JP2007047722A - Anti-glare hard coating film and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-glare hard coating film having high hardness, scratch resistance and satisfactory antiglare properties, to provide a manufacturing method of the anti-glare hard coating film, to provide an optical element that uses the anti-glare hard coating film, and to provide an image display device that is equipped with the film or the optical element. <P>SOLUTION: The anti-glare hard coating film 4 comprises a transparent film substrate 1 and; a hard coating layer 2 that contains fine particles 3 and is formed, on at least one side of the transparent film substrate 1, wherein the hard coating layer 2 has a thickness of ≥15 μm and ≤30 μm, the fine particles 3 have an average particle size of ≥30% and ≤75% of the thickness of the hard coating layer 2 and the fine particles 3 form unevenness with θa value of ≥0.4° and ≤1.5° in accordance with JIS B 0601. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antiglare hard coat film in which a hard coat layer is provided on at least one surface of a transparent film substrate and a method for producing the same. More specifically, an anti-polarization that can be suitably used for optical elements such as polarizing plates and image display devices such as CRT (Cathode Ray Tube), liquid crystal display (LCD), plasma display (PDP), and electroluminescence display (ELD). The present invention relates to a dazzling hard coat film and a method for producing the same.

  One of the various image display devices is the LCD. With the technological innovations related to higher viewing angle, higher definition, faster response, and color reproducibility of LCDs, applications that use LCDs are also notebook personal computers and monitors. To TV. The basic structure of an LCD is that flat glass substrates each having a transparent electrode are arranged opposite to each other via a spacer so as to form a gap with a predetermined interval, and a liquid crystal material is injected between the glass substrates and sealed. The liquid crystal cell is further provided with polarizing plates on the outer surfaces of the pair of glass substrates. Conventionally, a cover plate made of glass or plastic is attached to the surface of the liquid crystal cell to prevent damage to the polarizing plate attached to the surface of the liquid crystal cell. However, when a cover plate is attached, it is disadvantageous in terms of cost and weight, and a hard coat treatment is gradually applied to the surface of the polarizing plate.

  A hard coat film obtained by subjecting a transparent plastic film substrate to a hard coat treatment is usually about 2 to 10 μm on the transparent plastic film substrate using an ionizing radiation curable resin such as a thermosetting resin or an ultraviolet curable resin. Can be obtained by forming a thin hard coat layer. When a hard coat layer is provided by coating the above resin on glass, it exhibits a pencil hardness of 4H or more, but when the base is a transparent plastic film substrate, the thickness of the hard coat layer is If it is not sufficient, the pencil hardness is generally lowered to 3H or less due to the influence of the transparent plastic film substrate.

  With the transition of LCD applications to home TVs, general home TV users will handle TVs using LCDs in the same way as conventional TVs using glass CRTs. Is easily assumed. The pencil hardness of CRT made of glass is about 9H, and the difference from the pencil hardness characteristic of the current hard coat film is clear. Therefore, even if the pencil hardness does not reach 9H, further increase in the hardness of the hard coat film is required.

  In order to increase the hardness of the hard coat film, it is possible to increase the thickness of the hard coat layer. However, the increase in the layer thickness has a problem that particles contained in the hard coat layer are completely embedded in the hard coat layer, and sufficient antiglare properties cannot be exhibited. There is a method of increasing the amount of fine particles added in order to improve the antiglare property. However, in this case, there is a problem that the number of particles in the layer direction is increased, and as a result, the haze value is increased. Therefore, in recent years, the following Patent Documents 1 to 4 have been proposed as methods for solving the problems such as the antiglare property and the increase in the haze value that occur as a result of realizing the high hardness of the hard coat film.

  Patent Document 1 discloses an anti-glare film in which a hard coat layer mainly composed of particles having an average particle diameter of 0.6 to 20 μm, fine particles having an average particle diameter of 1 to 500 nm, and a hard coat resin is formed on a transparent substrate film. A functional film is disclosed. Further, it is described that the thickness of the hard coat layer is not more than the particle diameter of the particles, preferably not more than 80% of the average particle diameter (specifically, not more than 16 μm). However, if the thickness of the hard coat layer is about that, there is a problem that sufficient hardness cannot be exhibited.

  Patent Document 2 discloses a hard coat film in which at least one hard coat layer is formed on at least one surface of a plastic substrate film, and the hard coat layer has a thickness of 3 to 30 μm. Further, it is described that inorganic fine particles having a secondary particle size of 20 μm or less are added to the hard coat layer. Furthermore, there is a statement that the surface of the hard coat layer is uneven to impart antiglare properties, but in such a configuration, the surface roughness of the hard coat layer surface is not taken into account at all, and inorganic When the structure is such that the fine particles are completely embedded in the hard coat layer, there is a problem that sufficient antiglare properties cannot be exhibited.

  Patent Document 3 discloses an antireflection film obtained by laminating a hard coat film layer, a metal alkoxide and a hydrolyzate thereof as a main component on at least one surface of a plastic film, An antireflection film having an elastic modulus of 0.7 to 5.5 GPa below the fracture strain of the layer is disclosed. Further, it is also described that the film thickness of the hard coat layer is 0.5 μm or more and 20 μm or less, and the average particle diameter of the fine particles contained in the hard coat layer is 0.01 to 10 μm. However, in the invention described in Patent Document 3, although hardness and scratch resistance are improved, for example, fine particles having an average particle size of about 1.8 μm are added to a hard coat layer having a thickness of about 20 μm. In this case, there is a problem that the fine particles are completely embedded in the hard coat layer, and sufficient antiglare properties cannot be exhibited.

Patent Document 4 discloses an antiglare hard coat layer containing particles having an average particle diameter of 1 to 10 μm, inorganic fine particles having an average particle diameter of 0.001 to 0.2 μm, and photocurability on a transparent support. Of the organosilane hydrolyzate and / or its partial condensate, and a low-refractive index layer having a refractive index in the range of 1.35 to 1.49, which is sequentially formed from a composition containing a fluorine-containing polymer An antiglare antireflection film is disclosed which has a haze value in the range of 3 to 20% and an average reflectance of 450 nm to 650 nm of 1.8% or less. . Moreover, it describes that the film thickness of an anti-glare hard-coat layer is 1-10 micrometers. The invention described in Patent Document 4 is intended to improve scratch resistance, antiglare properties, etc., but has a problem that sufficient hardness is not obtained.
Japanese Patent Laid-Open No. 11-286083 JP 2000-326447 A JP 2001-194504 A JP 2001-264508 A

  The present invention has been made in view of the above problems, and its purpose is to provide an antiglare hard coat film excellent in high hardness, scratch resistance, and antiglare property, a method for producing the same, an optical element using the same, and them. An image display apparatus provided with

  In order to solve the above-mentioned conventional problems, the inventors of the present application have made extensive studies on an antiglare hard coat film, a method for producing the same, an optical element using the same, and an image display device including the same. As a result, the inventors have found that the object can be achieved by adopting the following configuration, and have completed the present invention.

  That is, the antiglare hard coat film according to the present invention has an antiglare hard coat film having a hard coat layer containing fine particles on at least one surface of a transparent film substrate in order to solve the above-mentioned problems. The film thickness of the hard coat layer is 15 μm or more and 30 μm or less, and the average particle diameter of the fine particles is 30% or more and 75% or less of the film thickness of the hard coat layer, and is formed by the fine particles. The θa according to the concavo-convex JIS B 0601 is 0.4 ° or more and 1.5 ° or less.

  With the above configuration, the hard coat layer has a thickness of 15 to 30 μm and thus has a structure in which insufficient hardness is suppressed. Further, the average particle diameter of the fine particles contained in the hard coat layer is set to 30% to 75% of the film thickness, and the uneven θa formed by the fine particles is set to 0.4 ° or more and 1.5 ° or less, and the hard coat layer Fine particles having a relatively large particle size compared with the film thickness of are used. Therefore, at least a part of the fine particles can be exposed from the surface layer portion of the hard coat layer, and the antiglare property can be improved. In addition, it is possible to suppress a decrease in scratch resistance that occurs when using small-sized fine particles that are not easily affected by gravity sedimentation. That is, according to the said structure, the anti-glare hard coat film with favorable hardness, anti-glare property, and abrasion resistance can be provided.

  It is preferable that the material for forming the hard coat layer includes urethane acrylate, polyol (meth) acrylate, and a (meth) acrylic polymer having an alkyl group containing two or more hydroxyl groups.

  By containing urethane acrylate as a material for forming the hard coat layer as in the above configuration, elasticity and flexibility can be imparted to the hard coat layer. In addition, the hard coat layer can be increased in hardness by containing polyol (meth) acrylate. Furthermore, by containing a (meth) acrylic polymer having a 3-hydroxypropyl group, a hard coat layer in which curing shrinkage is reduced and curling is suppressed can be obtained.

  The polyol (meth) acrylate is preferably composed of pentaerythritol triacrylate and pentaerythritol tetraacrylate.

  With this configuration, curling can be further suppressed while maintaining high hardness and good flexibility.

  Moreover, it is preferable that at least one antireflection layer is provided on the hard coat layer.

  When an antireflection layer is provided on the outer surface of the hard coat layer as in the above configuration, reflection of light at the interface between the hard coat layer and air can be reduced. Thereby, when the anti-glare hard coat film of the said structure is applied, for example to an image display apparatus etc., it can suppress that the visibility of the image of a display screen falls.

  The antireflection layer preferably contains hollow spherical silicon oxide ultrafine particles.

  In the antiglare hard coat film, the glossiness according to JIS K 7105 is preferably from 50 to 95. The “glossiness” means a 60-degree specular glossiness according to JIS K 7105 (1981 edition).

  Moreover, the manufacturing method of the anti-glare hard coat film which concerns on this invention is the anti-glare hard coat film which forms a hard-coat layer in the at least one surface of a transparent film base material in order to solve the said subject. In the manufacturing method, a step of preparing a material for forming a hard coat layer, wherein fine particles having an average particle size of 30% to 75% of the film thickness of the hard coat layer are added to the material. The step of preparing, the step of applying the forming material on at least one surface of the film base material to form a coating film, the coating film is cured, and the film thickness is 15 μm or more and 30 μm or less, And a step of forming a hard coat layer having a concavo-convex shape of JIS B 0601 formed by fine particles according to JIS B 0601 of 0.4 ° to 1.5 °.

  According to the said method, since the hard-coat layer whose film thickness is 15-30 micrometers is formed, the anti-glare hard-coat film which has sufficient hardness can be manufactured. In addition, since fine particles having an average particle diameter of 30% to 75% with respect to the film thickness of the hard coat layer are used, even if most of the fine particles are embedded in the hard coat layer, a part of the fine particles is used. A hard coat layer having at least an exposed structure can be formed. Furthermore, since the hard coat layer is formed so that θa is 0.4 ° or more and 1.5 ° or less, the antiglare property can be excellent. In addition, since fine particles having a relatively large particle size compared to the film thickness of the hard coat layer are used, it is possible to suppress a decrease in scratch resistance that occurs when using fine particles having a small particle size that are difficult to gravity settle. That is, with the above method, an antiglare hard coat film having good hardness, antiglare property and scratch resistance can be produced.

  It is preferable to use a material containing ethyl acetate as a diluent solvent for the material for forming the hard coat layer.

  Thereby, the hard-coat layer which is excellent in adhesiveness with a film base material and can reduce peeling from a film base material can be formed.

  Moreover, it is preferable that content of the said ethyl acetate is 20 weight% or more. This makes it possible to form a hard coat layer that is more excellent in adhesion to the film substrate.

  The optical element according to the present invention is characterized in that the antiglare hard coat film described above is provided on at least one surface of the optical member in order to solve the above-mentioned problems.

  In addition, a polarizing plate according to the present invention is provided with the antiglare hard coat film described above in order to solve the above-described problems.

  Furthermore, the polarizing plate according to the present invention is characterized in that the hard coat film described above is provided on at least one surface of a polarizer in order to solve the above-mentioned problems.

  In addition, an image display device according to the present invention includes the antiglare hard coat film described above, the optical element described above, or the polarizing plate described above in order to solve the above problems. Features.

The present invention has the following effects by the means described above.
That is, according to the present invention, an antiglare hard coat film having high hardness and excellent antiglare property and scratch resistance can be provided. Therefore, for example, the antiglare hard coat film is applied to various optical elements and image display devices. When used, it is possible to prevent these devices from being damaged, and to prevent the reflection of external light and the like with a good anti-glare effect.

  Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an outline of an antiglare hard coat film according to the present embodiment.

  As shown in FIG. 1, the antiglare hard coat film 4 has a structure having a hard coat layer 2 on one side of a transparent film substrate 1. Although not shown in FIG. 1, the hard coat layer 2 can be provided on both surfaces of the film substrate 1. Moreover, in FIG. 1, although the case where the hard-coat layer 2 is a single layer is illustrated, as long as it has the hard-coat layer of this invention, these may be two or more layers.

