JP3434592B2 - Conductive particle composition and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive particle composition capable of forming an excellent conductive layer and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, in resin products and clothes,
Antistatic treatment is applied to prevent the generation of static electricity. Examples of the antistatic treatment include a method of forming an electroconductive layer by applying an antistatic agent composed of an electroconductive particle composition onto the surface of a base material such as resin or fiber. The above-mentioned conductive particle composition is mainly composed of a conductive particle body, and is usually a dispersion type of a solution, an emulsion, a dispersion or the like, which is a coating type. Is used as. The conductive particles (conductive substance) include, for example, inorganic conductive particles such as metal, metal oxide, and carbon black, a surfactant, or silane-based particles such as organosiloxane. . In addition, the conductive particulate composition is required to have a transparent coating film (hereinafter also appropriately referred to as “transparency”) depending on its application so as not to impair the appearance of the product to be treated. It may be done. Further, in such a conductive particle composition capable of forming a conductive layer, its use is not limited to the above antistatic agent, and examples thereof include an antifogging agent and an antifouling agent.

[0003]

However, the electrically conductive particle composition which has been conventionally used has various problems described below, and its performance is not sufficient. That is, an emulsion-type conductive particle composition using inorganic conductive particles such as a metal causes the conductive particles to sediment over time, and the conductive particle composition is coated. Then, there is a problem that the coating film thickness becomes uneven and the transparency is poor. When a surfactant is used,
During coating, there are problems such as foaming of the coating liquid and deterioration of conductivity after coating over time.In addition, the water resistance of the coating film formed is low and it easily deteriorates due to moisture. There is a problem.

On the other hand, polysulfonic acid and its salts are excellent conductive polymers and are also excellent in transparency, so they are used as a conductive resin and also as a coating type conductive particle composition. Are also being considered. However, since polysulfonic acid and its salt alone have a low film-forming property, it is difficult to use them as a coating type as in the conventional conductive particle composition. As a means for solving this problem, it is considered that polysulfonic acid or the like is used by adding it to an aqueous resin having a good film-forming property, for example, a resin emulsion or the like. Therefore, there is a limit to the use as a coating type conductive particle composition because of the problem of the property.

Further, a technique has been proposed in which a polystyrene sulfonate obtained by sulfonation of polystyrene is used as a dispersant for emulsion polymerization (JP-A-1-268).
704, JP-A-3-203901). By doing so, not only the problem of film-forming property but also the problem of emulsion stability can be solved. However, since polysulfonate has a high hydrophilicity, even if a coating film to be a conductive layer is formed by the above-mentioned technique, the coating film is easily deteriorated by moisture, and the conductivity decreases with time. I have a problem. As described above, the conductive particle composition, for example, because it is used for antistatic of clothing,
This problem of water resistance is the largest problem to be solved when using polysulfonic acid and its salt as a conductive particulate composition.

The present invention has been made in view of such circumstances, and in addition to having excellent electroconductivity and transparency, in addition to these, an electroconductive particle composition having high film-forming property and water resistance and The purpose is to provide the manufacturing method.

[0007]

In order to achieve the above object, the first aspect of the present invention is a conductive particle composition containing the following (A) and (B). (A) A conductive particle body in which the following water-soluble polymer (a) is located on the outer periphery of the polymer particle body. (A) A water-soluble polymer having a sulfonic acid group and a carboxyl group. (B) At least one resin of a film-forming water-soluble resin and a film-forming water-dispersible resin.

In the present invention, a monomer having a polymerizable functional group is polymerized in an aqueous solvent containing the following water-soluble polymer (a), and a film-forming water-soluble resin and A second gist is a method for producing a conductive particle composition containing at least one film-forming water-dispersible resin. (A) A water-soluble polymer having a sulfonic acid group and a carboxyl group.

[0009]

That is, the present inventors focused on the development of a technique for imparting film-forming property and water resistance to polysulfonic acid and salts thereof without impairing the excellent conductivity and transparency of polysulfonic acid. Repeated research. In the process,
Paying attention to the technique of using polysulfonic acid and its salt as a dispersant for emulsion polymerization, various types of polysulfonic acid and its salt were experimentally produced. As a result, a water-soluble polymer having a sulfonic acid group and a carboxyl group was experimentally produced, and in a water-based solvent in which the water-soluble polymer was present, a monomer having a polymerizable functional group was polymerized to obtain an emulsion. As a result, a conductive particle body in which the water-soluble polymer was located on the outer periphery of the polymer particle body could be obtained. And when I tried to form a coating film using this,
It has been found that this conductive particle body exhibits film-forming properties and water resistance. However, this film-forming property and water resistance are
Since the present inventors did not reach the target level, further research was conducted. As a result, in addition to the above-mentioned conductive particle body, a conductive particle body composition was prepared using at least one resin of a film-forming water-soluble resin and a film-forming water-dispersible resin. It was found that the product has practically excellent film-forming property and water resistance, and also has good conductivity and transparency, and has reached the present invention.

