JP2010160464A - Antistatic hard coat film, and polarizing plate and display having antistatic hard coat film - Google Patents

Abstract

A combination of a π-conjugated conductive polymer having an electron conduction mechanism and a quaternary ammonium salt conductive monomer having an ionic conduction mechanism provides excellent transmittance and light resistance, and the surrounding environment (humidity). And a polarizing plate and a display having an antistatic hard coat film and an antistatic hard coat film which give good conductivity without depending on the above.
An antistatic hardware comprising: a base material; and a hard coat layer containing a π-conjugated conductive polymer and a quaternary ammonium salt conductive monomer or a polymer thereof on the base material. Coat film.
[Selection] Figure 1

Description

  The present invention relates to an antistatic hard coat film, a polarizing plate having an antistatic hard coat film, and a display. Particularly, a polarizing plate having an antistatic hard coat film and an antistatic hard coat film having good conductivity and high transmittance and applied to a display screen such as an LCD, PDP, CRT, projection display, EL display, etc. And a display.

  In general, a display is used in an environment where external light or the like is incident, regardless of whether the display is used indoors or outdoors. Incident light such as external light is specularly reflected on the display surface and the like, and the reflected image is mixed with the display image, thereby degrading the screen display quality. Therefore, it is essential to provide an antireflection function to the display surface or the like, and a combination of functions other than the antireflection function is required to improve the performance and productivity of the antireflection function.

  In general, the antireflection function can be obtained by forming a multilayer film (antireflection film) made of a transparent thin film such as a metal oxide on a substrate. These multilayer films can be formed by chemical vapor deposition (CVD) or physical vapor deposition (PVD), but the formation method by vacuum vapor deposition has a problem of low productivity and is not suitable for mass production. . On the other hand, as a method for forming a multilayer film, production of an antireflection film by a wet coating method, which can achieve a large area, continuous production, and cost reduction, has attracted attention.

  In addition, these multilayer films having an antireflection function are generally provided with a hard coat layer made of a polymer of an acrylic polyfunctional compound on the surface in order to impart surface hardness because the surface thereof is relatively flexible. A technique of forming an antireflection multilayer film is used. This hard coat layer has high surface hardness, gloss, transparency, and scratch resistance due to the characteristics of the acrylic resin, but it has high insulation properties, so it is easy to be charged, such as dust on the product surface provided with the hard coat layer. There have been problems such as contamination due to adhesion and troubles caused by charging in the display manufacturing process.

  Therefore, Patent Document 1 discloses a technique of kneading a conductive agent into the hard coat layer in order to impart an antistatic function. Patent Document 2 discloses a technique for providing an antistatic layer between a base material and a hard coat layer, and Patent Document 3 discloses a technique for providing an antistatic layer between a hard coat layer and an antireflection layer. ing. However, the techniques described in Patent Documents 2 and 3 are methods in which an antistatic layer is provided separately from a hard coat layer. If the antistatic layer is provided separately from the hard coat layer, the number of layers to be laminated as an antireflection film increases, so that the production process becomes complicated and the productivity may be reduced.

  Generally, the conductive agent used for imparting the antistatic function is a quaternary ammonium salt conductive monomer having an ion conduction mechanism, conductive fine particles having an electron conduction mechanism, or a π-conjugated conductive polymer. It is used.

  In general, a quaternary ammonium salt conductive monomer having an ionic conduction mechanism is colorless, and thus can exhibit conductivity without impairing the transmittance of the base material and the antistatic layer. Further, since it does not absorb light, it has high light resistance. However, moisture (water content) in the antistatic layer is indispensable for the appearance of conductivity because of its conduction mechanism, and there is a problem that the conductivity is greatly influenced by the surrounding environment (mainly humidity).

  On the other hand, conductive fine particles having an electron conduction mechanism are generally colored because they are metal oxide fine particles, and can exhibit good conductivity independent of the surrounding environment, but the antireflection film itself is colored by the metal oxide fine particles. , Has the problem of reduced transmittance.

  In addition, a π-conjugated conductive polymer having the same electron conduction mechanism can exhibit conductivity with a very small addition amount with respect to the resin component of the hard coat layer or conductive layer. In addition to being colored, and being an organic polymer, the light resistance is remarkably worse than that of other conductive materials, and there is a problem that the conductivity disappears after the light resistance test.

JP-A-11-92750 JP2007-29283A JP 2008-003122 A

  The present invention uses a combination of a π-conjugated conductive polymer having an electron conduction mechanism and a quaternary ammonium salt-based conductive monomer having an ion conduction mechanism, so that it has excellent transmittance and light resistance, and the surrounding environment ( It is an object to provide an antistatic hard coat film that gives good conductivity without depending on humidity), a polarizing plate having an antistatic hard coat film, and a display.

