JP2010001431A - Hard-coated film, method for producing the same, and antireflective film, polarizing plate and display device each using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stainproof hard-coated film maintaining its own scratch resistance and adhesivity and improved in flexibility and hardness, for hard-coated film used on the surface of such a display device as a liquid crystal display device (LCD) and for which high physical strength (e.g. scratch resistance) is required, and to provide antireflective film, polarizing plate and display device each using the above stainproof hard-coated film. <P>SOLUTION: The hard-coated film is such that, one side or both sides of a transparent film base is(are) provided with hard-coated layer(s) formed by coating and curing a resin composition comprising (A) a urethane-based reactive polymer having both vinyl and carboxy groups on the side chain, a weight-average molecular weight of 10,000-50,000 and the double bond equivalent of the vinyl groups of 500-2,000, (B) a polyfunctional (meth)acrylate monomer, (C) a silicone-modified fluororesin and (D) a photo-radical polymerization initiator. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an antifouling hard coat film that maintains scratch resistance and adhesion, and has improved flexibility and hardness, a method for producing the same, an antireflection film using the hard coat film, a polarizing plate, and a display device. Is.

  The recent development of the display field has been remarkable, and it has been used in every scene, indoors and outdoors. It is not just for displaying still images / moving images, but, as represented by touch panels, there are many opportunities for users to directly touch the display part of the display. The demand for strength to the environment is also increasing.

  Specifically, in various image display devices such as a liquid crystal display device (LCD), a plasma display panel (PDP), and an electroluminescence display (ELD), the film used on the surface has high physical strength (scratch resistance). Therefore, a hard coat layer is widely formed on the surface of the film.

  In Patent Document 1 below, as such a hard coat film, a hard coat layer forming material provided on at least one surface of a transparent film substrate includes urethane acrylate, polyol (meth) acrylate, and hydroxyl group. A hard coat film containing a (meth) acrylic polymer having an alkyl group containing two or more is disclosed.

According to Patent Document 1, a hard coat film having high hardness, curling due to curing shrinkage, and excellent flexibility can be obtained.
JP 2007-46031 A

  However, when using the hard coat layer for the purpose of protecting the surface of various display devices as described above, dirt such as human fingerprints (sebum), sweat, cosmetics and the like are likely to adhere. In addition, once attached dirt is difficult to remove, there is a problem that transparency and reflectivity are deteriorated and visibility is deteriorated, and dust (such as dust) which deteriorates the visibility of the display is applied to the surface of the hard coat film. Measures to prevent adhesion are required.

  Therefore, the conventional hard coat film described in Patent Document 1 has a problem that the antifouling property is insufficient.

  The purpose of the present invention is to meet the above-mentioned demands of the prior art, maintaining the scratch resistance and adhesion, improving the flexibility and hardness, and further providing a hard coat film having antifouling properties, An object is to provide a production method, an antireflection film using a hard coat film, a polarizing plate, and a display device.

  In order to achieve the above object, the invention of the hard coat film of claim 1 has a vinyl film and a carboxyl group in the side chain on one or both sides of the transparent film substrate, and a weight average molecular weight of 10,000 or more and 50,000. A polyurethane-based reactive polymer (A), a polyfunctional (meth) acrylate monomer (B), a silicone-modified fluororesin (C) having a vinyl group double bond equivalent of 500 or more and 2000 or less, and The radical photopolymerization initiator (D) is 100 to 50 parts by weight of the polyfunctional (meth) acrylate monomer (B), 4 to 50 parts by weight of the polyurethane-based reactive polymer (A), and the silicone-modified fluororesin (C). A resin composition containing 0.1 to 10 parts by weight and a radical photopolymerization initiator (D) of 0.1 to 10 parts by weight It is characterized in that the hard coat layer formed by curing is provided.

  The invention according to claim 2 is the hard coat film according to claim 1, wherein the polyfunctional (meth) acrylate monomer (B) is mainly composed of a trifunctional or higher functional (meth) acrylate monomer or the same oligomer. It is characterized by being.

  Invention of Claim 3 is a hard coat film of Claim 1 or 2, Comprising: Organic particle | grains or inorganic particle | grains with a primary particle diameter of 1 nm-100 nm are polyfunctional (meth) acrylate monomer ( 5) to 200 parts by weight is contained with respect to 100 parts by weight of B).

  Invention of Claim 4 is a manufacturing method of the hard coat film of Claim 1, Comprising: It has a vinyl group and a carboxyl group in a side chain, and a weight average molecular weight is 10,000 or more and 50000 or less, A polyurethane-based reactive polymer (A), a polyfunctional (meth) acrylate monomer (B), a silicone-modified fluororesin (C) having a double bond equivalent of 500 or more and 2000 or less, and a radical photopolymerization initiator (D ) With respect to 100 parts by weight of the polyfunctional (meth) acrylate monomer (B), 4 to 50 parts by weight of the polyurethane-based reactive polymer (A), 0.1 to 10 parts by weight of the silicone-modified fluororesin (C), And a radical photopolymerization initiator (D) in a proportion of 0.1 to 10 parts by weight to prepare a resin composition for forming a hard coat layer, and a transparent film On one or both surfaces of wood, coated with the hard coat layer-forming resin composition and cured, it is characterized by providing a hard coat layer.

  The invention of an antireflection film according to claim 5 is characterized in that a low refractive index layer is further provided on the hard coat layer of the hard coat film according to any one of claims 1 to 3. Yes.

  The invention of a polarizing plate according to claim 6 is characterized in that the hard coat film according to any one of claims 1 to 3 is used on one surface.

  The invention of a polarizing plate according to claim 7 is characterized in that the antireflection film according to claim 5 is used on one surface.

  An invention of a display device according to an eighth aspect is characterized by using the polarizing plate according to the sixth or seventh aspect.

  The invention of the hard coat film of claim 1 has a vinyl group and a carboxyl group in a side chain on one or both sides of a transparent film substrate, and has a weight average molecular weight of 10,000 or more and 50,000 or less and a double vinyl group. A polyurethane-based reactive polymer (A) having a bond equivalent of 500 or more and 2000 or less, a polyfunctional (meth) acrylate monomer (B), a silicone-modified fluororesin (C), and a radical photopolymerization initiator (D). , 100 to 100 parts by weight of the polyfunctional (meth) acrylate monomer (B), 4 to 50 parts by weight of the polyurethane-based reactive polymer (A), 0.1 to 10 parts by weight of the silicone-modified fluororesin (C), And a hard coat formed by applying and curing a resin composition containing 0.1 to 10 parts by weight of the radical photopolymerization initiator (D) According to the invention of the hard coat film of claim 1, the scratch resistance and adhesion are maintained, the flexibility and hardness are improved, and the antifouling property is sufficiently provided. There is an effect that there is.

  The invention according to claim 2 is the hard coat film according to claim 1, wherein the polyfunctional (meth) acrylate monomer (B) is mainly composed of a trifunctional or higher functional (meth) acrylate monomer or the same oligomer. Thus, according to the invention of claim 2, there is an effect of ensuring the hardness of the cured film.

  Invention of Claim 3 is a hard coat film of Claim 1 or 2, Comprising: Organic particle | grains or inorganic particle | grains with a primary particle diameter of 1 nm-100 nm are polyfunctional (meth) acrylate monomer ( 5) to 200 parts by weight with respect to 100 parts by weight of B). According to the invention of claim 3, antiglare properties, electrical conductivity, light scattering properties, slip properties, color correction and the like are imparted. There is an effect.

