TWI359834B - Hard-coated antiglare film, method of manufacturin - Google Patents

Description

1359834 IX. Description of the Invention The present invention relates to an antiglare hard coat film, a method for producing an antiglare hard coat film, an optical element, a polarizing plate, and an image display device. [Prior Art] With the advancement of technology in recent years, in addition to the previous CRT (Cathode Ray Tube), an image display device has been developed using a liquid crystal display (LCD ' Liquid Crystal Display) and a plasma display ( PDP 'Plasma Display Panel' and ElectiOluminescence Display). Among them, for 匕(3), with the technological innovations such as wide viewing angle, high definition, high-speed responsiveness, and color reproducibility, the application of LCD has gradually changed from a notebook PC or a monitor to a television. The basic structure of the LCD is as follows, that is, a glass substrate on a flat plate each having a transparent electrode is disposed oppositely via a spacer to form a gap therebetween, and a liquid crystal material is injected between the glass substrates and packaged. A liquid crystal cell is further provided, and further, a polarizing plate is provided on each of the outer surfaces of the pair of glass substrates. Previously, a cover plate made of glass or plastic was attached to the surface of the liquid crystal cell to prevent damage to the polarizing plate attached to the surface of the liquid crystal cell. However, the installation of the cover plate is disadvantageous in terms of cost and weight. Thus, the surface of the above polarizing plate has been gradually hard-coated. In the above hard coating treatment, generally, an anti-glare hard coating film ‘ is used to prevent reflection of a light source against the LCD. The anti-glare hard coat film is obtained by using a resin such as a thermosetting resin or an ultraviolet curable resin and fine particles on one side or both sides of a transparent plastic film 118150.doc 1359834. A thinner hard coating of about 10 μηι. The surface of the hard coating layer is concave-shaped due to the fine particles described above, whereby the anti-glare property can be exhibited. When the resin is coated on the glass to provide a hard coating, the pencil hardness is 4 Η or more, but when the bottom layer is a transparent plastic film substrate, the thickness of the hard coating layer is If it is insufficient, it is usually affected by the above-mentioned transparent plastic film substrate, and the hardness of the pen is reduced to less than 3 。. The application of φ LCD has been converted to a home TV, and it is easy to think that even if the TV uses an LCD ‘normal home TV user, it will perform the same operation as the previous TV using a glass CRT. Since the hardness of the lead of the glass crt is about 9 ,, the hardness of the anti-glare film used for the LCD is required to be increased. The hardness of the anti-glare hard coating film can be improved by increasing the layer thickness of the hard coating layer. Then, if the layer thickness is increased, the particles contained in the hard coat layer are completely embedded in the hard coat layer, and the anti-glare property (anti-glare property) of the charge 35 cannot be exhibited. In order to solve this problem, there is also a method of increasing the amount of addition of the above-mentioned fine particles. However, in this case, there is also a problem that the number of particles in the layer direction is increased, and as a result, the haze value is increased. The techniques disclosed in the following Patent Documents 1-4 to 4 have been proposed for the high hardness of the antiglare hard coat film and the accompanying problems of the antiglare property and the haze value. Further, Patent Document 1 discloses an anti-glare hard coating film in which particles having an average particle diameter of 〇·6 to 20 μη are formed on a transparent base film. A fine coating layer having a particle diameter of nm and a hard coating resin as a main component. Further, it is disclosed that the thickness of the coating layer of the hard 118150.doc 1359834 is not less than the particle diameter of the particles, and is preferably 80% or less (specifically, 16 μm or less) of the average particle diameter. Patent Document 2 discloses a hard coated film formed by forming at least one surface of a plastic substrate film to have a hard coating layer, and revealing that the thickness of the hard coating layer is Further, 3 to 30 μm is added, and further, inorganic fine particles having a secondary particle diameter of 2 μm or less are added to the hard coating layer. Further, it has been revealed that the surface of the hard coating layer has an uneven shape and imparts anti-glare properties. φ Patent Document 3 discloses that a hard coating film layer and an anti-reflection film layer are laminated on at least one surface of a plastic film, and the elastic modulus of the hard coating layer below the strain is 〇.7~5 An antireflection film of 5 GPa, wherein the antireflection film layer is mainly composed of a metal alkoxide and a hydrolyzate thereof. Further, the film thickness of the hard coat layer is 〇5 or more and pm or less, and the average particle diameter of the fine particles contained in the hard coat layer is 0.01 to 1 〇μιη. The anti-glare anti-reflection film is an anti-glare anti-reflective film which is laminated on a transparent support and has an anti-glare hard f coating layer and a low refractive index containing particles having an average particle diameter of 〜~】〇μιη. a layer having a low-refractive-index layer composed of 3 inorganic particles having a uniform particle size of 〇〇〇1 to 〇2 (4), a hydrolyzable organic photocell and/or a partial condensate thereof, and a combination of gas-containing polymers The material is formed and has a refractive index in the range of 135 to 49, and the anti-glare antireflection film has a haze value of 3 to 2% by weight, and an average reflectance of 45 Å to (10) of 1.8 / Å or less. Further, it is disclosed in the literature that the film thickness of the antiglare hard coating layer is 1 to 10 μm. However, these prior anti-glare hard coated films did not adequately address the two problems of hardness and anti-glare properties of 118150.doc 1359834. First, in the above-mentioned patent document, when the thickness of the hard coating layer is as described above, there is a problem that sufficient hardness cannot be exhibited. Further, in Patent Document 2, the above-described structure - when the surface roughness of the surface of the hard coating layer is not considered, when the structure is such that the inorganic fine particles are completely buried inside the hard coating layer There is a problem that sufficient anti-glare properties cannot be exerted. The antireflection film disclosed in Patent Document 3 has improved hardness and scratch resistance. However, there are problems in the following description. For example, an average particle diameter of about 1.8 μπι is added to a hard coating layer having a film thickness of about 20 Å. In the case of fine particles, the particles are completely buried inside the hard coating layer, and sufficient anti-glare properties cannot be exhibited. The anti-glare anti-reflection film disclosed in Patent Document 4 has a problem of improving scratch resistance and anti-glare property, but has a problem that sufficient hardness cannot be obtained. [Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. No. Hei. [Patent Document 4] Japanese Patent Laid-Open No. Hei 2645〇8 SUMMARY OF INVENTION [Problems to be Solved by the Invention] Therefore, the object of the present invention is to provide a hardness, a scratch resistance and an anti-glare property. An excellent anti-glare hard coating thin film, an optical element of the anti-glare hard coating film, a polarizing plate, an image display device, and a method for producing an anti-glare hard coating film. [Means for Solving the Problems] In order to achieve the above object, an anti-glare hard coat film of the present invention has a hard coat containing fine particles on at least one side of a 1 (8) 5 〇, d〇c 1359834 transparent plastic film substrate. The coating layer is characterized in that the thickness of the hard coating layer is in the range of 15 to 3 μm, and the weight average particle diameter of the fine particles is in the range of 30 to 75% of the thickness of the hard coating layer. The average inclination angle 0a of the surface uneven shape is in the range of 0.4 to 1.5 degrees, and the hard coating layer is formed using a resin for forming a hard coating layer containing the following components (A), (B), and (C). (A) Component: at least one of urethane acrylate and methacrylic acid methacrylate; (B) component: at least one of polyol acrylate and polyol methacrylic acid; (C) component: a polymer or copolymer formed by at least one of (C1) and (C2), or a mixed polymer of the above polymer and copolymer; (C1): at least one group having a hydroxyl group and an acryl group Alkyl propyl acetoate (C2): having an alkyl ester of methacrylic acid alkyl group containing at least one hydroxyl group and a propylene group of minced meat. The method for producing an anti-glare hard coat film of the present invention has a hard coat layer containing fine particles on at least one side of a transparent plastic film substrate, and is characterized in that it comprises the steps of: preparing a hard coat layer forming material, The hard coating layer forming material includes a resin for forming a hard coating layer, fine particles having a weight average particle diameter in a range of from 3 to 75% of the thickness of the hard coating layer, and a solvent; and the hard coating layer forming material. Applying on at least one side of the transparent plastic film substrate to form a coating film; and hardening the film coated with HB150.doc 1359834 to form a thickness of 15 to 30 μm, and the average inclination angle 0a of the surface uneven shape is The hard coating layer in the range of 0.4 to 1.5 degrees; and the resin for forming the hard coating layer described above comprises the following components (A), (B) and (C), and (A) component: acrylic At least one of a urethane and a methacrylate urethane; (B) a component: a polyol acrylate and a polyol methacrylate to a lesser one; (C) a composition: by the following (C1 ) and under (C2) at least one of the formed polymer or copolymer, or a mixed polymer of the above polymer and copolymer; (C1): an alkyl acrylate having a burnt group containing at least one group of a base group and an acrylic polymer group (C2): an alkyl methacrylate having a leuko group containing at least one of a hydroxyl group and an acryloyl group. The optical element of the present invention is disposed on at least one of the optical members, and has an anti-glare hard coating film, wherein the anti-glare hard coating film is the anti-glare hard coating film of the present invention. The polarizing plate of the present invention has a polarizer and an anti-glare hard coat film, and the anti-glare hard coat film is the anti-glare hard coat film of the present invention. The image display device of the present invention includes an anti-glare hard coating film, an optical element, or a polarizing plate, wherein the hard coating film is the hard coating film of the present invention, and the optical element is the above-described present invention. Optical element 'The above polarizing plate is the above-mentioned polarizing plate of the present invention. [Effects of the Invention] In the anti-glare hard coat film of the present invention, since the thickness of the hard coat layer is within the above-mentioned range to be determined, the hardness becomes sufficient; since the granular soap of the above-mentioned particles is the above-mentioned specific one The range and the average inclination angle h of the uneven shape on the surface of the hard coat layer are within the above-described specific range, so that the antiglare property is excellent and the scratch resistance is also excellent. Therefore, the image display device using the anti-glare hard-coated film of the present invention is excellent in image display characteristics because it is appropriately protected from the screen and has excellent operability and excellent anti-glare property. Further, in the anti-glare hard coat film of the present invention, since the hard coat layer is formed using a resin for forming a hard coat layer containing the above two components, the hardness is further improved to prevent breakage of the hard coat layer. And it can effectively prevent the occurrence of curl caused by hardening shrinkage of the hard coating layer. Further, such an anti-glare hard coat film of the present invention having high performance can be produced by the above-described production method of the present invention. However, the antiglare hard coat film of the present invention can also be produced by other production methods. [Embodiment] It is preferred that the component (B) contains at least one of pentaerythritol triacrylate and pentaerythritol tetraacrylate. The reason for this is that the hardness can be further improved, the flexibility can be maintained, and the generation of curl can be further effectively prevented. The antiglare hard coat film of the present invention may have a state in which an antireflection layer is formed on the hard coat layer. Preferably, the antireflection layer contains hollow spherical cerium oxide ultrafine particles. In the antiglare hard coat film of the present invention, it is preferred that JIS κ 7105 118150.doc 12 Ϊ359834 has an optical degree of 50 to 95. The above gloss means the 60 degree specular gloss of Jis & 7l〇5 (i98i edition). In the method for producing an antiglare hard coat film of the present invention, it is preferred that the cold cross section contains acetic acid. The reason for this is that in the obtained anti-glare hard coat film, the adhesion between the hard coat layer and the transparent plastic film base material can be improved, and peeling of the hard f coating layer can be prevented. Preferably,

