TW201026764A - Composition for forming hard-coat layer, hard-coat film, optical element, and image display - Google Patents

Abstract

This invention provides a composition for forming hard-coat layer capable of producing a hard-coat layer having enough hardness, restraining the occurring of cracks and the crimping caused by curing shrinkage and excellent abrasion resistance and a hard-coat film. This invention uses the composition for forming the hard-coat layer that contains: constituent (A): a curable compound containing at least one group of acrylate group and methacrylate group, constituent (B): surfaces of inorganic particles modified by organic compounds containing polymerism unsaturated groups, and constituent (C): reactive silica containing compounds represented by the following general formula (1) on at least one surface of a transparent plastic film substrate 11 to form the hard-coat layer 12. In the general formula (1), R is a substituted group selected from a substituted group having a siloxane structure, a substituted group containing at least one of acrylate group and methacrylate group, and a substituted group containing active hydrogen. Each R may be the same or not.)

Description

201026764 VI. Description of the invention: Technical field of the invention; j Field of the invention The present invention relates to a composition for forming a hard coat layer, a hard coat film, an optical element, and an image display device. [Prior Art 3] Background of the Invention With the advancement of technology in recent years, image display devices have been developed in addition to the conventional CRT (Cathode Ray Tube), liquid crystal display (LCD), plasma display (PDP), and electric field light-emitting display (ELD). Out, and can be used. Among them, the LCD has been innovated with technologies related to high viewing angle, high definition, high-speed response, color reproducibility, etc., and applications using LCDs have also been expanded from notebook personal computers or monitors to televisions. Diversified uses. The basic composition of the LCD means that the glass substrate on the flat plate having the transparent electrode is formed by interposing spacers as spacers in the opposite direction, and the liquid crystal material is injected and sealed between the glass substrates. A liquid crystal cell is formed, and then a composition of a polarizing plate is separately provided on the outer side surfaces of the pair of glass substrates. In the past, a cover plate made of glass or plastic was attached to the surface of the liquid crystal cell in order to prevent damage to the polarizing plate attached to the surface of the liquid crystal cell. However, if the cover is installed, it is disadvantageous in terms of cost and weight, and thus gradually changes to a hard coating treatment on the surface of the aforementioned polarizing plate. In the above hard coat treatment, a hard coat film having a thin hard coat layer having a thickness of 2 to 1 μm is formed on one side or both sides of a transparent plastic film substrate. The hard coat layer is usually formed using a composition for forming a hard coat layer such as a thermosetting resin or an ultraviolet curable resin 3 201026764. Since the application of the LCD is transferred to the home television set, it is easy to assume that the user of the general household television set, even the television using the coffee, performs the same operation as the television set using the conventional glass CRT. Therefore, it is required to increase the hardness for a hard coat film which is used for an LCD. It is possible to increase the layer thickness of the hard coat layer, thereby increasing the hardness of the hard coat film. However, if the layer thickness is increased, there is a tendency for curling to occur due to hardening shrinkage when the hard coat layer is formed. Further, in the case where a hard coat layer is formed on a roll-shaped adjacent thin material, the region in which the composition for forming a hard coat layer is applied and the uncoated region are applied in the width direction of the transparent plastic film substrate (that is, The hard coat film may be cracked in the vicinity of the boundary between the hard coat layer and the uncoated portion of the composition of the composition and the end of the transparent plastic film substrate. When the curl or crack of the hard coat film is formed, it may result in a hindrance to the continuous production step of the hard coat film or the work of attaching the laminate to the polarizing plate of the hard coat film. Here, a method of suppressing the occurrence of curling and cracking of the hard coat film by adding the inorganic fine particles to the hard coat layer and reducing the hardening shrinkage force at the time of the hard coat layer formation is proposed (see Patent Document 1). In this method, although the hardness of the hard coat layer is increased by the addition of micro, it is weak with respect to the scratch, or there is room for improvement in scratch resistance. [Patent Document 1] JP-A-2006-106427 [Exposure to the Invention] Disclosure of the Invention [Problems to be Solved by the Invention] 4 201026764 Here, an object of the present invention is to provide a sufficient hardness to be obtained due to hardening shrinkage. A composition for forming a hard coat layer of a hard coat layer which is excellent in scratch resistance and which is suppressed in the occurrence of curling and cracking. Further, an object of the present invention is to provide an optical element and an image display apparatus using the film which has sufficient hardness and which is caused by the occurrence of shrinkage and cracking of the hardening shrinkage, and which is excellent in scratch resistance. [Means for Solving the Problem] In order to achieve the above object, the composition for forming a hard coat layer of the present invention is a composition for forming a hard coat layer for forming a hard coat layer, characterized in that it contains the following (A ) ingredients, (B) ingredients, and (C) ingredients. (A) Component: a hardening type compound (B) containing a group of at least one of a acrylate group and a methacrylate group. Component: The surface of the inorganic oxide particle is modified with an organic compound containing a polymerizable unsaturated group. Particle (C) Component: Reactive cerium oxide containing a compound represented by the following general formula (1). 【化7】

In the above general formula (1), R is selected from the group consisting of a substituent having a decane structure, a substituent containing at least one of an acrylate group and a methacrylate group, and a substituent containing an active hydrogen. Substituents, each r may be the same or 5 201026764. The hard coat film of the present invention is a hard coat film having a hard coat layer on at least one side of a transparent plastic film substrate, characterized in that the hard coat layer is formed of the hard coat layer forming composition of the present invention. By. The optical element of the present invention is characterized in that the hard coat film of the present invention is laminated on at least one side of the optical member. The image display device of the present invention is an image display device comprising a hard coat film or an optical element, characterized in that the hard coat film is the hard coat film of the present invention, and the optical element is the optical element of the present invention. According to the hard coat film of the present invention formed of the composition for forming a hard coat layer of the present invention, the functions of the three components are combined with each other to have sufficient hardness, resulting in curling and cracking of the hard coat of the hard coat layer. The occurrence is contained, ^ and the scratch resistance is excellent. The long performance of the hard coat film achieved by the present invention is obtained by combining a combination of two components as described in the present invention, or may be obtained by each component of the above three components. For example, since the composition for forming a hard coat layer contains the component (8), for example, the hardness of the formed hard coat layer is improved 'and imparting elasticity and flexibility, and the component (B) is contained) For example, the hardening shrinkage force at the time of formation of the hard coat layer is reduced, and the curling of the hard coat film and the occurrence of the turtle S are effectively prevented; and the (C) forming process is included, for example, the surface structure of the formed hard coat layer becomes straight. At the same time, the smoothness is improved and the scratch resistance is excellent. Further, the hard coat film opening of the present invention has, for example, the above-mentioned (〇 component, and also functions as a so-called fingerprint wiping property and a pen-mark shrinkage property (a silky read-ready silk. Further, these respective ones become 201026764 points) The description of the function of the function is not intended to limit the present invention. [Embodiment 3] The best form for carrying out the invention The component (c) of the composition for forming a hard coat layer of the present invention, For example, the structure represented by the following general formula (2) can be used. The structure represented by the following general formula (2) is regarded as (6-isocyanatohexyl)isocyanurate (6-isocyanatohexyl) isocyanurate ) Unit (4) [Chem. 8] 〇/N, (2) Π 〇C-NH-(CH2)e X(CHi)e.NH-i