Next, the present invention will be described in detail.

The conductive particle composition of the present invention has a structure in which the water-soluble polymer (a) having a sulfonic acid group and a carboxyl group is located on the outer periphery of the particle body made of a polymer. The main component is the particle body (A), and at least one resin (B) selected from the film-forming water-soluble resin and the film-forming water-dispersible resin is mixed therein. The conductive particle composition of the present invention is usually used in the form of dispersion or emulsion dispersed in an aqueous solvent. Further, a curing agent is added to the conductive particle composition of the present invention, if necessary.

First, the special conductive particle body (A) which is a main constituent element of the present invention will be described.

In the conductive particle body (A), the water-soluble polymer (a) located on the outer periphery of the particle body is, for example,
It can be produced by copolymerizing a polymerizable monomer having a sulfonic acid group and a polymerizable monomer having a carboxyl group.

Examples of the polymerizable monomer having a sulfonic acid group include vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-acrylamidoethyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, Examples thereof include styrene sulfonic acid and the like and salts thereof. Of these, styrene sulfonic acid and salts thereof are preferably used because of their excellent conductivity.

Examples of the polymerizable monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, or dicarboxylic acids or dicarboxylic acid anhydrides. To be Among these, dicarboxylic acid is preferably used, and maleic acid is particularly preferable, because the formed coating film has higher water resistance.

Further, in the water-soluble polymer (a) of the present invention, other functional groups may be introduced in addition to the sulfonic acid group and the carboxyl group. Therefore, in addition to the above-mentioned polymerizable monomer, for example, a monomer having a copolymerizable vinyl group may be used.

The method of polymerizing the above-mentioned polymerizable monomer is not particularly limited, and a conventionally known method can be applied. Specifically, for example, in water, the polymerizable monomer having the sulfonic acid group and the polymerizable monomer having a carboxyl group, further other polymerizable monomers are dissolved as necessary, the polymerization initiator Polymerization can be performed by adding (for example, potassium persulfate) or the like and heating.

The water-soluble polymer (a) of the present invention is
It can also be manufactured by a method other than the above. That is, a polymerizable monomer having no sulfonic acid group and a polymerizable monomer having a carboxyl group are polymerized to prepare a copolymer, and the copolymer is also subjected to a sulfonation treatment to produce the above-mentioned aqueous solution. It is possible to obtain the high molecular weight polymer (a).

The polymerizable monomer having no sulfonic acid group is not particularly limited, and examples thereof include styrene and α-methylstyrene.

Then, the monomer is polymerized by the above-mentioned method to prepare a copolymer, and the sulfonation treatment is applied to this. The method of this sulfonation treatment is not particularly limited, and a conventionally known method can be applied. Specifically, the above copolymer is put into a solvent, and a sulfonation treatment is performed using a sulfonating agent.

As the above solvent, dichloromethane, 1,
Chlorinated hydrocarbons such as 2-dichloroethane, hydrocarbons such as n-hexane and cyclohexane, dioxane and the like are mentioned as good solvents. Among these, it is difficult to react with a sulfonating agent and does not form a salt during neutralization. Dichloroethane etc. can be mentioned as a suitable solvent.

As the sulfonating agent, S
Examples thereof include O ₃ , a complex of Lewis acid and SO _3, and chlorosulfonic acid. The reaction of the sulfonating agent in the above solvent is preferably carried out under low temperature conditions of 30 ° C or lower.

In such a water-soluble polymer (a), the ratio of the sulfonic acid group and the carboxylic acid group is a molar ratio of functional groups, that is, sulfonic acid group / carboxylic acid group = 10/9.
0 to 95/5, preferably sulfonic acid group / carboxylic acid group = 20/80 to 80/20, particularly preferably sulfonic acid group / carboxylic acid group = 30/70 to 60/40.

The water-soluble polymer (a) preferably has a weight average molecular weight of 1,000 to 500,000.
Particularly preferably, it is in the range of 2000 to 100,000. That is, the weight average molecular weight of the water-soluble polymer (a) is 10
If it is less than 00, the adsorption to the particle body becomes insufficient, and when the conductive particle composition of the present invention is used in the form of an emulsion or the like, the dispersion stability may deteriorate. . On the contrary, the weight average molecular weight is 50
This is because if it exceeds 10,000, when the conductive particle body (A) is produced by an emulsion polymerization method or the like, the viscosity of the aqueous solvent is increased, which may hinder the production.