The content ratio of the above-mentioned ethyl acetate to the entire solvent is (10)% by weight or more. Next, the present invention will be described in detail. However, the invention is not limited to the following description. The antiglare hard coat film of the present invention has a hard coat layer on one side or both sides of the transparent plastic film base material. The transparent plastic film substrate is not particularly limited. However, a light ray having a good light transmittance (preferably a light transmittance of 9% by weight or more) and excellent transparency (preferably fog) is preferable. A substrate having a degree of 1% or less. Examples of the material for forming the transparent plastic film substrate include polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, and cellulose resins such as cellulose diacetate and cellulose triacetate. Polymer, polycarbonate I-based polymer 'polyf-based acrylic acid methyl vinegar and other propylene (tetra) polymer. Moreover, as a material for forming the transparent plastic film substrate, for example, a styrene-based polymer such as polystyrene, acrylonitrile or a styrene copolymer, polyethylene, polypropylene, or a ring or A polyolefin copolymer such as a norbornene structure, a dilute hydrocarbon copolymer such as an ethylene-propylene copolymer, a gas-ethylene polymer, a guanamine polymer such as nylon or an aromatic polyamine. Further, as 118150.doc • 13· 1359834, for example, quinone imine

The material for forming the transparent plastic film substrate, for example, a polymer, a sulfone polymer, a polyether sulfone polymer, a polyphenylene sulfide polymer, a vinyl alcohol polymerized or a norbornene structure a film formed of an olefin or the like. Further, in the present invention, the transparent silicone film substrate # may be a photon itself. According to this configuration, the structure of the polarizing plate can be simplified without the need for a protective layer made of TAC (Triacetyl Cell, or triacetylcellulose), so that the number of manufacturing steps of the polarizing plate or the image display device can be reduced. ,Increase productivity. Moreover, with such a structure, the polarizing plate can be made thinner. Further, in the case where the above-mentioned plastic film substrate is a polarizer, the hard coat layer functions as a prior protective layer. Further, according to this configuration, the anti-glare hard coat film also functions as a cover attached to the surface of the liquid crystal cell. In the present invention, the thickness of the transparent plastic film substrate is not particularly limited. However, for example, in view of workability such as strength and workability, and lamellarity, it is preferable that 丨〇~5〇〇μηη The range is preferably a range of 2 〇 to 300 μηι, and most preferably a range of 30 to 200 μπι. The refractive index of the above transparent plastic film material is not particularly limited, and is, for example, in the range of 1 3 〇 to 18 〇, preferably in the range of 1.40 to 1.70. 118l50.doc 1359834 As described above, for example, the above-mentioned hard coating layer is formed using a resin for forming a hard coating layer containing the following components (A), (B) and (C), (A) Component: at least one of urethane acrylate and methacrylate acrylate; (B) component: at least one of polyol acrylate and polyol methacrylate; (C) component: by the following (C1) and a polymer or copolymer formed by at least one of the following (C2) or a mixed polymer of the above polymer and copolymer; (C1): having at least one group containing a hydroxyl group and an acrylonitrile group An alkyl acrylate of an alkane; (C2): a phenyl methacrylate having an alkyl group having at least one of a hydroxyl group and an acryl group. The above-mentioned (A) component, that is, the above-mentioned amino phthalic acid acrylate and methacrylic acid amide phthalate can be used as a constituent component containing acrylic acid, methacrylic acid, acrylate, decyl acrylate, and polyol 'diisocyanate. . For example, 'a monomer having at least one of acrylic acid, methacrylic acid, acrylate, and methacrylate, and a polyhydric alcohol, a hydroxy acrylate having one or more hydroxyl groups, and a hydroxy methacrylate having one or more hydroxyl groups. At least one of them is allowed to react with a diisocyanate, whereby at least one of urethane acrylate and methacrylate urethane can be produced. In the above-mentioned (A) component, the urethane amide and the methic acid amide hydrazine may be used singly or in combination of two or more kinds. Examples of the acrylic acid vinegar include, for example, alkyl acrylate such as methyl acrylate, ethyl acrylate 118150.doc 1359834 ester isopropyl acrylate or butyl acrylate; and acryloyl acrylate such as cyclohexyl acrylate. Examples of the mercaptoacrylate include alkyl methacrylate such as decyl methacrylate, ethyl thioglycolate, isopropyl methacrylate, and butyl methacrylate; A cyclopentyl methacrylate such as cyclohexyl acrylate. The above polyol is a compound having at least two hydroxyl groups, and examples thereof include ethylene glycol, 1,3-propanediol, and the like, 2' propylene glycol, diethylene glycol, dipropanol, and neopentyl glycol. 1,3·butanediol '丨^ butanediol, u-hexanediol, 1,9-nonanediol, ι,ΐ〇-nonanediol' 2,2,4_trimethyl d,3 pentylene Glycol, 3_mercapto-1,5-pentanol, neopentyl glycol hydroxypivalate, tricyclic brothel, 1,4-cyclohexanediol, spiroethylene glycol, three Cyclodecane dimethanol, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, dihydroxydecyl ethane, trimethylolpropane, glycerol, 3 • Methylpentane _ 1,3,5-triol, pentaerythritol, diisoamyltetraol 'triisotetrateol, glucose, and the like.

As the diisocyanate g, for example, various diisocyanates of aromatic, aliphatic or menic acid % can be used, and examples thereof include tetramethylene diisocyanate and diisocyanate diacetate. , isophorone diisocyanate, 2,4-toluene diisocyanate, 4,4-diphenyl diisocyanate, naphthalene diisocyanate 3,3-methyl 4,4-diphenyldiisoacetoic acid vinegar, xylene dinitrate vinegar, trimethylhexamethylene diacetate, 4,4-diphenylmethyl diisocyanate, etc., These hydrides and the like can be mentioned. There is no particular limitation on the ratio of the above (Α) ingredients. By using the above (eight) component', the softness of the formed hard coating layer and the transparent plasticity can be improved.

118150.doc -16 - 1359834 Adhesion of film substrates. From the viewpoint of the hardness of the hard coating layer, the ratio of the above-mentioned (Α) component to the entire resin component in the hard coating layer forming material is, for example, in the range of 15 to 55 wt%. Preferably, the range of 25 to 45% by weight "the above-mentioned resin component means the total amount of (Α) component, (Β) component, and (c) component, or when other moons are used to form a knife, The total amount of the components and the total amount of the above-mentioned resin components are the same as the following.