  The invention according to claim 1 of the present invention includes a base material, and a hard coat layer containing a π-conjugated conductive polymer and a quaternary ammonium salt conductive monomer or a polymer thereof on the base material. An antistatic hard coat film characterized by the above.

The invention according to claim 2 of the present invention is characterized in that the total light transmittance is 91% or more and the surface resistance value is 1 × 10 ¹⁰ (Ω / cm ² ) or less. This is an antistatic hard coat film.

The invention according to claim 3 of the present invention has a surface resistance value of 1 × 10 ¹⁰ (Ω / cm ² ) or less after being stored in an ultraviolet carbon arc lamp type light resistance tester defined in JIS B 7751 for 100 hours. The antistatic hard coat film according to claim 1 or 2, wherein the antistatic hard coat film is provided.

The invention according to claim 4 of the present invention has a surface resistance value of 1 × 10 ¹⁰ (Ω / cm ² ) or less after being stored in an ultraviolet carbon arc lamp type light resistance tester specified in JIS B 7751 for 500 hours. The antistatic hard coat film according to claim 1, wherein the antistatic hard coat film is provided.

In the invention according to claim 5 of the present invention, the surface resistance value measured in an environment of air temperature 20 ° C. to 40 ° C. and humidity 20% to 80% is 1 × 10 ¹⁰ (Ω / cm ² ) or less. The antistatic hard coat film according to any one of claims 1 to 3, wherein

  The invention according to claim 6 of the present invention is characterized in that an antireflection layer comprising one layer or a plurality of layers is formed on the hard coat layer. It is a coated film.

  The invention according to claim 7 of the present invention is the antistatic hard film according to claim 6, wherein the total light transmittance is 94% or more.

  The invention according to claim 8 of the present invention is a polarizing plate comprising the antistatic hard coat film according to any one of claims 1 to 7.

  The invention according to claim 9 of the present invention is a display comprising the antistatic hard coat film according to any one of claims 1 to 8.

  According to the present invention, by using a combination of a π-conjugated conductive polymer having an electron conduction mechanism and a quaternary ammonium salt-based conductive monomer having an ionic conduction mechanism, there are problems of the π-conjugated conductive polymer. Reduces the transmittance, and suppresses the deterioration of conductivity due to light resistance, and improves the dependence of the conductivity on the surrounding environment (humidity), which is a problem of quaternary ammonium salt conductive monomers having an ionic conduction mechanism. An antistatic hard coat film giving good conductivity, a polarizing plate having an antistatic hard coat film and a display can be provided.

It is a schematic sectional drawing which shows the antistatic hard coat film which concerns on embodiment of this invention. It is a schematic sectional drawing which shows the polarizing plate which has the antistatic hard coat film which concerns on embodiment of this invention. (A) And (b) is a schematic sectional drawing which shows the transmissive liquid crystal display which has the antistatic hard coat film which concerns on embodiment of this invention.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the embodiments, the same components are denoted by the same reference numerals, and redundant description among the embodiments is omitted.

  FIG. 1 is a schematic cross-sectional view showing an antistatic hard coat film 10 according to an embodiment of the present invention. As shown in FIG. 1, an antistatic hard coat film 10 according to an embodiment of the present invention includes a base 11, a hard coat layer 12 formed on the base 11, and an antireflection formed on the hard coat layer. Layer 13 is provided. The hard coat layer 12 includes a π-conjugated conductive polymer and a quaternary ammonium salt conductive monomer or a polymer thereof. By using the hard coat layer 12 according to the embodiment of the present invention, the antistatic hard coat film 10 can be formed without separately laminating the antistatic layer. The antireflection layer 13 is formed of one layer or a plurality of layers.

  The hard coat layer 12 of the antistatic hard coat film 10 according to the embodiment of the present invention contains a π-conjugated conductive polymer and a quaternary ammonium salt conductive monomer or a polymer thereof, thereby providing excellent transmission. Good conductivity can be obtained without depending on the surrounding environment (humidity) without deterioration of conductivity after the rate and light resistance test. Π-conjugated conductive polymer that has excellent conductivity but is colored, has low transmittance, and its conductivity deteriorates in the light resistance test. It is excellent in light resistance because the component does not absorb light, but it can be used in combination with a quaternary ammonium salt-based conductive monomer or polymer thereof whose conductivity greatly depends on the surrounding environment (humidity). Thus, it is possible to form the antistatic hard coat film 10 which is excellent in transmittance and light resistance and gives good conductivity without depending on the surrounding environment (humidity).

The antistatic hard coat film 10 according to the embodiment of the present invention has a total light transmittance of 91% or more and a surface resistance value of 1 × 10 ¹⁰ when the hard coat layer 12 is laminated on the substrate 11. (Ω / cm ² ) or less. Although the hard coat layer 12 contains a π-conjugated conductive polymer having an electron conduction mechanism, it has a high transmittance (91% or more) and a surface resistance value of 1 × 10 ¹⁰ ( Ω / cm ² ) or less.

