle-like crystals are aggregated and adsorbed, and the surface treatment agent for imparting conductivity cannot be sufficiently coated, so that the conductive function is sufficiently obtained. There is a tendency to become unable to demonstrate.

Another example of a white inorganic powder of calcium compound is calcium phosphate (true specific gravity 3.1 g / cm ³ ). For calcium phosphate, methods called a wet method, a hydrothermal method, and a dry method are used, and when they are industrially produced in large quantities, they are synthesized by a wet method. There are a precipitation method in which phosphoric acid is dropped into a calcium hydroxide slurry at room temperature and a hydrolysis method in which calcium carbonate is reacted with calcium hydrogen phosphate dihydrate. It may be calcium phosphate. Further, the obtained calcium phosphate may contain hydroxyapatite (Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ , but a content of less than 10% is desirable. 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 If the BET specific surface area Sw exceeds 80 m ² / g, the amount of the surface treatment agent required for coating the surface increases, and the strength of the resin composition is reduced. In some cases, the primary particles may aggregate to form poor dispersion in the resin, and the conductive function may not be exhibited.

Another white inorganic powder is a silicon compound, among which silica (true specific gravity 1.6 g / cm ³ ) is mentioned. In particular, the reaction of sodium silicate and sulfuric acid, or the reaction of sodium silicate with salts such as magnesium chloride to form silicate, and further decompose it with sulfuric acid or carbon dioxide gas to synthesize, or vaporized synthetic silica Dry synthetic silica synthesized by burning a mixture of silicon tetrachloride and hydrogen in air at 1600 to 2000 ° C. is preferred. With regard to the size of the particles, it has become possible to design a higher particle size by the advancement of the manufacturing technology described above, but the BET specific surface area is preferably 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 is obtained, and the working efficiency of the resin composition may be lowered. On the other hand, if the BET specific surface area Sw exceeds 300 m ² / g, the amount of the surface treatment agent necessary for coating the surface increases, and the strength of the resin composition may become too low. Furthermore, the primary particles may aggregate and become poorly dispersed in the resin, and the conductive function may not be fully exhibited.

On the other hand, if it can be surface-treated with a surface treatment agent containing a π-conjugated conductive polymer and a polyanion, it can be applied to organic powders. An example of a white organic powder having a true specific gravity of 4.3 g / cm ³ or less and often used in a resin composition is an acrylic resin balloon (true specific gravity of 0.1 to 0.3 g / cm ³ ). By heating a microcapsule in which liquid low-boiling hydrocarbons are wrapped in a thermoplastic polymer shell (shell), the polymer shell softens and the liquid hydrocarbon in it changes into a gas. Is produced by obtaining expanded particles. Applying this characteristic, thermally 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 or polymethyl methacrylate resin, and there are a crosslinked type and a non-crosslinked type. As the size of the particles, the BET specific surface area Sw is preferably ¹ to 10 m ² / g. When the BET specific surface area Sw is less than 1 m ² / g, measurement with a BET specific surface area meter is impossible, and the amount of the surface treatment agent is difficult to adjust, and it becomes difficult to obtain a conductive function. On the other hand, if the BET specific surface area Sw exceeds 10 m ² / g, it is difficult to produce the resin balloon, and secondary agglomeration may occur, resulting in conductive unevenness.

The white inorganic powder and the white organic powder having a true specific gravity of 4.3 g / cm ³ or less are not limited to those described above. As other white inorganic powders, magnesium hydroxide (true specific gravity 2.4), magnesium carbonate (about 2.9), basic magnesium carbonate (about 2.9), talc (2.7) ), Silica powder (2.2), silica powder (3.2), fine silica (1.2), fine calcium silicate (2.9), sericite (2.7), mica (2.8-3.2), bentonite (2.6), nepheline cynite (2.6), sepiolite (2.3), wollastonite (2.9), zonotlite (3.0), titanium Potassium acid (3.3 to 3.6), glass fiber (2.1 to 2.6), shirasu balloon (0.2 to 1.5), fly ash barn (0.7), glass balloon (0. 2), silica beads, glass beads (2.5) aluminum Fine powder aluminum silicate (2.6), kaolin clay (2.6), talc (2.7) aluminum hydroxide (2.4), alumina beads (3.6) as a compound, titanium oxide (3. 8 to 4.3) and potassium titanate (3.3 to 3.4). In the above-mentioned true specific gravity in parentheses, the unit g / cm ³ is omitted.

Other white organic powders include phenolic resins (true specific gravity 1.2 to 2.1) such as bisphenol A, bisphenol F, bisphenol M, bisxinol P, bisphenylhydroxyphenylmethane, polytetrafluoroethylene, polyfluorinated Fluorine resins (1.6 to 2.2) such as vinylidene, polychlorotrifluoroethylene, polyvinyl fluoride, perfluoroalkoxyfluorine, polystyrene resins (1.1), polyethylene such as low density polyethylene, high density polyethylene, polyethylene terephthalate Resin (0.90 to 1.05), polyvinyl chloride, polyvinyl chloride and other vinyl chloride resins (1.0 to 1.4), aromatic polyimide and pyromellitic anhydride and 4,4′-diaminodiphenyl ether Polyimide resin such as polymer with ( .42), as a woody system, cellulose powder (1.3 to 1.6), pulp powder (1.1 to 1.6), wood powder (1.0 or less), walnut powder (1.0 or less), Examples include cork powder (1.0 or less), starch (1.6), ebonite powder (1.2), and lignin (1.3 to 1.6). Note that the unit of g / cm ³ is omitted from the true specific gravity in the parentheses.