  The film substrate 1 is not particularly limited as long as it is excellent in visible light transmittance (preferably a light transmittance of 90% or more) and excellent in transparency (preferably a haze value of 1% or less). Specifically, for example, a film made of a transparent polymer such as a polyester polymer such as polyethylene terephthalate and polyethylene naphthalate, a cellulose polymer such as diacetyl cellulose and triacetyl cellulose, a polycarbonate polymer, and an acrylic polymer such as polymethyl methacrylate. Is mentioned. In addition, styrene polymers such as polystyrene and acrylonitrile / styrene copolymer, polyethylene, polypropylene, polyolefins having a cyclic or nobornene structure, olefin polymers such as ethylene / propylene copolymer, vinyl chloride polymers, nylon and aromatic polyamides. Examples thereof include a film made of a transparent polymer such as an amide polymer. Furthermore, imide polymers, sulfone polymers, polyether sulfone polymers, polyether ether ketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene Examples thereof include a film made of a transparent polymer such as a polymer, an epoxy polymer, and a blend of the above polymers. In particular, those having a small optical birefringence are preferably used. When the anti-glare hard coat film 4 according to the present embodiment is used as a protective film for a polarizing plate, the film substrate 1 includes triacetyl cellulose, polycarbonate, acrylic polymer, polyolefin having a cyclic or norbornene structure. Etc. are suitable. Further, the film base 1 may be a polarizer itself described later. With such a configuration, a protective layer made of TAC or the like is not required and the structure of the polarizing plate can be simplified, so that the number of manufacturing steps can be reduced and the production efficiency can be improved. Further, the polarizing plate can be further thinned. In the case where the film substrate 1 is a polarizer, the hard coat layer 2 serves as a conventional protective layer. The hard coat film also serves as a cover plate attached to the surface of the liquid crystal cell.

  The thickness of the film substrate 1 can be appropriately determined, but is generally about 10 to 500 μm in consideration of workability such as strength and handleability, and thin layer properties. 20-300 micrometers is especially preferable, and 30-200 micrometers is more preferable. Furthermore, it does not restrict | limit especially as a refractive index of the film base material 1, Usually, about 1.30-1.80, It is especially preferable that it is 1.40-1.70.

  The hard coat layer 2 is composed of urethane acrylate (A), polyol (meth) acrylate (B), and (meth) acrylic polymer (C) having an alkyl group containing two or more hydroxyl groups as a forming material.

  As said urethane acrylate (A), what contains (meth) acrylic acid and / or its ester, a polyol, and diisocyanate as a structural component is used. For example, a product produced by preparing hydroxy (meth) acrylate having at least one hydroxyl group from (meth) acrylic acid and / or its ester and polyol and reacting it with diisocyanate is used. (Meth) acrylic acid is acrylic acid and / or methacrylic acid, and (meth) has the same meaning in the present invention. Each of these components may be used alone or in combination of two or more.

  Examples of (meth) acrylic acid esters include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth) acrylate; cyclohexyl (meta And cycloalkyl (meth) acrylate such as acrylate.

  The polyol is a compound having at least two hydroxyl groups, such as ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decane glycol, 2,2,4-trimethyl-1,3-pentanediol, 3-methyl-1,5 -Pentanediol, hydroxypivalic acid neopentyl glycol ester, cyclohexane dimethylol, 1,4-cyclohexane diol, spiro glycol, tricyclodecane dimethylol, hydrogenated bisphenol A, ethylene oxide-added bisphenol A, propylene glycol Side addition bisphenol A, trimethylolethane, trimethylolpropane, glycerin, 3-methylpentane-1,3,5-triol, pentaerythritol, dipentaerythritol, tripentaerythritol, glucose, etc. can be mentioned.

  As the diisocyanate, various aromatic, aliphatic or alicyclic diisocyanates can be used. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 4,4 -Diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 3,3-dimethyl-4,4-diphenyl diisocyanate, xylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate, and hydrogenated products thereof It is done.

  If the amount of the urethane acrylate (A) added is too small, the flexibility and adhesion of the hard coat layer will decrease, and if too large, the hardness of the hard coat layer after curing will decrease. For this reason, urethane acrylate (A) is 15 wt% to 55 wt% with respect to all resin components of the hard coat forming material (the total amount of components A to C, or the total amount including the added resin material, if any). % By weight is preferred, with 25% to 45% by weight being more preferred. If the addition amount of the urethane acrylate (A) exceeds 55% by weight with respect to the total resin components of the hard coat forming material, the hard coat performance may be deteriorated, which is not preferable. On the other hand, if the blending amount is less than 15% by weight, flexibility and adhesion are not improved, which is not preferable.

  Examples of the component of the polyol (meth) acrylate (B) include pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Examples include 1,6-hexanediol (meth) acrylate. Moreover, what contains the monomer component which consists of a polymer of pentaerythritol triacrylate and pentaerythritol tetraacrylate is preferable. Furthermore, a mixed component containing pentaerythritol triacrylate and pentaerythritol tetraacrylate is particularly preferable.

  The blending amount of the polyol (meth) acrylate (B) is preferably 70 to 180% by weight, more preferably 100 to 150% by weight, based on the urethane acrylate (A). . When the blending amount of the polyol (meth) acrylate (B) exceeds 180% by weight with respect to the urethane acrylate (A), the curing shrinkage of the hard coat layer increases, and as a result, the curl of the hard coat film increases. In some cases, flexibility is deteriorated. On the other hand, when the ratio is less than 70% by weight, the hard coat property, that is, the hardness and the scratch resistance may be deteriorated, which is not preferable. The scratch resistance is preferably in the range of 0 to 0.7, more preferably in the range of 0 to 0.5, from a practical viewpoint. By setting the blending amount of the polyol (meth) acrylate (B) within the above range, the scratch resistance can be set within the above range. Here, the calculation of the scratch resistance will be described in Examples described later.

  As the (meth) acrylic polymer (C), those having an alkyl group containing two or more hydroxyl groups are used. More specifically, examples include (meth) acrylic polymers having 2,3-dihydroxypropyl groups and (meth) acrylic polymers having 2-hydroxyethyl groups and 2,3-dihydroxypropyl groups.

  The addition amount of the (meth) acrylic polymer (C) having an alkyl group containing two or more hydroxyl groups is preferably 25% by weight to 110% by weight with respect to the urethane acrylate (A), and 45% by weight. More preferred is a ratio of ˜85% by weight. If the blending amount exceeds 110% by weight, the coatability may be lowered, which is not preferable. On the other hand, when the blending amount is less than 25%, the occurrence of curling is remarkably increased, which is not preferable.

  In the present invention, by containing this (meth) acrylic polymer (C), curing shrinkage of the hard coat layer 2 is suppressed, and as a result, curling is prevented. From the viewpoint of manufacturing a hard coat film or the like, it is preferable to suppress the occurrence of curling within at least 30 mm, and workability and production efficiency can be further improved by suppressing the occurrence of curling within the range. .

  The hard coat layer 2 contains fine particles 3. The fine particles 3 mainly function as antiglare fine particles that impart antiglare properties. The fine particles 3 are classified into inorganic fine particles and organic fine particles. The inorganic fine particles are not particularly limited, and examples thereof include silicon oxide, titanium oxide, aluminum oxide, zinc oxide, tin oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate. The organic fine particles are not particularly limited. For example, polymethacrylic acid methyl acrylate resin powder, silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic styrene resin powder, benzoguanamine resin powder, melamine resin powder. Furthermore, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, polyfluoroethylene resin powder and the like can be mentioned. Two or more of these inorganic fine particles and organic fine particles may be used in combination.

  The average particle diameter of the fine particles 3 is 30% or more and 75% or less, more preferably 30% or more and 50 or less of the film thickness of the hard coat layer 2. When the average particle size is less than 30%, there is a disadvantage that a sufficient uneven shape cannot be formed on the surface and a sufficient antiglare function cannot be imparted. On the other hand, when the average particle size exceeds 75%, the unevenness of the surface becomes too large, and there is a disadvantage that the appearance is deteriorated or the scattering of reflected light becomes strong and white blurring occurs.

  The blending amount of the fine particles 3 is not particularly limited, and can be set as appropriate. Specifically, it is preferably 2 to 70 parts by weight, more preferably 4 to 50 parts by weight, and 15 to 40 parts by weight with respect to 100 parts by weight of the hard coat forming material. Is particularly preferred.

  In order to suppress light scattering generated at the interface between the fine particles 3 and the hard coat layer 2 as much as possible, it is necessary to reduce the difference in refractive index between the fine particles 3 and the hard coat layer 2. The refractive index of the hard coat layer 2 is generally 1.4 to 1.6. Therefore, as the fine particles 3, it is preferable to use organic fine particles that approximate the refractive index of the hard coat layer 2 or inorganic fine particles made of silicon oxide. The refractive index difference of the fine particles 3 with respect to the refractive index of the hard coat layer 2 is preferably less than 0.05. When the refractive index difference is 0.05 or more, light scattering becomes strong. As a result, for example, when applied to an image display device, there may be a problem that display content is blurred.

  The shape of the fine particles 3 is not particularly limited, and may be a bead-like substantially spherical shape or may be an irregular type such as a powder. These fine particles can be used by appropriately selecting one type or two or more types. The fine particles 3 are preferably substantially spherical with an aspect ratio of 1.5 or less. When substantially spherical particles or polygonal particles having an aspect ratio exceeding 1.5 are used, it may be difficult to control θa of the concavo-convex shape formed by the fine particles 3.

  The average inclination angle θa of the hard coat layer 2 needs to be not less than 0.4 ° and not more than 1.5 °. If θa is less than 0.4 °, sufficient anti-glare property cannot be exhibited, and there is a disadvantage that reflection of external light or the like occurs. On the other hand, if θa exceeds 1.5 °, there is a disadvantage that the haze value increases. Within the above range, the antiglare effect of the hard coat layer 2 can be improved, and reflection of external light or the like can be suitably prevented. The average inclination angle θa is a value obtained by a method according to JIS B 0601.

  When the refractive index difference between the film substrate 1 and the hard coat layer 2 is d, d is preferably 0.04 or less, and more preferably 0.02 or less. When a polyethylene terephthalate film is used as the film substrate 1, the refractive index of the polyethylene terephthalate film is blended with ultrafine particles having a particle size of 100 nm or less in an amount of about 35% of the total resin component of the hard coat forming material. D can be controlled to 0.02 or less with respect to about 1.64, and the occurrence of interference fringes can be suppressed.

  When a triacetyl cellulose film is used as the film substrate 1, silicon oxide is blended in ultrafine particles having a particle size of 100 nm or less to about 40% of the total resin components of the hard coat forming material. D can be controlled to 0.02 or less in the same manner as described above with respect to the refractive index of about 1.48, and the generation of interference fringes can be suppressed.

  The thickness of the hard coat layer 2 is preferably 15 to 30 μm, more preferably 18 to 25 μm. Even if the lower limit of the thickness is 15 μm, since the hard coat layer 2 contains the polyol (meth) acrylate (B), the hardness can be maintained at a certain level (for example, 4H or more in pencil hardness). Further, in order to further increase the hardness, even if the upper limit value of the thickness is 25 μm, the hard coat layer 2 contains the urethane acrylate (A) and the (meth) acrylic polymer (C) having a 3-hydroxypropyl group. The occurrence of curling and cracking can be sufficiently prevented. When the thickness is less than 15 μm, the hardness of the hard coat layer may be reduced. On the other hand, when the thickness exceeds 25 μm, cracks may occur in the hard coat layer itself, or the hard coat film may curl to the hard coat surface side due to curing shrinkage of the hard coat layer, which may be a practical problem.

  It does not specifically limit as a dilution solvent of a hard-coat formation material, A various thing is employable. Specifically, for example, dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, acetone, methyl ethyl ketone, diethyl Ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-pentyl acetate, acetylacetone, Diacetone alcohol, methyl acetoacetate, ethyl acetoacetate, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-methyl 2-butanol, hexanol consequent opening, isobutyl acetate, methyl isobutyl ketone, 2-octanone, 2-pentanone, to 2-cyclohexanone, the 2-heptanone, heptanone, and the like to the 3-. These can be used alone or in combination of two or more. Ethyl acetate is preferably 20% by weight or more, more preferably 25% by weight or more, and particularly preferably in the range of 30% by weight to 70% by weight with respect to the total dilution solvent. Thereby, when using triacetyl cellulose as the film base material 1, it becomes possible to form the hard-coat layer 2 excellent in especially adhesiveness. When the content of ethyl acetate exceeds 70% by weight with respect to the total dilution solvent, the volatilization rate is fast, so that coating unevenness and drying unevenness easily occur. It may be unfavorable because it decreases.

  For the hard coat layer 2, for example, the surface of the film used for the formation of the hard coat layer 2 is preliminarily roughened by an appropriate method such as sand blasting, embossing roll, chemical etching, and the like. By using a concavo-convex structure, the surface of the material for forming the hard coat layer 2 may be combined with a method for forming a fine concavo-convex structure, etc., so that the concavo-convex state on the surface of the hard coat layer 2 may be uneven. .

