KR20100061396A - Composition for forming hard-coat layer, hard-coat film, optical element, and image display - Google Patents

Abstract

PURPOSE: A composition for forming a hard coat layer is provided to obtain a hard coat layer having strong hardness, excellent scratch resistance, and antifouling property and to prevent scratch to a hard coat film. CONSTITUTION: A composition for forming a hard coat layer comprises; a curable compound having an acrylate group and a methacrylate group; particles which are obtained by modifying the surface of inorganic oxide particles into an organic compound containing a polymerizable unsaturated group; a reactive fluorine compound; and a reactive silicon compound. The reactive fluorine compound is marked as a chemical formula 1.

Description

Composition for hard coat layer formation, hard coat film, optical element, and image display device {COMPOSITION FOR FORMING HARD-COAT LAYER, HARD-COAT FILM, OPTICAL ELEMENT, AND IMAGE DISPLAY}

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.

BACKGROUND ART According to recent technological advances, in addition to the conventional CRT (Cathode Ray Tube), an image display device has been developed and put into practical use for liquid crystal display (LCD), plasma display (PDP), electro luminescence display (ELD), and the like. . Among them, LCDs have been expanded in applications such as high viewing angle, high definition, high-speed response, color reproducibility, and the like. Applications using LCDs have also been expanded from notebook PCs and monitors to televisions, and their use has been widely used. In the basic configuration of the LCD, the glass substrates on the flat plates each having the transparent electrodes are disposed to face each other via spacers so as to have a predetermined gap therebetween, and a liquid crystal material is injected and sealed between the glass substrates to form a liquid crystal cell. The polarizing plate was formed in the outer surface of a pair of glass substrate, respectively. Conventionally, the cover plate which consists of glass and plastics was attached to the liquid crystal cell surface, and the damage prevention to the polarizing plate adhering to the liquid crystal cell surface was aimed at. However, when the cover plate is attached, the surface of the polarizing plate is gradually subjected to a hard coat treatment due to disadvantages in cost and weight.

It is common to use the hard-coat film in which the hard-coat layer was formed in the single side | surface or both surfaces of the transparent plastic film base material for the said hard-coat process. The said hard coat layer is normally formed using the composition for hard-coat layer formation, such as thermosetting resin and an ultraviolet curable resin.

About a hard coat film, improvement of abrasion resistance and antifouling property is calculated | required. Then, in order to improve the scratch resistance and antifouling property of a hard coat layer, the hard coat layer using the curable composition containing the compound which has any atom of a fluorine atom and a silicon atom is proposed (for example, refer patent document 1). . In addition, it is also proposed to add a silicon compound or a fluorine compound to the hard coat layer so that the abundance ratio of silicon atoms or fluorine atoms on the outermost surface of the hard coat layer is in a specific range (see, for example, Patent Document 2). ). However, as the applications of LCDs are diversified, it is also assumed that the opportunities for scratches or contaminants on the surface will be diversified. With the diversification of the above applications, scratch resistance and antifouling at higher levels and the continuation of these characteristics are required.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2003-335984

[Patent Document 2] Japanese Unexamined Patent Publication No. 2007-264281

Then, an object of this invention is to provide the composition for hard-coat layer formation which can obtain the hard-coat layer which has sufficient hardness, is excellent in scratch resistance, and also excellent in antifouling property. Moreover, an object of this invention is to provide the hard-coat film which has sufficient hardness, is excellent in scratch resistance, and also excellent in antifouling property, the optical element using the same, and an image display apparatus.

In order to achieve the above object, the composition for forming a hard coat layer of the present invention,

As a composition for hard-coat layer formation used for formation of a hard-coat layer,

The following (A) component, (B) component, (C) component, and (D) component are contained, It is characterized by the above-mentioned.

(A) component: Curable compound which has at least one group of an acrylate group and a methacrylate group

(B) component: The particle | grains whose surface of an inorganic oxide particle is modified by the organic compound containing a polymerizable unsaturated group, and whose weight average particle diameter is 200 nm or less

(C) component: a reactive fluorine compound

(D) Component: Reactive Silicon Compound

The hard coat film of this invention is a hard coat film which has a hard-coat layer in the at least one surface of a transparent plastic film base material, The said hard-coat layer is formed from the composition for hard-coat layer formation of the said invention, It is characterized by the above-mentioned. .

