JP4116045B2 - Anti-glare hard coat film - Google Patents

Anti-glare hard coat film Download PDF

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JP4116045B2
JP4116045B2 JP2006136618A JP2006136618A JP4116045B2 JP 4116045 B2 JP4116045 B2 JP 4116045B2 JP 2006136618 A JP2006136618 A JP 2006136618A JP 2006136618 A JP2006136618 A JP 2006136618A JP 4116045 B2 JP4116045 B2 JP 4116045B2
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hard coat
film
layer
fine particles
resin
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JP2007041533A (en
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雄一 木村
誠一 楠本
大介 濱本
崇之 重松
勝則 高田
寛行 鷹尾
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日東電工株式会社
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  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. In more detail, the protective film 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, a polarizing plate provided therewith, and an image display device provided therewith.

  One of the various image display devices is the LCD. With the technological innovations related to high viewing angle, high definition, high-speed response, color reproducibility, etc., LCD-based applications are also used in 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, the surface of the polarizing plate sandwiched between two transparent plastic film substrates is roughened by an appropriate method such as sandblasting, embossing roll, chemical etching, etc. to give a fine uneven structure to the polarizing plate surface. Alternatively, the antiglare treatment has been performed by a method of dispersing fine particles in a hard coat layer separately provided on the surface of the transparent plastic film substrate to give a fine uneven structure.

  An antiglare hard coat film obtained by applying an antiglare treatment to a transparent plastic film substrate is usually a spherical or irregular shape having a particle size of several μm in an ionizing radiation curable resin such as a thermosetting resin or an ultraviolet curable resin. Obtained by dispersing a thin coating film of about 2 to 10 μm on a transparent plastic film substrate.

  Flat panel displays such as LCDs are applied to home TVs, improving display quality such as high viewing angle, high speed response, and high definition, as well as indoor fluorescent lamps and viewer images. Therefore, it is required to improve the antiglare property to prevent the image from appearing in the image and to further improve the display contrast in a bright place, that is, to improve the darkness of black during black display.

  However, the antiglare property and the display contrast in a bright place have a trade-off relationship. Therefore, in applications where display contrast is important, a hard coat layer having a smooth surface shape is disposed on the outermost surface of the display surface at the expense of anti-glare properties. In applications where anti-glare properties are important, an uneven hard coat layer (anti-glare layer) is disposed on the outermost surface of the display surface.

  Possible causes of the decrease in display contrast in bright places include reflection on the surface of the hard coat layer or antiglare layer having a smooth surface and the effect of light scattering inside the antiglare layer. In order to suppress the reduction of display contrast due to surface reflection, an antireflection layer is appropriately provided on the outermost surface of the display surface to reduce reflection of external light on the display surface and improve display contrast in bright places. I am trying.

  The trade-off relationship cannot be avoided even if an antiglare hard coat layer obtained by adding fine particles to the hard coat resin is simply used. This is because if the addition amount of the fine particles is appropriately adjusted in order to obtain a predetermined antiglare property, the display contrast is lowered. A method for solving the problem relating to the decrease in display contrast in such an antiglare hard coat film is disclosed, for example, in Patent Document 1 below.

  Patent Document 1 describes an antiglare antireflection film having at least one antiglare hard coat layer on a transparent support. The antiglare hard coat layer includes at least one first light-transmitting particle having an average particle size of 60% or more and less than 95% with respect to the layer thickness of the antiglare hard coat layer, and the same layer thickness. And at least one second translucent particle having an average particle size of 105% or more and less than 140%. However, in the case of the antiglare antireflection film having the above structure, both the antiglare property and the display contrast characteristic can be improved at the same time only by defining the average particle diameter of the light transmitting fine particles with respect to the film thickness of the hard coat layer. It is difficult.

JP 2003-248110 A

  The present invention has been made in view of the above problems, and its purpose is to suppress a decrease in display contrast of a display while maintaining antiglare properties when an antiglare hard coat layer is formed on a film substrate. An object of the present invention is to provide an antiglare hard coat film that can be used. Moreover, it is providing the polarizing plate provided with the said anti-glare hard coat film, and an image display apparatus provided with them.

  In order to solve the conventional problems, the inventors of the present application have studied an antiglare hard coat film, a polarizing plate provided therewith, or an image display device provided therewith. 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 comprises a hard coat layer containing fine particles and having an uneven surface on at least one surface of a transparent film substrate in order to solve the above-mentioned problems. An antiglare hard coat film, wherein the average particle diameter of the fine particles is 6 μm to 15 μm, and the average inclination angle θa of the concavo-convex shape formed by the fine particles is 0.4 ° or more and 1.5 ° or less. The average inclination angle θa is a value defined by the following mathematical formula (1), and the hard coat layer includes the following components (A), (B), and (C): It is formed using a material, and the amount of the fine particles is 2 to 70 parts by weight with respect to 100 parts by weight of the hard coat forming material, and the display contrast characteristic is 60 or more.
(A) component: urethane acrylate
Component (B): at least one of polyol acrylate and polyol methacrylate
Component (C): a polymer, copolymer, or a mixture of the polymer and copolymer formed from at least one of the following (C1) and (C2)
(C1): alkyl acrylate having an alkyl group having at least one of a hydroxyl group and an acryloyl group
(C2): alkyl methacrylate having an alkyl group having at least one of a hydroxyl group and an acryloyl group
Average inclination angle θa = tan −1 Δa (1)
(Δa: In the reference length L of the roughness curve defined in JIS B 0601 (1994 version), the sum of the difference (height h) between the apex of the adjacent mountain and the lowest point of the valley (The value divided by the reference length L.)

