TW201439232A - Conductive paint and adherend coated with the same conductive paint - Google Patents

Abstract

An electrically conductive coating material according to the present invention has good wettability on various adherends and, when the adherends are particles, can be coated on the surfaces of the particles uniformly by a specific production method. The present invention is an electrically conductive coating material comprising the following components (A) to (D): (A) polyethylene dioxythiophene; (B) polystyrene sulfonate; (C) water; and (D) a silane coupling agent having an alicyclic epoxy group and/or a silane-type coupling agent having a (meth)acrylic group.

Description

Conductive coating and coating of the conductive coating

The present invention relates to a conductive paint comprising a conductive polymer and an adherent coated with the conductive paint.

In recent years, various electronic devices have been manufactured and widely used. As a member of the electronic device, for example, a display surface of a display device such as a liquid crystal display, a window material such as a clean room, or a glass or plastic of a packaging material such as an IC (integrated circuit) package, or For example, various transparent substrates used for films such as overhead displays, photographs, etc., are usually insulators and are easily electrostatically charged. Therefore, garbage or dust is likely to adhere to the surface, which may cause problems such as a decrease in visibility, a defective product caused by the incorporation of the product, and an erroneous operation of the electronic device. Further, the influence of electromagnetic waves generated by such electronic devices on the human body is also a problem. Therefore, in order to resist static electricity or shield electromagnetic waves, conductive coatings are blended with conductive particles. The applicable case of the material is increasing.

Further, it is also useful to use a conductive paint which is a conductive adhesive when manufacturing an electronic device or when manufacturing parts for an electronic device. For example, when a sheet-shaped electrode is laminated with a dielectric layer, a substrate such as a printed circuit board is electrically connected to each other, or an element such as a semiconductor element is connected to a substrate, the conductive adhesive is It is widely used.

As such a conductive paint, a composition using insulating particles coated with a conductive polymer has been known. For example, as in the invention described in Patent Document 1, the manufacturing method has always used a ball mill while using a large amount of solvent. Further, since filtration is performed to recover the particles, most of the conductive polymer initially charged is filtered together with the solvent, so that it is not clear whether or not the conductive polymer remains on the surface of the insulating particles. Further, in the case of drying, there is also a case where primary particles are mutually fused to each other to form large secondary particles, and in the case of drying, the conductive polymer coated on the surface of the insulating particles may have surface tension. Biased concerns in some areas. The process is also multi-stage due to a combination of drying, filtration, washing, etc., and it is presumed to be complicated.

There is also a conductive paint produced by uniformly using a conductive polymer on the surface of the insulating particles while firmly adhering to the surface by using a multi-stage process as described in Patent Document 2. In the invention, the mother particles are physically doped into the surface of the daughter particles having an average particle diameter smaller than the mother particles, and then the conductive polymer is coated on the surface. It can be speculated In order to utilize the anchor effect, the conductive polymer is not peeled off. However, the manufacturing process is a multi-stage, and depending on the combination of the members, as in Patent Document 1, there is a concern that the coating of the conductive polymer is deflected to a partial region.

In addition, in recent years, the trend of the entire technical field of conductive coatings has been considered from the environmental impact or workability, and has been converted from a solvent system using an organic solvent to a water system. However, in the water system, there is a tendency that the compatibility of the conductive coating with the coating material is deteriorated compared to the solvent system. Therefore, it is more difficult to uniformly coat with a conductive paint without being deflected.

[Previous Technical Literature] (Patent Literature)

(Patent Document 1) Japanese Patent Laid-Open No. 2-120373

(Patent Document 2) Japanese Patent Laid-Open Publication No. 2009-170319

As described above, in the case of a conductive coating material containing a conductive polymer, particularly in the case of a water-based system, the wettability of the coating body is poor, so that it is difficult to uniformly coat the conductive coating material to various materials. Apply body. Further, in the case where the coating body is a particle, it is particularly difficult to uniformly coat the conductive coating material.

Accordingly, an object of the present invention is to provide a conductive paint which can improve the wettability of an applicator of various materials even in the case of a water-based conductive paint, and can uniformly coat various coats. Further, another object of the present invention is to provide an electroconductive particle obtained by uniformly coating a conductive paint of the present invention and a method for producing the same. Further, another object of the present invention is to provide a conductive adhesive and an anisotropic conductive adhesive which improve conductivity by using the conductive particles of the present invention.

