JP2007308549A - Antistatic coating material, antistatic membrane and antistatic film, optical filter and optical information-recording medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic coating material forming an antistatic membrane which has antistatic properties having no humidity dependency and high surface lubricity, and is excellent in any of flexibility, adhesion to a base material made of a resin, and transparency; and to provide the antistatic membrane. <P>SOLUTION: The antistatic coating material contains a π-conjugated conductive polymer, a polyanion, a polyether-modified non-reactive water-soluble silicone, and a solvent. The antistatic membrane is formed by coating the antistatic coating material. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antistatic paint for imparting antistatic properties and surface lubricity to a film or the like. The present invention also relates to an antistatic film having antistatic properties and surface lubricity. Furthermore, the present invention relates to an antistatic film used for packaging materials for foods and electronic parts, an optical filter used for liquid crystal displays and plasma displays, and an optical information recording medium such as CD and DVD.

In the resin film, the optical filter, and the optical information recording medium, the surface is required to have high hardness and high transparency, and to have antistatic properties in order to prevent dust from being attached due to static electricity. In particular, with respect to antistatic properties, the resistance value is stable in a region where the surface resistance is about 10 ⁶ to 10 ¹⁰ Ω, that is, stable antistatic properties are required.
In order to impart antistatic properties, for example, a method of applying a surfactant to the surface of a resin film, and a method of kneading a surfactant into a resin constituting the resin film or the antistatic film are known (for example, Non-Patent Document 1).

In addition, resin films, optical filters, and optical information recording media are required to suppress a phenomenon called blocking that adheres to each other when stacked (that is, high blocking resistance).
In general, in order to increase the blocking resistance, a method is known in which surface lubricity is enhanced by forming a silicone film on the surface.

As a method for obtaining a material having high antistatic property and surface lubricity, Patent Document 1 discloses a composition containing a radiation-curable modified polysiloxane compound and an antistatic reactive surfactant as a hard coating film for an optical disk. A method is described in which an antistatic silicone film is formed by applying to the surface and polymerizing the polysiloxane by irradiation of radiation.
Patent Document 2 describes that an external lubricant and an antistatic agent are attached to both surfaces of a styrene-based film substrate, and polyether-modified silicone is used as the external lubricant.
JP-A-5-132557 International Publication No. 01/040360 Pamphlet Issued by CMC, “Fine Chemical Antistatic Agents Recent Market Trends (Part 1)”, Vol. 16, No. 15, 1987, p. 24-36

  However, the antistatic property by the surfactant is exhibited based on a conductive mechanism by ionic conduction. The conduction mechanism based on ionic conduction is very susceptible to humidity, and the conductivity increases when the humidity is high, but the conductivity decreases when the humidity is low. Therefore, the antistatic property is lowered in an environment where the humidity is low and static electricity is likely to be generated, and the antistatic property is not exhibited when necessary.

  On the other hand, the conduction mechanism by electronic conduction is not affected by humidity. The conductive mechanism by electron conduction is exhibited in a layer containing metal, carbon, indium tin oxide (ITO), for example. However, when a layer containing metal or carbon is used, there is no transparency at all. When a layer containing ITO is used, sputtering or the like must be applied to the film formation, and the process is complicated. As a result, the manufacturing cost has increased. In addition, an inorganic metal oxide layer such as ITO has low flexibility, and when it is formed on a thin base material, the ITO layer is easily broken and may not exhibit conductivity. In addition, since the adhesiveness to the resin base material is low, peeling may occur at the interface between them and the transparency may be lowered.

  The present invention has been made in view of the above circumstances, has no antistatic humidity dependency, and has high surface lubricity, flexibility, adhesion to a resin substrate, and transparency. It is an object of the present invention to provide an antistatic paint capable of forming an excellent antistatic film. In addition, an antistatic film having high anti-static properties, high surface lubricity, flexibility, adhesion to a resin base material, and excellent transparency is provided. With the goal. Furthermore, it aims at providing the antistatic film provided with such an antistatic film, an optical filter, and an optical information recording medium.

The present invention includes the following configurations.
[1] An antistatic paint comprising a π-conjugated conductive polymer, a polyanion, a polyether-modified non-reactive water-soluble silicone, and a solvent.
[2] The antistatic paint according to [1], wherein the non-reactive water-soluble silicone has an HLB value of 7 to 16.
[3] The antistatic paint according to [1] or [2], which contains a binder resin.
[4] An antistatic film formed by applying the antistatic paint according to any one of [1] to [3].
[5] An antistatic film comprising a film base and the antistatic film according to [4] formed on at least one surface of the film base.
[6] An optical filter comprising the antistatic film according to [4].
[7] An optical information recording medium comprising the antistatic film according to [4].

The antistatic coating of the present invention has no antistatic humidity dependency, has high surface lubricity, and has excellent flexibility, adhesion to a resin base material, and excellent transparency. A prevention film can be formed.
The antistatic film of the present invention does not depend on humidity for antistatic properties, has high surface lubricity, and is excellent in flexibility, adhesion to a resin substrate, and transparency.
The antistatic film of the present invention does not have humidity dependency of antistatic properties, has high surface lubricity, and is excellent in both flexibility and adhesion to a resin substrate.
The optical filter of the present invention does not have humidity dependency of antistatic properties, has high surface lubricity, and is excellent in transparency.
The optical information recording medium of the present invention does not have humidity dependency of antistatic properties and has high surface lubricity.

(Antistatic paint)
The antistatic coating material of the present invention contains a π-conjugated conductive polymer, a polyanion, a polyether-modified non-reactive water-soluble silicone, and a solvent.