In addition, BET specific surface area Sw is a value at the time of measuring by BET method by the nitrogen adsorption method of surface treatment calcium carbonate, and is measured by the following method.
[Sample preparation method]
A glass cell is charged with 300 mg of sample, pretreated for 10 minutes at 200 ° C. while nitrogen is conducted, and then cooled to room temperature to obtain a measurement sample.
[Measurement method of BET specific surface area]
Measured by a one-point method with a BET specific surface area meter (Macsorb HMmodel-1210, manufactured by Mountec).

The specific gravity of the powder is indicated by true specific gravity or bulk specific gravity. The true specific gravity defined here is the weight per volume of the solid itself that does not include surface pores or internal voids. In the case of natural resource materials, the numerical value 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 true specific gravity.
[Measurement method of particle density (true specific gravity) by gas volume method]
The powder weighed with an electronic balance was set in a dry automatic densimeter (Accuic II 1340 10CC, manufactured by Shimadzu Corporation), and the volume of the powder was measured using helium gas in accordance with JIS M 8717. Weighing value ÷ powder volume value is the true specific gravity value.

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

  The π-conjugated conductive polymer refers to an organic polymer whose main chain is composed of π-conjugated systems, such as polythiophene, polypyrrole, polyacetylene, polyphenylene, polyphenylene vinylene, polyaniline, polythiophene vinylene, polyfluorene and their co-polymers. For example, coalescence. These may be used alone or in combination of two or more as required. Of these, polythiophene, polypyrrole, polyaniline, and polyfluorene are preferred from the viewpoint of the stability of conductivity. Furthermore, polythiophene is preferable from the viewpoint of ease of surface treatment and whiteness after the surface treatment.

Examples of polythiophene include poly (3,4-ethylenedioxythiophene), poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), poly ( 3-hexylthiophene), poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3- Bromothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene), poly ( 3-methoxythiophene), poly (3-ethoxythiophene), poly (3-butoxythiol) ), Poly (3-hexyloxythiophene), poly (3-heptyloxythiophene), poly (3-octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly ( 3-octadecylthiophene), poly (3,4-dihydroxythiophene), 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-propylenedioxythiophene), poly (3,4- Tendioxythiophene), poly (3-methyl-4-methoxythiophene), poly (3-methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3- Methyl-4-carboxyethylthiophene) and poly (3-methyl-4-carboxybutylthiophene). These may be used alone or in combination of two or more as required.
Among these, poly (3,4-ethylenedioxythiophene) is most preferable from the viewpoint of conductive function, heat resistance, whiteness, and transparency.

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

  Examples of polyaniline include poly (2-methylaniline), poly (2-ethylaniline), poly (3-isobutylaniline) and the like. 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], poly [9,9-bis- (2-ethylhexyl) -9-fluorene-2, 7-diyl], poly [9,9-di (3 ′, 7′-dimethyloctyl) fluorene-2,7-yleneethynylene], poly [9,9-di (2′-ethylhexyl) fluorene-2,7- Ylene ethynylene], poly [9,9-dihexyl-2,7-fluorene-alt-9-phenyl 3,6-carbazole] and the like. These may be used alone or in combination of two or more as required.

  Even if the surface of white inorganic powder or white organic powder is treated with only the π-conjugated conductive polymer, the surface of white inorganic powder or white organic powder is insufficient. It becomes a processing state, and it becomes easy to produce variation in an electroconductive function. Therefore, in order to contain a polyanion and to function as a dopant agent for a π-conjugated conductive polymer, it is important to use a dispersion for surface treatment and to improve the conductive function.

Polyanions include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyacrylamide sulfonic acid, polymethacryl sulfonic acid, polyisoprene sulfonic acid, polysulfoethyl methacrylate, polymethallyloxybenzene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid. Examples thereof include acid and dodecylbenzenesulfonic acid. These may be a single polymer or two or more types of copolymers, but the polyanion containing a sulfonic acid group improves surface conductivity and improves the conductive function. Most preferred.
In the present invention, as described above, the dispersion containing the π-conjugated conductive polymer and the polyanion exhibits the most conductive function, but the ratio of the polyanion amount to the total weight of the conductive polymer and the polyanion is usually 30 to 95% by weight.

  The feature of the conductive surface treatment powder filler of the present invention is that it is surface-treated with a surface treatment agent containing a π-conjugated conductive polymer and a polyanion. Alternatively, the surface treatment may be performed in combination with a general surface treatment agent used for the surface treatment of other powders. Common surface treatment agents include saturated fatty acids, unsaturated fatty acids, alicyclic carboxylic acids, resin acids and the like, and derivatives thereof include sodium salts, potassium salts, ammonium salts, amine salts and the like.

  As a saturated fatty acid, a C6-C31 saturated fatty acid is preferable, Preferably it is C8-26, More preferably, it is C9-21. 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, serotic acid, montan Examples include acid and melicic acid. Among these, it is preferable to use palmitic acid, stearic acid, and lauric acid in combination.

  An unsaturated fatty acid is a fatty acid having a double bond in the molecule, and is synthesized, for example, by a dehydration reaction of a saturated fatty acid. As an unsaturated fatty acid, a C6-C31 unsaturated fatty acid is preferable, More preferably, it is C8-26, More preferably, it is C9-21. Specific examples of the unsaturated fatty acid include obsilic acid, carloleic acid, undecylenic acid, Linderic acid, tuzuic acid, fizeteric acid, molistoleic acid, palmitoleic acid, petrothelic acid, oleic acid, elaidic acid, asclebic acid, vacsen Examples thereof include acid, gadoleic acid, gondoic acid, cetreic acid, erucic acid, brassic acid, ceracolonic acid, ximenoic acid, lumectric acid, sorbic acid, and linoleic acid. Among these, oleic acid, erucic acid, and linoleic acid are preferable.

