JP4350597B2 - Antistatic resin composition, antistatic resin paint, optical filter - Google Patents

Description

  The present invention provides a functional optical filter such as an antireflection film on both sides of a liquid crystal screen or a plasma display, an infrared absorption film, an electromagnetic wave absorption film, or the like, and an optical information recording medium such as a CD or a DVD. The present invention relates to an antistatic resin composition and an antistatic resin coating material that imparts properties. Furthermore, the present invention relates to an optical filter having an antistatic hard coat layer and an optical information recording medium.

Generally, a hard coat layer is formed on the surface of an optical filter or an optical information recording medium in order to prevent damage. In these applications, the hard coat layer is not only high in hardness, but also requires excellent transparency because it is used in optical applications, and further requires antistatic properties in order to prevent dust from adhering to static electricity. In particular, the antistatic property is required to have a stable resistance value (that is, a stable antistatic property) in a region where the surface resistance is about 10 ⁶ to 10 ¹⁰ Ω. Therefore, resin compositions having antistatic properties are used as hard coat materials for optical filters and optical information recording media.
Conventionally, as an antistatic resin composition, fine particles of transparent inorganic conductive oxide such as ITO (tin oxide doped indium oxide) or ATO (tin oxide antimony oxide), hard coating such as UV curable acrylic resin What was disperse | distributed to resin was used.

  For example, an antireflection film is disclosed in which an ITO transparent conductive film is formed by coating and drying ITO powder dispersed in a resin, an inorganic binder, or an organic solvent on the surface (see, for example, Patent Document 1). However, in such a coating film in which an inorganic conductive oxide such as ITO is dispersed, the resistance value is easily influenced by the dispersibility of the inorganic conductive oxide, and as a result, the antistatic property tends to be unstable. . In addition, the inorganic conductive oxide has a unique refractive index that is significantly different from that of organic resins. Therefore, when blended in a large amount, the haze increases and transparency is impaired, and the coating tends to become brittle. There is a drawback that the adhesion of the resin becomes low.

Moreover, as an antistatic resin composition, what melt | dissolved the conductive polymer which is organic in a solvent, and mixed it with hard-coat resin can be considered. However, since the conductive polymer is usually generated as insoluble and infusible particles, this resin composition was not obtained by uniformly dissolving the conductive polymer in a solvent. In addition, since the conductive polymer produced as particles is colored, the coating film in which the conductive polymer is dispersed tends to be brittle, as in the case where the inorganic conductive oxide is dispersed. It was in.
Thus, a conductive polymer in which a long-chain alkyl group is introduced at the β-position of pyrrole so that it can be dissolved in a solvent has been proposed (for example, see Patent Document 2).
JP-A-4-26768 Japanese Patent No. 3024867

Since the conductive polymer described in Patent Document 2 has a bulky alkyl chain, it is soluble in a solvent and can be mixed into a hard coat resin, but the conductivity is low, and the mixing amount is reduced. Unless it was increased, the desired antistatic property could not be obtained. As a result, there was a problem that the coating film was colored and the transparency was impaired. Furthermore, even the conductive polymer described in Patent Document 2 has not been put into practical use because it is not easy to mix into various hard coat resins having different polarities. Moreover, special monomers such as β alkyl pyrroles are very expensive and difficult to use in terms of cost.
The present invention has excellent antistatic stability (excellent stability in a high resistance range), high transparency, excellent adhesion to a substrate, and an inexpensive antistatic resin composition and antistatic An object of the present invention is to provide a functional resin coating. Furthermore, it aims at providing the optical filter and optical information recording medium using the same.

That is, the antistatic resin composition of the present invention comprises a soluble conductive polymer component comprising a solubilized polymer component having an anion group and / or an electron withdrawing group in the molecule and a conductive polymer component;
Containing hard coat ingredients ,
The solubilized polymer component having an anionic group in the molecule is polyallylsulfonic acid, polyacrylsulfonic acid, polymethacrylsulfonic acid, poly-2-acrylamido-2-methylpropanesulfonic acid, polyethyl methacrylatesulfonic acid, It contains polyacrylic acid ethylsulfonic acid or any of these polymer salts .
In the antistatic resin composition of the present invention, the soluble conductive polymer component preferably further contains a dopant.
The antistatic resin paint of the present invention is characterized in that the above-mentioned antistatic resin composition is dissolved or dispersed in a solvent.
The optical filter of the present invention is characterized by having an antistatic hard coat layer formed from the above-described antistatic resin composition or the above-described antistatic resin paint .

With the antistatic resin composition and antistatic resin coating of the present invention, a hard coat layer having excellent antistatic stability can be formed by a simple process such as coating, drying and curing. Moreover, the hard coat layer is excellent in transparency, excellent in adhesion to the substrate, and inexpensive.
In the optical filter and the optical information recording medium of the present invention, the underlying layer is protected by the hard coat layer. Further, since the hard coat layer is excellent in transparency, antistatic stability and adhesion, the quality of the optical filter or optical information recording medium is improved.

