JP5310985B2 - Paint and antistatic release film for forming antistatic release layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating for forming an antistatic release layer and an antistatic release film. <P>SOLUTION: The coating for forming the antistatic release layer includes an electroconductive polymer dispersed in an organic solvent, a silicon compound in which one or more of isocyanate groups are directly bonded to a silicon atom, a polyorganosiloxane having a terminally connected hydroxyl group, an acrylic resin having a hydroxyl number of 20 mg KOH/g or lower and/or an acid number of 20 mg KOH/g or lower and an amino resin, wherein the polyorganosiloxane and the acrylic resin are present in a solid part mass ratio of from 10:90 to 60:40. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a coating material for forming an antistatic release layer and an antistatic release film for producing a release film having excellent antistatic properties and exhibiting high peelability and low repellency.

In recent years, as the size and capacity of multilayer ceramic capacitors have increased, the thickness of ceramic green sheets tends to become increasingly thinner.
On the other hand, as the ceramic green sheet becomes thinner, the coating speed of the ceramic slurry becomes faster, and this increases the amount of static electricity generated. There has been a problem that foreign matter is adsorbed.
In addition, with the use of a thin film, the conventionally used release film may have insufficient wettability with respect to the ceramic slurry on the release surface, thereby causing the slurry to be easily repelled during ceramic slurry coating. was there. Therefore, the release surface of the release film is required to have good wettability with respect to the ceramic slurry. On the other hand, if a release film provided with a release layer with low repellency is used, the ceramic slurry is applied. Although it is possible to reduce repelling and shape deformation, there is a problem that it is difficult to peel off the green sheet thereafter.
Accordingly, the release film is required to be a release film that can solve the above-described problems, that is, has excellent antistatic properties and has high release properties and low repelling properties.

JP-A-2005-88389 discloses a release layer comprising an alkyd-modified silicone resin and / or an acrylic-modified silicone resin on an antistatic layer containing a conductive polymer obtained by polymerizing thiophene and / or a thiophene derivative. In addition, a release film is disclosed in which a stain prevention layer is formed on the opposite surface of the antistatic layer. The release film can be said to be an excellent method in that it can prevent the generation of static electricity even under low humidity by forming an antistatic layer.
However, the acrylic-modified silicone resin can suppress the repellency of the slurry, but it tends to increase the peeling force, which may make it difficult to peel off the green sheet. When is applied, the release layer dissolves and the green sheet cannot be peeled off, so that only an aqueous ceramic slurry can be used.

WO98 / 51490 pamphlet has a release layer with good wettability on at least one side of a biaxially stretched polyethylene-2,6-naphthalene dicarboxylate film, and is suitable for any ceramic sheet or the like. A release film is disclosed which can be peeled off with the force of the above and has a very small dimensional change due to a load under heating when used as a carrier film.
However, since this release film does not have antistatic performance, if it is used as a carrier sheet for a ceramic sheet, there is a possibility that defects will occur in the sheet due to static electricity generated when the ceramic sheet is peeled off or when ceramic slurry is applied. is there.
The release layer is mainly composed of a resin composition obtained by blending a resin mixture composed of an acrylic resin and a melamine crosslinking agent and a silicone resin, and the acrylic resin is the surface of the release layer in the resin composition. It is formulated to improve the wettability of the film, increase the toughness of the release layer, and obtain an appropriate level of peelability. However, increasing the amount of acrylic resin added to reduce repellency will result in sufficient peelability. May not be obtained.

In JP-A-11-300895, a conductive layer containing a π-electron conjugated conductive polymer is formed on at least one surface of a base film, and the surface of the conductive layer or the other surface of the base film A release film is disclosed in which a release layer is formed on the substrate. This release film is excellent in that it can prevent the generation of static electricity even under low humidity by providing a conductive layer containing a π-conjugated conductive polymer.
However, since the peelability of the release layer is high, the repellency of the surface becomes strong and the ceramic slurry is repelled by the release layer, which causes a problem that it is difficult to form a uniform layer of the coating liquid.
JP 2005-88389 A International Publication No. 98/51490 Pamphlet Japanese Patent Laid-Open No. 11-300895

  An object of the present invention is to provide a coating material for forming an antistatic release layer and an antistatic release film for producing a release film that is excellent in antistatic properties and exhibits high peelability and low repellency.

  As a result of intensive studies to solve the above problems, the inventors of the present invention formed a layer using a coating containing a conductive polymer and a specific component at a specific ratio. It has been found that the antistatic release layer can be an antistatic release layer having excellent antistatic properties, high peelability and low repellency, and that the antistatic release layer has the above-mentioned effects as a single layer, thereby completing the present invention. .

That is, the present invention
(1) A conductive polymer dispersed in an organic solvent, a silicon compound in which one or more isocyanato groups are directly bonded to a silicon atom, a polyorganosiloxane having a hydroxyl group at the terminal, a hydroxyl value of 20 mgKOH / g or less and / or an acid value Is a coating material for forming an antistatic release layer containing an acrylic resin and amino resin of 20 mg KOH / g or less, wherein the polyorganosiloxane and the acrylic resin have a solid content mass ratio of 10:90 to 60:40. (2) An antistatic release film comprising an antistatic release layer formed using the paint according to (1) on at least one surface of a substrate,
It is about.

  By using the coating material for forming the antistatic release layer of the present invention, it is possible to easily produce a release film that is excellent in antistatic properties and exhibits high peelability and low repellency.

  The coating material for forming the antistatic release layer of the present invention includes a conductive polymer dispersed in an organic solvent, a silicon compound in which one or more isocyanato groups are directly bonded to a silicon atom, a polyorganosiloxane having a hydroxyl group at the terminal, A coating material for forming an antistatic release layer comprising an acrylic resin having an hydroxyl value of 20 mgKOH / g or less and / or an acid value of 20 mgKOH / g or less, and an amino resin, wherein the polyorganosiloxane and the acrylic resin are: It is a paint having a solid mass ratio of 10:90 to 60:40.

As the conductive polymer in the conductive polymer dispersed in the organic solvent used in the paint of the present invention, conductive polymer fine particles obtained by polymerizing a monomer having a π-conjugated double bond can be used.
The monomer having a π-conjugated double bond is not particularly limited as long as it is a monomer used for producing a conductive polymer, and examples thereof include pyrrole, N-methylpyrrole, N-ethylpyrrole, and N-phenyl. Pyrrole, N-naphthylpyrrole, N-methyl-3-methylpyrrole, N-methyl-3-ethylpyrrole, N-phenyl-3-methylpyrrole, N
-Phenyl-3-ethylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-butylpyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-n-propoxypyrrole, 3-n-butoxypyrrole, 3 -Phenylpyrrole, 3-toluylpyrrole, 3-naphthylpyrrole, 3-phenoxypyrrole, 3-methylphenoxypyrrole, 3-aminopyrrole, 3-dimethylaminopyrrole, 3-diethylaminopyrrole, 3-diphenylaminopyrrole, 3-methyl Pyrrole derivatives such as phenylaminopyrrole and 3-phenylnaphthylaminopyrrole, aniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-methoxyaniline, m-methoxyaniline, p-methoxyaniline, o-ethoxy Aniline aniline derivatives such as m-ethoxyaniline, p-ethoxyaniline, o-methylaniline, m-methylaniline and p-methylaniline, thiophene, 3-methylthiophene, 3-n-butylthiophene, 3-n-pentylthiophene, 3-n-hexylthiophene, 3-n-heptylthiophene, 3-n-octylthiophene, 3-n-nonylthiophene, 3-n-decylthiophene, 3-n-undecylthiophene, 3-n-dodecylthiophene, Examples include thiophene derivatives such as 3-methoxythiophene, 3-naphthoxythiophene, and 3,4-ethylenedioxythiophene, preferably pyrrole, aniline, thiophene, and 3,4-ethylenedioxythiophene. Preferably, pyrrole is used.
The conductive polymer fine particles can be synthesized and used from the monomers having the π-conjugated double bonds listed above, but commercially available conductive polymer fine particles can also be used.

