TW201030108A - Composition for forming hard-coat layer, hard-coat film, optical element and image display (I) - Google Patents

Abstract

The invention provides a composition for forming a hard-coat layer, and a hard-coat film, capable of obtaining the hard-coat layer having enough hardness, excellent scratch resistance and excellent antifouling property. The invention applies the composition for forming the hard-coat layer on at least one surface of a transparent plastic film substrate 11 so as to form the hard-coat layer 12, the composition for forming the hard-coated layer containing (A) constituent: a hardening type compound containing at least one group of acrylic acid ester group and methacrylic acid ester group; (B) constituent: particles, in which the surfaces of inorganic oxide particles are modified by organic compounds that contain polymeric unsaturated groups and the weight average particle diameter is below 200nm; (C) constituent: reactive fluorine compound, and (D) constituent: reactive silicon compound.

Description

201030108 VI. Description of the Invention: [Ming ϋ-ϋ. 4 Stomach] 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. L· «tr Background of the Invention With the advancement of technology in recent years, video display devices have been developed in addition to the CRT (Cathode Ray Tube) in the past, such as liquid crystal display (LCD), plasma display (PDP) and electric field light-emitting display (ELD). Out, and it has been put into practical use. Among them, 'LCDs are accompanied by innovations in technology related to high viewing angle, high definition, high-speed responsiveness, color reproducibility, etc., and applications using Lcd are also expanded from pen-type 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 disposed so as to form a gap therebetween with the spacer as an intermediate, and the liquid crystal material is injected and sealed between the gaps of the glass substrate. 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 in which a hard coat layer is formed on one or both sides of a transparent plastic film substrate is usually used. 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. Hard coated films are required to improve scratch and stain resistance. Here, in order to improve the scratch resistance and the antifouling property of the hard coat layer, a hard coat layer using a hardenable composition containing a compound having a fluorine atom and an atom of any one of the atoms of the atom is proposed (see, for example, Patent Literature) 1). In addition, it is also proposed to add a smectite compound or a fluorine-based compound to the hard coat layer, and the ratio 6 of the surface of the hard coat layer or the fluorine atom is set to a predetermined range (see, for example, Patent Document 2). However, due to the diversity of LCD applications, the variety of opportunities for surface scratches or attachment of artifacts is also assumed. Along with the diversification of the aforementioned applications, a higher level of scratch resistance and stain resistance, as well as the persistence of such characteristics, are required. CITATION LIST Patent Literature [Patent Document 1] JP-A-2003-335984 (Patent Document 2) JP-A-H07-264281A In order to provide a hard coat layer-forming composition which can obtain a hard coat layer having sufficient hardness, excellent scratch resistance, and excellent antifouling properties. Further, an object of the present invention is to provide a hard coat film which has sufficient hardness, is excellent in scratch resistance, and is excellent in antifouling property, and an optical element and an image display apparatus using the film. Means for Solving the Problem 201030108 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 component (A). , (B) component, (C) component and (D) component. (A) Component: a hardening type compound (B) containing a group of at least one of an acrylate group and a thiol acrylate group. Component: The surface of the inorganic oxide particle is modified by an organic compound containing a polymerizable unsaturated group. Particles having a weight average particle diameter of 200 nm or less (C) Component: Reactive fluorine compound (D) Component: Reactive hydrazine compound The hard coat film of the present invention is a hard coat film on at least one side of a transparent plastic film substrate, and has a hard coat layer. A hard coat film of a layer characterized in that the hard coat layer is formed of the above-described composition for forming a hard coat layer of the present invention. The optical element of the present invention is characterized in that it laminates the aforementioned hard coat film of the present invention on at least one side of the optical member. The image display device of the present invention is characterized in that it comprises the above-described hard coat film of the present invention or the optical element of the present invention. Advantageous Effects of Invention The hard coat of the present invention formed by the composition for forming a hard coat layer of the present invention has the above-mentioned four components being combined with each other to have sufficient hardness, excellent scratch resistance, and excellent antifouling property. . According to the hard coating film of the present invention, it is difficult to adhere to the surface on a long-term use surface, and the dirt can be easily erased even in the case where dirt is attached. Since the hard-coated enamel of the present invention is excellent in the rubbing property, it is difficult to attach the mark to the 201030108 at the time of erasing. Therefore, the optical element and the image display apparatus using the hard coat film of the present invention can maintain good characteristics. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of a hard coat film of the present invention. C. Embodiment 3 In the composition for forming a hard coat layer of the present invention, the component (C) may have a structure represented by the following general formula (1), and the following general formula (1) Wherein at least one R is a substituent having a fluoroalkyl group, and at least one R is a substituent having at least one of an acrylate group or a methacrylate group. 【化1】

I (1)

R

In the composition for forming a hard coat layer of the present invention, the substituent containing the fluoroalkyl group in R of the above general formula (1) may have a structure represented by the following general formula (2). The structure represented by the following general formula (2) has a perfluoropolyether unit (-CF3-CF2-(O-CF2-CF2-CF2)n-〇-CF2-CF3) at its end. In the perfluoropolyether unit, η is an integer of 1 or more. [Chemical 2] 0 -(CH2)6-NH-C-0-CH2-CF2-CF2-(〇-CF2-CF2-CF2)n-〇-CF2-CF3 (2) 201030108 Hard coat formation of the present invention In the composition, the substituent containing the acrylate group in R of the above general formula (1) may have, for example, a substituent represented by the following general formula (3). (0) II 0 (II) -(CH2)6-NH-C-0-CH2-CH2-0-C-CH=CH2 (3) The above component (C) is represented by the above general formula (1). In the above R of the general formula (1), a substituent containing a fluoroalkyl group having the structure represented by the above general formula (2), and two acrylic groups having the structure represented by the above general formula (3) are preferable. a substituent of an ester group. In the composition for forming a hard coat layer of the present invention, the component (D) may have a structure represented by the following general formula (4). In the following general formula (4), 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. The substituents may be the same or different from each other. 【化4】

In the composition for forming a hard coat layer of the present invention, the component (D) may have a structure represented by the following general formula (9). The structure represented by the following general formula (9) is regarded as (6-isocyanatohexyl)isocyanurate 201030108 ((6-isocyanatohexyl) isocyanurate unit (a) [Chemical 5]

O (CHZ)