Further, fatty acids derived from animal raw materials such as beef tallow and pork fat, fatty acids derived from plant raw materials such as palm and palm, etc., in which these are mixed, may be used as long as the conductive function is not impaired.
Further, within the range that does not hinder the present invention, alicyclic carboxylic acids typified by naphthenic acid, abietic acid, pimaric acid, parastrinic acid, resin acids typified by neoabietic acid, and their disproportionated rosin, water An additive rosin, a dimer rosin, a modified rosin represented by a trimer rosin, and a sulfonic acid represented by an alkylbenzene sulfonic acid may be used.
The above-mentioned general surface treatment agents, acids and salts thereof, may be used alone or in combination of two or more as required.

In the present invention, the surface treatment agent amount As per unit specific surface area of the conductive surface treatment powder filler having a coating layer of the surface treatment agent (B) containing a π-conjugated conductive polymer and a polyanion is 0.00. it is a 12~8.4mg / m ^2. When the amount of the surface treatment agent As is less than 0.12 mg / m ² , an untreated surface may be present, the conductive function may be impaired, and dispersibility may be hindered. On the other hand, when the amount of the surface treatment agent As exceeds 8.4 mg / m ² , the amount of the surface treatment agent is excessive, and although an electrical conductivity effect is obtained, an economic burden is increased and dispersibility is hindered. Or the whiteness may be reduced. A 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 .

In addition, when the powder is surface-treated with a surface treatment agent containing a π-conjugated conductive polymer per unit specific surface area and a polyanion, the surface treatment containing a π-conjugated conductive polymer and a polyanion per 1 g of the surface-treated powder. It is calculated | required by dosage amount As [mg / m < ² >] = Tgx / Sw.
Tgx: amount of surface treatment agent containing π-conjugated conductive polymer and polyanion per gram of surface-treated powder [mg / g]
Sw: BET specific surface area [m ² / g] of the surface-treated powder.
And said Tgx is calculated | required by the heat loss [mg / g] per 1g of surface treatment powder of 200 to 500 degreeC.
[Measurement method of heat loss]
Using a thermal analyzer (ThermoPlus EVOII, manufactured by Rigaku Corporation), 30 mg of surface-treated inorganic powder was sampled on a sample pan (made of platinum) having a diameter of 5 mm and a depth of 5 mm, and from room temperature to 510 ° C. at a temperature rising rate of 15 ° C./min. The heat loss at 200 ° C. to 500 ° C. when the temperature is raised is measured to determine the heat loss (mg / g) per 1 g of the surface-treated powder.
In addition, when organic powder is surface-treated with a surface treatment agent containing a π-conjugated conductive polymer and a polyanion, the ratio is not known by the measurement method of heat loss, so the inorganic powder surface-treated with the same amount of the surface treatment agent. The body heat loss was defined as the amount of surface treatment agent for organic powder. In addition, when used in combination with a surface treatment agent such as fatty acid, fatty acid derivative, resin acid, resin acid derivative, sulfonic acid, etc. within a range not impairing the conductive function, a surface treatment agent containing a π-conjugated conductive polymer and a polyanion A conductive powder surface-treated alone was prepared separately, and the combined ratio was calculated from 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.
As the conductive rubber composition of the present invention, a composition using a rubber material such as ethylene propylene diene rubber (EPDM), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), epichlorohydrin rubber (CO, ECO, GECO). Things are given. Among these, acrylonitrile butadiene rubber and epichlorohydrin rubber used for the conductive rubber roller can obtain stable conductivity as a rubber component, but colloidal calcium carbonate compounded for the purpose of adjusting the hardness of the composition is insulating. Therefore, there is a case where the conductivity tends to be lowered or printing unevenness due to pressure sensitivity may occur. By blending the conductive surface-treated powder filler surface-treated with the surface-treating agent containing the π-conjugated conductive polymer of the present invention and a polyanion, the composition is more stable while maintaining low flexibility and flexibility. Thus, a rubber composition can be obtained which has a high 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 oil, polyester, A plasticizer such as phthalic acid, a diluent, and a filler such as carbon black can be added. In addition, if an ionic conductive agent such as sodium perchlorate, lithium perchlorate, stearyltrimethylammonium chloride, modified aliphatic dimethylethylammonium ethosulphate or stearyltetraethylammonium is added, the conductivity can be further improved. An electrically conductive rubber composition can be obtained.

  Examples of the conductive film composition of the present invention include general-purpose resins represented 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), polyethersulfone (PES), polyphenylene Engineers such as sulfide (PPS), polyarylate (PAR), polyetheretherketone (PEEK), polyimide (PI), polyetherimide (PEI), fluororesin (FR), liquid crystal polymer (LCP) A ring plastic, phenol, urea, melamine, alkyd, unsaturated polyester, epoxy, polyester amide, polyether ester, polyvinyl chloride, and a resin that is a copolymer containing these as main components are used. These resins are blended with general inorganic powders and organic powders to improve dispersibility, film reinforcing effect, and reflectivity, but by blending the conductive surface-treated powder filler of the present invention. In addition to maintaining the dispersibility, the reinforcing effect of the film, and the reflectivity, a film composition that has higher conductivity, more stable conductivity, and is effective in flexibility can be 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. If the conductive surface-treated powder filler of the invention is blended, these functional effects can be further enhanced.