The organic solvent in which the conductive polymer fine particles are dispersed is not particularly limited as long as it can be dispersed without damaging the conductive polymer. Examples of the organic solvent include aliphatic esters such as butyl acetate, aromatic solvents such as benzene, toluene, and xylene, ketones such as methyl ethyl ketone, cyclic saturated hydrocarbons such as cyclohexane, and chain structures such as n-octane. Highly volatile organic solvents such as saturated hydrocarbons, chain saturated alcohols such as n-octanol, aromatic esters such as methyl benzoate, aliphatic ethers such as diethyl ether, and, for example, mineral spirits, isoparaffins Low terpentine solvents such as limonene, turpentine, orange oil, P-menthane, α-pinene, β-pinene, terpineol, isobornyl acetate, terpinyl acetate, terpineol, α-terpineol, dihydroterpineol, etc. A volatile organic solvent is mentioned.
The solid content concentration of the conductive polymer in the dispersion is in the range of 0.2 to 10.0%, preferably 0.5 to 6.0%, more preferably 1.0 to 4.0%. It is.

Examples of silicon compounds in which one or more isocyanato groups are directly bonded to a silicon atom include tetraisocyanatosilane, monomethyltriisocyanatosilane, monoethyltriisocyanatosilane, monobutyltriisocyanatosilane, and monomethoxytriisocyanatosilane. Monoethoxytriisocyanatosilane, mono-n-propoxytriisocyanatosilane, monoisopropoxytriisocyanatosilane, monobutoxytriisocyanatosilane, mono-2-butoxytriisocyanatosilane, mono-t-butoxytriisocyanatosilane, etc. Although the silyl isocyanato compound of this is illustrated, it is not limited to these. These silicon compounds can be used alone or in admixture of two or more.

The polyorganosiloxane having a hydroxyl group at the terminal is a silicon compound having one or more hydroxyl groups in the molecule, and examples thereof include α, ω-dihydroxypolydimethylsiloxane. Of course, although not limited to those exemplified here, this compound may be a silicon compound in the range of 10 to 1,000,000 mm ² / s at room temperature, preferably 50
A compound having a viscosity in the range of ˜100,000 mm ² / s is used.

The acrylic resin having a hydroxyl value of 20 mg KOH / g or less and / or an acid value of 20 mg KOH / g or less is not particularly limited as long as it is an acrylic resin having a hydroxyl value and an acid value in the above-mentioned ranges. For example, polymethyl acrylate And polyacrylic acid esters such as polyethyl acrylate, polymethacrylic acid esters such as polymethyl methacrylate and polyethyl methacrylate, and acrylic acid esters such as higher alkyl acrylates and higher alkyl methacrylates. Further, a copolymer obtained by copolymerizing two or more kinds of acrylic resin monomers, or a copolymer obtained by copolymerizing an acrylic resin monomer and another resin monomer can also be used.

  Examples of amino resins include monomethoxymethylated melamine resins, dimethoxymethylated melamine resins, trimethoxymethylated melamine resins, tetramethoxymethylated melamine resins, pentamethoxymethylated melamine resins, hexamethoxymethylated melamine resins, butylated melamines. Resin, monomethylol melamine resin, dimethylol melamine resin, trimethylol melamine resin, tetramethylol melamine resin, pentamethylol melamine resin, hexamethylol melamine resin, imino group-containing methoxymethylated melamine resin, benzoguanamine resin, butylated benzoguanamine resin, glycol Examples include uril resins, butylated urea resins, and methylated methylol urea resins. Of course, although not limited to those exemplified here, these resins may be used alone or in combination of two or more. Also, a copolymer obtained by copolymerizing two or more amino resin monomers, or a copolymer obtained by copolymerizing an amino resin monomer and another resin monomer can be used.

The amount of the silicon compound in which one or more isocyanato groups are directly bonded to the silicon atom is used in the range where the solid content concentration in the coating is 0.01 to 1%.
The amount of the polyorganosiloxane having a hydroxyl group at the terminal is used in the range where the solid content concentration in the coating is 0.05 to 5%.
The use amount of the acrylic resin having a hydroxyl value of 20 mgKOH / g or less and / or an acid value of 20 mgKOH / g or less is used in a range where the solid content concentration in the paint is 0.1 to 5%.
The amount of amino resin used is such that the solid content concentration in the paint is in the range of 0.1 to 5%.
The mass ratio of the polyorganosiloxane to the acrylic resin (polyorganosiloxane: acrylic resin) is in the range of 10:90 to 60:40, and preferably in the range of 30:70 to 45:55. .

In addition to the above components, a catalyst, a surfactant, a solvent, and the like used for promoting the crosslinking of the amino resin can be added to the coating material of the present invention.
Examples of the catalyst used for promoting the crosslinking of the amino resin include ammonium chloride, aromatic sulfonic acid, acidic phosphate ester and / or salts of these compounds. Of course, although not limited to what was illustrated here, this compound can also be used individually or in mixture of 2 or more types.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, and fluoroalkyl carboxylic acid, perfluoroalkyl carboxylic acid, perfluoroalkyl benzene. Fluorine surfactants such as sulfonic acid, perfluoroalkyl quaternary ammonium, and perfluoroalkyl polyoxyethylene ethanol can be used.
The amount of the surfactant used is in the range of 0.2 to 2.0 parts by mass with respect to 1 part by mass of the conductive polymer.

Examples of the solvent include acetates such as ethyl acetate and butyl acetate, propylene glycol monomethyl acetate, ethyl cellosolve acetate, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, tetrahydrofuran, toluene, xylene, hexane, heptane, acetone, and cyclohexanone. , Methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and the like can be used alone or in combination of two or more.

In addition, as diluent solvents, for example, esters, ethers, hydrocarbons, ketones, amides, alcohols, and the like can be used. For example, ethyl acetate, acetate such as butyl acetate, propylene glycol monomethyl acetate, ethyl cellosolve acetate, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, tetrahydrofuran, toluene, xylene, hexane, heptane, acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl Ketone, N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, methanol, ethanol, isopropanol, n-butanol, t-butanol and the like can be used alone or in combination.
The amount of the solvent / dilution solvent used is such that the solid content concentration in the paint is 0.5 to 6.0%, preferably the solid content concentration is 1.0 to 4.0%. It is a range.

Moreover, it is also possible to add resin, such as a dispersion stabilizer, a thickener, and a binder, to the coating material of this invention as needed, such as a use and an application target object.
Examples of binders used in the binder include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), hydrocarbon resin, ketone resin, and phenoxy resin. , Polyamide, ethyl cellulose, vinyl acetate, ABS
Examples thereof include resins, polyurethane resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, and silicon resins.
The amount of the binder used is 0.1 to 10 parts by mass with respect to 1 part by mass of the conductive polymer.

