JP2011174975A - Hard coat film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hard coat film forming a hard coat layer which has a high contamination-proof function and antistatic function, has high adhesion with a base material, has high curling resistance, scratch resistance, and surface hardness, from which contamination (dust, fingerprint, or the like) is readily removed, and which has high visibility at all times, without degrading the characteristics. <P>SOLUTION: In the hard coat film, the hard coat layer contains a multifunctional (meth)acrylic monomer, photoradical polymerization initiator, fluorine-containing compound having a polymerization group, and metal oxidation fine particles having electrostatic properties. The additive amount of metal oxidation fine particles is 1.0-10.0 wt.% to the multifunctional (meth)acrylic monomer. The surface free energy is 15-20 mN/m or lower, the surface resistance value is 5E<SP>+9</SP>-2.0E<SP>+10</SP>Ω or lower, and the film thickness of the hard coat layer is 3-10 μm. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a hard coat layer forming composition and a hard coat film, which are used for the purpose of protecting the surface of a display such as a liquid crystal display (LCD), a plasma display panel (PDP), and a field emission display (FED). A composition for forming a hard coat layer that has high adhesion to a substrate, has excellent curl resistance and antifouling properties, and can impart excellent scratch resistance, antistatic properties, and surface hardness. It relates to the hard coat film used.

  A protective film for a circularly polarizing plate used for a polarizing plate protective film for a liquid crystal display, an organic EL display, or the like has a resin layer formed to have various functions. For example, an antistatic layer for providing an antistatic function, an antireflection layer for suppressing reflection, and a hard coat layer for improving surface hardness. In particular, the hard coat layer is indispensable for display applications, and is not only used as a single hard coat layer but also serves as a lower layer of an antireflection layer, which is an important technique.

  For example, Patent Document 1 discloses a thermoplastic norbornene-based material having a silicone-based hard coat layer having an adhesion in a cross-cut peel test of 50 or more in 100 on the surface of a substrate formed of a thermoplastic norbornene-based resin. A molded article made of a resin is disclosed, and Patent Document 2 is formed from a coating film component containing one or more organic components having a polymerizable functional group and an inorganic filler, and at least one of the organic components is A hard coat film for a plastic substrate film characterized by not having a hydrogen bond-forming group is disclosed. Patent Document 3 discloses a hard coat film which is a cured coating film layer on at least one surface of a transparent plastic film substrate. A hard coat film having a layer, wherein the hard coat layer forming material comprises urethane acrylate (A), isocyanuric acid acrylate (B) and Hard coat film characterized by containing inorganic ultrafine particles (B) is disclosed.

  In recent years, the demand for increasing the hardness of a hard coat film provided with a hard coat layer as a protective function of these polarizing plates has become very high. However, cellulose ester films are mainly used as the hard coat film substrate for the protective film of these polarizing plates, but since this film substrate is soft, it is very difficult to increase the hardness as a hard coat film. is there.

  In addition, as the application application of these polarizing plates spreads widely to liquid crystal televisions, notebook computers, etc., various characteristics are required, antireflection function with less reflection of fluorescent light, antistatic function that is hard to get dust, Characteristics such as an antifouling function capable of wiping off fingerprints have been required. In particular, notebook computers and the like often have fingerprints, sebum, sweat, cosmetics and the like attached by human use, and liquid crystal televisions and the like cause a decrease in contrast and flickering of the screen due to the adhesion of dust. Generally, since the surface energy of a polarizing plate is large, such dirt is likely to adhere. Moreover, since the surface of the antireflection film has fine irregularities, it is not easy to remove the dirt. Furthermore, only the portion where such dirt is attached becomes highly reflective, and there is a problem because the dirt is conspicuous.

  Therefore, as a means for solving these problems of contamination, there is a technology for forming an antifouling layer having a performance that makes it difficult for dirt to adhere and easily wipe off even if it adheres, and an antistatic layer that prevents the adhesion of dust on the surface of the optical member. Various proposals have been made.