In order to achieve the above object, the inventors of the present invention have carefully studied the results, and finally completed the conductive coating material containing the conductive polymer of the present invention and the coating body coated with the conductive coating material.

The gist of the present invention is explained below. A first embodiment of the present invention is a conductive coating comprising the components (A) to (D), wherein (A) is a polyethylenedioxythiophene and (B) is a polystyrene sulfonate. Polystyrenesulfonic acid, the component (C) is water, and the component (D) is a silane coupling agent having an alicyclic epoxy group and/or having a (meth)acrylic group. [(meth)acrylic group] decane coupling agent.

Figure 1 is a micro compression tester (microscopic Cormpression tester) The result of conducting determination of treated particles.

[Best Embodiment of the Invention]

The conductive paint of the present invention is a conductive paint containing a conductive polymer. By including the above components (A) and (B), the coating will be conductive. Since the component (C) is water, the conductive paint of the present invention is water-based, has little influence on the environment, and is excellent in workability. Further, by the decane coupling agent having an alicyclic epoxy group containing the component (D) and/or the decane coupling agent having a (meth)acrylic group, the components (A) to (D) are integrated as a whole ( Integrate) to obtain a conductive coating which can form a uniform film on various coating bodies. The present invention has an effect of being excellent in wettability to various coated bodies and obtaining an applicator which forms a uniform film. Further, in the case where the coating body is a particle, the conductive coating material can be uniformly coated on the surface of the particle by a preferable production method.

Hereinafter, the present invention will be described in detail as follows.

<(A) Ingredients: Polyethylenedioxythiophene>

The component (A) which can be used in the conductive paint of the present invention is poly(3,4-ethylenedioxythiophene) represented by the following formula 1. Further, derivatives thereof are also included in the scope of the present invention, and a plurality of (A) components may be used in combination. The poly 3,4-extended ethyldioxythiophene may also be a self-synthesis or a commercially available product. Commercial goods Examples of the body include Clevios MV2 manufactured by H.C. STARCK, etc., but are not limited thereto.

In the above formula 1, R ¹ and R ² represent an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group or a propyl group. Further, R ¹ and R ² may form a ring by a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. The substituent is an organic group, and more preferably an alkyl group having 1 to 10 carbon atoms. When R ¹ and R ² form a ring, it is more preferred that R ¹ and R ² are integrated to form an ethyl group or a propyl group. R ³ and R ⁴ each independently represent hydrogen, a halogen atom, or an organic group. The organic group is preferably an alkyl group having 1 to 10 carbon atoms. n is an integer.

In order to oxidatively polymerize the thiophene of the main skeleton of the component (A), it comprises iron (III) chloride, iron (III) chloride hydrate, iron (III) sulfide, copper perchlorate or perchloric acid. In addition to iron and iron (III) p-toluenesulfonate, other oxidizing agents and the like can also be used as the catalyst. In particular, iron (III) chloride or iron (III) p-toluenesulfonate is known to be excellent in yield, but is not limited thereto.

<(B) Ingredients: Polystyrenesulfonic acid>

The component (B) which can be used in the conductive coating of the present invention is polystyrenesulfonic acid. Further, the derivative thereof is also contained in the component (B) of the present invention, and may also be a compound (B) in which a plurality of components are mixed. The part of the sulfonic acid is A metal salt such as sodium, potassium or iron can be used if there is no problem in exhibiting conductivity.

In order to exhibit conductivity, it is known to apply p-type doping to the (A) component. As the dopant, various reagents such as an organic acid such as iodine, bromine, trifluoroacetic acid, propionic acid, and sulfonic acid can be used, but in the present invention, the component (B) is used as a dopant. By combining the components (A) and (B), it becomes a polymer capable of exhibiting conductivity. The components (A) and (B) may be synthesized separately, mixed or used, or a commercially available product. Commercially available products of the component (A) and the component (B) are known as P, F, and S types of the Clevios series manufactured by H.C. STARCK, and the Orgacon series manufactured by AGFA.

The mixing ratio of the component (A) to the component (B) is preferably 100 to 700 parts by mass based on 100 parts by mass of the component (A). In addition, when there are two or more types of (A) component and/or (B) component, it means the total amount of these. When the component (B) is 700 parts by mass or less (including 700 parts by mass), conductivity can be surely exhibited, and when it is 100 parts by mass or more (including 100 parts by mass), conductivity can be more reliably exhibited.