  By setting the average particle diameter of the fine particles to 6 μm to 15 μm, the surface of the antiglare hard coat film can be formed into a very smooth uneven shape. Moreover, antiglare property is made favorable by setting the average inclination angle θa of the concavo-convex shape to 0.4 ° to 1.5 °. Furthermore, by setting the display contrast characteristic to 60 or more, the display quality in a bright place is improved. That is, the antiglare hard coat film having both the antiglare property and the display contrast can be provided with the above structure. The display contrast characteristic is a value calculated by (contrast ratio of antiglare hard coat film) / (contrast ratio of hard coat film) × 100. The contrast ratio is a value represented by (brightness in white display / brightness in black display).

  In the antiglare hard coat film, the thickness of the hard coat layer is preferably 15 μm to 35 μm. By setting the film thickness of the hard coat layer to 15 μm or more, it is possible to prevent the hardness of the antiglare hard coat film itself from being excessively lowered. On the other hand, the occurrence of cracks in the antiglare hard coat film can be prevented by setting the film thickness to 35 μm or less. In addition, curling such that the hard coat layer side is on the inner side due to curing shrinkage of the antiglare hard coat film can be reduced.

  In the antiglare hard coat film, the fine particles are preferably substantially spherical.

In the antiglare hard coat film, the fine particles have a refractive index of 1.40 to 1.70, and the resin binder in the hard coat layer has a refractive index of 1.5 to 1.6. It is preferable.

  In order to solve the above problems, a polarizing plate according to the present invention includes the antiglare hard coat film described above.

  Thereby, the polarizing plate with favorable anti-glare property and display contrast can be provided.

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

  Thereby, it is possible to provide an image display device which is excellent in antiglare property and display contrast and has high display quality.

The present invention has the following effects by the means described above.
That is, according to the present invention, the average particle diameter of the fine particles is set to 6 μm to 15 μm, the average inclination angle θa of the uneven shape in the hard coat layer is set to 0.4 ° to 1.5 °, and the display contrast characteristic is 60. By doing so, it is possible to provide an antiglare hard coat film having both extremely good antiglare properties and display contrast, a polarizing plate provided therewith, and an image display device provided therewith.

  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 the figure, the antiglare hard coat film 4 according to the present embodiment has an antiglare hard coat layer (hereinafter simply referred to as a hard coat) on one surface of a film substrate 1 made of a transparent plastic. (Referred to as a layer). 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 norbornene 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 antiglare hard coat film 4 according to the present embodiment is used as a protective film for a polarizing plate, the film substrate 1 may be 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. Further, the antiglare 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 a layer in which fine particles 2b are added to the resin binder 2a and the surface portion thereof is formed in an uneven shape.

  The hard coat layer 2 comprises a urethane acrylate (A component), a polyol (meth) acrylate (B component), and an alkyl (meth) acrylate polymer, copolymer or copolymer having an alkyl group having at least one of a hydroxyl group and an acryloyl group. A mixture (C component) of the polymer and copolymer is formed as a forming material.

  As said urethane acrylate (A component), 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 (component 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 component) is 15% by weight to the total resin component 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). 55 weight% is preferable and it is more preferable that it is 25 weight%-45 weight%. If the addition amount of urethane acrylate (component 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 may be undesirable. 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 (component B) include pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. 1,6-hexanediol (meth) acrylate and the like. Further, a mixed component containing pentaerythritol triacrylate and pentaerythritol tetraacrylate is particularly preferable.

  The blending amount of the polyol (meth) acrylate (component B) is preferably 70% by weight to 180% by weight and preferably 100% by weight to 150% by weight with respect to the urethane acrylate (component A). More preferred. When the blending amount of the polyol (meth) acrylate (component B) exceeds 180% by weight with respect to the urethane acrylate (component A), the curing shrinkage of the hard coat layer increases, and as a result, the curl of the hard coat film increases. May be unfavorable because of poor flexibility. 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.

  Although it does not specifically limit as an alkyl group in the said C component, For example, a C1-C10 alkyl group is preferable. The alkyl group may be linear or branched. Examples of the C component include a polymer, a copolymer, or a mixture of the polymer and the copolymer containing a repeating unit represented by the following general formula (1). More specifically, for example, 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, 2-acryloyloxy-3-hydroxypropyl (meth) acrylate, 2,3- Examples thereof include polymers formed from monomers such as diacryloyloxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-acryloyloxyethyl (meth) acrylate, copolymers, and mixtures of the above polymers and copolymers.

In the general formula (1), R 1 represents an H group or a CH 3 group, and R 2 represents a CH 2 CH 2 X group or a functional group represented by the following general formula (2).