  Invention of Claim 4 is a manufacturing method of the hard coat film of Claim 1, Comprising: It has a vinyl group and a carboxyl group in a side chain, and a weight average molecular weight is 10,000 or more and 50000 or less, A polyurethane-based reactive polymer (A), a polyfunctional (meth) acrylate monomer (B), a silicone-modified fluororesin (C) having a double bond equivalent of 500 or more and 2000 or less, and a radical photopolymerization initiator (D ) With respect to 100 parts by weight of the polyfunctional (meth) acrylate monomer (B), 4 to 50 parts by weight of the polyurethane-based reactive polymer (A), 0.1 to 10 parts by weight of the silicone-modified fluororesin (C), And a radical photopolymerization initiator (D) in a proportion of 0.1 to 10 parts by weight to prepare a resin composition for forming a hard coat layer, and a transparent film The hard coat layer forming resin composition is applied to one side or both sides of the material and cured to provide a hard coat layer. According to the invention of claim 4, the scratch resistance and adhesion are maintained. The hard coat film according to claim 1, which has improved flexibility and hardness and has sufficient antifouling properties, can be produced efficiently and stably.

  The invention of the antireflection film according to claim 5 is the one in which a low refractive index layer is further provided on the hard coat layer of the hard coat film according to any one of claims 1 to 3. According to invention of claim | item 5, there exists an effect of providing antireflection property.

  The invention of the polarizing plate according to claim 6 uses the hard coat film according to any one of claims 1 to 3 on one side, and according to the invention of claim 6, the hard coating film according to the present invention is used. When a polarizing plate using a coat film is attached to a liquid crystal display panel, there is an effect that the visibility of the liquid crystal display panel is good.

  The invention of the polarizing plate of claim 7 uses the antireflection film of claim 5 on one surface, and according to the invention of claim 7, the polarizing plate using the antireflection film of the invention is a liquid crystal. When attached to the display panel, there is an effect that the visibility of the liquid crystal display panel is good.

  The invention of the display device of claim 8 uses the polarizing plate of claim 6 or 7, and according to the invention of claim 8, a polarizing plate using the hard coat film or antireflection film of the invention. The attached liquid crystal display panel has an effect of good visibility.

  Next, embodiments of the present invention will be described, but the present invention is not limited thereto.

  The hard coat film according to the present invention has a vinyl group and a carboxyl group in a side chain on one or both sides of a transparent film substrate, and has a weight average molecular weight of 10,000 to 50,000 and a polyurethane-based reactive polymer (A) The double bond equivalent of the vinyl group of the polyurethane-based reactive polymer (A), the polyfunctional (meth) acrylate monomer (B), the silicone-modified fluororesin (C), and the photoradical polymerization are 500 or more and 2000 or less. A hard coat layer formed by applying and curing a resin composition containing the initiator (D) is provided.

  According to the hard coat film of the present invention, the hard coat layer is excellent in adhesion to the base film (transparent film substrate), is excellent in transparency and scratch resistance, and further improves flexibility and hardness. In addition, it has an excellent antifouling effect, and can be effectively used as an antifouling film for displays such as display screens.

  In the above, if the weight average molecular weight of the polyurethane-based reactive polymer (A) having a vinyl group and a carboxyl group in the side chain is less than 10,000, the effect of imparting flexibility is small, which is not preferable. Moreover, when the weight average molecular weight of a polyurethane-type reactive polymer (A) exceeds 30000, since a liquid viscosity becomes high and causes appearance malfunctions, such as a stripe, it is unpreferable.

  In the hard coat film according to the present invention, if the double bond equivalent of the vinyl group of the polyurethane-based reactive polymer (A) in the resin composition forming the hard coat layer is less than 500, it is preferable because the hardness decreases. Absent. Further, when the double bond equivalent of the vinyl group of the polyurethane-based reactive polymer (A) in the resin composition of the hard coat layer exceeds 2000, curing shrinkage becomes strong and flexibility is lost, which is not preferable.

  In the resin composition forming the hard coat layer of the hard coat film according to the present invention, the polyurethane-based reactive polymer (A) is 4 to 50 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate monomer (B). It is preferable that 0.1 to 10 parts by weight of the silicone-modified fluororesin (C) and 0.1 to 15 parts by weight of the radical photopolymerization initiator (D) are blended.

  Here, if the polyurethane-based reactive polymer (A) is less than 4 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate monomer (B), the effect of improving flexibility is not exhibited, which is not preferable. . On the other hand, when the polyurethane-based reactive polymer (A) exceeds 50 parts by weight, the flexibility is improved, but the scratch resistance and hardness are extremely lowered, which is not preferable.

  In addition, since the silicone-modified fluororesin (C) is less than 0.1 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate monomer (B), no antifouling effect is exhibited. It is not preferable. On the other hand, if the silicone-modified fluororesin (C) exceeds 10 parts by weight, repelling occurs, which is not preferable.

  Furthermore, if the radical photopolymerization initiator (D) is less than 0.1 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate monomer (B), the generation of radicals is small and curing is difficult to proceed. It is not preferable. On the other hand, when the radical photopolymerization initiator (D) exceeds 15 parts by weight, light absorption by the initiator increases and film hardening is difficult to proceed.

  In the above, the polyfunctional (meth) acrylate monomer (B) is preferably a trifunctional or higher functional (meth) acrylate monomer or the same oligomer.

  In the resin composition forming the hard coat layer of the hard coat film of the present invention, organic particles or inorganic particles having a primary particle size of 1 nm to 100 nm are further added to 100 parts by weight of the polyfunctional (meth) acrylate monomer (B). 5 to 200 parts by weight are preferable.

  Here, if the primary particle diameter of the organic particles or inorganic particles is less than 1 nm, the characteristics of the particles are hardly expressed, which is not preferable. Moreover, when the primary particle diameter of an organic particle or an inorganic particle exceeds 100 nm, since the haze of a cured film will raise extremely, it is unpreferable.

  If the organic particles or inorganic particles are less than 5 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate monomer (B), it is not preferable because the characteristics of the particles are difficult to speak. Moreover, when organic particle | grains or an inorganic particle exceeds 200 weight part, since the haze of a cured film will raise extremely, it is unpreferable.

  In the present invention, as a method for producing the above hard coat film, first, the side chain has a vinyl group and a carboxyl group, the weight average molecular weight is from 10,000 to 50,000, and the double bond equivalent of the vinyl group is , 500 or more and 2000 or less, a polyurethane-based reactive polymer (A), a polyfunctional (meth) acrylate monomer (B), a silicone-modified fluororesin (C), and a radical photopolymerization initiator (D). 4 to 50 parts by weight of the polyurethane-based reactive polymer (A), 0.1 to 10 parts by weight of the silicone-modified fluororesin (C), and initiation of radical photopolymerization with respect to 100 parts by weight of the (meth) acrylate monomer (B) A resin composition for forming a hard coat layer is prepared by blending at a ratio of 0.1 to 10 parts by weight of the agent (D).

  Next, this hard coat layer-forming resin composition is applied to a thickness of, for example, 5 to 15 μm on one side or both sides of the transparent film base material and cured to provide a hard coat layer.

  According to the method for producing a hard coat film of the present invention, the hard coat film according to claim 1, which maintains scratch resistance and adhesion, improves flexibility and hardness, and has sufficient antifouling properties. It can be manufactured efficiently and stably.

  The hard coat film according to the present invention preferably has a haze of 0.30 to 0.50%. Here, the haze of the hard coat film can be measured according to the standard of JIS K 7165.