II i-NH-C- (95 O II / -C-NH-{CH2)6

N

ON, O li (CH2)6-NH-C- unit u) The composition for forming a hard coat layer of the present invention, in the R of the above general formula (4), may have a substituent of the above-described azepine structure. There is, for example, a structure represented by the following general formula (5). a structure represented by the following general formula (5), which has a polydimethylsiloxane siloxane unit (c) at its end, and the unit (c) is bonded to the methyl hydroxypropyl siloxane unit (b), and the unit (b) The hydroxy group is bonded to the isocyanate group at the terminal of the (6-isocyanatohexyl)iso-cyanurate of a part of the above unit (a). In the polybismethylsiloxane unit (c), η is an integer of 1 or more, preferably 1 to 7. [6] 0 ii .(CH2)6-NH.C-〇.CH2-CH2-CH2

Part (a) of the unit <a) (C) (5) 201030108 In the composition for forming a hard coat layer of the present invention, the substituent of the above-mentioned general formula (4) may contain a substituent of the active hydrogen. There are, for example, a substituent represented by the following general formula (6). In the substituent represented by the above general formula (6), the terminal isocyanate group of the (6-isocyanatohexyl)isocyanurate which is a part of the above unit (a) becomes a thiol group. Further, in the substituent represented by the above general formula (6), the above-mentioned rebel group may be converted into an amine group by a decarboxylation reaction. [化7] 0

II -iCH2)6-NH-C-0-H (6) *<-................................ A part of the unit (a) is a composition for forming a hard coat layer of the present invention, and the substituent containing the acrylate group in the rule of the above general formula (4) may have, for example, the following general formula. (7) The structure of the representation. The structure represented by the above general formula (7), which contains an aliphatic polyester unit (d) having an acrylate group at the end, and the above-mentioned unit (sentence, (particular to the heterogeneous hexyl group) of the above-mentioned unit (4) The isocyanate group at the terminal end of the trimeric acid is bonded to the amino carboxylic acid ethane. In the above formula (7), m and η are each an integer of 1 to 1 ,, which may be the same or different; (4) ～5 Integer 0 {cH2^NH-G(〇{cH2fm〇-c|CH^ 0TCH2X,〇m Ο II -c-ch=ch2

(d) (7) The component (D) having the structure represented by the above-mentioned general formula (9), and the substituent (G) having a structure represented by the above-mentioned general formula (5) to (7); When a derivative of isomeric cyanurate is used, the former S - , u, 乂 兀 (a). The above soap (b). The above unit (c): the proportion of the above unit (d) (Mohr ratio) When the unit (a) is set to 1 ,, the unit (b) is, for example, a range of 丨 to ribs, which is preferably in the range of 1 to 60, and the unit (4) is, for example, 10 to 4 〇〇. The range is conveniently in the range of 10 to 300 'the aforementioned unit (4) $ for example, ^ ~ 100 range, and is suitable for the range of 5 to 50. In the present invention, the ratio (molar ratio) of each component (unit) of the component (D) can be calculated from, for example, the integral curve of the spectrum. The weight average molecular weight (Mw) of the component (D) is, for example, in the range of 5 Å to 150,000, preferably in the range of 2 Å to 1 Torr. The aforementioned weight average molecular weight (MW) can be measured by, for example, gel permeation chromatography (Gpc).仃 A compound having the structure represented by the above general formula (1) is used as the component (C), and a compound having a structure represented by the above general formula (4) is preferably used as the component (D). By using a compound having a similar structure, it is presumed that it is easy to embody the respective functions in the formed hard coat layer. However, the present invention is not limited by this speculation. In the composition for forming a hard coat layer of the present invention, the weight average particle diameter of the component (B) is 从 from the viewpoint of preventing scattering of light, preventing a decrease in transmittance of the hard coat layer, preventing coloring and transparency, and the like. The range of ~(10)(4) is better. The weight average particle diameter can be measured by, for example, the method described in the examples below. In the composition for forming a hard coat layer of the present invention, the component (B) may, for example, be a fine particle such as titanium oxide, cerium oxide, aluminum oxide, oxidized iron, tin oxide or cerium oxide 201030108. Among them, it is preferable to use fine particles of titanium oxide, cerium oxide (Eryx emulsifier), aluminum oxide, zinc oxide, tin oxide, and cerium oxide. One type may be used alone or two or more types may be used. In the composition for forming a hard coat layer of the present invention, the component (B) is preferably in a range of from 100 to 200 parts by weight based on the weight of the above (A), and is in the range of from 100 to 200 parts by weight. Ingredients for the composition for forming a hard coat layer of the present invention,

100 parts by weight, the above-mentioned (C) component is in the range of 0.05 to 0.4 parts by weight, and the above-mentioned (D) component is mixed in the range of 〇. 〇 5 to 1 by weight. The step contains the following (6) The composition for forming a hard coat layer of the invention is preferably a component. (E) component: a diol compound represented by the following general formula (8) [9] (8) I ίΗί V \ CH2=CH-C· -〇-CH2-C-CH2|〇-CH2-CH- C--ch=ch2 ι\ ι〇Λ In the above formula (8), m and n are each an integer of 1 or more, and may be the same or different. In the composition for forming a hard coat layer of the present invention, the component (c) is mixed in a range of 0.05 to 0.4% by weight based on 100 parts by weight of the above (Α) component, and the component (D) and the above ( Ε) The ingredients are mixed in a range of 〇.1 to 1 by weight. In the hard coat film of the present invention, the outermost layer of the hard coat layer is analyzed by 201030108 ESCA (Electron Spectroscopy for Chemical Analysis), and the fluorine atom strength from the reactive fluorine compound is in the range of 5 to 30%, and The strength of the ruthenium atom derived from the reactive ruthenium compound is preferably in the range of 0.2 to 10%. If it is within this range, the scratch resistance and the antifouling property can be made better. Incidentally, the amount of the reactive fluorine compound or the reactive ruthenium compound to be added tends to be inconsistent with or not necessarily proportional to the above-mentioned respective atomic strengths of the outermost layer. For example, even in the case where a hard coat layer is formed using the composition for forming a hard coat layer of the same composition, if the film thickness of the hard coat layer is different, the above-mentioned respective atomic strengths in the outermost layer may be different. Therefore, when the hard coat layer forming composition of the present invention is used to obtain a hard coat film having better characteristics, it is effective to take an evaluation of the characteristics of each of the above atomic strengths. The fluorine atom strength is preferably in the range of 10 to 30%, more preferably in the range of 15 to 30%. The intensity of the aforementioned Shi Xi atom is 〇·2~8. /. The range is better, and the range of 〇 2 to 6% is better. In the hard coat film of the present invention, the thickness of the hard coat layer is not particularly limited, and the most suitable thickness can be set in accordance with the thickness of the transparent plastic film base material, etc., for example, in the range of 12 to 50 μm. By setting the aforementioned thickness to the above range, the reduction in hardness is not caused, and the occurrence of curling and cracking of the hard coat film can be prevented more effectively. The aforementioned thickness is preferably in the range of Μ 25 25 μm, more preferably in the range of 14 Ι 8 μm. In the hard coat film of the present invention, the surface hardness of the surface of the hard coat layer is preferably 4 Å or more in accordance with the pencil hardness of 500 g in accordance with JIS κ 5600-5-4. 12 201030108 In the hard coat film of the present invention, the surface free energy of the surface of the hard coat layer is preferably in the range of 15 to 25 mW. Surface free energy means the value calculated from the two components of the water/hexadecane of Kaelble Uy theory. The surface free energy is preferably in the range of 15 to 22 mJ/m2, more preferably in the range of 15 to 2 GmW. The surface free energy value is calculated from the value of the contact angle between the water and the sixteen lang, and can be calculated automatically by the "automatic contact angle meter DM7" manufactured by Kyowa Interface Science Co., Ltd.