  In the present invention, the transmittance is the total light transmittance and is measured based on JIS K 7105 (1981). In the present invention, the surface resistance value is measured based on JIS K 6911 (1995).

The antistatic hard coat film 10 according to the embodiment of the present invention is an ultraviolet carbon arc lamp type light resistance tester defined in JIS B 7751 (1990) when the hard coat layer 12 is laminated on the substrate 11. The surface resistance value after storage for 100 hours is 1 × 10 ¹⁰ (Ω / cm ² ) or less. When a π-conjugated conductive polymer is used as the antistatic material for the hard coat layer 12, the light resistance is poor, and the surface resistance is increased by the light resistance test. By combining with a quaternary ammonium salt conductive material, it is possible to form the antistatic hard coat film 10 that suppresses an increase in surface resistance due to a light resistance test.

More preferably, when the hard coat layer 12 is laminated on the substrate 11, the surface resistance value after storage for 500 hours in an ultraviolet carbon arc lamp type light resistance tester defined in JIS B 7751 (1990) is 1 ×. 10 ¹⁰ (Ω / cm ² ) or less. When the surface resistance value after storage for 500 hours is 1 × 10 ¹⁰ (Ω / cm ² ) or less, the antistatic hard coat film 10 having extremely high light resistance can be obtained.

The antistatic hard coat film 10 according to the embodiment of the present invention is measured in an environment having a temperature of 20 ° C. to 40 ° C. and a humidity of 20% to 80% when the hard coat layer 12 is laminated on the substrate 11. The surface resistance value is 1 × 10 ¹⁰ (Ω / cm ² ) or less. When a quaternary ammonium salt conductive material is used as the antistatic material of the hard coat layer 12, the surface resistance increases with a decrease in humidity from the conductive mechanism, and the surrounding environment is greatly affected. By having both the π-conjugated conductive polymer and the quaternary ammonium salt conductive material, the antistatic hard coat film 10 having excellent conductivity that does not depend on the surrounding humidity environment can be formed.

  As the base material 11 of the antistatic hard coat film 10 according to the embodiment of the present invention, films or sheets made of various organic polymers can be used. For example, the base material 11 normally used for optical members, such as a display, is mentioned, In consideration of various physical properties, such as optical characteristics, such as transparency and the refractive index of light, and also impact resistance, heat resistance, and durability. Polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polyethylene naphthalate, celluloses such as triacetyl cellulose, diacetyl cellulose and cellophane, polyamides such as 6-nylon and 6,6-nylon, polymethyl methacrylate And those made of organic polymers such as acrylic, polystyrene, polyvinyl chloride, polyimide, polyvinyl alcohol, polycarbonate, ethylene vinyl alcohol and the like. Among the base materials 11 described above, polyethylene terephthalate, triacetyl cellulose, polycarbonate, and polymethyl methacrylate are particularly preferable. Furthermore, it is possible to use those organic polymers that have been added with functions by adding additives such as ultraviolet absorbers, infrared absorbers, plasticizers, lubricants, colorants, antioxidants, flame retardants, and the like. it can.

  The hard coat layer 12 of the antistatic hard coat film 10 according to the embodiment of the present invention contains a hard coat material. The hard coat material is formed on the substrate 11, and an ionizing radiation curable material such as an ultraviolet curable material or an electron beam curable material can be used. As an ultraviolet curable material or an electron beam curable material, for the purpose of modifying the surface of the hard coat layer 12 and the surface of the antireflection layer 13, scratch resistance by a steel wool rubbing test, surface hardness by a pencil scratch test, and adhesion A resin can be selected and used so as to satisfy required specifications for various properties such as adhesion by a tape peeling test and cracking by a minimum bending test.

  Examples of the photopolymerizable polymer used as the ionizing radiation curable material include prepolymers such as polyester acrylate, epoxy acrylate, urethane acrylate, and polyol acrylate. These photopolymerizable polymers may be used alone or in combination of two or more.

  Examples of the photopolymerizable monomer used as the ionizing radiation curable material include polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol (meth) acrylate, and pentaerythritol tris. (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like. In particular, in the embodiment of the present invention, the hard coat layer 12 is preferably made of a polymer mainly composed of a polyfunctional monomer having a (meth) acryloyloxy group.

  In addition, a photopolymerization initiator is added to the hard coat material as necessary. As the photopolymerization initiator, for example, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, etc. may be used.

  Examples of the quaternary ammonium conductive monomer contained in the hard coat layer 10 of the antistatic hard coat film 10 according to the embodiment of the present invention include a (meth) acryl monomer containing a quaternary ammonium cation or a polymer thereof. be able to.