  In addition, the hard coat film according to the present invention preferably has a flexibility of 1 to 3 mm according to the following flexibility test.

  Here, the flexibility test of the hard coat film can be performed according to the standard of JIS K 5600-5-1. That is, for the bendability of the hard coat film, the size of the mandrel for bending test is selected, the crack and the peel of each hard coat film are confirmed, and the minimum diameter (mm) of the mandrel that starts to crack and peel is obtained.

  Furthermore, the hard coat film according to the present invention preferably has a pure water contact angle of 90 degrees or more and 110 degrees or less by the following contact angle measurement. Thereby, the hard coat film by this invention is excellent in antifouling property.

  Here, the contact angle measurement of the hard coat film can be performed using a contact angle meter according to the standard of JIS K 2396. The contact angle is measured using pure water.

  In the invention of the antireflection film according to the present invention, a low refractive index layer is further provided on the hard coat layer of the hard coat film according to the present invention, which will be described later.

  Next, a transparent film substrate that can be used for the hard coat film of the present invention will be described.

(Transparent film substrate)
The transparent film substrate used in the hard coat film of the present invention is easy to manufacture, has good adhesion to the actinic radiation curable resin layer, is optically isotropic, and optically It is mentioned as preferable requirements that it is transparent.

  In the present invention, the transparent film substrate is particularly preferably 1.4 to 4 m from the viewpoint of planarity.

  The term “transparent” as used in the present invention means that the visible light transmittance is 60% or more, preferably the transmittance is 80% or more, and particularly preferably the transmittance is 90% or more.

  Although it will not specifically limit if it has said property, For example, a cellulose-ester-type film, a polyester-type film, a polycarbonate-type film, a polyarylate-type film, a polysulfone (a polyethersulfone is also included) film, a polyethylene terephthalate, polyethylene Polyester film such as naphthalate, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose triacetate, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, Syndiotactic polystyrene film, polycarbonate film, cycloolefin Polymer film (Arton, manufactured by JSR), ZEONEX, ZEONOR (above, manufactured by Nippon Zeon), polymethylpentene film, polyetherketone film, polyetherketoneimide film, polyamide film, fluororesin film, nylon film, polymethyl A methacrylate film, an acrylic film, a glass plate, etc. can be mentioned. Of these, cellulose ester film, polycarbonate film, and polysulfone (including polyethersulfone) are preferable. Cellulose ester films include, for example, product names: Konica Minoltac-KC8UX2MW, KC4UX2MW, KC8UY, KC4UNY, KC5UN, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1, KC4FR-1, KC4FR-1K OPT Co., Ltd.) is preferably used from the viewpoint of production, cost, transparency, isotropic properties, adhesiveness, and the like.

  These films may be films produced by melt casting film formation or films produced by solution casting film formation.

  Next, the conductive particles used in the hard coat layer of the hard coat film of the present invention will be described.

  The conductive particles used in the present invention are at least one selected from the group consisting of antimony oxide, tin oxide, zinc oxide, tin indium acid (ITO), tin antimonate (ATO), and zinc antimonate. Conductive particles.

  The average particle diameter of primary particles of these conductive particles is in the range of 10 nm to 200 nm, more preferably 20 to 150 nm, and particularly preferably 30 to 100 nm. The average particle diameter of the conductive particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. Further, it may be measured by a particle size distribution meter using a dynamic light scattering method or a static light scattering method. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze is remarkably increased. The shape of the conductive particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.

  The conductive particles may be surface-treated with an organic compound. By modifying the surface of the conductive particles with an organic compound, the dispersion stability in an organic solvent is improved, the control of the dispersed particle size is facilitated, and aggregation and sedimentation over time can be suppressed. For this reason, the surface modification amount with a preferable organic compound is 0.1 to 5% by weight, more preferably 0.5 to 3% by weight with respect to the metal oxide particles. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Among these, the silane coupling agent mentioned later is preferable. Two or more surface treatments may be combined.

  The amount of the conductive particles used in the hard coat layer is preferably 5 to 85% by weight, more preferably 10 to 80% by weight, and most preferably 20 to 75% by weight. If the amount used is small, the desired refractive index cannot be obtained, and if it is too large, the film strength deteriorates.

  The said electroconductive particle is provided to the coating liquid for forming a hard-coat layer in the state of the dispersion disperse | distributed to the medium. As a dispersion medium for metal oxide particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ketone alcohol (eg, diacetone alcohol). , Esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene) Chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, diethyl ether, dioxane, Tiger hydrofuran), ether alcohols (e.g., 1-methoxy-2-propanol), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate. Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and methanol, ethanol, and isopropanol are particularly preferable.

  Moreover, electroconductive particle can be disperse | distributed in a medium using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder. It is also preferable to contain a dispersant.

  Furthermore, you may contain the electroconductive particle which has a core / shell structure. One layer of the shell may be formed around the core, or a plurality of layers may be formed in order to further improve the light resistance. The core is preferably completely covered by the shell.

  Specific examples of the polyurethane-based reactive polymer (A) having a vinyl group and a carboxyl group in the side chain include RU-140, RU-150, and RU-160 manufactured by Negami Kogyo Co., Ltd. .

  In the above, the polyfunctional (meth) acrylate monomer (B) is preferably a trifunctional or higher functional (meth) acrylate monomer or an oligomer thereof, specifically, trimethylolpropane. Tri (meth) acrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, trimethylolpropane tri (meth) acrylate, ethoxy Trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol tri (meth) acrylate, dipentaeryth Tall hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, trimethylolpropane di (meth) acrylate Epoxy acrylate, dicyclopentanyl dimethylene diacrylate and / or 5-ethyl-2- (2-hydroxy-1,1-dimethylethyl) -5- (hydroxymethyl) -1,3-dioxadiacrylate, neo Pentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol di (meth) acrylate, Ethylene glycol diacrylate, polyethylene glycol diacrylate, tetraethylene glycol diacrylate, triethylene glycol diacrylate, propylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, zinc diacrylate, bisphenol A-diglycidyl ether diacrylate , Epoxy acrylates such as bisphenol A-ethylene oxide modified diacrylate, neopentyl glycol diglycidyl ether diacrylate, 1,6-hexanediol diglycidyl ether diacrylate, polyhydric alcohol and polycarboxylic acid and / or anhydride and acrylic Polyester diacrylate, polyhydric alcohol, polyisocyanate obtained by esterification with acid And urethane diacrylate obtained by reacting the acrylate with a hydroxyl group-containing acrylate. Preferred examples include dipentaerythritol hexaacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, 1,6-hexanediol diacrylate, aliphatic urethane acrylate, and the like. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

  In this invention, when using an ultraviolet-ray as an active energy ray, the photoinitiator is contained in the composition for hard-coat layer formation of the hard-coat film of this invention.

  As a photopolymerization initiator, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone (Irgacure-907, manufactured by Ciba Geigy Japan Ltd.), 1-hydroxycyclohexyl phenyl ketone (Irgacure-184, A sufficient cured film can be obtained by adding Ciba-Geigy Corporation). Others, benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal, 2,4-diethylthioxanthone, benzyldiphenyl sulfide, Photopolymerization initiators such as tetramethylthiuram monosulfide, azobisisobutyronitrile, benzyl, dibenzyl, diacetyl, and β-chloroanthraquinone can also be used. In this case, the blending ratio is 1 to 10 parts by weight. If it is less than 1 part by weight, the polymerization initiation effect cannot be obtained, and if it exceeds 10 parts by weight, the yellowing degree becomes large and yellow. It is because it will also fall.