In the hard coat film of the present invention, it is preferred that the hard coat layer further contains fine particles. Next, the present invention will be described in detail. However, the present invention is not limited to the following description. The hard coat film of the present invention is a one having a hard coat layer on one or both sides of a transparent plastic film substrate. The transparent plastic film substrate is not particularly limited, but the light transmittance of visible light is excellent (preferably, the light transmittance is 9 G% or more), and the transparency is excellent (the haze value is preferably 1% or less). For example, a transparent (iv) film substrate described in Japanese Patent Laid-Open Publication No. 2008-90263. As the transparent plastic film substrate, a material having less optical birefringence can be suitably used. The hard coat film of the present invention can also be used as a 'for example, a protective film in a polarizing plate. In this case, the transparent plastic film substrate is polymerized with cellulose triacetate (TAC) and polycarbonate 'propionate. A film formed of a polyolefin having a ring shape or a norbornene structure is preferred. Further, in the present invention, the transparent plastic film substrate may be the polarizer itself. In the case of such a composition, since the protective layer composed of TAC or the like is not required, the structure of the polarizing plate can be simplistic by 13 201030108, so that the number of manufacturing steps of the polarizing plate or the image display device can be reduced, and the production efficiency can be 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 functions as a conventional protective layer. On the other hand, in the case of such a composition, the hard coat film functions as a cover plate mounted on the surface of the liquid crystal cell. In the present invention, the thickness of the transparent plastic film substrate is not particularly limited. The thickness is, for example, preferably in the range of 10 to 500 μm, preferably in the range of 20 to 300 μm, and most preferably in the range of 30 to 200 μm, in consideration of workability and thinness such as strength and workability. . The refractive index of the above transparent plastic film substrate is not particularly limited. The refractive index is, for example, in the range of 1.30 to 1.80, preferably in the range of 1.40 to 1.70. The hard coat layer is formed using a composition for forming a hard coat layer containing the above (Α) component, the above (Β) component, the component (C) and the component (D). _

For the above (Α) component, for example, a curable 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 above-mentioned (A) component can be exemplified by V, for example, Shixi resin, polyester resin, polyether resin, epoxy resin, polyurethane resin, alkyd resin, spiroacetal resin, polybutylene An oligomer or prepolymer such as an acrylate group or a methacrylate group of a polyfunctional compound such as a polybutadiene resin, a polythiol polyene resin or a polylactic acid. These may be used alone or in combination of two or more. The above component (A) can also be used, for example, to contain an acrylate group and a 14 201030108