  For example, Patent Document 4 discloses an anti-fouling and friction-resistant anti-reflection article in which an anti-reflection film mainly composed of silicon dioxide is provided on the surface of a base material and the surface is further treated with a compound containing an organosilicon substituent. Has been proposed. Patent Document 5 similarly proposes an antifouling and friction-resistant CRT filter in which the substrate surface is coated with a terminal silanol organopolysiloxane. Further, Patent Document 6 proposes an antifouling and low-reflective plastic having an antireflection film on its surface containing mono- and disilane compounds containing polyfluoroalkyl groups and halogen, alkyl or alkoxy silane compounds. ing.

  However, the antifouling layer formed by the conventional method has insufficient antifouling properties, and in particular, dirt such as fingerprints, sebum, sweat and cosmetics is difficult to wipe off, and the antifouling performance decreases greatly with use. In addition, in order to prevent the adhesion of dust, it is necessary to install another antistatic layer, which causes problems such as an increase in coating cost and adhesion. For this reason, the development of a hard coat layer having excellent antifouling properties and durability and imparted with antistatic properties by a simple technique is desired.

For example, Patent Document 7 uses conductive metal fine particles such as a tin oxide antistatic agent (SnO ₂ , ATO, ITO) as a component of the antistatic layer.

Japanese Unexamined Patent Publication No. 7-97468 JP 2000-159916 A JP 2006-106427 A Japanese Unexamined Patent Publication No. 1-086101 JP-A-4-338901 JP 61-247743 A JP 2006-337664 A

  None of the conventional hard coat films have antifouling properties such as fingerprint wiping properties, and even if antifouling properties are imparted, they have very weak antifouling performance. For this reason, there is a problem that fingerprints and the like are easily stained, and once attached, it is difficult to remove the stain. Even if the anti-smudge treatment is insufficient, simply wiping with ordinary paper or cloth will spread the dirt over the entire surface, and the contaminated surface will reflect external light, blocking transmitted light and displaying. There was a problem that the characteristics were remarkably lowered and the initial visibility could not be maintained.

  In addition, when a fluorine-based additive is added to impart antifouling properties to the hard coat surface, the normal fluorine-based additive does not have a reactive group, so the adhesion with the hard coat layer is not sufficient, When the surface is wiped, the antifouling component can be wiped off. Therefore, in general, many antifouling layers are provided separately from the hard coat layer to impart antifouling properties. Further, in order to prevent dust and the like, it is necessary to form another antistatic layer, and there are problems such as adhesion and coating cost.

  Accordingly, the object of the present invention is to solve such problems, and without providing a separate antifouling layer and antistatic layer, the hard coat layer is provided with an antifouling function and an antistatic function, In addition to having high adhesiveness, excellent curling resistance, scratch resistance, surface hardness can be imparted, dirt can be easily removed, and a hard coat layer with always high visibility can be formed without deterioration of its characteristics. The object is to provide a hard coat film using the composition for forming a hard coat layer.

As a means for solving the above problems, the invention according to claim 1 is the hard coat film in which the hard coat layer is laminated on at least one surface of the transparent substrate, wherein the hard coat layer is polyfunctional (meta). Addition of metal oxide fine particles (D) including acrylic monomer (A), photo radical polymerization initiator (B), fluorine-containing compound (C) having a polymerizable group, and metal oxide fine particles (D) having chargeability The surface of the hard coat layer is formed by using a hard coat layer-forming composition having an amount of 1.0 to 10.0% by weight based on the polyfunctional (meth) acrylic monomer (A). The energy is 15 mN / m to 20 mN / m or less, the surface resistance value is 5E ⁺⁹ Ω to 2.0E ⁺¹⁰ Ω or less, and the film thickness of the hard coat layer is 3 to 10 μm. It is a hard coat film.

  The invention according to claim 2 is the hard coat film according to claim 1, wherein the polyfunctional (meth) acrylic monomer (A) is mainly composed of urethane (meth) acrylate.

  In the invention according to claim 3, the addition amount of the fluorine-containing compound (C) having a polymerizable group is 0.01 to 10.0 with respect to the total of the polyfunctional (meth) acrylic monomer (A). It is weight%, It is a hard coat film in any one of Claims 1-2 characterized by the above-mentioned.

  The invention according to claim 4 is characterized in that the amount of the radical photopolymerization initiator (B) added is 0.01 to 10% by weight with respect to the polyfunctional (meth) acrylic monomer (A). It is a hard coat film in any one of Claims 1-3.