  X represents an H group or an acryloyl group represented by the following general formula (3), and each X may be the same or different.

  The amount of component C added is preferably 25% to 110% by weight, more preferably 45% to 85% by weight, based on urethane acrylate (component A). 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 C component, 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 2b. The fine particles 2b mainly function as antiglare fine particles that impart antiglare properties. The fine particles 2b 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, zirconium oxide, calcium oxide, indium oxide, calcium carbonate, barium sulfate, talc, kaolin, and calcium sulfate. Can be mentioned. 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 Examples thereof include polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, polyfluorinated ethylene resin powder, and polyethylene resin powder. 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 2b is more preferably 30% to 50% 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 50%, the unevenness of the surface becomes too large, resulting in inconvenience that the appearance is deteriorated and the scattering of reflected light becomes strong and white blurring occurs.

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

  The refractive index of the fine particles 2b needs to be appropriately selected in relation to the refractive index of the binder component 2a of the hard coat layer 2, but is preferably selected appropriately in the range of 1.40 to 1.70. . Further, in order to suppress as much light scattering as possible at the interface between the resin binder 2a and the fine particles 2b, it is necessary to reduce the refractive index difference between the resin binder 2a and the fine particles 2b. The refractive index of the resin binder 2a is generally 1.5 to 1.6. Therefore, as the fine particles 2b, organic fine particles having a refractive index close to the refractive index value of the organic resin binder 2a and fine particles made of an inorganic material such as silicon oxide are preferably used. The difference in refractive index of the fine particles 2b 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, and there may be a problem that the display image is unclear or the display contrast is lowered. Further, the refractive index difference of the fine particles 2b with respect to the refractive index of the hard coat layer 2 is more preferably less than 0.03, and particularly preferably less than 0.02.

  The average particle diameter of the fine particles 2b is in the range of 6 μm to 15 μm. If the average particle size is less than 6 μm, the reason is not clear even if the surface shape of the hard coat layer 2 satisfies the average inclination angle θa value described later, but the display contrast in a bright place decreases. There is a tendency. On the other hand, when the average particle diameter exceeds 15 μm, the size of the fine particles 2 b compared with the film thickness of the hard coat layer 2 becomes relatively large. This makes it difficult to control the degree of embedding of the fine particles 2b in the hard coat layer 2 during the formation of the hard coat layer 2, and the fine particles 2b are formed from the surface of the hard coat layer 2 due to overlapping of the fine particles 2b. Protruding and protruding defects may occur. In general, when a hard coat layer with a flat surface shape is used, when it is placed on the display screen of a display and the value of display contrast in a bright place is measured, reflection occurs on the display screen, but the value is Highest (except when an antireflection layer is formed on the hard coat layer). However, when the hard coat layer 2 containing the fine particles 2b having an average particle diameter in the range of 6 μm to 15 μm is used, the display contrast value in the bright place is lower than that in the case of the hard coat layer. Can be suppressed.

  Further, as the fine particles 2b, it is preferable to use substantially spherical particles having an aspect ratio of 1.5 or less. More preferably, it is preferable to use spherical fine particles. When spherical particles or polygonal particles having an aspect ratio exceeding 1.5 are used, it may be difficult to control the unevenness θa formed by the fine particles.

  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 antiglare 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.

  In the present invention, the average inclination angle θa is a value defined by the following mathematical formula (1).

In the formula (1), Δa is the apex of the adjacent mountain in the reference length L of the roughness curve defined in JIS B 0601 (1994 version) as shown in the following formula (2). And the sum (h 1 + h 2 + h 3 +... + H n ) of the difference (height h) between the lowermost point of the valley and the lowest point of the valley divided by the reference length L. The roughness curve is a curve obtained by removing a surface waviness component longer than a predetermined wavelength from a cross-sectional curve with a phase difference compensation type wide-area filter. The cross-sectional curve is a contour that appears at the cut end when the target surface is cut along a plane perpendicular to the target surface. FIG. 2 shows an example of the roughness curve, the height h, and the reference line L.

  When the difference in refractive index between the film substrate 1 and the hard coat layer 2 is d, d is preferably 0.04 or less. More preferably, it is 0.02 or less. When a polyethylene terephthalate film is used as the film substrate 1, about 35% of the total resin component of the hard coat forming material is blended with titanium oxide as inorganic ultrafine particles having a particle size of 100 nm or less. D can be controlled to 0.02 or less with respect to a refractive index of about 1.64, and generation of interference fringes can be suppressed. When a triacetyl cellulose film is used as the film substrate 1, about 40% of silicon oxide is blended as inorganic ultrafine particles having a particle size of 100 nm or less with respect to all resin components of the hard coat forming material, thereby triacetyl cellulose. D can be controlled to 0.02 or less in the same manner as described above with respect to the refractive index of the film of about 1.48, and the generation of interference fringes can be suppressed.