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 surface of the optical member.

The image display device of the present invention includes the hard coat film of the present invention or the optical element of the present invention.

The hard coat film of this invention formed from the composition for hard-coat layer formation of this invention has sufficient hardness by the function of the said four components mutually working, and is excellent in abrasion resistance, and also excellent in antifouling property. According to the hard coat film of this invention, it is hard to adhere a dirt to the surface for a long time, and even if a dirt adheres, the dirt can be wiped off easily. Since the hard coat film of this invention is excellent in abrasion resistance, it does not scratch well even when wiping the said. Therefore, the optical element and the image display apparatus using the hard coat film of this invention can maintain favorable characteristic.

In the composition for hard coat layer formation of the present invention, the component (C) may have a structure represented by the following General Formula (1), for example. In following General formula (1), at least 1 R is a substituent which has a fluoroalkyl group, and at least 1 R is a substituent which has at least one of an acrylate group and a methacrylate group.

[Formula 1]

In the composition for hard-coat layer formation of this invention, in R of the said General formula (1), the substituent which has the said fluoroalkyl group may have a structure represented by following General formula (2), for example. The structure represented by the following general formula (2) has a perfluoropolyether unit (-CF ₂ -CF _2- (O-CF ₂ -CF ₂ -CF ₂ ) _n -O-CF ₂ -CF ₃ ) at the terminal thereof. Have In the perfluoropolyether unit, n is an integer of 1 or more.

[Formula 2]

In the composition for hard-coat layer formation of this invention, in R of the said General formula (1), the substituent which has the said acrylate group may have a substituent represented by following General formula (3), for example.

(3)

The said (C) component is represented by the said General formula (1), and in R of the said General formula (1), has one substituent which has a fluoroalkyl group which has a structure represented by the said General formula (2), It is preferable to have two substituents which have an acrylate group which has a structure represented by General formula (3).

In the composition for hard coat layer formation of the present invention, the component (D) may have a structure represented by the following General Formula (4), for example. In the following general formula (4), R is a substituent selected from a substituent having a siloxane structure, a substituent having at least one of an acrylate group and a methacrylate group, and a substituent having an active hydrogen group, and each R is the same or You may differ.

[Formula 4]

In the composition for hard coat layer formation of the present invention, the component (D) may have a structure represented by the following General Formula (9), for example. Let the structure represented by following General formula (9) be a 6-isocyanate hexyl isocyanuric acid unit (a).

[Chemical Formula 5]

In the composition for hard-coat layer formation of this invention, in R of the said General formula (4), the substituent which has the said siloxane structure may have a structure represented by following General formula (5), for example. The structure represented by following General formula (5) has the polydimethylsiloxane unit (c) at the terminal, The said unit (c) is couple | bonded with the methylhydroxypropylsiloxane unit (b), The said unit (b The hydroxyl group is urethane-bonded with the terminal isocyanate group of 6-isocyanatehexyl isocyanuric acid which is a part of said unit (a). In the polydimethylsiloxane unit (c), n is an integer of 1 or more, and 1 to 7 are preferable.

[Formula 6]

In the composition for hard-coat layer formation of this invention, in R of the said General formula (4), the substituent which has the said active hydrogen group may have a substituent represented by following General formula (6), for example. In the substituent represented by following General formula (6), the terminal isocyanate group of 6-isocyanate hexyl isocyanuric acid which is a part of said unit (a) becomes a carboxyl group. Moreover, in the substituent represented by following General formula (6), the said carboxyl group may decarboxylate and may be an amino group.

[Formula 7]

In the composition for hard-coat layer formation of this invention, in R of the said General formula (4), the substituent which has the said acrylate group may have a structure represented by following General formula (7), for example. The structure represented by following General formula (7) has an aliphatic polyester unit (d) which has an acrylate group at the terminal, and the said unit (d) is the 6-isocyanate hexyl isocyanuric acid which is a part of said unit (a). The terminal isocyanate group is urethane-bonded. In following General formula (7), m and n are the integers of 1-10, respectively, and may be same or different. l is an integer of 1-5.