  In order to form a hard coat layer of a hard coat film according to the present invention, a hard coat layer forming resin containing an antifouling agent in a predetermined ratio with respect to the active energy ray-curable polyfunctional (meth) acrylate resin After adjusting the composition, the resin composition is applied on the transparent film substrate by any coating method such as gravure coating, Mayer bar coating, and then, if necessary, active energy rays such as ultraviolet rays are applied. By irradiating, a cured film can be formed in a very short time and can be easily formed. In general, the hard coat layer is preferably formed to a thickness of about 1 to 10 μm.

  Next, the silicone-modified fluororesin (C) as an antifouling agent contained in the hard coat layer of the hard coat film of the present invention is added to prevent the outermost surface of the hard coat film from being stained. It is also possible to impart scratch resistance to the coated film.

  Here, examples of the silicone-modified fluororesin (C) include ZX-022H, ZX-007C, ZX-049, and ZX-047-D manufactured by Fuji Chemical Industry Co., Ltd. Moreover, you may mix these compounds.

  In the hard coat film according to the present invention, in the resin composition forming the hard coat layer, the addition amount of the antifouling agent is 0.1 to 100 parts by weight of the active energy ray-curable polyfunctional (meth) acrylate resin. 10.0 parts by weight, preferably 0.3 to 2.0 parts by weight. The amount of the antifouling agent is, in short, sufficient antifouling function to be exhibited and without reducing the hardness of the hard coat film, and even if the antifouling agent is contained, the scratch resistance and water vapor of the film. It is preferable that the amount does not cause deterioration of the transmittance.

  In the hard coat film according to the present invention, in the composition for forming a hard coat layer, the filler is further contained in a proportion of 0.1 to 50 parts by weight with respect to 100 parts by weight of the active energy ray-curable polyfunctional (meth) acrylate resin. It is preferable that it is contained.

  Here, examples of the filler include fillers such as silica (including colloidal silica), silicone powder, mica, glass beads, acrylic fine powder, and hollow particles. In this case, when the filler is less than 0.1 part by weight with respect to 100 parts by weight of the polyfunctional acrylate, the antiglare property cannot be obtained, and when it exceeds 50 parts by weight, the film strength decreases.

(Antireflection film)
On the hard coat layer of the clear hard coat film of the present invention, an antireflection layer may be laminated in consideration of the refractive index, the film thickness, the number of layers, the layer order, etc. so that the reflectivity is reduced by optical interference. The antireflection layer is composed of a high refractive index layer having a refractive index higher than that of the transparent film substrate, a low refractive index layer having a refractive index lower than that of the transparent film substrate, and the like. The hard coat layer may also serve as the high refractive index layer.

  The low refractive index layer can form an antireflection film excellent in adhesion after the durability test by containing at least one kind of hollow silica fine particles described below, which is porous or hollow inside. In the antireflection film, a high refractive index layer may be interposed between the hard coat layer and the low refractive index layer.

(Low refractive index layer)
Next, the low refractive index layer will be described. A layer having a lower refractive index than the refractive index of the transparent film substrate is referred to as a low refractive index layer. A specific refractive index is preferably in the range of 1.30 to 1.45 at 23 ° C. and a wavelength of 550 nm. Further, the film thickness of the low refractive index layer is preferably 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and further preferably 30 nm to 0.2 μm, from the characteristics as the optical interference layer. It is preferable to contain hollow silica particles in the low refractive index layer from the viewpoint of properties as an optical interference layer such as adhesion after a durability test and lowering of the refractive index. Hollow silica particles (hereinafter also referred to as hollow particles) are: (1) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles; The object is a hollow particle filled with a solvent, gas or porous material.

  The coating composition for forming the low refractive index layer preferably contains an organic solvent. Specific examples of organic solvents include alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters (eg, methyl acetate, ethyl acetate). , Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Group hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate. Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and butanol are particularly preferable.

  The solid concentration in the coating composition for forming the low refractive index layer is preferably 1 to 4% by weight. By setting the solid content concentration to 4% by weight or less, coating unevenness is less likely to occur, and 1% by weight. By setting it as% or more, the drying load is reduced.

  The coating composition for forming the low refractive index layer can contain other silica particles. Here, the other silica particles are not particularly limited, and examples thereof include colloidal silica. Specific examples of colloidal silica are those in which silicon dioxide is dispersed in water or an organic solvent in a colloidal form, and are not particularly limited, but are spherical, acicular or beaded.

  The average particle size of the colloidal silica is preferably in the range of 50 to 300 nm, and is preferably monodispersed with a coefficient of variation of 1 to 40%. The average particle diameter can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc.

  Colloidal silica is commercially available, and examples thereof include the Snowtex series of Nissan Chemical Industries, the Cataloid-S series of Catalytic Chemical Industry, and the Lebasil series of Bayer. Further, bead-like colloidal silica in which primary particles of colloidal silica or silica cation-modified with alumina sol or aluminum hydroxide are bonded to each other with metal ions having a valence of 2 or more and connected in a bead shape is also preferably used. There are beaded colloidal silicas such as SNOWTEX-AK series, SNOWTEX-PS series, SNOWTEX-UP series of NISSAN CHEMICAL INDUSTRIES, and specifically IPS-ST-L (isopropanol dispersion, particle size 40-50 nm, Silica concentration 30%), MEK-ST-MS (methyl ethyl ketone dispersion, particle diameter 17-23 nm, silica concentration 35%) and the like. When colloidal silica is contained in the coating composition for forming a low refractive index layer, it is preferably 10 to 60% by weight, more preferably 30 to 60% by weight, based on the solid content in the low refractive index layer, from the viewpoint of film strength. .

  In addition, other inorganic fine particles may be contained, and examples thereof include MgF 2. Specifically, MFS-10P (isopropyl alcohol-dispersed magnesium fluoride sol, particle system 100 nm), NF-10P manufactured by Nissan Chemical Industries, Ltd. Etc.

  Moreover, it is preferable that 5-80 weight% of binders are included in the coating composition for low refractive index layer formation with respect to solid content in a low refractive index layer. The binder has a function of adhering particles such as hollow silica particles and maintaining the structure of the low refractive index layer including voids. The usage-amount of a binder is adjusted so that the intensity | strength of a low-refractive-index layer can be maintained, without filling a space | gap.

  Examples of binders include alkoxy metal compounds, hydrolysates thereof or polycondensates thereof, polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resins. , Fluoroacrylate, fluorine-containing polymer and the like. Examples of the fluoropolymer include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.) Examples include acrylic acid partial or fully fluorinated alkyl ester derivatives [for example, Biscoat 6FM (manufactured by Osaka Organic Chemical Co., Ltd.) and M-2020 (manufactured by Daikin)], and complete or partially fluorinated vinyl ethers. Are perfluoroolefins, and hexafluoropropylene is particularly preferable from the viewpoint of refractive index, solubility, transparency, availability, and the like.

(Reflectivity of antireflection film)
The reflectance of the antireflection film described above can be measured with a spectrophotometer. At that time, after roughening the back side of the measurement side of the sample, light absorption treatment is performed using a black spray, and then reflected light in the visible light region (400 to 700 nm) is measured. The lower the reflectivity, the better. However, the average value in the visible light wavelength is preferably 2.5% or less, and the minimum reflectivity is preferably 1.5% or less. It is preferable to have a flat reflection spectrum in the visible light wavelength region.