O

Unit (a) In the composition for forming a hard coat layer of the present invention, the substituent having the above-mentioned Wei fluorene structure in R of the above general formula (1) may have, for example, the following formula (3). structure. The structure represented by the following general formula (7) has a terminal of a bis-methyl oxy-burning unit (4); the unit (4) is bonded to a methyl group via a propyl group (b); a precursor (9) The base is bonded to the ethyl acetoacetate of the (6-isocyanatohexyl)isotrifluorouric acid terminal isocyanate (is〇Cyanato gr〇up) of the above-mentioned unit (:). In the above polydimethyl methine unit (e), the above integer is preferably from 1 to 7. 7 201026764 【化9】 Ο11(CH2)6-NH-CTM. 〇.ch2-ch2-ch2 ----- Part of unit (a)

♦~—-—TM—TM^~----—!► unit (b) I unit (e)

In the composition for forming a hard coat layer of the present invention, the substituent containing the active hydrogen in R of the above general formula (1) may have, for example, a substituent represented by the following general formula (4). In the substituent represented by the above general formula (4), the terminal isocyanate group of the (6-isocyanatohexyl)isocyanurate which is a part of the above unit (a) becomes a carboxyl group. Further, in the substituent represented by the above formula (4), the carboxyl group may be converted into an amine group by a decarboxylation reaction. [化10] 0

II - (CH2)g~NH-C-0-H* · * (4). Domain 丨 - ^ Part of the unit (a) The composition for forming a hard coat layer of the present invention, the general formula (1) In R, the substituent containing the acrylate group may have a structure represented by the following general formula (5). The structure represented by the above general formula (5) contains an aliphatic polyester unit (d) having an acrylate group at the end; the above unit (d) and a part of the above-mentioned 201026764 unit (a) (6-isocyanate hexyl group) The hetero-acid acid group at the end of the isomeric cyanurate is subjected to an amino phthalate linkage. In the above general formula (5), m and n are each an integer of 1 to 10, and may be the same or different; and 1 is an integer of 1 to 5. [化11] 〇Γ 0 I 0

•|cH2]^NH-C 〇|cH2^p-C*^CH2^ O^CH2^〇~C-CH=CH2 ,

When the component (C) contains the unit (a) having the structure represented by the above general formula (2), and contains the substituent represented by the above general formulas (3) to (5) (6-isocyanatohexyl group) Derivative of isocyanurate 'The aforementioned unit (a): the above unit (b): the above unit (c): the ratio of the composition of the above unit (d) (mol ratio), in the above unit (a) In the case of 1 ', the aforementioned unit (b) is preferably in the range of 1 to 80, for example, in the range of 1 to 60, and the unit (c) is in the range of, for example, 10 to 400, in the range of 10 to 300. Preferably, the unit (d) is preferably in the range of 5 to 50, for example, in the range of 1 to 100. In the present invention, the ratio (molar ratio) of each component (unit) of the component (C) can be calculated from, for example, an integral curve of an iH-NMR spectrum. The weight average molecular weight (Mw) of the component (C) described above is preferably in the range of, for example, 500 to 150,000 in the range of 2,000 to 100,000. The aforementioned weight average molecular weight (Mw)' can be measured by, for example, a gel permeation chromatography (GPC) method. In the composition for forming a hard coat layer of the present invention, the weight average particle diameter of the component (B) is from the point of preventing light scattering, preventing the transmittance of the hard coat layer from being lowered, preventing coloring and transparency, and the like. It is preferably 2GGnm or less. The above-mentioned weight average particle (four) is simply carried out, for example, in the method described in the examples below.

Determination. The aforementioned weight flat plexus H-knife blade amount ' is preferably in the range of 1 to 100 nm. __ The composition of the hard coat layer is as follows. The component (B) may, for example, be a fine particle such as titanium oxide, oxidized work, lanthanum oxide, aluminum oxide, zinc oxide, tin oxide or oxidation. For example, it is preferable to use titanium oxide, cerium oxide (cerium oxide), aluminum oxide to oxidize fine particles of tin oxide or cerium oxide. These may be used alone or in combination of two or more.

The hard coat layer of the present invention forms a crepe scarf, and the component (B) is preferably mixed in a range of just to a weight fraction with respect to the weight of the component. The hard coat forming composition of the present invention preferably contains a component. (D) component: a diol-based compound represented by the following general formula (6): CH2=CH~C'II 〇CH3 o-ch2-c-ch2-ch3 〇-ch2-ch-c--ch =ch2 CH3 % · -(6)