Next, a method for producing polypyrrole will be described as an example of a method for producing a conductive polymer used in the present invention. Polypyrrole can be produced, for example, by the following production method (1) and production method (2).
(1) A monomer of pyrrole and / or a pyrrole derivative is added to an O / W type emulsion obtained by mixing and stirring an organic solvent, water, and an anionic surfactant, and the monomer is oxidatively polymerized. Manufacturing method.
(2) Polymerization is initiated in an aqueous medium containing an amount of pyrrole and / or a pyrrole derivative, an anionic surfactant and / or a nonionic surfactant, and an oxidizing agent that can be solubilized in the aqueous medium, and the polymerization rate of polypyrrole The manufacturing method by adding an organic solvent to this polymerization system at the time when becomes 10 to 60% and further proceeding the polymerization.
The manufacturing conditions and operations of the manufacturing methods (1) and (2) will be described below.

Manufacturing method (1)
Examples of pyrrole and / or pyrrole derivative monomers that can be used in the production method (1) include pyrrole, N-methylpyrrole, N-ethylpyrrole, N-phenylpyrrole, N-naphthylpyrrole, and N-methyl-3-methylpyrrole. N-methyl-3-ethylpyrrole, N-phenyl-3-methylpyrrole, N-phenyl-3-ethylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-butylpyrrole, 3-methoxypyrrole, 3-ethoxypyrrole, 3-n-propoxypyrrole, 3-n-butoxypyrrole, 3-phenylpyrrole, 3-toluylpyrrole, 3-naphthylpyrrole, 3-phenoxypyrrole, 3-methylphenoxypyrrole, 3-aminopyrrole, 3-dimethylaminopyrrole, 3-diethylaminopyrrole, - diphenylamino pyrrole, 3-methylphenylamino pyrrole, 3-phenyl naphthyl amino pyrrole, and the like. Particularly preferred is pyrrole.

Various anionic surfactants used in the production method (1) can be used, but those having a plurality of hydrophobic ends (for example, those having a branched structure in a hydrophobic group or those having a plurality of hydrophobic groups). Is preferred. By using such an anionic surfactant having a plurality of hydrophobic ends, stable micelles can be formed.
Among anionic surfactants having multiple hydrophobic ends, di-2-ethylhexyl sodium sulfosuccinate (4 hydrophobic ends), di-2-ethyloctyl sodium sulfosuccinate (4 hydrophobic ends) and branched type Alkyl benzene sulfonate (two hydrophobic ends) can be preferably used.

  The amount of the anionic surfactant in the reaction system is preferably less than 0.2 mol, more preferably 0.05 mol to 0.15 mol, relative to 1 mol of the monomer of pyrrole and / or a pyrrole derivative. If the amount is less than 0.05 mol, the yield and the dispersion stability are lowered. On the other hand, if the amount is 0.2 mol or more, the resulting conductive fine particles may have a conductivity humidity dependency.

  In the production method (1), the organic solvent forming the organic phase of the emulsion has a solubility in water of 1% or less, and the volatilization rate when the volatilization rate of butyl acetate is 100 is high. Volatile organic solvent. Specifically, it is an aromatic hydrocarbon solvent such as toluene, xylene and benzene, but the highly volatile organic solvent can be used alone or as a mixture of two or more.

  The ratio of the organic phase to the aqueous phase in the emulsion is preferably 75% by volume or more in the aqueous phase. When the water phase is 20% by volume or less, the amount of pyrrole monomer dissolved is reduced and the production efficiency is deteriorated.

  Examples of the oxidizing agent used in the production method (1) include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and chlorosulfonic acid, organic acids such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid, potassium persulfate and ammonium persulfate. And peroxides such as hydrogen peroxide can be used. These may be used alone or in combination of two or more. Polypyrrole can be polymerized even with a Lewis acid such as ferric chloride, but the produced particles may aggregate and the polypyrrole may not be finely dispersed. Particularly preferred oxidizing agents are persulfates such as ammonium persulfate.

  The amount of the oxidizing agent in the reaction system is preferably 0.1 mol or more and 0.8 mol or less, more preferably 0.2 to 0.6 mol with respect to 1 mol of pyrrole and / or pyrrole derivative monomer. . If the amount is less than 0.1 mol, the degree of polymerization of the monomer decreases, making it difficult to separate and collect the conductive fine particles. On the other hand, if the amount is 0.8 mol or more, the polypyrrole aggregates to increase the particle size of the conductive fine particles. Stability deteriorates.

The production method (1) is performed by, for example, the following steps:
(A) a step of preparing an emulsion by mixing and stirring an anionic surfactant, an organic solvent and water;
(B) a step of dispersing a monomer of pyrrole and / or a pyrrole derivative in an emulsion, (c) a step of oxidative polymerization of the monomer to cause polyanol to contact and adsorb on an anionic surfactant,
(D) A step of separating the organic phase and collecting the conductive fine particles.

Each of the above steps can be performed using means known to those skilled in the art. For example, the mixing and stirring performed at the time of preparing the emulsion is not particularly limited. For example, a magnetic stirrer, a stirrer, a homogenizer, or the like can be selected as appropriate. The polymerization temperature is 0 to 25 ° C, preferably 20 ° C or less. If the polymerization temperature exceeds 25 ° C., side reactions occur, which is not preferable.

Manufacturing method (2)
Examples of pyrrole and / or pyrrole derivatives that can be used in the production method (2) include pyrrole, N-methylpyrrole, N-ethylpyrrole, N-phenylpyrrole, N-naphthylpyrrole, N-methyl-3-methylpyrrole, N -Methyl-3-ethylpyrrole, N-phenyl-3-methylpyrrole, N-phenyl-3-ethylpyrrole, 3-methylpyrrole, 3-ethylpyrrole, 3-n-butylpyrrole, 3-methoxypyrrole, 3- Ethoxypyrrole, 3-n-propoxypyrrole, 3-n-butoxypyrrole, 3-phenylpyrrole, 3-toluylpyrrole, 3-naphthylpyrrole, 3-phenoxypyrrole, 3-methylphenoxypyrrole, 3-aminopyrrole, 3- Dimethylaminopyrrole, 3-diethylaminopyrrole, 3-diphe Le aminopyrrole, 3-methylphenylamino pyrrole, 3-phenyl naphthyl amino pyrrole, and the like. Particularly preferred is pyrrole.

The amount of pyrrole and / or pyrrole derivative that can be solubilized in an aqueous medium is 80 g / L or less, particularly preferably 20 g / L to 1 g / L, relative to water.
When an amount of pyrrole and / or a pyrrole derivative that cannot be solubilized in an aqueous medium is added (a pyrrole and / or pyrrole derivative having a saturation concentration or more), a massive polypyrrole is generated immediately after the start of polymerization, and the desired fine particles are obtained. I can't. On the other hand, when the monomer of pyrrole and / or pyrrole derivative is 1 g / L or less, the polymerization reaction is extremely slow, and it takes a long time to obtain desired fine particles.

As the anionic surfactant that can be used in the production method (2), a commonly used anionic surfactant can be used, and it is not particularly limited, but one having a plurality of hydrophobic ends (for example, hydrophobic) Those having a branched structure in the group and those having a plurality of hydrophobic groups are preferred. By using such an anionic surfactant having a plurality of hydrophobic ends, stable micelles can be formed, and separation of the aqueous phase and the organic solvent phase after polymerization is easy. Conductive fine particles dispersed in are easily available. Among anionic surfactants having multiple hydrophobic ends, di-2-ethylhexyl sulfosuccinate (4 hydrophobic ends), di-2-octyl sodium sulfosuccinate (4 hydrophobic ends) and branched alkylbenzene sulfone Acid salts (two hydrophobic ends) can be preferably used.
Moreover, said anionic surfactant can be used individually or in mixture of 2 or more types.

Nonionic surfactants that can be used in the production method (2) include, for example, polyoxyethylene alkyl ethers, alkyl glucosides, fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxy Examples include ethylene fatty acid esters, fatty acid alkanolamides, and polyoxyethylene alkylphenyl ethers.
Said nonionic surfactant can be used individually or in mixture of 2 or more types.