The invention according to claim 5 is characterized in that the charged metal oxide fine particles (D) include metal fine particles composed of one or more of SnO ₂ , ATO, ITO and the like. 4. The hard coat film according to any one of 4 above.

  According to the present invention, an antifouling layer and an antistatic layer are not separately provided, and the hard coat layer is provided with an antifouling function and an antistatic function, and has high adhesion to the substrate and is excellent. Hard coat layer forming composition and hard coat which can impart curl resistance, scratch resistance and surface hardness, can easily remove dirt, and can always form a hard coat layer with high visibility without deterioration of its properties Can provide film.

It is a schematic sectional drawing of the hard coat film of one Example of this invention.

  As a result of examining the imparting of antifouling properties and antistatic properties to the hard coat layer on the transparent substrate, the inventor of the present invention has a polyfunctional (meth) acrylic monomer (A) of the present invention and a hydroxyl group (meth). A composition for forming a hard coat layer comprising an acrylic monomer (B), a radical photopolymerization initiator (B), a fluorine-containing compound (C) having a polymerizable group, and metal oxide fine particles (D) having chargeability is used. Thus, the present inventors have found that the conventional problems can be solved.

  Hereinafter, embodiments of the present invention will be described in detail.

  The polyfunctional (meth) acrylic monomer (A) constituting the composition for forming a hard coat layer of the present invention has two or more hydroxyl groups of a polyhydric alcohol having two or more alcoholic hydroxyl groups in one molecule. A compound which is an esterified product of (meth) acrylic acid is preferred. Others include polyester acrylates, urethane acrylates, epoxy acrylates and polyether acrylates, including those with reactive acrylic groups bonded to acrylic resin skeletons, and rigid skeletons such as melamine and isocyanuric acid. An acrylic group-bonded one or the like can also be used, but in the present invention, particularly when a urethane (meth) acrylate monomer and / or oligomer is used, the hardness and flexibility of the hard coat layer can be remarkably improved.

  In the present invention, “(meth) acrylic monomer” indicates both “acrylic monomer” and “methacrylic monomer”. For example, “polyfunctional (meth) acrylic monomer” indicates both “polyfunctional acrylic monomer” and “polyfunctional methacrylic monomer”. Moreover, the polyfunctional (meth) acrylic monomer (A) of the present invention may be an oligomer.

  As the urethane acrylate as the polyfunctional (meth) acrylic monomer (A) preferred in the present invention, it is generally easy to react a polyester polyol with an isocyanate monomer or a product obtained by reacting a prepolymer with an acrylate monomer having a hydroxyl group. Can be mentioned.

  Specific examples include pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate toluene diisocyanate urethane prepolymer. Pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate isophorone diisocyanate urethane prepolymer, and the like can be used. Moreover, these monomers can be used 1 type or in mixture of 2 or more types. Further, these may be monomers in the coating liquid, or may be oligomers that are partially polymerized.

  Commercially available polyfunctional acrylic monomers include Mitsubishi Rayon Co., Ltd. (trade name “Diabeam” series, etc.), Nagase ChemteX Corporation (trade name “Denacol” series, etc.), Shin-Nakamura Chemical Co., Ltd .; (Product name “NK Ester” series, etc.), Dainippon Ink and Chemicals Co., Ltd .; (Product name “Unidic” series, etc.), Toa Gosei Co., Ltd. (product name “Aronix” series, etc.) (Product name "Blemmer" series, etc.), Nippon Kayaku Co., Ltd .; (Product name "KAYARAD" series, etc.), Kyoeisha Chemical Co., Ltd. (Product names "Light ester" series, "Light acrylate" series, etc.) Can be used.

  As the radical photopolymerization initiator (B) constituting the composition for forming a hard coat layer of the present invention, a compound that generates radicals by irradiating ionizing radiation and initiates a polymerization reaction of an acrylic monomer is preferable.

  Specific examples of the photo radical polymerization initiator (B) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4 ′. -Dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, p-isopropyl-α-hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2,2 -Carbonyl compounds such as dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, tetramethylthiuramdisulfur And sulfur compounds such as thioxanthone, 2-chlorothioxanthone and 2-methylthioxanthone can be used. These photopolymerization initiators may be used alone or in combination of two or more.