A reactive diluent for the group of at least one of the acrylate groups. The above reactive diluent contains, for example, a monofunctional acrylate, a monofunctional methacrylic acid, a polyfunctional acrylic acid, a polyfunctional methacrylic acid S, and the like. The aforementioned monofunctional acrylate contains, for example, an acrylate of an ethylene oxide-modified phenol, an acrylate of a propylene oxide-modified phenol, an acrylate of an oxirane-modified phenol, and a propylene oxide-modified phenol. Acrylate, 2-ethylhexyl carbitol acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, acrylic acid with acetoacetate, propyl acrylate, hydroxybutyl acrylate, hydroxyhexyl acrylate , diethylene glycol monoacrylate, triethylene glycol monoacrylate, tripropylene glycol monoacrylate, and the like. The monofunctional thiol acrylate includes, for example, a methacrylate of an ethylene oxide-modified phenol, a methacrylate of a propylene oxide-modified phenol, a methacrylate of an ethylene oxide-modified phenol, Propylene oxide modified methyl acrylate of nonylphenol, 2-ethylhexyl carbitol methacrylate, isobornyl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl methacrylate, Hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyhexyl methacrylate, diethylene glycol monomethacrylate, triethylene glycol monomethacrylate, tripropylene glycol monomethacrylate, and the like. The polyfunctional acrylate contains, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylic acid vinegar, tripropylene glycol diacrylic acid vinegar, tetrapropylene glycol dipropionate S, Polypropylene glycol diacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, ethylene oxide modified neopentyl glycol diacrylate Ethylene oxide modified bisphenol A diacrylate, propylene oxide modified bisphenol A diacrylate, ethylene oxide modified hydrogenated bisphenol A 15 201030108 diacrylate, trimethylolpropane Diacrylate, trimethylolpropane allyl ether diacrylate, trishydroxypropyl propane triacrylate, ethylene oxide modified trishydroxypropyl propane triacrylate, propylene oxide modified trishydroxypropyl Burning triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetrapropyl acrylate, dipentaerythritol hexaacrylate, and the like. The aforementioned polyfunctional methacrylate contains, for example, diethylene glycol dimethacrylate, triethylene glycol dimercapto acrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol II Methacrylate, polypropylene glycol dimercapto acrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimercapto acrylate, ring Ethylene oxide modified neopentyl glycol dimercapto acrylate, ethylene oxide modified bisphenol A dimethacrylate, propylene oxide modified bisphenol A dimethacrylate, epoxy B Alkyl modified hydrogenated bisphenol A dimethacrylate, trimethylolpropane dimercapto acrylate, trimethylolpropane allyl dimercapto acrylate, trishydroxypropyl propane tridecyl acrylate, Ethylene oxide modified trishydroxypropyl propane trimethacrylate, propylene oxide modified trimethylolpropane trimethacrylate, pentaerythritol tetramethyl propionate, dipentaerythritol tetramethacrylate, Dipentaerythritol hexamethacrylate or the like. The reactive diluent is preferably a trifunctional or higher acrylate or a trifunctional or higher methacrylate. This is because the hardness of the hard coat layer can be made better. Further, as the component (A), for example, butanediol glycidyl ether diacrylate, isomeric cyanuric acid acrylate, isomeric cyanuric acid methacrylate or the like can be mentioned. The component (A) may be used singly or in combination of two or more. The above component (B) is as described above. Among the components (B), the inorganic oxide 16 201030108 particles may be, for example, microparticles such as oxygen cut, titanium oxide, oxidized crystal, sulfurized tin oxide, or cerium oxide. Among them, fine particles of oxidized stone (cerium dioxide), titanium oxide 'oxidized|g, zinc oxide, tin oxide, and zirconium oxide are preferred. These may be used alone or in combination of two or more. In the composition for forming a hard coat layer of the present invention, the weight average particle diameter of the component (B) is as follows: from the viewpoint of preventing scattering of light, preventing the transmittance of the hard coat layer from being lowered, preventing coloring and transparency, and the like. The following range, that is, the nanoparticle of the δ stomach. The weight average particle diameter can be measured by, for example, the method described in the examples below. The weight average particle diameter is preferably in the range of 1 nm to 100 nm. In the above-mentioned (B) component, the inorganic oxide particles are bonded to the organic compound containing a polymerizable unsaturated group (surface modification). The polymerizable unsaturated group is subjected to reaction hardening with the component (A) to increase the hardness of the hard coat layer. The aforementioned polymerizable unsaturated group is, for example, an acrylonitrile group, a methacrylic group, a vinyl group, an acryl group, a butadienyl group, a styrene group, a ethyl hexyl group, a cinnamyl group, a maleate group, Acrylamine is preferred. Further, the organic compound containing the above polymerizable unsaturated group is preferably a compound having a stanol group in the molecule or a compound which is decomposed by hydrolysis to form a calcined alcohol group. The organic compound containing the above polymerizable unsaturated group is preferably one containing a photo-sensitive group. The amount of the component (B) to be mixed is preferably in the range of 100 to 200 parts by weight based on 1 part by weight of the component (A). By setting the amount of the component (B) to be 100 parts by weight or more, it is possible to effectively prevent the occurrence of curling and cracking of the hard coat film, and the transmission is set to 200 parts by weight or less, thereby producing scratch resistance 17 201030108 And the pencil hardness is high. The compounding amount of the component (B) is preferably in the range of 120 to 180 parts by weight based on 1 part by weight of the component (A). It is possible to adjust the mixing amount of the above-mentioned (B) component by adjusting the refractive index of, for example, the aforementioned hard coat layer. From the viewpoint of preventing the occurrence of interference fringes at the interface between the transparent plastic film substrate and the hard coat layer, it is preferable to reduce the difference in refractive index between the transparent plastic film substrate and the hard coat layer. The aforementioned interference fringes are phenomena in which the reflected light of the outdoor light incident on the hard coat film exhibits a rainbow hue. Recently, most of the three-wavelength fluorescent lamps with excellent definition have been used in offices and the like. Under the aforementioned three-wavelength fluorescent lamp, the aforementioned interference pattern is remarkably exhibited. In order to prepare the composition for forming a hard coat layer, it is preferred to adjust the mixing amount of the component (B) to reduce the difference in the refractive index. The difference in refractive index is preferably 〇.04 or less, preferably 0.02 or less. In the case of a ship, for example, a PET film (refractive index of about 1.64) is used as the transparent plastic film substrate, and titanium oxide is used in the component (B), relative to the composition for forming a hard coat layer. By mixing all of the resin components to about 30 to 40% by weight, the difference in refractive index can be controlled to 0.02 or less, and generation of interference fringes can be suppressed. In addition, for example, when a TAC film (refractive index: about 1.48) is used as the transparent plastic film substrate, cerium oxide (cerium oxide) is used for the component (B), and the composition for forming a hard coat layer is used. All the resin components in the mixture can be mixed to a thickness of about 35 to 45 wt/❶, whereby the difference in refractive index can be controlled to be less than 〇.2, and the occurrence of interference fringes can be suppressed. The component (C) and the component (D) described above are as described above. By using the aforementioned 201030108 component, the surface free energy value of the obtained hard coat layer is lowered, and the antifouling property of the aforementioned hard coat layer is improved. On the other hand, if the amount of the component (c) is excessively mixed, the scratch resistance of the obtained hard coat layer tends to be lowered. Further, since the component (D) is used, for example, the surface structure of the hard coat layer formed becomes rigid, and the smoothness is improved, and the scratch resistance is excellent. On the other hand, if the amount of the component (D) is excessively mixed, the antifouling property of the obtained hard coat layer tends to be lowered. The mixing ratio of the component (C) to the component (D) is preferably in the range of 0.05 to 0.4 part by weight based on 100 parts by mass of the component (A), and the component (C) is in a range of 0.05 to 0.4 part by weight. The component (D) is in the range of 0.05 to 1.0 part by weight; preferably, the component (C) is in the range of 0.1 to 0.3 part by weight, and the component (D) is in the range of 0.2 to 1.0 part by weight. In the hard coat film of the present invention, for example, a composition for forming a hard coat layer in which the above four components are dissolved or dispersed in a solvent is prepared, and the hard coat layer is coated on at least one surface of the transparent plastic film substrate. After the coating composition is formed into a coating film, the coating film is cured to form a hard coat layer. The aforementioned solvent is not particularly limited. The aforementioned solvent contains, for example, dibutyl ether, dimethoxy decane, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-two-degree smoldering (l, 4- Dioxane), 1,3 -dioxolane, 1,3,5-trioxane, 1,4,5-trioxane, tetrahydrofuran, acetone, methyl ethyl ketone (MEK) , diethyl ketone, diacetone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, ethyl formate, propyl citrate, n-decyl formate, methyl acetate, ethyl acetate, C Methyl ester, ethyl propionate, n-amyl propionate, n-amyl acetate, acetoacetone, diacetone alcohol, decyl acetate, ethyl acetate, methanol, ethanol, 1-propanol, 2 -propanol, pudin 19 201030108 Alcohol, 2-butanol, 1-pentanol, 2-mercapto-2-butanol, cyclohexanol, isobutyl acetate, decyl isobutyl ketone (MIBK), 2- Octanone, 2-pentaline, 2-hexanone, 2-heptanone, 3-heptanone, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycolate Ether, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, and the like. These can be used alone or in combination of two or more. As described above, the composition for forming a hard coat layer' is preferably further contained in the component (E). In the case of using the component (E), it is preferred to prepare a mixture of the component (E) and the component (D) in the preparation of the composition for forming a hard coat layer. _ A material containing the aforementioned mixture, for example, a sleek product may 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 average molecular weight (Mw) of the material containing the aforementioned mixture is not particularly limited. _ Since the above-mentioned (E) component is used, for example, the surface of the hard coat layer formed becomes rigid, and the smoothness is improved, so that the scratch resistance becomes excellent.