  The amount of the anionic surfactant and / or nonionic surfactant used is preferably less than 0.2 mol, more preferably 0.05 mol to 0.15 mol, relative to 1 mol of the monomer of pyrrole and / or a pyrrole derivative. If the amount is less than 0.05 mol, the yield and the dispersion stability are lowered. On the other hand, if the amount is 0.2 mol or more, the resulting conductive fine particles may have a conductivity humidity dependency.

  Examples of the oxidizing agent used in the production method (2) include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and chlorosulfonic acid, organic acids such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid, potassium persulfate and ammonium persulfate. And peroxides such as hydrogen peroxide can be used. These may be used alone or in combination of two or more. Polypyrrole can be polymerized even with a Lewis acid such as ferric chloride, but the produced particles may aggregate and the polypyrrole may not be finely dispersed. Particularly preferred oxidizing agents are persulfates such as ammonium persulfate.

  The amount of the oxidizing agent to be used is preferably 0.1 mol or more and 0.8 mol or less, more preferably 0.2 to 0.6 mol, with respect to 1 mol of pyrrole and / or pyrrole derivative monomer. If the amount is less than 0.1 mol, the degree of polymerization of the monomer decreases, making it difficult to separate and collect the conductive fine particles. On the other hand, if the amount is 0.8 mol or more, the polypyrrole aggregates to increase the particle size of the conductive fine particles. Stability deteriorates.

The aqueous medium used in the production method (2) is basically water, and if desired, a dopant or the like can be added for the purpose of improving the conductivity of the formed polypyrrole fine particles and reducing the change with time of the conductivity. .
The amount of the aqueous medium to be used is an amount capable of solubilizing the pyrrole and / or pyrrole derivative to be used, that is, an amount such that the concentration of pyrrole and / or pyrrole derivative is 80 g / L or less as defined above. Particularly preferred is an amount of 20 g / L to 1 g / L.

As described above, in the production method (2), a dopant can be added.
In the production method (2), by adding a predetermined dopant to the aqueous medium, it may be possible to improve the conductivity and reduce the change with time.
The kind of the dopant when the dopant is used in the production method (2) is not particularly limited as long as it is soluble in the monomer of pyrrole and / or pyrrole derivative, and generally a polymer of pyrrole and / or pyrrole derivative is used. An acceptor dopant suitably used for the conductive fine particles can be used as appropriate. Typical examples thereof include polystyrene sulfonic acid, paratoluene sulfonic acid, methane sulfonic acid, trifluoromethane sulfonic acid, and anthraquinone sulfonic acid. Sulfonic acids such as benzenesulfonic acid, naphthalenesulfonic acid, sulfosalicylic acid, dodecylbenzenesulfonic acid and allylsulfonic acid, halogens such as perchloric acid, chlorine and bromine, Lewis acid and protonic acid. These may be in the acid form or in the salt form. Preferred from the viewpoint of solubility in monomers, tetrabutylammonium perchlorate, tetraethylammonium perchlorate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium trifluoromethanesulfonate, tetrabutylammonium trifluorosulfonimide, dodecylbenzene Examples thereof include sulfonic acid and paratoluenesulfonic acid.

  When the dopant is used, the dopant is preferably used in an amount of 0.01 to 0.3 molecule of dopant per pyrrole polymer unit unit to be generated. When the amount is 0.01 molecule or less, the amount of dopant necessary to form a sufficient conductive path is insufficient, and it is difficult to obtain high conductivity. On the other hand, addition of 0.3 molecule or more does not improve the doping rate, so the addition of 0.3 molecule or more dopant is not economically preferable. Here, the pyrrole polymer unit unit refers to a repeating portion corresponding to one molecule of a pyrrole polymer monomer obtained by polymerizing a pyrrole monomer.

In the production method (2), after initiating polymerization in an aqueous medium containing an amount of pyrrole and / or a pyrrole derivative, an anionic surfactant and / or a nonionic surfactant, and an oxidizing agent that can be solubilized in the aqueous medium, An organic solvent is added when the polymerization rate of polypyrrole reaches 10 to 60%. More preferably, the organic solvent is added when the polymerization rate of the polypyrrole reaches 20 to 50%. When the organic solvent is added when the polymerization rate is less than 10%, the conjugated double bond of polypyrrole is not sufficiently grown, so that predetermined conductivity cannot be obtained. Further, the subsequent polymerization becomes extremely slow, and the separation of water and the organic solvent becomes extremely poor. On the contrary, when the organic solvent is added when the polymerization rate exceeds 60%, the size of the polypyrrole particles transferred to the organic solvent becomes large particles of several hundred nm or more, and the dispersion stability is also poor.
The polymerization rate can be easily calculated from the ratio of the initially added monomer amount and the residual monomer amount by measuring the residual monomer using gas chromatography.

The presence of a certain amount of residual monomer (unreacted monomer) in the reaction system is considered important in order not to make the particle size of the polypyrrole too large and to cause aggregation of the polypyrrole particles. Therefore, it is considered that when the polymerization rate is improved and the amount of the residual monomer is decreased, the particle size of the polypyrrole is suddenly increased and the polypyrrole particles are aggregated.
That is, in order not to make the particle size of polypyrrole too large and to cause aggregation of polypyrrole particles, the amount of residual monomer (unreacted monomer) in the reaction system is 40 to 90 of the amount of monomer initially added. It can be said that it is important to add an organic solvent at the time when% remains.

Similarly, the size of the fine particles dispersed in the aqueous medium at the time of adding the organic solvent is also extremely important. In the relationship between the polymerization rate (%) of polypyrrole in an aqueous medium and the average particle size (nm) of polypyrrole obtained at that time, the average particle size of polypyrrole increases rapidly when the polymerization rate of polypyrrole exceeds a certain value. . Therefore, for example, even when an organic solvent is added when the average particle size of polypyrrole exceeds 100 nm, the size of the polypyrrole particles transferred to the organic solvent tends to be large particles of several hundred nm or more as a result. Dispersion stability tends to be poor.
Therefore, it is preferable to add the organic solvent when the particle size of the polypyrrole is 100 nm or less.
In addition, the average particle diameter of polypyrrole can be easily measured by a laser Doppler method.

As the organic solvent to be added, a highly volatile organic solvent, a low volatile organic solvent, or a mixture of a high volatile organic solvent and a low volatile organic solvent can be used. Aliphatic esters such as butyl acetate, aromatic solvents such as toluene, ketones such as methyl ethyl ketone, cyclic saturated hydrocarbons such as cyclohexane, chain saturated hydrocarbons such as n-octane, and chains such as n-octanol Examples thereof include saturated alcohols, aromatic esters such as methyl benzoate, aliphatic ethers such as diethyl ether, etc. Examples of the low volatile organic solvent include mineral spirit, isoparaffin, turpentine oil, orange limonene , P-menthane, α-pinene, β-pinene, terpinolene, isobornyl acetate, terpinyl acetate, Examples include terpentine solvents such as -pineol, α-terpineol, and dihydroterpineol, and terpentine solvents are preferred.
Moreover, limonene is preferable in that it is naturally derived and environmentally friendly.
The amount of the organic solvent to be used is preferably 5 to 40% (v / v), particularly preferably 10 to 25% (v / v) by volume with respect to the amount of water used in the polymerization reaction.
If it is less than 5% (v / v), the particle density becomes high and the dispersibility becomes poor, resulting in aggregation. When it exceeds 40% (v / v), the particle density becomes relatively low, so the repulsive force between the particles becomes small and dispersion cannot be maintained.