Examples of the above (Β) component include: anthraquinone diacrylate S曰, pentaerythritol triacrylate, pentaerythritol tetraacrylate, diisoamyltetraol hexaacrylate, hydrazine, 6-hexanediol acryl oxime ester, Isopentanol dimercapto acrylic acid, pentaerythritol tridecyl acrylate vinegar, pentaerythritol tetradecyl acrylate, bis-isopentaerythritol hexamethylene acrylate, hydrazine, 6-hexanediol methyl Acrylic vinegar, etc., these may be used alone or in combination of two or more types. For example, as the polyol acrylate, a monomer component containing a polymer of pentaerythritol triacrylate and pentaerythritol tetraacrylate, and a mixed component containing pentaerythritol triacrylate and pentaerythritol tetraacrylate are preferable. There is no particular limitation on the ratio of the above (Β). For example, it is preferred that the ratio of the above (Β) component to the above (Α) component is in the range of from 7 〇 to 18 〇 by weight, and more preferably in the range of from 1 Torr to 150% by weight. When the ratio of the component (8) to the above (Α) component is 18% by weight or less, the hard coating of the formed hard coating layer can be effectively prevented from being cured, and as a result, the anti-glare hard coating film can be prevented. Curl, thereby preventing a decrease in f curvature. Further, when the blending ratio of the component (B) is 7 〇 118150.doc 17 (s > 1359834% by weight or more of the component (A), the hardness of the hard coating layer to be formed can be further increased, thereby improving The surface group of (CM) and (6)) is not particularly limited, and is, for example, an alkyl group having 1 to 10 carbon atoms, and may be linear or branched. shape. The component (C) may, for example, be a polymer or a copolymer containing a repeating unit of the following formula (1) or a mixture of the above polymer and the above copolymer. [Chemical 1]

r Λ .ch2—c c 二ο I Ο—R2

J n (1) In the above formula (1), R 丨 is -H or -CH 3 , R 2 is -CH 2 CH 2 〇 X or a group represented by the following formula (2), and the above X-form is - or is of the following formula ( 3) The propylene brewing base indicated. [Chemical 2]

-CH2 — CH —CH——Ο—X Ο •I X...(2) 118150.doc -18·

!359834 In the above formula (2), the parent Η Η ', Η or the acrylonitrile group represented by the following formula (3) may be the same or different. [Chemical 3] —C — CH z:CH2 II 2 〇 _·_(3)

As the component (C), for example, a polymer, a copolymer, or a mixture of the above polymer and the copolymer formed of a monomer selected from the group below may be used. It is composed of 2 3 · dihydroxy acrylate, vinegar, 2,3-dipropylene methoxy propyl acrylate, 2 _ propyl propyl acrylate, 2-propenyl oxy hydroxy group Propyl acrylate, 2,3-dihydroxypropyl propyl acrylate, 2,3-dipropylene methoxy propyl acrylate, hydrazine hydroxy-3-propenyl propyl acrylate, 2 propylene methoxy group _3 _hydroxy fluorenyl

It is composed of propyl acrylate, ethyl 2-hydroxyacrylate, 2-propylene acryloxyacetate, 2-hydroxyethyl methacrylate and 2-propylene methoxy methacrylate. The proportion of the above component (c) is not particularly limited. For example, the ratio of the above component (c) to the above (Α) component is preferably in the range of 251 〇 by weight, more preferably 45 to 85 by weight. / Range of 〇. When the blending ratio of the component (c) is 110% by weight or less, the coating property of the hard coating layer forming material is excellent, and when the blending ratio of the component (c) is 25% by weight or more, the formed hard material can be prevented. The hardening shrinkage of the coating layer, the result 118150.doc 1359834 is 'curable to prevent the anti-glare hard coating film from being curled. The hard coating layer contains fine particles in order to impart an anti-glare property to the surface structure. Examples of the fine particles include inorganic fine particles and organic fine particles 11. The inorganic fine particles are not particularly limited, and examples thereof include: cerium oxide fine particles, titanium oxide fine particles, alumina fine particles, zinc oxide fine particles, tin oxide fine particles, and calcium carbonate fine particles. Sulfuric acid, cerium particles, talc particles, kaolin particles, calcium sulfate particles, and the like. Further, the organic fine particles are not particularly limited, and examples thereof include polymethyl methacrylate resin powder (PMMA fine particles), oxime resin powder, polystyrene resin powder, polycarbonate resin powder, and acrylic styrene resin. Powder, stupid melamine resin powder, melamine resin powder, polyolefin resin powder, polyester resin powder, polyamidamine resin powder, polyimine resin powder, polyvinyl fluoride resin powder, and the like. The inorganic fine particles and the organic fine particles may be used alone or in combination of two or more.

The weight average particle diameter of the fine particles is in the range of 3 Å to 75% of the film thickness of the hard coating layer, preferably in the range of 3 Å to 5 % by weight. When the weight average particle diameter of the fine particles is 30% or more, a sufficient uneven shape can be formed on the surface of the hard coating layer, and a sufficient antiglare function can be imparted. On the other hand, when the weight average particle diameter of the fine particles is 75% or less, the unevenness of the surface unevenness can be made appropriate, and the appearance can be improved, and the scattering of the reflected light can be appropriately performed. The weight average particle diameter of the above fine particles can be measured, for example, by the method described in the examples below. In the present invention, it is preferable that the shape of the fine particles is not particularly limited, and for example, it is substantially spherical, and may be an irregular shape such as a powder. n8J50.doc -20- In the case where the above-mentioned fine particles are average particles, the above-mentioned fine particles mean: several kinds of fine particles. The material has a weight-average particle diameter of -^^. θ ^ ) from 隹8 θ8 to two or more. As described above, the above-mentioned fine particles are preferably substantially spherical lower particles 'better, and substantially spherical particles having an aspect ratio of 1.5 or less. 1 ααι , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , set up. The ratio of the upper portion to the fine particle portion is, for example, 2 to 7 η 旦 / 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 ' ' ' ' ' ' ' ' ' ' ' ' ' It is a range of 15 to 4 G parts by weight. The average inclination angle of the uneven shape on the surface of the hard coating layer is *4 1.5 degrees. When the average tilt angle is equal to or higher than the above average tilt angle, the haze value is within an appropriate range. In the present invention, the above average tilt angle θα' is preferably Ο. The range of degrees is better than the range of degrees. In the present invention, the average tilt angle can be, for example, appropriately selected from the type of the hard coat layer forming resin, the thickness of the hard coat layer, the type of the fine particles, and the average particle diameter of the fine particles. The adjustment, as long as it is a person skilled in the art, does not cause an excessive test error, and the above-described average tilt angle h can be set within a specific range of the present invention. In the present invention, the average inclination angle ea is a value defined by the following formula (1). The above average tilt angle Qa is a value measured by, for example, the method described in the examples below. 118150.doc 21 i S > 1359834 Average inclination angle Gattan.^a (ι) In the above formula (1), as shown in the following formula (2), Aa is specified in JIS b 0601 (1994 edition) The reference length of the roughness curve [, the difference between the adjacent peak apex and the lowest point of the valley (the total value of the height (hl + h2 + h3 ... + hn) is divided by the above reference length [the obtained value. The roughness curve is a curve obtained by removing a surface undulation component longer than a specific wavelength from a profile curve by a phase difference compensation type high-band filter. The profile curve is obtained by cutting a target surface at a plane perpendicular to the target surface. The outline of the slit. Fig. 3 shows an example of the roughness curve and the height Μ reference line L. Δ a - (hl+h2+h3 - ^hn) / L (2) One of the roughness of the surface... ι must be called the ancestral degree Ka), for example, the range of 〇·〇5~0.3 μιη, preferably the range of 〇〇7~〇2 _, better Different street average roughness Ra (arithmetic average table

In the case of the above-mentioned arithmetic mean surface fineness, which is defined by JIS Β 0601 (1994 edition), for example, 敎.〇9 to 0.15 (4), the method of the embodiment described later is used. In the present invention, the material has a rough surface roughness R'. For example, the type of the hard coating layer forming resin, the thickness of the hard coating layer, the type of the fine particles, and the weight of the fine particles can be appropriately selected. The average particle diameter or the like can be adjusted as long as the person skilled in the art 'will not have an excessive test error, and the above arithmetic mean surface roughness Ra can be made to the above specific range. The shot prevents the light scattering and interference fringes (4) generated at the interface between the fine particles and the hard coating layer, and the traces are reduced to reduce the particles and the upper coating layer. The difference in refractive index. The interference fringe described above refers to a phenomenon in which the reflected light of the external light incident on the hard coated enamel film exhibits a hazy color tone. Most of the work: In the room, etc., the three-wavelength fluorescent lamp with excellent clarity is used, and the interference fringes are prominently displayed under the three-skin fluorescent lamp. Since the refractive index of the hard coating layer is generally in the range of 1 > 4 to 16, it is preferred that the refractive index of the fine particles is close to the refractive index range. Preferably, the difference in refractive index between the fine particles and the hard coating layer is less than 0.05.