(Antistatic resin composition)
The antistatic resin composition of the present invention contains a soluble conductive polymer component and a hard coat component.
<Soluble conductive polymer component>
The soluble conductive polymer component in the present invention is obtained by mixing the conductive polymer component with a solubilized polymer component having an anionic group and / or an electron-withdrawing group in the molecule, and the monomer type, substituted or unsubstituted It has high solvent solubility regardless of the above.

[Conductive polymer component]
The conductive polymer component in the present invention is advantageous in terms of resistance value, cost, and reactivity, and is therefore substituted or unsubstituted polyaniline, substituted or unsubstituted polypyrrole, substituted or unsubstituted polythiophene, and these (Co) polymers composed of one or two selected from: In particular, polypyrrole, polythiophene, poly N-methylpyrrole, poly-3-methylthiophene, poly-3-methoxythiophene, poly (3,4-ethylenedioxythiophene), (co) heavy consisting of one or two selected from these Coalescence is preferred.
In particular, alkyl-substituted compounds such as poly N-methylpyrrole and poly-3-methylthiophene are advantageous because of the effect of improving solvent solubility. Among alkyl groups, a methyl group is preferred because it does not adversely affect conductivity.
An alkylenedioxy-substituted compound such as poly (3,4-ethylenedioxythiophene) can be used by dissolving in water or a mixed solution of water and an organic solvent.

[Solubilized polymer component]
The solubilized polymer component is a polymer having an anionic group and / or an electron-withdrawing group in the molecule, and makes the conductive polymer component soluble in a solvent.
Examples of the solubilized polymer component having an anionic group in the molecule include substituted or unsubstituted polyalkylene, substituted or unsubstituted polyalkenylene, substituted or unsubstituted polyimide, substituted or unsubstituted polyamide, substituted or unsubstituted A polymer selected from substituted polyesters, comprising a structural unit having an anionic group and a structural unit having no anionic group, wherein m is the number of structural units having an anionic group, and the structural unit has no anionic group. Examples where m / n ≦ 1 when the number is n are mentioned.

Here, polyalkylene is a polymer whose main chain is composed of repeating methylene. Examples of polyalkenylene include polymers composed of structural units containing one vinyl group in the main chain, and there is an interaction between an unsaturated bond and a π-conjugated conductive polymer, and a substituted or unsubstituted polymer. Since it is easy to synthesize using butadiene as a starting material, substituted or unsubstituted butenylene can be exemplified.
Examples of polyimide include pyromellitic dianhydride, biphenyltetracarboxylic dianhydride, benzophenonetetracarboxylic dianhydride, 2,2,3,3-tetracarboxydiphenyl ether dianhydride, 2,2- [4,4 Examples include polyimides from acid anhydrides such as' -di (dicarboxyphenyloxy) phenyl] propane dianhydride and diamines such as oxydianiline, paraphenylenediamine, metaphenylenediamine, and benzophenonediamine.
Examples of polyamides include polyamide 6, polyamide 6,6, polyamide 6, 10 and the like.
Examples of the polyester include polyethylene terephthalate and polybutylene terephthalate.

  Examples of the substituent of the polymer constituting the solubilized polymer component having an anionic group include an alkyl group, a hydroxy group, a carboxyl group, a cyano group, a phenyl group, a phenol group, an ester group, an alkoxy group, and a carbonyl group. . Alkyl groups can increase solubility and dispersibility in polar or nonpolar solvents, compatibility and dispersibility in resins, and hydroxy groups form hydrogen bonds with other hydrogen atoms. This makes it easy to increase solubility in organic solvents, compatibility with resins, dispersibility, and adhesion. 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 hydroxy group, an ester group, and a cyano group are preferable.

  Examples of the alkyl group include 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 hydroxy group include a hydroxy group directly bonded to the main chain of the polyanion, a hydroxy 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 to 2 carbon atoms bonded to the main chain of the polyanion. And a hydroxy group bonded to the terminal of 7 alkenyl group. Among these, a hydroxy group bonded to the terminal of an alkyl group having 1 to 6 carbon atoms bonded to the main chain is more preferable from the viewpoint of compatibility with a resin and solubility in 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.

  The cyano group includes 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 to 2 carbon atoms bonded to the main chain of the polyanion. And a cyano group bonded to the terminal of 7 alkenyl group.

  In the solubilized polymer component having an anion group in the molecule, the anion group may be any functional group that can cause chemical oxidation doping to the π-conjugated conductive polymer. From this viewpoint, a monosubstituted sulfate group, a monosubstituted phosphate group, a carboxylic acid group, a sulfonic acid 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 sulfonic acid group and a monosubstituted sulfate group are more preferable.