In the above formula (6), the integers in which m and n are each 1 or more may be the same or different. In the composition for forming a hard coat layer of the present invention, it is preferable that the component (C) and the component (D) are mixed in a range of a total weight of the knife relative to the former (A, 100 parts by weight). The thickness of the aforementioned hard coat layer in the film is not limited to 10 201026764, but it is, for example, in the range of 10 to 50 μm. Since the aforementioned thickness is set to the above range, the hardness is not lowered, and the hardness can be effectively suppressed. The thickness of the coating film is preferably in the range of 1 〇 to 4 〇 μη. In the hard coating film of the present invention, the surface of the hard coating layer is increased according to the specification of κ 5600-5-4. The hardness of the pen base at 500 g is preferably 4H or more. The hard coat film of the present invention has a light reflection at the interface between the hard coat layer and the air, and may be formed on the outer surface of the hard coat layer to form an antireflection layer. In the image display device, for example, the image display device can be used to improve the visibility of the image on the display side. Next, the present invention will be described in detail. The invention is not limited The hard coat film of the present invention is a hard coat film having a hard coat layer on one or both sides of the transparent plastic film substrate. The transparent plastic film substrate is not particularly limited, but is excellent in light transmittance of visible light ( It is preferable that the light transmittance is at least %), and the transparency is excellent (it is preferably a haze value of 1% or less), and for example, the special transparent sheet (four) material of JP-A-2008-90263 is used. The plastic film substrate can be suitably used with a material having less optical birefringence. The hard (four) (4) of the present invention can be used as a polarizing plate as, for example, a protective film. In this case, the aforementioned transparent __substrate, with triacetic acid It is preferable that cellulose (TAC), polycarbonate, vinegar vinegar-based polymer, or the like having a ring shape or a thin structure of a norbornene is formed. Further, in the invention of the present invention, the transparent plastic The film substrate may also be the polarizer itself. If it is such a composition, since the protective layer composed of TAC or the like is not required, the structure of the polarizing plate can be simplified, so that it can be designed to be used for a polarizing plate or an image display device. The number of manufacturing steps is reduced, and the production efficiency is improved. However, if it is such a composition, the polarizing plate can be made thinner. Further, when the transparent plastic/film substrate is a polarizer, the hard coat layer is It will function as a conventional protective layer, and if it is such a composition, the hard-coated film will have the function of a cover plate mounted on the surface of the liquid crystal cell. In the present invention, the thickness of the aforementioned transparent plastic film substrate is The thickness is, for example, preferably in the range of 1 〇 to 500 μm, and preferably in the range of 2 〇 to 3 〇〇 μηη, in consideration of workability and thinness such as strength and workability. The range of 30 to 2 〇〇μηη. The refractive index of the transparent plastic film substrate is not particularly limited. The refractive index is, for example, a range of h30 to 丨80, preferably in the range of 1.40 to 1.70. The hard coat layer is formed using the composition for forming a hard coat layer containing the component (A), the component (B) and the component (C). As the component (A), for example, a hardening type compound containing at least one of an acrylate group and a methacrylate group which is cured by heat, light (ultraviolet rays, etc.) or an electron beam can be used. The component (A) may, for example, be a "crushed resin, a polyester resin, a polyether resin, an epoxy resin, a polyurethane resin, an alked resin, a spiroacetal resin, or a polybutylene. Oligomers or prepolymers such as polybutadiene resin, p〇lythi〇i polyene resin, polyfunctional compound such as acrylic acid styrene or methacrylate group Wait. It can be used alone or in combination of two or more types. As the component (A), for example, a reactive diluent containing a group of at least one of an acrylate group and a methacrylate group can also be used. The aforementioned reactive diluent contains, for example, a monofunctional acrylate, a monofunctional methacrylate, a polyfunctional acryl vinegar, a polyfunctional methacrylate, and the like. The monofunctional acrylic acid S is intended to contain, for example, an acrylate modified by epoxidizer, an acrylate of propylene oxide modified phenol, an acrylic acid modified by ethylene oxide, and a ring. The oxypropylene conversion is called _, diethylhexyl carbitol acrylate vinegar, isobornyl acrylate, tetrahydrofurfuryl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate Vinegar, hydroxyhexyl acrylate, diethylene glycol monoacrylate, triethylene glycol monoacrylic acid _, tripropylene glycol mono, _ and so on. The aforementioned monofunctional methacrylic acid vinegar contains, for example, epoxy ethene modified benzene _ methyl propyl vinegar, epoxy propylene modified benzene, methyl methacrylate, epoxy styrene modified phenolic methacrylate , propylene oxide modified phenolic methacrylate vinegar, 2_ethylhexyl carbitol methyl propyl _ 5, methyl acrylate acid iso- ice S, methyl methacrylate tetrahydro vinegar, Hydroxyethyl methacrylate, methacrylic acid, propyl vinegar, methyl acrylate, butyl vinegar, methyl hydroxy hexanoic acid, diethylene glycol monomethacrylic acid, triethylene glycol monomethyl propyl Dilute _, tripropylene glycol monomethacrylate vinegar and the like. The above polyfunctional group contains, for example, diethylene glycol diacrylate vinegar, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol diacrylate vinegar, M- Butanediol diperate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, cyclohexane modified neopentyl glycol 13 201026764 diacrylate, epoxy B Alkyl modified bisphenol A diacrylate, propylene oxide modified bisphenol A diacrylate, ethylene oxide modified hydrogenated bisphenol A diacrylate, trimethylolpropane diacrylate, trihydroxy Methylpropane allyl ether diacrylate, trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide modified trimethylolpropane triacrylate, pentaerythritol Tetraacetic acid S, dipentaerythritol tetraacrylic acid S, dipentaerythritol hexaacrylate, and the like. The aforementioned polyfunctional mercapto acrylate contains, for example, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol II Methacrylate, polypropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimercapto acrylate, 1,6-hexanediol dimethacrylate, ring Ethylene oxide modified neopentyl glycol dimethacrylate, ethylene oxide modified bisphenol A dimercapto acrylate, propylene oxide modified bisphenol A dimercapto acrylate, epoxy B Alkyl modified hydrogenated bisphenol A dimethacrylate, trimethylolpropane dimethacrylate, trishydroxypropyl propane allyl ether dimethacrylate, trishydroxypropyl propane tridecyl acrylate, Ethylene oxide modified trishydroxypropyl propane tridecyl acrylate, propylene oxide modified trimethylolpropane trimethacrylate, pentaerythritol tetradecyl acrylate, dipentaerythritol tetramethacrylate, dipentaerythritol Hexamethyl acrylate and the like. The reactive diluent is preferably a trifunctional or higher acrylate or a trifunctional or higher thioacrylate. This is because the hardness of the hard coat layer can be made better. Examples of the component (A) include butanediol glycidyl ether diacrylate, isopropyl methacrylate acrylate, and isocyanuric acid methacrylate. In the above component (A), one type of 201026764 may be used alone or two or more types may be used. In the above-mentioned component (B), the inorganic oxide particles include, for example, oxidized oxide (external titanium dioxide, oxidized, oxidized, tin oxide, oxidized, etc.). It is preferable that the microparticles of the oxygen cut (cerium dioxide), the tantalum titanium, the oxidation 18, the oxidation, the tin oxide, and the cerium oxide are used. These may be used alone or in combination of two or more. In the composition for forming a coating layer, the component (B) has a weight average particle diameter of 1 nm to 2 Å from the viewpoint of preventing scattering of light, preventing the transmittance of the hard coat layer from being lowered, and preventing coloration and transparency. The range of 11111 is preferably a so-called nanoparticle. The weight average particle diameter can be carried out by, for example, carrying out a method of calculating the weight. The weight average particle diameter is preferably in the range of 1 nm to 100 nm. In the component (B), the inorganic oxide particles are bonded to the organic compound containing a polymerizable unsaturated group (surface modification), and the polymerizable unsaturated filaments are passed through the ageing reaction to form a hard coat. The hardness of the layer • Increase. The aforementioned poly The unsaturated group is, for example, acrylonitrile, fluorenyl fluorenyl, vinyl, propyl, butyl succinyl, styrene, ethynyl, cinnamyl, maleic acid, propyl In addition, the organic compound containing the polymerizable unsaturated group is preferably a compound containing an anthracene group in the molecule or a compound formed by an alcohol group. The organic compound having a polymerizable unsaturated group is preferably a photo-sensitive group. The compounding amount of the component (8) is preferably in the range of 100 to 200 parts by weight based on the weight of the component (A). By setting the mixing amount of 15 201026764 of the above component (8) to 100 parts by weight or more, it is possible to more effectively suppress the occurrence of curling and cracking of the hard coat film, and the abrasion resistance can be obtained by setting the amount of the hard coating film to 200 parts by weight or less. The amount of the component (B) is preferably in the range of 120 to 180 parts by weight based on 100 parts by weight of the component (A). The amount of the component (B) is adjusted to adjust, for example, The refractive index of the aforementioned hard coat layer is possible. It is preferable to reduce the difference in refractive index between the transparent plastic film substrate and the hard coat layer at a point where interference light is generated at the interface between the transparent plastic film substrate and the hard coat layer, etc. The interference light is incident. The reflected light of the outdoor light to the hard-coated film exhibits an iridescent color. Recently, in the office, most of the three-wavelength fluorescent lamps with excellent definition are used. Under the aforementioned three-wavelength fluorescent lamp, the aforementioned interference light is remarkable. In order to prepare the composition for forming a hard coat layer, it is preferable to adjust the amount of the component (B) to reduce the difference in refractive index, and the refractive index difference is 0.04 or less. Preferably, it is preferably 0. 02 or less. Specifically, for example, a PET film (refractive index: about 164) is used as the case of the above-mentioned transparent plastic thin job material. The entire resin component of the composition for forming a hard coat layer can be suppressed by the control of the refractive index difference of 〇〇2 = lower by suppressing the synthesis of 3G to 4G by about #%. Further, for example, in the case where the tac thin refractive index (about M8) is used as the transparent plastic film substrate, oxidized stone (cerium dioxide) is used in the component (B) of the month, and the hard coating is used for the hard coating. It is possible to control the refractive index difference to be equal to or less than 〇〇2, and to suppress the generation of interference fringes, by mixing all of the resin components in the composition by a mixture of three particles and a quantity of 〇. 16 201026764 • The above component (c), as described above. The R of the compound represented by the above general formula 0) may be all different or the same. It is sufficient that the component (c) contains a substituent having a ruthenium oxide structure, a substituent having at least one of an acrylate group and an acrylate group, and a substituent having an active hydrogen. The mixing ratio of the above component (C) is not particularly limited. By using the above component (C), for example, the surface structure of the hard coat layer formed becomes rigid, and the smoothness is improved, and the scratch resistance becomes excellent. The mixing ratio of the component (c) is preferably in the range of 001 to 5 parts by weight, preferably in the range of 0. 