When the difference between the refractive index of the above-mentioned transparent plastic (four) target material and the refractive index of the hard coating layer is set, it is preferable that the above (5) or less. If the above d is 0 · 04 or less, the target is determined to suppress the interference fringes. More preferably, the above 3 is 0.02 or less. The thickness of the hard coating layer is in the range of 15 to 3 〇μηη, preferably 18 Å μηη_β# The thickness is the above specified range, and the hard coating layer is hard and wide. The filling knife (for example, 4 Η or more in terms of pencil hardness) can also prevent curling more effectively.

For example, the anti-glare hard coat film of the present invention can be produced by preparing a hard coat layer forming material which is a hard coat layer containing the above three components. The forming resin, the fine particles, and the cooling agent 'coat the hard coating layer forming material to the transparent plastic film and the earth. On one of the sides, a coating film is formed to harden the coating film described above. The above-mentioned granules are not particularly limited, and various solvents can be used, and examples thereof include dibutyl ether, tianmu-methoxymethane, dimethoxyethane, diethoxy ethoxylate, propylene oxide, and 14_. Bis & oxalate hexane, 1,3-dioxolane, 118I50.doc -23- 1359834 1,3,5-dioxane, tetrahydrofuran, acetone, butanone 'diethyl ketone 'Dipropyl _, diisobutyl ketone, cyclopentanone 'cyclohexanone 'methyl cyclohexanone, ethyl formate, propyl formate, n-amyl formate, methyl acetate, ethyl acetate, propionate Ester, ethyl propionate, n-amyl acetate, acetamidine, dipropanol, methyl acetate, ethyl acetate, methanol, ethanol, hydrazine, propanol

Propyl alcohol, butanol, 2-butanol, dipentyl alcohol, 2-methyl-2-butanol, cyclohexanol, isobutyl acetate, methyl isobutyl ketone (ΜΙΒΚ), 2-octyl Ketone, 2-戍-, 2-hexanone, 2-heptanone' 3-heptanone, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoterpene ether , propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and the like. These may be used alone or in combination of two or more. Further, from the viewpoint of improving the adhesion between the transparent plastic film substrate and the hard coating layer, it is preferred that the solvent contains ethyl acetate in a ratio of 20% by weight or more based on the whole, more preferably The proportion of 25% by weight or more of the whole contains ethyl acetate, and most preferably, it contains ethyl acetate in a ratio of 30 to 70% by weight. If it is 7 〇 weight.