<(C) Ingredients: Water>

The component (C) which can be used in the conductive paint of the present invention is water. It is preferred to use an ion-free impurity such as purified water or distilled water. Since water is used as a solvent, the conductive paint of the present invention is a water-based paint, which has little influence on the environment and also has improved workability. It is used by dispersing the component (A) and the component (B) in the water of the component (C), but it can be self-modulated, or A commercial product in a state in which these components are dispersed in water is used. From the viewpoint of handling property or prevention of harmfulness, it is preferred that the mixture of the component (A) and the component (B) is dispersed in the component (C) (dispersion), and examples thereof include: HCSTARCK Clevios P, PH, etc., but not limited to this.

The mixing ratio is assumed to be 100 parts by mass of the mixture of the component (A) and the component (B), and preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, based on the component (C). a mixture of (A) ingredients and (B) ingredients. It is assumed that the mixture of the component (A) and the component (B) is 100 parts by mass, and if the mixture of the component (A) and the component (B) is contained in the water of the component (C), 0.1% by mass or more, Then, the conductivity of the coating film is confirmed, and when it is contained in an amount of 10% by mass or less (including 10% by mass), it becomes a coating material suitable for work.

In the present invention, the phrase "the coating is water-based" means that the main solvent is water, and as described above, assuming that the mixture of the component (A) and the component (B) is 100 parts by mass, the component (C) is The water contains 0.1 to 10% by mass of a mixture of the component (A) and the component (B). Further, in the present invention, an organic solvent containing the component (E) described later is preferably used as an additive. In this case, when water in the above range is contained, water acts also as a solvent, and the environmental impact can be reduced. And the effect of improved workability. On the other hand, the component (E) is an additive, and by adding this, the effect of improving the conductivity of the film can be obtained.

<(D) component: a decane coupling agent having an alicyclic epoxy group and having (a) At least one of the acryl-based decane coupling agents >

The component (D) which can be used in the conductive coating material of the present invention is at least one of a decane coupling agent having an alicyclic epoxy group and a decane coupling agent having a (meth)acrylic group.

The decane coupling agent having an alicyclic epoxy group is not limited thereto, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane is preferably used. A commercially available product of a decane coupling agent having an alicyclic epoxy group may, for example, be KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.; and Unicar Co., Ltd. ( Unicar) A-186 and so on.

The decane coupling agent having a (meth)acrylic group is not limited thereto, and examples thereof include 3-propenyloxypropyltrimethoxydecane and 3-methylpropenyloxypropylmethyl. Dimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyl three Ethoxy decane and the like. Among them, 3-methylpropenyloxypropyltrimethoxydecane is more preferable for the desired effect of the present invention. A commercially available product of a methacrylic acid-based decane-based coupling agent, KBM-502, KBM-503, KBE-502, KBE-503, and KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd. It is well known but not limited to this.

Further, it is also possible to mix and use two or more different (D) components. In the coating film, the content of the mixture of the component (A) and the component (B) is preferably 100 to 1000 parts by mass, more preferably 10 to 500 parts by mass, based on 100 parts by mass of the mixture of the component (B). In addition, when the component (D) is two or more, it means the total amount of these. If it is 10 parts by mass or more, it is easier When the coating film is formed in an amount of 1000 parts by mass or less (including 1000 parts by mass), the component (D) can be prevented from remaining on the coating film. Further, in the coating liquid, the component (D) is preferably 0.01 to 10 parts by mass, more preferably 100 parts by mass based on the total of the components (A), (B) and (C). It is 0.1 to 5 parts by mass.

<(E) component: at least one selected from the group consisting of a diol derivative, a pyrrolidone derivative, and an anthracene derivative>

The conductive coating material of the present invention preferably further comprises a solvent selected from at least one of a glycol derivative, a pyrrolidone derivative, and a sulfoxide derivative. (E) Ingredients. According to a second aspect of the invention, the conductive paint according to the first aspect of the invention, further comprising at least one selected from the group consisting of a diol derivative, a pyrrolidone derivative, and an anthracene derivative. Solvent, as component (E). Further, it is also possible to mix and use two or more different (E) components. Although the reason for the clearness is not clear, it has been found that the conductivity of the coating film of the conductive paint can be improved by adding the component (E).