[Π-conjugated conductive polymer]
The π-conjugated conductive polymer can be used as long as the main chain is an organic polymer having a π-conjugated system. Examples thereof include polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, and copolymers thereof. From the viewpoint of easy polymerization and stability in air, polypyrroles, polythiophenes and polyanilines are preferred.
Even if the π-conjugated conductive polymer remains unsubstituted, sufficient conductivity can be obtained. However, in order to further increase the conductivity, an alkyl group, a carboxyl group, a sulfo group, an alkoxyl group, a hydroxyl group, a cyano group It is preferable to introduce a functional group such as a group into the π-conjugated conductive polymer.

  Specific examples of such π-conjugated conductive polymers include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), Poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly ( 3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3-hydroxypyrrole), poly (3-methoxypyrrole), polythiophene, poly (3-methylthiophene), Poly (3-hexylthiophene), poly (3-heptylthiophene), poly (3-octylthiophene), poly (3-de Ruthiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene), poly ( 3-hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxythiophene), poly ( 3-octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene), poly (3-octadecyloxythiophene), poly (3,4-dihydroxythiophene), poly (3,4 Dimethoxythiophene), poly (3,4-ethylenedioxythiophene) , Poly (3,4-propylenedioxythiophene), poly (3,4-butenedioxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl -4-carboxyethylthiophene), poly (3-methyl-4-carboxybutylthiophene), polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-anilinesulfonic acid), poly ( 3-anilinesulfonic acid) and the like.

  Among them, from one or two kinds selected from polypyrrole, polythiophene, poly (N-methylpyrrole), poly (3-methylthiophene), poly (3-methoxythiophene), and poly (3,4-ethylenedioxythiophene). The (co) polymer is preferably used from the viewpoints of resistance and reactivity. Furthermore, polypyrrole and poly (3,4-ethylenedioxythiophene) are more preferable from the viewpoint of higher conductivity and improved heat resistance.

[Polyanion]
The polyanion is a homopolymer or copolymer selected from substituted or unsubstituted polyalkylene, substituted or unsubstituted polyalkenylene, substituted or unsubstituted polyimide, substituted or unsubstituted polyamide, substituted or unsubstituted polyester And having a structural unit having an anionic group. Moreover, you may have a structural unit which does not have an anion group as needed.
The polyanion not only solubilizes the π-conjugated conductive polymer in a solvent, but also functions as a dopant for the π-conjugated conductive polymer.

  Here, polyalkylene is a polymer whose main chain is composed of repeating methylene. For example, polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyvinyl alcohol, polyvinylphenol, poly (3,3,3-trifluoropropylene), polyacrylonitrile, polyacrylate, polystyrene and the like can be mentioned.

Polyalkenylene is a polymer composed of structural units containing one or more unsaturated bonds (vinyl groups) in the main chain. Among these, substituted or unsubstituted butenylene is preferable because of the interaction between the unsaturated bond and the π-conjugated conductive polymer and the ease of synthesis using substituted or unsubstituted butadiene as a starting material.
Specific examples of polyalkenylene include propenylene, 1-methylpropenylene, 1-butylpropenylene, 1-decylpropenylene, 1-cyanopropenylene, 1-phenylpropenylene, 1-hydroxypropenylene, 1-butenylene, 1-methyl-1-butenylene, 1-ethyl-1-butenylene, 1-octyl-1-butenylene, 1-pentadecyl-1-butenylene, 2-methyl-1-butenylene, 2-ethyl-1-butenylene, 2- Butyl-1-butenylene, 2-hexyl-1-butenylene, 2-octyl-1-butenylene, 2-decyl-1-butenylene, 2-dodecyl-1-butenylene, 2-phenyl-1-butenylene, 2-butenylene, 1-methyl-2-butenylene, 1-ethyl-2-butenylene, 1-octyl-2-butenylene 1-pentadecyl-2-butenylene, 2-methyl-2-butenylene, 2-ethyl-2-butenylene, 2-butyl-2-butenylene, 2-hexyl-2-butenylene, 2-octyl-2-butenylene, 2- Decyl-2-butenylene, 2-dodecyl-2-butenylene, 2-phenyl-2-butenylene, 2-propylenephenyl-2-butenylene, 3-methyl-2-butenylene, 3-ethyl-2-butenylene, 3-butyl 2-butenylene, 3-hexyl-2-butenylene, 3-octyl-2-butenylene, 3-decyl-2-butenylene, 3-dodecyl-2-butenylene, 3-phenyl-2-butenylene, 3-propylenephenyl- 2-butenylene, 2-pentenylene, 4-propyl-2-pentenylene, 4-butyl-2-pentenylene, 4-he Selected from sil-2-pentenylene, 4-cyano-2-pentenylene, 3-methyl-2-pentenylene, 4-ethyl-2-pentenylene, 3-phenyl-2-pentenylene, 4-hydroxy-2-pentenylene, hexenylene, etc. And polymers containing one or more structural units.

As polyimide, pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-tetracarboxydiphenyl ether dianhydride, 2,2 ′-[ Examples include polyimides from anhydrides such as 4,4′-di (dicarboxyphenyloxy) phenyl] propane dianhydride and diamines such as oxydiamine, paraphenylenediamine, metaphenylenediamine, and benzophenonediamine.
Examples of the polyamide include polyamide 6, polyamide 6,6, polyamide 6,10 and the like.
Examples of the polyester include polyethylene terephthalate and polybutylene terephthalate.