[Formula 8]

6-isocyanate hexyl isocyanuric acid which contains the unit (a) which is a structure represented by the said General formula (9), and also contains the substituent represented by the said General formula (5)-(7). In the case of the derivative of the unit, the component ratio (molar ratio) of the unit (a): the unit (b): the unit (c): the unit (d) is the unit (a) of 100. b) is the range of 1-80, for example, Preferably it is the range of 1-60, The said unit (c) is the range of 10-400, for example, Preferably it is the range of 10-300, The unit (d) is, for example, in the range of 1 to 100, and preferably in the range of 5 to 50.

In this invention, the ratio (molar ratio) of each structural component (unit) of the said (D) component can be calculated | required from the integral curve of a ¹ H-NMR spectrum, for example. The weight average molecular weight (Mw) of the said (D) component is the range of 500-150000, for example, Preferably it is the range of 2000-100000. The said weight average molecular weight (Mw) can be measured by the gel permeation chromatography (GPC) method, for example.

It is preferable to use the compound which has a structure represented by the said General formula (1) as said (C) component, and to use the compound which has a structure represented by the said General formula (4) as said (D) component. It is speculated that by using a compound having a similar structure, it is likely to be expressed in the hard coat layer in which the action each has is formed, but the present invention is not limited by this speculation at all.

In the composition for forming a hard coat layer of the present invention, the weight average particle diameter of the component (B) is preferably in the range of 1 to 100 nm in terms of prevention of light scattering, prevention of decrease in transmittance of the hard coat layer, prevention of coloring, transparency, and the like. Do. The said weight average particle diameter can be measured by the method as described in the Example mentioned later, for example.

In the composition for hard coat layer formation of the present invention, examples of the component (B) include fine particles such as titanium oxide, silicon oxide, aluminum oxide, zinc oxide, tin oxide, and zirconium oxide. Among these, fine particles of titanium oxide, silicon oxide (silica), aluminum oxide, zinc oxide, tin oxide, and zirconium oxide are preferable. These may be used individually by 1 type and may use two or more types together.

In the composition for forming a hard coat layer of the present invention, the component (B) is preferably blended in a range of 100 to 200 parts by weight based on 100 parts by weight of the component (A).

In the composition for hard coat layer formation of the present invention, the component (C) is blended in the range of 0.05 to 0.4 part by weight based on 100 parts by weight of the component (A), and the component (D) is 0.05 to 1 weight. It is preferable to mix | blend in the range of wealth.

It is preferable that the composition for hard-coat layer formation of this invention contains the following (E) component further.

(E) component: The glycol compound represented by following General formula (8)

[Formula 9]

In said Formula (8), m and n are 1 or more integers, respectively, and may be same or different.

In the composition for hard coat layer formation of the present invention, the component (C) is blended in the range of 0.05 to 0.4 part by weight based on 100 parts by weight of the component (A), and the component (D) and the component (E) It is preferable that the component is mix | blended in the range of 0.1-1 weight part in total.

In the hard coat film of the present invention, the outermost layer of the hard coat layer has a fluorine atom strength derived from a reactive fluorine compound in an analysis by ESCA (Electron Spectroscopy for Chemical Analysis) within a range of 5 to 30%, Moreover, it is preferable that the silicon atom intensity | strength derived from a reactive silicon compound exists in 0.2 to 10% of range. If it is this range, abrasion resistance and antifouling property can be made more compatible.

By the way, there exists a tendency for the addition amount of a reactive fluorine compound and a reactive silicon compound, and the said atomic strength in an outermost layer to not necessarily correspond or become proportional. For example, even when a hard coat layer is formed using a composition for forming a hard coat layer of the same composition, and when the film thicknesses of the hard coat layer are different, the respective atomic strengths in the outermost layer do not become the same. There is also. Therefore, when using the composition for hard-coat layer formation of this invention to obtain the hard-coat film which has a more favorable characteristic, it is effective to evaluate the characteristic which focused on each said atomic strength.

As for the said fluorine atom intensity | strength, it is more preferable to exist in 10 to 30% of range, and it is still more preferable to exist in 15 to 30% of range. As for the said silicon atom intensity | strength, it is more preferable to exist in 0.2 to 8% of range, and it is still more preferable to exist in 0.2 to 6% of range.