  The amount of the photo radical polymerization initiator (B) used in the present invention is such that the polyfunctional (meth) acrylic monomer (A) of the hard coat layer forming composition and the (meth) acrylic monomer (B) having the hydroxyl group are used. 0.01 to 10% by weight is appropriate based on the total. When the amount is less than 0.01% by weight, a sufficient curing reaction does not proceed when the ionizing radiation is irradiated. When the amount exceeds 10% by weight, the ionizing radiation does not reach the lower part of the hard coat layer.

  The amount of the fluorine-containing compound (C) having a polymerizable group of the present invention is such that the polyfunctional (meth) acrylic monomer (A) of the hard coat layer forming composition and the (meth) acrylic monomer having a hydroxyl group ( 0.01 to 10% by weight is suitable with respect to the sum of B). When the amount is less than 0.01% by weight, sufficient antifouling properties are not exhibited, and the surface energy is larger than 20 mN / m. There are cases where the scratch resistance is lowered and inconvenience such as poor surface quality is caused.

  As the fluorine-containing compound (C) having a polymerizable group constituting the hard coat layer forming composition of the present invention, it is possible to impart antifouling properties to the hard coat layer surface by adding a fluorine-based additive. However, in the case of a fluorine-based additive having no polymerizable group, the additive floats on the surface of the hard coat layer, so that it is removed from the surface of the hard coat by wiping with a cloth or the like. For this reason, once the surface is wiped with a cloth or the like, the antifouling property is lost. In the present invention, by adding a polymerizable group to the fluorine compound having antifouling properties, the fluorine additive is also polymerized at the time of forming the hard coat layer, and the antifouling properties can be obtained even if the surface is wiped with a cloth or the like. Has the advantage of being maintained.

  The fluorine-containing compound (C) having a polymerizable group of the present invention is more preferably a compound in which this polymerizable group has a (meth) acrylate group. This is because it can be copolymerized with a polyfunctional (meth) acrylate compound, and high hardness can be achieved by radical polymerization by ionizing radiation.

  As such a fluorine-containing compound (C) having a polymerizable group of the present invention, OPTOOL DAC (manufactured by Daikin Industries, Ltd.), SUA1900L10, SUA1900L6 (manufactured by Shin-Nakamura Chemical Co., Ltd.), UT3971 (Nihon Gosei Co., Ltd.) )), Defencer TF3001, Defencer TF3000, Defencer TF3028 (Dainippon Ink Co., Ltd.), Light Procoat AFC3000 (Kyoeisha Chemical Co., Ltd.), KNS5300 (Shin-Etsu Silicone Co., Ltd.), UVHC1105, UVHC8550 (GE) Toshiba Silicone Co., Ltd.).

  The amount of the fluorine-containing compound (C) having a polymerizable group of the present invention is such that the polyfunctional (meth) acrylic monomer (A) of the hard coat layer forming composition and the (meth) acrylic monomer having a hydroxyl group ( 0.01 to 10% by weight is suitable with respect to the sum of B). When the amount is less than 0.01% by weight, sufficient antifouling properties are not exhibited, and the surface energy is larger than 20 mN / m. When the amount exceeds 10% by weight, the compatibility with the polymerizable monomer and the solvent is high. Since it is not good, the coating liquid may become cloudy and precipitate may occur, which may cause inconveniences such as generation of defects in the coating liquid and hard coat layer.

  In the present invention, as a modifier for the hard coat layer, a coating property improver, an antifoaming agent, a thickener, an antistatic agent, inorganic particles, organic particles, an organic lubricant, an organic polymer compound, an ultraviolet ray, Absorbers, light stabilizers, dyes, pigments, stabilizers, and the like can be used, and these are used as a composition component of the coating layer constituting the hard coat layer within a range that does not impair the reaction by actinic radiation. Accordingly, the characteristics of the hard coat layer can be improved.

  In the present invention, the metal oxide fine particles (D) having chargeability are used as the hard coat layer forming composition, and an antistatic function can be easily provided at low cost without forming a separate antistatic layer.

  In the present invention, the amount of the metal oxide fine particles (D) having chargeability is 1.0 to 10% by weight based on the polyfunctional (meth) acrylic monomer (A) of the hard coat layer forming composition. Is appropriate. When the amount is less than 1.0% by weight, the antistatic property cannot be sufficiently exhibited, and there is a problem that dust and the like are easily attached. When it exceeds 10% by weight, the metal oxide fine particles having charging properties may be aggregated to cause defects such as defective foreign matters on the film surface.