Examples of the diol derivative include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-butyl ether. From the viewpoint of availability or cost, ethylene glycol is more preferred.

The pyrrolidone derivative may, for example, be 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or N-butyl-2-pyrrolidone. N-vinyl-2-pyrrolidone, 5-methyl-2-pyrrolidone, N-phenyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-hydroxyethyl- 2-pyrrolidone and the like. More preferably, it is N-methyl-2-pyrrolidone from the viewpoint of availability or cost.

Examples of the fluorene derivative include a dialkyl fluorene such as dimethyl hydrazine, tetramethylene fluorene, dioctyl hydrazide or diphenylmethyl fluorene; diphenyl fluorene and di-pair. a diaryl sulfonium such as tolyl hydrazine or bis-(p-chlorophenyl) anthracene. From the standpoint of availability or cost, it is more preferred to be dimethyl sulfoxide.

According to a third aspect of the invention, the conductive coating material according to the second aspect, wherein the component (E) is selected from the group consisting of ethylene glycol and N-methyl-2-pyrrolidone (N) -methyl-2-pyrrolidone) and at least one of dimethyl sulfoxide.

In the coating liquid, the component (E) is preferably contained in an amount of 10 to 1000 parts by mass, more preferably 200 to 700 parts by mass, per 100 parts by mass of the mixture of the component (A) and the component (B). If there are two or more cases of (E) components, they refer to the total amount of the components. When the amount is 10 parts by mass or more, the conductivity can be improved. When the amount is 1000 parts by mass or less (including 1000 parts by mass), the component (E) is volatile, and the coating film is preferably dried. In addition, in the coating liquid, the component (E) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10, based on 100 parts by mass of the total of the components (A), (B) and (C). Parts by mass.

<Other ingredients>

In the conductive coating of the present invention, it is also possible not to damage the present In the range of efficacy of the invention, a suitable amount of pigment, dye, etc. coloring agent, metal powder, calcium carbonate, talc, silica, alumina, aluminum hydroxide, etc., inorganic filler, flame retardant, organic Additives such as fillers, plasticizers, antioxidants, antifoaming agents, leveling agents, rheology control agents, and the like. By adding these or the like, a coating film excellent in conductivity, flexibility, adhesion strength, workability, and the like can be obtained.

<Coating body with coating film>

The conductive paint described above can be applied to a coating material of various materials to form a uniform coating film. In other words, the fourth embodiment of the present invention is a coated body having a coating film which is coated with a conductive coating material according to any one of the first to third embodiments. to make.

The material to be coated is not particularly limited. It can be used: (meth) acrylate resin, glass, polyphenylene sulfide, polybutylene terephthalate, polyethylene, nylon (nylon) , polyacetal, liquid crystal polymer, hard vinyl chloride, polycarbonate, polyethylene terephthalate, cycloolefin resin, Polystyrene resin, phenol resin, acrylonitrile-butadiene-styrene resin, and the like.

According to a fifth aspect of the present invention, there is provided a coating material comprising a coating film, wherein the coating material is (meth) acrylate resin, glass, polyphenylene sulfide, poly (terephthalic acid). Butylene glycol ester, polyethylene, nylon, polyacetal, liquid crystal polymer, hard vinyl chloride, polycarbonate, poly pair Ethylene phthalate, a cyclic olefin resin, a polystyrene resin or a phenol resin. In the case of such a coating, it is preferred to form a uniform coating film by using the conductive coating of the present invention. In particular, a general coating film can be formed for a general-purpose acrylic resin or glass.

The shape of the coating body is not limited to a film shape, a sheet shape, a plate shape, or a flat shape, and may be applied to various coating bodies such as a spherical shape, a cylindrical shape, or a particle shape such as a spherical shape. membrane.

In order to form a film of a conductive paint on a coating body, there is no particular limitation, and a bar coat method, a spray coat method, or a curtain coat method may be used. A method such as a spin coat method, a gravure coat method, an inkjet method, a dip method, or the like. The coating thickness is preferably adjusted so that the film thickness after drying is from 1 to 600 nm, more preferably from 10 to 300 nm. Next, the coating film formation can be formed by drying at 40 to 150 ° C in a hot air drying oven or the like to form a coating film. When it is 150 ° C or less (including 150 ° C), even if it is heated, it does not cause too high a temperature, and the conductivity of the conductive polymer can be maintained without being lowered. In addition, the bumping of the component (C) can also be prevented. As described above, an applicator having a coating film of the conductive coating material of the present invention can be obtained.