From the viewpoints of resistance to rubbing resistance and antifouling property, the mixing ratio of the above component (E) is preferably '100 parts by weight relative to the above component (A), and the above (C) component is 0〇5 Q 〇.4. In the range of the weight fraction, the component (D) and the component (E) are in the range of 0.1 to 1 part by weight in total; preferably, the component (C) is in the range of 0.1 to 3 parts by weight, and the foregoing The component (D) and the component (E) described above are in the range of 0.2 to 1 part by weight. As described in the composition for forming a hard coat layer, it may also contain a pigment, a filler, a dispersant, a plasticizer, a UV absorber, a surfactant, an antioxidant, a shake-reduction adhesive, as long as it does not impair the performance. For the additives (Thixotropic 20 201030108 agem), the additives may be used singly or in combination of two or more. By adding fine particles to the composition for forming a hard coat layer, a hard coat film having anti-glare properties can be further obtained. The fine particles impart anti-glare properties after forming the uneven shape on the surface of the hard coat layer formed as described above, and the haze of the hard coat layer is controlled to be the main function. The haze of the front (hard) can be set by controlling the difference in refractive index between the microparticles and the composition for forming the hard coat layer. It depends on the former, such as inorganic microparticles and organic microparticles. The inorganic fine particles are not particularly limited, and examples thereof include oxidized fine particles, titanium oxide fine particles, oxidized fine particles, oxidized fine particles, tin oxide fine particles, calcium carbonate fine particles, barium sulfate fine particles, talc' micro particles, kaolin particles, sulfuric acid. Calcium microparticles, etc. Further, the organic fine particles are not particularly limited, and examples thereof include poly-f-acrylic acid methyl vinegar resin powder (PMMA fine particles), Shishi resin powder, polystyrene resin powder, polycarbonate resin powder, and styrene-acrylic resin powder. Benzoquinone resin (BenZ〇gUanamine resin) powder, melamine resin powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimine resin powder, polyvinyl fluoride resin powder Wait. These inorganic fine particles and organic fine particles may be used alone or in combination of two or more. In the composition for forming a hard coat layer, when the component (A) contains a photocurable compound, for example, a conventionally known photopolymerization initiator can be used as described in JP-A-2008-883-9. 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 mixing amount is preferably in the range of 1 to 25 parts by weight, preferably in the range of 1 to 30 parts by weight, based on 100 parts by mass of the above-mentioned 21 201030108. The method of applying the composition for forming a hard coat layer on the transparent plastic film substrate may be, for example, a spray coating method, a die coating method, or a spin coating method. Coating methods such as a method, a spray coating method, a gravure coating method, a roll coating method, and a bar coating method. 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 curing 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 active energies can be used in the aforementioned hardening method. The aforementioned activity can be preferably ultraviolet light. The energy light source is preferably a light source such as a high pressure mercury lamp, a halogen lamp, a xenon lamp, a metal tooth lamp, a nitrogen laser, an electron beam accelerator, 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 coloration of the formed hard coat layer 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 side of the transparent plastic film substrate. Further, the hard coat film of the present invention can also be produced by a production method other than the above method. 201030108 In the schematic sectional view of Fig. 1, the structure of the hard coat film of the present invention is shown in the 'n figure' as being easy to understand. The size, ratio, and the like of the respective constituent members are different from actual ones. As shown in the figure, in the hard coat film 1 , the hard coat layer 12 is formed on one side of the transparent plastic film substrate U. However, the present invention is not limited thereto. 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 base material. 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 structure in which a plurality of layers of two or more layers are laminated. In this case, at least the hard coat layer formed of the composition for forming a hard coat layer of the present invention may be located on the outermost surface. In the hard coat film of the present invention, at least one of the transparent plastic film substrate and the hard coat layer described above should be surface-treated. 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 subjected to surface treatment, the adhesion to the polarizer or the polarizing plate is further improved. The surface treatment just mentioned may be, for example, low pressure plasma treatment, ultraviolet irradiation treatment, corona treatment, flame treatment, acid or alkali treatment. The above transparent plastic film substrate is preferably treated with a base treatment when a TAC film is used. This alkali treatment can be carried out, for example, by bringing the surface of the TAC film into contact with an alkali solution, followed by washing with water and drying. As the alkali solution, for example, a potassium hydroxide solution or a sodium hydroxide solution can be used. The predetermined concentration (molar concentration) of the hydroxide ion of the alkali solution is preferably in the range of 〇.i to 3 0N (m〇)/L, preferably 0.5 to 2.0 N (mol/L·). range. For the transparent plastic thin film substrate, the hard coating film of the hard coating layer is formed on the surface of the transparent plastic film base 23 201030108, in order to prevent curling.

Since the hard coat layer is formed and the curling force cancels each other, the curling prevention can be carried out by bringing the other transparent plastic film agent into contact. Further, the above-mentioned transparent plastic film substrate may be formed by forming a hard coat film of the hard coat layer on one surface of the transparent material, or a transparent resin layer may be formed on the other surface. @ Occurs. Similarly, in order to prevent the occurrence of curling of the plastic film substrate, the transparent resin layer may, for example, be a layer containing a lion, a radiation hardening type, a thermosetting resin, and other reactive resin as a main component. Among them, a layer mainly composed of a thermoplastic resin is preferable. The hard coat film of the present invention can be usually bonded to an optical member for an LCD or an ELD by an adhesive or an adhesive, which is a side of the transparent plastic film substrate. 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. Polarizer - © General means a composition of a transparent protective film on one or both sides of the polarizer. The transparent protective film on both the inner and outer sides may be the same material or different materials on both sides of the polarizer. The polarizing plates are usually disposed on both sides of the liquid crystal cell. Further, the polarizing plate is disposed such that the absorption axes of the two polarizing plates are slightly orthogonal to each other. Next, the optical element of the hard coat film of the present invention is laminated, and a polarizing plate will be described as an example. The 24 201030108 hard coat film of the present invention is laminated with a polarizer or a polarizing plate by using an adhesive or a dry agent or the like, whereby a polarizing plate having the function of the present invention can be obtained. The polarizer is not particularly limited, and various materials can be used. The polarizing plate may, for example, be a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film or an ethylene vinyl acetate copolymer partially saponified film, or a dichroic dye. After the coloring matter is uniaxially stretched, a polyolefin-based oriented film such as a dehydrated material of polyvinyl alcohol or a dehydrochlorinated product of polyethylene gas 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 south molecular film described in JP-A-2001-343529 (W001/37007) is also known as the transparent protective film. The polymer film described in the above-mentioned 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 bond, and (B) a side chain having a substituted benzene. A polymer film formed of a resin composition of a phenyl group and a nitrile group thermoplastic resin of at least one of a phenyl group and an unsubstituted phenyl group. The polymer film formed of the resin composition may, for example, be a polymer comprising an alternating copolymer of isobutylene and N-methylmaleimide and a resin composition of a acrylonitrile-styrene copolymer. film. The polymer film can be produced by extrusion molding the resin composition into a film form. Since the phase difference of the above-mentioned polymer film is small and the photoelastic coefficient is small, when it is applied to a protective film such as a polarizing plate, defects such as color unevenness (mura) caused by stress can be eliminated. Top 25 201030108 The polymer film is excellent in humidity durability because of its low moisture permeability. The transparent protective film ' is preferably a film made of a cellulose resin such as TAC or a thin film made of a norbornene resin, from the viewpoints of polarization characteristics and durability. The commercially available product of the transparent protective film is, for example, "FUJITAC" (manufactured by Fujifilm Holdings Corporation), trade name "ZEONOR" (manufactured by Zeon Corporation), and trade name "ARTON" (manufactured by JIS Corporation). .