When the polyanion has another substituent, examples of the substituent include an alkyl group, a hydroxyl group, an amino group, a cyano group, a phenyl group, a phenol group, an ester group, an alkoxyl group, and a carbonyl group. In view of solubility in a solvent, heat resistance, compatibility with a resin, and the like, an alkyl group, a hydroxyl group, a phenol group, and an ester group are preferable.
Alkyl groups can increase solubility and dispersibility in polar or nonpolar solvents, compatibility and dispersibility in resins, etc., and hydroxyl groups form hydrogen bonds with other hydrogen atoms and the like. It can be made easy, and the solubility in an organic solvent, the compatibility with a resin, the dispersibility, and the adhesiveness can be increased. In addition, the cyano group and the hydroxyphenyl group can increase the compatibility and solubility in the polar resin, and can also increase the heat resistance.
Among the above substituents, an alkyl group, a hydroxyl group, an ester group, and a cyano group are preferable.

Examples of the alkyl group include chain alkyl groups such as methyl, ethyl, propyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, decyl, and dodecyl, and cycloalkyl groups such as cyclopropyl, cyclopentyl, and cyclohexyl. . In consideration of solubility in an organic solvent, dispersibility in a resin, steric hindrance, and the like, an alkyl group having 1 to 12 carbon atoms is more preferable.
Examples of the hydroxyl group include a hydroxyl group directly bonded to the main chain of the polyanion or a hydroxyl group bonded via another functional group. Examples of other functional groups include an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an amide group, and an imide group. Hydroxyl groups are substituted at the ends or in these functional groups. In these, the hydroxyl group couple | bonded with the terminal of the C1-C6 alkyl group couple | bonded with the principal chain is more preferable from the compatibility to resin and the solubility to an organic solvent.
Examples of the ester group include an alkyl ester group directly bonded to the main chain of the polyanion, an aromatic ester group, and an alkyl ester group or an aromatic ester group having another functional group interposed therebetween.
Examples of the cyano group include a cyano group directly bonded to the main chain of the polyanion, a cyano group bonded to the terminal of the alkyl group having 1 to 7 carbon atoms bonded to the main chain of the polyanion, and 2 carbon atoms bonded to the main chain of the polyanion. And a cyano group bonded to the terminal of the alkenyl group of ˜7.

  The anion group of the polyanion may be a functional group capable of undergoing chemical oxidation doping to the π-conjugated conductive polymer. Among them, from the viewpoint of ease of production and stability, a monosubstituted sulfate group, A monosubstituted phosphate group, a phosphate group, a carboxyl group, a sulfo group and the like are preferable. Furthermore, from the viewpoint of the doping effect of the functional group on the π-conjugated conductive polymer, a sulfo group, a monosubstituted sulfate group, and a carboxyl group are more preferable.

Specific examples of polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly (2-acrylamido-2-methylpropane sulfonic acid), polyisoprene. Sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly (2-acrylamido-2-methylpropane carboxylic acid), polyisoprene carboxylic acid, polyacrylic acid, etc. Can be mentioned. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.
Among these, polystyrene sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid ethyl sulfonic acid, and polyacrylic acid butyl sulfonic acid are preferable. If these polyanions are contained in the antistatic coating, the antistatic property of the resulting antistatic film can be improved, and the thermal decomposition of the π-conjugated conductive polymer can be alleviated.

  The degree of polymerization of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.

  The content of the polyanion in the antistatic coating is preferably in the range of 0.1 to 10 mol, and more preferably in the range of 1 to 7 mol, with respect to 1 mol of the π-conjugated conductive polymer. When the polyanion content is less than 0.1 mol, the doping effect on the π-conjugated conductive polymer tends to be weak, and the conductivity may be insufficient. In addition, the dispersibility and solubility in the solvent are reduced, making it difficult to obtain a uniform dispersion. On the other hand, when the polyanion content is more than 10 mol, the content of the π-conjugated conductive polymer in the antistatic coating decreases, and it is difficult to obtain sufficient conductivity.

[Non-reactive water-soluble silicone]
Non-reactive water-soluble silicone is a polyether-modified non-reactive water-soluble silicone. The molecular structure of this non-reactive water-soluble silicone may be either linear or cyclic. When the non-reactive water-soluble silicone is linear, the modification site of the polyether may be a side chain of silicone or a terminal of silicone.

The HLB value of the non-reactive water-soluble silicone is preferably 7 to 16 because the compatibility with the π-conjugated conductive polymer and the polyanion is increased. Here, the HLB value is a value representing the degree of hydrophilicity or lipophilicity of the surfactant. Specifically, for an ethylene oxide addition-type nonionic surfactant, the HLB value of a hypothetical compound having an infinitely long hydrophilic group added to a lipophilic group and having the greatest hydrophilicity is set to 20, It is a value representing the degree of hydrophilicity or lipophilicity when the HLB value of a lipophilic compound that does not have is defined as 0.
The HLB value of the non-reactive water-soluble silicone is determined by the formula {(mass of polyether moiety) / (mass of non-reactive water-soluble silicone)} × (100/5).

  Specific examples of the non-reactive water-soluble silicone include, for example, non-reactive silicone oils KF-351, KF-352, KF-354L, KF-355A, KF-618, KF-6011, X-manufactured by Shin-Etsu Chemical Co., Ltd. 22-4272 and the like. Among these, KF-355A is preferable because of excellent storage stability and solubility of the antistatic coating.

  The content of the non-reactive water-soluble silicone in the antistatic coating is preferably 0.01 to 5.0% by mass. If the content of the non-reactive water-soluble silicone is less than 0.01% by mass, the resulting surface lubricity may not be sufficiently exhibited, and if it exceeds 5% by mass, the blocking resistance may be reduced. .