  Examples of the conductive sealant composition and adhesive composition of the present invention include silanol groups or reactive silyl groups at the terminals of silicone, modified silicone, acrylic silicone, silicone modified epoxy, silylated urethane, polyisobutylene, cyanoacrylate, etc. A resin having a crosslinkable silicon group, a polyurethane resin, a polysulfide resin, an acrylic resin, an epoxy resin, or the like is used. In particular, a resin having a crosslinkable silicon group is used as an alternative material for soldering a printed circuit board by blending metal powder such as silver powder or copper powder to exhibit a conductive function. By blending the conductive surface-treated powder filler of the present invention, flexibility can be imparted compared to a composition blended with silver powder and copper powder, and more stable without blending silver powder and copper powder. The conductive function can be exhibited. These resin compositions use silicone oil, plasticizers such as phthalic acid, and high-boiling solvents such as isoparaffins and naphthenes. However, the conductive surface-treated powder filler of the present invention is blended. Therefore, 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. In addition, conductive sealant compositions and adhesive compositions usually include pigments, UV absorbers, antioxidants, catalysts, etc., sealants, adhesive processability, flexibility, reaction rate, durability, heat resistance. However, by adding the conductive surface-treated powder filler of the present invention, these conductive sealant compositions and adhesive compositions are lightweight without increasing the specific gravity and bonded. 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. These paint resin compositions include silicone oil, plasticizers such as phthalic acid, high-boiling solvents such as isoparaffins and naphthenes, or methanol, ethanol, acetone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, etc. 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 coating resin compositions, the coating film strength is improved and stable conductivity can be imparted.

  As the conductive plastisol composition of the present invention, acrylic resin, vinyl chloride resin, polyester resin, polyurethane resin and the like are used. In particular, vinyl chloride resin is used as a main resin for plastisols such as undercoats and body sealers for automobiles. Usually, these include quick lime, talc, clay, mica, wet silica, dry silica, colloidal calcium carbonate, heavy calcium carbonate, glass balloons, acrylic resin balloons, diatomaceous earth and other fillers, phthalic acid plasticizers, etc. High-boiling solvents such as isoparaffins and naphthenes are used as additives. These plastisol compositions have no conductive function and are insulative, but by incorporating the conductive surface-treated powder filler of the present invention, the adhesion to the electrodeposition plate of an automobile is improved, and the anti-slip performance Can be greatly improved, and an antistatic effect required for automotive applications can be imparted.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but these do not limit the present invention in any way.
In the following description, for various properties and physical properties, in addition to the measured values, four-step judgment results by ◎, ○, Δ, and × are shown for reference, but these are relative to the end. It is only a guide for the time being and is not bound by these.

The whiteness and volume resistivity of the conductive surface-treated powder filler were measured according to the following method.
[Whiteness]
10 g of filler was weighed into a 100 ml polycup, and further 10 g of plasticizer DINP (diisononyl phthalate) was weighed and stirred for 60 seconds with a planetary defoaming stirrer manufactured by Kurabo Industries. The obtained powder paste was measured for L value representing 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 produce a powder molded product having a diameter of 10 mm. The obtained molded product was measured for volume resistivity 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 less than 1 × 10 ⁷ Ω · cm Δ; 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% colloidal calcium carbonate water slurry adjusted to a BET specific surface area of 7 m ² / g by reacting carbon dioxide with calcium hydroxide was charged into a 10 L tank, and poly (3,4-ethylenedioxythiophene) 0. 200 g of a dispersion liquid (manufactured by Sigma Aldrich) prepared at a mixing ratio of 5 wt% and polystyrene sulfonic acid 0.7 wt%, that is, 2.4 g of a conductive material component was charged and stirred for 30 minutes by a motor with a metal blade. The obtained surface-treated colloidal calcium carbonate slurry was 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 aragonite calcium carbonate water slurry adjusted to a BET specific surface area of 7 m ² / g was put into a 10 L tank, 0.5 wt% of poly (3,4-ethylenedioxythiophene) and 0.7 wt% of polystyrene sulfonic acid 200 g of a dispersion liquid (manufactured by Sigma Aldrich) prepared at a mixing ratio of 2.4 g, that is, 2.4 g of a conductive material component, was added and stirred for 30 minutes by a motor with metal blades. The obtained surface-treated aragonite calcium carbonate slurry was dehydrated, dried at 105 ° C. for 4 hours, and pulverized to have a true specific gravity of 2.8, a BET specific surface area of 6.8 m ² / g, and a treatment amount of 12.00 mg / g. Aragonite calcium carbonate filler was prepared.

Example 3
All except that the dispersion prepared in Example 1 with a mixing ratio of 0.5 wt% of poly (3,4-ethylenedioxythiophene) and 0.7 wt% of polystyrene sulfonic acid was changed to 15 g (0.18 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 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% by weight of poly (3,4-ethylenedioxythiophene) and 0.7% by weight of polystyrene sulfonic acid, that is, 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 that the dispersion prepared in Example 1 with a mixing ratio of 0.5 wt% of poly (3,4-ethylenedioxythiophene) and 0.7 wt% of polystyrenesulfonic acid was changed 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 that the dispersion prepared in Example 1 with a mixing ratio of 0.5 wt% poly (3,4-ethylenedioxythiophene) and 0.7 wt% polystyrene sulfonic acid was changed 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 produced in the same manner as in Example 1.

Example 7
Example 1 All except that the dispersion liquid (manufactured by Sigma Aldrich) prepared in 0.5 wt% of polypyrrole-block-poly (caprolactam) in the colloidal calcium carbonate of Example 1 is changed to 480 g, that is, 2.4 g of the conductive material component. In the same manner, 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 12.00 mg / g was prepared.