<Electrically conductive particles>

A sixth embodiment of the present invention is the conductive particle coated with the conductive coating material according to any one of the first to third embodiments. Made of particles. As described above, the conductive paint of the present invention can be applied to various coating materials to form a uniform coating film, and is particularly suitable for coating a particle-shaped coating body to obtain conductive particles. The conductive particles of the present invention are those corresponding to the prior art plating powder. However, since no metal is used, inexpensive conductive particles can be produced without using a multistage step.

The coating body constituting the particles is not particularly limited, and those obtained by molding the above-mentioned coating body into particles may be used. Among them, in particular, since the particles are rich in change and a more uniform coating film can be formed by using the conductive coating of the present invention, (meth) acrylate resin particles are preferable. According to a seventh aspect of the invention, the conductive particles according to the sixth aspect, wherein the particles are composed of a (meth) acrylate resin.

When the conductive particles of the present invention are added to a curable resin, a conductive adhesive or an anisotropic conductive adhesive can be produced. The above two types of adhesives can be separately produced depending on the amount of the conductive particles added. That is, in the case of the conductive adhesive, the amount of the conductive particles added is 70 to 99% by mass, and the amount of the conductive adhesive in the opposite direction is 1 to 10% by mass. The hardening method is also different. In the case of a conductive adhesive, it is cured after application to exhibit electrical conductivity. On the other hand, in the case of the conductive additive in the opposite direction, it is necessary to perform hardening in a state where the adhesive is sandwiched between the two electrodes, whereby the electrodes are electrically conductive. In other words, the ninth embodiment of the present invention is the conductive adhesive comprising the conductive particles according to the sixth or seventh embodiment or the production method according to the eighth embodiment. Conductive particles. this Further, a tenth embodiment of the present invention is an anisotropic conductive adhesive comprising the conductive particles according to the sixth or seventh embodiment or the production method according to the eighth embodiment. The conductive particles produced.

Further, in the hardened form of the curable resin, various types of hardening such as thermosetting, photocuring, anaerobic curing, and moisture curing can be used. The thermosetting can be used for, but not limited to, a curable epoxy resin, a curable urethane resin, an addition type silicone resin, and the like. . Examples of the photocuring include a curable acrylate resin, a curable methacrylate resin, and a curable vinyl ether resin, but are not limited thereto. The term "anaerobic hardening" means a form in which the resin is cured by contact with the coating body in the case where the coating body is a metal. The composition of the methacrylate compound and saccharin is representative, but is not limited thereto. The moisture hardening is exemplified by a condensation type polyphthalocene resin, but is not limited thereto.

In the case where metal particles are to be added to the photocurable resin to produce an anisotropic conductive adhesive, the photocurable resin is colored and becomes opaque due to the influence of the metal particles. However, when the conductive particles of the present invention are added to the photocurable resin, an anisotropic conductive adhesive having no coloration and good transparency can be produced. On the other hand, when metal particles are to be added to an anaerobic curable resin to produce an anisotropic conductive adhesive, the metal particles cause gelation of the resin and gelation. However, since the conductive particles of the present invention are not metals, they are not gelled even when added to an anaerobic curable resin, and can be produced. An anaerobic hardening heterogeneous conductive adhesive.

The conductive adhesive or the isotropic conductive adhesive of the present invention may be blended with a suitable amount of a coloring agent such as a pigment or a dye, metal powder, calcium carbonate, talc, or the like insofar as the effect of the present invention is not impaired. An inorganic filler such as cerium oxide, aluminum oxide or aluminum hydroxide; an additive such as a flame retardant, an organic filler, a plasticizer, an antioxidant, an antifoaming agent, a leveling agent, and a rheology control agent. By adding these, it is possible to obtain a composition excellent in conductivity, flexibility, adhesion strength, workability, and the like.

The above-mentioned conductive adhesive and the opposite-direction conductive adhesive can be used as electrical connection materials in the field of electrical electronics.