  In the embodiment of the present invention, “(meth) acrylic monomer” indicates both “acrylic monomer” and “methacrylic monomer”.

Examples of the (meth) acrylic monomer containing a quaternary ammonium cation include the following (Chemical Formula 1).

In this case, X ⁻ may be Cl ⁻ , Br ⁻ , I ⁻ , F ⁻ , HSO ₄ ⁻ , SO ₄ ²⁻ , NO ₃ ⁻ , PO ₄ ³⁻ , HPO ₄ ²⁻ , H ₂ PO ₄ ⁻ , SO _3. ^-, OH ^-, and the like can be given

R ₁ , R ₂ , R ₃ and R ₄ are selected from a hydrogen group or an organic group, and at least one of R ₁ , R ₂ , R ₃ and R ₄ is a (meth) acrylic group. Including. R ₁ , R ₂ , R ₃ , and R ₄ may be cyclically bonded to each other.

  The π-conjugated conductive polymer contained in the hard coat layer 12 of the antistatic hard coat film 10 according to the embodiment of the present invention is polyacetylene, polyaniline, polythiophene, polypyrrole, polyphenylene sulfide, poly (1,6-heptadiyne). ), Polybiphenylene (polyparaphenylene), polyparafinylene sulfide, polyphenylacetylene, poly (2,5-thienylene) and their derivatives, or a mixture of two or more thereof can be used. As these π-conjugated conductive polymers, a heat-drying type or an ionizing radiation curable type conductive organic material that is cured by irradiating with an ionizing irradiation ray such as ultraviolet rays can be used. Among these, polythiophene and derivatives thereof can be suitably used as the π-conjugated conductive polymer.

  The antistatic hard coat film 10 according to the embodiment of the present invention can be formed by applying a coating liquid for forming the hard coat layer 12 containing a conductive material on the substrate 11 by a wet film forming method. it can.

  A (meth) acrylic monomer having no quaternary ammonium cation or a polymer thereof can be added to the coating liquid for forming the hard coat layer 12 for the purpose of improving the surface hardness.

  Examples of (meth) acrylic monomers having no quaternary ammonium cation include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and nonanediol. Di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate Di (meth) acrylates such as tripropylene glycol di (meth) acrylate and hydroxypivalate neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxy Trimethylolpropane tri (meth) acrylate, tris 2-hydroxyethyl isocyanurate tri (meth) acrylate, tri (meth) acrylate such as glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri ( Trifunctional (meth) acrylate compounds such as (meth) acrylate and ditrimethylolpropane tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate Rate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane It is possible to use a polyfunctional (meth) acrylate compound having three or more functional groups such as hexa (meth) acrylate, or a polyfunctional (meth) acrylate compound in which a part of these (meth) acrylates is substituted with an alkyl group or ε-caprolactone. it can.

  At this time, a solvent is added to the coating liquid for forming the hard coat layer 12 as necessary. By adding a solvent, coating suitability can be improved. Solvents include aromatic hydrocarbons such as toluene, xylene, cyclohexane and cyclohexylbenzene, hydrocarbons such as n-hexane, dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, dioxane, dioxolane, and trioxane. , Ethers such as tetrahydrofuran, anisole and phenetole, and ketones such as methyl isobutyl ketone, methyl butyl ketone, acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, and methylcyclohexanone , Ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, Esters such as acid n-pentyl and γ-ptyrolactone, cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, cellosolve acetate, alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, ethylene glycol It is appropriately selected from water and the like in consideration of appropriate coating.

  In the coating liquid for forming the hard coat layer 12, an additive called a surface conditioner is used to prevent the occurrence of coating film defects such as repellency and unevenness in the coating film formed on the base material 11. May be added. The surface modifier is also called a leveling agent, an antifoaming agent, an interfacial tension modifier, or a surface tension modifier depending on its function, and all have a function of reducing the surface tension of the coating film to be formed.

  Further, in the coating liquid for forming the hard coat layer 12, other additives may be added to the coating liquid in addition to the surface conditioner described above. As the functional additive, an ultraviolet absorber, an infrared absorber, an adhesion improver, a curing agent, or the like can be used.

  The hard coat layer 12 can be formed by applying a coating solution for forming the hard coat layer 12 obtained by adjusting the materials described above onto the substrate 11 by a wet film forming method to form a coating film. In the case of using an ionizing radiation curable material, the hard coat layer 12 is formed by irradiating ultraviolet rays or electron beams as ionizing radiation after drying the coating film as necessary. . In the case where a heat drying type material is used as the binder matrix forming material, the hard coat layer 12 is formed by drying, heating, or the like.