05 to 3 parts by weight, based on 100 parts by weight of the component (A). More preferably, it ranges from 〇丨2 to 2 parts by weight. In the hard coat film of the present invention, for example, a composition for forming a hard coat layer obtained by dissolving or dispersing the above three components in a solvent may be applied, and the hard coat layer may be applied to at least one surface of the transparent plastic film substrate. After the layer forming composition is formed into a coating film, the coating film is cured to form the hard coat layer. • The above solvents are not particularly limited. The above solvent contains, for example, dibutyl mystery, dimethoxymethoxy, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane (i, 4_di〇xane) , 13 dioxolane (l,3-di〇X〇lane), U5-trioxan (13 5_tri〇xane), tetrahydrofuran, acetone, methyl ethyl ketone (MEK), di-, di-propyl, di-iso-butyl Ketone, cyclopenta, cyclohexanone, nonylcyclohexanone, ethyl citrate, formic acid propyl vinegar, formic vinegar formic acid, vinegar acetate, ethyl acetate, methyl vinegar, ethyl acetonate, propionic acid N-pentanyl acetate, n-amyl acetate, acetoacetone, dipropanol, decyl acetate, ethyl acetate, methanol, ethanol, κ propanol, 2-propanol, N-butanol, 17 201026764 2-butanol, 1-pentanol, 2-mercapto-2-butanol, cyclohexanol, isobutyl acetate, mercaptoisobutyl ketone (MIBK), 2-octanone, 2-pentanone, 2- Hexanone, 2-heptanone, 3-heptanone, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monoterpene ether and the like. These may be used alone or in combination of two or more. The solvent is preferably ethyl acetate in an amount of 20% by weight or more, and preferably 25% by weight, from the viewpoint of improving the adhesion between the transparent plastic film substrate and the hard coat layer. The above ratio contains ethyl acetate, and most preferably, ethyl acetate is contained in a proportion of 30 to 70% by weight. When the ratio of the ethyl acetate in the solvent is 70% by weight or less, the volatilization rate of the solvent can be suitably adjusted, and uneven coating or uneven drying can be effectively prevented. The type of the solvent of the ethyl acetate described above is not particularly limited. The solvent contains, for example, butyl acetate, methyl ethyl ketone, ethylene glycol monobutyl ether, propylene glycol monomethyl ether or the like. As described above, the composition for forming a hard coat layer preferably further contains the component (D) described above. The mixing ratio of the above component (D) is not particularly limited. Since the component (D) is used, for example, the surface structure of the hard coat layer formed becomes rigid, and the smoothness is also improved, so that the scratch resistance becomes excellent. In the case of using the component (D), it is preferred to prepare a mixture of the component (D) and the component (C) in the preparation of the composition for forming a hard coat layer. As the material containing the aforementioned mixture, for example, a commercially available product can also be used. For example, the product name "GRANDIC PC-4100" manufactured by Otsuka Ink Chemical Industry Co., Ltd., and the like can be mentioned. The weight of the material containing the aforementioned mixture is 201026764. The average molecular weight (Mw) is not particularly limited. The mixing amount of the component (D) described in the above (C) component (IV) is the mixing amount of the component (4), and the weight of the component (A) is preferably in the range of 〇〇1 to 1 〇, preferably 0.05 to 8 by weight. The range of the fraction is more preferably in the range of 1 to 5 parts by weight. A composition for forming a hard coat layer, if necessary, may also contain a pigment, a filler, a dispersant, a plasticizer, a UV absorber, a surfactant, an antioxidant, and shake, within a range not damaging the month b. The anti-tack agent (Thix〇tr〇pic agent) or the like may be used alone or in combination of two or more. In the case of the composition for forming a hard coat layer, the component (A) contains a photocurable compound. For example, a conventionally known photopolymerization initiator can be used as described in JP-A-2-88-883. The photopolymerization initiator may be used singly or in combination of two or more. The amount of the photopolymerization initiator to be mixed is not particularly limited. The amount of the above-mentioned compounding is in the range of 1 to 25 parts by weight in the range of, for example, 1 to 3 parts by weight, based on the above (A); The method of applying the composition for forming a hard coat layer on the transparent plastic film substrate can be, for example, a spray coating method, a squeeze coating method such as coating, or a spin coating method. Coating methods such as spray coating, gravure coating, roll coating, and bar coating. The composition for forming a hard coat layer is applied, a coating film is formed on the transparent plastic film substrate, and the coating film is cured. The coating film is preferably dried before the hardening. The aforementioned drying may be, for example, or naturally dried, or air-dried or dried by heating, or may be a combination thereof. The method of hardening the coating film of the composition for forming a hard coat layer is not particularly limited. The aforementioned hardening method is preferably hardened by ionizing radiation. Various activation energies can be used in the aforementioned hardening method. The aforementioned activation energy is preferably ultraviolet light. The source of energy radiation is preferably a radiation source such as a high pressure mercury lamp, a halogen lamp, a xenon lamp, a metal halide lamp, a nitrogen laser, an electron beam acceleration device, or a radioactive element. The irradiation amount of the energy radiation source is preferably in the range of 50 to 5000 mJ/cm 2 of the cumulative exposure amount at an ultraviolet wavelength of 365 nm. When the irradiation amount is 50 mJ/cm2 or more, the hardening is more sufficient, and the hardness of the hard coat layer formed is also sufficient. When the irradiation amount is 5 〇〇〇mj/cm2 or less, the coloring of the hard coat layer formed by the soil can be prevented, and the transparency can be improved. In this manner, the hard coat film of the present invention can be produced by forming the hard coat layer on at least one surface of the transparent plastic film substrate. Further, the hard coat film of the present invention may be produced by a production method other than the above method. In the schematic sectional view of Fig. 1, an example of the composition of the hard coat film of the present invention is shown. In the same figure, the dimensions, ratios, and the like of the respective constituent members are different from actual ones for ease of understanding. As shown, in the hard coat film 1 , the hard coat layer 12 is formed on one side of the transparent plastic film substrate. However, the present invention is not limited to this. The hard coat film 'of the present invention' may also be a composition in which a hard coat layer is formed on both sides of a transparent plastic film substrate. Further, the hard coat layer 12 of this example is a single layer. However, the invention is not limited thereto. In the hard coat film of the present invention, the hard coat layer may have a multi-layer structure in which two or more layers are laminated. In the schematic sectional view of Fig. 2, another example of the composition of the hard coat film of the present invention is shown. As shown, the hard coat film 2'' is formed by forming a hard coat layer 22 on one side of the transparent plastic film substrate 21, and the outer surface 彤 20 201026764 of the hard coat layer 22 is composed of an anti-reflection layer 23. When light illuminates an object, reflection of its interface occurs repeatedly, internal absorption, discoloration, and transmission to the back side of the object. For example, in the case where a hard coat film is mounted on an image display device, one of the causes of the decrease in visibility of the image is exemplified by the & reflection occurring at the interface between the air and the hard coat layer. The anti-reflection layer is such that the surface reflection is lowered. Further, in the hard coat film 2 shown in Fig. 2, the hard coat layer 22 and the antireflection layer 23' are formed on one surface of the transparent plastic film substrate 21. However, the present invention is not limited to this. The hard coat film of the present invention may also be a structure in which a hard coat layer and an antireflection layer are formed on both sides of a transparent plastic film substrate. Further, in the hard coat film 20 shown in Fig. 2, the hard coat layer 22 and the antireflection layer 23 are each a single layer. However, the invention is not limited thereto. In the hard coat film of the present invention, the hard coat layer and the antireflection layer may each have a plurality of layers of two or more layers. In the present invention, the antireflection layer is an optical film in which thickness and refractive index are strictly controlled or two or more layers are laminated on the optical film. In the anti-reflection layer described above, the anti-reflection function is generated by the interference effect of light by canceling the inverted phases of the incident light and the reflected light. The wavelength range of the visible light rays for generating the antireflection function is, for example, in the range of 380 to 780 nm, and particularly, the wavelength range in which the visibility is high is in the range of 450 to 650 nm. The antireflection layer is preferably designed in a state where the reflectance at a center wavelength of 550 nm is minimized. When the light-reflecting layer is designed based on the interference effect of light, a method of improving the interference effect thereof is, for example, a method of increasing the refractive index difference between the anti-reflection layer and the hard coat layer. Generally, in a multilayer anti-reflection layer having a structure in which two to five optical thin layers 21 201026764 (strictly controlled thickness and refractive index) are laminated, components having different refractive indices are formed into a plurality of layers only at a fixed thickness. . Therefore, the degree of freedom in the optical design of the antireflection layer is improved, and the antireflection effect can be further improved. The spectral reflection characteristic can also be made uniform (flat) in the visible light range. In the optical enthalpy, the degree of accuracy β is generally performed in the form of dry true = evaporation, sputtering, CVD, or the like. The multilayer anti-reflection layer is preferably a layer of a low-indexed oxidized stone layer on a titanium oxide layer having a high refractive index (refractive index: ι·8) (refractive index: preferably about "two-layer structure". Jia Wei, a layer of oxidized stone layer is deposited on the titanium oxide layer, and another oxidized layer is laminated thereon, and then a layer of other layers of the oxidized stone layer is laminated thereon. The layer or the quad & anti-reflective layer 'is uniformly reduced in the wavelength range of visible light (for example, in the range of 380 to 780 nm). A single-layer optical film (anti-reflective layer) is formed on the aforementioned hard coat layer to exhibit resistance. A reflection effect is also possible. Generally, when a single-layer reflective layer is formed, for example, a wet coating method (—η时❹ ing), die coating (die c〇ating), spin coating Coating method such as spray coating, gravure coating, roll coating, and bar coating. The material for forming the single-layer antireflection layer contains, for example, an ultraviolet ray-curable 4 acryl resin 4 resin-based material, and inorganic fine particles such as 8 acid gel. Dispersed in the resin The mixed resin-based material is a sol-gel material formed of a metal alkoxide such as tetraethoxysilane or tetraethoxytitanium. The above-mentioned forming material 'containing a fluorine-based material for imparting surface antifouling properties 22 201026764 Preferably, the material to be formed is preferably a material having a large content of an inorganic component, preferably a sol-gel-based material, for reasons of resistance to rubbing, etc. The sol-gel material may be The anti-reflection layer (low-refractive-index layer) is composed of a sulfonium oxide conjugate having a number average knives in terms of ethylene glycol in an amount of 500 to 1 GGGG, and based on polystyrene. a material having a fluorinated compound having a number average molecular weight of 5,000 or more and having a fluoroalkyl group structure and a polycrystalline m structure (special opening)