<Method for Producing Conductive Particles>

An eighth aspect of the invention is the manufacturing method according to the sixth or seventh aspect, further comprising the step of applying the conductive paint to the particles using a turbulent flow layer granulation coating device.

In the case of producing a particulate coating body, a conductive coating material is adhered to the surface of the coated particles and heated and dried to form conductive particles. A device for forming conductive particles is preferably used: a rotary fluidized coating device (for example, a rotary flow coating device - MP-01 (manufactured by Powrex Corporation), etc.), a centrifugal flow coating Cloth granulating device (for example, GRANUREX (Freund Corporation) (Freund Corporation)), a composite granulation coating device (for example, SPIR-A-FLOW (Freund Industries Co., Ltd.), etc.) , Fluidized bed granulator (for example, GPCG/WSG-CT series (manufactured by Powrex)), FLO-COATER (manufactured by Freund Industries Co., Ltd.), microparticle coating, granulation device-SFP A series (manufactured by Powrex Co., Ltd.), a microparticle coating device GPCG-SCP series (manufactured by Powrex Co., Ltd.), a stirring and mixing granulation device (for example, a Vertical Granulator (manufactured by Powrex Co., Ltd.), etc.). Among them, a rotary flow coating device is particularly preferred.

Regarding the production of the conductive particles, depending on the method of adhering the conductive coating on the surface of the particles, secondary aggregates sometimes occur, and once the secondary aggregates are generated, the original primary particles are caused. The concern about the change in particle size distribution. In addition, there is also a case where the conductive coating is biased on the surface of the particles so that a uniform coating film cannot be formed. Therefore, it has been found that in order to obtain primary particles having a uniform coating film formed, it is greatly dependent on the specification of the processing apparatus or the application method of dripping or spraying of the stock solution. Therefore, in order to obtain the specifications of the conductive particles of the present invention, it is more preferable to use a rotary flow coating device. The rotary flow coating device is a device for granulating and coating fine particles, and has a flow layer granulation device having a flow of powder and granules by a gas flow and a high efficiency drying effect, and has a mechanical action The device of the characteristics of the powder granule flow ‧ rotation ‧ compaction stirring granulation device Further, the feeding method of the stock solution is preferably a spray method.

"Embodiment"

Next, the present invention will be described in more detail by way of examples, but the invention is not limited by the examples. (In the following, it will be "conductive" "Skin paint" is simply called "paint". )

[Examples 1 to 7 and Comparative Examples 1 to 5]

Prepare the following ingredients for the preparation of the coating: (A) component: polyethylenedioxythiophene, (B) component: polystyrenesulfonic acid, and (C) component: water mixture

水1% by mass solid content of aqueous dispersion of ethyldioxythiophene and polystyrenesulfonic acid ((A) component and (B) component: (C) component mass ratio is 1:99)

Contains other conductive polymers and (C) components: a mixture of water

5A solid content of 5% by mass of polyaniline aqueous solution (polyaniline: (C) component mass ratio of 5:95)

(D) Component: a decane coupling agent having an alicyclic epoxy group and/or a decane coupling agent having a (meth)acrylic group

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.)

̇3-Methyl propylene methoxy propyl trimethoxy decane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.)

(D') Ingredients: decane coupling agents other than (D)

̇3-glycidoxypropyltrimethoxydecane (KBM-403, Shin-Etsu Chemical Co., Ltd.)

̇N-2-(Aminoethyl)-3-aminopropyltriethoxydecane (KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.)

̇Vinyl trimethoxy decane (KBM-1003, Shin-Etsu Chemical Industry Co., Ltd.) System

(E) component: a solvent selected from at least one of a diol derivative, a pyrrolidone derivative, and a hydrazine derivative

Ethylene glycol (reagent)

̇N-methyl-2-pyrrolidone (reagent)

Dimethyl hydrazine (reagent)

(E') Ingredients: solvents other than (E)

̇Ethanol (reagent)

In Examples 1 to 6, the (A) component to the (E) component was weighed and stirred. In Example 7, the components (A) and (D) and (E') were weighed and stirred. In the case of Comparative Examples 1 to 4, only the component (A) to the component (C) or the component (A) to the component (C) and the component (D') were used. In Comparative Example 5, another conductive polymer and (C) component were used. The detailed modulation amount is based on Table 1-1 and Table 1-2, and the numerical values are all expressed in parts by mass.