  At this time, as a wet film forming method, a coating method using a roll coater, a reverse roll coater, a gravure coater, a micro gravure coater, a knife coater, a bar coater, a wire bar coater, a die coater, or a dip coater can be used.

  In addition, the antistatic hard coat film 10 according to the embodiment of the present invention can form the antireflection layer 13 on the hard coat layer 12. Hereinafter, although an example regarding the antireflection layer 13 is described, the embodiment of the present invention is not limited thereto.

  The antistatic hard coat film 10 according to the embodiment of the present invention has a total light transmittance of 94% or more when the base material 11, the hard coat layer 12, and the antireflection layer 13 are laminated. By laminating the antireflection layer 13 on the hard coat layer 12 of the antistatic hard coat film 10 according to the embodiment of the present invention having a high transmittance, a high transmittance (94% or more) due to its antireflection performance. The antistatic hard coat film 10 can be formed.

  The case where a coating liquid for forming a low refractive index layer containing low refractive index particles and a binder matrix forming material is applied to the surface of the hard coat layer 12 as the antireflection layer 13 and a wet film forming method is used will be described. At this time, the film thickness (d) of the single layer of the low refractive index layer which is the antireflection layer 13 is an optical film thickness obtained by multiplying the film thickness (d) by the refractive index (n) of the low refractive index layer ( nd) is designed to be equal to ¼ of the wavelength of visible light. As the low refractive index layer, a layer in which low refractive particles are dispersed in a binder matrix can be used. Here, the antireflection layer 13 may be referred to as a low refractive index layer.

The low-refractive particles are made of a low-refractive material such as LiF, MgF, 3NaF.AlF or AlF (all having a refractive index of 1.4), or Na ₃ AlF ₆ (cryolite, having a refractive index of 1.33). Low refractive index particles can be used. Moreover, the particle | grains which have a space | gap inside a particle | grain can be used suitably. In the case of particles having voids inside the particles, the voids can be made to have a refractive index of air (≈1), so that they can be low refractive index particles having a very low refractive index. Specifically, porous silica particles and low refractive index silica particles having voids inside can be used.

  The low refractive index particles used in the low refractive index layer preferably have a particle size of 1 nm to 100 nm. More preferably, the particle size is 30 nm or more and 70 nm or less. When the particle diameter exceeds 100 nm, light is remarkably reflected by Rayleigh scattering, and the low refractive index layer tends to be whitened and the transparency of the antireflection film tends to be lowered. On the other hand, when the particle size is less than 1 nm, problems such as non-uniformity of particles in the low refractive index layer due to aggregation of particles occur.

As the binder matrix forming material, a hydrolyzate of silicon alkoxide can be used. Furthermore, the silicon alkoxide represented by the general formula (1), R _x Si (OR) _4-x (wherein R represents an alkyl group and x is an integer satisfying 0 ≦ x ≦ 3). Hydrolyzate can be used.

  Examples of the silicon alkoxide represented by the general formula (1) include tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, and tetra-sec-butoxy. Silane, tetra-tert-butoxysilane, tetrapentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-proxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyl Trimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethan Kishishiran, dimethyl propoxysilane, dimethyl-butoxy silane, can be used methyl dimethoxysilane, methyl diethoxy silane, hexyl trimethoxy silane. The hydrolyzate of silicon alkoxide may be obtained by using a metal alkoxide represented by the general formula (1) as a raw material. For example, it can be obtained by hydrolysis with hydrochloric acid.

Furthermore, as a binder matrix forming material for the low refractive index layer, the silicon alkoxide represented by the general formula (1) may be replaced with the general formula (2), R ′ _z Si (OR) _4-z (where R is 'Represents a non-reactive functional group having an alkyl group, a fluoroalkyl group or a fluoroalkylene oxide group, and z is an integer satisfying 1 ≦ z ≦ 3). Accordingly, antifouling property can be imparted to the surface of the low refractive index layer (antireflection layer 13) of the antistatic hard coat film 10, and the refractive index of the low refractive index layer can be further reduced.

  Examples of the silicon alkoxide represented by the general formula (2) include octadecyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane, and the like.

  An ionizing radiation curable material can also be used as the binder matrix forming material. As the ionizing radiation curable material, the photopolymerizable polymer and the photopolymerizable monomer exemplified as the hard coat material can be used, and polyfunctional acrylates such as polyfunctional urethane acrylate can be used. Besides these, as ionizing radiation type materials, polyether resins having an acrylate functional group, polyester resins, epoxy resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and the like can be used. .