When the water-soluble polymer (a) is added to the aqueous solvent, it becomes acidic due to the sulfonic acid and carboxylic acid, but it may be neutralized or not neutralized. In the case of neutralizing, as the neutralizing agent, Na ⁺ , K ⁺ , Li ⁺ , Ca ²⁺ , NH ₄ are used as the counter ion of the neutralizing agent.
There are cationic ions such as ⁺ , specifically, for example,
NaOH, KOH, LiOH, Ca (OH) ₂ , NH ₄
Inorganic or organic alkaline substances such as OH, triethanolamine and 2-amino-2-methylpropanol can be used.

Next, the polymer which is the main body of the particles is prepared by polymerizing a monomer having a polymerizable functional group, and such a monomer is, for example, a vinyl monomer. Examples thereof include polyfunctional vinyl monomers and epoxy group-containing monomers, which may be used alone or in combination of two or more.

Examples of the vinyl monomer include aromatic vinyl monomers such as styrene and α-methylstyrene, acrylic acid such as methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate, or Ester of methacrylic acid, monocarboxylic acid or dicarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, or dicarboxylic acid anhydride, vinyl halide monomer such as vinyl chloride and vinylidene chloride , Vinyl esters such as vinyl acetate,
Examples thereof include conjugated dienes such as butadiene and isoprene.

Examples of the polyfunctional vinyl monomer include divinylbenzene, trivinylbenzene, diallyl phthalate, allyl acrylate, allyl methacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate and the like. .

Examples of the epoxy group-containing monomer include glycidyl acrylate and glycidyl methacrylate.

Among these monomers having a polymerizable functional group, it is preferable to use a polyfunctional vinyl monomer because the coating film to be formed has more excellent water resistance.

In addition to the above-mentioned monomer, a monomer having a vinyl group and another functional group capable of reacting can be mentioned. It is preferable to use this for the same reason as above. The other functional group capable of reacting is an epoxy group,
Functional groups such as a methylol group, an oxazoline group, and an isocyanate group are included. In addition, specific examples of the monomer having these functional groups include glycidyl acrylate, glycidyl methacrylate, N-methylol acrylamide, N-
Methylol methacrylamide, vinyl oxazoline, 2
-Propenyl-2-oxazoline, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like can be mentioned.

Next, the special resin (B) which is another component of the conductive particle composition of the present invention will be described.

The special resin (B) is at least one of a film-forming water-soluble resin and a film-forming water-dispersible resin. In addition, in the present invention, the film-forming property is not limited to that which forms a continuous coating film at room temperature when a resin is applied, and in addition to this, when there is a baking condition at a high temperature or when a film-forming aid is used. The property of forming a continuous coating film even when an agent or the like can be added.

The resin (B) is not particularly limited as long as it has a film forming property and can be used in an aqueous system regardless of its water solubility and water dispersibility. Examples of such a resin (B) include a polymer obtained by polymerizing a polymerizable monomer such as a vinyl monomer.

Examples of the vinyl monomer include styrene and α
-Aromatic vinyl monomers such as methylstyrene, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, esters of acrylic acid or methacrylic acid such as methyl methacrylate, acrylic acid, methacrylic acid, crotonic acid, maleic acid Acid, fumaric acid, itaconic acid and other monocarboxylic acids or dicarboxylic acids or dicarboxylic acid anhydrides, vinyl chloride, vinylidene chloride and other halogenated vinyl monomers, vinyl acetate and other vinyl esters, butadiene, isoprene and other conjugated dienes Further, polyfunctional vinyl monomers such as divinylbenzene, trivinylbenzene, diallyl phthalate, allyl acrylate, allyl methacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate and the like can be mentioned. Further, examples of the monomer having an epoxy group include glycidyl acrylate and glycidyl methacrylate.

The polymerization reaction of such a polymerizable monomer is not particularly limited, and a conventionally known method such as an emulsion polymerization method is applied. In addition, in this polymerization, a surfactant for polymerization, a seed emulsion, or a water-soluble polymer for providing a place for polymerization may be used, if necessary. Further, it is preferable to add an appropriate amount of a polymerization initiator, an inorganic substance, a chain transfer agent, etc., and perform the polymerization under a nitrogen gas atmosphere at an appropriate temperature.