Since the non-reactive water-soluble silicone constituting the antistatic coating of the present invention is a polyether-modified one, water solubility, water dispersibility, and emulsification can be increased, especially for aqueous antistatic coatings. High solubility.
Further, since the silicone is non-reactive, side reactions with other components contained in the antistatic paint are suppressed, so that the storage stability of the antistatic paint can be prevented from being lowered.

[solvent]
Examples of the solvent include water and / or an organic solvent.
Examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylene phosphortriamide, N-vinylpyrrolidone, N-vinylformamide, N- Polar solvents such as vinylacetamide, phenols such as cresol, phenol, xylenol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, glycerin, di Glycerin, D-glucose, D-glucitol, isoprene glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentylglyco Polyhydric aliphatic alcohols such as ruthenium, ketones such as acetone and methyl ethyl ketone, hydrocarbons such as hexane, benzene and toluene, carboxylic acids such as formic acid and acetic acid, carbonate compounds such as ethylene carbonate and propylene carbonate, dioxane and diethyl Ether compounds such as ether, chain ethers such as dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, heterocyclic compounds such as 3-methyl-2-oxazolidinone, acetonitrile, glutarodinitrile, methoxy Examples thereof include nitrile compounds such as acetonitrile, propionitrile, and benzonitrile. These solvents may be used alone or as a mixture of two or more.

[Dopant]
In the antistatic coating material of this invention, in order to improve the antistatic property of the antistatic film obtained more, other dopants other than a polyanion may be contained.
Examples of other dopants include halogen compounds, Lewis acids, proton acids, and the like. Specifically, organic acids such as organic carboxylic acids and organic sulfonic acids, organic cyano compounds, fullerenes, hydrogenated fullerenes, fullerene hydroxides, Examples thereof include carboxylic acid fullerene and sulfonic acid fullerene.

Examples of organic acids include alkylbenzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl naphthalene disulfonic acid, naphthalene sulfonic acid formalin polycondensate, melamine sulfonic acid formalin polycondensate, naphthalene disulfonic acid, naphthalene trisulfonic acid, dinaphthylmethane disulfonic acid, Examples include organic sulfonic acid compounds such as anthraquinone sulfonic acid, anthraquinone disulfonic acid, anthracene sulfonic acid, and pyrene sulfonic acid, and organic carboxylic acid compounds such as acetic acid, oxalic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, and malonic acid. It is done. These metal salts can also be used.
As the organic cyano compound, a compound having two or more cyano groups in a conjugated bond can be used. Examples include tetracyanoethylene, tetracyanoethylene oxide, tetracyanobenzene, dichlorodicyanobenzoquinone (DDQ), tetracyanoquinodimethane, and tetracyanoazanaphthalene.

[Binder resin]
In addition, the antistatic paint preferably contains a binder resin because the antistatic film obtained has high scratch resistance and surface hardness and higher adhesion to a resin substrate. If the antistatic paint contains a binder resin, the pencil hardness (JIS K 5600-5-4) of the antistatic film formed from the antistatic paint is likely to be HB or higher.
The binder resin may be a thermosetting resin or a thermoplastic resin as long as it is compatible or mixed and dispersible with the antistatic paint. For example, polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polyimides such as polyimide and polyamideimide; polyamides such as polyamide 6, polyamide 6,6, polyamide 12, and polyamide 11; polyvinylidene fluoride, polyvinyl fluoride, poly Fluorine resin such as tetrafluoroethylene, ethylenetetrafluoroethylene copolymer, polychlorotrifluoroethylene; vinyl resin such as polyvinyl alcohol, polyvinyl ether, polyvinyl butyral, polyvinyl acetate, polyvinyl chloride; epoxy resin; xylene resin; aramid resin; Polyimide silicone; polyurethane; polyurea; melamine resin; phenol resin; polyether; acrylic resin and copolymers thereof. It is.
These binder resins may be dissolved in an organic solvent, may be provided with a functional group such as a sulfo group or a carboxyl group, may be formed into an aqueous solution, or may be dispersed in water such as emulsification.

Among the binder resins, at least one resin selected from the group consisting of polyurethane, polyester, acrylic resin, polyamide, polyimide, epoxy resin, and polyimide silicone is preferable because it can be easily mixed.
Acrylic resins are suitable for applications such as optical filters because they have high hardness and excellent transparency.

The acrylic resin preferably contains a liquid polymer that is cured by heat and / or light.
Here, examples of the liquid polymer that is cured by heat include a reactive polymer and a self-crosslinking polymer.
The reactive polymer is a polymer in which a monomer having a substituent is polymerized, and examples of the substituent include a carboxyl group, an acid anhydride, an oxetane group, a glycidyl group, and an amino group. Specific monomers include malonic acid, succinic acid, glutamic acid, pimelic acid, ascorbic acid, phthalic acid, acetylsalicylic acid, adipic acid, isophthalic acid, benzoic acid, m-toluic acid and other carboxylic acid compounds, anhydrous Maleic acid, phthalic anhydride, dodecyl succinic anhydride, dichloromaleic anhydride, tetrachlorophthalic anhydride, tetrahydrophthalic anhydride, acid anhydrides such as pimelic anhydride, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane Oxetane compounds such as 3-methyl-3-hydroxymethyloxetane and azidomethylmethyloxetane, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, phenol novolac polyglycidyl ether, N, N-diglycidyl-p-aminophenol Glycidyl ether compounds such as cidyl ether, tetrabromobisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether (ie, 2,2-bis (4-glycidyloxycyclohexyl) propane), N, N-diglycidylaniline, tetra Glycidylamine compounds such as glycidyldiaminodiphenylmethane, N, N, N, N-tetraglycidyl-m-xylylenediamine, triglycidyl isocyanurate, N, N-diglycidyl-5,5-dialkylhydantoin, diethylenetriamine, triethylenetetramine, Dimethylaminopropylamine, N-aminoethylpiperazine, benzyldimethylamine, tris (dimethylaminomethyl) phenol, DHP30-tri (2-ethylhexoate), Amine compounds such as taphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, dicyandiamide, boron trifluoride, monoethylamine, menthanediamine, xylenediamine, ethylmethylimidazole, etc. Among compounds containing two or more oxirane rings in one molecule Glycidyl compound of epichlorohydrin of bisphenol A, or an analog thereof.