The article - the deletion of the No. 27 public material record reading material), the combination can be both financial scraping and low reflection and so on. In the 刖4 reflecting layer (low refractive index layer), in order to increase the strength of the film, it is possible to contain inorganic rotation. The aforementioned inorganic sol is not particularly limited. The above inorganic sol contains, for example, dioxo, oxyfluoride or the like. It is preferred to use a dioxygen sol in the material. The mixing ratio of the above-mentioned inorganic rotation is in the range of the above-mentioned anti-reflection layer-shaped read_full "formation_:" 纟0~_. The range of the above inorganic _ is preferred. The range of 乂2 to 50 (10) is preferably 5 to 30 Å. Among the materials for forming the antireflection layer, Shishi granules are preferred. Before the money cut, there is a _-like emulsification of 300 nm, preferably 1 () / with a weight average particle size of 5 ~ particles, which is preferable in the case of having fine pores. The foregoing oxidized stone has a hollow spherical shape in which the preparation is hollow. At least one. Further, it is preferable that the solvent and the gas precursor in the case of using _ into / fine particles are the aforementioned hollow hoppers which remain in the front granules. The thickness of the outer casing 23 201026764 is in the range of 1 to 50 nm, and the particle diameter _, the range of the left and right is preferably the average particle coating layer. Preferably, the foregoing oxidized oxide particles are sealed by the outer casing by a plurality of the aforementioned cavities. In this case, the pores are occluded, and the pores or voids of the first two reverse = oxygen-cut microparticles are further advanced to lower the refractive index of the reflective layer. / Method of manufacturing particles, suitable for the production of the shape of the milk-cutting micro-manufactured by the oxidized frequency particles: Open 2001-11