Further, in addition to the polymer (resin) obtained from the above-mentioned polymerizable monomer, it is also possible to use the resins shown below. That is, a polyester resin obtained by a polycondensation reaction of a polyol component and a polycarboxylic acid, and a modified polyester resin obtained by modifying this polyester resin with a fatty acid or an epoxy resin or by acrylic grafting are mentioned. As the polyol component, trimethylolethane, trimethylolpropane,
Examples thereof include glycerin, ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,6-hexanediol and pentaerythritol. Also,
Examples of the polycarboxylic acid include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, adipic acid and trimellitic acid. Further, a modified epoxy resin obtained by adding an acid anhydride to an esterified product or an etherified product of the above-mentioned polyester resin or modified polyester resin bisphenol / epichlorohydrin type epoxy resin, urethane resin and the like can be used.

The blending ratio of the film-forming water-soluble resin or the like (B) is usually 5 to 500 parts, preferably 100 parts by weight (hereinafter referred to as "part") of the conductive particle body (A). Two
It is 0 to 300 parts, and particularly preferably 30 to 100 parts.

Next, it is preferable to add a curing agent to the conductive particle composition of the present invention. That is, the addition of the curing agent makes the electroconductive particle composition more excellent in film-forming property and water resistance. The above curing agent may be one having two or more functional groups in one molecule which react with the carboxyl group of the conductive particle body (A) or the carboxyl group of the film-forming water-soluble resin or the like (B). However, it is not particularly limited. Examples of such a functional group include an epoxy group, a methylol group, an aziridinyl group, an oxazoline group, an isocyanate group, and a carbodiimide group. As the curing agent having such a functional group, for example, as the above-mentioned curing agent having an epoxy group, one having a polyfunctional epoxy group and dispersed in water using an appropriate emulsifier, or the curing agent itself is Some are water-soluble. Examples of using the above emulsifier include bisphenol type epoxy resin and novolac type epoxy resin. Examples of the water-soluble curing agent itself include glycerin-modified epoxy resin and polyoxyalkylene-modified epoxy resin. As specific examples of the curing agent having a functional group other than the epoxy group, examples of the curing agent having a methylol group include melamine resin, methylolphenol resin, and urea resin. Further, as those having an aziridinyl group, tris-2,4,4
6- (1-aziridinyl) -1,3,5-triazine,
Examples include tris [1- (2-methyl) aziridinyl] phosphine oxide and the like. As those having an oxazoline group, 2,2- (1,3-phenylene) -bis (2
-Oxazoline) and the like. Examples of compounds having an isocyanate group include blocked isocyanates obtained by masking isocyanate such as hexamethylene diisocyanate and isophorone diisocyanate with a blocking agent such as ε-caprolactam, phenols or alcohols. Examples of compounds having a carbodiimide group include trimethylolpropane-tris- [β- (N-aziridinyl) propionate].

Among the above-mentioned curing agents, it is preferable to use an epoxy resin because of its low toxicity and preferable reactivity, and a water-soluble epoxy resin is particularly preferable.

The mixing ratio of the above-mentioned curing agent is usually 0.5 to 50 parts, preferably 1.0 to 30 parts, particularly preferably 5 to 20 parts, relative to 100 parts of the conductive particle (A). Is.

As the curing agent to be added to the conductive particle composition of the present invention, in addition to the above organic curing agent,
Examples thereof include polyvalent metal compounds, which may be used alone or in combination with the above curing agents. Examples of such polyvalent metal compounds include basic aluminum, zinc oxide, titanium oxide, and zirconium oxide. The compounding ratio of the polyvalent metal compound is such that the conductive particle body (A) 10
Usually, 0.5 to 50 parts, preferably 1.0 to 0 parts
-30 parts, particularly preferably 5-20 parts.

Furthermore, the conductive particle composition of the present invention is
For example, when it is used as a conductive paint, various additives such as fillers and pigments can be added depending on the application.

Examples of the filler include inorganic powders such as calcium carbonate, magnesium carbonate and silica.

Examples of the pigment include titanium oxide, carbon black, aluminum, red iron oxide, talc, clay and the like.

Further, other additives include, for example, a viscosity modifier, a leveling agent, a defoaming agent, a preservative and the like.

The mixing ratio of these additives is appropriately determined depending on the use of the conductive particle composition.

Next, a method for producing the conductive particle composition of the present invention will be described.

According to the method for producing the conductive particle composition of the present invention, the conductive particle body (A) is prepared, and at least one of the film-forming water-soluble resin and the film-forming water-dispersible resin ( It can be prepared by blending B) and, if necessary, a curing agent and various additives.

That is, first, the conductive particle body (A)
Is produced, for example, by a method of polymerizing the monomer having a polymerizable functional group in an aqueous solvent in which the water-soluble polymer (a) is present. Specifically, it is carried out by a polymerization method such as an emulsion polymerization method, a suspension polymerization method or a dispersion polymerization method.