In the hard coat film of this invention, the thickness of the said hard coat layer is not specifically limited, Although an optimal thickness can be set according to the thickness etc. of the said transparent plastic film base material, it is the range of 12-50 micrometers, for example. By making the said thickness into the said range, generation | occurrence | production of the curl and folding of a hard coat film can be prevented more effectively, without causing a fall of hardness. The thickness is more preferably in the range of 14 to 25 µm, and still more preferably in the range of 14 to 18 µm.

In the hard coat film of this invention, it is preferable that the pencil hardness in weight 500 g based on the specification of JISK5600-5-4 of the said hard-coat layer surface is 4H or more.

In the hard coat film of this invention, it is preferable that the surface free energy of the surface of the said hard coat layer is 15-25 mJ / m <2>. Surface free energy means the value computed by calculation of the two components of water / hexadecane of Kaelble Uy theory. As for the said surface free energy, it is more preferable that it is the range of 15-22 mJ / m <2>, More preferably, it is the range which is 15-20 mJ / m <2>. The said surface free energy value measures a contact angle with respect to each of water and hexadecane, and is computed from the value, It can automatically calculate by Kyowa Interface Science, Ltd. "Full automatic contact angle meter DM700".

In the hard coat film of this invention, it is preferable that the said hard coat layer contains microparticles | fine-particles further.

Next, the present invention will be described in detail. However, this invention is not limited to the following description.

The hard coat film of this invention has a hard coat layer in the single side | surface or both surfaces of a transparent plastic film base material.

Although the said transparent plastic film base material is not specifically limited, It is preferable that it is excellent in the light transmittance of visible light (preferably 90% or more of light transmittance), and excellent in transparency (preferably having a haze value of 1% or less), For example, the transparent plastic film base material of Unexamined-Japanese-Patent No. 2008-90263 is mentioned. As said transparent plastic film base material, the thing with little birefringence optically is used preferably. The hard coat film of this invention can also be used for a polarizing plate, for example as a protective film, In this case, as said transparent plastic film base material, a triacetyl cellulose (TAC), a polycarbonate, an acryl-type polymer, cyclic thru-norbor Preference is given to films formed of polyolefins having a linen structure and the like. Moreover, in this invention, the said transparent plastic film base material may be polarizer itself. In such a configuration, since the structure of the polarizing plate can be simplified without the need for a protective layer made of TAC or the like, the number of manufacturing steps of the polarizing plate or the image display device can be reduced, and the production efficiency can be improved. Moreover, if it is such a structure, a polarizing plate can be further thinned. In addition, when the transparent plastic film base material is a polarizer, the hard coat layer serves as a conventional protective layer. Moreover, if it is such a structure, a hard coat film will also function as a cover plate attached to the liquid crystal cell surface.

In the present invention, the thickness of the transparent plastic film base material is not particularly limited. The thickness is preferably in the range of 10 to 500 µm, more preferably in the range of 20 to 300 µm, in consideration of aspects such as workability such as strength and handleability, and thinness. It is the range of 30-200 micrometers. The refractive index of the transparent plastic film base material is not particularly limited. The said refractive index is the range of 1.30-1.80, for example, Preferably it is the range of 1.40-1.70.

The said hard coat layer is formed using the composition for hard-coat layer formation containing the said (A) component, the said (B) component, the said (C) component, and the said (D) component.

As said (A) component, the curable compound which has at least one group of an acrylate group and a methacrylate group hardened | cured by heat, light (ultraviolet rays etc.), an electron beam, etc. can be used, for example. As said (A) component, For example, polysilicon, such as a silicone resin, a polyester resin, a polyether resin, an epoxy resin, a urethane resin, an alkyd resin, a spiroacetal resin, a polybutadiene resin, a polythiol polyene resin, a polyhydric alcohol, etc. And oligomers or prepolymers such as acrylates and methacrylates of functional compounds. These may be used individually by 1 type and may use two or more types together.