It can effectively prevent the type of solvent to be applied without ketone or ethylene glycol monobutyl or less. The solvent can be volatilized at a moderate rate, resulting in unevenness in distribution or uneven drying. The ethyl acetate is particularly limited, and examples thereof include butyl acetate, butyl ether, and propylene glycol monomethyl ether. In the above-mentioned hard coating layer forming material, various leveling agents may be added at T, t τ . Examples of the above-mentioned homogenizing agent include a sputum Α β "fluorine-based or poly fluorene-based homogenizing agent, and a preferred cerium-polyoxygen-based homogenizing agent. The chemical agent may, for example, be a reactive polyfluorene oxide, a polydimethylsiloxane, a polyether-modified polydimethyloxane or a polymethylalkyloxirane. The homogenizing agent 118150.doc • 24 1359834 2 is preferably the above reactive oxygen. By adding the above reactive rock oxygen, the surface material can be smoothed and the scratch resistance is continued for a long time. When the reactive polyphosphorus has a warp group, the antireflection layer and the hard coating layer are formed when an antireflection layer (low::::r shape) is formed on the refractive coating layer. The amount of the above-mentioned leveling agent in the layer is, for example, in the range of 5 parts by weight of the above-mentioned resin in the range of 5 parts by weight. It is preferably 5 or less and less than the following. , in the above-mentioned properties of the material 'in the absence of damage agents, UV one agent, these additives can be used alone and resistant: A chemical agent, a thixotropic agent, etc.. The dry sputum can be used in combination with the above-mentioned hard coating layer forming material. The polymerization initiator can be used as a light of the above-mentioned photopolymerization. Usa water. The initiator may, for example, be: -methoxy-2-phenylacetophenone, phenethyl -2-epoxyacetophenone, 4 benzobenzazole, 4 ah, ketone , 3-american, 1-methoxybenzophenone, loyal white ether, kaki dimethyl ketal, hydrazine, Ν'Ν·, Ν, -tetrafyl _4 4, / benzophenone Ketone, isopropylphenyl group: the amine group is the same as the method of the above-mentioned hard coating layer forming material coating material, for example, f-gel 4 membrane base can be used. Dough cloth printing method, drag coating method, spray coating method, μ c barrier coating method, bar coating method, etc. gravure coating method, light coating 118150.doc -25- (s > 1359834 Coating the hard coating layer forming material to form a coating film on the transparent plastic film substrate, and then curing the coating film. Preferably, the coating film is dried before the upper surface is cured. Drying case For example, it can be either a natural dry '35' or it can be air-dried by blowing air. Or it can be heated and dried, or: two methods are combined. 1 The hard coating method of the hard coating layer forming material is hardened. There is no particular limitation, however, ionizing radiation hardening is preferred. Various active energies can be used in the method, however, ultraviolet rays are preferred. As the energy radiation source, for example, a high pressure mercury lamp or a tooth lamp is preferred. , gas lamp, metal tooth lamp ^ laser, electron beam accelerated placement, radioactive elements and other light source. The amount of energy light source, preferably, the ultraviolet wavelength is the cumulative exposure of the coffee 'It is 50 to 5000 mW. If the irradiation amount is 5 〇mJ/cm2 or more, the hardening becomes more sufficient, and the hardness of the formed hard coating layer becomes more sufficient. Further, when it is 5 〇〇〇 mJ/cm2 or less, the formed hard coating layer can be prevented from being colored, and transparency can be improved. • As described above, the hard coating layer is formed on at least one of the transparent plastic film substrates, whereby the anti-glare hard coating film of the present invention can be produced. Further, the anti-glare hard coat film of the present invention can also be produced by a method other than the above-described method. The hardness of the glare@gastric coated film of the present invention is based on the pencil hardness, for example, a hardness of 4. One of the antiglare hard coat films of the present invention is exemplified in the cross-sectional pattern of the drawing. As shown in the figure, the anti-glare hard coating film 4 of this example is formed on one side of the transparent plastic film substrate i. The hard coating containing the particles 3 is 118150.doc • 26· 1359834 layer 2 . Further, the present invention is not limited to the configuration of Fig. 1, and may be an anti-glare hard coating film in which the hard coating layer 2 is formed on both surfaces of the transparent plastic film substrate 1. Further, the hard coating layer 2 of this example is a single layer. However, the present invention is not limited thereto. The hard coating layer 2 may have a plurality of layers of two or more layers. In the anti-glare hard coating film of the present invention, an anti-reflection layer (low-refractive-index layer) may be disposed on the hard coating layer. The anti-glare hard coating film of the present invention having an anti-reflection layer may be used. An example is shown in the cross-sectional pattern of Figure 2. As shown in the figure, the anti-glare hard coating film 6 of this example has a structure in which a hard coating layer 2' containing fine particles 3 is formed on one surface of the transparent plastic film substrate 1 on the hard coating layer 2. The anti-reflection layer is formed. When the light reaches the object, the reflection at the interface and the absorption and scattering phenomenon inside the surface are generated, and the light is transmitted to the back surface of the object. For example, in the case where an anti-glare hard coat film is attached to an image display device, one of the causes of the decrease in visibility of the image is reflection of light between the interface of the air and the hard coat layer. The anti-reflective layer reduces this surface reflection. Further, in the anti-glare hard coat film 6 shown in FIG. 2, the hard coat layer 2 and the anti-reflection layer 5 are formed on one side of the transparent plastic film substrate 1, but the present invention is not limited thereto. The hard coating layer 2 and the anti-reflection layer 5 can be formed on both surfaces of the transparent plastic film substrate 1. Further, in the anti-glare hard coat film 6 shown in Fig. 2, the hard coat layer 2 and the anti-reflection layer 5 are each a single layer, but the present invention is not limited thereto, and the hard coat layer 2 and the anti-reflection layer are not limited thereto. 5 can also be a multi-layer structure with two or more layers. In the present invention, the antireflection layer is a layer of 118150.doc -27-1359834 optical film having a thickness and a refractive index or a layer of the above optical film laminated with two or more layers. The anti-reflection layer exhibits an anti-reflection function by canceling the phases of the reversal of the incident light and the reflected light by utilizing the coherence effect of the light. The wavelength region of the visible light showing the anti-reflection function is, for example, 380 to 780 nm, and in particular, the wavelength region having a higher visuality is in the range of 45 〇 to 65 〇 nm, and preferably, the anti-reflection layer is designed so that Its central wavelength, 550 nm, has the lowest reflectivity. When the antireflection layer is designed in accordance with the coherence effect of light, as a method for improving the coherence effect, for example, there is a method of increasing the refractive index difference between the antireflection layer and the hard coating layer. In general, in a multilayer anti-reflection layer having a structure in which two to five optical thin layers (thickness controlling a film of thickness and refractive index) are laminated, a component having a different refractive index is formed into a plurality of layers with a specific thickness, thereby improving The degree of freedom in the optical design of the anti-reflection layer can further enhance the anti-reflection effect, and can also make the spectral reflection characteristic uniform (flat) in the visible light region. In the above optical film, since high thickness precision is required, in general, the formation of each layer is carried out by dry vapor deposition, sputtering, CVD (Chemical Vapor Deposition) or the like. As the multilayer antireflection layer, it is preferred to laminate a two-layer structure of a ruthenium oxide layer having a low refractive index (refractive index: about 1.45) on a titanium oxide layer having a high refractive index (refractive index of about 1.8). More preferably, a ruthenium oxide layer is laminated on the titanium oxide layer, a titanium oxide layer is laminated on the ruthenium oxide layer, and a four-layer structure in which a ruthenium oxide layer is laminated on the oxidized layer. By forming the two anti-reflection layers or the four anti-reflection layers, the reflection of the wavelength region of the visible light (for example, in the range of 380 to 780 nm) can be uniformly reduced. 118150.doc •28- 1359834 and 'form an early optical film (anti-reflective layer) on the hard coating layer, by Μ ^ m ^ δ, for example, forming a single anti-reflective layer The method is from the cloth, the coating material, the main coating, the extrusion coating, the rotary coating, the gravure printing, the single-layer anti-reflective layer forming material, and the like. For example, a resin material such as an ultraviolet curable acrylic resin is used, and a mixed material such as colloidal cerium oxide such as colloidal cerium oxide is dispersed in the red eucalyptus, and a tetraethoxy group is used. A sol-gel material such as decane or a tetraethoxy group metal oxide. Further, in the above-mentioned forming material, 'the surface is imparted with a ruthenium, and it is preferable to contain Dunke. In the case of the material of the above-mentioned material, it is preferable that the inorganic material has a large amount of a forming material, and more preferably the above sol-gel material. The above sol-gel-type material can be partially condensed and used. For the anti-reflection layer (low-refractive-index layer), it is formed of the following materials (materials disclosed in Japanese Patent Laid-Open Publication No. 4-16), because it can have both resistance, damage, and low reflection. Therefore, it is preferable that the material has a weight average molecular weight of 5 〇〇〇 or more in the range of 500 to 10% in terms of an ethylene glycol equivalent number, and a polystyrene oxide. A material having a fluorine compound having an oxonium structure and a polyoxyalkylene structure. The antireflection layer (low refractive index layer) is not particularly limited as long as it is used to increase the film strength, and may also contain an inorganic/gelatinized ruthenium. For example, it may be oxidized in the form of a monohydrate. Lu, fluorinated town and other inorganic sol, its towel, it is better to dissolve the dioxide. The blending ratio of the above-mentioned inorganic solvent is, for example, in the range of 10 to 80 parts by weight based on the total solid content of the above-mentioned antireflection layer forming material with a weight loss of 100 Å. The particles of the inorganic fine particles in the above inorganic sulfonium I i8150.doc -29- 1359834 preferably have a diameter of from 2 to 50 nm, more preferably from 5 to 3 Å. Among the materials for forming the antireflection layer, it is preferred to contain hollow spherical oxidized ultrafine particles. The average particle diameter of the above-mentioned oxidized stone ultrafine particles is preferably about 00 nm', more preferably in the range of 1 〇 to 2 〇〇 nm. The above-mentioned oxidized oxide ultrafine particles are formed in a hollow spherical shape in which a cavity is formed in a pore-containing outer casing, and at least one of a solvent and a :: in the preparation of the above-described oxidized fine particles are contained in the hollow. Preferably, X ' is a precursor material for forming the above-mentioned voids of the above-mentioned cerium oxide supercapped in the above-mentioned cavity. Preferably, the thickness of the outer shell is in the range of about L nm and is about 1/5 of the average particle diameter of the oxygen-cut ultrafine particles. Preferably, the outer casing is formed by a plurality of layers of cladding. Further, in the above-mentioned oxidized fine particles, it is preferred that the pores are clogged and the void is sealed by the outer casing. The reason for this is that the above-mentioned antireflection layer t maintains the porosity or void of the above-mentioned oxidized fine particles, thereby further reducing the refractive index of the antireflection layer. As a method for producing such hollow spherical oxygen-cut ultrafine particles, for example, a method for producing cerium oxide-based fine particles disclosed in Japanese Laid-Open Patent Publication No. Hei. No. 2-233611 can be preferably used. The drying and hardening temperature at the time of forming the antireflection layer (low refractive index layer) is not particularly limited to, for example, 6 G to 15 (the range of rc, preferably the range of 7 () to 13 generations; the above drying and hardening The time, for example, is in the range of 3 minutes, in consideration of the productivity, it is preferably in the range of 丨~(7) minutes and after the above drying and hardening, further heat treatment is performed, whereby anti-reflection can be obtained. An anti-glare hard coating film having a high hardness and a high hardness. The temperature of the heat treatment is not particularly limited, and is, for example, 4 〇 to 13 〇. 〇 范 -30-118150.doc 1359834, preferably 50~ The range of the 10CTC; the heat treatment time is not particularly limited. For example, it is a minute to 100 hours, and the scratch resistance is improved. The better heat is performed for 1 hour or more. The above heat treatment can be utilized. It is carried out by a method such as a hot plate, an oven, a belt furnace, etc. When the hard coat film having the antireflection layer is attached to the U shape of the image display device, the antireflection layer has a higher frequency of the outermost layer, so that it is easy Subject to the Z environment Dyeing. The anti-reflective layer is more likely to show contamination than a transparent plate or the like. For example, surface reflectance may change due to adhesion of fingerprints, hand sludge, sweat or hairdressing materials, or obvious deposits may be observed. The ground is convex and the display content is unclear. In order to prevent the adhesion of the contaminants and improve the ease of removing the attached contaminants, it is preferred to laminate the anti-reflective layer with a fluorine-containing compound or The anti-pollution layer formed by the gas-containing organic compound or the like. The anti-glare hard coating of the present invention preferably has a surface of at least one of the transparent plastic film substrate and the hard coating layer. The surface of the transparent plastic film substrate is subjected to surface treatment to improve the adhesion to the hard coating layer or the polarizer or the polarizing plate. Further, if the surface of the hard coating layer is surfaced For the treatment, the adhesion to the antireflection layer or the polarizer or the polarizing plate is further mentioned. Table 2 is for example: low plasma treatment, ultraviolet radiation treatment, electricity treatment Treatment, flame treatment, acid or inspection treatment = when the vitamin film is used as the transparent plastic film substrate, as a surface treatment, it is preferably a treatment. The inspection treatment, for example, can be performed by a lower speed method. After the application, the surface of the triacetate fiber and the test solution is contacted with the test solution 118150.doc -3] 1359834, and then washed with water and then added (4). For the acidic solution, for example, a gas oxidizing solution or a sodium hydroxide solution can be used. : Use ^ by (4 ears ▲ degrees)' is preferably 0·1~3.0 N (moI/L) range 'better is 0.5~2.0N (m〇"L) range. In the anti-glare hard coating film in which the above-mentioned layer is formed on the surface of the transparent plastic (four) film substrate, in order to prevent curling, the solvent treatment may be performed on the other two (4) treatments by using the transparent plastic substrate. The solvent to be dissolved or the solvent which can be swollen is brought into contact. By the solvent treatment described above, the other side is also imparted with a force to be curled, whereby the curling force generated by the formation of the hard coating layer can be offset to prevent curling. Similarly, in the anti-glare hard coating film in which the hard coating layer is formed on the surface of the transparent plastic film substrate, in order to prevent the occurrence of the contact, the dielectric layer may be formed on the other surface. Floor. The transparent resin layer 'is, for example, a layer which is mainly composed of a thermoplastic resin, a radiation-cured f-tree, a thermosetting resin, and another reactive resin, and particularly preferably a thermoplastic resin. The layer of the main component. The anti-glare hard coating film of the present invention can be bonded to an optical member used for an LCD or an ELD via an adhesive or a bonding adhesive. Further, in the case of the bonding, the surface of the transparent plastic film substrate may be subjected to various surface treatments as described above. As the optical member, for example, a polarizer or a polarizing plate can be cited. Generally, the 5' polarizing plate has a transparent protective film on one side or both sides of the polarizer. When a transparent protective film is provided on both sides of the polarizer, the surface 118150.doc •32· 1359834 The transparent protective film of the Yan Yan surface can be the same material or different materials. The light board is disposed on both sides of the liquid crystal unit. Further, the polarizing plates are arranged such that the absorption axes of the two polarizing plates are substantially orthogonal to each other. Further, as an example of the polarizing plate, an optical member in which the antiglare hard coat film of the present invention is laminated will be described. The polarizing plate having the function of the present invention can be obtained by laminating the anti-glare hard coat film of the present month with a polarizer or a polarizing plate by using an adhesive or a bonding agent.