The method for producing the polypyrrole fine particles is performed, for example, in the following steps:
(A) a step of adding an anionic surfactant and / or a nonionic surfactant, a monomer of pyrrole and / or a pyrrole derivative and optionally a dopant to water and mixing and stirring;
(B) adding an oxidizing agent to start oxidative polymerization;
(C) adding an organic solvent when the polymerization rate becomes 10 to 60%,
(D) a step of mixing and stirring to further advance the polymerization reaction;
(E) A step of separating the organic phase and collecting polypyrrole fine particles nano-dispersed in the organic solvent layer.

  Each of the above steps can be performed using means known to those skilled in the art. For example, the mixing and stirring is not particularly limited. For example, a magnetic stirrer, a stirrer, a homogenizer, and the like can be selected as appropriate. The polymerization temperature is 0 to 25 ° C, preferably 20 ° C or less. If the polymerization temperature exceeds 25 ° C., side reactions occur, which is not preferable.

  The polypyrrole fine particles nano-dispersed in the organic solvent layer obtained by the production method (1) or the polypyrrole fine particles nano-dispersed in the organic solvent layer obtained by the production method (2) may be used as a polypyrrole dispersion as it is. it can. Moreover, it can also be used as a polypyrrole dispersion after concentrating as needed and diluting to the required extent with another solvent that does not cause layer separation.

The present invention relates to an antistatic release film comprising an antistatic release layer formed on at least one surface of a substrate using a coating material for forming the antistatic release layer.
The antistatic release film can be easily produced by applying a coating material for forming the above-described antistatic release layer on a substrate, followed by drying and heat treatment as necessary.

  The substrate used for the antistatic release film of the present invention is not particularly limited as long as it is a substrate that is usually used for green sheets. For example, a polyester film can be used. Although it will not specifically limit if it is used for the polyester film, For example, a polyethylene terephthalate etc. are mentioned.

The method for applying the coating material to the base material for forming the antistatic release layer is not particularly limited. For example, a screen printing machine, a gravure printing machine, a flexographic printing machine, an ink jet printing machine, an offset printing machine, dipping, a spin coater, a roll. Printing or coating can be performed using a coater or the like.
The antistatic release layer formed has a thickness in the range of 50 nm to 200 nm.

EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to an Example.
Production Example 1
1.5 mmol of di-2-ethylhexyl sodium sulfosuccinate was dissolved in 50 mL of toluene, and further 100 mL of ion-exchanged water was added and stirred until emulsification was maintained at 20 ° C. To the obtained emulsion, 21.2 mmol of pyrrole monomer was added and stirred for 30 minutes, and then 50 mL (corresponding to 6 mmol) of a 0.12 M aqueous ammonium persulfate solution was added dropwise little by little and reacted for 4 hours. After completion of the reaction, the organic phase was recovered and washed several times with ion-exchanged water to obtain a polypyrrole dispersion (solid content concentration 1.3%) in which black polypyrrole was dispersed in toluene.

Example 1
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 0.6 parts by mass of hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone), 0.1 parts by mass of tetraisocyanatosilane, 1.9 parts by mass of fully alkylmethylated melamine resin “Cymel 300” (Mitsui Cytec Co., Ltd.), 0.01 part by mass of aromatic sulfonic acid catalyst “Catalyst 600” (Mitsui Cytec Co., Ltd.), acrylic Resin “Polynal 500” (manufactured by Ohashi Chemical Industry Co., Ltd .: hydroxyl value 0 mg KOH / g, acid value 0 mg KOH / g) 6.7 parts by mass, surfactant “homogenol L-100” (manufactured by Kao Corporation) 10 mass And diluted with a mixed solvent of ethyl acetate and isopropyl alcohol, and then stirred at 100 rpm with a disper mixer. It was stirred for 30 minutes, to prepare a solid concentration of 2.3% of the paint.

Example 2
Polyaniline organic solvent dispersion “ORMECON NX-B001X” (Nissan Chemical Industry Co., Ltd.) 33 parts by mass, hydroxyl group-containing silicone oil “PRX-413” (Toray Dow Corning Silicone Co., Ltd.) 0.6 parts by mass , 0.1 part by mass of tetraisocyanatosilane, 1.9 parts by mass of fully alkylmethylated melamine resin “Cymel 300” (manufactured by Mitsui Cytec Co., Ltd.), aromatic sulfonic acid catalyst “Catalyst 600” (Mitsui Cytec ( Co., Ltd.) 0.01 parts by mass, acrylic resin “Polynal 500” (Ohashi Chemical Industries, Ltd .: hydroxyl value 0 mg KOH / g, acid value 0 mg KOH / g) 6.7 parts by mass, surfactant “Homogenol L- 100 ”(manufactured by Kao Corporation) is added in an amount of 10 parts by mass and mixed with ethyl acetate, xylene and isopropyl alcohol. After dilution, the mixture was stirred for 30 minutes at a stirring speed of 100 rpm with a disper mixer to prepare a paint having a solid content concentration of 2.3%.

Example 3
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 0.6 part by mass of hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone Co., Ltd.), 0.1 part by mass of monomethyltriisocyanatosilane 1.9 parts by mass of a fully alkylmethylated melamine resin “Cymel 300” (Mitsui Cytec Co., Ltd.), 0.01 part by mass of an aromatic sulfonic acid catalyst “Catalyst 600” (Mitsui Cytec Co., Ltd.), Acrylic resin “Polynal 500” (manufactured by Ohashi Chemical Industry Co., Ltd .: hydroxyl value 0 mg KOH / g, acid value 0 mg KOH / g) 6.7 parts by mass, surfactant “homogenol L-100” (manufactured by Kao Corporation) 10 After adding a part by mass and diluting with a mixed solvent of ethyl acetate and isopropyl alcohol, the stirring speed is 100 with a disper mixer. It was stirred for 30 minutes at pm, to prepare a solid concentration of 2.3% of the paint.

Example 4
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 0.3 parts by mass of hydroxyl group-containing silicone oil “XF3905” (manufactured by Momentive Performance Materials), 0.1 parts by mass of tetraisocyanatosilane, complete alkylmethyl Melamine resin “Cymel 300” (Mitsui Cytec Co., Ltd.) 1.9 parts by mass, aromatic sulfonic acid catalyst “Catalyst 600” (Mitsui Cytec Co., Ltd.) 0.01 parts by mass, acrylic resin “Polynal” 500 ”(manufactured by Ohashi Chemical Industry Co., Ltd .: hydroxyl value 0 mg KOH / g, acid value 0 mg KOH / g) 6.7 parts by mass, surfactant“ homogenol L-100 ”(manufactured by Kao Corporation) 10 parts by mass And diluted with a mixed solvent of ethyl acetate and isopropyl alcohol, and then stirred at a speed of 100 r with a disper mixer. It was stirred for 30 minutes at m, to prepare a solid concentration of 2.3% of the paint.

Example 5
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 0.6 parts by mass of hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone), 0.1 parts by mass of tetraisocyanatosilane, 1.9 parts by mass of fully alkylmethylated melamine resin “Cymel 300” (Mitsui Cytec Co., Ltd.), 0.01 part by mass of aromatic sulfonic acid catalyst “Catalyst 600” (Mitsui Cytec Co., Ltd.), acrylic Resin “Thermolac EF-36” (manufactured by Soken Chemical Co., Ltd .: hydroxyl value 8 mgKOH / g, acid value 4 mgKOH / g) 6.7 parts by mass, surfactant “homogenol L-100” (manufactured by Kao Corporation) After adding 10 parts by mass and diluting with a mixed solvent of ethyl acetate and isopropyl alcohol, the stirring speed is 100 rpm with a disper mixer. It was stirred for 30 minutes to prepare a solid concentration of 2.3% of the paint.