Water is usually used as the above-mentioned aqueous solvent, but alcohols such as ethanol and propanol can be used in addition to this, and an organic solvent may be used if necessary.

In the above aqueous solvent, the water-soluble polymer (a)
Dissolve. This water-soluble polymer (a) is, for example,
What was neutralized with sodium hydroxide etc. can be used. The mixing ratio of this water-soluble polymer (a) is
10 to 5 with respect to 100 parts of the monomer having a polymerizable functional group
The amount is 00 parts, preferably 100 to 400 parts, and particularly preferably 200 to 300 parts. That is, if the ratio is less than 10 parts, the stability of the resulting particles is insufficient, and the dispersion stability of the conductive particles (A) obtained in the emulsion form tends to be poor. Further, if it exceeds 500 parts, the film-forming property and the water resistance of the obtained coating film tend to be lowered. Then, a conductive particle body (A) can be obtained in an emulsion form by introducing a monomer having a polymerizable functional group into this aqueous solvent and performing emulsion polymerization, for example. Note that, as described above, the polymerization of the monomer having a polymerizable functional group is not limited to emulsion polymerization, and may be suspension polymerization or dispersion polymerization as long as a desired particle body can be formed. That is, it is meant that the obtained solution or dispersion includes not only those which appear transparent to the naked eye but also those in which the particles produced are in the form of fine particles. Further, the polymerization reaction is preferably performed in a nitrogen gas atmosphere.

If necessary, the above-mentioned aqueous solvent may be used.
You may mix | blend surfactant for emulsion polymerization, a seed emulsion, and other water-soluble polymer in the range which does not affect the performance of the electroconductive particle body (A) which is a product.

Examples of the surfactant for emulsion polymerization include anionic surfactants such as fatty acid salts, alkylbenzene sulfonates and higher alcohol sulfate ether salts, and nonionic surfactants such as polyethylene glycol alkylphenyl ethers. To be

Examples of the seed emulsion include acrylic emulsion and acrylic / styrene emulsion, and specific examples include styrene / butyl methacrylate / methacrylic acid.

Examples of the above other water-soluble polymer include polyvinyl alcohol, acrylic resin, polyester resin and the like.

The mixing ratio of the emulsion polymerization surfactant, seed emulsion and water-soluble polymer is 0.5 to 5 with respect to 100 parts of the monomer having a polymerizable functional group.
The range is 00 copies.

Further, in addition to the above surfactants, a polymerization initiator such as persulfate such as potassium persulfate, an inorganic substance such as sodium tripolyphosphate, and a chain transfer agent such as n-dodecyl mercaptan can be added.

When a monomer having a vinyl group and another functional group capable of reacting is used as the monomer having a polymerizable functional group, the reaction is performed in an aqueous solvent for the purpose of promoting the above reaction. You may mix | blend an accelerator. Examples of this reaction accelerator include aqueous ammonia, triethylamine, triethanolamine, triethylammonium chloride and the like.

Then, at least one resin (B) selected from a film-forming water-soluble resin and a film-forming water-dispersible resin, a curing agent, etc. are added to the conductive particle body (A) thus obtained. The conductive particle composition of the present invention can be prepared by blending in a predetermined ratio.

In the present invention, the conductive particle body (A) is
The reason for further blending the film-forming water-soluble resin or the like (B) is as follows.

That is, the conductive particle body (A) has a film-forming property by itself, and the formed coating film (conductive layer) also has water resistance. Therefore, the conductive particles (A) alone can be sufficiently used for applications such as a coating type antistatic agent. Therefore, the applicant of the present invention separately applied for this conductive particle body (A) (filed on the same day as the present invention).

The present inventors presume that the conductive particle body (A) has water resistance in addition to film-forming property for the following reason. That is, as shown in the schematic view of FIG. 1, the conductive particle body (A)
Has a structure in which the water-soluble polymer (a) 3 having a sulfonic acid group and a carboxyl group is located on the outer periphery of the particle body 2. In the figure, 1 indicates a conductive particle body.
Then, due to the action of the sulfonic acid group, the obtained coating film has high conductivity. Further, due to the carboxyl group of the water-soluble polymer (a), interaction occurs between the conductive particle bodies (A) and in the conductive particle body (A), so that the coating film has water resistance. It is thought that it will be expressed. Examples of this interaction include hydrogen bonding and crosslinking reaction.

However, this conductive particle body (A) alone is not sufficient in water resistance in a severe usage mode. Therefore, as a result of studies aimed at further improving the film-forming property and water resistance, the present inventors have found that the film-forming water-soluble resin and the film-forming water-dispersible resin are added to the conductive particles (A). We have developed a technology to mix at least one resin (B). Then, as shown in the section of Examples described later, the conductive particle body composition of the present invention having the above-mentioned configuration is compared with the conductive particle body (A) alone,
It has excellent film forming properties and water resistance. This is the greatest feature of the present invention.