  The film thickness of the hard coat layer 2 is preferably 15 to 35 μm, more preferably 20 to 30 μm. Even if the lower limit of the film thickness is set to 15 μm, the hard coat layer 2 contains polyol (meth) acrylate (component B), so that 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 film thickness is set to 35 μm, the hard coat layer 2 contains urethane acrylate (A component) and C component, thereby sufficiently preventing the occurrence of curling and cracking. be able to. When the film thickness is less than 15 μm, the hardness may decrease due to the influence of the film base material 1 as a base. On the other hand, if the film thickness exceeds 35 μm, cracks may occur in the hard coat layer 2 itself, or the hard coat film may curl on the hard coat surface due to curing shrinkage of the hard coat layer 2, which may be a practical problem. . In order to obtain a hardness of 4H or more in the pencil hardness test according to JIS K-5400, the film thickness is preferably 20 μm or more.

  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 nonuniform. .

  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 appropriately used, and a silicone-based leveling agent is more preferable. Examples of the silicone leveling agent include 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 antiglare hard coat forming material.

  In the case of using ultraviolet rays as a curing means for the hard coat forming material, if a fluorine-based or silicone-based leveling agent is added to the hard coat forming material, the fluorine-based or silicone-based leveling agent is used during preliminary drying and solvent drying. Bleeds to the air interface. Thereby, the inhibition of curing of the ultraviolet curable resin by oxygen can be prevented, and the hard coat layer 2 having sufficient hardness even on the outermost surface of the hard coat layer 2 can be obtained. In addition, when the silicone leveling agent bleeds to the surface of the hard coat layer 2, the hard coat layer 2 is given slipperiness. Thereby, abrasion 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.

  In order to form the hard coat layer 2, a hard coat forming material containing at least urethane acrylate (A component), polyol (meth) acrylate (B component) and C component is applied on the film substrate 1, and then cured. Let 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 decrease. Moreover, when it exceeds 5000 mJ / cm < 2 >, a hard-coat layer may color and transparency may fall.

  The antiglare hard coat film 4 according to the present embodiment can exhibit good display contrast characteristics without providing an antireflection layer that reduces surface reflection of light. However, an antireflection layer is not provided on the antiglare hard coat film of the present invention to prevent an antiglare antireflection hard coat film.

  FIG. 3 shows an antiglare antireflection hard coat film provided with an antireflection layer. 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. 3, the hard coat layer 2 and the antireflection layer 5 can be provided on both surfaces of the film substrate 1. FIG. 3 illustrates the case where one hard coat layer 2 and one antireflection layer 5 are provided, but the antireflection layer 5 is 2 if the hard coat layer 2 of the present invention is provided. 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 a multilayer antireflection layer in which 2 to 5 optical thin films (thin films with strictly controlled film thickness and refractive index) are laminated on a substrate, a plurality of components having different refractive indexes are formed in a predetermined thickness. Thus, the degree of freedom in the optical design of the antireflection layer 5 is increased, the antireflection effect is further improved, and the spectral reflection characteristics can be flattened in the visible light region. Since the film 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.

  As the antireflection layer 5, titanium oxide, zirconium oxide, silicon oxide, magnesium fluoride or the like is 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. 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 film thickness accuracy is not as strict as the film thickness accuracy of the multilayer antireflection layer, and in the range of ± 10% of the design film thickness, that is, when the design wavelength is 95 nm If it is in the range of 86 nm to 105 nm, it can be used without any 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 group-containing compound in order to impart surface contamination resistance. 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 compounds, those in which n is 2 to 6 are 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 antireflection layer 5 can contain hollow spherical silicon oxide ultrafine particles for the purpose of reducing the refractive index. The hollow and spherical silicon oxide ultrafine particles preferably have an average particle diameter of about 5 nm to 300 nm, and the ultrafine particles are hollow spheres in which cavities are formed in the outer shells having pores. 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 nm 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.

  As described above, the average particle diameter of the silicon oxide ultrafine particles is preferably 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 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, and the transparency of the antireflection layer containing the ultrafine particles tends to be lowered. 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).

(A) A silicate aqueous solution and / or an acidic silicate solution and an alkali-soluble inorganic compound aqueous solution 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 ) in the range 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 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 coatability. . Specifically, for example, conventionally used polyester resin, acrylic resin, urethane resin, vinyl chloride resin, epoxy resin, melamine resin, fluororesin, silicone resin, butyral resin, phenol resin, vinyl acetate resin, UV curing Examples thereof include resins, electron beam curable resins, emulsion resins, water-soluble resins, hydrophilic resins, mixtures of these resins, and organic resins for paints such as copolymers and modified products of these resins. Further, hydrolyzable organosilicon compounds such as alkoxysilanes exemplified as the material for forming the antireflection layer 5 with the single layer can be used as the 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 and the matrix dispersed in an organic solvent can be diluted with an appropriate organic solvent to obtain an antireflection-forming coating solution.

  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, when the weight ratio is less than 1:99, the effect of adding the silicon oxide ultrafine particles may be difficult to be revealed.