The thickness 'the transparent protective film' is not particularly limited. The thickness of the transparent film is expressed in the range of, for example, '1 to 500 μm' from the viewpoints of workability such as strength and workability, and film properties. 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 thickness is preferably in the range of 5 to 200 μm, preferably in the range of 10 to 150 μm. film

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 polarizer and a transparent protective film laminated on the hard coat film, or may be hard. The composition of the laminated polarizer and the transparent protective film is applied. The hard coat film of the present invention using the composition for forming a hard coat layer of the present invention and the use of a pure fiber element such as the thin polarizing plate can be suitably used in various image display devices such as liquid crystal display devices. According to the present invention, in addition to the use of the hard coat film of the present invention, the image display device of the present invention is in the form of a liquid crystal display device. Optical components such as a liquid crystal cell and a polarizing plate, and various components such as an illumination system (backlight, etc.) 26 201030108 p. The liquid crystal cell is not particularly limited. For example, in the present invention, the TN type, the STN type, and the π type are used. The liquid crystal display device is exemplified in the liquid crystal, and is limited in color, and can be displayed as h (five). The liquid crystal display device or the liquid crystal display device of the light system or the reflective plate is specially designed in the liquid crystal display device.

It can be the same or different when it is placed on one side or both sides of the liquid crystal unit it. Also, it can be placed in the center, for example, diffusing plate, anti-glare (insulting) ... =, protective plate, prism array, lens array plate _y ―), diffuser, f material, various optical components and optical components.

Add a drive circuit and so on. The aforementioned liquid crystal cell, and the like. The image display device of the present invention can be used in any suitable application. For example, an OA machine such as a personal computer, a notebook computer, or a copy machine can carry a household computer, a clock, a digital camera, a personal digital assistant (PDA), a portable game (four), a camera, a television, a microwave oven, and the like. Vehicles such as reversing monitors, monitors for car navigation systems, car audio and video, car monitors for commercial shops, display devices for surveillance monitors, surveillance monitors, nursing monitors, medical monitors, etc. Medical machines, etc. [Embodiment] Next, an embodiment of the present invention will be described together with a comparative example. 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 by the following methods or 27 201030108. (Thickness of Hard Coating Layer) The thickness of the hard coat film was measured using a Micro-gauge type thickness meter manufactured by Mitutoyo Co., Ltd., and the thickness of the transparent plastic film substrate was subtracted from the full thickness to calculate the hard coat layer. thickness. (Scratch resistance) The scratch resistance of the hard coat layer was evaluated by the following test contents. (1) A sample of 15 mm×50 mm was cut out from the center of the hard coat film, and the surface on which the hard coat layer was not formed was placed on the glass plate. Θ (2) On a smooth section of a cylinder with a diameter of 11 mm, uniformly install steel wool _00, with a load of 1.5 kg, repeatedly rubbing the surface of the sample one second at a speed of about i〇〇mm per second, The number of scratches on the surface of the sample was visually counted, and the following indicators were used for the determination. A : The number of scratches is 1 or less - B. The number of scratches is 11 or more and 29 or less C: The number of scratches is 30 or more (wrong hardness) Ο

A 100 mm x 50 mm sample was cut out and placed on a glass plate without h loading. The jis K was applied from the center of the hard coated film. The surface on which the hard coat layer was formed was in the shape of 5600-5-4 below (4) hardness. The pen hardness of 5 〇〇g is 5 〇〇g. The pen ("10)" manufactured by Mitsubishi Phillips Co., Ltd. (the Japanese Paint I Association of the Written Scratch Test was completed). (surface free energy)

28 201030108 Measure the contact angle of water and hexadecane and use the analytical software FAMAS to generate surface free energy. The calculation method uses a 2-component analysis based on the KaelbleUy theory. (Atomic strength was measured by ESCA) The atomic intensity was measured using "Quantum 2" manufactured by ULVAC-PHI Co., Ltd. The X-ray source is a single-color AIK a, and the X-ray output power is 30 W (15 kV). The measurement range is 2 〇〇 μηιφ, and the measurement angle is 45° to the surface of the sample. Energy correction was performed by correcting the peak of the C-C bond attributed to the Cls spectrum to 285.0 eV. A full-width scan was performed on any two points of the sample at 0 to llOOeV, and qualitative analysis was performed. A narrow scan of the detected elements is performed to calculate the elemental ratio (atomic%). The Si2p spectrum was subjected to waveform analysis using peaks of respective bonds belonging to the bifunctional ruthenium and the polyfunctional ruthenium and SiOx to calculate the intensity of the ruthenium atom derived from the reactive ruthenium compound. The atomic strength from the outermost surface of the sample to a depth of about 5 to 10 nm can be measured in accordance with the above conditions. (weight average particle diameter of particles (component (B))) The resin raw material containing the component (B) was diluted to a solid content concentration of 10% using ethyl ketone (MEK), and a dynamic light scattering type particle size distribution measuring apparatus was used ( LB-500, manufactured by Horiba, Ltd., and measured the particle size distribution. The weight average particle diameter was calculated from the obtained particle size distribution. (Weight average molecular weight) The weight average molecular weight was measured by gel permeation chromatography (GPC) using a polyethylene sample as a standard sample. Specifically, the measurement was carried out by the following apparatus and measurement conditions. 29 201030108 Analytical device: manufactured by TOSOH Co., Ltd., trade name "SC-8020" Column · ShowaDenko Co., Ltd., product name "Shodex" Column size: 20.0mm φχ500ιηπι Column temperature: Room temperature eluent: Tri-gas methane flow rate: 3.5 mL/min. inlet pressure: 70 kgf/cm2 (6.9 MPa) [Example 1] (Preparation of a composition for forming a hard coat layer) The surface of a particle was modified by using an organic compound containing a polymerizable unsaturated group. The nano cerium oxide particles (the component (B)) are dispersed, and the resin raw material (manufactured by JSR Corporation, trade name "Opstar-Z7540", solid content: 56% by weight, solvent: Butyl acetate / ethyl ketone (MEK) = 76 / 24 (weight ratio)). The resin raw material contains, as a total of (A) components: (B) component = 2:3, as a component (A) (ultraviolet curing type compound), dipentaerythritol and isophorone diisocyanate type polyurethane, as In the component (B), the surface of the cerium oxide microparticles (weight average particle diameter: 100 nm or less) is modified with an organic molecule. The refractive index of the hardened film of the above resin material was 1.485. The reactive compound (manufactured by Dankin Industry, Ltd., trade name "Optool (registered trademark DAC)" 'fixed open' was added to the resin (100% by weight) of the solid content of the resin material: 20 〇 / 〇 'solvent: 1H, 1H , 3H-tetrafluoropropanol) 〇.2 parts by weight, a reactive ruthenium compound (manufactured by Dainippon Ink and Chemicals Co., Ltd., trade name 201030108 "GRANDIC PC-4100") 0.5 parts by weight, and a photopolymerization initiator (Ciba)