In the reactive polymer, at least a bifunctional or higher functional crosslinking agent is used. Examples of the crosslinking agent include melamine resin, epoxy resin, metal oxide and the like. Examples of the metal oxide include basic metal compounds Al (OH) ₃ , Al (OOC · CH ₃ ) ₂ (OOCH), Al (OOC · CH ₃ ) ₂ , ZrO (OCH ₃ ), Mg (OOC · CH _3). ), Ca (OH) ₂ , Ba (OH) _{3 and the} like can be used as appropriate.

  The self-crosslinking polymer is one that self-crosslinks between functional groups by heating, and examples thereof include those containing a glycidyl group and a carboxyl group, and those containing both an N-methylol and a carboxyl group.

Examples of the liquid polymer that is cured by light include oligomers or prepolymers such as polyester, epoxy resin, oxetane resin, polyacryl, polyurethane, polyimide, polyamide, polyamideimide, and polyimide silicone.
Examples of monomer units constituting a liquid polymer that is cured by light include bisphenol A / ethylene oxide-modified diacrylate, dipentaerythritol hexa (penta) acrylate, dipentaerythritol monohydroxypentaacrylate, and dipropylene glycol diacrylate. , Trimethylolpropane triacrylate, glycerin propoxytriacrylate, 4-hydroxybutyl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, polyethylene glycol diacrylate, penta Erythritol triacrylate, tetrahydrofurfuryl acrylate, trimethylolpropane triacrylate Acrylates such as tripropylene glycol diacrylate, tetraethylene glycol dimethacrylate, alkyl methacrylate, allyl methacrylate, 1,3-butylene glycol dimethacrylate, n-butyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, diethylene glycol dimethacrylate, 2-ethylhexyl methacrylate , Glycidyl methacrylate, 1,6-hexanediol dimethacrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, phenoxyethyl methacrylate, t-butyl methacrylate, tetrahydrofurfuryl methacrylate, methacrylates such as trimethylolpropane trimethacrylate Allylic Glycidyl ethers such as sidyl ether, butyl glycidyl ether, higher alcohol glycidyl edel, 1,6-hexanediol glycidyl ether, phenyl glycidyl ether, stearyl glycidyl ether, diacetone acrylamide, N, N-dimethylacrylamide, dimethylaminopropyl acrylamide, Dimethylaminopropyl methacrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylformamide, N-methylacrylamide, N-isopropylacrylamide, Nt-butylacrylamide, N-phenylacrylamide , Acrylics such as acryloylpiperidine and 2-hydroxyethylacrylamide (methacrylic) ) Of amides, vinyl ethers such as 2-chloroethyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, hydroxybutyl vinyl ether, isobutyl vinyl ether, triethylene glycol vinyl ether, and vinyl carboxylates such as vinyl butyrate, vinyl monochloroacetate and vinyl pivalate A monofunctional monomer and a polyfunctional monomer are mentioned.

  A liquid polymer that is cured by light is cured by a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones. Furthermore, n-butylamine, triethylamine, tri-n-butylphosphine, or the like can be mixed as a photosensitizer.

  Further, the antistatic coating material may contain a synthetic rubber component for improving the impact resistance of the resulting antistatic film, an antioxidant for improving the weather resistance, an ultraviolet absorber, and the like.

By containing the specific non-reactive water-soluble silicone, the antistatic coating described above can improve the surface lubricity without deteriorating the transparency of the resulting antistatic film. In addition, since the π-conjugated conductive polymer exhibits a conductive mechanism by electron conduction, the obtained antistatic film has no humidity dependency of the antistatic property. Furthermore, since the antistatic coating is not composed of an inorganic oxide, the resulting antistatic film is excellent in flexibility and adhesion to a resin substrate.
That is, the above-described antistatic coating has no humidity dependency on the antistatic property, has high surface lubricity, and has excellent flexibility, adhesion to the resin base material, and transparency. An antistatic film can be formed.

(Antistatic film)
The antistatic film of the present invention is formed by applying the antistatic coating material on a substrate. Examples of the application method of the antistatic coating include immersion, comma coating, spray coating, roll coating, gravure roll coating, and spin coating.
The base material to which the antistatic coating is applied is not particularly limited, but antistatic properties are particularly exerted when a resin molded body, particularly a resin film, that is susceptible to static electricity is applied.
After applying the antistatic paint, the solvent is removed by heating, and the antistatic film can be obtained by curing by heating or light.
As a heating method for removing the solvent by heating, for example, a normal method such as hot air heating or infrared heating can be employed. In addition, as a light irradiation method when an antistatic film is formed by photocuring, for example, a method of irradiating ultraviolet rays from a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp is adopted it can.