  In the present invention, the method for curing the hard coat layer forming composition is preferably a method of irradiating actinic rays, particularly ultraviolet rays. When these methods are used, the hard coat layer forming composition is used. The product can be cured by ultraviolet irradiation by adding a radical photopolymerization initiator. In the ultraviolet irradiation, light having a wavelength of 400 nm or less may be used. For example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, a halogen lamp, or the like can be used. Moreover, you may add a heating process as needed.

  The composition for forming a hard coat layer of the present invention can be made into a hard coat film by coating on a substrate to form a hard coat layer.

  As a method for applying the hard coat layer forming composition, the hard coat layer forming composition may be applied using a known coating means such as a bar coater, applicator, doctor blade, roll coater, die coater, and comma coater. Can do.

  At this time, a solvent is added to the composition for forming a hard coat layer as necessary. Solvents include methyl isobutyl ketone, cyclohexanone, acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, cyclopentanone, methyl cyclohexanone, ethyl cyclohexanone, 2-butanone, ethyl formate, propyl formate, n-pentyl formate, methyl acetate, acetic acid Ethyl, methyl propionate, ethyl propionate, n-pentyl acetate, and γ-ptyrolactone, isobutyl acetate, butyl acetate, toluene, xylene, 2-propanol, 1-butanol, cyclopentanol, diacetone alcohol, ethylene glycol monomethyl ether , Propylene glycol monomethyl ether, dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, dioxane, dioxo Emissions, can be used trioxane, tetrahydrofuran, anisole, phenetole, methyl cellosolve, cellosolve, butyl cellosolve, cellosolve acetate, dichloromethane, trichloromethane, trichlorethylene, ethylene chloride, trichloroethane, tetrachloroethane, N, N- dimethylformamide, and chloroform. Note that the solvent is not limited to one type, and a plurality of solvents may be mixed to form a mixed solvent.

  As a base material, the film-form thing which has translucency is preferable, and should just have moderate transparency and mechanical strength as a base material. For example, polyethylene terephthalate (PET), cellulose triacetate (TAC), diacetyl cellulose, acetyl cellulose butyrate, polyethylene naphthalate (PEN), cycloolefin polymer, polyimide, polyethersulfone (PES), polymethyl methacrylate (PMMA), A film such as polycarbonate (PC) can be used. Among them, when a hard coat film is provided on the front surface of the liquid crystal display, cellulose triacetate (TAC) is preferably used because it has no optical anisotropy.

  In the present invention, a hard coat film having antifouling properties is provided. FIG. 1 shows an explanatory cross-sectional view of the hard coat film of the present invention. In the hard coat film of the present invention, the outermost layer is provided with a hard coat layer. At this time, the hard coat film of the present invention preferably has a surface energy of 20 mN / m or less on the surface of the hard coat layer.

  This is surface free energy as an index of a method for evaluating the antifouling property of the hard coat layer surface, and the presence / absence / absence of the antifouling property of the hard coat surface can be estimated from this surface energy. The surface free energy can be obtained from the surface contact angle by the extended Fowkes equation, and the smaller this value, the better the antifouling property. In the hard coat film of the present invention, since the surface energy is 20 mN / m or less, a hard coat film having high antifouling properties can be obtained.

As an index for evaluating the antistatic property of the hard coat layer surface, there is a surface electric resistance value, which is desirably 1.0E ⁺¹¹ [Ω] or less. If the value is larger than this, a problem such as dust adhering to the surface may occur. Since the surface resistance value of the hard coat film of the present invention is 5.0E ^{+ 09 to} 2.0E ^{+ 10} [Ω], it has high antistatic properties.

  Although the film thickness of the hard coat layer obtained by coating is determined by the required hardness, the preferable film thickness is 3 to 10 μm. When the film thickness is less than 3 μm, sufficient hardness cannot be obtained. On the other hand, when the film thickness exceeds 10 μm, the base material is extremely curled due to curing shrinkage of the hard coat layer, and problems such as breakage occur in the next process.