Example 6
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 0.6 parts by mass of hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone), 0.1 parts by mass of tetraisocyanatosilane, 1.9 parts by mass of fully alkylmethylated melamine resin “Cymel 300” (Mitsui Cytec Co., Ltd.), 0.01 part by mass of aromatic sulfonic acid catalyst “Catalyst 600” (Mitsui Cytec Co., Ltd.), acrylic Resin “Hyperl M-5002HO” (manufactured by Negami Kogyo Co., Ltd .: hydroxyl value 20 mgKOH / g, acid value 0 mgKOH / g) 6.7 parts by mass, surfactant “homogenol L-100” (manufactured by Kao Corporation) 10 After adding a part by mass and diluting with a mixed solvent of ethyl acetate and isopropyl alcohol, the stirring speed is 100 with a disper mixer. It was stirred for 30 minutes at pm, to prepare a solid concentration of 2.3% of the paint.

Example 7
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 0.6 parts by mass of hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone), 0.1 parts by mass of tetraisocyanatosilane, 1.9 parts by mass of fully alkylmethylated melamine resin “Cymel 300” (Mitsui Cytec Co., Ltd.), 0.01 part by mass of aromatic sulfonic acid catalyst “Catalyst 600” (Mitsui Cytec Co., Ltd.), acrylic Resin “Dianal BR-73” (Mitsubishi Rayon Co., Ltd .: hydroxyl value 0 mgKOH / g, acid value 3 mgKOH / g) 4.5 parts by mass and acrylic resin “Actoflow CB-3060” (manufactured by Soken Chemical Co., Ltd.) : Hydroxyl value 0 mgKOH / g, acid value 0 mgKOH / g) mixture with 2.2 parts by mass (hydroxyl value 0 mgKOH / g, acid value 20 m Used as an acrylic resin of KOH / g), 10 parts by mass of a surfactant “Homogenol L-100” (manufactured by Kao Corporation), diluted with a mixed solvent of ethyl acetate and isopropyl alcohol, and then a disper mixer Was stirred for 30 minutes at a stirring speed of 100 rpm to prepare a paint having a solid content concentration of 2.3%.

Example 8
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 0.6 parts by mass of hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone), 0.1 parts by mass of tetraisocyanatosilane, 1.9 parts by mass of fully alkylmethylated melamine resin “Cymel 300” (Mitsui Cytec Co., Ltd.), 0.01 part by mass of aromatic sulfonic acid catalyst “Catalyst 600” (Mitsui Cytec Co., Ltd.), acrylic Resin “Polynal 500” (manufactured by Ohashi Chemical Industry Co., Ltd .: hydroxyl value 0 mgKOH / g, acid value 0 mgKOH / g) 8.3 parts by mass, surfactant “homogenol L-100” (manufactured by Kao Corporation) 10 masses And diluted with a mixed solvent of ethyl acetate and isopropyl alcohol, and then stirred at 100 rpm with a disper mixer. It was stirred for 30 minutes, to prepare a solid concentration of 2.6% of the paint.

Example 9
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 0.6 parts by mass of hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone), 0.1 parts by mass of tetraisocyanatosilane, 1.9 parts by mass of fully alkylmethylated melamine resin “Cymel 300” (Mitsui Cytec Co., Ltd.), 0.01 part by mass of aromatic sulfonic acid catalyst “Catalyst 600” (Mitsui Cytec Co., Ltd.), acrylic Resin “Polynal 500” (manufactured by Ohashi Chemical Industry Co., Ltd .: hydroxyl value 0 mg KOH / g, acid value 0 mg KOH / g) 1.7 parts by mass, surfactant “homogenol L-100” (manufactured by Kao Corporation) 10 mass And diluted with a mixed solvent of ethyl acetate and isopropyl alcohol, and then stirred at 100 rpm with a disper mixer. It was stirred for 30 minutes, to prepare a solid concentration of 1.6% of the paint.

Example 10
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 0.6 parts by mass of hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone), 0.1 parts by mass of tetraisocyanatosilane, 1.9 parts by mass of a methylol-based methylated melamine resin “Cymel 370” (Mitsui Cytec Co., Ltd.), 0.01 part by mass of an aromatic sulfonic acid catalyst “Catalyst 602” (Mitsui Cytec Co., Ltd.), Acrylic resin “Polynal 500” (manufactured by Ohashi Chemical Industry Co., Ltd .: hydroxyl value 0 mg KOH / g, acid value 0 mg KOH / g) 6.7 parts by mass, surfactant “homogenol L-100” (manufactured by Kao Corporation) 10 After adding a part by mass and diluting with a mixed solvent of toluene and isopropyl alcohol, the stirring speed is 100 rpm with a disper mixer. It was stirred for 30 minutes, to prepare a solid concentration of 2.3% of the paint.

Example 11
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 0.6 parts by mass of hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone), 0.1 parts by mass of tetraisocyanatosilane, 1.9 parts by mass of fully alkylmethylated melamine resin “Cymel 300” (Mitsui Cytec Co., Ltd.), 0.01 part by mass of aromatic sulfonic acid catalyst “Catalyst 600” (Mitsui Cytec Co., Ltd.), acrylic After adding 6.7 parts by mass of resin “Polynal 500” (manufactured by Ohashi Chemical Industry Co., Ltd .: hydroxyl value 0 mg KOH / g, acid value 0 mg KOH / g), the mixture was diluted with a mixed solvent of ethyl acetate and isopropyl alcohol, and then a disper mixer Was stirred for 30 minutes at a stirring speed of 100 rpm to prepare a paint having a solid content concentration of 2.4%.

Example 12
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 0.6 parts by mass of hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone), 0.1 parts by mass of tetraisocyanatosilane, 1.9 parts by mass of fully alkylmethylated melamine resin “Cymel 300” (Mitsui Cytec Co., Ltd.), 0.01 part by mass of aromatic sulfonic acid catalyst “Catalyst 600” (Mitsui Cytec Co., Ltd.), acrylic Resin “Polynal 500” (manufactured by Ohashi Chemical Co., Ltd .: hydroxyl value 0 mg KOH / g, acid value 0 mg KOH / g) 6.7 parts by mass, surfactant “homogenol L-18” (manufactured by Kao Corporation) 10 mass 3 parts and diluted with a mixed solvent of ethyl acetate and isopropyl alcohol, then 3 with a disperser mixer at a stirring speed of 100 rpm. Stirring minutes to prepare a solid concentration of 2.3% of the paint.

Comparative Example 1
Hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone Co., Ltd.) 0.6 parts by mass, tetraisocyanatosilane 0.1 parts by mass, fully alkylmethylated melamine resin “Cymel 300” (Mitsui Cytec ( 1.9 parts by mass), 0.01 part by mass of the aromatic sulfonic acid catalyst “Catalyst 600” (Mitsui Cytec Co., Ltd.) is diluted with ethyl acetate, and then stirred at 100 rpm with a disper mixer. The mixture was stirred for 30 minutes to prepare a paint having a solid content concentration of 0.7%.