  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. Micro unevenness is formed on the surface of the hard coat layer 2 containing ultrafine particles, which affects 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 temperature of drying and curing when forming the antireflection layer (low refractive index layer) 5 is not particularly limited, and is 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. Moreover, after drying and hardening, a higher hardness antireflection hard coat film 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, it is preferable to laminate a fluorine group-containing silane-based compound, a fluorine group-containing organic compound, or the like 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 a trace amount may remain, but preferably 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 bonding, 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. Usually, 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 polarizing plates are usually disposed on both sides of the liquid crystal cell. Usually, the polarizing plates are arranged so that the absorption axes of the two polarizing plates are substantially orthogonal to each other. 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 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 and 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 retardation value in the film thickness direction of −90 nm to +75 nm is preferably used. By using a film having a retardation value (Rth) in the film thickness direction of −90 nm to +75 nm, the coloration (optical coloration) 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 film thickness direction may affect the viewing angle characteristics of the liquid crystal display device, the one having the optimized retardation value should be used. Is preferred. 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 film 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.

  The polarizing plate on which the antiglare hard coat film 4 or the like is laminated may be obtained by sequentially laminating a transparent protective film, a polarizer and a transparent protective film on the hard coat film or the like, or a polarizer on the antiglare hard coat film or the like. 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 film 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, 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.

  Next, another optical member used in combination with the polarizing plate according to the present embodiment will be described. Although there is no limitation in particular about said other optical member, For example, the reflective polarizing plate or semi-transmissive polarizing plate by which a reflecting plate or a semi-transmissive reflecting plate is further laminated | stacked on an elliptically polarizing plate or a circularly-polarizing plate is mentioned. . Further, it may be a reflective elliptical polarizing plate or a semi-transmissive elliptical polarizing plate that combines the above-mentioned reflective polarizing plate or transflective polarizing plate and a retardation plate. In addition, when the antiglare hard coat film 4 or the antiglare antireflection hard coat film 6 or the polarizing plate according to the present embodiment is used for a transmissive or transflective liquid crystal display device, a commercially available luminance is used. By using in combination with an improvement film (a polarized light separation film having a polarization selective layer, for example, D-BEF manufactured by Sumitomo 3M Co., Ltd.), a display device with higher display characteristics can be obtained.

  The antiglare hard coat film 4 or the antiglare antireflection hard coat film 6 and the polarizing plate or the like can be formed by sequentially laminating them separately in the manufacturing process of the image display device. However, stacking in advance is preferable because it is excellent in quality stability, stacking workability, and the like, and the manufacturing efficiency of an image display device and the like can be improved.

  The antiglare hard coat film 4, the antiglare antireflection hard coat film 6, or the polarizing plate provided with them according to the present embodiment is mounted on various image display devices such as a liquid crystal display device and an organic EL display device. Can do.

  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. “Parts” and “%” are based on weight unless otherwise specified.

(Example 1)
Resin raw material (made by Dainippon Ink Co., Ltd.) containing a resin component containing A component, B component and C component shown below and a photopolymerization initiator in a mixed solvent of ethyl acetate and butyl acetate at a solid content concentration of 66%. , Trade name: GRANDIC PC1071). 30 parts of acrylic resin particles (refractive index 1.49) having an average particle diameter of 8 μm and 0.5 part of a reactive leveling agent are added to 100 parts of this resin raw material, and further butyl acetate: ethyl acetate (weight ratio) = 46: 54 ( The hard coat forming material was prepared by diluting with ethyl acetate so that the solid concentration was 55% at an ethyl acetate ratio of 54% with respect to the total solvent. 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.

Component A: urethane acrylate (100 parts) composed of pentaerythritol acrylate and hydrogenated xylene diisocyanate
Component B: dipentaerythritol hexaacrylate (49 parts), pentaerythritol triacrylate (24 parts) and pentaerythritol tetraacrylate (41 parts)
Component C: a mixture of a polymer and a copolymer having a repeating unit represented by the general formula (1) (59 parts)
Photopolymerization initiator: Irgacure 184 (trade name, manufactured by Ciba Specialty Chemicals)
Mixed solvent: butyl acetate: ethyl acetate (weight ratio) = 89: 11

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 25 μm, thereby producing an antiglare hard coat film according to this example. The refractive index of the hard coat layer was 1.52. Further, the aspect ratio of most fine particles was 1.05.

(Example 2)
In this example, acrylic resin particles having an average particle diameter of 10 μm and a refractive index of 1.49 were used as fine particles, the addition amount was 15 parts with respect to all resin components, and the film thickness was changed to 22 μm. Produced an antiglare hard coat film according to this example in the same manner as in Example 1. Further, the aspect ratio of most fine particles was 1.05.

(Example 3)
In this example, the same procedure as in Example 2 was performed, except that the amount of acrylic resin particles added was changed to 30 parts with respect to all resin components, and the film thickness of the hard coat layer was changed to 33 μm. An antiglare hard coat film according to an example was produced.

Example 4
In this example, an antiglare hard coat film according to this example was produced in the same manner as in Example 3 except that the film thickness of the hard coat layer was changed to 31 μm.

(Example 5)
In this example, an antiglare hard coat film according to this example was produced in the same manner as in Example 2 except that the film thickness of the hard coat layer was changed to 24 μm.

(Example 6)
In this example, an antiglare hard coat film according to this example was produced in the same manner as in Example 2 except that the film thickness of the hard coat layer was changed to 26 μm.