As said (A) component, the reactive diluent which has at least one group of an acrylate group and a methacrylate group can also be used, for example. Such reactive diluents include, for example, monofunctional acrylates, monofunctional methacrylates, polyfunctional acrylates, polyfunctional methacrylates, and the like. The monofunctional acrylate is, for example, an acrylate of ethylene oxide modified phenol, an acrylate of propylene oxide modified phenol, an acrylate of ethylene oxide modified nonylphenol, an acrylate of propylene oxide modified nonylphenol, 2-ethylhexylcarbitol Acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyhexyl acrylate, diethylene glycol monoacrylate, triethylene glycol Monoacrylate, tripropylene glycol monoacrylate, and the like. The monofunctional methacrylate is, for example, methacrylate of ethylene oxide modified phenol, methacrylate of propylene oxide modified phenol, methacrylate of ethylene oxide modified nonylphenol, methacrylate of propylene oxide modified nonylphenol, 2 Ethylhexylcarbitol methacrylate, isobornyl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyhexyl methacrylate Laterate, diethylene glycol monomethacrylate, triethylene glycol monomethacrylate, tripropylene glycol monomethacrylate and the like. Examples of the polyfunctional acrylate include diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, and polypropylene glycol diacrylate. Rate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diacrylate of ethylene oxide modified neopentyl glycol, diacrylate of ethylene oxide modified bisphenol A , Diacrylate of propylene oxide modified bisphenol A, diacrylate of ethylene oxide modified hydrogenated bisphenol A, trimethylolpropanediacrylate, trimethylolpropaneallyl ether diacrylate, trimethylolpropane triacrylate, ethylene oxide modified trimethylol Propane triacrylate Agent, and the like propylene oxide-modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate. The polyfunctional methacrylate is, for example, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate , Polypropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, dimethacrylate of ethylene oxide modified neopentyl glycol, Dimethacrylate of ethylene oxide modified bisphenol A, Dimethacrylate of propylene oxide modified bisphenol A, Dimethacrylate of ethylene oxide modified bisphenol A, Trimethylol propane dimethacrylate, Trimethylol propane allyl ether dimethacryl Latex, trimethylolpropanetrimethacrylate, ethylene oxide And trimethylolpropane trimethacrylate, propylene oxide modified trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate and the like. . As said reactive diluent, a trifunctional or more than trifunctional acrylate and a trifunctional or more than methacrylate are preferable. This is because the hardness of the hard coat layer can be made more excellent. As said (A) component, butanediol glycerol ether diacrylate, the acrylate of isocyanuric acid, the methacrylate of isocyanuric acid, etc. are mentioned, for example. The said (A) component may be used individually by 1 type, and may use two or more types together.

The said (B) component is as above-mentioned. In said (B) component, microparticles | fine-particles, such as a silicon oxide (silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide, a zirconium oxide, are mentioned as an inorganic oxide particle, for example. Among these, fine particles of silicon oxide (silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide, and zirconium oxide are preferable. These may be used individually by 1 type and may use two or more types together.

In the composition for forming a hard coat layer of the present invention, in terms of preventing scattering of light, preventing a decrease in transmittance of the hard coat layer, preventing coloring, transparency, and the like, the component (B) is a so-called weight average particle diameter in a range of 200 nm or less. Nanoparticles. The said weight average particle diameter can be measured by the method as described in the Example mentioned later, for example. The said weight average particle diameter becomes like this. Preferably it is the range of 1 nm-100 nm.

In the said (B) component, the said inorganic oxide particle is couple | bonded (surface modification) with the organic compound containing a polymerizable unsaturated group. The said polymerizable unsaturated group reacts and hardens with the said (A) component, and improves the hardness of a hard-coat layer. As said synthetic unsaturated group, acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, maleate group, and acrylamide group are preferable, for example. Moreover, it is preferable that the organic compound containing the said polymerizable unsaturated group is a compound which has a silanol group in a molecule | numerator, or a compound which produces a silanol group by hydrolysis. It is also preferable that the organic compound containing the said polymerizable unsaturated group has a photosensitive group.

It is preferable that the compounding quantity of the said (B) component is 100-200 weight part with respect to 100 weight part of said (A) component. By making the compounding quantity of the said (B) component 100 weight part or more, generation | occurrence | production of the curl and fold of a hard-coat film can be prevented more effectively, and setting it as 200 weight part or less can make abrasion resistance and pencil hardness high. . The compounding quantity of the said (B) component becomes like this. More preferably, it is the range of 120-180 weight part with respect to 100 weight part of said (A) component.