Example 8
In the colloidal calcium carbonate of Example 1, poly [9,9-bis- (2-ethylhexyl) -9Hfluorene-2,7-diyl] 1.2 wt% (THF solvent, manufactured by Sigma Aldrich) was prepared. In the same manner as in Example 1, except that the amount is changed to 200 g, that is, 2.4 g of the conductive material component, 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 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 Talc 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 polystyrene sulfonic acid 0.7 wt% is mixed with 5000 g, that is, 60 g of the conductive material component, and the 10 L mixer is changed to a Henschel mixer and stirred at 110 ° C. for 60 minutes for dry processing. It was. Then, it moved to the metal bucket and dried at 110 degreeC for 4 hours. The obtained powder was pulverized to produce a conductive talc filler having a true specific gravity 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 adjusted to a BET specific surface area of 10 m ² / g (TITON A-110 manufactured by Sakai Chemical Industry Co., Ltd.), and poly (3,4-ethylenedioxythiophene) ) 2860 g of the dispersion prepared at a mixing ratio of 0.5 wt% and polystyrene sulfonic acid 0.7 wt%, that is, 34.3 g of the conductive material component, the 10 L mixer was changed to a Henschel mixer and stirred at 110 ° C. for 60 minutes, Dry processing was performed. Then, it moved to the metal bucket and dried at 110 degreeC for 4 hours. The obtained powder was pulverized to produce a conductive titanium oxide filler having a true specific gravity 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 (Matsumoto Yushi Seiyaku Co., Ltd. Microsphere FN-80SDE) adjusted to a BET specific surface area of 3 m ² / g, and poly (3,4-ethylene Dioxythiophene) The dispersion prepared at a mixing ratio of 0.5 wt% and polystyrenesulfonic acid 0.7 wt% was changed 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. Stir, dry treatment and drying. The obtained powder was not pulverized to produce a conductive acrylic resin balloon filler having a true specific gravity of 0.1, a BET specific surface area of 2.8 m ² / g, and a treatment amount of 5.00 mg.

Example 12
In Example 1, the colloidal calcium carbonate was changed to 2000 g of a polytetrafluoroethylene resin (Microdisparth 200 manufactured by Techno Chemical Co., Ltd.) adjusted to a BET specific surface area of 10 m ² / g, and poly (3,4-ethylenedioxy Thiophene) Dispersion prepared in a mixing ratio of 0.5 wt% and polystyrene sulfonic acid 0.7 wt% was changed 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. Then, dry processing was performed. Then, it moved to the metal bucket and dried at 110 degreeC for 4 hours. The obtained powder was not pulverized, and a conductive Teflon (registered trademark) filler having a true specific gravity of 2.0, a BET specific surface area of 9.8 m ² / g, and a treatment amount of 17.00 mg was prepared.

Example 13
To 140 g of a 7 wt% wet synthetic silica water slurry adjusted to a BET specific surface area of 100 m ² / g synthesized by silicate formation and further decomposed with sulfuric acid or carbon dioxide gas, poly (3,4-ethylenedioxy) was added. Thiophene) 140 g of a dispersion (Sigma Aldrich) prepared at a mixing ratio of 0.5 wt% and polystyrene sulfonic acid 0.7 wt%, 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 produce a conductive silica filler having a true specific gravity 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 by mixing 0.5% by weight of poly (3,4-ethylenedioxythiophene) and 0.7% by weight of polystyrene sulfonic acid is changed to 10 g, that is, 0.12 g of the conductive material component. Except for all, 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 of conductive silica filler were prepared in the same manner as in Example 9.

Example 15
In the silica of Example 13, the dispersion prepared by mixing 0.5% by weight of poly (3,4-ethylenedioxythiophene) and 0.7% by weight of polystyrene sulfonic acid is changed to 620 g, that is, 7.44 g of the conductive material component. Except for the above, 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.

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) 1430 g of the dispersion prepared at a mixing ratio of 0.5 wt% and polystyrene sulfonic acid 0.7 wt%, that is, 17.2 g of the conductive material component is changed to a Henschel mixer and stirred at 110 ° C. for 30 minutes. Processing and drying were performed. The obtained powder was pulverized to produce conductive titanium oxide powder having a true specific gravity 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
Except for changing the dispersion prepared in Example 1 at a mixing ratio of 0.06 wt% poly (3,4-ethylenedioxythiophene) and 1.14 wt% polystyrene sulfonic acid 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 produced 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% by weight of poly (3,4-ethylenedioxythiophene) and 0.7% by weight of polystyrene sulfonic acid, that is, 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, 1000 g (12.0 g of the same solid) of a dispersion prepared by mixing 0.5 wt% poly (3,4-ethylenedioxythiophene) and 0.7 wt% polystyrene sulfonic acid. 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 change.

Comparative Example 3
The colloidal calcium carbonate of Example 1 was changed to 2000 g of zinc oxide adjusted to a BET specific surface area of 10 (first grade manufactured by Hakusui Tech Co., Ltd.), 0.5% by weight of poly (3,4-ethylenedioxythiophene) and polystyrene sulfone. The dispersion prepared with a mixing ratio of 0.7 wt% of acid was changed 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, followed by dry treatment and drying. The obtained powder was not pulverized to produce a conductive zinc oxide filler having a true specific gravity 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
In the colloidal calcium carbonate of Example 1, barium sulfate adjusted to a BET specific surface area of 5 (precipitated barium sulfate 110 manufactured by Sakai Chemical Industry Co., Ltd.) was changed to 2000 g, and poly (3,4-ethylenedioxythiophene) 0. A dispersion prepared by mixing 5 wt% and polystyrene sulfonic acid 0.7 wt% was changed 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 to perform dry processing. went. Then, it moved to the metal bucket and dried at 110 degreeC for 4 hours. The obtained powder was not pulverized to produce a conductive barium sulfate filler having a true specific gravity of 4.6, a BET specific surface area of 4.8 m ² / g, and a throughput of 8.58 mg / g.