(Example 7)
In this example, an antiglare hard coat film according to this example was produced in the same manner as in Example 2 except that the film thickness of the hard coat layer was changed to 21 μm.

(Example 8)
In this example, acrylic-styrene resin particles having an average particle diameter of 10 μm and a refractive index of 1.51 were used as fine particles, the addition amount was 20 parts with respect to all resin components, and the film thickness was changed to 22 μm. Except for this, an antiglare hard coat film according to this example was produced in the same manner as in Example 1. The aspect ratio of most fine particles was 1.05. The acrylic-styrene resin particles are obtained by emulsion polymerization of an acrylic monomer and a styrene monomer. The refractive index was adjusted by changing the blending ratio of acrylic monomer and styrene monomer.

Example 9
In this example, acrylic-styrene resin particles having an average particle diameter of 10 μm and a refractive index of 1.52 were used as fine particles, the addition amount was 20 parts with respect to all resin components, and the film thickness was changed to 22 μm. Except for this, an antiglare hard coat film according to this example was produced in the same manner as in Example 1. The aspect ratio of most fine particles was 1.05.

(Example 10)
In this example, acrylic-styrene resin particles having an average particle diameter of 10 μm and a refractive index of 1.53 were used as fine particles, the addition amount was 20 parts with respect to all resin components, and the film thickness was changed to 23 μm. Except for this, an antiglare hard coat film according to this example was produced in the same manner as in Example 1. The aspect ratio of most fine particles was 1.05.

(Example 11)
In this example, acrylic-styrene resin particles having an average particle diameter of 10 μm and a refractive index of 1.54 were used as fine particles, the addition amount was 20 parts with respect to all resin components, and the film thickness was changed to 22 μm. Except for this, an antiglare hard coat film according to this example was produced in the same manner as in Example 1. The aspect ratio of most fine particles was 1.05.

(Example 12)
In this example, acrylic resin particles having an average particle diameter of 15 μm and a refractive index of 1.49 are used as fine particles, the amount added is 25 parts with respect to all resin components, and the solid content concentration of the hard coat forming material is 35. %, And an antiglare hard coat film according to this example was produced in the same manner as in Example 1 except that the film thickness was changed to 20 μm. The aspect ratio of most fine particles was 1.05.

(Comparative Example 1)
In this comparative example, acrylic resin particles having an average particle diameter of 3 μm and a refractive index of 1.49 are used as fine particles, the addition amount is 30 parts with respect to all resin components, and the film thickness is changed to 23 μm. Produced an antiglare hard coat film according to this comparative example in the same manner as in Example 1. The aspect ratio of most fine particles was 1.05.

(Comparative Example 2)
In this comparative example, acrylic resin particles having an average particle diameter of 5 μm and a refractive index of 1.49 are used as fine particles, the addition amount is 30 parts with respect to all resin components, and the film thickness is changed to 20 μm. Produced an antiglare hard coat film according to this comparative example in the same manner as in Example 1. The aspect ratio of most fine particles was 1.05.

(Comparative Example 3)
100 parts of UV curable resin, 0.5 part of leveling agent (Defenser MCF323), 6.5 parts of silicon oxide particles having an average particle size of 1.3 μm (Silo Hovic 100, manufactured by Fuji Silysia Chemical), 2.5 μm of average particle size Prepared by diluting 7.5 parts of silicon oxide particles (Silo Hovic 702, manufactured by Fuji Silysia Chemical) and 5 parts by weight of a polymerization initiator (trade name; Irgacure 184) with toluene to a solid content concentration of 45%. did. The ultraviolet curable resin is composed of 40% urethane acrylate, 40% polyester acrylate, and 20% butyl acetate.

The hard coat forming material is applied 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 3 minutes. 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 3 μm, thereby producing an antiglare hard coat film according to this example. The refractive index of the hard coat layer was 1.53. The aspect ratio of most fine particles was 1.6 or more.

(Comparative Example 4)
In this comparative example, 6.5 parts of silicon oxide particles having an average particle diameter of 1.8 μm (Silo Hovic 200, manufactured by Fuji Silysia Chemical) as fine particles and silicon oxide particles having an average particle diameter of 2.5 μm (Silo Ho The antiglare hard coat film according to this comparative example was produced in the same manner as in Comparative Example 3 except that 6.5 parts of BIC 702, manufactured by Fuji Silysia Chemical Co., Ltd. were used and the film thickness was further changed to 8 μm. The aspect ratio of each fine particle was almost 1.6 or more.

(Comparative Example 5)
In this comparative example, 13 parts of silicon oxide particles having an average particle size of 1.3 μm (Silo Hovic 200, manufactured by Fuji Silysia Chemical) were used as the fine particles, the solid content concentration of the hard coat forming material was 40%, and An antiglare hard coat film according to this comparative example was produced in the same manner as in Comparative Example 3 except that the film thickness was changed to 6 μm. The aspect ratio of each fine particle was almost 1.6 or more.

(Comparative Example 6)
In this comparative example, 14 parts of polystyrene particles having an average particle size of 3.5 μm (trade name: SX350H, manufactured by Soken Chemical Co., Ltd.) were used as the fine particles, and the film thickness was changed to 5 μm. Thus, an antiglare hard coat film according to this comparative example was produced. The aspect ratio of each fine particle was almost 1.6 or more.