By adjusting the compounding quantity of the said (B) component, the refractive index of the said hard-coat layer can be adjusted, for example. It is preferable to reduce the refractive index difference of the said transparent plastic film base material and the said hard-coat layer from the point which prevents the interference fringe which arises in the said transparent plastic film base material and the said hard-coat layer interface. The interference fringe is a phenomenon in which reflected light of external light incident on the hard coat film exhibits an iridescent color. In recent years, three-wavelength fluorescent lamps excellent in clarity have been used in offices and the like. Under the three-wavelength fluorescent lamp, the interference fringes appear remarkably. In these respects, it is preferable to adjust the compounding quantity of the said (B) component in preparation of the said composition for hard-coat layer formation so that the said refractive index difference may become small.

The refractive index difference is preferably 0.04 or less, and more preferably 0.02 or less. Specifically, for example, when using a PET film (refractive index: about 1.64) as said transparent plastic film base material, titanium oxide is used for the said (B) component, and this whole resin component in the said composition for hard-coat layer formation is used. By blending about 30 to 40% by weight, the refractive index difference can be controlled to 0.02 or less, and generation of interference fringes can be suppressed. For example, when using a TAC film (refractive index: about 1.48) as the said transparent plastic film base material, silicon oxide (silica) is used for the said (B) component, and this is a resin component in the said composition for hard-coat layer formation. By mix | blending about 35 to 45 weight% with respect to the whole, the said refractive index difference can be controlled to 0.02 or less, and generation | occurrence | production of an interference fringe can be suppressed.

The said (C) component and the said (D) component are as above-mentioned. By use of the said (C) component, the surface free energy value of the hard-coat layer obtained falls and the antifouling property of the said hard-coat layer improves. On the other hand, when the compounding quantity of the said (C) component becomes excess, there exists a tendency for the scratch resistance of the hard-coat layer obtained to fall. Moreover, by use of the said (D) component, for example, the hard-coat layer surface structure formed becomes rigid, slipperiness | lubricacy improves and it is excellent in scratch resistance. On the other hand, when the compounding quantity of the said (D) component becomes excess, there exists a tendency for the antifouling property of the hard-coat layer obtained to fall. In these respects, the blending ratio of the component (C) and the component (D) is in the range of 0.05 to 0.4 parts by weight based on 100 parts by weight of the component (A), and the (D) It is preferable that a component is the range of 0.05-1.0 weight part, More preferably, the said (C) component is the range of 0.1-0.3 weight part, and the said (D) component is the range which is 0.2-1.0 weight part.

The hard coat film of this invention prepares the composition for hard-coat layer formation which melt | dissolved or disperse | distributed the said 4 components in the solvent, for example, and makes the said hard-coat layer formation composition into the at least one surface of the said transparent plastic film base material. It can manufacture by coating, forming a coating film, hardening the said coating film, and forming the said hard-coat layer.

The solvent is not particularly limited. The solvent is, for example, dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, Tetrahydrofuran, acetone, methyl ethyl ketone (MEK), diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, ethyl formate, propyl formate, n-pentyl formate, Methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-pentyl acetate, acetylacetone, diacetone alcohol, methyl acetoacetate, ethyl acetoacetate, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2- Butanol, 1-pentanol, 2-methyl-2-butanol, cyclohexanol, isobutyl acetate, methyl isobutyl 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 monomethyl ether and the like. These may be used individually by 1 type and may use two or more types together.

As mentioned above, it is preferable that the said composition for hard-coat layer formation contains the said (E) component further.

When using the said (E) component, in preparation of the said composition for hard-coat layer formation, it is preferable to prepare the said (E) component as a mixture with the said (D) component. As a material containing the said mixture, you may use a commercial item, for example. As said commercial item, the brand name "GRANDIC PC-4100" by Dainippon Ink Chemical Industries, Ltd., etc. are mentioned, for example. The weight average molecular weight (Mw) of the material containing the mixture is not particularly limited.