In the antistatic film, the total light transmittance (JIS K7361-1) is preferably 85% or more, more preferably 90% or more, and particularly preferably 96% or more.
Further, the haze (JIS K7105) is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.
Furthermore, the surface resistance value of the antistatic film is preferably 1 × 10 ³ to 1 × 10 ¹² Ω in order to sufficiently exhibit antistatic properties. However, the surface resistance value is preferably adjusted as appropriate in consideration of the optical characteristics.
The pencil hardness of the antistatic film is preferably B or more because the scratch resistance becomes high. When the antistatic film also serves as a hard coat layer, it is preferably HB or more.
In addition, the total light transmittance, haze, surface resistance value, and pencil hardness of the antistatic film can be adjusted by the thickness of the antistatic film.

  The friction coefficient (static friction coefficient and dynamic friction coefficient) of the antistatic film is preferably small. If the friction coefficient of the antistatic film is small, the surface lubricity becomes higher and the blocking resistance becomes higher. Specifically, the friction coefficient is preferably 0.50 or less.

  Since the above-described antistatic film is formed from the above-mentioned antistatic coating, the antistatic property does not depend on humidity, and has high surface lubricity, and is flexible and has a resin base material. Both adhesion and transparency are excellent.

(Antistatic film)
The antistatic film has a film substrate and the antistatic film formed on at least one surface of the film substrate.
[Film substrate]
The film substrate is not particularly limited. For example, a low density polyethylene film, a high density polyethylene film, an ethylene-propylene copolymer film, a polypropylene film, an ethylene-vinyl acetate copolymer film, an ethylene-methyl methacrylate copolymer film. Polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film, polyimide film, 6-nylon film, 6,6-nylon film, polymethyl methacrylate film, polystyrene film, styrene-acrylonitrile-butadiene copolymer film, polyacrylonitrile Film, cellulose triacetate film, cellulose propionate film, polyvinyl chloride film, polyvinyl chloride Film, polyvinylidene fluoride film, polytetrafluoroethylene film, polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film, polycarbonate film, polysulfone film, polyethersulfone film, polyetheretherketone film, polyphenylene oxide film, etc. Can be mentioned.

  The surfaces of these film substrates are usually oleophilic and are difficult to apply when an antistatic coating dissolved in an aqueous solvent is applied. Therefore, when applying an antistatic coating dissolved in an aqueous solvent to form an antistatic film, etching treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion and oxidation is performed on the surface of the film substrate. It is preferable to carry out hydrophilic treatment such as coating or undercoating in advance. Furthermore, dust may be removed and cleaned by solvent cleaning, ultrasonic cleaning, or the like as necessary.

  Since the above-described antistatic film has the above-mentioned antistatic film, the antistatic property does not depend on humidity, and the surface lubricity is high, and flexibility and adhesion to the film substrate are not affected. Thigh is excellent.

(Optical filter)
Next, an embodiment of the optical filter of the present invention will be described.
FIG. 1 shows an optical filter of this embodiment. The optical filter 1 includes a film substrate 10, an antistatic film 20 formed on the film substrate 10, and an antireflection layer 30 formed on the antistatic film 20. The antistatic film 20 in the optical filter 1 also serves as a hard coat layer.
When the optical filter 1 is attached to the display surface of the display device, a transparent adhesive layer is provided on the surface of the optical filter 1 on the film substrate 10 side, and the optical filter 1 is attached via the adhesive layer.

As the film substrate 10, various plastic films having transparency can be used. Examples of the transparent plastic film include films made of polyethylene terephthalate, polyimide, polyethersulfone, polyetheretherketone, polycarbonate, polypropylene, polyamide, acrylamide, cellulose propionate, and the like.
Similarly to the antistatic film, the surface of the film substrate 10 used for the optical film 1 is subjected to etching treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, and undercoating treatment. It is preferable that Further, the surface of the film substrate 10 may be dust-removed and cleaned by solvent cleaning, ultrasonic cleaning, or the like as necessary before providing the antistatic film 20.

  The antistatic film 20 is a film formed from an antistatic paint as described above, and also serves as a hard coat layer. Therefore, as described above, the antistatic film 20 preferably has a surface hardness (pencil hardness) of HB or higher. Moreover, since it is an optical use, it is preferable that the total light transmittance (JIS K7361-1) of the antistatic film 20 is 85% or more, more preferably 90% or more, and 96% or more. Particularly preferred. Further, the haze (JIS K7105) of the antistatic film 20 is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.

The antireflection layer 30 is a layer that prevents reflection of light. This layer may be a single layer or a multilayer. In the case of a single layer, the refractive index is preferably in the range of 1.38 to 1.45, and the optical film thickness is preferably in the range of 80 to 100 nm.
The antireflection layer 30 can be formed by either a dry method or a wet method. Examples of the dry method include a physical vapor deposition method such as an electron beam evaporation method, a dielectric heating evaporation method, a resistance heating evaporation method, a sputtering method, and an ion plating method, and a plasma CVD method. When the antireflection layer 30 is formed by a dry method, examples of the components of the antireflection layer 30 include silicon oxide, magnesium fluoride, niobium oxide, titanium oxide, tantalum oxide, aluminum oxide, zirconium oxide, indium oxide, and oxidation. Inorganic compounds such as tin can be used.
Moreover, as a wet method, the method of apply | coating the coating material containing a sclerosing | hardenable compound by well-known methods, such as a comma coat, spray coat, roll coat, and gravure printing, for example, and the method of hardening this are mentioned. When the antireflection layer 30 is formed by a wet method, as the curable compound, for example, a fluorine-containing compound such as a fluorine-containing organic compound, a fluorine-containing organic silicon compound, or a fluorine-containing inorganic compound can be used.