(Comparative Example 7)
In this comparative example, acrylic resin particles having an average particle diameter of 10 μm and a refractive index of 1.49 are used as fine particles, the addition amount is 3 parts with respect to all resin components, and the film thickness is changed to 20 μm. In the same manner as in Example 1, an antiglare hard coat film according to this Comparative Example was produced. The aspect ratio of each fine particle was almost 1.6 or more.

(Reference Example 1)
The following antireflection layer-forming material is coated on the antiglare hard coat film obtained in Comparative Example 6, dried and cured, and then has an antiglare layer having a thickness of 100 nm. A hard coat film was produced.

  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 of OPSTAR JTA105, 1 part of JTA105A, 590 parts of Colcoat N103, and 151.5 parts of butyl acetate were mixed to prepare an antireflection layer forming material. The antireflection layer-forming material was coated on the hard coat layer with a die coater so as to have the same width as the hard coat layer. Further, it was dried and cured by heating at 120 ° C. for 3 minutes to form an antireflection layer (low refractive index layer, thickness 0.1 μm, refractive index 1.43). Thereby, an antiglare antireflection hard coat film having a reflectance of 2.2% was produced.

(Refractive index of transparent plastic film substrate and hard coat layer)
The refractive index of the transparent plastic film substrate and the hard coat layer was measured using an Abbe refractometer manufactured by Atago Co., Ltd. That is, the measurement light was made incident on the measurement surfaces of the transparent plastic film substrate and the hard coat layer, and the measurement was performed by the specified measurement method shown in the apparatus.

(Refractive index of fine particles)
The refractive index of each fine particle was measured as follows. That is, the fine particles are placed on a slide glass, the refractive index standard solution is dropped on the fine particles, and the cover glass is covered to prepare a sample. The sample was observed with a microscope, and the refractive index of the refractive index standard solution in which the contour of the fine particles was most hardly visible at the interface with the refractive index standard solution was defined as the refractive index of the fine particles.

(Hard coat layer thickness)
The film thickness of the hard coat layer was determined by measuring with a micro gauge thickness meter manufactured by Mitutoyo Corporation. The thickness of the antiglare hard coat film in which the antiglare hard coat layer was provided on the transparent plastic film substrate was measured, and the thickness of the hard coat layer was calculated by subtracting the thickness of the substrate. The results are shown in Tables 1 and 2.

(Antireflection layer thickness)
The film thickness of the antireflection layer was calculated from the waveform from the interference spectrum using MCPD2000 (trade name) which is an instantaneous multi-photometry system manufactured by Otsuka Electronics.

(Reflectance)
In the transparent plastic film base material, a black acrylic plate (2.0 mmt) made by Mitsubishi Rayon is bonded to the surface side (back surface) on which the hard coat layer is not formed with an adhesive material having a thickness of about 20 μm. And lost light reflection. Next, the spectral reflectance (specular reflectance + diffuse reflectance) is measured with a Shimadzu UV2400PC (with 80 tilting integrating sphere) spectrophotometer, and the total reflectance (Y value) of the C light source / 20 field of view is calculated. Determined by

(Pencil hardness)
In the pencil hardness test, the obtained hard coat film was attached to a glass plate with an adhesive material having a thickness of about 20 μm, and the test was performed according to the pencil hardness test described in JIS K-5400 (however, the load was 500 g). The results are shown in Tables 1 and 2.

(Haze)
The measuring method of haze was measured using haze meter HR300 (Murakami Color Research Laboratory Co., Ltd.) according to JIS-K7136 haze (cloudiness). 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 °.

(Arithmetic average surface roughness Ra and average inclination angle θa)
On the surface of the antiglare hard coat film on which the antiglare hard coat layer was not formed, MATUNAMI glass (thickness: 1.3 mm) was bonded with an adhesive. Measurement was performed with a high-precision fine shape measuring instrument (trade name: Surfcorder ET4000, Kosaka Laboratory Ltd.), and an arithmetic average surface roughness Ra value and an average interval Sm value of irregularities described in JIS B0601-1994 were obtained. The average inclination angle θa value was also obtained by automatic calculation with the same measuring device.

(Display contrast)
(1) The prepared antiglare hard coat film was bonded to a polarizing plate having a smooth surface by attaching an acrylic adhesive having a film thickness of about 20 μm to the surface where the antiglare hard coat layer was not formed ( 50 mm x 50 mm).

  (2) A polarizing plate with an antiglare hard coat film was attached to the central portion of a panel (panel model number: LQ150X1LAJO) manufactured by Sharp Corporation.

  (3) With respect to the mounted panel, a light receiver (manufactured by MINOLTA, SPECTRADIOMETER CS1000A) is set so as to be parallel to the upper side by 50 cm, and ring illumination (diameter 37 mm: MHF-G150LR made by MORITEX) is positioned at a height of 27 mm Set. The irradiation angle of the light applied to the panel from the ring illumination light at this set position was set to 30 °.