Degree: =1; reverse: low: and _) dry * and hardened temperature 15 〇. "Cheng (five) (four) hardening temperature is, for example, 6〇~

The time gate is suitable, and the range is 7〇~13〇t. The above-mentioned drying and hardening are, for example, in the range of 1 to 3 minutes, and it is preferable to read _ when considering productivity. In addition, after the hardening and hardening, by the film: = heat treatment, the high hardness hard coating with the anti-reflection layer can be obtained. The temperature of the second is not special _ ° The heat treatment is: for example, ' 40~_ range, spit in the range of 5〇~boots. Don't worry about the heat treatment time, there is no special limit. The aforementioned heat treatment 2 is 'for example'! The range from the minute to the hour of the hour is preferably from 1 to 10 hours from the viewpoint of improvement in resistance to rubbing. The above heat treatment can be carried out by a method such as a hot plate, an oven, or a belt furnace. When the hard coat film containing the antireflection layer described above is mounted in an image display device, the frequency at which the antireflection layer forms the outermost layer is high. Therefore, the aforementioned anti-reflection layer 'is easily contaminated from the external environment. The antireflection layer is more likely to be contaminated than a simple transparent plate or the like. The above-mentioned anti-24 201026764 reflective layer may be caused to be unclear due to adhesion of contaminants such as fingerprints, hand scale, sweat or hairdressing articles, or changes in surface reflectance or the discovery of white floating matter. In order to prevent the adhesion of the contaminants and the ease of removing the contaminants attached thereto, it is preferable to laminate an antifouling layer formed of a fluorine-containing lanthanum-based compound or a fluorine-containing organic compound or the like on the antireflection layer. In the hard coat film of the present invention, it is preferred to surface-treat at least one of the transparent plastic film substrate and the hard coat layer. When the surface of the transparent _ plastic film substrate is surface-treated, the adhesion to the hard coat layer or the polarizer or the polarizing plate is further improved. When the surface of the hard coat layer is surface-treated, the adhesion to the antireflection layer or the polarizer or the polarizing plate is further improved. The surface treatment may be, for example, a low-grade plasma treatment, an external radiation treatment, a corona treatment, a flame treatment, an acid or an alkali treatment. The above-mentioned transparent plastic film substrate is preferably subjected to surface treatment when a TAC film is used. The alkali treatment can be carried out, for example, by bringing the TAC secret surface into contact with the test solution, washing with water, and drying. For the foregoing test solution, it is possible to make a solution such as a potassium hydroxide solution or a sodium hydroxide solution. The predetermined concentration (mole concentration) of the hydroxide ions of the test solution is preferably in the range of 04 to 3.0 N (m〇1/L), preferably 〇5 to 2 〇N (m〇1/L). The scope. For a transparent plastic film substrate of 3, a hard coat film of the hard coat layer is formed on the surface of the transparent plastic film base, and the other side may be subjected to a solvent treatment to prevent curling. The solvent treatment described above can be carried out by contacting the moon-transparent plastic film substrate with a solvent which can be dissolved or 4 with a swelling solvent. The solvent treatment can also impart a curling force to the other surface of the transparent plastic film substrate, whereby the transparent plastic 25 201026764 film substrate can cancel the curling force due to the (4) of the hard coating layer. Prevent curling from occurring. Similarly, in the case of the above-mentioned transparent plastic film substrate, the hard coat film in which the hard coat layer is formed on one surface of the transparent substrate may be formed on the other surface to prevent the occurrence of curl. The transparent resin layer may, for example, be a layer mainly composed of a thermoplastic resin, a light-curing resin, a thermosetting resin, or another reactive resin. It is preferable to use a layer which is mainly composed of heat and can be recorded. The hard coat film of the present invention can usually be attached to the optical member using kLCD or eld by a drying agent or an adhesive agent. At the time of the bonding, the surface of the transparent plastic film substrate may be subjected to various surface treatments as described above. The optical member may be, for example, a polarizer or a polarizing plate. The polarizing plate generally means a composition having a transparent protective film on one side or both sides of the polarizing plate. In the case where a transparent protective film is disposed on both sides of the polarizer, the transparent protective films on the inner and outer sides may be the same material 'or different materials. The polarizing plates are usually disposed on both sides of the liquid crystal cell. Further, the polarizing plate is such that the absorption axes of the two polarizing plates are slightly orthogonal to each other. Next, an optical element in which the hard coat film of the present invention is laminated will be described by taking a polarizing plate as an example. The hard coat film of the present invention is laminated with a polarizer or a polarizing plate by using an adhesive or an adhesive or the like to obtain a polarizing plate having the function of the present invention. The polarizer is not particularly limited, and various materials can be used. In the polarizing plate, for example, a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized poly 26 201026764 vinyl alcohol film, or an ethylene vinyl acetate copolymer partially saponified film is used to absorb iodine or a dichroic dye. After the dichroic material, the uniaxially stretched product, the dehydrated material of the polyethylene glycol, or the polysulfide-based oriented film such as the dehydrochlorinated product of the gas-gathered woman is used. The transparent protective film disposed on one or both sides of the polarizer preferably has excellent transparency, mechanical strength, thermal stability, water repellency, and stability of phase difference. The material for forming the transparent protective film may be, for example, the same as the transparent plastic film substrate. The transparent protective film may, for example, be a south molecular film which is contained in § 2001-343529 (WO01/3 7〇〇7). The south molecular film described in the above publication is, for example, a thermoplastic resin containing an amine group having at least one of a substituted amino group and an unsubstituted amino group in the (A) side chain, and a side chain having a substituted phenyl group and a non- A polymer film formed by a resin composition of a thermoplastic resin having at least one of a phenyl group and a nitrile group substituted with a phenyl group. The ruthenium molecular film formed of the foregoing resin composition may, for example, be formed by a composition comprising an alternating copolymer of isobutylene and N-methyl•maleimide and an acrylonitrile-styrene copolymer. Molecular film. The resin composition can be extruded into a film form to produce the polymer film. Since the above-mentioned high molecular weight film has a small phase difference and a small photoelastic coefficient, it is possible to eliminate defects such as color unevenness (mura) caused by stress when applied to a polarizing plate or the like. Since the above polymer _ is ΜλΙ, it is excellent in durability. The transparent protective film is preferably a film made of a cellulose (tetra) fat such as TAC or a film made of an ice-reducing (four) resin, from the viewpoint of polarizing characteristics and durability. The commercially available product of the transparent protective film is exemplified by the trade name: 27 201026764 "FUJITAC" (manufactured by Fujifilm Holdings Corporation), the product name "ZEONOR" (manufactured by Zeon Corporation), and the trade name rART〇N" (JIS). Corporation made) and so on. There is no particular limitation on the thickness of the transparent protective film. The thickness of the transparent protective film is, for example, in the range of 1 to 500 μΐ from the viewpoints of workability such as strength and workability, and lamellarity. When the thickness is 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, and can maintain stable optical characteristics. The aforementioned thickness is preferably in the range of 5 to 200 gings, preferably 10 to 150 Å. The composition of the polarizing plate having the hard coat film of the present invention is not particularly limited, but may be, for example, a layer of a transparent protective film, a polarizing #, and a transparent protective layer laminated on the hard coat film, or may be hard. A composition of a polarizer and a transparent protective film is sequentially laminated on the coated film. The hard coat film of the present invention using the composition for forming a hard coat layer of the present invention and various optical trees such as the use of the material enthalpy deviation can be suitably used in various image display devices such as liquid crystal display devices. The liquid crystal display device of the present invention has the same composition as the conventional liquid crystal display device except that the hard coat film of the present invention is used. In the liquid crystal display device of the present invention, for example, a liquid crystal cell, a polarizing (four) optical element, and a component such as a backlight system (such as a backlight) are mounted, and then a driving circuit is mounted, and the liquid crystal cell is not particularly limited. The aforementioned liquid crystal cell