In Examples 1 to 7 and Comparative Examples 1 to 5, coating performance (acrylic acid) confirmation, coating property (glass) confirmation, and surface resistivity measurement were performed as follows. . The results of the assessment are summarized in Tables 2-1 and 2-2 below.

[coating performance confirmation]

The coating was applied onto the substrate by using a bar coater, and placed in a hot air drying oven at 100 ° C for 5 minutes in the atmosphere to volatilize water to obtain a coating film of 100 nm. In the case of the acrylate resin plate and the glass plate, "coating property (acrylic)" and "coating property (glass)" were confirmed. The judgment criteria were visually confirmed by the following three grades: ○: the coating film was uniform in thickness; Δ: although coated, the composition was locally deflected; X: completely incompatible so that it could not be coated cloth.

[Measurement of surface resistance value]

The glass plate was produced in the same manner as the coating film described above, and the surface resistivity (unit: Ω)". In Table 2-2, M means 10 ⁶ .

Depending on the prior art, in the case where the compatibility of the conductive coating with respect to the coating body is poor, the composition sometimes deflects even in the state after coating. Moreover, when exposed to the atmosphere of 100 ° C, sometimes the coating is temporarily low-viscosity and aggregated. However, from the results of Table 2, it was confirmed that the coating materials of Examples 1 to 7 in which the component (D) was added had a uniform coating film formed on both the acrylate resin and the glass. Further, in Examples 2 and 4 to 6 to which the component (E) was added, the comparison of Examples 1, 3, and 7 in which the component (E) was not added confirmed the decrease in the surface resistance value, and thus was known. A conductive coating material having more excellent conductivity can be obtained. On the other hand, in Comparative Examples 2 to 4 containing no (D) component and (D' containing a substituted (D) component, a coating film could not be formed on the acrylate resin. Further, in Comparative Example 5 containing no component (A) to component (C), a coating film could not be formed on both the acrylate resin and the glass.

Next, regarding the conductive coating material obtained in Example 2, the coating property was confirmed by using a material other than glass and acrylate as a coating material. The test method and the criterion for judgment were carried out in the same manner as the above-mentioned confirmation of the coating property. The results are summarized in Table 3 below. As is apparent from Table 3, although some materials have the "X" symbol, a good coating film can be formed for various materials in addition to acrylate or glass.

[Example 8 and Comparative Examples 5 to 6]

The surface of the polymethyl methacrylate particle (SSX-115, manufactured by Sekisui Plastics Co., Ltd.) having an average particle diameter of 15 μm was coated on the surface of the conductive coating obtained in Example 2, To produce conductive particles. In the case of the coated particles, the coatings were adhered to the surface of the particles while being dried using the following apparatuses 1 to 3. (Hereinafter, the particles subjected to the treatment using the device are referred to as "treated particles".) The specifications of the respective devices are summarized in Table 4 below. Further, the conductivity measurement of the treated particles was carried out as described later.

̇ device 1 (rotary flow coating device): it is a fluidized layer granulation device (flow of powder and granules by airflow, high-efficiency drying) and agitating granulation device (flow and rotation of powder and granules by mechanical action) A particle or microparticle coating device characterized by a compacting action.

Tantalum device 2 (UV type vibrating mixer): It is a batch type longitudinal type dryer in which a vibrating mechanism mounts two vibrating motors on the side of the body to generate a semi-elliptical vibration obliquely upward. The object to be dried inside the body is spiraled in the circumferential direction and flows up and down in the radial direction.

The crucible device 3 (high-speed vacuum dryer): The inside of the can body is decompressed, and jacket heating is performed from the bottom surface and the side surface of the can body. By stirring and rotating the object to be dried, uniform heating and drying in a short time can be performed.

[Measured particle conductivity test]

The particles produced in accordance with Table 4 were measured for conductivity using a micro compression tester manufactured by Shimadzu Corporation. The measurement value when the particles having a particle diameter of 15 μm were compressed to 70% (10 μm) while being compressed at a load rate of 3.8 mN/sec was used as a resistance value. The results of Example 8 are shown in Figure 1. The X axis is the displacement (unit: μm), and the displacement of the probe to the particle is 0 μm. The Y-axis is the resistance value at that time (unit: × 10 ⁶ Ω). In Example 8, the electrical conductivity of 0.06 × 10 ⁶ Ω was exhibited, but Comparative Examples 5 and 6 were insulated and the resistance value could not be measured.