  In addition, the reflection hue on the surface of the display device that has been subjected to the antireflection treatment is often colored red or blue because the reflectance in the short wavelength region and the long wavelength region is high in the visible light region due to the design of the antireflection film. The color tone of the reflected light varies depending on the application, and when used on the outermost surface of a flat-screen television or the like, a neutral color tone is preferred.

In this case, the generally preferred reflection hue range is the XYZ color system (CIE 1931 color system).
0.17 ≦ x ≦ 0.27,
0.07 ≦ y ≦ 0.17.

  The film thicknesses of the high refractive index layer and the low refractive index layer can be obtained by calculation according to a conventional method in consideration of the reflectance and the color of reflected light based on the refractive index of each layer.

(surface treatment)
You may surface-treat before apply | coating each above-mentioned layer. Examples of the surface treatment method include a cleaning method, an alkali treatment method, a flame plasma treatment method, a high frequency discharge plasma method, an electron beam method, an ion beam method, a sputtering method, an acid treatment, a corona treatment method, and an atmospheric pressure glow discharge plasma method. It is done.

  The corona treatment is a treatment performed by applying a high voltage of 1 kV or higher between the electrodes under atmospheric pressure and discharging it, and using a device commercially available from Kasuga Electric Co., Ltd. or Toyo Electric Co., Ltd. Can be done. The intensity of the corona discharge treatment depends on the distance between the electrodes, the output per unit area, and the generator frequency.

  As one electrode (A electrode) of the corona treatment apparatus, a commercially available one can be used, but the material can be selected from aluminum, stainless steel and the like. The other is an electrode (B electrode) for holding a plastic film, and is a roll electrode installed at a certain distance from the A electrode so that the corona treatment is carried out stably and uniformly. A commercially available one can also be used, and the material is preferably a roll made of ceramic, silicon, EPT rubber, hyperon rubber or the like on a roll made of aluminum, stainless steel, or a metal thereof. It is done. The frequency used for the corona treatment is a frequency of 20 kHz or more and 100 kHz or less, and a frequency of 30 kHz to 60 kHz is preferable. When the frequency is lowered, the uniformity of the corona treatment is deteriorated and unevenness of the corona treatment occurs. In addition, when the frequency is increased, there is no particular problem when performing high-output corona treatment, but when performing low-output corona treatment, it becomes difficult to perform stable processing, resulting in uneven processing. Will occur. The output of the corona treatment is 1 to 5 W · min. / M2, but 2 to 4 W · min. An output of / m 2 is preferred. The distance between the electrode and the film is 5 mm or more and 50 mm or less, preferably 10 mm or more and 35 mm or less. When the gap opens, a higher voltage is required to maintain a constant output, and unevenness is likely to occur. On the other hand, if the gap is too narrow, the applied voltage becomes too low and unevenness is likely to occur. Further, when the film is transported and continuously processed, the film comes into contact with the electrodes and scratches are generated. As the alkali treatment method, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonia solution or the like can be used as the aqueous alkaline solution, and an aqueous sodium hydroxide solution is particularly preferable.

  The alkali concentration of the aqueous alkali solution, for example, sodium hydroxide concentration is preferably 0.1 to 25% by weight, and more preferably 0.5 to 15% by weight. The alkali treatment temperature is usually 10 to 80 ° C, preferably 20 to 60 ° C.

  The alkali treatment time is 5 seconds to 5 minutes, preferably 30 seconds to 3 minutes. The film after the alkali treatment is preferably neutralized with acidic water and then thoroughly washed with water.

(Back coat layer)
In the present invention, it is preferable to provide a backcoat layer on the side opposite to the side on which the hard coat layer of the transparent film substrate such as a cellulose ester film is provided.

  The back coat layer is provided in order to correct curl caused by providing an active energy ray-curable resin layer or other layers. That is, the degree of curling can be balanced by imparting the property of being rounded with the surface on which the backcoat layer is provided facing inward. The backcoat layer is preferably applied also as an antiblocking layer. In this case, it is preferable that fine particles are added to the backcoat layer coating composition in order to provide an antiblocking function.

  As fine particles added to the back coat layer, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, tin oxide, and oxidation. Mention may be made of indium, zinc oxide, ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. Fine particles containing silicon are preferable in terms of low haze, and silicon dioxide is particularly preferable.

  These fine particles are, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (above, manufactured by Nippon Aerosil Co., Ltd.), Seahoster KE-P10, KE-P30, KE-P50. KE-P100, KE-P150, and KE-P250 (above, manufactured by Nippon Shokubai Co., Ltd.) can be used. Among these, particularly preferred are Sea Hoster KE-P30, KE-P50, and KE-P100.

  Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.), and can be used.

  Examples of the polymer fine particles include silicone resin, fluororesin, and acrylic resin. Silicone resin fine particles are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (above, manufactured by Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.

  The fine particles contained in the backcoat layer are 0.1 to 50% by weight, preferably 0.1 to 10% by weight, based on the binder. When the back coat layer is provided, the increase in haze is preferably 1% or less, more preferably 0.5% or less, and particularly preferably 0.0 to 0.1%.

  Specifically, the back coat layer is formed by applying a composition containing a solvent for dissolving or swelling a cellulose ester film. The solvent to be used may include a solvent to be dissolved and / or a solvent to be swollen in addition to a solvent that does not dissolve, and a composition and coating in which these are mixed at an appropriate ratio depending on the curl degree of the transparent film and the type of resin. Do with quantity.

  In order to enhance the curl prevention function, it is effective to increase the mixing ratio of the solvent for dissolving the solvent composition to be used and / or the solvent for swelling, and to decrease the ratio of the solvent not to be dissolved. This mixing ratio is preferably (solvent to be dissolved and / or solvent to be swollen) :( solvent to be dissolved) = 10: 0 to 1: 9. Examples of the solvent for dissolving or swelling the transparent film contained in such a mixed composition include dioxane, acetone, methyl ethyl ketone, N, N-dimethylformamide, methyl acetate, ethyl acetate, trichloroethylene, methylene chloride, ethylene chloride, tetrachloride. There are chloroethane, trichloroethane, chloroform and the like. Examples of the solvent that does not dissolve include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butanol, cyclohexanol, and hydrocarbons (toluene, xylene).

  These coating compositions are preferably applied to the surface of the transparent film with a wet film thickness of 1 to 100 μm using a gravure coater, dip coater, reverse coater, wire bar coater, die coater, spray coating, ink jet coating or the like. In particular, the thickness is preferably 5 to 30 μm.

  Examples of the resin used as the binder of the backcoat layer include vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, vinyl acetate-vinyl alcohol copolymer, partially hydrolyzed vinyl chloride-vinyl acetate copolymer. Polymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, etc. Vinyl polymer or copolymer, nitrocellulose, cellulose acetate propionate (preferably acetyl group substitution degree 1.2-2.3, propionyl group substitution degree 0.1-1.0), diacetyl cellulose, cellulose Cellulose derivatives such as acetate butyrate resin, maleic acid and / or Or acrylic acid copolymer, acrylic ester copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin Rubber resins such as polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene-butadiene resin, butadiene-acrylonitrile resin, Examples thereof include, but are not limited to, silicone resins and fluorine resins. For example, as an acrylic resin, Acrypet MD, VH, MF, V (manufactured by Mitsubishi Rayon Co., Ltd.), Hyperl M-4003, M-4005, M-4006, M-4202, M-5000, M-5001, M- 4501 (manufactured by Negami Kogyo Co., Ltd.), Dianal BR-50, BR-52, BR-53, BR-60, BR-64, BR-73, BR-75, BR-77, BR-79, BR-80 , BR-82, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR-95, BR-100, BR-101, BR-102, BR-105, BR -106, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118 and the like (made by Mitsubishi Rayon Co., Ltd.) Methacrylic monomers and the commercially available various homopolymers and copolymers, etc. was prepared as a raw material, it is also possible to select a preferred mono from this appropriate.