The above-mentioned polarizer is not particularly limited, and the seed species can be polarized. Examples of the polarizer include a hydrophilic polymer film such as a polyvinyl alcohol film, a partially methylated polyvinyl alcohol film, or an ethylene/ethylene acetate copolymerized partial saponified film, which adsorbs iodine or two colors. A dichroic material such as a dye is obtained by one-axis stretching, and a dehydrated material of polyethylene glycol or a polydisperse alignment film such as polyvinyl chloride or a dehydrochlorinated product. In the sputum, the polarized dichroic ratio of the polarizer including the polyvinyl alcohol: film and moth is higher. The thickness of the above-mentioned polarizer is not particularly limited, however, it is, for example, about 5 to 80 μηι. A polarizer obtained by performing a color-matching process on a polyvinyl alcohol-based film and stretching it by one axis can be produced by, for example, sandwiching A to form a polyvinyl alcohol film/re This is color-killed in an aqueous solution of iodine, and is extended to 3 to 7 times the original length. The above aqueous iodine solution _ is also zinc or the like as needed. In addition, there may be an aqueous solution of fox's sulphate or sulphuric acid such as sulphuric acid, sulphur (tetra) or zinc sulphate, which is impregnated with polyvinyl alcohol, and the film may be, if necessary, The polyethylene film is impregnated with an enol film and washed with water, thereby washing the surface of the polyethylene film on the surface of the polyethylene film. 118150.doc -33- Preventing the agglomerating agent' In addition to this, the vinylidene alcohol film is swollen, and thus the uneven dyeing can be effectively prevented - and the h A and _ are not uniform. The extension can be carried out after iodine dyeing, or it can be dyed while carrying the reverse armor and can be dyed with iodine after extension. The hydrazine such as boric acid or potassium iodide may be extended by <not/liquid combined or in a water bath. The transparent protective film provided on one or both sides of the above-mentioned polarizer is preferably excellent in transparency, mechanical strength, thermal stability, moisture shielding property, stability of phase difference, and the like. The material for forming the transparent protective film may, for example, be the same material as the transparent plastic film substrate. Further, as the transparent protective film, a polymer film disclosed in Japanese Laid-Open Patent Publication No. 343529 (W_37GG7) is mentioned. The polymer film 'for example' disclosed in the above publication may, for example, be a molecular film formed of a resin composition containing at least a substituted quinone imine group and an unsubstituted quinone group in a side chain. One type of thermoplastic resin, and (B) a thermoplastic resin having at least one of a substituted phenyl group and an unsubstituted phenyl group in the side chain, and a nitrile group. The polymer film formed of the above resin composition may, for example, be a polymer film formed of a resin composition containing the following cross-copolymer and an acrylonitrile-styrene copolymer, and the cross-copolymer contains isobutylene. Dilute with N-methyl maleimide. The above polymer film can be produced by extrusion molding the above resin composition into a film shape. Since the south molecular film has a small phase difference and a small photoelastic coefficient, when used in a protective film such as a polarizing plate, the unevenness caused by strain can be eliminated, and The wettability is small, so the humidifying durability is excellent. 118150.doc 34- 1359834 The transparent protective film is preferably a film made of a cellulose resin such as cellulose diacetate or a film made of a norbornene resin, from the viewpoints of polarization characteristics and durability. As a commercial item of the above-mentioned transparent protective film, for example, the product name, 'Fujitack" (made by Fujifilm Co., Ltd.), the trade name "Ze〇n〇r" (made by Nippon Paint Co., Ltd.), and the trade name "Art〇 n" (manufactured by JSR Corporation). The thickness of the transparent protective film is not particularly limited, and is, for example, in the range of 丨 5 5 pm, from the viewpoints of work such as strength and workability, and thin layer properties. Within the above range, the polarizer can be mechanically protected, and the polarizer does not shrink even when exposed to high temperature and high humidity, thereby maintaining stable optical characteristics. The thickness of the transparent protective film is preferably 5 to 2 〇. The range of 〇pm is more preferably in the range of 10 to 150 μm. The structure of the polarizing plate in which the antiglare hard coating film is laminated is not particularly limited, and for example, it may be the following on the antiglare hard coating film. The structure in which a transparent protective film, a polarizer, and a transparent protective film are laminated in this order may be used, or a structure in which a polarizer 'transparent protective film is laminated on the anti-glare hard coat film in the following order. Various optical members such as a hard coating film and a polarizing plate using the same can be preferably used in various image display devices such as liquid crystal display devices. The liquid crystal display device of the present invention uses the anti-glare hard coating film of the present invention. In addition, the structure is the same as that of the conventional liquid crystal display device. For example, an optical component such as a liquid crystal cell or a polarizing plate can be appropriately assembled, and various components such as an illumination system (such as a backlight) can be appropriately assembled as needed, and a drive circuit or the like can be incorporated. Further, the liquid crystal cell is not particularly limited. For example, various types such as a ΤΝ type, an STN type, and a 71 type can be used. H8l50.doc -35· 1359834 In the present invention, the structure of the liquid crystal display device is not particularly limited. The liquid crystal display device in which the optical member is disposed on one side or both sides of the liquid crystal cell, or a liquid crystal display device in which a backlight or a reflector is used in an illumination system, etc., in the liquid crystal display device, the optical component of the present invention can be used. Arranged on one side or both sides of the liquid crystal cell. When optical components are disposed on both sides of the liquid crystal cell, the optical Further, for example, in the liquid crystal display device, a diffusion plate, an antiglare layer, an antireflection layer, a protective plate, a tantalum array, a lens array plate, a light diffusing plate, a backlight, etc. may be disposed. Various optical components and optical components. [Embodiment] Next, an embodiment of the present invention will be described with reference to comparative examples. However, the present invention is not limited to the following examples and comparative examples. The various characteristics in the comparative examples were evaluated or measured by the following methods. (Thickness of Hard Coating Layer) The anti-glare hard coating was measured using a micr〇gauge type thickness meter manufactured by Mitutoyo Co., Ltd. The thickness of the coated film is calculated by subtracting the thickness of the transparent plastic film substrate from the overall thickness, thereby calculating the thickness of the hard coating layer. Further, in the surface, the thickness of the hard coat layer is expressed as "film thickness". (Thickness of Antireflection Layer) The thickness of the antireflection layer was calculated from the waveform of the coherent spectrum using an instantaneous multi-side optical system MCPD2000 (trade name) manufactured by Otsuka Electronics Co., Ltd. 118150.doc -36- Shangli 9834 (haze) Based on the haze (turbidity) of JIS Κ7136 (1981 edition), the haze was measured using the product name haze meter HR300 (manufactured by Murakami Color Technology Research Co., Ltd.). value. (Glossiness) The glossiness was measured by using a commercial name digital variable angle gloss system UGV-5DP (manufactured by SUGA Test Machine Co., Ltd.) based on JIS K7105 (1981 edition). (Pencil hardness) A pencil hardness test (in which the load is 5 依照) according to JIS κ 〇〇 54〇〇 after placing the anti-glare hard coat film on the glass plate with the surface on which the hard coating layer is not formed. 〇g) 'The pencil hardness was measured on the surface of the above hard coating layer. (Scratch resistance) According to the following test content, "Evaluation of scratch resistance of an anti-glare hard coat film" (1) The sample was cut into a size of at least 25 mm in width and 1 mm or more in length. And placed on a glass plate. (2) Mount the steel wool #〇〇〇〇 evenly on the flat moon surface of a cylinder with a diameter of 25' with a load of 1.5 kg on the surface of the sample at a distance of about 100 mm per second, and after 3 round trips. The judgment was made by visual evaluation based on the following indicators. 〇: No damage at all. △. There are minor damages, but it does not affect the visibility. X · . There is obvious damage, affecting visibility. 118150.doc -37- 1359834 (Arithmetic average surface roughness Ra and average inclination angle ea) The glass of MATSUNAMI is bonded to the surface of the anti-glare hard coating film on which the hard coating layer is not formed by an adhesive. Plate (thickness: K3 mm) 'The above-mentioned arithmetic mean surface was determined by measuring the surface shape of the hard coating layer using a high-precision fine shape measuring device (trade name: Surfcoder. ET4, manufactured by Kosaka Research Co., Ltd.) Roughness Ra value and the above average • Tilt angle 0a value. Further, the high-precision fine shape measuring device automatically calculates φ the arithmetic mean surface roughness Ra and the average tilt angle 0a. (Reflectance) An adhesive layer having a thickness of about 20 μm was formed on the surface of the anti-glare hard coating film on which the hard coating layer was not formed, and a black acrylic plate (thickness of 2.0 mm, Mitsubishi Rayon (Ray) was attached. 〇n) Manufactured by the company) to eliminate the reflection of the back side of the above-mentioned anti-glare hard coating film. The reflectance of the surface of the hard coat layer was determined for the antiglare hard coat film. Manufactured by Shimadzu Corporation = Trade name UV24〇OPC (with an integrating sphere with a tilt of 8.) Spectrophotometer • Set the spectroscopic reflectance (specular reflectance + diffuse reflectance) and calculate the C light source /2. The reflectance is obtained by the total reflectance (γ value) of the field of view. (Reflective Index of Hard Coating Layer) The refractive index of the hard coating layer is a multi-wavelength Abbe refractometer (made by Atag Co., Ltd. - J Exhibition & quotient (10) name · DR~M2/1550) Measure 0 (refractive index of the particles) cover = ΓΓ on the fragment, drop the refractive index standard solution onto the particles, and cover the slide to make a sample. Observing the sample with a microscope, the refractive index of the refractive index standard solution of the particle profile was observed as the refractive index of the particle at the interface between the particle and the refractive index standard solution. (Adhesiveness) The adhesion of the hard coating layer to the transparent plastic film substrate was evaluated by a cross-hatch test revealed by JIS K 5400. Specifically, the peeling test was performed 100 times, and the number of times the hard coating layer was peeled off from the film substrate was counted, and the number of peeling times was expressed by 100. (weight average particle diameter of the fine particles) by the call counting method using a particle size distribution analyzer (trade name: Coulter Multisizer, manufactured by Beckman Coulter Co., Ltd.) using a pore resistance method The number average particle diameter and the volume of the fine particles corresponding to the volume of the fine particles at the time of the pores were measured to measure the weight average particle diameter of the fine particles. (Example 1) A resin material (manufactured by Otsuka Ink Co., Ltd., trade name: GraNDIC PCI 071) was prepared, and the resin material was contained in a mixed solvent of ethyl acetate and butyl acetate in a solid content of 66% by weight. A resin component containing the component (A), the component (B), the component (C), and a photopolymerization initiator is shown. 3 parts by weight of pmM A particles (weight average particle diameter of 10 μηι, refractive index of 1.49) and 0.5 part by weight of a leveling agent were added to 1 part by weight of the resin raw material, and further, ethyl acetate was used. Diluted to prepare butyl acetate: ethyl acetate (weight ratio) = 55:45 (45% by weight of ethyl acetate to total solvent), and a solid content concentration of 55% by weight to prepare a hard coating layer material. Further, the above homogenizing agent is dimethyloxane: hydroxypropyl decane: H8150.doc -39· 1359834 6-isocyanate hexyl isocyanuric acid: aliphatic polyester = 6·3 : h〇 : 2·2 : a copolymer of 1.0 molar ratio copolymerized. Component (A): Acrylic urethane containing isopentyl alcohol acrylate and hydrogenated xylene diisocyanate (100 parts by weight)