Specific examples of the solubilized polymer component having an anionic group include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid. , Polyisoprene sulfonic acid, polyacrylic acid and the like.
Of these, polyacrylsulfonic acid and polymethacrylsulfonic acid absorb heat energy and decompose by themselves, so that thermal decomposition of the conductive polymer component is alleviated, so heat resistance and environmental resistance are excellent. Furthermore, since it has an ester group, it is particularly preferable because it has excellent compatibility and dispersibility with the hard coat component.

  Examples of the electron-withdrawing group of the solubilized polymer component having an electron-withdrawing group include compounds having a cyano group, a nitro group, a formyl group, a carbonyl group, and an acetyl group. Examples of the compound having a cyano group include acrylonitrile. And / or methacrylonitrile. Since the cyano group has high polarity and contributes to improvement of compatibility with the hard coat component and acidity, acrylonitrile and methacrylonitrile are particularly preferably used.

  Specific examples of the solubilized polymer component having an electron withdrawing group include polyacrylonitrile, polymethacrylonitrile, acrylonitrile-styrene resin, acrylonitrile-butadiene resin, acrylonitrile-butadiene-styrene resin, hydroxyl group or amino group-containing resin. Examples include cyanoethylated resins (for example, cyanoethyl cellulose), polyvinyl pyrrolidone, alkylated polyvinyl pyrrolidone, and nitrocellulose.

The solubilized polymer component may be a copolymer, for example, a copolymer containing two or more solubilized polymer components having an anionic group and an electron-withdrawing group as described above, or different types. It may be a copolymer having a different anionic group or a copolymer having a different kind of electron-withdrawing group.
Furthermore, the vinyl compound may be copolymerized with the solubilized polymer component. Examples of the vinyl compound include a halogenated vinyl compound, an aromatic vinyl and / or a derivative thereof, a heterocyclic vinyl compound and / or a derivative thereof. Derivatives, aliphatic vinyl compounds and / or derivatives thereof, acrylic compounds, diene compounds, and maleimide compounds.
Specific examples of the other vinyl compounds include polymerizable vinyl compounds such as styrene, butadiene, acrylic acid, methacrylic acid, hydroxyacrylic acid, hydroxymethacrylic acid, acrylic acid ester, methacrylic acid ester, and p-vinyltoluene. By copolymerizing these other vinyl compounds, solvent solubility and compatibility with the hard coat component can be controlled.

  The solubilized polymer component may contain a synthetic rubber component for improving impact resistance, an anti-aging agent, an antioxidant, and an ultraviolet absorber for improving environmental resistance. However, amine compound antioxidants may interfere with the action of the oxidizer used when polymerizing the above conductive polymer, so the antioxidant may be phenolic or mixed after polymerization. It is necessary to take measures such as

[Dopant]
The soluble conductive polymer component preferably contains a dopant in order to improve its conductivity and heat resistance. Usually, halogen compounds, Lewis acids, proton acids, etc. are used as dopants. Specifically, organic acids such as organic carboxylic acids and organic sulfonic acids, organic cyano compounds, fullerenes, hydrogenated fullerenes, carboxylated fullerenes, sulfones and the like. Examples include fullerene oxide.

Here, as the organic acid, 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 Examples include disulfonic acid, anthraquinone sulfonic acid, anthraquinone disulfonic acid, anthracene sulfonic acid, and pyrene sulfonic acid. These metal salts can also be used.
Examples of the organic cyano compound include dichlorodicyanobenzoquinone (DDQ), tetracyanoquinodimethane, and tetracyanoazanaphthalene.

[Method for producing soluble conductive polymer component]
In order to produce a soluble conductive polymer component, the solubilized polymer component is dissolved in a solvent that dissolves the polymer component, and the precursor monomer of the conductive polymer and a dopant as necessary are mixed sufficiently and mixed. Polymerization proceeds by dropping an oxidant into the mixture. The soluble conductive polymer component is obtained by removing and purifying the oxidizing agent, residual monomer, and by-products from the composite of the solubilized polymer component and the conductive polymer thus obtained.

  As the oxidizing agent for polymerizing the precursor monomer of the conductive polymer, known ones can be used, for example, metal halogen compounds such as ferric chloride, boron trifluoride, aluminum chloride, hydrogen peroxide, benzoyl peroxide. And persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, ozone, oxygen, and the like.

  The ratio of the conductive polymer component to the solubilized polymer component is preferably in the range of 5:95 to 99: 1 solubilized polymer component: conductive polymer component as a mass ratio. If the ratio of the conductive polymer component is less than 1, sufficient conductivity may not be obtained, and if it exceeds 95, the solvent solubility tends to be poor.