  (4) An illuminometer (manufactured by TOPCOM, ILLUMINANCE METER) was used to adjust the illuminance to 1000 Lx.

  (5) The image on the panel was switched between black display and white display, and the measurement was performed with the black display brightness and the white display brightness at the center of the polarizing plate as black brightness and white brightness, respectively. The contrast ratio (white luminance / black luminance) was calculated based on the value.

  (6) Using the hard coat film produced in the same manner as in Example 1 except that no fine particles were blended as a reference value, the contrast ratio was measured by the methods (1) to (5), The value was normalized as 100 (actual value: 312). The characteristic values related to the surface roughness of the reference hard coat film were an Ra value of 0.003 μm and a θa value of 0.06 °.

(Anti-glare)
(1) A black acrylic plate (2.0 mmt) manufactured by Mitsubishi Rayon was bonded to the surface side of the antiglare hard coat film where the hard coat layer was not formed, thereby eliminating light reflection on the back surface.

  (2) The antiglare property of the film sample prepared above was visually confirmed in an office environment (about 1000 Lx) generally using a display. The criteria for visual inspection are ◎ when there is almost no image reflection, ○ when there is image reflection, but there is little impact on visibility, there is image reflection, but there are practical problems The case where there was no image was indicated by Δ, and the case where an image was reflected was indicated by ×.

(Darkness of black)
(1) An acrylic adhesive having a film thickness of about 20 μm was attached to the surface of the produced antiglare hard coat film on which the antiglare hard coat layer was not formed, and was attached to a polarizing plate having a smooth surface.

  (2) A polarizing plate with an antiglare hard coat film was mounted on a panel manufactured by Sharp Corporation (panel model number: LQ150X1LAJO).

  (3) In general, the panel was driven with black display in an office environment (about 1000 Lx) using a display, and the darkness of black was visually confirmed. The criteria for visual inspection are ◎ when the degree of black is very good, ◯ when the degree of black is good, △ when it is slightly whitish but no problem in practical use, white blurring occurs The case where it is doing was made into x.

  As described above, the antiglare hard coat film of the present invention is an antiglare hard coat film having an antiglare hard coat layer mainly composed of fine particles and a hard coat resin on at least one surface of a film substrate. In the actual use environment, an uneven shape is formed by fine particles having an average particle diameter of 6 μm to 15 μm, and the average inclination angle θa of the uneven shape is in the range of 0.4 ° to 1.5 °. The display contrast of the display at the place can be 60 or more. Furthermore, the hard coat film of the present invention can be suitably used for an optical film such as a polarizing plate by an adhesive material or an adhesive, and an LCD equipped with the polarizing plate is a sufficient protection even when used as a home television. Since it has glare and display contrast characteristics, it can be suitably used.

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 explanatory drawing for demonstrating the measuring method of the uneven | corrugated shaped average inclination | tilt angle (theta) a in the said glare-proof hard coat film surface. 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 2a Resin binder 2b Fine particle 4 Anti-glare hard coat film 5 Antireflection layer 6 Anti-glare antireflection hard coat film

Claims (6)

  1. An anti-glare hard coat film comprising fine particles on at least one surface of a transparent film substrate and having a hard coat layer with an uneven surface,
    The average particle size of the fine particles is 6 μm to 15 μm,
    And the average inclination angle θa of the concavo-convex shape formed by the fine particles is 0.4 ° or more and 1.5 ° or less,
    The average inclination angle θa is a value defined by the following mathematical formula (1),
    The hard coat layer is formed using a hard coat forming material containing the following component (A), component (B) and component (C):
    The amount of the fine particles is 2 to 70 parts by weight with respect to 100 parts by weight of the hard coat forming material,
    An anti-glare hard coat film having a display contrast characteristic of 60 or more.
    (A) component: urethane acrylate
    Component (B): at least one of polyol acrylate and polyol methacrylate
    Component (C): a polymer, copolymer, or a mixture of the polymer and copolymer formed from at least one of the following (C1) and (C2)
    (C1): alkyl acrylate having an alkyl group having at least one of a hydroxyl group and an acryloyl group
    (C2): alkyl methacrylate having an alkyl group having at least one of a hydroxyl group and an acryloyl group
    Average inclination angle θa = tan −1 Δa (1)
    (Δa: In the reference length L of the roughness curve defined in JIS B 0601 (1994 version), the sum of the difference (height h) between the apex of the adjacent mountain and the lowest point of the valley (The value divided by the reference length L.)
  2.   The film thickness of the said hard-coat layer is 15 micrometers-35 micrometers, The anti-glare hard coat film of Claim 1 characterized by the above-mentioned.
  3.   The antiglare hard coat film according to claim 1 or 2, wherein the fine particles have a substantially spherical shape.
  4. The refractive index of the fine particles is 1.40 to 1.70, and the refractive index of the resin binder in the hard coat layer is 1.5 to 1.6. Dazzling hard coat film.
  5. A polarizing plate comprising the antiglare hard coat film according to any one of claims 1 to 4 .
  6. Antiglare hard coat film according to any one of claims 1-4, or an image display apparatus comprising the polarizing plate according to claim 5.
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