To manufacture. Formerly visiting the Emirates 4. From +_. σ, there is no special restriction, the liquid crystal of the aforementioned optical element 28 201026764 display device or liquid crystal display device using backlight or reflector in the illumination system. In these liquid crystal display devices, the optical element of the present invention can be disposed on one side or both sides of the liquid crystal cell. When the optical elements described above are disposed on both sides of the liquid crystal cell, they may be the same or different. Further, various opticals such as a diffusion plate, an anti-glare layer, an anti-reflection layer, a protective plate, a prism down, a lens array sheet, a light diffusing plate, and a backlight may be disposed in the liquid crystal display device. Components and optical components. The image display device of the present invention can be used for any suitable purpose. For example, a personal computer such as a notebook computer, a copying machine, a mobile phone, a clock, a digital camera, a personal digital assistant (pDA), a portable game machine, and the like can be used as a portable computer such as a camera, a television, a microwave oven, and the like. Vehicles such as reversing monitors, monitors for car navigation systems, car audio and video equipment, such as display devices for commercial shops, monitoring devices such as monitors, monitors for medical monitors, medical monitors, etc. Medical machines, etc. [Examples] Next, examples of the present invention will be described together with comparative examples. However, the present invention is not limited to the following examples and comparative examples. Further, various characteristics in the following examples and comparative examples were evaluated or measured by the following methods. (Thickness of hard coat layer) The thickness of the hard coat film was measured by using a Micro-gauge type thickness meter manufactured by Mitutoyo Co., Ltd. 'The thickness of the transparent plastic film substrate was subtracted from the above full thickness, thereby calculating the hard coat layer. thickness. 29 201026764 (Scratch resistance) The scratch resistance of the hard coating was evaluated by the following test contents. (1) A sample of 150 mm >< 5 mm was cut out from the center of the hard coat film, and placed on the glass plate with the surface on which the hard coat layer was not formed as the lower surface. (2) On a smooth section of a cylinder of 25 mm in diameter, uniformly install steel wool #0000, and repeatedly rub the surface of the sample 30 times at a speed of about 100 mm per second with a load of 1.5 kg, and visually count the surface of the sample. The number of scratches is judged by the following indicators. A : The number of traces is 10 or less. B: The number of scratches is 11 or more and 29 or less. C: The number of scratches is 30 or more (character hardness). Cut out from the center of the hard coated film. The sample of 〇mm><50mm was placed on the glass plate with the surface on which the hard coat layer was not formed, and the load was measured according to the pencil hardness test described in JIS κ 5600-5-4. Pencil hardness under g. The pencil was "Uni" manufactured by Mitsubishi Pencil Co., Ltd. (the pencil coating scratch test was completed by the Japan Coatings Industry Association). (bending value) A sample of 1 〇〇mmx 1 〇〇mm was cut out from the center of the hard coat film, and the width (W) of the sample after curling was measured using a digital caliper, and the curl value was calculated by the following formula (I). (mm). Curl value (mm)=l〇〇—W ".(I) W ·Width of sample after crimping (min) A. Curl value less than 75mm 201026764 B: Curl value is less than 75mm above 75mm C: Curl value is above 80mm ((weight average particle diameter of particles (component (B))) The resin raw material containing the component (B) was diluted with methyl ethyl ketone (MEK) to a solid content concentration of 10%, and a dynamic light scattering type particle size distribution measuring apparatus was used (( LB-500), the particle size distribution was measured, and the weight average particle diameter was calculated from the obtained particle size distribution. (Weight average molecular weight) The weight average molecular weight was determined by gel permeation chromatography (GPC). In particular, the measurement of the β-specific measurement of the polystyrene as a standard sample is carried out by the following apparatus, apparatus, and measurement conditions. Analytical apparatus: manufactured by TOSOH Co., Ltd., trade name "SC-8020" Column: ShowaDenko Co., Ltd. System, trade name "shodex" Column size: 20.0mmcpx500mm Column temperature: room temperature eluent: three gas methane flow rate: 3.5mL / min inlet pressure: 70kgf / cm2 (6.9MPa) [Example 1] Polymeric unsaturated group organic compound to modify particle table The nano cerium oxide particles (the component (B)) are dispersed, and the resin raw material (manufactured by JSR Corporation, trade name "〇pstar_Z754〇", solid content: 56% by weight, solvent : butyl acetate / methyl ethyl ketone (MEK) = 76 / 24 (weight ratio. 31 201026764 The above-mentioned resin raw material 'to a total of (A) components: (B) component = 2 · 3 weight 1 ratio contains as the above (A) component (ultraviolet rays (a hardening type compound), dipentaerythritol and isophorone diisocyanate type polyurethane, as the component (B), 'cerium oxide fine particles (weight average particle diameter: 100 nm or less) whose surface is modified with an organic molecule. A mixture of the component (C), the component (D) and the solvent (manufactured by Otsuka Ink Chemical Industry Co., Ltd., trade name "GRANDIC PC-4100"). (C) Component: The above general formula (1) The reactive cerium oxide (in the range of X1 : X2 : X3 : X4 (mr ratio) = 187 : 39 : 100 : 57), the polybiguanide group of the above unit (c) of the general formula (3) Polydimethyl-siloxane unit (XI) and the alkyl hydroxy group of the early element (b) of the above general formula (3) a oxoxane unit (X2) and a (6-isocyanatohexyl)isomeric cyanate unit (X3) of the above general formula (2) and a unit (d) of the above general formula (5) Substituent (X4)) (6.85 parts by weight) (D) Component: diol compound represented by the above general formula (6) (3·15 parts by weight) Solvent: ethyl acetate (90 parts by weight) (Preparation of hard coat) In the composition of the layer of the resin, 0.5 parts by weight of the mixture and 0.5 parts by weight of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals Holding Inc., trade name "1^11 127") were added. The composition for forming a hard coat layer was prepared by diluting the solid content concentration to 50 parts by using butyl acetate. 32 201026764 (Production of hard coat film) The above-mentioned hard coat was applied on a transparent plastic film substrate (TAC film having a thickness of 40 μm and a width of 300 mm, manufactured by Konica Minolta Holdings, Inc., trade name "KC4UYW") using a bar coater. The composition for layer formation is then formed into a coating film. After the application, the coating film was dried by heating at 1 °C for 1 minute. The dried coating film was irradiated with ultraviolet light having a cumulative light amount of 300 mJ/cm 2 using a high pressure mercury lamp to form a thick film.

A 17 μm hard coating. In this manner, a hard coat film of the example was produced. [Comparative Example 1] The same procedure as in Example 1 was carried out except that the following reactive cerium oxide (manufactured by Dainippon Ink and Chemicals, Inc., trade name "GRANDIC PC-4131") was used instead of the above mixture. The hard coat film of this comparative example. Reactive cerium oxide: poly bismethyl methoxy olefin unit: 3 acryloyl 2 - hydroxy-propoxy propyl fluorene unit: 2-propenyl hydrazine - 3 - hydroxy - propoxy propyl Oxygen firing unit (weight ratio) = 55 : 36 : 9. [Comparative Example 2] This Comparative Example was produced in the same manner as in Example 1 except that the following reactive non-oxidation # (manufactured by Dainippon Ink and Chemicals, Inc., trade name "GRANDICPC_4151") was used instead of the above mixture. Hard coated film. Reactive sulphur dioxide eve: poly dimethyl weiwei unit: methyl PEG containing acetamino group at the end _ money burning unit: terminal methyl group containing polyethylene glycol (10) Wei material element: end Polyethylene glycol containing a propylene (tetra) group, a trans group and a phase group-based group (weight: 15:8:13. 33 201026764 [Comparative Example 3] Except for the use of the following ultraviolet curing resin (Daily Ink Chemical Industry) Hard of the comparative example was produced in the same manner as in Example 1 except that the product name was "GRANDIC PC-1070", the solid content: 66% by weight, and the thickness of the hard coat layer was changed to 20 μm. Film coating Dipentaerythritol acrylate (18 parts by weight) Aliphatic polyurethane acrylate (36 parts by weight) Pentaerythritol diacrylate (〇_5 parts by weight) Pentaerythritol triacrylate (9 parts by weight) Pentaerythritol tetraacrylate (15 Weight component) A mixture of a polymer and a copolymer containing a repeating unit represented by the following general formula (7) (21 parts by weight) Photopolymerization initiator: a total of 3 parts by weight of a product name "Irgacurel 84" (Ciba Specialty Ch) Amicals Holding Inc. and the trade name "LucirinTPO" (BASF Du) Mixed solvent: butyl acetate: ethyl acetate (weight ratio) = 89 : u [Chemical 13] Λ CH2 - c