The purification method is not particularly limited, and for example, a reprecipitation method, an ultrafiltration method, or the like can be adopted, but the ultrafiltration method is simple and preferable.
The ultrafiltration is a method in which a solution in a solution is circulated on a porous ultrafiltration membrane and a liquid in the solution is passed through the ultrafiltration membrane to be filtered. In this method, a differential pressure is generated between the circulating solution side and the permeated solution side with the ultrafiltration membrane interposed therebetween, so that part of the solution on the circulating solution side permeates the permeated solution side and relieves the pressure on the circulating solution side . As the circulating solution permeates, some of the particles, dissolved ions, etc. smaller than the diameter of the ultrafiltration membrane in the circulating solution move to the permeate solution side, so that the particles and dissolved ions can be removed. The ultrafiltration membrane to be used can be appropriately selected from the range of a molecular weight cut-off of 1,000 to 1,000,000 depending on the particle diameter and ion species to be removed.

  The addition method of the dopant may be a method other than the method of mixing with the precursor monomer of the conductive polymer. For example, after purifying the complex of the solubilized polymer component and the conductive polymer, the dopant is added. The method of adding may be sufficient.

  The soluble conductive polymer component may be used after being dissolved in a solvent. Examples of the solvent include water, methanol, ethanol, propylene carbonate, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, and toluene.

<Hard coat component>
The hard coat component used in the present invention includes a component in which the pencil hardness (JIS K 5400) of the coating film when cured is harder than H. When cured, for example, polyester, epoxy resin, It is one or more of oxetane resin, polyacryl, polyurethane, polyimide, polyamide, polyamideimide, polyimide silicone and the like.
Further, the hard coat component can be used by adding a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier and the like, if necessary.

The hard coat component preferably contains a liquid polymer that is cured by heat energy and / or light energy.
Here, examples of the liquid polymer that is cured by thermal energy 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 sidyl ether, tetrabromobisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether (ie 2,2-bis (4-glycidyloxycyclohexyl) propane), N, N-diglycidyl aniline, 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 And glycidyl compound of epichlorohydrin of bisphenol A, or the like.

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 self-crosslinking 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 energy 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 energy include bisphenol A / ethylene oxide-modified diacrylate, dipentaerythritol hexa (penta) acrylate, dipentaerythritol monohydroxypentaacrylate, and dipropylene glycol diacrylate. Acrylate, trimethylolpropane triacrylate, glycerin propoxytriacrylate, 4-hydroxybutyl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, polyethylene glycol diacrylate, Pentaerythritol triacrylate, tetrahydrofurfuryl acrylate, trimethylolpropane tria Relates, 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- Such as ethylhexyl methacrylate, glycidyl methacrylate, 1,6-hexanediol dimethacrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, lauryl methacrylate, phenoxyethyl methacrylate, t-butyl methacrylate, tetrahydrofurfuryl methacrylate, trimethylolpropane trimethacrylate, etc. Methacrylates Glycidyl ethers such as allyl glycidyl 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 , Dimethylaminopropylmethacrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylformamide, N-methylacrylamide, N-isopropylacrylamide, Nt-butylacrylamide, N-phenyl Acrylics such as acrylamide, acryloylpiperidine, 2-hydroxyethylacrylamide ( Methacryl) amides, 2-chloroethyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, hydroxybutyl vinyl ether, isobutyl vinyl ether, vinyl ethers such as triethylene glycol vinyl ether, carboxylic acid vinyl esters such as vinyl butyrate, vinyl monochloroacetate and vinyl pivalate And monofunctional monomers as well as polyfunctional monomers.

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

  When the hard coat component that is cured by thermal energy and / or light energy contains a liquid polymer, the soluble conductive polymer component can be dissolved in the liquid polymer. A solvent-type antistatic resin coating can be obtained. In the case of a solventless paint, the hard coat layer can be easily formed because it can be cured by light irradiation without drying after coating.

  The mixing amount of the soluble conductive polymer component and the hard coat component is appropriately selected depending on the required antistatic property, but soluble conductive polymer component: hard coat component = 0.001: 99.999-99.9: It is the range of 0.1 (mass ratio), Preferably it is the range of 5: 95-95: 5.

(Antistatic resin paint)
The antistatic resin paint of the present invention is obtained by dissolving or dispersing the antistatic resin composition in a solvent.
Here, the same solvent as the solvent that dissolves the soluble conductive polymer component can be used as the solvent. For example, water, methanol, ethanol, propylene carbonate, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene and the like can be mentioned. These may be used alone or in combination.

  In the antistatic resin paint, the hard coat component may be a liquid polymer. When a liquid polymer is contained, when the antistatic resin coating is applied and dried, self-aggregation of the soluble conductive polymer component can be suppressed by solvation of the liquid polymer, so that a decrease in conductivity can be prevented. .