The product of "Hergacurel 27", manufactured by Specialty Chemicals Holding Inc., was diluted with a butyl acetate to a concentration of 50% by weight to prepare a composition for forming a hard coat layer. In addition, the reactive fluorine compound is represented by the above formula (1), and R' of the above general formula (1) has a substituent containing a fluoroalkyl group having a structure represented by the above general formula (2). Two compounds containing a substituent of the acrylate group having the structure represented by the above general formula (3) are main components. Further, the above-mentioned reactive hydrazine compound ' contains a mixture of the component hydrazine, the component 2 and the solvent shown below. Component 1: The reactive cerium oxide represented by the above general formula (4) (containing XI: Χ2: Χ3: Χ4 (mole ratio) = 187: 39: 100: 57, the general formula (5) a polydimethyf siloxane unit (XI) of the unit (c) and a methyl hydroxypropyl siloxane unit (X2) of the unit (b) of the above general formula (5), The (6-isocyanatohexyl)isotrimeric cyanide unit (X3) of the above general formula (9) and the substituent (Χ4) of the unit (d) of the above general formula (7) (6·85) Weight component) Component 2: The disaccharide compound represented by the above general formula (8) (3.15 parts by weight) Solvent: ethyl acetate (90 parts by weight) (manufactured by hard coating film) on a transparent plastic film substrate (thickness 40 μm A TAC film having a refractive index of 1.48, manufactured by Konica Minolta Holdings, Inc., trade name "KC4UY", was coated with a composition for forming a hard coat layer by a comma coater to form a coating film. After the aforementioned coating, it was 6 Torr. (: The coating film was dried by the method of heating for 1 minute. The coating film after drying was irradiated with ultraviolet rays having a cumulative light amount of 300 mJ/cm 2 by a high-pressure mercury lamp to form a hard coat layer having a thickness of 7 μm. A hard coat film of the present example was produced. [Example 2] A hard coat film of this example was obtained in the same manner as in Example 1 except that the thickness of the hard coat layer was 15 μm. [Example 3] The hard coat film of this example was obtained in the same manner as in Example 1 except that the reactive fluorine compound was used in an amount of 0.1 part by weight, and the reactive ruthenium compound was changed to 0.5 part by weight. [Example 4] The hard coat film of this example was obtained in the same manner as in Example 1 except that the reactive fluorine compound was 0.2 parts by weight and the reactive ruthenium compound was 0.2 parts by weight. [Example 5] The hard coating of this example was obtained in the same manner as in Example 1 except that the reactive fluorine compound was used in an amount of 0.1 part by weight, and the reactive hydrazine compound was changed to 1 part by weight. [Example 6] A hard coat film of this example was obtained in the same manner as in Example 1 except that the reactive fluorine compound was 0.2 parts by weight and the reactive ruthenium compound was changed to 1 part by weight. [Example 7] The same procedure as in Example i was carried out except that the reactive fluorine compound was used in an amount of 0.1 part by weight, and the reaction 32 201030108 J · 5 化 5 was 〇 2 parts by weight. The hard coat film of the present Example. [Example 8] The reaction was carried out except that the reactive fluorine compound of the above-mentioned four was defined as 0.1 part by weight, and the reaction was carried out as the weight fraction of ruthenium. The hard coating film of this example was produced in the same manner. [Example 9] The above reactive fluorinated compound was determined to be 〇 2 by weight, and the above reactive hydrazine compound was set to ο. 1 by weight. The hard coat film of this example was obtained in the same manner as in Example 1. [Comparative Example 1] The same procedure as in Example 1 was carried out except that the reactive fluorine compound and the reactive ruthenium compound were not added. Hard coated film of the comparative example. Example 2] A hard coat film of this comparative example was obtained in the same manner as in Example 1 except that the reactive fluorinated compound was not added and the above reactive ruthenium compound was changed to 0.2 part by weight. [Comparative Example 3] The hard coat film of the comparative example was obtained in the same manner as in Example 1 except that the reactive fluorinated compound was not added and the reactive ruthenium compound was changed to 1 part by weight. [Comparative Example 4] The hard coat film of this comparative example was prepared in the same manner as in Example 1 except that the reactive fluorine compound was added in an amount of 0.2 part by weight, except that the above-mentioned 33 201030108 reactive hydrazine compound was added. [Comparative Example 5] The hard coat film of this comparative example was prepared in the same manner as in Example 1 except that the fluorine compound was used in an amount of 1 part by weight. 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. 34 201030108