In the conductive particle body (A), the carboxyl group of the water-soluble polymer (a) mainly expresses an interaction during the formation of a coating film, but during the production thereof,
In some cases, interaction may be expressed. Even in this case,
There is no effect on the performance of the conductive particulate composition of the present invention.

In the conductive particle body (A), the fact that the water-soluble polymer (a) is located on the outer periphery of the particle body means that a part of the water-soluble polymer (a) is embedded in the particle body. It is intended to include the included mode. That is, even if a part of the water-soluble polymer (a) is embedded in the particle body,
This is because if the other part is located on the outer periphery of the particle body, a predetermined performance is exhibited.

The conductive particles (A) can be produced by increasing the mixing ratio of the water-soluble polymer (a) as shown in FIGS.
The form is as shown in. In the figure, 1a and 1b
Shows the conductive particle body (A) of the present invention, and other parts are denoted by the same reference numerals as those in FIG. In the present invention, such a form is also included in the conductive particle body (A). Further, the particle diameter of the conductive particle body (A) of the present invention is usually 0.01 to 2.0 μm, preferably 0.
It is 04 to 0.1 μm.

The conductive particle composition of the present invention may be in the form of a sol or powder obtained by partially or completely removing the aqueous solvent, in addition to the emulsion and dispersion described above. . When it is made into a sol or a powder, it can be used again as a coating type by dispersing it in an aqueous solvent at the time of use, and can also be kneaded and used as a raw material at the time of producing a resin product or the like. It is possible.

[0069]

INDUSTRIAL APPLICABILITY As described above, the conductive particle composition of the present invention has a conductivity in which the water-soluble polymer (a) having a sulfonic acid group and a carboxyl group is located on the outer periphery of the particle body. The main component is the particle body (A), and at least one resin (B) selected from the film-forming water-soluble resin and the film-forming water-dispersible resin is mixed therein. Therefore, since the sulfonic acid group of the conductive particle body (A) exhibits excellent conductivity, when the conductive particle composition of the present invention is used for a resin product, clothes, etc., the surface thereof has excellent conductivity. It becomes possible to effectively prevent generation of static electricity by forming a coating film as a layer. Further, the conductive particle composition of the present invention is a coating film formed by the action of the water-soluble polymer (a) and the film-forming water-soluble resin (B) in addition to the action of the carboxyl group. Has extremely high water resistance. For this reason, when the conductive particle composition of the present invention is used to form a coating film (conductive layer) on the surface of a substrate such as a fiber, the coating film does not deteriorate even under severe wet conditions, and thus the electrostatic discharge for a long period of time is avoided. It becomes possible to effectively prevent the occurrence of. Further, the conductive particle composition of the present invention is excellent in film forming property and transparency,
By using this, a conductive layer can be easily formed on an article to be treated such as clothing without impairing its appearance.
In addition, when the conductive particle composition of the present invention is used in combination with a curing agent, the water resistance of the coating film formed is further improved. Then, the method for producing the conductive particle composition of the present invention is a production method in which the conventional emulsion polymerization method or the like can be applied, and therefore, it is not necessary to use special equipment or devices, and can be carried out in a simple process. Is a method that can Further, the conductive particle composition of the present invention is excellent in various properties such as film-forming property, transparency, conductivity, and water resistance, so that it can be used in a wide variety of coating type antistatic agents, antifogging agents, antifouling agents and the like. It can be applied to the intended use.

Next, examples will be described together with comparative examples.

[0071]

Example 1 700 parts of water was put into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen introducing tube.
Copolymer sodium salt of styrene sulfonic acid and maleic acid (polymerization molar ratio, styrene sulfonic acid: maleic acid =
3: 1) 100 parts was added with stirring to obtain an aqueous solution.
Then, nitrogen gas was introduced through the above-mentioned nitrogen introducing pipe to make the inside of the reaction vessel a nitrogen gas atmosphere. After that, add 8
The temperature was raised to 0 ° C. 90 parts of styrene, 10 parts of glycidyl methacrylate, and 100 parts of potassium persulfate aqueous solution (concentration: 1% by weight) were added dropwise to this aqueous solution, and the polymerization reaction was carried out at 80 ° C. under reflux of nitrogen gas to obtain the target conductive particles. The body (A) was obtained. In addition, this electroconductive particle body (A) is an emulsion form.