By use of the said (E) component, while the hard-coat layer surface structure formed, for example, becomes rigid, slipperiness | lubricacy improves and abrasion resistance becomes more excellent. From the viewpoint of both scratch resistance and antifouling resistance, the blending ratio of the component (E) is in the range of 0.05 to 0.4 parts by weight based on 100 parts by weight of the component (A), and the (D) The component and the component (E) are preferably in the range of 0.1 to 1 part by weight in total, and more preferably the component (C) is in the range of 0.1 to 0.3 part by weight, and the component (D) and the component (E) A component is the range of 0.2-1 weight part in total.

The said composition for hard-coat layer formation may contain a pigment, a filler, a dispersing agent, a plasticizer, an ultraviolet absorber, surfactant, antioxidant, a thixotropic agent, etc. in the range which does not impair performance as needed. These additives may be used individually by 1 type, and may use two or more types together.

By adding microparticles | fine-particles to the said composition for hard-coat layer formation, the hard coat film which also has anti-glare property can be obtained further. The microparticles | fine-particles make it the main function to provide anti-glare property by making the surface of the hard-coat layer formed into uneven | corrugated shape, and to control the haze value of the said hard-coat layer. The haze value of the said hard coat layer can be designed by controlling the refractive index difference of the said microparticles | fine-particles and the said composition for hard-coat layer formation. Examples of the fine particles include inorganic fine particles and organic fine particles. The inorganic fine particles are not particularly limited, and for example, silicon oxide fine particles, titanium oxide fine particles, aluminum oxide fine particles, zinc oxide fine particles, tin oxide fine particles, calcium carbonate fine particles, barium sulfate fine particles, talc fine particles, kaolin fine particles, calcium sulfate fine particles and the like. Can be mentioned. Further, the organic fine particles are not particularly limited, and for example, polymethyl methacrylate resin powder (PMMA fine particles), silicone resin powder, polystyrene resin powder, polycarbonate resin powder, acrylic styrene resin powder, benzoguanamine resin powder, melamine Resin powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, polyfluoroethylene resin powder, and the like. These inorganic fine particles and organic fine particles may be used individually by 1 type, and may use two or more types together.

In the said composition for hard-coat layer formation, when the said (A) component contains a photocurable compound, the conventionally well-known photoinitiator of Unexamined-Japanese-Patent No. 2008-88309 can be used, for example. The said photoinitiator may be used individually by 1 type, and may use two or more types together. The compounding quantity of the said photoinitiator is not specifically limited. The said compounding quantity is the range of 1-30 weight part with respect to 100 weight part of said (A) components, Preferably it is the range of 1-25 weight part.

As a method of coating the said hard-coat layer formation composition on the said transparent plastic film base material, for example, a fountain coat method, a die coat method, a spin coat method, a spray coat method, the gravure coat method, the roll coat method, the bar Coating methods, such as a coating method, can be used.

Coating the composition for forming the hard coat layer to form a coating film on the transparent plastic film base material to cure the coating film. It is preferable to dry the said coating film before the said hardening. For example, the drying may be natural drying, air drying to blow out wind, heat drying, or a combination thereof.

The hardening means of the coating film of the said composition for hard-coat layer formation is not specifically limited. The curing means is preferably ionizing radiation curing. Various activation energy can be used for the said hardening means. The active energy is preferably ultraviolet light. As the energy source, for example, a source such as a high pressure mercury lamp, a halogen lamp, a xenon lamp, a metal halide lamp, a nitrogen laser, an electron beam accelerator, or a radioactive element is preferable. The irradiation amount of the energy source is preferably in the range of 50 to 5000 mJ / cm 2 as an integrated exposure amount at an ultraviolet wavelength of 365 nm. When the said irradiation amount is 50 mJ / cm <2> or more, hardening becomes more enough and the hardness of the said hard-coat layer formed becomes more sufficient. When the said irradiation amount is 5000 mJ / cm <2> or less, coloring of the said hard coat layer formed can be prevented, and transparency can be improved.

As described above, 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 base material. Moreover, you may manufacture the hard coat film of this invention other than the method mentioned above.