  In addition, a solvent and various additives can be added to the formation coating liquid of a low refractive index layer as needed. Solvents include aromatic hydrocarbons such as toluene, xylene, cyclohexane and cyclohexylbenzene, hydrocarbons such as n-hexane, dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, dioxane, dioxolane, and trioxane. , Ethers such as tetrahydrofuran, anisole and phenetole, and ketones such as methyl isobutyl ketone, methyl butyl ketone, acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, and methylcyclohexanone , Ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, Suitable for coating from among esters such as acid n-pentyl and γ-ptyrolactone, cellosolves such as methyl cellosolve, cellosolve, butyl cellosolve, cellosolve acetate, alcohols such as methanol, ethanol, isopropyl alcohol, water, etc. Etc. are selected as appropriate. Moreover, a surface adjusting agent, a leveling agent, a refractive index adjusting agent, an adhesion improver, a photosensitizer, etc. can be added to the coating liquid as additives.

  Further, when an ionizing radiation curable material is used as the binder matrix forming material and the low refractive index layer is formed by irradiating with ultraviolet rays, a photopolymerization initiator is added to the coating liquid. Examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, and the like.

  A coating solution for forming a low refractive index layer obtained by adjusting the above materials is applied onto the hard coat layer 12 by a wet film forming method to form a coating film, and a low refractive index layer (antireflection layer 13) is formed. Can be formed. When ionizing radiation curable materials are used as the binder matrix forming material, the coating film is dried if necessary, and then irradiated with ultraviolet rays or electron beams, which are ionizing radiation, to reduce the refractive index. A layer is formed. Further, when a metal alkoxide is used as the binder matrix forming material, the low refractive index layer is formed by drying, heating, or the like.

  At this time, as a wet film forming method, a coating method using a roll coater, a reverse roll coater, a gravure coater, a micro gravure coater, a knife coater, a bar coater, a wire bar coater, a die coater, or a dip coater can be used.

  The antistatic hard coat film 10 according to the embodiment of the present invention can be suitably used for the display surface. Examples of the display include LCD, PDP, CRT, projection display, EL display and the like. It can also be used inside a display. Hereinafter, the case where the antistatic hard coat film 10 which concerns on embodiment of this invention is used as a member of a liquid crystal display is demonstrated.

  FIG. 2 is a schematic sectional view showing a polarizing plate 20 having the antistatic hard coat film 10 according to the embodiment of the present invention. The polarizing plate 20 according to the embodiment of the present invention includes a polarizing layer 22 and a base material 21 in this order on the surface of the base material 11 opposite to the surface on which the hard coat layer 12 is formed. The polarizing plate 20 according to the embodiment of the present invention has a structure in which a polarizing layer 22 is sandwiched between two substrates 11 and 21. Polarized light having excellent conductivity without depending on the surrounding environment (humidity) by forming the polarizing plate 20 using the antistatic hard coat film 10 according to the embodiment of the present invention. A board can be obtained.

  3A and 3B are schematic cross-sectional views showing transmissive liquid crystal displays 60 and 70 having the antistatic hard coat film 10 according to the embodiment of the present invention. The transmissive liquid crystal display 60 shown in FIG. 3A includes a backlight unit 50, a polarizing plate 40, a liquid crystal cell 30, a polarizing plate 20, and an antistatic hard coat film 10 in this order. At this time, the formation surface side of the antireflection layer 13 of the antistatic hard coat film 10 becomes the observation side, that is, the display surface.

  The backlight unit 50 includes a light source and a light diffusion plate. The liquid crystal cell 30 includes an electrode on one base material and an electrode and a color filter on the other base material. That is, it has a structure in which liquid crystal is sealed between both electrodes. The polarizing plates 20 and 40 provided so as to sandwich the liquid crystal cell 30 have a structure in which the polarizing layers 22 and 42 are sandwiched between the base materials 21, 23, 41, and 43.

  The transmissive liquid crystal display 60 shown in FIG. 3A is a transmissive liquid crystal display 60 provided with the base material 11 of the antistatic hard coat film 10 and the base materials 21 and 23 of the polarizing plate 20 separately. On the other hand, the transmissive liquid crystal display 70 shown in FIG. 3B is the transmissive liquid crystal display 70 having the polarizing plate 20 shown in FIG. 2 and is opposite to the antireflection layer 13 of the base material 11 of the antistatic hard coat film 10. A polarizing layer 22 is provided on the side surface, and the base material 11 has a structure that serves as the base material of the antistatic hard coat film 10 and the base material 21 of the polarizing plate 20.

  In addition, the transmissive liquid crystal displays 60 and 70 according to the embodiment of the present invention may include other functional members. As other functional members, for example, a diffusion film, a prism sheet, a brightness enhancement film, and a phase difference between the liquid crystal cell 30 and the polarizing plates 20 and 40 for effectively using light emitted from the backlight unit 50 are compensated. For example, the transmissive liquid crystal displays 60 and 70 according to the embodiment of the present invention are not limited to these. In addition, these can use a well-known thing.