N surface by JJ/mJ 16.0 15.9 18.0 15.8 18.7 16.3 17.6 17.5 15.7 37.8 24.3 24.1 15.7 15.2 孤s ffi ffi X ffi ffi ffi ffi X ffi ffi ffi ffi ffi ffi m inch mm ΓΛ mm cn mr^i C^ii To rub 1 <<<< c 03 PQ CQ UU uuu ^ ^ ^ 0.81 0.42 3.38 0.30 3.52 2.20 1.39 1.06 0.45 0.32 0.75 7.53 0.14 0.14 • ui S8 十^ 3^ 25.55 21.50 17.00 27.15 19.45 25.00 20.55 18.60 22.00 0.00 0.00 0.00 23.00 30.25 0.25 Ο Ο Ο Ο 〇〇〇〇 o 〇〇〇〇o 〇〇^ 3 ϊ> One (>l> Dependent Telluride [Quantity] yn ο in ο in ο (Ν d ο ο » —η CN oodo (N dooo shouts 2 amount of acid; (Ν Ο (Ν Ο ο (Ν Ο Ο (Ν TH o TH o CN dooo (N o (Ν m inch in 00 C\ (N inch meal) %c Ik Κ IK -Ο -Ο £ 〇3 35 201030108 As shown in Table 1 above, the hard coat film of the examples is represented by scratch resistance and surface free energy value. The antifouling property was good, and in particular, the excellent scratch resistance was exhibited in Examples 1 to 6. Further, the hard coat film of the example had high pencil hardness and good curling properties. The film was coated, and the scratch resistance was insufficient. The hard coat films of Comparative Examples 1 to 3 had a large surface free energy value and were not excellent in antifouling properties. The hard coat films of Comparative Examples 4 and 5 had small surface free energy values. However, the hard coat film of the present invention using the hard-coat layer forming composition of the present invention has sufficient hardness, excellent scratch resistance, and excellent antifouling property. By. Therefore, the hard coat film of the present invention is suitably used for, for example, optical elements such as a polarizing plate, various image display devices such as CRT, LCD, PDP, and ELD, and its use is not limited, and it can be applied to a wide range of fields. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view showing an example of a hard coat film of the present invention. [Description of main component symbols] 10···hard coated film 11···transparent plastic substrate 12···hard coating · 36

Claims (1)

201030108 VII. Patent application scope: 1. A composition for forming a hard coat layer, which is a composition for forming a hard coat layer for forming a hard coat layer, characterized by containing the following components (A) and (B) (C) component and (D) component, (A) Component: a hardening type compound (B) containing a group of at least one of an acrylate group and a methacrylate group. Component: The surface of the inorganic oxide particle is polymerized. A compound having a polyunsaturated group modified, and a particle having a weight average particle diameter of 200 nm or less (C) Component: Reactive fluorine compound (D) Component: a reactive compound. 2. The composition for forming a hard coat layer according to the first aspect of the invention, wherein the component (C) has a structure represented by the following general formula (1), wherein N, Ο the above general formula (1) And at least one R is a substituent containing a fluoroalkyl group, and at least one R is a substituent containing at least one of an acrylate group and a methacrylate group. 3. The composition for forming a hard coat layer according to the second aspect of the invention, wherein, in the R of the general formula (1), the substituent containing the fluoroalkyl group has a structure represented by the following general formula (2). 37 201030108 【化 u】 -(CH2)e.NH-C〇^H2^F2.CF2.(0-CF2-CF2-CF2)n-0-CF2.CF3 (2) In the above general formula (2), η is an integer of 1 or more. 4. The composition for forming a hard coat layer according to the second aspect of the invention, wherein, in the R of the general formula (1), the substituent containing the acrylate group has a substitution represented by the following general formula (3). Base, [12] 〇•(CH2)6_NH*C-〇.CH2*CH2*〇jLcH=CH2 (3) 5. The composition for forming a hard coat layer according to the above-mentioned claim, wherein the component (D) has the following general formula (4) Structure of representation, [Chem. 13] (4) In the above general formula (4), R is a substituent selected from a substituent having a decane structure, a substituent containing at least one of an acrylate group and a methacrylate group, and a substituent selected from an active hydrogen-containing substituent. The feet can be the same or different. The composition for forming a hard coat layer according to the fifth aspect of the invention, wherein the substituent of the aforementioned general formula (4) 'the above-mentioned substituent having a oxoxane structure 38 201030108 has the following general formula (5) The structure shown, [Chem. 14] 0 -(CH2)6-NH-S-0-CHrCH2-CH2 /?HA (5) -Si-Oj-Si-Oj-CH3 \CH3/n The above general formula (5) In the above, n is an integer of 1 or more. 7. The composition for forming a hard coat layer according to claim 5, wherein in the R of the general formula (4), the active hydrogen-containing substituent has a substituent represented by the following general formula (6). [Chemical 15] 0 (6) -(CH2)6-NH-C-0-H 〇 8. The composition for forming a hard coat layer according to claim 5, wherein in the R of the general formula (4), the substituent containing the acrylate group has a substituent represented by the general formula (7). (7) - (ch2^nh-c o{ch2^oc{ch2^o{ch2^oc-ch=ch2 (7) In the above general formula (7), m and η are each an integer of 1 to 10, The composition for forming a hard coat layer according to the first aspect of the invention, wherein the weight average particle diameter of the (Β) component is in the range of 1 to 100 nm. 39 201030108 A composition for forming a hard-coat layer, which is selected from the group consisting of titanium oxide, cerium oxide, and aluminum oxide, and is contained in the hard component of the first aspect of the invention, and is contained in the component (B). a composition selected from the group consisting of oxidized zinc oxide, tin oxide, and zirconia to form a cold t-layer, wherein the component (B) is in a hard coat as described in the item i of the patent application, and the above (A) The composition is 1 part by weight, and the range of ~200 parts by weight is mixed. 12. The hard coat layer is formed as described in the first item of the patent application. a composition in which the component (6) is mixed with a range of 1 part by weight of the above-mentioned (A), and the component (D) is mixed at a weight of 5 to 1 by weight. The composition for forming a hard coat layer according to claim 1, wherein the component (E) is further contained, and the component (E) is represented by the following general formula (8). Alcohol compound [Chemistry 17] In the above general formula (8), m and η are each an integer of 1 or more, and may be the same or different. 14. The composition for forming a hard coat layer according to the thirteenth aspect of the invention, wherein the component (C) is in a range of from 0.1 to 5 parts by weight based on 100 parts by weight of the component (c). Further, the component (P) and the component (E) are mixed in a total amount of 0.1 to 1 part by weight. 40 201030108 15. 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 in that the hard coat layer is hard coated as described in claim 1 A layer forming composition is formed. 16. The hard coat film according to claim 15, wherein the outermost layer of the hard coat layer is in the range of 5 to 30% of the fluorine atom derived from the reactive fluorine compound in the analysis by ESCA. Further, the intensity of the ruthenium atom derived from the reactive ruthenium compound is in the range of 0.2 to 10%. 17. The hard coat film according to claim 15, wherein the hard coat layer has a thickness in the range of 12 to 50 μm. 18. The hard coat film according to claim 15, wherein the surface of the hard coat layer has a hardness of 4H or more at a weight of 500 g as specified in JIS Κ 5600-5-4. 19. The hard coat film according to claim 15, wherein the surface of the hard coat layer has a surface free energy in the range of 15 to 25 mJ/m2. 20. The hard coat film according to claim 15, wherein the hard coat layer further contains fine particles. An optical element characterized in that a hard coat film according to claim 15 is laminated on at least one side of the optical member. 22. An image display apparatus comprising the hard coat film of claim 15 of the patent application. 23. An image display apparatus comprising the optical element described in claim 21 of the patent application. 41