  In order to form a coating film (hard coat layer) of an antistatic resin paint or an antistatic resin composition (solvent-free antistatic resin paint) whose hard coat component is a liquid polymer, these are immersed, After coating on a substrate such as polyester film or triacetyl cellulose (TAC) film by methods such as comma coating, spray coating, roll coating, gravure printing, etc., remove the solvent by heating, or cure by heat or light. That's fine.

  As a heating method when forming a coating film by heating, for example, a normal method such as hot air heating or infrared heating can be adopted, and as a light irradiation method when forming a coating film by photocuring, for example, an ultra-high pressure A method of irradiating ultraviolet rays from a light source such as a mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp can be employed.

In the obtained coating film, the visible light transmittance (JIS Z 8701) when the film thickness is 1 μm is preferably 80% or more, more preferably 90% or more, and 96% or more. Particularly preferred.
The haze (JIS K 6714) is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.
Furthermore, the surface resistance value is preferably 1 × 10 ⁴ to 1 × 10 ¹³ Ω.
The light transmittance, haze, and surface resistance value of the coating film can be adjusted by the coating film thickness.

According to the antistatic resin composition and the antistatic resin coating described above, the surface resistance is stable within a range of about 10 ⁶ to 10 ¹⁰ Ω by a simple process such as coating, drying, and curing, and antistatic A hard coat layer with excellent stability can be formed. Moreover, since the hard coat layer is a layer in which the conductive polymer component is uniformly dispersed, the haze is small, the light transmittance is high, and the transparency is excellent. Furthermore, such a hard coat layer is excellent in adhesion to the substrate.
The antistatic resin composition and antistatic resin paint having such properties can be suitably used particularly for optical filters and optical information recording media.

(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 hard coat layer 20 (hereinafter abbreviated as a hard coat layer 20) formed on the film substrate 10, and a reflection formed on the hard coat layer 20. And a prevention layer 30.
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 base 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. Specifically, polyethylene terephthalate, polyimide, polyethersulfone, polyetheretherketone, polycarbonate, polypropylene, polyamide, acrylamide, cellulose propionate Etc.
Moreover, it is preferable that the film base material 10 is subjected to etching treatment or undercoating treatment such as sputtering, corona discharge, flame, ultraviolet ray irradiation, electron beam irradiation, chemical conversion and oxidation on the surface. If such a treatment is applied to the surface, the adhesion to the hard coat layer 20 can be further improved.
Furthermore, 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 hard coat layer 20.

The hard coat layer 20 is a layer formed from the above-described antistatic resin composition or antistatic resin paint.
As a method for forming the hard coat layer 20, a known method such as dipping an antistatic resin composition or an antistatic resin paint on the film substrate 10, comma coating, spray coating, roll coating, gravure printing, or the like is used. And then the solvent is dried or cured by heat or UV.

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, an antifouling layer may be further provided on the antireflection layer 30. If the antifouling layer is provided, it is possible to prevent the dust and dirt from adhering or to remove them even if they adhere.
The antifouling layer is not particularly limited as long as it does not inhibit the antireflection function of the antireflection layer 30, exhibits high water repellency and oil repellency, and can prevent adhesion of contamination, and is a layer made of an organic compound. It may be a layer made of an inorganic compound. For example, a layer containing an organic silicon compound having a perfluorosilane group or a fluorocycloalkyl group or a fluorine organic compound can be given.
The method for forming the antifouling layer can be appropriately selected depending on the type of the antifouling layer. For example, the vapor deposition method, the sputtering method, the physical vapor deposition method such as the ion plating method, the chemical vapor deposition method, the plasma polymerization method, etc. A vacuum process, a micro gravure method, a screen coating method, a dip coating method, etc. can be adopted.

In the optical filter 1 described above, the hard coat layer 20 that protects the film substrate 10 is formed, and the hard coat layer 20 is formed from the antistatic resin composition or the antistatic resin paint. Excellent transparency and excellent adhesion to the film substrate 10. Moreover, this optical filter 1 is a filter excellent in antistatic stability, and it is difficult for dust to adhere to the surface.
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.