(Component B): 49 parts by weight of diisoamyltetraol hexaacrylate (hereinafter referred to as "B1 component (monomer)), and 41 parts by weight of pentaerythritol tetraacrylate (hereinafter referred to as B4 component (monomer)) And 24 parts by weight of pentaerythritol triacrylate (hereinafter referred to as B5 component (monomer)) (C) component: a polymer, a copolymer or the above polymer containing a repeating unit represented by the above formula (1) and the above Mixture of copolymer (59 parts by weight) Photopolymerization initiator: 3 parts by weight of commercial product sIrgacurel 84 (manufactured by Ciba Specialty Chemicals Co., Ltd.) Mixed solvent: butyl acetate: ethyl acetate (weight ratio) = 89 : 11 The above-mentioned hard coating layer forming material was applied onto a transparent plastic film substrate (triacetate film (refractive index: 1.48) having a thickness of 8 μm) by heating at 10 ° C using a coating bar. The coating film was dried by i minutes. Thereafter, 1 Meng halogen lamp is irradiated with an ultraviolet light of 3 jaws " coffee 2, and is hardened to form a hard coating layer having a thickness of 2 〇 μηη, and the anti-glare property of the example is prepared. Hard coated film. (Example 2), the addition of ruthenium particles was carried out in the same manner as in Example 1 except that the film was coated with a film. The amount is changed to 15 parts by weight to make an anti-glare hard 118150.doc 1359834 (Example 3) In this example, 3 parts by weight of PMMA particles (refractive index of U9) having a weight average particle diameter of Η(4) are added, and further Change the solids concentration to • 35. /. In addition to the above, an anti-glare 'hard coating film was produced by the same method as the above. (Example 4) In the present example, 30 parts by weight of φ ΡΜΜΑ particles having a weight average particle diameter of 8 pm (refractive index of 1.49) were added, and the film thickness of the hard coating layer was changed to 16 μηι, An anti-glare hard coat film was produced in the same manner as in Example} (Example 5) In the present example, the film thickness of the hard coat layer was changed to 16 and the examples were In the same manner, an anti-glare hard coated film is produced. (Example 6) An antiglare hard coat film was produced in the same manner as in Example i except that the film thickness of the hard coat layer was changed to 29 μm. (Example 7) In the present example, % by weight plus 30 parts by weight of PMMA particles having a weight average of Η _ (refractive index of M9), and the film thickness of the hard coating layer was changed to 23 A, In the same manner as in Example i, a (d) glare hard coating film was produced. (Example 8) -41 - I18150.doc In the present Example _, an anti-reflection layer was provided on the hard temporary coating layer, and otherwise, in the same manner as in Example 1, an anti-glare hardness was produced. Apply a film. • The formation of the anti-reflection layer is performed in the following manner. First, prepare an alkylene oxide oligomer having an average molecular weight of snn 1Λ • 00 to 1000 乙二醇 in an ethylene glycol (C〇) C〇at N103 (Colcoat Co., Ltd. 4, limited to △, manufactured by solid-state 2% by weight)), as an antireflection layer; 祖Q, 科' and its number average molecular weight was determined. The result is an average of 950 knives in a few. In addition, the product name of Opstar • JTA1〇5 (manufactured by JSR Co., Ltd., solid content is 5% by weight), and the number average molecular weight in terms of polystyrene is 5〇〇〇 or more, and it has a gas-fired structure and a poly The fluorine compound of the structure of the oxy-compound is measured, and the number average molecular weight of the fluorine compound is determined by the number average molecular weight in terms of polystyrene. Further, the product name JTA105A (manufactured by JSR Co., Ltd., solid content: 5 wt%) was used as a curing agent. Next, an antireflection layer forming material was prepared by mixing 100 parts by weight of 〇pstar JTA1〇5, i parts by weight of JTA105A, 590 parts by weight of c〇k〇at... and 5 parts by weight of butyl butyl acetate. The antireflection layer forming material was applied onto the hard coating layer by extrusion coating in the same manner as the hard coating layer, and heated at 120 ° C for 3 minutes to thereby dry and harden. An antireflection layer (low refractive index layer having a thickness of 〇.1 and a refractive index of 143) was formed. (Example 9) In the present Example, an antireflection layer was formed on the hard coat layer of the antiglare hard coat film obtained in Example 1, and an antiglare antireflection hard coat film was produced. The antireflection layer is formed in the manner described below. That is, 1 part by weight of 118150.doc • 42-1359834 bis-isopentyl alcohol acrylate, 15 parts by weight of a polyfluorene-based polymer having a mercapto acryloxypropyl group and a butyl group, 2 5 parts by weight of hexylene glycol propionate, 6 parts by weight of a Lucidn type photopolymerization initiator, and a hollow sphere having a diameter of 6 〇 nm which is hydrophobized by surface treatment with a decane coupling agent having a propenyl group The cerium oxide ultrafine particles are dispersed in a mixed solvent (IPA/MIBK/butyl cellosolve/methyl stupid (8〇/9/1〇5/〇5)) to adjust the solid content to 3% by weight to obtain an antireflection layer. material. Use the anti-

The reflective layer forming material was formed into an antireflection layer on the hard coat layer in the same manner as in Example 7. (Embodiment 10)

First, in the same manner as in Example 1, the antiglare hard coat film of this example was produced. Then, using a wire bar coater, the coating liquid described later is applied to the non-hard coated surface of the cellulose triacetate film (the surface opposite to the surface on which the hard coating layer is formed) so that the wet thickness is 20 μm. , drying at i〇〇 for 8 minutes. Further, a mixed solvent of acetone:ethyl acetate:IpA (isopropyl alcohol η·· 58 : 5 (weight ratio)) was used as the above coating liquid. (Example 11) First, the same procedure as in Example i was carried out. An anti-glare hard coating film of the present embodiment, which is coated with H on a non-hard coated surface of a triacetylcellulose film (surface opposite to the surface on which the hard coating layer is formed). The coating liquid described later was dried at a temperature of 8 μm at a wet film thickness of 20 μm, and further prepared by using diethylcellulose at a ratio of acetone to acetic acid. Isopropanol 37: 58: 5 (by weight) mixed solvent having a solid content concentration of 0.5% as the above coating liquid. I18150.doc -43- 1359834 (Example 12) The same as 1 in this example (Comparative Example 1) An anti-glare hard coat film was produced without using a leveling agent.