  Particularly preferred are cellulosic resin layers such as diacetylcellulose, triacetylcellulose, cellulose acetate propionate, and cellulose acetate butyrate.

  The order of coating the backcoat layer may be before or after coating the active energy ray-curable resin layer of the cellulose ester film, but when the backcoat layer also serves as an antiblocking layer, it is desirable to coat it first. . Alternatively, the backcoat layer can be applied in two or more steps.

(Polarizer)
Next, a polarizing plate using the hard coat film of the present invention will be described.

  The polarizing plate can be produced by a general method. The back side of the hard coat film of the present invention is subjected to alkali saponification treatment, and the treated film is attached to at least one surface of a polarizing film produced by immersing and stretching in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. It is preferable to match. The film may be used for the other surface, or another polarizing plate protective film may be used. With respect to the hard coat film of the present invention, the polarizing plate protective film used on the other surface has an in-plane retardation (Ro) of 590 nm, a retardation of 20 to 70 nm, and a thickness direction retardation (Rt) of 100 to 400 nm. An optical compensation film (retardation film) having These can be prepared, for example, by the methods described in JP-A No. 2002-71957 and Japanese Patent Application No. 2002-155395. Further, it is preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optically anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal. For example, the optically anisotropic layer can be formed by the method described in JP-A-2003-98348. Alternatively, a non-oriented film having an in-plane direction retardation (Ro) of 590 nm to 0 to 5 nm and a thickness direction retardation (Rt) of -20 to +20 nm is preferably used, and has excellent planarity and a stable viewing angle widening effect. Can be obtained.

  As a polarizing plate protective film used on the back side, as a commercially available cellulose ester film, KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC4UEW, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1, KC4F-1, -2 (manufactured by Konica Minolta Opto Co., Ltd.) and the like are preferably used.

  The polarizing film, which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction. A typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film. There are ones in which iodine is dyed on a system film and ones in which a dichroic dye is dyed, but it is not limited to this. As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound. A polarizing film having a thickness of 5 to 30 μm, preferably 8 to 15 μm, is preferably used. On the surface of the polarizing film, one side of the hard coat film of the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.

(Image display device)
By incorporating a polarizing plate using the hard coat film of the present invention on the viewing surface side of the image display device, various image display devices with excellent visibility can be produced. The hard coat film of the present invention is a reflective type, transmissive type, transflective type LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type, etc. Preferably used. Moreover, it is excellent in flatness and is preferably used for various display devices such as a plasma display, a field emission display, an organic EL display, an inorganic EL display, and electronic paper.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1
A hard coat film according to the present invention was prepared.

(Composition for forming hard coat layer)
100 parts by weight of dipentaerythritol hexaacrylate (B) [Polyfunctional (meth) acrylate monomer, trade name: Light acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.]
10 parts by weight of polyurethane-based reactive polymer (A1) (trade name RA-160, manufactured by Negami Kogyo Co., Ltd., weight average molecular weight:
35000, double bond equivalent: 1100)
Silicone-modified fluororesin (C) 3 parts by weight (trade name ZX-049, manufactured by Fuji Chemical Industry Co., Ltd.)
Photopolymerization initiator (D) 5 parts by weight (trade name Irgacure 184, manufactured by Ciba Specialty Chemicals)
5 parts by weight of organic particles (E1) (trade name FS-201, manufactured by Nippon Paint Co., Ltd., primary particle size: 60 nm)
A methyl acetate / MIBK = 50/50 solvent was added to the above composition to obtain a solid content of 50% by weight to obtain a resin composition for forming a hard coat layer.

  Next, a triacetyl cellulose film having a thickness of 80 μm was used as a transparent film substrate. A mixed solution of the stirred resin composition is applied to one side of the transparent film substrate by a gravure coating method so that the WET film thickness is 10 μm (DRY film thickness after drying is 5 μm), dried, and then a high-pressure mercury lamp. Was irradiated with ultraviolet rays of 200 mJ to obtain a hard coat film.

Examples 2 and 3
A hard coat film according to the present invention is produced in the same manner as in Example 1, except that the amount of the polyurethane-based reactive polymer (A1) is shown in Table 1 below. As such, there is a change. Other points of the second and third embodiments are the same as those of the first embodiment.

Examples 4-6
Although the hard coat film by this invention is produced similarly to the case of the said Examples 1-3, a different point from the case of the said Examples 1-3 is a polyurethane-type reactive polymer (A1). Polymer (A2) (trade name RA-140, manufactured by Negami Kogyo Co., Ltd., weight average molecular weight: 17000, double bond equivalent: 1100), and organic particles (E1) are changed to inorganic particles (E2) (product Name snowtex 40, manufactured by Nissan Chemical Industries, Ltd., primary particle size: 20 nm). Other points of Examples 4 to 6 are the same as those of Examples 1 to 3.

Examples 7-9
Although the hard coat film by this invention is produced similarly to the case of the said Example 1 and 2, the points different from the case of the said Example 1 and 2 differ the compounding quantity of silicone modified fluororesin (C) below. As shown in Table 1, there is a change. Other points of Examples 7 to 9 are the same as those of Examples 1 and 2.

Examples 10-12
Although the hard coat film by this invention is produced similarly to the case of the said Example 4 and 5, the difference from the case of the said Example 4 and 5 is the compounding quantity of silicone modified fluorine-type resin (C) below. As shown in Table 1, there is a change. Other points of Examples 10 to 12 are the same as those of Examples 4 and 5.

Example 13
A hard coat film according to the present invention is produced in the same manner as in Example 2, except that the amount of organic particles (E1) is different from that in Example 2 as shown in Table 1 below. There is a change. Other points of the thirteenth embodiment are the same as those of the second embodiment.

Example 14
A hard coat film according to the present invention is produced in the same manner as in Example 5, except that the amount of inorganic particles (E2) is as shown in Table 1 below. There is a change. Other points of the embodiment 14 are the same as those of the embodiment 5.

Comparative Examples 1-4
For comparison, a hard coat film is prepared in the same manner as in Example 2 above. However, the difference from Example 2 is that in Comparative Example 1, silicone-modified fluorine is used. It is in the point which did not mix | blend a system resin (C). Moreover, in the comparative example 2, it exists in the point which did not mix | blend a polyurethane-type reactive polymer (A). Furthermore, in Comparative Examples 3 and 4, the amount of the polyurethane-based reactive polymer (A1) is changed. Other points of Comparative Examples 1 to 4 are the same as in the case of Example 2.

Comparative Examples 5 and 6
For comparison, a hard coat film is prepared in the same manner as in Example 4 above. However, as shown in Table 1 below, the polyurethane-based reactive polymer (A2) is different from that in Example 4 above. It is in the point which changed the compounding quantity. The other points of Comparative Examples 5 and 6 are the same as in Example 4 above.

Comparative Examples 7 and 8
For comparison, a hard coat film is prepared in the same manner as in Example 2 above. However, as shown in Table 1 below, the silicone-modified fluororesin (C) is different from that in Example 2 above. It is in the point which changed the compounding quantity. The other points of Comparative Examples 7 and 8 are the same as in Example 2 above.