  Note that the optical filter of the present invention is not limited to the above-described embodiment example, and may have a hard coat layer formed from the antistatic resin composition or the antistatic resin 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 side or both sides of a polyvinyl alcohol resin film adsorbed and oriented with a dichroic dye, and iodine or a dichroic dye is used as the 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, a disc-shaped transparent resin substrate 40 made of polycarbonate, polymethyl methacrylate, or the like, a first dielectric layer 50, an optical information recording layer 60, a second dielectric layer 70, The metal reflective layer 80 and the antistatic hard coat layer 90 (hereinafter abbreviated as hard coat layer 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 means 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 means such as a vacuum deposition method, a sputtering method, or an ion plating method. 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 hard coat layer 90 is formed from the antistatic resin composition or the antistatic resin paint. The hard coat layer 90 can prevent the surface of the optical information recording medium 2 from being damaged, can prevent oxidation of the metal reflective layer 80, and can suppress adhesion of dust due to static electricity.
The thickness of the hard coat layer 90 is preferably 3 to 15 μm. When the thickness is less than 3 μm, it tends to be difficult to form a uniform film, and sufficient antistatic properties, surface damage prevention properties, and antioxidant properties of the metal reflective layer 80 may not be exhibited. On the other hand, if it is thicker than 15 μm, the internal stress increases, and the mechanical properties of the optical information recording medium 2 may be deteriorated.

  In order to form the hard coat layer 90, an antistatic resin composition or an antistatic resin paint is used on the metal reflective layer 80 by using a known method such as comma coating, spray coating, roll coating, or gravure printing. After coating, the solvent is dried or cured by heat or UV.

  In the optical information recording medium 2 described above, a hard coat layer 90 that protects the optical information recording layer 60 and the metal reflective layer 80 is formed, and the hard coat layer 90 is formed of the antistatic resin composition or It is formed from an antistatic resin paint. Therefore, since the hard coat layer 90 has a small haze and a high light transmittance, the hard coat layer 90 is excellent in transparency at the reading laser wavelengths of 780 nm and 635 nm. Further, since the hard coat layer 90 has antistatic properties, dust adhesion due to static electricity is suppressed, and a recording / reading error and a writing error are prevented.

  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 a hard coat layer are sequentially formed.

Hereinafter, the present invention will be described in more detail with reference to examples.
(Production Example 1) Synthesis of solubilized polymer component containing electron-withdrawing group 50 g of acrylonitrile and 10 g of styrene were dissolved in 500 ml of toluene, 1.5 g of azoisobutyronitrile was added as a polymerization initiator, Polymerized for 5 hours. Thereafter, the polymer produced by the polymerization was washed with methanol.
(Production Example 2) Synthesis of a solubilized polymer component containing an anion group To ion-exchanged water (100 ml), 43.4 g of sodium ethyl sulfonate (trade name: Antox, manufactured by Nippon Emulsifier Co., Ltd.) was added. Keep at 80 ° C. while stirring, add 0.114 g ammonium persulfate and 0.04 g ferric sulfate complex oxidizer solution previously dissolved in 10 ml ion exchange water, then stir for 3 hours while keeping at 80 ° C. did.
After completion of the reaction, the reaction solution was cooled to room temperature, 1000 ml of ion exchange water was added thereto, and 30 g of 50% by mass sulfuric acid aqueous solution was added, and then the solution was concentrated to 300 ml. This operation was repeated 4 times.
Furthermore, the operation of adding 2000 ml of ion exchange water and concentrating to 300 ml was repeated until the permeated solution became neutral, and the resulting concentrated solution was dried in an oven to obtain polyethyl methacrylatesulfonic acid.
(Production Example 3) Synthesis of a solubilized polymer component containing a copolymer of a component having an anionic group and a component having an electron-withdrawing group Ion exchange of 40 g of sodium acrylate ethyl sulfonate and 20 g of methacrylonitrile with acetonitrile In addition to 500 ml of water (7: 3), kept at 80 ° C. with stirring, a combined oxidant solution of 0.14 g potassium persulfate and 0.04 g ferric sulfate dissolved in 10 ml ion-exchanged water in advance. After the addition, the mixture was stirred for 3 hours while maintaining at 80 ° C.
After completion of the reaction, the reaction solution was cooled to room temperature, 1000 ml of ion exchange water was added thereto, and 30 g of 50% by mass sulfuric acid aqueous solution was added, and then the solution was concentrated to 300 ml. This operation was repeated 4 times.
Further, the operation of adding 2000 ml of ion-exchanged water and concentrating to 300 ml was repeated until the permeated solution became neutral, and the resulting concentrated solution was dried in an oven to co-polymerize ethyl acrylate acrylate and methacrylonitrile. Coalescence was obtained.

[Preparation of antistatic resin paint]
(Example 1)
10 g of the solubilized polymer component of Production Example 1 was dissolved in 90 g of acetonitrile, 50 g of thiophene and 20 g of sodium octadecylnaphthalenesulfonate were added, and the mixture was stirred for 1 hour while cooling to −20 ° C.
To this solution, an oxidizing agent solution in which 250 g of ferric chloride was dissolved in 1250 ml of acetonitrile was dropped over 2 hours while maintaining 20 ° C., and stirring was continued for 12 hours to polymerize thiophene.
After completion of the reaction, 2000 ml of methanol was added to the solution containing the thiophene polymer, washed by ultrafiltration and the precipitate was filtered, and this precipitate was dissolved in dimethylformamide (DMF) to a concentration of 5% by mass. A solution of a soluble conductive polymer was prepared.
Ethyl vinyl ether was mixed with this soluble conductive polymer solution, and polyester acrylate (manufactured by Toa Gosei Co., Ltd.), which is a hard coat component, was mixed with the mixed solution and stirred to obtain an antistatic resin paint.