On the other hand, in addition to the above reaction vessel, another same reaction vessel was prepared, and 50 parts of styrene, 48 parts of butyl acrylate, 2 parts of acrylic acid, 8 parts of sodium dodecylbenzenesulfonate, 8 parts of persulfuric acid were prepared. 100 parts of an aqueous potassium solution (concentration: 1% by weight) was added dropwise, and a polymerization reaction was carried out at 80 ° C. under a nitrogen gas reflux to form a film-forming water-dispersible resin (B).
Was produced.

Then, 50 parts of the film-forming water-dispersible resin (B) was added to 100 parts of the conductive particle body (A) to prepare a target conductive particle composition.

[0074]

Example 2 To 150 parts of the conductive particle composition of Example 1, 10 parts of a water-soluble polyglycerol polyglycidyl ether (epoxy equivalent: 166) was added as a curing agent with stirring to obtain the object. A conductive particle composition was obtained.

[0075]

Example 3 To 150 parts of the conductive particle composition of Example 1, 1.5 parts of aluminum acetate was added with stirring to obtain a target conductive particle composition.

[0076]

[Embodiment 4] In the embodiment 1, the conductive particle body (A) 1 is used.
For 00 parts, film-forming water-dispersible resin 400 (upper limit compounding)
Parts were mixed to obtain a desired conductive particle composition.

[0077]

Fifth Embodiment In the first embodiment, the conductive particle body (A) 1 is used.
The film-forming water-dispersible resin 10 (lower limit compounding) part was mixed with 00 parts to obtain the target conductive particle composition.

[0078]

Example 6 A film-forming water-soluble resin (B) was prepared as follows. That is, a mixture of hexamethylene diisocyanate / 1,4-butanediol / dimethylolpropionic acid = 55/28/17 (molar ratio) was added to 1
It was neutralized with triethylamine equivalent to 7 (molar ratio) and dispersed and dissolved in water to obtain a film-forming water-soluble resin.

Then, 100 parts of the conductive particle body (A) produced in the same manner as in Example 1 was mixed with 50 parts of the above film-forming water-soluble resin (B) to obtain a target conductive particle body composition. Got

[0080]

Example 7 As the water-soluble polymer (a), the molar ratio of the sulfonic acid group and the carboxyl group was sulfonic acid group: carboxyl group = 33: 67 (styrene sulfonic acid / maleic acid copolymer sodium salt). )It was used. Other than this, the target conductive particle composition was obtained in the same manner as in Example 1.

[0081]

Example 8 A water-soluble polymer having a sulfonic acid group / carboxyl group molar ratio of sulfonic acid group: carboxyl group = 90: 10 (2-acrylamido-2methylpropanesulfonic acid / acrylic acid copolymer) (Coalescence: unneutralized product)
It was used. Other than this, the target conductive particle composition was obtained in the same manner as in Example 1.

[0082]

Example 9 A paint-type conductive particle composition was prepared by mixing 100 parts of the conductive particle composition of Example 1 with 10 parts of TiO ₂ dispersed in 10 parts of water.

[0083]

Reference Example A conductive particle composition comprising only the conductive particle body (A) of Example 1 was prepared.

[0084]

Comparative Example 100 parts of polystyrene sulfonic acid sodium salt was used as the water-soluble polymer, and 90 parts of styrene and 10 parts of butyl acrylate were used as the monomer which is a material for forming the particle body. Other than this, in the same manner as in Example 1,
The target conductive particle composition was obtained.

Example products 1 to 9 thus obtained,
Various properties such as film-forming property, transparency, water resistance, and conductivity were examined for the conductive particle composition of the reference example product and the comparative example product. The results are shown in Tables 1 and 2 below. The above characteristics were evaluated by the following test methods.

[Film Formability, Transparency] Using a 6.86 μm applicator, the conductive particle composition was coated on a glass plate and dried under the conditions of 140 ° C. × 30 minutes to form a coating film. Then, this coating film was visually observed, and a continuous transparent coating film was represented by ◯, and a cracked discontinuous coating film or an opaque coating film was represented by x.

[Water resistance] A coating film prepared on a glass plate in the same manner as in the above film-forming property test was kept at room temperature (20 ° C.) for 1 hour.
Immersed in water. Then, after pulling this from water, the coating film was visually observed, and those in which no abnormality was found in the coating film were ⊚, those in which a slight change was confirmed in the coating film were ○, and a part of the coating film was observed. The change was confirmed by Δ, and the coating film was eluted by X.