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

Comparative Example 6
In the silica of Example 13, the dispersion prepared by mixing 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 by mixing 0.5% by weight of poly (3,4-ethylenedioxythiophene) and 0.7% by weight of polystyrene sulfonic acid was changed to 630 g, that is, 7.56 g of the conductive material component. Except for the above, 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.

Comparative Example 8
In the silica of Example 13, a 7 wt% concentration wet synthetic silica water slurry adjusted to a BET specific surface area of 100 was mixed with 0.5 wt% of poly (3,4-ethylenedioxythiophene) and 0.7 wt% of polystyrene sulfonic acid. A true specific gravity of 1.6, a BET specific surface area of 98.0 m ² / g, and an untreated silica filler were all used in the same manner as in Example 9, except that the dispersion prepared at a ratio was not charged and changed to an untreated state. Produced.

Comparative Example 9
In the colloidal calcium carbonate of Example 1, a dispersion prepared by mixing a poly (3,4-ethylenedioxythiophene) 1.2 wt% and polystyrene sulfonic acid 0 wt% 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 the poly (3,4-ethylenedioxythiophene) 0 wt% and the polystyrene sulfonic acid 1.2 wt% 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.

  In Table 1, the characteristic of the filler obtained in Examples 1-17 and Comparative Examples 1-10 was shown.

Examples 18-34, Comparative Examples 1-20
[Conductive rubber composition]
The fillers obtained in Examples 1 to 17 and Comparative Examples 1 to 10 were kneaded using an open roll (manufactured by Kansai Roll Co., Ltd.) at 60 ° C. under the conditions shown below and the composition shown in Table 2. A dust compound was prepared.
(Combination)
Epichlorohydrin rubber Daiso EPION-301 100 parts by weight Fillers of Examples 1 to 17 and Comparative Examples 1 to 10 Variables *
Vulcanizing agent Hosoi Chemical Sulfur powder 2 parts by weight vulcanization accelerator Ouchi Shinsei Kagaku Noxeller M 1 part by weight vulcanization accelerating agent Ouchi Shinsei Kagaku Noxeller TET 1 part by weight Stearic acid Kao Stearic acid cherry 1 part by weight Zinc Hana HAXITEC Oxidation 2 types of zinc 5 parts by weight * Adjusted to an appropriate blending amount to make a compound according to the particle size of the filler.

The obtained compound was made into a rubber sheet shape having a thickness of 2 mm, and the following measurements were performed under a temperature condition of 23 ° C. and a humidity of 50%.
[Whiteness, stiffness, elongation at break, volume 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. Further, the hardness value after 1000 g load was measured with a hardness meter (type C manufactured by Asker Co., Ltd.). Moreover, it punched out with the dumbbell No. 3, the tension test (tensile speed of 200 mm / min.) Based on JISK6253 was done, and elongation at break was measured.
Further, the obtained compound was made into a rubber sheet shape having a width of 120 mm, a length of 100 mm, and a thickness of 2 mm, and allowed to stand at 23 ° C. × 50% humidity for 3 hours, and then composed with an Agilent resist meter 4339B. 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 (determination criteria of hardness value)
◎; 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
(Judgment criteria for elongation at break)
◎; 300% or more ○; 200% or more to less than 300% △; 100% or more to less than 200% ×; less than 100% (judgment 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 less than 1 × 10 ⁷ Ω · cm Δ; 1 × 10 ⁷ Ω · cm or more to 1 × 10 ¹⁰ Ω · cm or less ×; 1 × 10 ¹⁰ Ω · cm or more

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

Examples 35-51, Comparative Examples 21-30
[Conductive film composition]
White polyethylene resin films were prepared with the formulations shown below for the fillers obtained in Examples 1 to 17 and Comparative Examples 1 to 10.
(Combination)
Polyethylene resin Nippon Polypenco 100 parts by weight Examples 1-10, 12, 16, 17, Comparative Examples 1-5, 9, 10, 10 fillers 50 parts by weight Example 11 fillers 5 parts by weight Examples 13-15, Comparative Example 6 Filler of ~ 8 6 parts by weight Filler into polyethylene resin into Henschel mixer, dispersed and stirred for 30 minutes, then kneaded extruder (labor plast mill 2D25W type; manufactured by Toyo Seiki Co., Ltd.) 130 ° C And granulated into pellets. After the obtained pellets were dried at 110 ° C. for 1 hour, the pellets were extruded into a film form from a T-type die using a film extruder (laboplast mill D2025 type; manufactured by Toyo Seiki Co., Ltd.). The film was cooled and solidified with a cooling drum to obtain an unstretched film. 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 transverse direction to obtain a film composition having a thickness of 180 μm.

About the obtained film, the following physical property was measured or evaluated.
[Whiteness, dispersibility, volume resistivity, reflectivity, 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.
Dispersibility: The dispersibility was evaluated by the number of fish eyes due to aggregates and coarse particles in a film of 300 mm × 300 mm.
Volume resistivity: A film having a thickness of 180 μm, a width of 150 mm × a length of 100 mm was allowed to stand at 23 ° C. × 50% humidity for 3 hours or more, and the volume resistivity was measured with a resist meter 4339B manufactured by Agilent.
Reflectivity: An ultraviolet-visible spectrophotometer (UV3101PC, manufactured by Shimadzu Corporation) was used to measure the wavelength range of reflectivity 0.30 to 0.80 μm when the barium sulfate white plate was 100%, and the reflectivity was 0.45 μm. Representative values were used.
Tensile properties: according to the tensile properties of JIS Z 1702 polyethylene film, 500 mm / min. The breaking strength and the elongation at break when measured at a speed of 5 were measured.