  By forming a display using the antistatic hard coat film 10 according to the embodiment of the present invention, a display having excellent transmittance and light resistance and having good conductivity independent of the surrounding environment (humidity) is obtained. be able to.

  EXAMPLES The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

  According to the following adjustment examples 1 to 4, the coating liquid for forming the hard coat layer 12 was adjusted. Moreover, according to the adjustment example 5, the coating liquid for forming the low refractive index layer (antireflection layer) 13 was adjusted.

[Adjustment Example 1]
(Coating liquid 1 for forming hard coat layer 12)
Baytron P CH 8000 containing π-conjugated conductive polymer (manufactured by AC Starck Co., Ltd. (solid content 3%)) 16 parts by weight, light ester DQ100 containing quaternary ammonium cation (manufactured by Kyoeisha Chemical Co., Ltd.) 5 weights Parts, 25 parts by mass of dipentaerythritol triacrylate, 25 parts by mass of pentaerythritol tetraacrylate, 50 parts by mass of urethane acrylate, 5 parts by mass of Irgacure 184 (manufactured by Ciba Specialty Chemicals (photopolymerization initiator)), and dissolved in methyl ethyl ketone. Then, the forming coating liquid 1 for the hard coat layer 12 was prepared.

[Adjustment Example 2]
(Coating liquid 2 for forming hard coat layer 12)
33 parts by weight of Baytron P CH 8000 (manufactured by H.C. Starck (solid content 3%)) containing π-conjugated conductive polymer, 25 parts by mass of dipentaerythritol triacrylate, 25 parts by mass of pentaerythritol tetraacrylate, Using 50 parts by mass of urethane acrylate and 5 parts by mass of Irgacure 184 (manufactured by Ciba Specialty Chemicals (photopolymerization initiator)), the coating solution 2 for forming the hard coat layer 12 was prepared by dissolving in methyl ethyl ketone.

[Adjustment Example 3]
(Coating liquid 3 for forming hard coat layer 12)
10 parts by weight of light ester DQ100 containing quaternary ammonium cation (manufactured by Kyoeisha Chemical Co., Ltd.), 25 parts by mass of dipentaerythritol triacrylate, 25 parts by mass of pentaerythritol tetraacrylate, 50 parts by mass of urethane acrylate, Irgacure 184 (manufactured by Ciba Specialty Chemicals) (Photopolymerization initiator) Using 5 parts by mass, the coating solution 3 for forming the hard coat layer 12 was prepared by dissolving in methyl ethyl ketone.

[Adjustment Example 4]
(Coating liquid 4 for forming hard coat layer 12)
Using 25 parts by mass of dipentaerythritol triacrylate, 25 parts by mass of pentaerythritol tetraacrylate, 50 parts by mass of urethane acrylate, and 5 parts by mass of Irgacure 184 (manufactured by Ciba Specialty Chemicals (photopolymerization initiator)), dissolved in methyl ethyl ketone. The coating solution 4 for forming the hard coat layer 12 was prepared.

[Adjustment Example 5]
(Coating liquid for forming low refractive index layer 13)
Porous silica fine particle dispersion (average particle size 50 nm, solid content 20%, solvent: methyl isobutyl ketone) 14.94 parts by weight, EO-modified dipentaerythritol hexaacrylate (trade name: DPEA-12, manufactured by Nippon Kayaku Co., Ltd.) 1 .99 parts by weight, polymerization initiator (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 184), 0.07 parts by weight, TSF4460 (trade name, manufactured by GE Toshiba Silicone Co., Ltd .: alkyl polyether-modified silicone oil) ) 0.20 part by weight was diluted with 82 parts by weight of methyl isobutyl ketone as a solvent to prepare a coating solution for forming the low refractive index layer 13.

[Example 1]
(Formation of hard coat layer 12)
First, as shown in FIG. 1, a triacetyl cellulose film (manufactured by Fuji Film) having a film thickness of 80 μm was used for the base material 11. Next, the coating liquid 1 for forming the hard coat layer 12 is applied onto the substrate 11 and dried in an oven at 80 ° C. for 60 seconds. After drying, an ultraviolet irradiation device (Fusion UV System Japan, light source H bulb) is used. Then, a transparent hard coat layer 12 having a dry film thickness of 5 μm was formed by performing ultraviolet irradiation at an irradiation dose of 300 mJ / m ² .

(Formation of the low refractive index layer 13)
Next, a coating liquid for forming the low refractive index layer (antireflection layer) 13 was applied on the hard coat layer 12 so that the film thickness after drying was 100 nm. An antistatic hard coat film 10 was obtained by forming the low refractive index layer 13 by irradiating with an ultraviolet ray irradiation at an irradiation dose of 192 mJ / m ² using an ultraviolet ray irradiation device (Fusion UV System Japan, light source H bulb).