  Various leveling agents can be added to the hard coat forming material. As the leveling agent, a fluorine-based or silicone-based leveling agent can be used as appropriate, and a silicone-based leveling agent is more preferable. Examples of the silicone leveling agent include reactive silicone, polydimethylsiloxane, polyether-modified polydimethylsiloxane, and polymethylalkylsiloxane. Of these silicone leveling agents, reactive silicones are particularly preferred. By adding reactive silicone, slipperiness is imparted to the surface and scratch resistance is maintained. Further, when a layer containing a siloxane component is used as the low refractive index layer, the adhesiveness is improved by using a reactive silicone having a hydroxyl group.

Examples of the leveling agent for the reactive silicone include those having a siloxane bond, an acrylate group and a hydroxyl group. More specifically,
(1) (Dimethylsiloxane / methyl) :( 3-acryloyl-2-hydroxypropoxypropylsiloxane / methyl) :( 2-acryloyl-3-hydroxypropoxypropylsiloxane) = 0.8: 0.16: 0.04 Molar ratio copolymer (2) Dimethylsiloxane: hydroxypropylsiloxane: 6-isocyanatohexylisocyanuric acid: aliphatic polyester = Molar ratio copolymer (6.3: 1.0: 2.2: 1.0) 3) Dimethylsiloxane: Methyl polyethylene glycol propyl ether siloxane having terminal acrylate: Methyl polyethylene glycol propyl ether siloxane having terminal hydroxyl group = 0.08: 0.07: 0.05 .

  The blending amount of the leveling agent is preferably 5 parts by weight or less, more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the total resin components of the hard coat forming material.

  In the case of using ultraviolet rays as a curing means for the hard coat forming material, if the leveling agent is oriented to the hard coat forming material, the leveling agent bleeds to the air interface during preliminary drying and solvent drying. Hardening inhibition of the ultraviolet curable resin by oxygen can be prevented, and the hard coat layer 2 having sufficient hardness even on the outermost surface can be obtained. In addition, since the silicone leveling agent is provided with slipperiness by bleeding on the surface of the hard coat layer 2, the scratch resistance can also be improved.

  The material for forming the hard coat layer 2 may be a pigment, a filler, a dispersant, a plasticizer, a UV absorber, a surfactant, an antioxidant, a thixotropic agent, etc. May be added. These additives may be used alone or in combination of two or more.

  A conventionally well-known photoinitiator can be used for the hard-coat formation material which concerns on this Embodiment. For example, 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, benzoinpropyl ether, benzyldimethyl ketal, N, N, N ′ , N′-tetramethyl-4,4′-diaminobenzophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, other thioxanthates, and the like can be used.

  The hard coat layer 2 is formed by forming a hard coat containing at least a urethane acrylate (A), a polyol (meth) acrylate (B), and a (meth) acrylic polymer (C) having an alkyl group containing two or more hydroxyl groups. The material is applied onto the film substrate 1 and then cured. The hard coat forming material can be applied as a solution dissolved in a solvent. When the hard coat forming material is applied as a solution, it is cured after drying.

  As a method for coating the hard coat forming material on the film substrate 1, known coating methods such as fan ten coat, die coat, spin coat, spray coat, gravure coat, roll coat, and bar coat can be used. .

The curing means for the hard coat forming material is not particularly limited, but ionizing radiation curing is preferable. Various active energies can be used as the means, but ultraviolet rays are preferred. As the energy ray source, for example, a high pressure mercury lamp, a halogen lamp, a xenon lamp, a metal halide lamp, a nitrogen laser, an electron beam accelerator, a radioactive element, or the like is preferable. The irradiation amount of the energy ray source is preferably 50 to 5000 mJ / cm ² as an integrated exposure amount at an ultraviolet wavelength of 365 nm. When the irradiation amount is less than 50 mJ / cm ² , curing becomes insufficient, and the hardness of the hard coat layer may be reduced. Moreover, when it exceeds 5000 mJ / cm < ² >, a hard-coat layer may color and transparency may fall.

  As shown in FIG. 2, an antireflection layer 5 can be provided on the hard coat layer 2 to form an antiglare antireflection hard coat film 6. FIG. 2 is a schematic cross-sectional view showing an outline of the antiglare and antireflection hard coat film 6 according to the present embodiment. When light strikes an object, it repeats phenomena such as reflection at the interface, absorption inside, and scattering, and passes through the back of the object. When a hard coat film is mounted on an image display device, one of the factors that lower the image visibility is the reflection of light at the interface between air and the hard coat layer. The antireflection layer 5 reduces the surface reflection. Although not shown in FIG. 2, the hard coat layer 2 and the antireflection layer 5 can be provided on both surfaces of the film substrate 1. FIG. 2 illustrates the case where one hard coat layer 2 and one antireflection layer 5 are provided. However, if the hard coat layer 2 of the present invention is provided, the antireflection layer 5 is 2. It may be a layer or more.

  Examples of the antireflection layer 5 include those obtained by laminating an optical thin film (antireflection layer) whose thickness and refractive index are strictly controlled on the surface of the hard coat layer 2. This is a method of developing an antireflection function by canceling out the reversed phases of incident light and reflected light using the light interference effect.

  In designing the antireflection layer 5 based on the light interference effect, as a means for improving the interference effect, there is a method of increasing the refractive index difference between the antireflection layer 5 and the hard coat layer 2. In general, in a multilayer antireflection layer in which 2 to 5 layers of optical thin films (thin films whose thickness and refractive index are strictly controlled) are laminated on a base material, a plurality of layers having different refractive indexes of a predetermined thickness are provided. By forming, the degree of freedom in optical design of the antireflection layer 5 is increased, the antireflection effect is further improved, and the spectral reflection characteristics can be made flat in the visible light region. Since the thickness accuracy of each layer of the optical thin film is required, each layer is generally formed by a dry method such as vacuum deposition, sputtering, or CVD.

  In the hard coat forming material, titanium oxide, zirconium oxide, silicon oxide, magnesium fluoride, etc. are used. In order to express the antireflection function more greatly, a laminate of a titanium oxide layer and a silicon oxide layer is used. It is preferable to use a body. In the laminate, a titanium oxide layer having a high refractive index (refractive index: about 1.8) is formed on the hard coat layer, and a silicon oxide layer having a low refractive index (refractive index: about 1.) is formed on the titanium oxide layer. A two-layer laminate in which 45) is formed, and a four-layer laminate in which a titanium oxide layer and a silicon oxide layer are formed in this order on the two-layer laminate is preferable. By providing such an antireflection layer of a two-layer laminate or a four-layer laminate, reflection in the visible light wavelength region (380 to 780 nm) can be reduced uniformly.

  Further, the antireflection effect can be exhibited also by laminating a single-layer optical thin film on the film substrate 1. Even in a design in which the antireflection layer 5 is a single layer, the refractive index difference between the antireflection layer 5 and the hard coat layer 2 needs to be increased in order to maximize the antireflection function. When the thickness of the antireflection layer 5 is d, the refractive index is n, and the wavelength of incident light is λ, the relational expression nd = λ / 4 is established between the thickness of the antireflection layer 5 and the refractive index. To do. When the antireflective layer 5 is a low refractive index layer whose refractive index is smaller than the refractive index of the film substrate 1, the reflectance is minimized under the condition that the relational expression is satisfied. For example, when the refractive index of the antireflection layer 5 is 1.45, the film thickness of the antireflection layer 5 that minimizes the reflectance with respect to incident light having a wavelength of 550 nm in visible light is 95 nm.

  The wavelength region of visible light that exhibits the antireflection function is 380 to 780 nm, and the wavelength region with particularly high visibility is in the range of 450 to 650 nm, and the design that minimizes the reflectance of 550 nm, which is the central wavelength, is designed. It is generally done.

  When designing the antireflection layer 5 as a single layer, the thickness accuracy is not as strict as the thickness accuracy of the multilayer antireflection layer, and in the range of ± 10% with respect to the design thickness, that is, when the design wavelength is 95 nm, 86 nm to If it is the range of 105 nm, it can be used without a problem. For this reason, generally, a wet method such as phanten coating, die coating, spin coating, spray coating, gravure coating, roll coating, bar coating, etc., is used to form the single-layer antireflection layer 5. The

  As a material for forming the antireflection layer 5 as a single layer, for example, a resin material such as an ultraviolet curable acrylic resin, a hybrid material in which inorganic fine particles such as colloidal silica are dispersed in the resin, tetraethoxysilane, titanium tetra Examples thereof include sol-gel materials using metal alkoxides such as ethoxide. In addition, each material can use a fluorine-containing compound in order to impart antifouling properties to the surface. From the aspect of scratch resistance, antireflection layer materials having a high content of inorganic components tend to be excellent, and sol-gel materials are particularly preferable. Sol-gel materials can be used after partial condensation.

Examples of the sol-gel material containing a fluorine group include perfluoroalkylalkoxysilane. As perfluoroalkyl alkoxysilane, for example, general formula: CF ₃ (CF ₂ ) _n CH ₂ CH ₂ Si (OR) ₃ (wherein R represents an alkyl group having 1 to 5 carbon atoms, n is And an integer of 0 to 12). Specifically, for example, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltri And ethoxysilane. Among these, the compound wherein n is 2 to 6 is preferable.

  As a low refractive index layer (antireflection layer), a siloxane oligomer having a number average molecular weight in terms of ethylene glycol of 500 to 10000 described in JP-A No. 2004-167827 and a number average molecular weight in terms of polystyrene of 5000 or more And a hard coat forming material containing a fluorine compound having a fluoroalkyl structure and a polysiloxane structure can be preferably used.

  An inorganic sol can be added to the low refractive index layer (antireflection layer) in order to improve the film strength. The inorganic sol is not particularly limited, and examples thereof include silica, alumina, magnesium fluoride, and the like, and silica sol is particularly preferable. The addition amount of the inorganic sol can be appropriately set within a range of 10 to 80 parts by weight with respect to 100 parts by weight of the total solid content of the low refractive index forming material. The particle size of the inorganic sol is preferably in the range of 2 to 50 nm, more preferably in the range of 5 to 30 nm.

  The material for forming the antireflection layer 5 preferably contains hollow spherical silicon oxide ultrafine particles. The hollow and spherical silicon oxide ultrafine particles preferably have an average particle diameter of about 5 to 300 nm, and the ultrafine particles are hollow spheres in which cavities are formed inside the outer shell having pores, and the cavities It contains the solvent and / or gas at the time of preparation of the fine particles. It is preferable that a precursor material for forming the cavity remains in the cavity. The thickness of the outer shell is preferably in the range of about 1 to 50 nm and in the range of about 1/50 to 1/5 of the average particle diameter. The outer shell is preferably composed of a plurality of coating layers. It is preferable that the pores are closed and the cavity is sealed by the outer shell. In the antireflection layer 5, the porosity or the cavity is maintained, and the refractive index of the antireflection layer 5 can be reduced, so that it can be preferably used.

  The average particle diameter of hollow spherical silicon oxide ultrafine particles is about 5 to 300 nm. If the average particle diameter is less than 5 nm, the volume ratio of the outer shell in the spherical fine particles tends to increase and the volume ratio of the cavity tends to decrease. On the other hand, if the average particle diameter exceeds 300 nm, it is difficult to obtain a stable dispersion. Moreover, it is because the transparency of the antireflection layer containing the ultrafine particles tends to decrease. The preferable average particle diameter of hollow spherical silicon oxide ultrafine particles is in the range of 10 to 200 nm. The average particle diameter can be determined by a dynamic light scattering method.

The method for producing hollow and spherical silicon oxide ultrafine particles includes, for example, the following steps (a) to (c). Hollow spherical silicon oxide ultrafine particles are obtained as a dispersion. As a method for producing such hollow and spherical silicon oxide ultrafine particles, for example, the method for producing silica-based fine particles disclosed in JP-A-2004-203683 is suitably employed. That is,
(A) An aqueous solution of silicate and / or an acidic silicic acid solution and an aqueous solution of an alkali-soluble inorganic compound are simultaneously added to an alkaline aqueous solution having a pH of 10 or more or an alkaline aqueous solution having a pH of 10 or more in which seed particles are dispersed as required. And a nuclear particle dispersion having a molar ratio (MO _x / SiO ₂ ) of 0.3 to 1.0 when silicon oxide is represented by SiO ₂ and an inorganic compound other than silicon oxide is represented by MO _x Preparing step.
(B) A step of forming a first silicon oxide coating layer on the core particles by adding a silicon oxide source to the core particle dispersion.
(C) A step of adding an acid to the dispersion to remove part or all of the elements constituting the core particles.

  The average particle diameter of the hollow spherical silicon oxide ultrafine particles of the present invention is in the range of 5 to 300 nm. If the average particle diameter is less than 5 nm, the volume ratio of the outer shell in the spherical fine particles increases and the volume ratio of the cavity decreases. On the other hand, if the average particle diameter exceeds 300 nm, it is difficult to obtain a stable dispersion. Moreover, it is because the transparency of the antireflection layer containing the ultrafine particles tends to decrease. The preferable average particle diameter of hollow spherical silicon oxide ultrafine particles is in the range of 10 to 200 nm. The average particle diameter can be determined by a dynamic light scattering method.