Comparative Example 2
Hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone Co., Ltd.) 0.6 parts by mass, tetraisocyanatosilane 0.1 parts by mass, fully alkylmethylated melamine resin “Cymel 300” (Mitsui Cytec ( 1.9 parts by mass, aromatic sulfonic acid catalyst “Catalyst 600” (Mitsui Cytec Co., Ltd.) 0.01 parts by mass, acrylic resin “Polynal 500” (manufactured by Ohashi Chemical Industries, Ltd.): 6.7 parts by mass of a hydroxyl value of 0 mg KOH / g, an acid value of 0 mg KOH / g) and 10 parts by mass of a surfactant “Homogenol L-100” (manufactured by Kao Corporation) were diluted with ethyl acetate, and then stirred with a disper mixer. The mixture was stirred at a speed of 100 rpm for 30 minutes to prepare a paint having a solid content concentration of 1.6%.

Comparative Example 3
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 26.7 parts by mass of curable silicone “KS-779H” (manufactured by Shin-Etsu Chemical Co., Ltd.), platinum catalyst “CAT-PL-50T” (Shin-Etsu Chemical) 0.27 parts by mass of an acrylic resin “Polynal 500” (manufactured by Ohashi Chemical Industry Co., Ltd .: hydroxyl value 0 mg KOH / g, acid value 0 mg KOH / g) was added and diluted with toluene. After that, the mixture was stirred with a disper mixer at a stirring speed of 100 rpm for 30 minutes to prepare a paint having a solid content concentration of 5.7%.

Comparative Example 4
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 27.1 parts by mass of curable silicone “KS-719” (manufactured by Shin-Etsu Chemical Co., Ltd.), tin catalyst “CAT-PS-8S” (Shin-Etsu Chemical) 1.4 parts by mass of acrylic resin “Polynal 500” (manufactured by Ohashi Chemical Industry Co., Ltd .: hydroxyl value 0 mgKOH / g, acid value 0 mgKOH / g) was added and diluted with toluene. Then, the mixture was stirred for 30 minutes at a stirring speed of 100 rpm with a disper mixer to prepare a coating material having a solid content concentration of 5.3%.

Comparative Example 5
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 0.6 parts by mass of hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone), 0.1 parts by mass of tetraisocyanatosilane, Add 1.9 parts by mass of fully alkylmethylated melamine resin “Cymel 300” (Mitsui Cytec Co., Ltd.) and 0.01 part by mass of aromatic sulfonic acid catalyst “Catalyst 600” (Mitsui Cytec Co., Ltd.) Then, after diluting with a mixed solvent of ethyl acetate and isopropyl alcohol, the mixture was stirred with a disper mixer at a stirring speed of 100 rpm for 30 minutes to prepare a paint having a solid content concentration of 1.4%.

Comparative Example 6
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 0.6 parts by mass of hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone), 0.1 parts by mass of tetraisocyanatosilane, 1.9 parts by mass of fully alkylmethylated melamine resin “Cymel 300” (Mitsui Cytec Co., Ltd.), 0.01 part by mass of aromatic sulfonic acid catalyst “Catalyst 600” (Mitsui Cytec Co., Ltd.), acrylic Resin “Thermolac EF-42” (manufactured by Soken Chemical Co., Ltd .: hydroxyl value 21 mgKOH / g, acid value 4 mgKOH / g) 6.7 parts by mass, surfactant “homogenol L-100” (manufactured by Kao Corporation) After adding 10 parts by mass and diluting with a mixed solvent of ethyl acetate and isopropyl alcohol, the stirring speed was 100 rp with a disper mixer. In stirred 30 minutes to prepare a solid concentration of 2.6% of the paint.

Comparative Example 7
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 0.6 parts by mass of hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone), 0.1 parts by mass of tetraisocyanatosilane, 1.9 parts by mass of fully alkylmethylated melamine resin “Cymel 300” (Mitsui Cytec Co., Ltd.), 0.01 part by mass of aromatic sulfonic acid catalyst “Catalyst 600” (Mitsui Cytec Co., Ltd.), acrylic Resin “Dianal BR-73” (manufactured by Mitsubishi Rayon Co., Ltd .: hydroxyl value 0 mgKOH / g, acid value 3 mgKOH / g) 3.3 parts by mass and acrylic resin “Actoflow CB-3060” (manufactured by Soken Chemical Co., Ltd.) : Hydroxyl value 0 mg KOH / g, Acid value 60 mg KOH / g) A mixture with 3.3 parts by mass (hydroxyl value 0 mg KOH / g, acid value 30 used as an acrylic resin of gKOH / g), 10 parts by mass of a surfactant “Homogenol L-100” (manufactured by Kao Corporation), diluted with a mixed solvent of ethyl acetate and isopropyl alcohol, and then a disper mixer The mixture was stirred for 30 minutes at a stirring speed of 100 rpm to prepare a paint having a solid content concentration of 2.6%.

Comparative Example 8
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 0.6 parts by mass of hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone), 0.1 parts by mass of tetraisocyanatosilane, 1.9 parts by mass of fully alkylmethylated melamine resin “Cymel 300” (Mitsui Cytec Co., Ltd.), 0.01 part by mass of aromatic sulfonic acid catalyst “Catalyst 600” (Mitsui Cytec Co., Ltd.), acrylic 20 parts by mass of resin “Polynal 500” (manufactured by Ohashi Chemical Industry Co., Ltd .: hydroxyl value 0 mgKOH / g, acid value 0 mgKOH / g) was added and diluted with a mixed solvent of ethyl acetate and isopropyl alcohol. The mixture was stirred at a stirring speed of 100 rpm for 30 minutes to prepare a paint having a solid content concentration of 4.5%.

Comparative Example 9
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 0.6 parts by mass of hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone), 0.1 parts by mass of tetraisocyanatosilane, 1.9 parts by mass of fully alkylmethylated melamine resin “Cymel 300” (Mitsui Cytec Co., Ltd.), 0.01 part by mass of aromatic sulfonic acid catalyst “Catalyst 600” (Mitsui Cytec Co., Ltd.), acrylic Disperser mixer after adding 0.7 parts by mass of resin “Polynal 500” (manufactured by Ohashi Chemical Industry Co., Ltd .: hydroxyl value 0 mg KOH / g, acid value 0 mg KOH / g) and diluting with a mixed solvent of ethyl acetate and isopropyl alcohol Was stirred for 30 minutes at a stirring speed of 100 rpm to prepare a paint having a solid content concentration of 1.5%.

Comparative Example 10
To 100 parts by mass of the polypyrrole dispersion prepared in Production Example 1, 0.6 parts by mass of hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone), 0.1 parts by mass of tetraisocyanatosilane, After adding 6.7 parts by mass of acrylic resin “Polynal 500” (manufactured by Ohashi Chemical Industry Co., Ltd .: hydroxyl value 0 mg KOH / g, acid value 0 mg KOH / g), the mixture was diluted with a mixed solvent of ethyl acetate and isopropyl alcohol, and then dispersed. The mixture was stirred with a mixer at a stirring speed of 100 rpm for 30 minutes to prepare a paint having a solid content concentration of 1.3%.