  This antistatic resin paint was evaluated as follows. That is, Dicure 1173 (manufactured by Ciba Specialty Chemicals), which is a polymerization initiator, is added to an antistatic resin coating, applied onto a PET film with a comma coater, dried, cured by exposure to a high-pressure mercury lamp, and thickened. A 1 μm antistatic hard coat layer was formed. And the surface resistance value, visible light transmittance, and haze of this layer were measured. The results are shown in Table 1.

(Example 2)
10 g of the solubilized polymer component of Production Example 1 was dissolved in 90 g of acetonitrile, 50 g of pyrrole was added, and the mixture was stirred for 1 hour while cooling to −20 ° C.
To this solution, an oxidant solution in which 250 g of ferric chloride was dissolved in 1250 ml of acetonitrile was dropped over 2 hours while maintaining −20 ° C., and stirring was further continued for 12 hours to polymerize pyrrole.
After completion of the reaction, 2000 ml of methanol was added to the solution containing the pyrrole polymer, washed by ultrafiltration, and the precipitate was filtered. The precipitate was dissolved in dimethylformamide (DMF) to a concentration of 5% by mass. A solution of a soluble conductive polymer was prepared.
Dipentaerythritol hexaacrylate was mixed with the soluble conductive polymer solution, and epoxy acrylate (manufactured by Nippon Shokubai Co., Ltd.) as a hard coat component was mixed with the mixed solution, followed by stirring to obtain an antistatic resin paint. The antistatic resin paint was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 3)
10 g of the solubilized polymer component of Production Example 2 was dissolved in 90 g of acetonitrile, 50 g of 3-methoxythiophene and 25 g of sodium p-toluenesulfonate were added, and the mixture was stirred for 1 hour while cooling to −20 ° C.
To this solution, an oxidizing agent solution in which 250 g of ferric chloride was dissolved in 1250 ml of acetonitrile was dropped over 2 hours while maintaining -20 ° C., and stirring was further continued for 12 hours to polymerize 3-methoxythiophene.
After completion of the reaction, 2000 ml of methanol was added to the solution containing the polymer of 3-methoxythiophene, washed by ultrafiltration, the precipitate was filtered, this precipitate was dissolved in dimethylformamide (DMF) and the concentration was 5 A solution of a soluble conductive polymer was prepared as a mass%.
This soluble conductive polymer solution is mixed with tetrabromobisphenol A diglycidyl ether, which is a hard coat component, and mixed with Al (OH) ₃ as a cross-linking agent and stirred to obtain an antistatic resin coating. It was. The antistatic resin paint was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Example 4)
10 g of the solubilized polymer component of Production Example 3 was dissolved in 90 g of water, 50 g of pyrrole was added, and the mixture was stirred for 1 hour while cooling to −20 ° C.
To this solution, an oxidant solution in which 200 g of ammonium persulfate was dissolved in 1250 ml of water was dropped over 2 hours while maintaining -20 ° C., and stirring was further continued for 12 hours to polymerize pyrrole.
After completion of the reaction, the precipitate was filtered by washing with an ultrafiltration method, and the precipitate was concentrated to a concentration of 5% by mass to prepare a solution of a soluble conductive polymer.
This soluble conductive polymer solution was mixed with allyl methacrylate, and the mixed solution was mixed with urethane acrylate (manufactured by Negami Kogyo Co., Ltd.) as a hard coat component and stirred to obtain an antistatic resin paint. The antistatic resin paint was evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
15 g of ITO powder, 60 g of dimethylformamide (DMF), 75 g of ethanol, and 200 g of zirconia beads are mixed and stirred for about 1 to 24 hours using a ball mill, and then the pH of the obtained ITO colloid solution is in the range of 2 to 8. Adjusted. This ITO colloid solution is diluted with a mixed solvent of methanol, ethanol, butanol, 2-methoxyethanol, and 1-methoxy-2-propanol so that the ITO concentration becomes 1.0 to 1.5% by mass, and colloidal ITO coating A solution was prepared.
The obtained ITO colloid coating solution was spin-coated on the hard coat layer of the film base at a speed of 300 rpm to form an ITO layer. Next, a silica coating solution was spin-coated on the ITO layer at a speed of 300 rpm, and heated at 100 ° C. for 30 minutes to obtain a laminate having a film base / hard coat layer / ITO layer / silica layer.
The evaluation results of this laminate are shown in Table 1.