  The hollow spherical silicon oxide ultrafine particle dispersion can be mixed with various matrix components to prepare an antireflection-forming coating solution. The various matrix components refer to components that can form a film on the surface of the hard coat layer 2, and can be selected and used from resins that meet conditions such as adhesion to the substrate, hardness, and coating properties. For example, conventionally used polyester resin, acrylic resin, urethane resin, vinyl chloride resin, epoxy resin, melamine resin, fluorine resin, silicone resin, butyral resin, phenol resin, vinyl acetate resin, UV curable resin, electron beam Examples thereof include curable resins, emulsion resins, water-soluble resins, hydrophilic resins, mixtures of these resins, and organic resins such as copolymers and modified products of these resins. Moreover, the hydrolyzable organosilicon compound etc. which were illustrated as a material which forms the antireflection layer 5 with the said single layer can be used as a matrix component.

  When an organic resin is used as the matrix component, for example, an organic solvent dispersion obtained by replacing water as a dispersion medium of the hollow spherical silicon oxide ultrafine particles with an organic solvent such as alcohol, and if necessary, the ultrafine particles may be added. After the treatment with a known coupling agent, the organic solvent dispersion liquid dispersed in an organic solvent and the matrix can be diluted with an appropriate organic solvent to obtain an antireflection-forming coating liquid.

  On the other hand, when a hydrolyzable organosilicon compound is used as the matrix component, for example, a partially hydrolyzed product of alkoxysilane is obtained by adding water and an acid or alkali as a catalyst to a mixture of alkoxysilane and alcohol. The dispersion can be mixed with this and diluted with an organic solvent as necessary to obtain a coating solution.

  The weight ratio of the silicon oxide ultrafine particles and the matrix component in the coating solution is preferably in the range of silicon oxide ultrafine particles: matrix = 1: 99 to 9: 1. If the weight ratio exceeds 9: 1, the strength of the antireflection layer 5 may be insufficient and may lack practicality. On the other hand, if the weight ratio is less than 1:99, the effect of adding the silicon oxide ultrafine particles may not be apparent.

  The refractive index of the antireflection layer 5 formed on the surface of the hard coat layer 2 varies depending on the mixing ratio of the silicon oxide ultrafine particles and the matrix components and the refractive index of the matrix used, but is 1.2 to 1.42. And a low refractive index. In addition, the refractive index of the silicon oxide ultrafine particles per se of the present invention is 1.2 to 1.38.

  The antiglare antireflection hard coat film 6 in which the antireflection layer 5 is provided on the hard coat layer 2 of the hard coat film is preferable in terms of pencil hardness. The surface of the hard coat layer 2 containing ultrafine particles has minute irregularities, which influence the slip of the pencil (the pencil is easily caught and the force is easily transmitted). In the case where the antireflection layer 5 is provided, the unevenness becomes smooth, and normally, the hard coat layer 2 having a pencil hardness of about 3H can have a pencil hardness of 4H.

  As a method for producing such hollow and spherical silicon oxide ultrafine particles, for example, the method for producing silica-based fine particles disclosed in JP-A-2000-233611 is suitably employed.

  The drying and curing temperatures for forming the antireflection layer (low refractive index layer) 5 are not particularly limited, and are usually 60 ° C. to 150 ° C., preferably 70 ° C. to 130 ° C., usually 1 minute to 30 minutes, In view of productivity, about 1 to 10 minutes is more preferable. In addition, after drying and curing, an antireflection hard coat film with higher hardness can be obtained by further heat treatment. The temperature of the heat treatment is not particularly limited, and is usually 40 ° C. to 130 ° C., preferably 50 ° C. to 100 ° C., usually 1 minute to 100 hours, and more preferably 10 hours or more in order to improve the scratch resistance. preferable. The temperature and time are not limited to the above ranges and can be adjusted appropriately. For the heating, a method using a hot plate, an oven, a belt furnace or the like is appropriately employed.

  Since the antireflection layer 5 is frequently attached to the outermost surface of the image display device, the antireflection layer 5 is easily contaminated by the external environment. In particular, contaminants such as fingerprints, hand stains, sweat, and hair styling are likely to adhere to the person around you, and the surface reflectance changes due to the attachment, and the contents appear to appear white and the display content is blurred. Contamination is more conspicuous than in the case of a simple transparent plate. In such a case, a fluorine group-containing silane compound, a fluorine group-containing organic compound, or the like can be laminated on the antireflection layer 5 in order to impart functions relating to the adhesion prevention property and the easy removal property.

  By performing various surface treatments on the film base 1 or the hard coat layer 2 coated on the film base 1, the film base 1 and the hard coat layer 2, the film base 1 and the polarizer or the hard coat The adhesion between the layer 2 and the antireflection layer 5 can be improved. As the surface treatment, low-pressure plasma treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment can be used. Further, an alkali saponification treatment that is preferably used as a surface treatment when triacetyl cellulose is used as a film substrate will be specifically described. It is preferable to carry out the cycle in which the cellulose ester film surface is immersed in an alkaline solution, then washed with water and dried. Examples of the alkaline solution include a potassium hydroxide solution and a sodium hydroxide solution, and the prescribed concentration of hydroxide ions is preferably 0.1N to 3.0N, and more preferably 0.5N to 2.0N. preferable. The alkali solution temperature is preferably in the range of 25 ° C to 90 ° C, more preferably 40 ° C to 70 ° C. Then, the water washing process and the drying process are performed and the triacetyl cellulose which performed the surface treatment can be obtained.

  Further, the following solvent treatment may be performed on the back surface of the film substrate 1 (surface opposite to the surface on which the hard coat layer 2 is formed) for the purpose of preventing curling. The solvent treatment is performed by applying a composition containing a solvent capable of dissolving the film substrate 1 or a solvent capable of swelling by a conventionally known method. By applying such a solvent, the film base 1 provided with the hard coat layer 2 is imparted with the property of being rounded to the back side of the film base 1. Curling is prevented by offsetting the force to curl to the side.

  In addition to a solvent to be dissolved and / or a mixture of solvents to be swollen, the solvent may further include a solvent that is not dissolved. These are performed using a composition and a coating amount mixed at an appropriate ratio depending on the curl degree of the film substrate 1 and the type of resin.

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

  Using these gravure coaters, dip coaters, reverse coaters or extrusion coaters, these solvent compositions have a wet film thickness (film thickness before drying) of 1 to 100 μm, more preferably 5 to 30 μm on the surface of the film substrate 1. Apply as follows.

  Each solvent applied in this manner may be scattered after drying, or may remain in a small amount, but it is preferable that no solvent remains on the coated surface.

  Moreover, you may provide the transparent resin layer described below in the back surface (surface on the opposite side to the formation surface of the hard-coat layer 2) of the film base material 1 for the purpose of preventing generation | occurrence | production of a curl. Examples of the transparent resin layer include a layer mainly composed of a thermoplastic resin, a radiation curable resin, a thermosetting resin, and other reactive resins. Among these, a layer mainly composed of a thermoplastic resin is particularly preferable.

  Examples of the thermoplastic resin include vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, copolymer of vinyl acetate and vinyl alcohol, partially hydrolyzed vinyl chloride-vinyl acetate copolymer, vinyl chloride. -Vinyl polymers such as vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer Or a copolymer, a cellulose derivative such as nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate resin, a copolymer of maleic acid and / or acrylic acid, an acrylate copolymer, an acrylonitrile-styrene copolymer, Chlorinated polyethylene, acrylonitrile-salt Polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide Examples thereof include resins, amino resins, styrene-butadiene resins, rubber resins such as butadiene-acrylonitrile resins, silicone resins, and fluorine resins. Of these thermoplastic resins, a cellulose resin layer using, for example, diacetyl cellulose is particularly preferable as the transparent resin layer.

  Further, the antiglare hard coat film 4 and the antiglare antireflection hard coat film 6 are usually provided on the side of the film substrate 1 as an optical member used in LCDs and ELDs via an adhesive or an adhesive. Can be pasted together. In pasting, the film substrate 1 can be subjected to the same surface treatment as described above.

  Examples of the optical member include a polarizer and a polarizing plate. In general, a polarizing plate having a transparent protective film on one side or both sides of a polarizer is generally used. When providing a transparent protective film on both surfaces of a polarizer, the same material may be sufficient as the transparent protective film of front and back, and a different material may be sufficient as it. The polarizing plates are usually disposed on both sides of the liquid crystal cell. Further, the polarizing plates are arranged so that the absorption axes of the two polarizing plates are substantially orthogonal to each other.

  Next, an optical element in which the antiglare hard coat film 4 or the antiglare antireflection hard coat film 6 of the present invention is laminated will be described by taking a polarizing plate as an example. The antiglare hard coat film 4 or the antiglare antireflection hard coat film 6 of the present invention is a polarization having the function of the present invention by laminating with a polarizer or a polarizing plate using an adhesive or a pressure-sensitive adhesive. A board can be obtained.

  The polarizer is not particularly limited, and various types can be used. For example, dichroic substances such as iodine and dichroic dyes are adsorbed on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films. And polyene-based oriented films such as a uniaxially stretched product, a polyvinyl alcohol dehydrated product and a polyvinyl chloride dehydrochlorinated product. Among these, a polarizer comprising a polyvinyl alcohol film and a dichroic substance such as iodine is particularly preferable because of its high polarization dichroic ratio. The thickness of these polarizers is not particularly limited, but is generally about 5 to 80 μm.

  A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous solution of iodine and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing.

  In addition to washing the polyvinyl alcohol film surface with dirt and anti-blocking agents by washing the polyvinyl alcohol film with water, it also has the effect of preventing unevenness such as uneven coloring by swelling the polyvinyl alcohol film. is there. Stretching may be performed after dyeing with iodine, or may be performed while dyeing, or may be performed with dyeing after iodine. The film can be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.

  As the transparent protective film provided on one side or both sides of the polarizer, those having excellent transparency, mechanical strength, thermal stability, moisture shielding property, retardation value stability and the like are preferable. Examples of the material for forming the transparent protective film include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, cellulose resins such as diacetyl cellulose and triacetyl cellulose, acrylic resins such as polymethyl methacrylate, polystyrene, acrylonitrile, Styrene copolymer, styrene resin, acrylonitrile / styrene resin, acrylonitrile / butadiene / styrene resin, acrylonitrile / ethylene / styrene resin, styrene / maleimide copolymer, styrene resin such as styrene / maleic anhydride copolymer, polycarbonate Examples thereof include resins. In addition, cycloolefin resin, norbornene resin, polyolefin resin such as polyethylene, polypropylene, ethylene / propylene copolymer, vinyl chloride resin, amide resin such as nylon and aromatic polyamide, aromatic polyimide, polyimide amide, etc. Imide resins, sulfone resins, polyether sulfone resins, polyether ether ketone resins, polyphenylene sulfide resins, vinyl alcohol resins, vinylidene chloride resins, vinyl butyral resins, arylate resins, polyoxymethylene resins Examples of the resin that forms the transparent protective film include a polymer film made of a resin, an epoxy resin, or a blend of the resins. The transparent protective film can also be formed as a cured layer of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, or silicone.

  Further, a polymer film described in JP-A-2001-343529 (WO01 / 37007), for example, (A) a thermoplastic resin having a substituted and / or unsubstituted imide group in the side chain, and (B) in the side chain. Examples thereof include resin compositions containing a substituted and / or unsubstituted phenyl and a thermoplastic resin having a nitrile group. Specific examples include a polymer film of a resin composition containing an alternating copolymer composed of isobutylene and N-methylmaleimide and an acrylonitrile / styrene copolymer. As the film, a film made of a mixed extruded product of the resin composition or the like can be used. These films have a small phase difference and a small photoelastic coefficient, so when applied to a protective film such as a polarizing plate, it is possible to eliminate defects such as unevenness due to distortion. Excellent.

  As the transparent protective film, a cellulose resin such as triacetyl cellulose and a norbornene resin are preferably used from the viewpoints of polarization characteristics and durability. Specific examples include the product name “Fujitac” manufactured by Fuji Photo Film Co., Ltd., the product name “Zeonor” manufactured by ZEON Corporation, and the product name “ARTON” manufactured by JSR Corporation.

  The thickness of the transparent protective film can be appropriately determined, but is generally about 1 to 500 μm from the viewpoints of workability such as strength and handleability, and thin layer properties. More preferably, it is 5-200 micrometers. Especially preferably, it is 10-150 micrometers. If it is the said range, a polarizer will be protected mechanically, and even if it exposes to high temperature and high humidity, a polarizer will not shrink | contract and it can maintain the stable optical characteristic.