[Conductivity] The coating film prepared on the glass plate in the same manner as in the film forming test was immersed in water under the same conditions as in the water resistance test. Then, after pulling this from water, it was left in an atmosphere of 50% humidity for 1 day, and then the surface resistance of the coating film was measured. Then, × surface resistance of the coating film, those of less than 10 ⁹ Ω ◎, ○ a of less than 10 ¹⁰ Omega, those less than 10 ¹¹ Omega △, more than a 10 ¹¹ Omega
Indicated by.

[0089]

[Table 1]

[0090]

[Table 2]

From the results shown in Table 1 above, it can be seen that the conductive particle compositions of all the examples are excellent in all of the film forming property, transparency, water resistance and conductivity. In particular, it was confirmed that the electrically conductive particle compositions of Example product 2 containing the curing agent and Example product 3 containing the aluminum acetate had significantly improved water resistance and conductivity. In addition, in the product of Example 9,
A white coating as intended could be formed. From the results of Table 2 above, the conductive particle composition of the reference example product consisting of the conductive particle body (A) showed superior performance to that of the comparative example product, but under the severe conditions described above. In the test, the tendency was slightly inferior to that of the example product.
On the other hand, from the results of Table 2 above, when the conductive particle composition of Comparative Example product was immersed in water, the coating film immediately eluted.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of the configuration of a conductive particle body (A).

FIG. 2 is a schematic diagram showing another example of the configuration of the conductive particle body (A).

FIG. 3 is a schematic view showing another example of the structure of the conductive particle body (A).

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L C09D 5/24

Claims (17)

(57) [Claims] 1. A conductive particle composition comprising the following (A) and (B): (A) A conductive particle body in which the following water-soluble polymer (a) is located on the outer periphery of the polymer particle body. (A) A water-soluble polymer having a sulfonic acid group and a carboxyl group. (B) At least one resin of a film-forming water-soluble resin and a film-forming water-dispersible resin. 2. The conductive particle composition according to claim 1, wherein the sulfonic acid group of the water-soluble polymer (a) is derived from a styrenesulfonic acid monomer. 3. The conductive particle composition according to claim 1, wherein the particle body made of a polymer is a polymer obtained by polymerizing an epoxy group-containing monomer. 4. The conductive particle composition according to claim 1, wherein the particle body made of a polymer is a polymer obtained by polymerizing a polyfunctional vinyl monomer. 5. The water-soluble polymer of (a) above is a copolymer of styrene sulfonic acid and maleic acid.
The conductive particle body composition according to any one of items 1 to 4. 6. A film-forming water-soluble resin having at least one of the film-forming water-soluble resin and a film-forming water-dispersible resin (B) having a carboxyl group and a film-forming water having a carboxyl group. The conductive particle composition according to claim 1, which is at least one resin of a dispersible resin. 7. The conductive particle composition according to claim 1, which contains a curing agent having an epoxy group. 8. The method according to claim 1, further comprising a curing agent for the metal compound.
The conductive particle composition according to any one of items 1 to 7. 9. The conductive particle composition according to claim 1, which contains various additives such as a filler and a pigment. 10. A monomer having a polymerizable functional group is polymerized in an aqueous solvent containing a water-soluble polymer of the following (a), and a film-forming water-soluble resin and a film-forming water are added thereto. A method for producing a conductive particle composition, which comprises blending at least one resin of a dispersible resin. (A) A water-soluble polymer having a sulfonic acid group and a carboxyl group. 11. The method for producing a conductive particle composition according to claim 10, wherein the sulfonic acid group of the water-soluble polymer (a) is derived from a styrenesulfonic acid monomer. 12. The method for producing a conductive particle composition according to claim 10, wherein the monomer having a polymerizable functional group is an epoxy group-containing monomer. 13. The method for producing a conductive particle composition according to claim 10, wherein the monomer having a polymerizable functional group is a polyfunctional vinyl monomer. 14. The conductive particle composition according to any one of claims 10 to 13, wherein the water-soluble polymer (a) is a copolymer of styrene sulfonic acid and maleic acid. Manufacturing method. 15. The blending ratio of the water-soluble polymer of (a) and the monomer having a polymerizable functional group is the above (100 parts by weight of the monomer having a polymerizable functional group). The water-soluble polymer of a) is 10 to 500 parts by weight.
15. The method for producing the conductive particle composition according to any one of items 1 to 14. 16. A styrenesulfonic acid / maleic acid molar ratio of styrenesulfonic acid / maleic acid = 50/5.
The method for producing a conductive particle composition according to claim 14 or 15, which is in the range of 0 to 95/5. 17. At least one of the film-forming water-soluble resin and the film-forming water-dispersible resin has at least a carboxyl group-containing film-forming water-soluble resin and a carboxyl group-containing film-forming water-dispersible resin. It is one resin, The manufacturing method of the electroconductive particle body composition of any one of Claims 10-16.