Comparative Examples 9 and 10
For comparison, a hard coat film is produced in the same manner as in Example 5, except that the silicone-modified fluororesin (C) is different from Example 5 as shown in Table 1 below. It is in the point which changed the compounding quantity. The other points of Comparative Examples 9 and 10 are the same as those of Example 5 above.

(Performance test of hard coat film)
Next, in order to test the performance of the hard coat films of Examples 1 to 14 and Comparative Examples 1 to 10, samples of each hard coat film were tested by the following method, and the obtained results were as follows. It showed in Table 1.

(1) Measurement of haze The haze was measured according to the standard of JIS K 7165. The haze (%) of each hard coat film sample was measured with a haze meter (trade name 300A, manufactured by Tokyo Denshoku Co., Ltd.) using a D65 light source.

(2) Flexibility test The flexibility of the hard coat film was measured according to JIS K 5600-5-1. The size of the mandrel for bending test was selected, and cracking and peeling of each hard coat film were confirmed. The minimum diameter (mm) of the mandrel that began to crack and peel was determined.

(3) Contact angle measurement The contact angle (°) of each hard coat film sample was measured using a contact angle meter according to JIS K 2396. Pure water was used for the measurement of the contact angle.

Here, if the contact angle of pure water of the hard coat film is 90 degrees or more, the antifouling property is excellent.

  As is clear from the results in Table 1 above, according to the hard coat films of Examples 1 to 14 of the present invention, the scratch resistance and adhesion are maintained, the flexibility and hardness are improved, and the antifouling property is further improved. It turned out to be equipped.

  On the other hand, it was found that the hard coat films of Comparative Examples 1 to 10 could not achieve both antifouling property, flexibility and haze.

Example 15
Next, an antireflection film was produced using the hard coat film produced in Examples 1-14.

(surface treatment)
First, the hard coat films prepared in Examples 1 to 14 were each immersed in a 2 mol / L sodium hydroxide solution at a temperature of 60 ° C. for 90 seconds, then washed with water and dried to perform alkali surface treatment.

(Preparation of antireflection film)
The following coating composition for a low refractive index layer is die-coated on the hard-coated film subjected to the above surface treatment, dried at a temperature of 80 ° C. for 1 minute, and then irradiated with 0.1 J / cm ² of ultraviolet light with a high-pressure mercury lamp. The film was further cured at a temperature of 120 ° C. for 1 minute to form a low refractive index layer having a thickness of 90 nm and a refractive index of 1.35 to produce an antireflection film.

(Coating composition for low refractive index layer)
Silane hydrolyzate 50 parts by weight Hollow silica-based particle dispersion 30 parts by weight 3-acryloxypropyltrimethoxysilane 3 parts by weight (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.)
1 part by weight of aluminum ethyl acetoacetate diisopropylate (ALCH, manufactured by Kawaken Fine Chemical Co., Ltd.)
Polyoxyalkylene dimethyl polysiloxane copolymer (FZ-2207, manufactured by Toray Dow Corning Co., Ltd.) 10% propylene glycol monomethyl ether solution 2 parts by weight Propylene glycol monomethyl ether 450 parts by weight Isopropyl alcohol 450 parts by weight (Preparation of silane hydrolyzate)
By mixing 205 g of tetraethoxysilane, 25 g of tridecafluorooctyltrimethoxysilane, and 440 g of ethanol and adding 120 g of 2% aqueous acetic acid solution thereto, the mixture is stirred for 20 hours in a water bath at a temperature of 25 ° C. A hydrolyzate was prepared.

(Preparation of hollow silica-based particle dispersion)
Step a: A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by weight and 1900 g of pure water was heated to a temperature of 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of 0.98 wt% sodium silicate aqueous solution as SiO ₂ and 9000 g of 1.02 wt% sodium aluminate aqueous solution as Al ₂ O ₃ were simultaneously added to the mother liquor. Added. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ core particle dispersion with a solid content concentration of 20 wt%.

Step b: Silica solution obtained by adding 1700 g of pure water to 500 g of this core particle dispersion and heating to 98 ° C. and keeping the temperature while dealkalizing the sodium silicate aqueous solution with a cation exchange resin. (SiO ₂ concentration 3.5 wt%) 3000 g was added to obtain a dispersion of core particles on which the first silica coating layer was formed.

  Step c: Next, 1125 g of pure water is added to 500 g of the core particle dispersion liquid on which the first silica coating layer having a solid content concentration of 13 wt% is formed by washing with an ultrafiltration membrane, and concentrated hydrochloric acid (35.5% ) Was dropped to adjust the pH to 1.0, and dealumination treatment was performed.

Next, while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, the aluminum salt dissolved in the ultrafiltration membrane was separated, and SiO _2. A dispersion of Al ₂ O ₃ porous particles was prepared.

A mixture of 1500 g of the porous particle dispersion, 500 g of pure water, 1750 g of ethanol, and 626 g of 28% ammonia water is heated to 35 ° C., and then 104 g of ethyl silicate (SiO ₂ concentration: 28 wt%) is added. The surface of the porous particles on which the first silica coating layer was formed was coated with a hydrolyzed polycondensate of ethyl silicate to form a second silica coating layer. Next, a hollow silica-based particle dispersion having a solid content concentration of 20% by weight was prepared by replacing the solvent with ethanol using an ultrafiltration membrane.

The thickness of the first silica coating layer of the hollow silica-based particles was 3 nm, the average particle size was 45 nm, MO _X / SiO ₂ (molar ratio) was 0.0017, and the refractive index was 1.28. Here, the average particle diameter was measured by a dynamic light scattering method.

(Antireflection evaluation)
As a result of measuring the reflectance of the prepared antireflection film sample using CM-3700d (manufactured by Konica Minolta Sensing Co., Ltd.), the antireflection film sample using the hard coat films of Examples 1 to 14 of the present invention was In any case, the luminous reflectance was in the range of 1.2 to 1.4% and had good antireflection performance.

  Moreover, as a result of evaluating in the same manner as in Examples 1 to 14, the antireflection film sample using the hard coat film of the present invention maintains scratch resistance and adhesion, and improves flexibility and hardness. Furthermore, it was satisfactory with sufficient antifouling properties.

Comparative Example 11
For comparison, an antireflection film was prepared in the same manner as in Example 15 using the hard coat film prepared in Comparative Examples 1 to 10.

  As a result of measuring the reflectance of the prepared comparative antireflection film sample in the same manner as in Example 15, the comparative antireflection film sample using the hard coat film prepared in Comparative Examples 1 to 10 was In any case, the luminous reflectance was in the range of 1.5 to 1.6%, and the antireflection performance was poor.

  Moreover, as a result of evaluating in the same manner as in Examples 1 to 14, the comparative antireflection film sample using the hard coat film prepared in Comparative Examples 1 to 10 has both antifouling property, flexibility, and haze. It turned out that it was not done.

Example 16
Next, KC4FR-1 (Konica Minolta Opto, which is a cellulose ester-based optical compensation film, is used as the polarizing plate protective film using the hard coat film prepared in Examples 1 to 14 and the antireflection film prepared in Example 15 respectively. A polarizing plate was produced in combination with (made by Co., Ltd.).

(Preparation of polarizing film)
100 parts by weight of polyvinyl alcohol (hereinafter referred to as PVA) having a saponification degree of 99.95 mol% and a polymerization degree of 2400 is impregnated with 10 parts by weight of glycerin and 170 parts by weight of water. The film was melt-extruded from a T die onto a metal roll to form a film. Then, it dried and heat-processed and obtained the PVA film. The obtained PVA film had an average thickness of 40 μm, a moisture content of 4.4%, and a film width of 3 m.