  Moreover, it is preferable that a transparent protective film has as little color as possible. Therefore, Rth = (nx−nz) · d (where nx is the refractive index in the slow axis direction in the film plane, nz is the refractive index in the film thickness direction, and d is the film thickness). A protective film having a direction retardation value of −90 nm to +75 nm is preferably used. By using a film having a thickness direction retardation value (Rth) of −90 nm to +75 nm, the coloring (optical coloring) of the polarizing plate caused by the protective film can be almost eliminated. The thickness direction retardation value (Rth) is more preferably −80 nm to +60 nm, and particularly preferably −70 nm to +45 nm.

  As the transparent protective film, since the retardation value in the film plane and the retardation value in the thickness direction may affect the viewing angle characteristics of the liquid crystal display device, the one having an optimized retardation value may be used. preferable. However, the transparent protective film for which optimization of the retardation value is desired is a transparent protective film laminated on the surface of the polarizer on the side close to the liquid crystal cell, and is laminated on the surface of the polarizer on the side far from the liquid crystal cell. This is not the case because the transparent protective film does not change the optical characteristics of the liquid crystal display device.

  As the retardation value of the transparent protective film laminated on the surface of the polarizer on the side close to the liquid crystal cell, the retardation value (Re: (nx−ny) · d) in the film plane is 0 to 5 nm. Is preferred. More preferably, it is 0-3 nm. More preferably, it is 0-1 nm. The retardation value (Rth) in the thickness direction is preferably 0 to 15 nm. More preferably, it is 0-12 nm. More preferably, it is 0-10 nm. Especially preferably, it is 0-5 nm. Most preferably, it is 0-3 nm.

  A polarizing plate laminated with an antiglare hard coat film or the like may be one obtained by sequentially laminating a transparent protective film, a polarizer, and a transparent protective film on a hard coat film, or a polarizer on an antiglare hard coat film, A transparent protective film may be sequentially laminated.

  In addition, the surface of the transparent protective film on which the polarizer is not adhered may be a hard coat layer, a sticking prevention film or a treatment intended. The hard coat treatment is applied for the purpose of preventing scratches on the surface of the polarizing plate. For example, a transparent protective film with a cured film excellent in hardness, sliding properties, etc. by an appropriate ultraviolet curable resin such as acrylic or silicone is used. It can be formed by a method of adding to the surface of the film. Further, the anti-sticking treatment is performed for the purpose of preventing adhesion with an adjacent layer. The hard coat layer, the anti-sticking layer, etc. can be provided on the transparent protective film itself, or can be provided separately from the transparent protective film as an optical layer.

  In addition, a hard coat layer, a primer layer, an adhesive layer, an adhesive layer, an antistatic layer, a conductive layer, a gas barrier layer, a water vapor barrier layer, a moisture barrier layer, etc. are inserted between the layers of the polarizing plate, or to the surface of the polarizing plate. You may laminate. Also. In the stage of forming each layer of the polarizing plate, for example, conductive particles or antistatic agents, various fine particles, plasticizers, and the like may be added to the material for forming each layer, mixed, or the like, if necessary.

  The method of laminating the transparent protective film with the polarizer is not particularly limited. For example, an adhesive made of an acrylic polymer or a vinyl alcohol polymer, or vinyl alcohol such as boric acid, borax, glutaraldehyde, melamine, or oxalic acid. It can be carried out through an adhesive or the like comprising at least a water-soluble crosslinking agent of a polymer. As a result, it is difficult to peel off due to the influence of humidity and heat, and the light transmittance and the degree of polarization can be improved. As the adhesive, a polyvinyl alcohol-based adhesive is preferably used from the viewpoint of excellent adhesiveness with polyvir alcohol, which is a raw material of a polarizer.

  The polymer film containing the norbornene-based resin is used as a transparent protective film, and as a pressure-sensitive adhesive when laminated with a polarizer, it has excellent transparency, low birefringence, etc., and exhibits sufficient adhesive strength when used as a thin layer. What can be done is preferred. As such an adhesive, for example, an adhesive for dry lamination in which a polyurethane resin solution and a polyisocyanate resin solution are mixed, a styrene butadiene rubber adhesive, an epoxy two-component curable adhesive, for example, an epoxy resin and a polythiol Can be used, and those composed of two liquids of epoxy resin and polyamide can be used. Solvent type adhesives and epoxy type two liquid curable adhesives are particularly preferable, and transparent ones are preferable. Some adhesives can improve the adhesive force by using an appropriate adhesive primer, and when such an adhesive is used, it is preferable to use an adhesive primer.

  The adhesive primer is not particularly limited as long as it is a layer capable of improving adhesiveness, for example, reactive functional groups such as amino group, vinyl group, epoxy group, mercapto group, chloro group and the like in the same molecule. Silane coupling agent having hydrolyzable alkoxysilyl group, titanate coupling agent having hydrolyzable hydrophilic group containing titanium and organic functional group in the same molecule, and aluminum in the same molecule So-called coupling agents such as aluminate coupling agents having hydrolyzable hydrophilic groups and organic functional groups, and organic reactions such as epoxy resins, isocyanate resins, urethane resins, and ester urethane resins A resin having a functional group can be used. Especially, it is preferable that it is a layer containing a silane coupling agent from a viewpoint that it is easy to handle industrially.

  The polarizing plate is preferably provided with an adhesive layer or a pressure-sensitive adhesive layer on both sides or one side in order to facilitate lamination to the liquid crystal cell.

  It does not restrict | limit especially as an adhesive agent or an adhesive used for the said adhesive bond layer or an adhesive layer. For example, acrylic polymer, silicone polymer, polyester, polyurethane, polyamide, polyvinyl ether, vinyl acetate / vinyl chloride copolymer, modified polyolefin, epoxy-based, fluorine-based, natural rubber, synthetic rubber and other rubber-based polymers Can be appropriately selected and used. In particular, an acrylic pressure-sensitive adhesive is preferably used in that it is excellent in optical transparency, exhibits appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and is excellent in weather resistance and heat resistance.

  The adhesive or pressure-sensitive adhesive can contain a crosslinking agent according to the base polymer. In addition, the pressure-sensitive adhesive layer may include, for example, natural and synthetic resins, glass fibers and glass beads, fillers and pigments made of metal powder and other inorganic powders, colorants, antioxidants, and the like. Appropriate additives can also be blended. Moreover, it can also be set as the adhesive layer which contains a transparent fine particle and shows light diffusibility.

  The transparent fine particles include, for example, conductive inorganic fine particles such as silica, calcium oxide, alumina, titania, zirconia, tin oxide, indium oxide, cadmium oxide, and antimony oxide having an average particle size of 0.5 to 20 μm. Alternatively, one or two or more suitable materials such as crosslinked or uncrosslinked organic fine particles made of a suitable polymer such as polymethyl methacrylate and polyurethane can be used.

  The adhesive or pressure-sensitive adhesive is usually used as an adhesive solution having a solid content concentration of about 10 to 50% by weight in which a base polymer or a composition thereof is dissolved or dispersed in a solvent. As the solvent, an organic solvent such as toluene or ethyl acetate or a solvent such as water can be appropriately selected and used.

  The adhesive or pressure-sensitive adhesive may be provided on one or both sides of a polarizing plate or an optical film as a laminate having different compositions or types. The thickness of the adhesive or pressure-sensitive adhesive can be appropriately determined according to the purpose of use and adhesive force, and is generally 1 to 500 μm, preferably 5 to 200 μm, and particularly preferably 10 to 100 μm.

  The exposed surface such as the adhesive layer or the pressure-sensitive adhesive layer is temporarily covered with a release paper or a release film (also referred to as a separator) for the purpose of preventing contamination until it is put to practical use. . Thereby, it can prevent contacting an adhesive bond layer or an adhesive layer in the usual handling state. Examples of the separator include plastic films, rubber sheets, paper, cloth, non-woven fabrics, nets, foam sheets and metal foils, and suitable thin leaf bodies such as laminates thereof. An appropriate one according to the prior art, such as a system or a coating treatment with an appropriate release agent such as molybdenum sulfide, can be used.

  As an optical element, in practical use, an optical film in which another optical member (optical layer) is laminated on the polarizing plate can be used. The optical layer is not particularly limited. For example, for forming a liquid crystal display device such as a reflection plate, a semi-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), and a viewing angle compensation film. One or two or more optical layers that may be used can be used. In particular, a reflective polarizing plate or a semi-transmissive polarizing plate in which a polarizing plate is further laminated with a reflecting plate or a semi-transmissive reflecting plate, an elliptical polarizing plate or a circular polarizing plate in which a retardation plate is further laminated on a polarizing plate, a polarizing plate A wide viewing angle polarizing plate in which a viewing angle compensation film is further laminated on a plate, or a brightness enhancement film (a polarization separation film having a polarization selection layer, such as D-BEF manufactured by Sumitomo 3M Co., Ltd.) is laminated on a polarizing plate. A polarizing plate is preferable. In an elliptically polarizing plate, a polarizing plate with optical compensation, etc., a hard coat film is provided on the polarizing plate side.

  Furthermore, if necessary, various properties such as scratch resistance, durability, weather resistance, moisture and heat resistance, heat resistance, moisture resistance, moisture permeability, antistatic properties, conductivity, interlayer adhesion improvement, mechanical strength improvement, Processing for imparting a function or the like, or insertion or lamination of a functional layer can also be performed.

  A reflective polarizing plate is a polarizing plate provided with a reflective layer, and is used to form a liquid crystal display device or the like that reflects incident light from the viewing side (display side). Such a light source can be omitted, and the liquid crystal display device can be easily thinned. The reflective polarizing plate can be formed by an appropriate method such as a method in which a reflective layer made of metal or the like is provided on one surface of the polarizing plate via the transparent protective film or the like, if necessary.

  Specific examples of the reflective polarizing plate include those in which a reflective layer is formed by attaching a foil or a vapor deposition film made of a reflective metal such as aluminum on one surface of a transparent protective film matted as necessary.

  The reflection plate can be used as a reflection sheet in which a reflection layer is provided on an appropriate film according to the transparent film instead of the method of directly applying to the transparent protective film of the polarizing plate. Since the reflective layer is usually made of metal, the usage form in which the reflective surface is covered with a transparent protective film, a polarizing plate or the like is used to prevent the reflectance from being lowered due to oxidation, and thus to maintain the initial reflectance for a long time. In addition, it is more preferable to avoid a separate attachment of the protective layer.

  The transflective polarizing plate can be obtained by using a transflective reflective layer such as a half mirror that reflects and transmits light in the reflective layer described above. A transflective polarizing plate is usually provided on the back side of a liquid crystal cell, and displays an image by reflecting incident light from the viewing side (display side) when a liquid crystal display device is used in a relatively bright atmosphere. In a relatively dark atmosphere, a liquid crystal display device of a type that displays an image using a built-in light source such as a built-in backlight can be formed. In other words, the transflective polarizing plate can save energy for using a light source such as a backlight in a bright atmosphere, and can be used with a built-in light source even in a relatively dark atmosphere. Useful for.

  An elliptically polarizing plate or a circularly polarizing plate in which a retardation plate is further laminated on a polarizing plate will be described. A phase difference plate or the like is used when changing linearly polarized light to elliptically polarized light or circularly polarized light, changing elliptically polarized light or circularly polarized light to linearly polarized light, or changing the polarization direction of linearly polarized light. In particular, a so-called quarter-wave plate (also referred to as a λ / 4 plate) is used as a retardation plate that changes linearly polarized light into circularly polarized light or changes circularly polarized light into linearly polarized light. A half-wave plate (also referred to as a λ / 2 plate) is usually used when changing the polarization direction of linearly polarized light.

  The elliptically polarizing plate is effectively used for black and white display without the above color by compensating (preventing) the coloration (blue or yellow) generated by the birefringence of the liquid crystal layer of the super twist nematic (STN) type liquid crystal display device. It is done. Further, the one in which the three-dimensional refractive index is controlled is preferable because it can compensate (prevent) coloring that occurs when the screen of the liquid crystal display device is viewed from an oblique direction. The circularly polarizing plate is effectively used, for example, when adjusting the color tone of an image of a reflective liquid crystal display device in which an image is displayed in color, and also has an antireflection function. Specific examples of the retardation plate described above include a birefringent film obtained by stretching a film made of an appropriate polymer such as polycarbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polypropylene, other polyolefins, polyarylate, and polyamide. And an alignment film of a liquid crystal polymer, and a liquid crystal polymer alignment layer supported by a film. The retardation plate may have an appropriate retardation according to the purpose of use, such as those for the purpose of compensating for various wavelength plates or birefringence of the liquid crystal layer, viewing angle, and the like. What laminated | stacked the phase difference plate and controlled optical characteristics, such as phase difference, etc. may be used.

  The elliptically polarizing plate and the reflective elliptical polarizing plate are obtained by laminating a polarizing plate or a reflective polarizing plate and a retardation plate in an appropriate combination. Such an elliptically polarizing plate or the like can also be formed by sequentially laminating them sequentially in the manufacturing process of the liquid crystal display device so as to be a combination of a (reflection type) polarizing plate and a retardation plate. An optical film such as a polarizing plate has an advantage that it can improve the production efficiency of a liquid crystal display device and the like because of excellent quality stability and lamination workability.