  The hard coat film of the present invention is provided with a functional layer as necessary. The functional layer is provided between the transparent substrate and the hard coat layer or on the transparent substrate surface on the side where the hard coat layer is not provided. Examples of these functional layers include an antireflection layer, an antiglare layer, an electromagnetic wave shielding layer, an infrared absorption layer, an ultraviolet absorption layer, and a color correction layer. These functional layers may be a single layer or a plurality of layers. A hard coat film in which a hard coat layer is formed on a transparent substrate and a hard coat film provided with these functional layers are bonded to various display surfaces such as a liquid crystal display, a plasma display, and a CRT display. Therefore, it is possible to provide a display having excellent scratch resistance and antifouling properties.

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

<Example 1>
Using a cellulose triacetate film substrate with a thickness of 80 μm,
-Urethane acrylate: UV-1700B (Nippon Synthetic Chemical) 79.5 parts by weight-Initiator: Irgacure 184 (Ciba Specialty Chemicals) 10.0 parts by weight-Fluorine-based additive: Defensa TF3001 (DIC) 0.5 part by weight Metal oxide fine particles: ATO fine particles 10.0 parts by weight mixed with a solvent (MEK / EtOH) and stirred to apply a coating solution to a cured film thickness of 5 μm by the bar coating method, dried, and 400 mJ with a metal halide lamp. A hard coat layer was formed by irradiating with / cm ² of ultraviolet rays. The total light transmittance, haze, scratch resistance test, pencil hardness, surface resistance value, and antifouling property measurement results of this hard coat film are summarized in (Table 1).

<Example 2>
Using a cellulose triacetate film substrate with a thickness of 80 μm,
-Urethane acrylate: UV-1700B (Nippon Synthetic Chemical) 79.5 parts by weight-Initiator: Irgacure 184 (Ciba Specialty Chemicals) 10.0 parts by weight-Fluorine-based additive: Optool DAC (Daikin Industries) 0.5 weight Part ・ Metal oxide fine particles: ATO fine particles 10.0 parts by weight mixed and stirred with a solvent (MEK / EtOH) was applied and dried to a cured film thickness of 5 μm by a bar coating method, and then a metal halide lamp was used. A hard coat layer was formed by irradiating ultraviolet rays of 400 mJ / cm ² . The total light transmittance, haze, scratch resistance test, pencil hardness, surface resistance value, and antifouling property measurement results of this hard coat film are summarized in (Table 1).

<Example 3>
Using a cellulose triacetate film substrate with a thickness of 80 μm,
-Urethane acrylate: UV-1700B (Nippon Synthetic Chemical) 81.5 parts by weight-Initiator: Irgacure 184 (Ciba Specialty Chemicals) 10.0 parts by weight-Fluorine-based additive: Optool DAC (Daikin Industries) 0.5 weight Part ・ Metal oxide fine particles: ATO fine particles 8.0 parts by weight mixed with a solvent (MEK / EtOH) and stirred, coated with a bar coating method to a cured film thickness of 5 μm, dried, and then with a metal halide lamp A hard coat layer was formed by irradiating ultraviolet rays of 400 mJ / cm ² . The total light transmittance, haze, scratch resistance test, pencil hardness, surface resistance value, and antifouling properties of the hard coat film are shown in Table 1.

<Example 4>
Using a cellulose triacetate film substrate with a thickness of 80 μm,
-Urethane acrylate: UV-1700B (Nippon Synthetic Chemical) 79.5 parts by weight-Initiator: esacure 150 (Lamberti) 10.0 parts by weight-Fluorine-based additive: Optool DAC (Daikin Industries) 0.5 part by weight-Metal Oxidized fine particles: ATO fine particles 10.0 parts by weight with a solvent (MEK / EtOH) mixed and stirred, applied to a cured film thickness of 5 μm by a bar coating method, dried, and 400 mJ / cm by a metal halide lamp. ² was irradiated to form a hard coat layer. The total light transmittance, haze, scratch resistance test, pencil hardness, surface resistance value, and antifouling properties of the hard coat film are shown in Table 1.