(Whiteness criteria)
◎; 90 or more ○; 85 or more to less than 90 Δ; 80 or more to less than 85 ×; less than 80 (determination criteria for dispersibility)
◎: 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 resistance Criteria for rate)
◎; 1 × 10 ⁴ Ω · cm or more to less than 1 × 10 ⁶ Ω · cm ○; 1 × 10 ⁶ Ω · cm or more to less than 1 × 10 ⁸ Ω · cm △; 1 × 10 ⁸ Ω · cm or more to 1 × 10 ¹⁰ Ω · cm or less ×; 1 × 10 ¹⁰ Ω · cm or more (reflectance criteria)
◎; 96% or more ○; 93% or more to less than 96% △; 90% or more to less than 93% ×; less than 90% (judgment criteria)
(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) Elongation at break ◎: 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 are maintained without impairing conductivity and dispersibility, Further, it can be seen that the breaking strength and breaking elongation have sufficient performance.

Examples 52-68, Comparative Examples 31-40
[Conductive sealant composition]
Modified silicone sealants were prepared using the fillers obtained in Examples 1 to 17 and Comparative Examples 1 to 10 with the following formulations and the formulations shown in Table 4.
(Combination)
Modified silicone polymer Kaneka MS polymer S-203 100 parts by weight amide wax Ito Oil Co., Ltd. ASA-T-1800 Variables *
Fillers of Examples 1-17 and Comparative Examples 1-10
Heavy calcium carbonate Maruo calcium Super S Variable *
Plasticizer JPLUS DINP 60 parts by weight Dehydrating agent Shin-Etsu Chemical KBM-1003 6 parts by weight Tin catalyst Nitto Kasei Neostan U-220H 2 parts by weight Adhesive agent Shin-Etsu Chemical KBM-603 2 parts by weight * Amide wax, filler The heavy calcium carbonate was appropriately changed according to the type.

  The filler, heavy calcium carbonate, and amide wax were put into a 5 L Dalton mixer (manufactured by Dalton Co., Ltd.) in a state of being dried or melted at 110 ° C. for 3 hours, and stirred under reduced pressure. Next, a plasticizer, a dehydrating agent catalyst, and an adhesion-imparting agent were added and stirred in the same manner to produce a modified silicone sealant. The obtained sealant was filled into 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 protruded from the cartridge and filled into a 100 ml PP cup, and a B type viscometer (manufactured by Tokimec Co., Ltd.) Rotor No. 7 was used to measure 1 rpm viscosity and 10 rpm viscosity. At the same time, the TI value (1 rpm viscosity / 10 rpm viscosity) serving as a measure of workability was measured.
Whiteness: The whiteness of the obtained sealant was measured 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 is filled into a sheet of 2 mm thickness, 20 mm width and 100 mm length, cured at 23 ° C. × 14 days + 35 ° C. × 14 days, punched into No. 3 dumbbell, and in accordance with JIS K 6253 Tensile properties were measured.
Volume resistivity: The obtained sealant was filled into a sheet of 2 mm thickness, width 120 mm × length 100 mm, cured at 23 ° C. × 14 days + 35 ° C. × 14 days, and kept at 23 ° C. × 50% humidity for 3 hours or more. The volume resistivity of the composition was measured with a resist meter 4339B manufactured by Agilent.
(Viscosity criteria)
◎: 1rpm viscosity value / 10rpm viscosity value = 6.5 or more ○: 6.0 or more to less than 6.5 △; 5.0 or more to less than 6.0 ×: Same as 5.0 (determination of whiteness) Criteria)
◎; 90 or more ○; 85 or more to less than 90 Δ; 80 or more to less than 85 ×; less than 80 (criteria for tensile properties)
(1) 50% tensile stress (stress when the distance between the marked lines 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) Elongation at break ◎: 400% or more ○; 350% or more and less than 400% △; 300% or more and less than 350% ×: Less than 300% (volume resistivity criterion)
◎; 1 × 10 ⁴ Ω · cm or more to less than 1 × 10 ⁶ Ω · cm ○; 1 × 10 ⁶ Ω · cm or more to less than 1 × 10 ⁸ Ω · cm △; 1 × 10 ⁸ Ω · cm or more to 1 × 10 ¹⁰ Ω · cm or less ×; 1 × 10 ¹⁰ Ω · cm or more

  The measurement results are shown in Table 4.

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

Examples 69-85, Comparative Examples 41-50
[Preparation of conductive plastisol composition]
Vinyl chloride resin plastisols were prepared with the formulations shown below and the formulations shown in Table 5 for the fillers obtained in Examples 1 to 17 and Comparative Examples 1 to 10.
[Combination]
PVC paste resin PCH-22 Kaneka Corporation 250 parts by weight Polyamide Co., Ltd. Henkel Co., Ltd. 15 parts by weight DINP Co., Ltd. J Plus Co., Ltd. 250 parts by weight Turpen 37 parts by weight Quicklime 15 parts by weight manufactured by Wako Pure Chemical Industries, Ltd. Examples 1-17 , Fillers for Comparative Examples 1-10 Variable *
Heavy Calcium Carbonate Super S (manufactured by Maruo Calcium Co., Ltd.) Variable Disparon # 309 Variable * Because the effect of imparting viscosity differs depending on the type and particle size, the filler was varied as shown in Table 5.