In the optical filter 1 described above, the antistatic film 20 that protects the film substrate 10 is formed, and the antistatic film 20 is formed of the above antistatic paint, so that it has excellent antistatic stability. It is a filter that is difficult for dust to adhere to the surface. In addition, the optical filter 1 has a high surface lubricity of the antistatic film 20 and is excellent in blocking resistance. And it is excellent in transparency and is excellent also in adhesiveness with the film base material 10.
And such an optical filter 1 is used suitably for a liquid crystal screen, the antireflection film of both surfaces of a plasma display, an infrared absorption film, an electromagnetic wave absorption film, etc.

  The optical filter of the present invention is not limited to the above-described embodiment example, and it is sufficient that the optical filter has an antistatic film formed from the antistatic paint. For example, a polarizing plate can be used instead of the film substrate. Examples of the polarizing plate include those in which a protective film is laminated on one or both sides of a polyvinyl alcohol resin film adsorbed and oriented with a dichroic dye. Can do. Such an optical filter can be provided on the outermost surface of the liquid crystal display device.

(Optical information recording medium)
An embodiment of the optical information recording medium of the present invention will be described.
FIG. 2 shows an optical information recording medium of this embodiment. This optical information recording medium 2 is a rewritable disc, and a first dielectric layer 50, an optical information recording layer 60, and a second dielectric are formed on one surface of a disc-shaped transparent resin substrate 40 made of polycarbonate, polymethyl methacrylate, or the like. The layer 70, the metal reflection layer 80, and the antistatic film 90 are sequentially formed.

As a material constituting the first dielectric layer 50 and the second dielectric layer 70, for example, an inorganic material such as SiN, SiO, SiO ₂ , Ta ₂ O ₅ can be used.
These dielectric layers are formed with a thickness of 10 to 500 nm by a known method such as vacuum deposition, sputtering, or ion plating.

Examples of the material constituting the optical information recording layer 60 include inorganic magneto-optical recording materials such as Tb—Fe, Tb—Fe—Co, Dy—Fe—Co, and Tb—Dy—Fe—Co, and TeOx. , Te-Ge, Sn-Te-Ge, Bi-Te-Ge, Sb-Te-Ge, Pb-Sn-Te, Tl-In-Se, and other inorganic phase conversion recording materials, cyanine dyes, polymethine Organic dyes such as a dye, a phthalocyanine dye, a merocyanine dye, an azulene dye, and a squalium dye are used.
When the optical information recording layer 60 is made of an inorganic magneto-optical recording material, the optical information recording layer 60 can be formed with a thickness of 10 to 999 nm by a known method such as vacuum deposition, sputtering, or ion plating. Moreover, when it consists of an organic pigment | dye, the solution which melt | dissolved the organic pigment | dye in solvents, such as acetone, diacetone alcohol, ethanol, methanol, can be formed by thickness 10-999 nm with a well-known printing method or the apply | coating method.

  The metal reflective layer 80 exhibits light reflectivity, and is composed of a metal such as Al, Cr, Ni, Ag, Au, and oxides, nitrides, and the like alone or in combination of two or more. The metal reflective layer 80 is formed with a thickness of 2 to 200 nm by sputtering or vacuum deposition.

The antistatic film 90 is formed from the antistatic paint. The antistatic film 90 can prevent the surface of the optical information recording medium 2 from being scratched by preventing the surface of the optical information recording medium 2 from being scratched by setting the surface hardness to HB or higher, and can also prevent dust from being attached due to static electricity. it can.
The thickness of the antistatic film 90 is preferably 3 to 15 μm. If the thickness of the antistatic film 90 is less than 3 μm, it tends to be difficult to form a uniform film, and sufficient antistatic properties and anti-blocking properties may not be exhibited. On the other hand, if the thickness is greater than 15 μm, the internal stress increases, and the mechanical properties of the optical information recording medium 2 may be degraded.

  In order to form the antistatic film 90, an antistatic coating is applied on the metal reflective layer 80 using a known method such as comma coating, spray coating, roll coating, gravure printing, and the solvent is then dried. Or it is cured by heat or light.

  In the optical information recording medium 2 described above, an antistatic film 90 for protecting the optical information recording layer 60 and the metal reflective layer 80 is formed, and the antistatic film 90 is formed from the antistatic paint. Yes. Therefore, since the antistatic film 90 has antistatic properties, dust adhesion due to static electricity is suppressed, and recording / reading errors and writing errors are prevented. Further, this optical information recording medium 2 has high surface lubricity of the antistatic film 90 and is excellent in blocking resistance. In addition, since the antistatic film 90 has a small haze and a high light transmittance, it has excellent transparency at the reading laser wavelengths of 780 nm and 635 nm.

  Note that the optical information recording medium of the present invention is not limited to the above-described embodiment, and for example, the optical information recording medium may be a write-once disc. The write-once disc has, for example, a structure in which a transparent resin substrate (organic base material), an optical information recording layer, a reflective metal layer, and an antistatic film are sequentially formed.