Since only Example 8 exhibited conductivity, it was found that the state of the coating film was greatly affected by the device for forming the coating film. In particular, regarding the feeding method of the composition, it can be considered that, in the case of dropping, on the surface of the particle A coating film which is uneven and deflected is formed, and it is considered that the spray forms a uniform coating film. In the case of the present invention, the method of rotation/flow is considered to be more suitable for agitation than vibration.

[Example 9]

In order to prepare the anisotropic conductive adhesive by using the conductive particles obtained in Example 8, the following components were prepared. All of the following ingredients were weighed and stirred for 30 minutes. The detailed modulation amount is based on Table 5, and the numerical values are all marked in parts by mass.

̇Polyethylene glycol #400 diacrylate (A-400, manufactured by Shin-Nakamura Chemical Co., Ltd.)

̇1-Hydroxycyclohexyl phenyl ketone (IRGACURE 184, manufactured by BASF)

导电Electroconductive particles of Example 8

[Measurement of continuity]

The conductivity of the above Example 9 was measured. Two sheets of 10 mm x 25 mm ITO glass sheets surface-treated with ITO (indium tin oxide) were prepared. On the side of the conduction surface of one of the sheets, a strip-shaped PET film having a thickness of 12 μm was placed on both ends of the ITO glass plate as spacers. The heterogeneous conductive adhesive of Example 9 was coated with 0.5 mg between PET films. The conductive film of the other ITO glass was bonded to the coating film so that the bonding surface became 5 mm × 5 mm. After the bonded ITO glass was fixed by a clip, light irradiation was performed at an integrated light amount of 3000 mJ/cm ² to harden the adhesive. The resistance value between the ITO glasses of the test piece produced as described above was measured, and the total resistance value of the ITO glass and the conductive particles was measured and found to be 300 Ω.

[Industrial use possibility]

The invention of the present invention is a conductive paint which can form an organic conductive layer for a coating material of various materials. In the production of conductive particles, it is possible to efficiently manufacture by using a device of a specific type. Further, the conductive particles correspond to the electroplating powder, but since no metal is used, inexpensive conductive particles can be produced without using a multistage step. Further, in the use of the opposite-direction conductive adhesive of the conductive particles, a cured product which is visually transparent and translucent can be formed.

In addition, the present application is based on the Japanese Patent Application No. 2013-075640, the entire disclosure of which is hereby incorporated by reference.

Claims (10)

A conductive coating comprising the following components (A) to (D), wherein (A) is a polyethylenedioxythiophene, (B) is a polystyrenesulfonic acid, and (C) is a component In the case of water, the component (D) is a decane coupling agent having an alicyclic epoxy group and/or a decane coupling agent having a (meth)acrylic group. The conductive paint according to claim 1, further comprising a solvent selected from the group consisting of a diol derivative, a pyrrolidone derivative, and a hydrazine derivative, as the component (E). The conductive paint according to claim 2, wherein the component (E) is at least one selected from the group consisting of ethylene glycol, N-methyl-2-pyrrolidone, and dimethyl hydrazine. An applicator having a coating film, which is obtained by coating the conductive coating material according to any one of claims 1 to 3 on a coating body. The coating body having a coating film according to claim 4, wherein the coating body is a (meth) acrylate resin, glass, polyphenylene sulfide, polybutylene terephthalate, polyethylene, or nylon. , polyacetal, liquid crystal polymer, hard vinyl chloride, polycarbonate, polyethylene terephthalate, cycloolefin resin, polystyrene resin or phenol resin. A conductive particle obtained by applying the conductive coating material according to any one of claims 1 to 3 to particles. The conductive particle according to claim 6, wherein the particles are composed of a (meth) acrylate resin. A method for producing conductive particles according to claim 6 or 7, which comprises the step of applying the conductive paint to the particles using a turbulent flow layer granulation coating device. A conductive adhesive comprising the conductive particles according to claim 6 or 7, or the conductive particles produced by the production method according to claim 8. An electrically conductive particle according to claim 6 or 7, or a conductive particle produced by the production method according to claim 8.