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

The following physical properties of the obtained plastisol were measured.
[Viscosity, whiteness, slip resistance, dispersibility, volume resistivity]
Viscosity: The obtained plastisol was filled into a 100 ml PP cup, and a BH viscometer (manufactured by Tokimec Co., Ltd.) rotor No. 7 was used to measure 2 rpm viscosity and 20 rpm viscosity. At the same time, the TI value (2 rpm viscosity / 20 rpm viscosity) serving as a measure of workability was measured.
Whiteness: The whiteness of the obtained plastisol was measured 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 was packed in a 100 ml PP cup, allowed to stand at 23 ° C. for 3 days, applied to a 130 mm × 60 mm adherend with a length of 100 mm on a 12 mm semicircular bead, and then kept at 23 ° C. The distance the sol slipped off after 30 minutes was measured by a ruler.
Dispersibility: measured by the following method.
Fill each 5L universal mixing stirrer (manufactured by Dalton) with each compounding agent and filler under compacting condition, knead for 3 minutes, once open the lid, scrape off the compounding agent adhering to the wall, and then again in vacuum atmosphere Knead under 10 minutes. The sol after kneading was defoamed with a planetary defoaming kneader (Kurabo Co., Ltd./KK-500) under kneading conditions 5-5-18 to prepare a vinyl chloride sol for measuring dispersibility.
Dispersibility was measured by spreading a polyvinyl sol for measuring dispersibility thinly on a glass plate with a spatula so that the length was 5 cm or more, 5 cm or more, and thickness within 1 mm.
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 at 23 ° C. × 50% humidity for 3 hours or more, using an Agilent resist meter 4339B. The volume resistivity of the composition was measured.

(Viscosity criteria)
The determination was made according to the following criteria according to the Ti value of 2 rpm viscosity / 20 rpm viscosity.
◎: 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 criteria)
◎: 90 or more ○: 85 or more and less than 90 Δ: 80 or more and less than 85 ×: less than 80 (slip resistance judgment criteria)
○: 0 mm
Δ: Over 0 mm and less than 10 mm ×: 10 mm or more (determination criteria for dispersibility)
The number of particles of 0.5 mm or more per 5 cm square on the surface of the vinyl chloride sol coated on the glass plate was counted.
○: 0 or more 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 (volume resistivity criterion)
◎; 1 × 10 ⁴ Ω · cm or more to less than 1 × 10 ⁶ Ω · cm ○; 1 × 10 ⁶ Ω · cm or more to less than 1 × 10 ⁸ Ω · cm △; 1 × 10 ⁸ Ω · cm or more to 1 × 10 ¹⁰ Ω · cm or less ×; 1 × 10 ¹⁰ Ω · cm or more

  The measurement results are shown in Table 5.

  From the measurement results in Table 5, by adding the conductive surface-treated powder filler of the present invention, a plastisol composition having excellent conductivity can be obtained, and the plastisol can be obtained without impairing the dispersibility and slip resistance functions. 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 that forms a conductive path by dispersing the filler in a composition blended with a resin such as rubber, plastic, film, sealing material, adhesive, paint, and plastisol. Can take structure.
Therefore, the conductive surface-treated powder filler of the present invention not only imparts a conductive function, but also has excellent colorability due to high whiteness, which is a characteristic of the original powder, enables transparency, A conductive resin composition other than the ones can be obtained.
Compared to other metal powders containing inorganic metal compounds such as indium, tin, silver, copper, zinc, aluminum, and antimony, it has excellent dispersibility and a small true specific gravity. However, it is possible to obtain a resin composition having a conductive effect and having a reinforcing function inherent in the powder, a flexible function such as high elongation of the conductive polymer, and a weight reducing function.

Claims (15)

A surface treatment agent (B) containing a π-conjugated conductive polymer and a polyanion on the surface 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, which is a surface-treated powder having a coating layer and 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 the surface-treated powder obtained by the following formula
As = Tgx / Sw
Tgx: amount of surface treatment agent containing π-conjugated conductive polymer and polyanion per gram of surface-treated powder [mg / g]
Sw: BET specific surface area of the surface-treated powder [m ² / g]   The conductive surface-treated powder filler according to claim 1, 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.   2. The conductive material according to claim 1, 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, fluorine resin, phenol resin, and wood powder. Surface treatment powder filler.   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 4, wherein the polythiophene is poly (3,4-ethylenedioxythiophene).   The conductive surface-treated powder filler according to any one of claims 1 to 5, wherein the polyanion is at least one selected from the group consisting of polystyrene sulfonic acid, polyvinyl sulfonic acid, and polyacrylamide sulfonic acid. The conductive surface-treated powder filler according to any one of claims 1 to 6, which has a volume resistivity of 10 ⁸ Ω · cm or less.   Contains a water 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) comprising a π-conjugated conductive polymer and a polyanion 8. The conductive surface-treated powder filler according to claim 1, wherein the particles of the powder (A) are surface-treated by mixing and stirring with the dispersion liquid to be produced. Method.   A conductive resin composition comprising the conductive surface-treated powder filler according to claim 1.   A conductive rubber composition comprising the conductive surface-treated powder filler according to any one of claims 1 to 7.   The electroconductive film composition formed by containing the electroconductive surface treatment powder filler of any one of Claims 1-7.   The electroconductive sealing material composition formed by containing the electroconductive surface treatment powder filler of any one of Claims 1-7.   The electroconductive adhesive composition formed by containing the electroconductive surface treatment powder filler of any one of Claims 1-7.   The electroconductive coating composition formed by containing the electroconductive surface treatment powder filler of any one of Claims 1-7.   The electroconductive plastisol composition formed by containing the electroconductive surface treatment powder filler of any one of Claims 1-7.