  The viewing angle compensation film is a film for widening the viewing angle so that an image can be seen relatively clearly even when the screen of the liquid crystal display device is viewed from a slightly oblique direction rather than perpendicular to the screen. As such a viewing angle compensation phase difference plate, for example, a retardation film, an alignment film such as a liquid crystal polymer, or an alignment layer such as a liquid crystal polymer supported on a transparent substrate is used. A normal retardation plate uses a birefringent polymer film uniaxially stretched in the plane direction, whereas a retardation plate used as a viewing angle compensation film stretches biaxially in the plane direction. Birefringent polymer film, biaxially stretched film such as polymer with birefringence with a controlled refractive index in the thickness direction that is uniaxially stretched in the plane direction and stretched in the thickness direction, etc. Used. Examples of the inclined alignment film include a film obtained by bonding a heat shrink film to a polymer film and stretching or / and shrinking the polymer film under the action of the contraction force by heating, and a film obtained by obliquely aligning a liquid crystal polymer. Can be mentioned. The raw material polymer for the phase difference plate is the same as the polymer described in the previous phase difference plate, preventing coloration due to a change in the viewing angle based on the phase difference by the liquid crystal cell and expanding the viewing angle for good visual recognition. An appropriate one for the purpose can be used.

  Also, from the viewpoint of achieving a wide viewing angle with good visibility, an optically compensated phase difference in which a liquid crystal polymer alignment layer, in particular an optically anisotropic layer composed of a discotic liquid crystal polymer gradient alignment layer, is supported by a triacetylcellulose film. A plate can be preferably used.

  A polarizing plate obtained by bonding a polarizing plate and a brightness enhancement film is usually provided on the back side of a liquid crystal cell. The brightness enhancement film reflects a linearly polarized light having a predetermined polarization axis or a circularly polarized light in a predetermined direction when natural light is incident by a backlight of a liquid crystal display device or the like or reflection from the back side, and transmits other light. In addition, a polarizing plate in which a brightness enhancement film is laminated with a polarizing plate allows light from a light source such as a backlight to enter to obtain transmitted light in a predetermined polarization state, and reflects light without transmitting the light other than the predetermined polarization state. The The light reflected on the surface of the brightness enhancement film is further inverted through a reflective layer or the like provided behind the brightness enhancement film and re-incident on the brightness enhancement film, and part or all of the light is transmitted as light having a predetermined polarization state. Luminance can be improved by increasing the amount of light transmitted through the enhancement film and increasing the amount of light that can be used for image display and the like by supplying polarized light that is difficult to absorb into the polarizer. That is, when light is incident through the polarizer from the back side of the liquid crystal cell without using a brightness enhancement film, light having a polarization direction that does not coincide with the polarization axis of the polarizer is almost polarized. It is absorbed by the polarizer and does not pass through the polarizer. That is, although depending on the characteristics of the polarizer used, approximately 50% of the light is absorbed by the polarizer, and the amount of light that can be used for liquid crystal image display or the like is reduced accordingly, resulting in a dark image. The brightness enhancement film allows light having a polarization direction that is absorbed by the polarizer to be reflected once by the brightness enhancement film without being incident on the polarizer, and further inverted through a reflective layer provided on the rear side thereof. Repeatedly re-enter the brightness enhancement film, and the brightness enhancement film transmits only polarized light whose polarization direction is such that the polarization direction of light reflected and inverted between the two can pass through the polarizer. Therefore, light such as a backlight can be efficiently used for displaying an image on the liquid crystal display device, and the screen can be brightened.

  A diffusion plate may be provided between the brightness enhancement film and the reflective layer. The polarized light reflected by the brightness enhancement film is directed to the reflective layer or the like, but the installed diffusion plate uniformly diffuses the light passing therethrough and at the same time cancels the polarized state and becomes a non-polarized state. That is, the diffuser plate returns the polarized light to the original natural light state. The light in the non-polarized state, that is, the natural light state is directed to the reflection layer and the like, reflected through the reflection layer and the like, and again passes through the diffusion plate and reenters the brightness enhancement film. Thus, while maintaining the brightness of the display screen by providing a diffuser plate that returns polarized light to the original natural light state between the brightness enhancement film and the reflective layer, etc., at the same time, the unevenness of the brightness of the display screen is reduced, A uniform and bright screen can be provided. By providing such a diffuser plate, it is considered that the first incident light has a moderate increase in the number of repetitions of reflection, and in combination with the diffusion function of the diffuser plate, a uniform bright display screen can be provided.

  The brightness enhancement film has a characteristic of transmitting linearly polarized light having a predetermined polarization axis and reflecting other light, such as a multilayer thin film of dielectric material or a multilayer laminate of thin film films having different refractive index anisotropies. Such as an alignment film of a cholesteric liquid crystal polymer or an alignment liquid crystal layer supported on a film substrate, which reflects either left-handed or right-handed circularly polarized light and transmits other light. Appropriate things, such as a thing, can be used.

  Therefore, in the brightness enhancement film of the type that transmits linearly polarized light having the predetermined polarization axis as described above, the transmitted light is incident on the polarizing plate with the polarization axis aligned as it is, thereby efficiently transmitting while suppressing absorption loss due to the polarizing plate. Can be made. On the other hand, in a brightness enhancement film of a type that transmits circularly polarized light such as a cholesteric liquid crystal layer, it can be directly incident on a polarizer, but from the point of suppressing absorption loss, the circularly polarized light is linearly polarized through a retardation plate. It is preferable to make it enter into a polarizing plate. In addition, circularly polarized light can be converted into linearly polarized light by using a quarter wave plate as the retardation plate.

  A retardation plate that functions as a quarter-wave plate in a wide wavelength range such as a visible light region exhibits, for example, a retardation layer that functions as a quarter-wave plate for light-color light having a wavelength of 550 nm and other retardation characteristics. A phase difference layer, for example, a phase difference layer that functions as a half-wave plate, can be used to superimpose. Accordingly, the retardation plate disposed between the polarizing plate and the brightness enhancement film may be composed of one or more retardation layers.

  It should be noted that the cholesteric liquid crystal layer is also a combination of layers having different reflection wavelengths and has an arrangement structure in which two layers or three or more layers are superposed to obtain a layer that reflects circularly polarized light in a wide wavelength range such as the visible light region. Based on this, transmitted circularly polarized light in a wide wavelength range can be obtained.

  Further, the polarizing plate may be formed by laminating a polarizing plate and two or three or more optical layers like the above-described polarization separation type polarizing plate. Therefore, a reflective elliptical polarizing plate, a semi-transmissive elliptical polarizing plate, or the like, which is a combination of the above-mentioned reflective polarizing plate or transflective polarizing plate and a retardation plate, may be used.

  Lamination of the hard coat film on the optical element, and further lamination of various optical layers on the polarizing plate can be carried out by a method of separately laminating sequentially in the manufacturing process of a liquid crystal display device or the like. The laminated product is excellent in quality stability, assembly work, and the like, and has an advantage of improving the manufacturing process of a liquid crystal display device and the like. For the lamination, an appropriate adhesive means such as an adhesive layer can be used. When adhering the polarizing plate and other optical films, their optical axes can be set at an appropriate arrangement angle in accordance with the target retardation characteristics.

  The hard coat film is provided on at least one surface of the optical member such as the polarizing plate described above or an optical film in which at least one polarizing plate is laminated, but the surface on which the hard coat film is not provided. An adhesive layer for adhering to other members such as a liquid crystal cell can also be provided. The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited. For example, an acrylic polymer, silicone-based polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based polymer is appropriately selected. Can be used. In particular, those having excellent optical transparency such as an acrylic pressure-sensitive adhesive, exhibiting appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and being excellent in weather resistance, heat resistance and the like can be preferably used.

  In addition to the above, from the viewpoints of prevention of foaming and peeling phenomena due to moisture absorption, deterioration of optical characteristics due to differences in thermal expansion, prevention of warping of liquid crystal cells, and formation of a liquid crystal display device with high quality and excellent durability. An adhesive layer having a low moisture absorption rate and excellent heat resistance is preferred.

  The adhesive or pressure-sensitive adhesive may contain a crosslinking agent according to the base polymer. In addition, the adhesive layer and the like are, for example, natural and synthetic resins, in particular, tackifier resins, fillers and pigments made of glass fibers, glass beads, metal powders, other inorganic powders, colorants, antioxidants, etc. It may contain an additive to be added to the adhesive layer such as an agent. Moreover, the adhesion layer etc. which contain microparticles | fine-particles and show light diffusibility may be sufficient.

  Attachment of the adhesive layer to an optical element such as a polarizing plate or an optical film can be performed by an appropriate method. For example, a pressure sensitive adhesive solution of about 10 to 40% by weight in which a base polymer or a composition thereof is dissolved or dispersed in a solvent composed of an appropriate solvent alone or a mixture such as toluene and ethyl acetate is prepared. There is a method of attaching it directly on the optical element by an appropriate development method such as a casting method or a coating method, or a method of forming an adhesive layer on the separator according to the above and transferring it onto the optical element. Can be mentioned. The pressure-sensitive adhesive layer can also be provided as an overlapping layer of different compositions or types in each layer. The thickness of the pressure-sensitive adhesive layer can be appropriately determined according to the purpose of use and adhesive force, and is generally 1 to 500 μm, preferably 5 to 200 μm, particularly preferably 10 to 100 μm.

  On the exposed surface of the adhesive layer, a separator is temporarily attached and covered for the purpose of preventing contamination until it is put to practical use. Thereby, it can prevent contacting an adhesion layer in the usual handling state. As the separator, except for the above thickness conditions, for example, a suitable thin leaf body such as a plastic film, rubber sheet, paper, cloth, non-woven fabric, net, foamed sheet or metal foil, or a laminate thereof, silicone type or Appropriate ones according to the prior art, such as those coated with an appropriate release agent such as long-chain alkyl, fluorine-based or molybdenum sulfide, can be used.

  In the present invention, each layer such as a polarizer, a transparent protective film, an optical layer, and the like that form the optical element described above, and an adhesive layer, for example, a salicylic acid ester compound, a benzophenol compound, a benzotriazole compound, Those having an ultraviolet absorbing ability by a method such as a method of treating with an ultraviolet absorber such as a cyanoacrylate compound or a nickel complex salt compound may be used.

Moreover, you may use the anti-glare hard coat film of this invention as a surface treatment film in a glass crack prevention laminated body. The glass crack preventing laminate is a structure in which a surface treatment film is further provided on a glass crack preventing adhesive layer provided on one side of an optical film for liquid crystal display via an undercoat layer. The agent layer has a dynamic storage elastic modulus G ′ at 20 ° C. of 1 × 10 ⁷ Pa or less. Even when the antiglare hard coat film of the present invention is used for the glass crack preventing laminate having such a configuration, the glass substrate of the liquid crystal panel can be prevented from being broken by an external impact, and the optical film for liquid crystal is heated and humidified. It is possible to prevent the peeling and lifting from being caused by the durability test.

  The optical element provided with the hard coat film of the present invention can be preferably used for forming various devices such as a liquid crystal display device. The liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by appropriately assembling components such as a liquid crystal cell, an optical element, and an illumination system as necessary, and incorporating a drive circuit. There is no particular limitation except that an optical element is used. As the liquid crystal cell, any type such as a TN type, an STN type, or a π type can be used.

  An appropriate liquid crystal display device such as a liquid crystal display device in which the optical element is disposed on one side or both sides of a liquid crystal cell, or a backlight or a reflector used in an illumination system can be formed. In that case, the optical element according to the present invention can be installed on one or both sides of the liquid crystal cell. When optical elements are provided on both sides, they may be the same or different. Further, when forming the liquid crystal display device, for example, a single layer or a suitable layer such as a diffusing plate, an antiglare layer, an antireflection layer, a protective plate, a prism array, a lens array sheet, a light diffusing plate, a backlight, etc. Two or more layers can be arranged.

  Next, an organic electroluminescence device (organic EL display device) will be described. Generally, in an organic EL display device, a transparent electrode, an organic light emitting layer, and a metal electrode are sequentially laminated on a transparent substrate to form a light emitter (organic electroluminescent light emitter). Here, the organic light emitting layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer made of a triphenylamine derivative and the like and a light emitting layer made of a fluorescent organic solid such as anthracene, Alternatively, a structure having various combinations such as a laminate of such a light-emitting layer and an electron injection layer made of a perylene derivative, or a stack of these hole injection layer, light-emitting layer, and electron injection layer is known. It has been.

  In organic EL display devices, holes and electrons are injected into the organic light-emitting layer by applying a voltage to the transparent electrode and the metal electrode, and the energy generated by recombination of these holes and electrons excites the phosphor material. Then, light is emitted on the principle that the excited fluorescent material emits light when returning to the ground state. The mechanism of recombination in the middle is the same as that of a general diode, and as can be predicted from this, the current and the emission intensity show strong nonlinearity with rectification with respect to the applied voltage.