& Diluting 1 〇 0 parts by weight of urethane urethane violet with a mixed solvent of B and toluene (butyl acetate vinegar·toluene 3: weight ratio): a linear hardening resin, a weight average of 15 parts by weight Polystyrene particles having a particle size of 3 5 (four) (refractive index · 159), Q 5 parts by weight of a sulphurizing agent (trade name: ^gafUek 147_' manufactured by Dainippon Ink and Chemicals Co., Ltd.), 2.5 parts by weight The synthetic bentonite and 5 parts by weight of a photopolymerization initiator (trade name: iragacure 907, Ciba Speciahy (manufactured by Ciba Speciahy)) were prepared so that the solid concentration was 35% by weight to prepare a hard coat. The formation material of the coating.

Next, the above-mentioned hard coating layer forming material was applied onto a transparent plastic film substrate (a thickness of 80 μηι 3 cellulose acetate film (refractive index: 1.48)) using a coating bar to form a coating film. Heat the coated film under 〇〇〇c! Allow it to dry in minutes. Further, the coating film was irradiated with ultraviolet light having a cumulative light amount of 300 mJ/cm 2 by a metal element lamp, and hardened to form a hard coating layer having a thickness of 5 μm. Thus, the antiglare hard coat film of this comparative example was produced. (Comparative Example 2) An antiglare hard coat film of this comparative example was obtained in the same manner as in Example 1 except that the amount of the ruthenium particles added was changed to 3 parts by weight. 1 (8) 50.doc 44- 丄妁9834 (Comparative Example 3) In this comparative example, the comparison was carried out in the same manner as in Example 1 except that the amount of addition of PMMA particles was changed to 7 Å. An anti-glare hard coated film. (Comparative Example 4) In the comparative example, the fine particles were a zizi (refractive index 1. 1.49) of a weight average particle diameter of 3 pm and the amount of addition was changed to parts by weight, and other examples were compared with the comparative examples. In the same manner, an anti-glare hard coat film of this comparative example was obtained. With respect to each of the antiglare hard coat films of the examples and the comparative examples thus obtained, various characteristics were measured or evaluated. The results are shown in Table 1 below. [Table 1]

118150.doc -45 - 1359834 As shown in the above Table 1, the anti-glare hard coat film of the present embodiment is excellent in all properties such as hardness, scratch resistance, anti-glare property, and adhesion, and is comparatively excellent. An anti-glare hard-coated film of the anti-glare hard coat film of the anti-glare hard coat film of the anti-glare film of Comparative Example 2, and the anti-glare property of the anti-glare hard coat film of the anti-glare film Poor scratch resistance. [Industrial availability]

The (iv) hard f-coated film of the present invention is excellent in hardness, scratch resistance and anti-glare property. The anti-glare hard coat film of the present invention can be suitably used for, for example, an optical element such as a polarizing plate, a CRT, an LcD pDM p, or the like, and the like. In the field. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an antiglare hard coat film of the present invention. '

Fig. 2 is a schematic cross-sectional view showing the structure of the present invention. The other examples of the glare hard coat film are shown in Fig. 3 which is a schematic view showing a roughness curve and an example. One of the relationship between the south degree h and the reference length L [Description of main component symbols] Transparent plastic film substrate Hard coating layer Particles, 6 Anti-glare hard coating thin film Anti-reflection layer ll8150.d〇c ·46·

Claims (1)

Patent Application No. 096,110,873, Patent Application No.: Towel _Fibre Circumference 1 -, anti-glare hard coating (4) film, which is at least in the middle of a transparent plastic (four) film substrate having a hard coating containing particles The layer is characterized in that the thickness of the hard coating layer is 15 to 3, and the weight average particle diameter of the fine particles is in the range of 3 to 75% of the thickness of the hard coating layer. The average inclination angle of the (5) convex shape of the face is 0 to 1.5 degrees, and the average inclination angle ea is a value defined by the following formula (1): Φ average inclination angle 0a"tan-iAa (1) Δ a - For the reference length L of the roughness curve defined in JIS B 0601 (1994 edition), the total value of the difference (height h) between the adjacent peak apex and the lowest valley point is divided by the reference length l The hard coating layer is formed by using a resin for forming a hard coating layer containing the following components (A), (B), and (C): (A) component: acrylic acid At least one of ester and mercapto acrylate phthalate; ® (B): At least one of a diol acrylate and a polyol methacrylate; (C) component: a polymer or copolymer formed of at least one of the following (C1) and the following (C2), or a copolymer and copolymer (C1): an alkyl acrylate having an alkyl group containing at least one of a hydroxyl group and an acrylonitrile group; (C2): an alkane 118150 having at least one group containing a hydroxyl group and an acrylonitrile group In the resin for forming a hard coating layer, the ratio of the component (B) to the component (A) is in the range of 70 to 180% by weight, relative to the alkyl methacrylate. In the above-mentioned component (A), the ratio of the bismuth component is in the range of 25 to 110% by weight, and the total amount of the resin component for forming the hard coating layer is 〇〇 by weight. 2. The anti-glare hard coat film of claim 1, wherein the component (B) comprises at least one of pentaerythritol triacrylate vinegar and pentaerythritol tetraacrylate vinegar. Paint The film is coated with an antireflection layer formed on the hard coating layer. 4. The antiglare hard coating film according to claim 3, wherein the antireflection layer contains hollow spherical cerium oxide ultrafine particles. An anti-glare hard coating film of the claim item, wherein the gloss of JIS κ 71〇5 is in the range of 50 to 95. 6. An anti-glare hard coating. A method for producing a film, which is in a transparent plastic film. A hard coating layer containing fine particles on at least one side of the substrate, characterized in that it comprises the step of preparing a material for forming a hard coating layer, wherein the hard coating layer forming material contains a resin for forming a hard coating layer, a fine particle having a weight average particle diameter of 3 to 75% of the thickness of the hard coating layer and a solvent; and a step of forming a coating film, wherein the hard coating layer forming material is applied to at least the transparent plastic film substrate a U8150-1000822.doc 1359834 53⁄43⁄4 surface to form a coating film; and a step of forming a hard coating layer, the coating film is hardened to form a thickness of 15 to 30 μηη, and the surface has a concave-convex shape The hard coating layer having a uniform inclination angle 0a of 0.4 to 1.5 degrees; the average inclination angle 0a is a value defined by the following formula (1): average inclination angle eastarfka (1) Δ a : on JIS B 0601 ( In the reference length L of the roughness curve defined in the 1994 edition), the value obtained by dividing the total value of the difference between the peak apex of the adjacent peak and the lowest point of the valley (height h) by the reference length L; Further, the hard coating layer-forming resin contains the following components (A), (b), and (C): (A) at least one of an amino acrylate and an amino phthalic acid decanoate. (B) Component: at least one of a polyol acrylate and a polyol methacrylate; (C) Component: formed by at least one of the following (C1) and the following (C2); a polymer or a copolymer, or a mixed polymer of the above polymer and copolymer; (C1): an alkyl acrylate having an alkyl group containing at least one of a hydroxyl group and an acrylonitrile group; (C2): having a hydroxyl group And the alkyl thio acrylate of the alkyl group of at least one group of the acrylonitrile group, wherein the ratio of the component (b) is 7 〇 to the weight of the component (A). The range of %, 118150-1000822.doc 1359834, %|positive replacement page relative to the above (A) component 'the ratio of the above (C) component is 25 to 110 weight. The range of the amount of %, _ relative to the above hard coating layer The total amount of the resin component to be formed is 'the proportion of the above-mentioned fine particles blended in the range of 2 to 70 parts by weight. 7. The method for producing an antiglare hard coat film according to claim 6, wherein the component (B) comprises at least one of pentaerythritol triacrylate and pentaerythritol tetraacrylate. 8. The method of producing an antiglare hard coat film according to claim 6, wherein the solvent contains ethyl acetate. 9. The method for producing an antiglare hard coat film according to claim 8, wherein the content ratio of the ethyl acetate to the total solvent is 2% or more. 10·---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- Anti-glare hard coating thin. A polarizing plate comprising a polarizer and an anti-glare hard coating film, wherein the anti-glare hard coating film is an anti-glare hard coating film of claim i. An image display device comprising an anti-glare hard coat film, characterized in that the hard coat film is a hard coat film of claim 1. An image display device comprising an optical element, wherein the optical element is an optical element of claim 1 . An image display device comprising a polarizing plate, characterized in that the polarizing plate is a polarizing plate of claim 11. 118150-1000822.doc