  The hard coat layer formed from the antistatic resin paint of Examples 1 to 4 containing a specific soluble conductive polymer component and a hard coat component has a small surface resistance value (antistatic property) and transmits visible light. The rate was high and the haze was small. On the other hand, the hard coat layer formed from the antistatic resin paint of Comparative Example 1 in which ITO was mixed with the hard coat component had a large surface resistance value (antistatic property), a low visible light transmittance, and a large haze. .

(Example 5) Production of optical filter The other surface of a PET film (film substrate) in which an adhesive layer and a cover film were laminated on one surface was subjected to corona treatment. Next, the antistatic resin paint of Example 1 was applied to the corona-treated surface of the PET film with a comma coater. After drying, it was cured by exposure to a high-pressure mercury lamp to form a hard coat layer having antistatic properties. Next, a solution obtained by adding 42.0 g of ethanol to 80 g of an ethanol dispersion of hollow silica (catalyst chemical industry Co., Ltd., solid content concentration 15.6% by mass) having fine pores inside on the hard coat layer Was applied. Then, it dried and heat-processed at 100 degreeC for 1 hour, the 90-mm antireflection layer was formed, and the optical filter was obtained.

The obtained optical filter was evaluated for visible light transmittance, haze, surface resistance, pencil hardness, and adhesion.
[Measurement of Visible Light Transmittance / Haze / Surface Resistance] The visible light transmittance was 96.3%, the haze was 0.4%, and the surface resistance value was 1 × 10 ⁵ Ω.
[Pencil Hardness Test] Using a test pencil specified in JIS S 6006, according to JIS K 5400, the hardness at which no scratch was observed at a load of 1 kg was measured, and the pencil hardness was 2H.
[Adhesion Test] An adhesion test was performed in accordance with the grid tape method (JIS K 5400). Specifically, 11 cuts in each length and width were made at 1 mm intervals on the surface of the optical film on the antireflection layer side by a cutter (a total of 100 square cells were formed). After sticking an adhesive tape on this, it peeled and the number of the grids which remained on the PET film was counted. As a result, in this optical film, all 100 squares remained (100/100).
That is, in this optical filter, the hard coat layer had sufficient hardness, and was excellent in transparency, antistatic properties, and adhesion to the substrate.

Example 6 Production of Optical Information Recording Medium On a disc-shaped polycarbonate substrate formed by injection molding, 300 nm of Ta ₂ O ₅ was formed as a first dielectric layer by sputtering, and 500 nm as an optical information recording layer. The Tb—Fe layer was formed, 300 nm Ta ₂ O ₅ was formed as the second dielectric layer, and the 100 nm aluminum layer was formed as the metal reflective layer. Next, the antistatic resin paint of Example 1 was applied on the metal reflective layer with a comma coater, dried, and then cured by exposure to a high-pressure mercury lamp to form an antistatic hard coat layer to form an optical information recording medium. Obtained. This optical information recording medium was evaluated as follows.

[Surface resistance measurement, pencil hardness measurement, adhesion test]
When surface resistance measurement, pencil hardness measurement, and adhesion test were performed in the same manner as in Example 5, the surface resistance value of this optical information recording medium was 1 × 10 ⁵ Ω, and the pencil hardness of the antistatic hard coat layer was 2H. In the adhesion test, all 100 squares remained.
[Measurement of transmittance] The transmittance of the antistatic hard coat layer at 780 nm and 635 nm, which are emission wavelengths of the reading laser diode of the optical information recording medium, was measured with a spectrophotometer. As a result, the transmittance at 780 nm was 98.9%, and the transmittance at 635 nm was 98.6%.
That is, this optical information recording medium was excellent in transparency at wavelengths of 780 nm and 635 nm, and also excellent in antistatic property, scratch resistance, and adhesion between the antistatic hard coat layer and the substrate. .

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 20,90 Antistatic hard coat layer (hard coat layer)

Claims (4)

A soluble conductive polymer component comprising a solubilized polymer component having an anionic group and / or an electron-withdrawing group in the molecule and a conductive polymer component;
Containing hard coat ingredients ,
The solubilized polymer component having an anionic group in the molecule is polyallylsulfonic acid, polyacrylsulfonic acid, polymethacrylsulfonic acid, poly-2-acrylamido-2-methylpropanesulfonic acid, polyisoprenesulfonic acid, polymethacrylic acid. An antistatic resin composition comprising ethyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, or a salt of these polymers .   The antistatic resin composition according to claim 1, wherein the soluble conductive polymer component further contains a dopant.   An antistatic resin coating composition comprising the antistatic resin composition according to claim 1 or 2 dissolved or dispersed in a solvent.   An optical filter comprising an antistatic hard coat layer formed from the antistatic resin composition according to claim 1 or 2 or the antistatic resin paint according to claim 3.

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