  In the organic EL display device, in order to extract light emitted from the organic light emitting layer, at least one of the electrodes must be transparent, and is usually a transparent electrode formed of a transparent conductor such as indium tin oxide (ITO). Is used as the anode. On the other hand, in order to facilitate electron injection and increase luminous efficiency, it is important to use a material having a small work function for the cathode, and usually metal electrodes such as Mg—Ag and Al—Li are used.

  In the organic EL display device having such a configuration, the organic light emitting layer is formed of a very thin film having a thickness of about 10 nm. For this reason, the organic light emitting layer transmits light almost completely like the transparent electrode. As a result, light that is incident from the surface of the transparent substrate at the time of non-light emission, passes through the transparent electrode and the organic light emitting layer, and is reflected by the metal electrode is again emitted to the surface side of the transparent substrate. The display surface of the organic EL display device looks like a mirror surface.

  In an organic EL display device including an organic electroluminescent light emitting device including a transparent electrode on a front surface side of an organic light emitting layer that emits light by application of a voltage and a metal electrode on a back surface side of the organic light emitting layer, the transparent electrode In addition, a polarizing plate can be provided on the surface side, and a retardation plate can be provided between the transparent electrode and the polarizing plate.

  Since the retardation plate and the polarizing plate have a function of polarizing light incident from the outside and reflected by the metal electrode, there is an effect that the mirror surface of the metal electrode is not visually recognized by the polarization action. In particular, the mirror surface of the metal electrode can be completely shielded by configuring the retardation plate with a quarter-wave plate and adjusting the angle formed by the polarization direction of the polarizing plate and the retardation plate to π / 4. .

  That is, only the linearly polarized light component of the external light incident on the organic EL display device is transmitted by the polarizing plate. This linearly polarized light becomes generally elliptically polarized light by the phase difference plate, but becomes circularly polarized light particularly when the phase difference plate is a quarter wavelength plate and the angle formed by the polarization direction of the polarizing plate and the phase difference plate is π / 4. .

  This circularly polarized light is transmitted through the transparent substrate, the transparent electrode, and the organic thin film, is reflected by the metal electrode, is again transmitted through the organic thin film, the transparent electrode, and the transparent substrate, and becomes linearly polarized light again on the retardation plate. And since this linearly polarized light is orthogonal to the polarization direction of a polarizing plate, it cannot permeate | transmit a polarizing plate. As a result, the mirror surface of the metal electrode can be completely shielded.

  Hereinafter, preferred embodiments of the present invention will be described in detail by way of example. However, the materials, blending amounts, and the like described in the examples are not intended to limit the scope of the present invention only to them, but are merely illustrative examples, unless otherwise specified. In each example, all parts and percentages are based on weight unless otherwise specified.

Example 1
100 parts of urethane acrylate composed of pentaerythritol acrylate and hydrogenated xylene diisocyanate as urethane acrylate (hereinafter referred to as A component), and dipentaerythritol hexaacrylate (hereinafter referred to as B1 component (monomer) as polyol (meth) acrylate (hereinafter referred to as B component) )) 49 parts, 24 parts of pentaerythritol triacrylate (hereinafter referred to as B2 component (monomer)) and 41 parts of pentaerythritol tetraacrylate (hereinafter referred to as B3 component (monomer)), and having an alkyl group containing two or more hydroxyl groups (meta) ) 59 parts of (meth) acrylic polymer (Dainippon Ink and Chemicals, PC 1097) having 2-hydroxyethyl group and 2,3-dihydroxypropyl group was blended as acrylic polymer (hereinafter referred to as component C). . Furthermore, 30 parts of PMMA particles (refractive index: 1.49) having an average particle diameter of 10 μm, 0.5 part of a reactive leveling agent, and 5 parts of a polymerization initiator (Irgacure 184) with respect to all resin components. Was diluted with a mixed solvent having a mixing ratio of butyl acetate and ethyl acetate of 55:45 (ethyl acetate ratio to all solvents 45%) to a solid content concentration of 55% to prepare a hard coat forming material. . The reactive leveling agent was copolymerized at a molar ratio of dimethylsiloxane: hydroxypropylsiloxane: 6-isocyanatohexyl isocyanuric acid: aliphatic polyester = 6.3: 1.0: 2.2: 1.0. It is a copolymer.

The hard coat forming material is coated on a triacetyl cellulose film (refractive index: 1.48) having a thickness of 80 μm as a film base using a bar coater and heated at 100 ° C. for 1 minute. Was dried. Thereafter, ultraviolet rays having an integrated light quantity of 300 mJ / cm ² were irradiated with a metal halide lamp and cured to form a hard coat layer having a thickness of 20 μm, thereby producing an antiglare hard coat film according to this example.

(Example 2)
In this example, an antiglare hard coat film was produced in the same manner as in Example 1 except that the amount of PMMA particles added was changed to 15 parts.

(Example 3)
In this example, 30 parts of PMMA particles having an average particle diameter of 15 μm (refractive index 1.49) were added, and the solid content concentration was changed to 35%. An antiglare hard coat film was produced.

Example 4
In this example, the same method as in Example 1 was applied except that 30 parts of PMMA particles (refractive index 1.49) having an average particle diameter of 8 μm were added and the thickness of the hard coat layer was changed to 16 μm. Thus, an antiglare hard coat film was produced.

(Example 5)
In this example, an antiglare hard coat film was produced in the same manner as in Example 1 except that the thickness of the hard coat layer was changed to 16 μm.

(Example 6)
In this example, an antiglare hard coat film was produced in the same manner as in Example 1 except that the film thickness of the hard coat layer was changed to 29 μm.

(Example 7)
In this example, the same method as in Example 1 was applied except that 30 parts of PMMA particles (refractive index: 1.49) having an average particle size of 15 μm were added and the film thickness of the hard coat layer was changed to 23 μm. Thus, an antiglare hard coat film was produced.

(Example 8)
In this example, an antiglare hard coat film was produced in the same manner as in Example 1 except that an antireflection layer was provided on the hard coat layer.

  The antireflection layer was formed as follows. First, as a material for forming the antireflection layer, a siloxane oligomer (Colcoat N103 (manufactured by Colcoat Co., Ltd., solid content: 2% by weight)) having an average molecular weight in terms of ethylene glycol of 500 to 10,000 is prepared, and the number average molecular weight is determined. It was measured. As a result, the number average molecular weight was 950. In addition, Opstar JTA105 (trade name, manufactured by JSR Corporation, solid content 5% by weight) is prepared as a fluorine compound having a number average molecular weight in terms of polystyrene of 5000 or more and having a fluoroalkyl structure and a polysiloxane structure. When the number average molecular weight of this fluorine compound was measured, the number average molecular weight in terms of polystyrene was 8,000. Further, as a curing agent, JTA105A (manufactured by JSR Corporation, solid content 5% by weight) was used.

  Next, 100 parts by weight of OPSTAR JTA105, 1 part by weight of JTA105A, 590 parts by weight of Colcoat N103 and 151.5 parts by weight of butyl acetate were mixed to prepare an antireflection layer forming material. This antireflection layer forming material is coated on the hard coat layer with a die coater so as to have the same width as the hard coat layer, dried and cured by heating at 120 ° C. for 3 minutes, and the antireflection layer ( A low refractive index layer having a thickness of 0.1 μm and a refractive index of 1.43) was formed.

Example 9
In this example, an antireflection layer was formed on the hard coat layer of the antiglare hard coat film obtained in Example 1 to produce an antiglare antireflection hard coat film.

  The antireflection layer was formed as follows. That is, 100 parts of dipentaerythritol acrylate, 15 parts of silicone polymer having methacryloxypropyl group and butyl group, 2.5 parts of hexanediol acrylate, 6 parts of lucillin type photopolymerization initiator, and acrylic group Surface treatment with a silane coupling agent and hydrophobized hollow spherical silicon oxide ultrafine particles with a diameter of 60 nm are mixed with a mixed solvent (IPA / MIBK / Puchicello / Toluene (80/9 / 10.5 / 0.5) ) To obtain a material for forming an antireflection layer by adjusting the solid content to 3%. Using this antireflection layer forming material, an antireflection layer was formed on the hard coat layer by the same method as in Example 7.

(Example 10)
First, in the same manner as in Example 1, an antiglare hard coat film according to this example was produced. Next, the coating liquid described later is applied to the hard coated surface of the triacetyl cellulose film (the surface opposite to the surface on which the hard coat layer is formed) with a wire bar so that the wet thickness is 20 μm. And a drying treatment at 80 ° C. for 1 minute. As the coating solution, a mixed solvent of acetone: ethyl acetate: IPA (isopropyl alcohol) = 37: 58: 5 was used.

(Example 11)
First, in the same manner as in Example 1, an antiglare hard coat film according to this example was produced. Next, the coating liquid described later is applied to the hard coated surface of the triacetyl cellulose film (the surface opposite to the surface on which the hard coat layer is formed) with a wire bar so that the wet thickness is 20 μm. And a drying treatment at 80 ° C. for 1 minute. In addition, as said coating liquid, what mix | blended diacetyl cellulose so that solid content concentration might be 0.5% with respect to the mixed solvent of acetone: ethyl acetate: IPA (isopropyl alcohol) = 37: 58: 5 is used. It was.

(Example 12)
In this example, a mixed solvent having a mixing ratio of butyl acetate and ethyl acetate of 79:21 (ethyl acetate ratio to the total solvent of 21%) is used, and the solid content concentration is further set to 63%. A hard coat film was produced in the same manner as in Example 1 except that a hard coat layer was formed using a diluted hard coat forming material.

(Example 13)
In this example, except that a mixed solvent in which the mixing ratio of butyl acetate and MIBK (methyl isobutyl ketone) was 55:45 (ethyl acetate ratio to all solvents: 45%) was used as the hard coat forming material. In the same manner as in Example 10, an antiglare antireflection hard coat film according to this example was produced.

(Example 14)
In this example, as the hard coat forming material, a mixed solvent having a mixing ratio of butyl acetate and butyl alcohol of 55:45 (ethyl acetate ratio to all solvents: 45%) was used. Similarly, an antiglare antireflection hard coat film according to this example was produced.

(Example 15)
In this example, an antiglare hard coat film was produced in the same manner as in Example 1 except that no reactive leveling agent was used.

(Example 16)
100 parts of urethane acrylate composed of pentaerythritol acrylate and hydrogenated xylene diisocyanate as urethane acrylate (hereinafter referred to as A component), and dipentaerythritol hexaacrylate (hereinafter referred to as B1 component (monomer) as polyol (meth) acrylate (hereinafter referred to as B component) )) 49 parts, 65 parts of a polymerization component of pentaerythritol triacrylate and pentaerythritol tetraacrylate (hereinafter referred to as B2 component (monomer)), and a (meth) acrylic polymer having an alkyl group containing two or more hydroxyl groups (hereinafter referred to as C component) ) 59 parts of (meth) acrylic polymer having a 2-hydroxyethyl group and a 2,3-dihydroxypropyl group (Dainippon Ink Chemical Co., Ltd., PC 1097) and PMMA particles having an average particle size of 10 μm (Refractive index: 1.49) 30 parts, a reactive leveling agent 0.5 part, and a polymerization initiator (Irgacure 184) 5 parts, the mixing ratio of butyl acetate and ethyl acetate is 55:45 (based on the total solvent) A hard coat forming material was prepared by diluting with a mixed solvent having an ethyl acetate ratio of 45% to a solid content concentration of 55%. The reactive leveling agent was copolymerized at a molar ratio of dimethylsiloxane: hydroxypropylsiloxane: 6-isocyanatohexyl isocyanuric acid: aliphatic polyester = 6.3: 1.0: 2.2: 1.0. It is a copolymer.

The hard coat forming material is coated on a triacetyl cellulose film (refractive index: 1.48) having a thickness of 80 μm as a film base using a bar coater and heated at 100 ° C. for 1 minute. Was dried. Thereafter, ultraviolet rays having an integrated light quantity of 300 mJ / cm ² were irradiated with a metal halide lamp and cured to form a hard coat layer having a thickness of 20 μm, thereby producing an antiglare hard coat film according to this example.

(Example 17)
In this example, an antiglare hard coat film was produced in the same manner as in Example 16 except that the amount of PMMA particles added was changed to 15 parts.

(Example 18)
In this example, 30 parts of PMMA particles having an average particle diameter of 15 μm (refractive index 1.49) were added, and the solid content concentration was changed to 35%. An antiglare hard coat film was produced.

Example 19
In this example, the same method as in Example 16 was applied except that 30 parts of PMMA particles (refractive index: 1.49) having an average particle diameter of 8 μm were added and the film thickness of the hard coat layer was changed to 16 μm. Thus, an antiglare hard coat film was produced.

(Example 20)
In this example, an antiglare hard coat film was produced in the same manner as in Example 16 except that the film thickness of the hard coat layer was changed to 16 μm.