The paints prepared in Examples 1 to 12 and Comparative Examples 1 to 10 are summarized in Table 1.
In the table, the values of “hydroxyl value” and “acid value” indicate mgKOH / g, and the value of “solid content mass ratio” indicates the solid content mass ratio of polyorganosiloxane and acrylic resin (polyorganosiloxane: Acrylic resin), “solid content concentration” indicates the solid content concentration (%) in the prepared paint, the numerical values of the amounts of each component indicate parts by mass, and the types of each component are listed below. Show.
<Conductive polymer dispersion>
A1: Polypyrrole dispersion prepared in Production Example 1 A2: Polyaniline organic solvent dispersion “ORMECON NX-B001X” (manufactured by Nissan Chemical Industries, Ltd.)
<Silicon compound>
B1: Tetraisocyanatosilane B2: Monomethyltriisocyanatosilane <polyorganosiloxane>
C1: Hydroxyl group-containing silicone oil “PRX-413” (manufactured by Toray Dow Corning Silicone)
C2: Hydroxyl group-containing silicone oil “XF3905” (made by Momentive Performance Materials)
C3: curable silicone “KS-779H” (manufactured by Shin-Etsu Chemical Co., Ltd.)
C4: Curable silicone “KS-719” (manufactured by Shin-Etsu Chemical Co., Ltd.)
<Amino resin>
E1: Fully alkylmethylated melamine resin “Cymel 300” (Mitsui Cytec Co., Ltd.)
E2: Methylol group methylated melamine resin “Cymel 370” (manufactured by Mitsui Cytec Co., Ltd.)
<Acrylic resin>
D1: Acrylic resin “Polynal 500” (manufactured by Ohashi Chemical Industry Co., Ltd .: hydroxyl value 0 mgKOH / g, acid value 0 mgKOH / g)
D2: Acrylic resin “Thermolac EF-36” (manufactured by Soken Chemical Co., Ltd .: hydroxyl value 8 mgKOH / g, acid value 4 mgKOH / g)
D3: acrylic resin “Hyperl M-5002HO” (manufactured by Negami Kogyo Co., Ltd .: hydroxyl value 20 mgKOH / g, acid value 0 mgKOH / g)
D4: Acrylic resin “Dianar BR-73” (manufactured by Mitsubishi Rayon Co., Ltd .: hydroxyl value 0 mgKOH / g, acid value 3 mgKOH / g)
D5: Acrylic resin “Actoflow CB-3060” (manufactured by Soken Chemical Co., Ltd .: hydroxyl value 0 mgKOH / g, acid value 60 mgKOH / g)
D6: Acrylic resin “Thermolac EF-42” (manufactured by Soken Chemical Co., Ltd .: hydroxyl value 21 mgKOH / g, acid value 4 mgKOH / g)
<Catalyst>
F1: Aromatic sulfonic acid catalyst "Catalyst 600" (Mitsui Cytec Co., Ltd.)
F2: Aromatic sulfonic acid catalyst “Catalyst 602” (Mitsui Cytec Co., Ltd.)
F3: Platinum catalyst “CAT-PL-50T” (manufactured by Shin-Etsu Chemical Co., Ltd.)
F4: Tin catalyst “CAT-PS-8S” (manufactured by Shin-Etsu Chemical Co., Ltd.)
<Surfactant>
G1: Surfactant “homogenol L-100” (manufactured by Kao Corporation)
G2: Surfactant “homogenol L-18” (manufactured by Kao Corporation)
<Organic solvent>
H1: Mixed solvent of ethyl acetate and isopropyl alcohol H2: Mixed solvent of ethyl acetate, xylene and isopropyl alcohol H3: Mixed solvent of toluene and isopropyl alcohol H4: Ethyl acetate H5: Toluene Table 1

Example 13: Preparation of release film After applying the coating materials prepared in Examples 1 to 12 and Comparative Examples 1 to 10 on one side of a base material (PET film) by a kiss reverse method using a 150 mesh gravure roll The film was dried at a speed of 10 m / min and a temperature of 110 ° C. to obtain a release film having a coating thickness of 250 nm.

Test Example 1: Evaluation of physical properties / performance of release film Physical properties / performance evaluation of release films prepared in Examples (release films prepared using paints prepared in Examples 1 to 12 and Comparative Examples 1 to 10) were performed. .
Measurement methods and evaluation methods are as follows.
The results obtained are summarized in Table 2.
(1) Surface resistance value The surface resistance value was measured using a low efficiency meter (Hiresta UP MCP-HT450, manufactured by Dia Instruments Co., Ltd.) at an ambient temperature of 25 ° C and a humidity of 40%. Further, the measurement was performed by a two-terminal method, and a UA probe (MCP-HTP111) was used. A surface resistance value of 10 ¹⁰ Ω or less is an appropriate range for antistatic properties.
(2) Peel strength Adhesive tape (Nitto 31B, width 250 mm, length 500 mm) was bonded to the formed coating film, pressure-bonded with a 5 kg pressure roller, maintained at room temperature of 25 ° C. for 20 hours, and then peeled off. The peeling force between the layer and the adhesive tape was measured with a tensile tester. In addition, an average load of 1.0 N or less is an appropriate range as releasability.
(3) Release chargeability The charge amount on the release film side immediately after the release layer and the adhesive tape bonded together in the same manner as in (2) above were peeled off at a release angle of 180 degrees was measured by ELECTROSTATIC VOLTMETER manufactured by Trek Japan. Measurements were made using MODEL 520. Measurement is performed at room temperature of 25 ° C. and humidity of 50%. The average value obtained by 10 measurements is taken as the charge amount. When the charge amount is less than 1.0 kV, ○, when it is 1.0 kV or more It evaluated as x.
(4) Static voltage decay time 5 kV was applied to a 10 cm × 20 cm film, and the time until decay to 0 kV (0%) was measured.
(5) Wetability of ceramic slurry To 100 parts by mass of barium titanate, 6.5 parts by mass of polyisobutyl methacrylate as a binder, 40 parts by mass of methyl ethyl ketone as a solvent and 30 parts by mass of toluene are mixed, dispersed, and dispersed into a ceramic slurry. Got. This ceramic slurry was applied to the release surface of each release film prepared in Example 13 so that the thickness after drying was 1 μm, and dried to produce a green sheet. At this time, the wettability of the ceramic slurry (repel, presence or absence of uneven coating) was visually observed and evaluated according to the following criteria.
○: Good without repelling or coating unevenness Δ: Repelling at the end ×: Repelling as a whole (6) Peelability of the ceramic sheet Regarding the peelability of the green sheet, the green produced by the method of (5) The peelability when the sheet was peeled off with an adhesive tape (Nitto 31B) was evaluated according to the following criteria. ○: Easy peeling Δ: Peeling strength is large and difficult to peel ×: Does not peel (7) Residual adhesion rate Cold rolled stainless steel plate (SUS plate 304) as defined in JIS G4305 polyester adhesive tape (Nitto 31B) Measure the peel force after pasting to the base, and adhesive strength (f ₀ )
And The polyester pressure-sensitive adhesive tape is pressure-bonded to the coated surface of the film sample with a 2 kg pressure roller and left for 30 seconds, and then the tape is peeled off. And the peeled adhesive tape is affixed on said stainless steel plate, the peeling force of this bonding part is measured, and it is set as residual adhesive force (f). Based on the obtained basic adhesive force (f ₀ ) and residual adhesive force (f), the residual adhesive rate was calculated and evaluated using the following formula.
Residual adhesion rate (%) = (f / f ₀ ) × 100
In addition, the preferable range of a residual adhesive rate is 85% or more. When the residual adhesion rate is less than 85%, for example, when the release film is rolled and stored, the components constituting the release layer are transferred to the surface of the adjacent film (so-called back transfer), and the release layer It is not preferable because characteristics such as wettability and peelability may be poor.
Table 2

Claims (2)

Conductive polymer dispersed in an organic solvent, silicon compound in which one or more isocyanato groups are directly bonded to a silicon atom, polyorganosiloxane having a hydroxyl group at the terminal, a hydroxyl value of 20 mgKOH / g or less and an acid value of 20 mgKOH / g or less A coating material for forming an antistatic release layer comprising an acrylic resin and an amino resin, wherein the polyorganosiloxane and the acrylic resin are in a mass ratio of 10:90 to 60:40.
An antistatic release film comprising an antistatic release layer formed using the paint according to claim 1 on at least one side of a substrate.