<Example 5>
Using a cellulose triacetate film substrate with a thickness of 80 μm,
Urethane acrylate: UA-306H (Kyoeisha Chemical) 79.5 parts by weight Initiator: Irgacure 184 (Ciba Specialty Chemicals) 10.0 parts by weight Fluorine-based additive: Defensa TF3001 (DIC) 0.5 part by weight Metal oxide fine particles: ATO fine particles 10.0 parts by weight mixed with a solvent (MEK / EtOH) and stirred to apply a coating solution to a cured film thickness of 5 μm by the bar coating method, dried, and 400 mJ / A hard coat layer was formed by irradiating ultraviolet rays of cm ² . The total light transmittance, haze, scratch resistance test, pencil hardness, surface resistance value, and antifouling properties of the hard coat film are shown in Table 1.

<Comparative Example 1>
Using a cellulose triacetate film substrate with a thickness of 80 μm,
-Urethane acrylate: UV-1700B (Nippon Synthetic Chemical) 89.5 parts by weight-Initiator: Irgacure 184 (Ciba Specialty Chemicals) 10.0 parts by weight-Fluorine-based additive: OPTOOL DAC (Daikin Industries) 0.5 weight the coating solution was mixed and stirred with the solvent (MEK / EtOH) to parts, a bar coating method by coating so as to cure the film thickness 5 [mu] m, dried, a hard coat layer was irradiated with ultraviolet rays of 400 mJ / cm ² by a metal halide lamp Formed. The total light transmittance, haze, scratch resistance test, pencil hardness, surface resistance value, and antifouling properties of the hard coat film are shown in Table 1.

<Comparative example 2>
Using a cellulose triacetate film substrate with a thickness of 80 μm,
-Urethane acrylate: UV-1700B (Nippon Synthetic Chemical) 74.5 parts by weight-Initiator: Irgacure 184 (Ciba Specialty Chemicals) 10.0 parts by weight-Fluorine-based additive: Optool DAC (Daikin Industries) 0.5 weight Part ・ Metal oxide fine particles: ATO fine particles 15.0 parts by weight with a solvent (MEK / EtOH) mixed and stirred, applied by a bar coating method to a cured film thickness of 5 μm, dried, and then with a metal halide lamp A hard coat layer was formed by irradiating ultraviolet rays of 400 mJ / cm ² . The total light transmittance, haze, scratch resistance test, pencil hardness, surface resistance value, and antifouling properties of the hard coat film are shown in Table 1.

<Comparative Example 3>
Using a cellulose triacetate film substrate with a thickness of 80 μm,
-Urethane acrylate: UV-1700B (Nippon Synthetic Chemical) 79.5 parts by weight-Initiator: Irgacure 184 (Ciba Specialty Chemicals) 10.0 parts by weight-Silicone-based additive: BYK-UV3500 (Bic Chemie) 0.5 weight Part ・ Metal oxide fine particles: ATO fine particles 10.0 parts by weight mixed and stirred with a solvent (MEK / EtOH) was applied and dried to a cured film thickness of 5 μm by a bar coating method, and then a metal halide lamp was used. A hard coat layer was formed by irradiating ultraviolet rays of 400 mJ / cm ² . The total light transmittance, haze, scratch resistance test, pencil hardness, surface resistance value, and antifouling properties of the hard coat film are shown in Table 1.

<Comparative example 4>
Using a cellulose triacetate film substrate with a thickness of 80 μm,
-Urethane acrylate: UV-1700B (Nippon Synthetic Chemical) 78.0 parts by weight-Initiator: Irgacure 184 (Ciba Specialty Chemicals) 10.0 parts by weight-Fluorine-based additive: OPTOOL DAC (Daikin Industries) 2.0 weight Part ・ Metal oxide fine particles: ATO fine particles 10.0 parts by weight mixed and stirred with a solvent (MEK / EtOH) was applied and dried to a cured film thickness of 5 μm by a bar coating method, and then a metal halide lamp was used. A hard coat layer was formed by irradiating ultraviolet rays of 400 mJ / cm ² . The total light transmittance, haze, scratch resistance test, pencil hardness, surface resistance value, and antifouling properties of the hard coat film are shown in Table 1.