[Comparative Example 1]
An antistatic hard coat film 10 was obtained in the same manner as in Example 2 except that the coating liquid 2 for forming the hard coat layer 12 was used.

[Comparative Example 2]
An antistatic hard coat film 10 was obtained in the same manner as in Example 2 except that the coating liquid 3 for forming the hard coat layer 12 was used.

[Comparative Example 3]
An antistatic hard coat film 10 was obtained in the same manner as in Example 2 except that the coating liquid 4 for forming the hard coat layer 12 was used.

  The antireflection hard coat film 10 obtained in Example 1 and Comparative Examples 1 to 3 was evaluated by the following method.

(Spectral reflectance, average luminous reflectance)
About the surface of the low refractive index layer 13 of the obtained antistatic hard coat film 10, the spectral reflectance at an incident angle of 5 ° was measured using an automatic spectrophotometer (manufactured by Hitachi, Ltd., U-4000). Further, the average luminous reflectance was obtained from the obtained spectral reflectance curve. In the measurement, a matte black paint was applied to the surface of the triacetyl cellulose film as the substrate 11 where the low refractive index layer 13 was not formed, and an antireflection treatment was performed.

(Surface resistance value)
The surface resistance value of the surface of the low refractive index layer 13 of the obtained antistatic hard coat film 10 was measured according to JIS K 6911. Further, the obtained anti-static hard coat film 10 was stored for 100 hours and 500 hours using an ultraviolet carbon arc lamp type light resistance tester stipulated in JIS B 7751 (1990). The surface resistance value of the surface of the low refractive index layer 13 of the coat film 10 was measured according to JIS K 6911 (1995).

(Total light transmittance and haze value)
About the obtained antistatic hard coat film 10, the total light transmittance and the haze value are measured based on JIS K 7105 (1981) using an image clarity measuring device (manufactured by Nippon Denshoku Industries Co., Ltd., NDH-2000). did.

(Pencil hardness)
The surface of the low refractive index layer 13 of the obtained antistatic hard coat film 10 was evaluated with a load of 500 g by a test method according to JIS K 5600-5-4 (1999).

  The evaluation results are shown in Table 1. As for “3H-5 / 5” in pencil hardness, the surface of the low-refractive index layer of the antistatic film was subjected to a pencil hardness test 5 times using a 3H pencil, and no flaws were confirmed in all 5 times. Represents.

  As shown in Table 1, in the antistatic hard coat film 10 of Example 2, good conductivity was exhibited even after 23 ° C.-25% environment and light resistance test. Moreover, the antistatic hard coat film 10 having a high total light transmittance is obtained. From this, the antistatic hard coat film 10 of the present invention did not change the conductivity even in the environment and light resistance test, and the antistatic hard coat film 10 having high transmittance could be obtained.

DESCRIPTION OF SYMBOLS 10 ... Antistatic hard coat film, 11 ... Base material, 12 ... Hard coat layer, 13 ... Antireflection layer, 20 ... Polarizing plate, 21 ... Base material, 22 ... Polarizing layer, 23 ... Base material, 30 ... Liquid crystal cell, 4
DESCRIPTION OF SYMBOLS 0 ... Polarizing plate, 41 ... Base material, 42 ... Polarizing layer, 43 ... Base material, 50 ... Backlight unit, 6
0 and 70: transmissive liquid crystal display

Claims (9)

A substrate;
A hard coat layer containing a π-conjugated conductive polymer and a quaternary ammonium salt conductive monomer or a polymer thereof on the substrate;
An antistatic hard coat film comprising: ^2. The antistatic hard coat film according to claim 1, wherein the total light transmittance is 91% or more and the surface resistance value is 1 × 10 ¹⁰ (Ω / cm ² ) or less. The surface resistance value after storage for 100 hours in an ultraviolet carbon arc lamp type light resistance tester specified in JIS B 7751 is 1 × 10 ¹⁰ (Ω / cm ² ) or less. The antistatic hard coat film as described in 1. The surface resistance value after storage for 500 hours in an ultraviolet carbon arc lamp type light resistance tester specified in JIS B 7751 is 1 × 10 ¹⁰ (Ω / cm ² ) or less. The antistatic hard coat film according to any one of the above. 5. The surface resistance value measured in an environment where the temperature is 20 ° C. to 40 ° C. and the humidity is 20% to 80% is 1 × 10 ¹⁰ (Ω / cm ² ) or less. An antistatic hard coat film according to claim 1.   The antistatic hard coat film according to any one of claims 1 to 5, wherein an antireflection layer comprising one layer or a plurality of layers is formed on the hard coat layer.   7. The antistatic hard coat film according to claim 6, wherein the total light transmittance is 94% or more.   A polarizing plate comprising the antistatic hard coat film according to claim 1.   A display comprising the antistatic hard coat film according to claim 1.

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