  This PVA film was continuously processed in the order of pre-swelling, dyeing, uniaxial stretching by a wet method, fixing treatment, drying, and heat treatment to prepare a polarizing film.

  That is, the PVA film was immersed in water at a temperature of 30 ° C. for 30 seconds and pre-swelled, and then immersed in an aqueous solution having an iodine concentration of 0.4 g / L and a temperature of 35 ° C. and a potassium iodide concentration of 40 g / L for 3 minutes. Next, the film was uniaxially stretched 6 times under the condition that the tension applied to the film was 700 N / m in an aqueous solution with a boric acid concentration of 4% at a temperature of 50 ° C., and a potassium iodide concentration of 40 g / L, a boric acid concentration of 40 g / L, The fixing treatment was performed by immersing in an aqueous solution having a zinc chloride concentration of 10 g / L at a temperature of 30 ° C. for 5 minutes. Thereafter, the PVA film was taken out, dried with hot air at a temperature of 40 ° C., and further subjected to heat treatment at a temperature of 100 ° C. for 5 minutes. The obtained polarizing film had an average thickness of 15 μm.

(Preparation of polarizing plate)
Then, according to the following Step 1 to Step 5, the polarizing film, the optical compensation film, the hard coat film of Examples 1 to 14, and the protective film for polarizing plate made of the antireflection film of Example 15 are bonded together. Thus, a polarizing plate was produced.

  Step 1: The optical compensation film, the hard coat film of Examples 1 to 14 and the antireflection film of Example 15 were each immersed in a 2 mol / L sodium hydroxide solution at a temperature of 60 ° C. for 90 seconds, and then washed with water. , Dried.

  Step 2: Next, the polarizing film was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by weight for 1 to 2 seconds.

  Step 3: The excess adhesive adhered to the polarizing film in Step 2 was lightly removed, and the polarizing film was subjected to alkali treatment in Step 1 and the hard coat film of Examples 1 to 14 or of Example 15 It was sandwiched between antireflection films and laminated.

Process 4: It bonded together by the speed of about 2 m / min with the pressure of 20-30 N / cm < ² > with the two rotating rollers.

  Step 5: The sample prepared in Step 4 was dried for 2 minutes in a dryer at 80 ° C. to prepare a polarizing plate.

(Production of liquid crystal display panel for testing)
Next, the polarizing plate on the outermost surface of a commercially available liquid crystal display panel (VA type) was carefully peeled off, and polarized light using the hard coat films of Examples 1 to 14 and the antireflection film of Example 15 produced above. Each of the plates was attached to prepare a test liquid crystal display panel.

  Each liquid crystal display panel obtained as described above was placed on a desk 80 cm high from the floor, and a daylight direct fluorescent lamp (FLR40S • D / MX-X) was placed on the ceiling 3 m high from the floor. Matsushita Electric Industrial Co., Ltd.) 10 sets of 40W × 2 were set as one set at intervals of 1.5 m.

  Here, when the evaluator is in front of the display surface of the liquid crystal display panel, the fluorescent lamp is arranged so that the fluorescent lamp comes to the ceiling portion from the evaluator's overhead to the rear. The liquid crystal display panel was tilted by 25 ° from the vertical direction with respect to the desk, and the fluorescent lamp was reflected so that the visibility of the screen (visibility) was evaluated as follows.

A: You don't mind from the reflection of the nearest fluorescent lamp, and you can clearly read characters with a font size of 8 or less. B: The reflection of the nearby fluorescent lamp is a little worrisome, but you don't care about the distance. Can manage to read characters with a font size of 8 or less C: It is difficult to read characters with a font size of 8 or less. It is considerably worrisome, and the portion of the reflection cannot read characters with a font size of 8 or less. As a result of the evaluation, the hard coat film of the present invention of Examples 1 to 14 and the antireflection of the present invention of Example 5 All of the liquid crystal display panels to which the polarizing plate using the film was attached had an evaluation result of “B or higher”, and the visibility was good.

Comparative Example 12
For comparison, the hard coat film prepared in Comparative Examples 1 to 10 and the antireflection film prepared in Comparative Example 11 were used as a protective film for a polarizing plate, and for comparison, in the same manner as in Example 16 above. A polarizing plate was produced.

  Next, the polarizing plates using the hard coat films of Comparative Examples 1 to 10 and the antireflection film of Comparative Example 11 were respectively applied to commercially available liquid crystal display panels (VA type) in the same manner as in Example 16. A liquid crystal display panel for comparison was manufactured by pasting.

  About each liquid crystal display panel for comparison obtained in this way, when the visibility of the screen (visibility) was evaluated in the same manner as in Example 16, the hard coat film of Comparative Examples 1 to 10, and All of the liquid crystal display panels to which the polarizing plate using the antireflection film of Comparative Example 11 was attached had an evaluation result of “C or less”, and the visibility was poor.

Claims (8)

  One side or both sides of the transparent film substrate has a vinyl group and a carboxyl group in the side chain, and the weight average molecular weight is 10,000 or more and 50,000 or less, and the double bond equivalent of the vinyl group is 500 or more and 2,000 or less. A polyurethane-based reactive polymer (A), a polyfunctional (meth) acrylate monomer (B), a silicone-modified fluororesin (C), and a radical photopolymerization initiator (D) are mixed into a polyfunctional (meth) acrylate monomer (B). 4 to 50 parts by weight of the polyurethane-based reactive polymer (A), 0.1 to 10 parts by weight of the silicone-modified fluororesin (C), and 0 to the radical photopolymerization initiator (D). A hard coat layer formed by applying and curing a resin composition containing 1 to 10 parts by weight is provided. Coat film.   The hard coat film according to claim 1, wherein the polyfunctional (meth) acrylate monomer (B) is mainly composed of a trifunctional or higher functional (meth) acrylate monomer or the same oligomer.   The resin composition further includes organic particles or inorganic particles having a primary particle diameter of 1 nm to 100 nm in an amount of 5 to 200 parts by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate monomer (B). The hard coat film according to claim 1 or 2.   It is a manufacturing method of the hard coat film of Claim 1, Comprising: It has a vinyl group and a carboxyl group in a side chain, and the weight average molecular weight is 10,000 or more and 50000 or less, and the double bond equivalent of a vinyl group is 500 As described above, a polyurethane-based reactive polymer (A) having a molecular weight of 2000 or less, a polyfunctional (meth) acrylate monomer (B), a silicone-modified fluororesin (C), and a photoradical polymerization initiator (D) are mixed with a polyfunctional (meta ) 4 to 50 parts by weight of the polyurethane-based reactive polymer (A), 0.1 to 10 parts by weight of the silicone-modified fluororesin (C), and a photo-radical polymerization initiator (100 parts by weight of the acrylate monomer (B)) D) A resin composition for forming a hard coat layer is prepared by blending at a ratio of 0.1 to 10 parts by weight, The surface, coating the hard coat layer-forming resin composition and cured, and providing a hard coat layer, the production method of the hard coat film.   The antireflective film characterized by further providing the low-refractive-index layer on the hard-coat layer of the hard-coat film as described in any one of Claims 1-3.   The hard coat film as described in any one of Claims 1-3 is used for one surface, The polarizing plate characterized by the above-mentioned.   A polarizing plate using the antireflection film according to claim 5 on one surface.   A display device comprising the polarizing plate according to claim 6.