Example 1
14.2 g of 3,4-ethylenedioxythiophene and a solution of 36.7 g of polystyrene sulfonic acid dissolved in 2000 ml of ion-exchanged water were mixed at 20 ° C.
While maintaining the mixed solution thus obtained at 20 ° C. and stirring, 29.64 g of ammonium persulfate dissolved in 200 ml of ion exchange water and 8.0 g of ferric sulfate oxidation catalyst solution were slowly added, The reaction was stirred for 3 hours.
2000 ml of ion-exchanged water was added to the resulting reaction solution, and about 2000 ml of solution was removed using an ultrafiltration method. This operation was repeated three times.
Then, 200 ml of sulfuric acid diluted to 10% by mass and 2000 ml of ion-exchanged water are added to the resulting solution, and about 2000 ml of solution is removed using an ultrafiltration method, and 2000 ml of ion-exchanged water is added thereto. About 2000 ml of solution was removed using ultrafiltration. This operation was repeated three times.
Furthermore, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solution was removed using an ultrafiltration method. This operation was repeated 5 times to obtain a solution containing about 1.5% by mass of blue polystyrenesulfonic acid-doped poly (3,4-ethylenedioxythiophene) (PEDOT-PSS). 2 g of imidazole was added to 100 g of this solution, and further 25 g of 30% by mass of a water-soluble polyurethane solution (Rezamine D-6300, manufactured by Dainichi Seika Kogyo Co., Ltd.) was added to obtain a conductive polymer solution A. .
Antistatic paint A is obtained by adding 0.01 g of non-reactive water-soluble silicone (polyether-modified silicone oil KF-355A, manufactured by Shin-Etsu Chemical Co., Ltd.) to 100 g of the obtained conductive polymer solution A. It was.

Antistatic paint A was applied onto a 144 μm thick polyethylene terephthalate film by a comma coater and dried to form an antistatic film having a thickness of about 0.1 μm.
The surface resistance value of this antistatic film was measured with a Loresta (Mitsubishi Chemical Corporation).
Further, the surface lubricity was evaluated by measuring the static friction coefficient and the dynamic friction coefficient according to ASTM D1891 using a surface property tester (Haydon Tribogear type 14D, manufactured by Shinto Kagaku Co., Ltd.). The wear piece used at that time was a non-woven fabric, and measurement was performed with a flat indenter of 63.5 mm, a speed of 10 mm / min, and a load of 200 g.
Furthermore, the total light transmittance of the obtained antistatic film was measured according to JIS K 7361-1, and the haze was measured according to JIS K 7105.
Table 1 shows the results of surface resistance, static friction coefficient, dynamic friction coefficient, total light transmittance, and haze.

(Example 2)
An antistatic paint B was obtained in the same manner as in Example 1 except that the amount of the non-reactive water-soluble silicone added to 100 g of the conductive polymer solution A obtained in Example 1 was changed to 0.1 g. . Then, an antistatic film was formed and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Example 3)
An antistatic paint C was obtained in the same manner as in Example 1 except that the amount of non-reactive water-soluble silicone added to 100 g of the conductive polymer solution A obtained in Example 1 was changed to 0.5 g. . Then, an antistatic film was formed and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 4
An antistatic paint D was obtained in the same manner as in Example 1 except that the amount of the non-reactive water-soluble silicone added to 100 g of the conductive polymer solution A obtained in Example 1 was changed to 1.0 g. . Then, an antistatic film was formed and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 1)
The conductive polymer solution A obtained in Example 1 was applied to a polyethylene terephthalate film to form an antistatic film and evaluated. The evaluation results are shown in Table 1.

(Comparative Example 2)
To 100 g of the conductive polymer solution A obtained in Example 1, 0.01 g of reactive water-soluble silicone (X-12-2400E, which is a hydrolyzate of a silane compound having an acrylic group, manufactured by Shin-Etsu Chemical Co., Ltd.) Was added to obtain antistatic paint E. Then, an antistatic film was formed and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

(Comparative Example 3)
An antistatic paint F was obtained in the same manner as in Example 1 except that the amount of the reactive water-soluble silicone added to 100 g of the conductive polymer solution A obtained in Example 1 was changed to 0.1 g. . Then, an antistatic film was formed and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

The antistatic films of Examples 1 to 4 formed by applying an antistatic paint containing a non-reactive water-soluble silicone have a high surface resistance value, excellent antistatic properties, and a π-conjugated conductive polymer. Since it exhibits conductivity, there is no humidity dependence of antistatic properties. Further, the static friction coefficient and the dynamic friction coefficient were small, the surface lubricity was high, and the blocking resistance was excellent. Further, the total light transmittance was high, the haze was small, and the transparency was excellent. Furthermore, since the antistatic film is mainly composed of a resin, it has excellent adhesion to a base material made of polyethylene terephthalate.
On the other hand, the antistatic film of Comparative Examples 2 and 3 formed by applying an antistatic coating containing reactive water-soluble silicone, antistatic containing no reactive water-soluble silicone as well as non-reactive water-soluble silicone The antistatic film of Comparative Example 1 formed by applying a paint had a large static friction coefficient and a dynamic friction coefficient, low surface lubricity, and low blocking resistance.

1 is a cross-sectional view illustrating an embodiment of an optical filter of the present invention. It is sectional drawing which shows one example of embodiment of the optical information recording medium of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Optical filter 2 Optical information recording medium 10 Film base material 20 Antistatic film 30 Antireflection layer 40 Transparent resin substrate 50 1st dielectric layer 60 Optical information recording layer 70 2nd dielectric layer 80 Metal reflecting layer 90 Antistatic film

Claims (7)

  An antistatic paint comprising a π-conjugated conductive polymer, a polyanion, a polyether-modified non-reactive water-soluble silicone, and a solvent.   The antistatic paint according to claim 1, wherein the non-reactive water-soluble silicone has an HLB value of 7 to 16.   The antistatic paint according to claim 1 or 2, further comprising a binder resin.   An antistatic film formed by applying the antistatic paint according to claim 1.   An antistatic film comprising a film substrate and the antistatic film according to claim 4 formed on at least one surface of the film substrate.   An optical filter comprising the antistatic film according to claim 4.   An optical information recording medium comprising the antistatic film according to claim 4.

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