(Example 21)
In this example, an antiglare hard coat film was produced in the same manner as in Example 16 except that the film thickness of the hard coat layer was changed to 29 μm.

(Example 22)
In this example, the same method as in Example 16 was applied except that 30 parts of PMMA particles (refractive index 1.49) having an average particle diameter of 15 μm were added and the film thickness of the hard coat layer was changed to 23 μm. Thus, an antiglare hard coat film was produced.

(Example 23)
In this example, an antiglare hard coat film was produced in the same manner as in Example 16 except that an antireflection layer was provided on the hard coat layer.

  The antireflection layer was formed as follows. First, as a material for forming the antireflection layer, a siloxane oligomer (Colcoat N103 (manufactured by Colcoat Co., Ltd., solid content: 2% by weight)) having an average molecular weight in terms of ethylene glycol of 500 to 10,000 is prepared, and the number average molecular weight is determined. It was measured. As a result, the number average molecular weight was 950. In addition, Opstar JTA105 (trade name, manufactured by JSR Corporation, solid content 5% by weight) is prepared as a fluorine compound having a number average molecular weight in terms of polystyrene of 5000 or more and having a fluoroalkyl structure and a polysiloxane structure. When the number average molecular weight of this fluorine compound was measured, the number average molecular weight in terms of polystyrene was 8,000. Further, as a curing agent, JTA105A (manufactured by JSR Corporation, solid content 5% by weight) was used.

  Next, 100 parts by weight of OPSTAR JTA105, 1 part by weight of JTA105A, 590 parts by weight of Colcoat N103 and 151.5 parts by weight of butyl acetate were mixed to prepare an antireflection layer forming material. This antireflection layer forming material is coated on the hard coat layer with a die coater so as to have the same width as the hard coat layer, dried and cured by heating at 120 ° C. for 3 minutes, and the antireflection layer ( A low refractive index layer having a thickness of 0.1 μm and a refractive index of 1.43) was formed.

(Example 24)
In this example, an antireflection layer was formed on the hard coat layer of the antiglare hard coat film obtained in Example 16 to produce an antiglare antireflection hard coat film.

  The antireflection layer was formed as follows. That is, 100 parts of dipentaerythritol acrylate, 15 parts of silicone polymer having methacryloxypropyl group and butyl group, 2.5 parts of hexanediol acrylate, 6 parts of lucillin type photopolymerization initiator, and acrylic group Surface treatment with a silane coupling agent and hydrophobized hollow spherical silicon oxide ultrafine particles with a diameter of 60 nm are mixed with a mixed solvent (IPA / MIBK / Puchicello / Toluene (80/9 / 10.5 / 0.5) ) To obtain a material for forming an antireflection layer by adjusting the solid content to 3%. Using this antireflection layer forming material, an antireflection layer was formed on the hard coat layer in the same manner as in Example 22.

(Example 25)
First, in the same manner as in Example 16, an antiglare hard coat film according to this example was produced. Next, the coating liquid described later is applied to the hard coated surface of the triacetyl cellulose film (the surface opposite to the surface on which the hard coat layer is formed) with a wire bar so that the wet thickness is 20 μm. And a drying treatment at 80 ° C. for 1 minute. As the coating solution, a mixed solvent of acetone: ethyl acetate: IPA (isopropyl alcohol) = 37: 58: 5 was used.

(Example 26)
First, in the same manner as in Example 16, an antiglare hard coat film according to this example was produced. Next, the coating liquid described later is applied to the hard coated surface of the triacetyl cellulose film (the surface opposite to the surface on which the hard coat layer is formed) with a wire bar so that the wet thickness is 20 μm. And a drying treatment at 80 ° C. for 1 minute. In addition, as said coating liquid, what mix | blended diacetyl cellulose so that solid content concentration might be 0.5% with respect to the mixed solvent of acetone: ethyl acetate: IPA (isopropyl alcohol) = 37: 58: 5 is used. It was.

(Example 27)
In this example, a mixed solvent having a mixing ratio of butyl acetate and ethyl acetate of 79:21 (ethyl acetate ratio to the total solvent of 21%) is used, and the solid content concentration is further set to 63%. A hard coat film was produced in the same manner as in Example 16 except that the hard coat layer was formed using the diluted hard coat forming material.

(Example 28)
In this example, except that a mixed solvent in which the mixing ratio of butyl acetate and MIBK (methyl isobutyl ketone) was 55:45 (ethyl acetate ratio to all solvents: 45%) was used as the hard coat forming material. In the same manner as in Example 25, an antiglare antireflection hard coat film according to this example was produced.

(Example 29)
In this example, Example 25 and Example 25 were used except that a mixed solvent having a mixing ratio of butyl acetate and butyl alcohol of 55:45 (ethyl acetate ratio to all solvents: 45%) was used as the hard coat forming material. Similarly, an antiglare antireflection hard coat film according to this example was produced.

(Example 30)
In this example, an antiglare hard coat film was produced in the same manner as in Example 16 except that no reactive leveling agent was used.

(Comparative Example 1)
100 parts of urethane acrylate UV curable resin, 15 parts of polystyrene particles (refractive index: 1.59) with an average particle size of 3.5 μm, leveling agent (trade name; MegaFuck F470N, manufactured by Dainippon Ink & Chemicals, Inc.) ) 0.5 part, 2.5 parts of synthetic smectite, 5 parts of a polymerization initiator (trade name; Irgacure 907), a solid content concentration of 35 with a mixed solvent of butyl acetate and toluene (butyl acetate: toluene = 13: 87). The material for forming the hard coat layer was prepared by diluting to a percentage of%.

Next, the hard coat layer forming material is coated on a triacetyl cellulose film (refractive index: 1.48) having a thickness of 80 μm as a transparent plastic film substrate by a bar coater to form a coating film, This coating film was dried by heating at 100 ° C. for 1 minute. Further, the coating film was irradiated with ultraviolet rays having an integrated light quantity of 300 mJ / cm ² with a metal halide lamp and cured to form a hard coat layer having a thickness of 5 μm. This produced the anti-glare hard coat film concerning this comparative example.

(Comparative Example 2)
In this comparative example, an antiglare hard coat film according to this comparative example was obtained in the same manner as in Example 1 except that the amount of PMMA particles added was changed to 3 parts.

(Comparative Example 3)
In this comparative example, an antiglare hard coat film according to this comparative example was obtained in the same manner as in Example 1 except that the amount of PMMA particles added was changed to 70 parts.

(Comparative Example 4)
In this comparative example, the fine particles were PMMA particles having an average particle diameter of 3 μm (refractive index: 1.49), and the addition amount was changed to 30 parts. Thus, an antiglare hard coat film according to this comparative example was obtained.

(Thickness of hard coat layer)
Measurement was performed with a micro gauge thickness gauge manufactured by Mitutoyo Corporation. The film thickness of the hard coat layer was calculated by measuring the thickness of the hard coat film in which the hard coat layer was provided on the transparent film substrate and subtracting the thickness of the substrate. The results are shown in Tables 1 and 2.

(Thickness of antireflection layer)
MCPD2000 (trade name), which is an instantaneous multi-side optical system manufactured by Otsuka Electronics Co., Ltd., was used for calculation from the waveform of the interference spectrum.

  Moreover, the following evaluation was performed about the obtained anti-glare hard coat film (including an anti-glare anti-reflection hard coat film). The results are shown in Tables 1 and 2.

(Haze)
According to haze (cloudiness) of JIS K7136 (1981 version), it was measured using a haze meter HR300 (trade name, manufactured by Murakami Color Research Laboratory Co., Ltd.). The results are shown in Tables 1 and 2.

(Glossiness)
The glossiness was measured using a Suga Test Instruments Co., Ltd. product (digital variable glossiness meter UGV-5DP) according to JIS K7105-1981 with a measurement angle of 60 °.

(Pencil hardness)
After the surface of the antiglare hard coat film on which the hard coat layer is not formed is placed on a glass plate, the surface of the hard coat layer (or antireflection layer) is subjected to the pencil hardness test described in JIS K-5400 (however, , Load 500 g). The results are shown in Tables 1 and 2.

(Abrasion resistance)
The value for the strength of the scratch resistance of the antiglare hard coat film was determined by the following test contents.
(1) The sample is cut into a size of at least 25 mm in width and 100 mm in length, and placed on a glass plate.
(2) Steel wool # 0000 is uniformly attached to a smooth cross section of a cylinder having a diameter of 25 mm, and the sample surface is reciprocated 30 times at a speed of about 100 mm per second with a load of 1.5 kg. Judged.
○: No scratch at all.
Δ: Although there are fine scratches, the visibility is not affected.
X: There is an obvious scratch and the visibility is impaired.

(Center line average surface roughness Ra and average inclination angle θa)
A glass plate (thickness: 1.3 mm) made of MATUNAMI was bonded to the surface of the antiglare hard coat film on which the hard coat layer was not formed with an adhesive. The Ra value and the θa value described in JIS B0601-1994 were obtained by measurement with a high-precision fine shape measuring instrument (trade name: Surfcorder ET4000, manufactured by Kosaka Laboratory Ltd.).

(Adhesion)
The adhesion of the hard coat layer to the film substrate was evaluated by conducting a cross-cut peel test described in JIS K 5400. That is, 100 peel tests were performed, the number of peeled hard coat layers from the film substrate was counted, and the number of peels / 100 was shown in Tables 1 and 2.

(Reflectance)
A non-glare hard coat film with a hard coat layer formed on a black acrylic board (thickness: 2.0 mm) made by Mitsubishi Rayon with an adhesive of about 20 μm thick and with no reflection on the back. The reflectance of the antireflection layer surface was measured. The reflectance was measured using a UV2400PC (with 8 ° tilt integrating sphere) spectrophotometer manufactured by Shimadzu Corporation, and the spectral reflectance (specular reflectance + diffuse reflectance) was measured. Total reflectance (Y value) was obtained by calculation. The results are shown in Tables 1 and 2.

It is a cross-sectional schematic diagram which shows the outline of the glare-proof hard coat film which concerns on one Embodiment of this invention. It is a cross-sectional schematic diagram which shows the outline of the anti-glare antireflection hard coat film which concerns on other embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Film base material 2 Hard-coat layer 3 Fine particle 4 Anti-glare hard coat film 5 Antireflection layer 6 Anti-glare anti-reflection hard coat film

Claims (13)

An antiglare hard coat film having a hard coat layer containing fine particles on at least one surface of a transparent film substrate,
The film thickness of the hard coat layer is 15 μm or more and 30 μm or less, and the average particle diameter of the fine particles is 30% or more and 75% or less of the film thickness of the hard coat layer,
An anti-glare hard coat film having an uneven shape of JIS B 0601 formed by the fine particles according to JIS B 0601 of 0.4 ° to 1.5 °. The antiglare hard coat film according to claim 1,
The anti-glare hard coat film, wherein the hard coat layer forming material includes urethane acrylate, polyol (meth) acrylate, and a (meth) acrylic polymer having an alkyl group containing two or more hydroxyl groups. The antiglare hard coat film according to claim 2,
The anti-glare hard coat film, wherein the polyol (meth) acrylate comprises pentaerythritol triacrylate and pentaerythritol tetraacrylate. The antiglare hard coat film according to any one of claims 1 to 3,
An anti-glare hard coat film, wherein at least one antireflection layer is provided on the hard coat layer. The antiglare hard coat film according to claim 4,
An antiglare hard coat film, wherein the antireflection layer contains hollow spherical silicon oxide ultrafine particles. The antiglare hard coat film according to any one of claims 1 to 5,
An antiglare hard coat film having a glossiness of 50 or more and 95 or less according to JIS K 7105. In the method for producing an antiglare hard coat film for forming a hard coat layer on at least one surface of a transparent film substrate,
A step of preparing a forming material of the hard coat layer, the step of preparing by adding fine particles having an average particle size of 30% to 75% of the film thickness of the hard coat layer to the forming material;
Applying the forming material to at least one surface of the film substrate to form a coating film; and
The coating film is cured to form a hard coat layer having a film thickness of 15 μm or more and 30 μm or less and an uneven shape JIS B 0601 formed by the fine particles of θa of 0.4 ° or more and 1.5 ° or less. A method for producing an antiglare hard coat film. It is a manufacturing method of the anti-glare hard coat film according to claim 7,
A method for producing an antiglare hard coat film, comprising using a material containing ethyl acetate as a diluting solvent for the hard coat layer forming material. It is a manufacturing method of the anti-glare hard coat film according to claim 8,
The method for producing an antiglare hard coat film, wherein the ethyl acetate content is 20% by weight or more.   An optical element, wherein the antiglare hard coat film according to any one of claims 1 to 6 is provided on at least one surface of an optical member.   A polarizing plate comprising the antiglare hard coat film according to any one of claims 1 to 6.   A polarizing plate comprising the antiglare hard coat film according to claim 1 provided on at least one surface of a polarizer.   An image display comprising the antiglare hard coat film according to any one of claims 1 to 6, the optical element according to claim 10, or the polarizing plate according to claim 11 or 12. apparatus.

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