<Comparative Example 5>
Using a cellulose triacetate film substrate with a thickness of 80 μm,
-Urethane acrylate: UV-1700B (Nippon Synthetic Chemical) 84.5 parts by weight-Initiator: Irgacure 184 (Ciba Specialty Chemicals) 5.0 parts by weight-Fluorine-based additive: Optool DAC (Daikin Industries) 0.5 weight Part ・ Metal oxide fine particles: ATO fine particles 10.0 parts by weight mixed and stirred with a solvent (MEK / EtOH) was applied and dried to a cured film thickness of 5 μm by a bar coating method, and then a metal halide lamp was used. A hard coat layer was formed by irradiating ultraviolet rays of 400 mJ / cm ² . The total light transmittance, haze, scratch resistance test, pencil hardness, surface resistance value, and antifouling properties of the hard coat film are shown in Table 1.

  The performance of the prepared hard coat film was evaluated according to the following method.

"Haze measurement"
In haze measurement, measurement was performed according to JIS-K7105 using NDH-2000 manufactured by Nippon Denshoku.

"Total light transmittance measurement"
The total light transmittance was measured according to JIS-K7105 using Nippon Denshoku NDH-2000.

"Pencil hardness test"
In the pencil hardness test, evaluation was performed according to JIS-K5400.

"Abrasion resistance test"
In the scratch resistance test, # 0000 steel wool was used for 10 reciprocations while applying a load of 200 g / cm ² , and the presence or absence of scratches was confirmed. In the test judgment, “No” indicates no scratch and “×” indicates that there is a scratch.

"Surface resistance measurement"
In the measurement of the surface resistance value, measurement was performed at 500 V-10 s using a surface resistance measuring instrument Hi-Lester.

"Anti-fouling evaluation"
For evaluation of the antifouling property, a fingerprint is applied to the hard coat surface, and the fingerprint is wiped off using a cellulose nonwoven fabric (Pencot M-3: manufactured by Asahi Kasei Co., Ltd.) while applying a load of 250 g / cm ^2. Ease was determined by visual judgment.

The judgment criteria were as follows.
○: Fingerprints can be completely wiped off.
Δ: A fingerprint trace remains.
X: The fingerprint cannot be wiped off.

  The evaluation results of Examples 1 to 5 and Comparative Examples 1 to 5 are summarized in Table 1 below.

  From the comparison of (Example 1) and (Example 3), and (Comparative Example 1) and (Comparative Example 2), the content of fine particles of ATO is different, which affects the surface resistance value and the surface property. I understand. When the content is small, the AS property is insufficient, and when the content is too large, it causes a surface defect due to a foreign matter defect.

  From comparison between (Example 1), (Example 4), and (Comparative Example 5), when the initiator is different, the surface resistance value is different, and when the content is small, the scratch resistance and pencil hardness are reduced. I understand.

  From the comparison of (Example 1), (Example 2), (Comparative Example 3), and (Comparative Example 4), it can be seen that the antifouling property varies depending on the type of additive. It can also be seen that when the amount added is too large, the scratch resistance deteriorates and the problem of poor surface quality occurs.

Claims (5)

In a hard coat film in which a hard coat layer is laminated on at least one surface of a transparent substrate,
The hard coat layer comprises a polyfunctional (meth) acrylic monomer (A), a radical photopolymerization initiator (B), a fluorine-containing compound having a polymerizable group (C), and electrically charged metal oxide fine particles (D). And the added amount of the metal oxide fine particles (D) is 1.0 to 10.0% by weight based on the polyfunctional (meth) acrylic monomer (A). ,
And, wherein the surface free energy of the hard coat layer surface is not more than 15mN / m~20mN / m, and the surface resistivity ^{5E +10 Ω~2.0E +10 Ω} or less, further, the thickness of the hard coat layer is 3 A hard coat film having a thickness of 10 μm to 10 μm.   The hard coat film according to claim 1, wherein the polyfunctional (meth) acrylic monomer (A) contains urethane (meth) acrylate as a main component.   The addition amount of the fluorine-containing compound (C) having the polymerizable group is 0.01 to 10.0% by weight based on the total of the polyfunctional (meth) acrylic monomer (A). Item 3. The hard coat film according to any one of Items 1 and 2.   The amount of the radical photopolymerization initiator (B) added is 0.01 to 10% by weight with respect to the polyfunctional (meth) acrylic monomer (A). Hard coat film as described in 2. The hard coat film according to claim 1 wherein the metal oxide fine particles having a chargeability (D) is characterized in that it comprises fine metal particles composed of SnO 2, _ATO, one or more of ITO, .

Images