c=o

I O-R2

In the above formula (7), 'R1 is -H or -CH3, R2 is _CH2CH2OX or a group represented by the following general formula (8), and the above X is or is represented by the following general formula (9) 34 (8) 201026764 Acryl sulfhydryl group [Chem. 14] -CH2 — CH~CH2—0 ο

I

X In the above general formula (8), the above X is -H or an acryl fluorenyl group represented by the following general formula (9), and the above X may be the same or different. [化15] -C - CH zCH, (9)

II 〇 [Comparative Example 4] A hard coat film of this comparative example was produced in the same manner as in Comparative Example 3 except that the thickness of the hard coat layer was changed to 15 μm. Each of the obtained hard coat films of the examples and the comparative examples thus obtained was subjected to measurement or evaluation of various characteristics. The results are shown in Table 1 below. [Table 1] Thickness (um) of reactive ceria hard coat layer Cursity value of rubbing pen hardness Example 1 PC-4100 17 A 5H A (74.4 mm) Comparative Example 1 PC-4131 17 C 5H A (73.9 mm) Comparative Example 2 PC-4151 17 C 5H A (74.0 mm) Comparative Example 3 PC-4100 20 A 4H C (82.5 mm) Comparative Example 4 PC-4100 15 A 3H B (78.9 mm) As shown in Table 1 above As shown, the hard coat film of Example 1 has good scratch resistance, and 35 201026764 has a high penetard hardness and good curling properties. On the other hand, in the comparative state and the comparative example 2, the hard coating was high in pencil hardness, but scratch resistance. In addition, the hard coat film of Comparative Example 3 was excellent in abrasion resistance, but the pencil hardness was low and the curl property was poor. . The hard coat film of Comparative Example 4 was excellent in scratch resistance, but the hardness of the recording pen was low and the pencil hardness was slightly inferior. [Industrial Applicability] The hard coat film of the present invention using the composition for forming a hard coat layer of the present invention has sufficient hardness, and curling and cracking due to hardening shrinkage of the hard coat layer are suppressed. And it is excellent in resistance to rubbing. Therefore, the hard coat film of the present invention is suitable for use in various types of image display devices such as optical components such as a button, CRT, LCD, PDP, and ELD, and is not limited, and can be applied to a wide range of fields. BRIEF DESCRIPTION OF THE DRAWINGS The schematic view is a schematic sectional view showing an example of the hard-coated chess of the present invention. · Fig. 2 is a view showing the hard coating of the present invention_Other exemplary mode breaks [Main component symbol description] Lu 10, 20... Hard coated film 11, 21··· Transparent plastic substrate 12, 22... Hard coated Layer 23...antireflection layer 36

Claims (1)

201026764 VII. Patent application scope: 1. A composition for forming a hard coat layer, a composition for forming a hard coat layer for forming a hard coat layer, characterized by containing the following components (A) and (B) And (C) component, (A) component: a hardening compound containing a group of at least one of an acrylate group and a methacrylate group (B) A particle which is modified by an organic compound containing a polymerizable unsaturated group on the surface of the inorganic oxide particle (C) Component: a reactive cerium oxide containing a compound represented by the following general formula (1), [Chemical Formula 1] =:?'_' The substituent having the money-burning structure, and the substitution base of at least two of the methacrylic acid 81 group and the third active hydrogen are the same or different. For the substituent, each R may be 2. The structure of the hard-coat layer formed by the component (C) as described in the first paragraph of the application of the patent application, which is represented by the following general formula (2), 37 201026764 [Chemical 2] The composition for forming a hard coat layer according to the first aspect of the invention, wherein, in the R of the general formula (1), the substituent having a decane structure has a general formula (3): Structure, [chemical 3] In the above general formula (3), η is an integer of 1 or more. 4. The composition for forming a hard coat layer according to the first aspect of the invention, wherein, in the R of the general formula (1), the substituent containing the active hydrogen has a substituent represented by the following general formula (4). 【化4】 (4) The composition for forming a hard coat layer according to the first aspect of the invention, wherein the substituent of the above-mentioned acrylate group in the R of the general formula (1), 38 (5) 201026764 has the following The substituent represented by the general formula (5), [Chem. 5] OfCH, 0 r〇-h ο CH, |_0-C-CH=CH, in the above general formula (5), m and n are each 1 to 10, respectively. Integers can be the same or different; 1 is an integer from 1 to 5. 6. The composition for forming a hard coat layer according to the first aspect of the invention, wherein the (Β) component has a weight average particle diameter of 200 nm or less. 7. The composition for forming a hard coat layer according to claim 1, wherein the component (B) contains a group consisting of titanium oxide, oxidation, oxidized oxidized, zinc oxide, tin oxide, and cerium oxide. At least one type of microparticles are selected. 8. The composition for forming a hard coat layer according to the first aspect of the invention, wherein the component (B) is mixed in a range of 100 to 200 parts by weight based on 100 parts by weight of the component (A). 9. The composition for forming a hard coat layer according to the first aspect of the invention, further comprising the component (D), wherein the component (D) is a diol compound represented by the following general formula (6). Γ3 CH2=CH-CfO-CH2-C-CH r . 0 \ CH, In the above general formula (6), m and η are each an integer of 1 or more, and may be the same as 39 201026764. 10. The composition for forming a hard coat layer according to claim 9, wherein the component (C) and the component (D) are in a total amount of 0.01 to 10 parts by weight based on 100 parts by weight of the component (A). The range is mixed. 11. A hard coat film which is a hard coat film having a hard coat layer on at least one side of a transparent plastic film substrate, characterized by The hard coat layer is formed by the composition for forming a hard coat layer according to the first aspect of the invention. 12. The hard coat film according to claim 11, wherein the hard coat layer has a thickness in the range of 10 to 50 μm. 13. The hard coat film according to claim 11, wherein the hard coat layer has a hardness of 4H or more at a weight of 500 g as defined in JIS Κ 5600-5-4. 14. The hard coat film according to claim 11, wherein the outer surface of the hard coat layer is laminated with an antireflection layer. An optical element characterized in that a hard coat film according to claim 11 is laminated on at least one side of the optical member. 16. An image display apparatus characterized by comprising the hard coat film of claim 11 of the patent application. 17. An image display apparatus comprising the optical element described in claim 15 of the patent application. 40