An example of the hard-coat film structure of this invention is shown to the schematic cross section of FIG. In the same figure, in order to make it easy to understand, the magnitude | size, ratio, etc. of each structural member differ from an actual thing. As shown, in this hard coat film 10, the hard coat layer 12 is formed in the single side | surface of the transparent plastic film base material 11. As shown in FIG. However, this invention is not limited to this. The hard coat film of this invention may be the structure in which the hard-coat layer was formed in both surfaces of the transparent plastic film base material. In addition, the hard coat layer 12 of this example is a single layer. However, this invention is not limited to this. In the hard coat film of the present invention, the hard coat layer may have a multilayer structure in which two or more layers are laminated. In this case, the hard coat layer formed from the composition for hard-coat layer formation of this invention should just be in the outermost surface.

In the hard coat film of this invention, it is preferable to surface-treat at least one of the said transparent plastic film base material and the said hard coat layer. When surface-treating the said transparent plastic film base material surface, adhesiveness with the said hard-coat layer, a polarizer, or a polarizing plate further improves. When surface treatment of the said hard-coat layer surface, adhesiveness with the said polarizer or a polarizing plate further improves. As said surface treatment, a low pressure plasma treatment, an ultraviolet irradiation treatment, a corona treatment, a flame treatment, an acid or an alkali treatment is mentioned, for example. As a surface treatment at the time of using a TAC film as said transparent plastic film base material, alkali treatment is preferable. This alkali treatment can be performed, for example, by making a TAC film surface contact with alkaline solution, and then washing with water and drying. As said alkaline solution, a potassium hydroxide solution and a sodium hydroxide solution can be used, for example. The prescribed concentration (molar concentration) of the hydroxide ions in the alkali solution is preferably in the range of 0.1 to 3.0 N (mol / L), more preferably in the range of 0.5 to 2.0 N (mol / L).

In the hard-coat film which contains the transparent plastic film base material and the said hard-coat layer is formed in one surface of the said transparent plastic film base material, in order to prevent generation | occurrence | production of a curl, even if it performs a solvent process on the other surface. do. The said solvent process can be performed by making the solvent which can melt | dissolve the said transparent plastic film base material, or the solvent which can swell. By the solvent treatment, the transparent plastic film base material is imparted with the force to be curled to the other side, whereby the transparent plastic film base material cancels the force to be curled by the formation of the hard coat layer. Can be prevented. Similarly, in the hard coat film which contains the said transparent plastic film base material, and the said hard-coat layer is formed in one surface of the said transparent plastic film base material, in order to prevent generation | occurrence | production of a curl, it is transparent on the other side. You may form a layer. As said transparent resin layer, the layer which has a thermoplastic resin, radiation curable resin, a thermosetting resin, and other reactive resin as a main component is mentioned, for example. Among these, especially the layer which has a thermoplastic resin as a main component is preferable.

The hard coat film of this invention can make the said transparent plastic film base material side adhere to the optical member currently used for LCD and ELD through an adhesive or an adhesive agent normally. In this adhesion | attachment, you may perform the above-mentioned various surface treatment with respect to the said transparent plastic film base material surface.

As said optical member, a polarizer or a polarizing plate is mentioned, for example. The structure which a polarizing plate has a transparent protective film in the one side or both sides of a polarizer is common. When providing a transparent protective film on both surfaces of a polarizer, the transparent protective film of front and back may be the same material, and may be a different material. The polarizing plate is usually disposed on both sides of the liquid crystal cell. Moreover, the polarizing plates are arrange | positioned so that the absorption axes of two polarizing plates may mutually orthogonally cross.

Next, the optical element which laminated | stacked the hard-coat film of this invention is demonstrated using an polarizing plate as an example. The polarizing plate which has the function of this invention can be obtained by laminating | stacking the hard coat film of this invention with a polarizer or a polarizing plate using an adhesive agent, an adhesive, etc.

It does not specifically limit as said polarizer, Various things can be used. As said polarizer, dichroic substances, such as iodine and a dichroic dye, are used for hydrophilic polymer films, such as a polyvinyl alcohol-type film, a partially formalized polyvinyl alcohol-type film, and an ethylene-vinyl acetate copolymerization system partial saponification film, for example. Polyene type orientation films, such as the thing uniaxially stretched by adsorption, the dehydration process of polyvinyl alcohol, and the dehydrochlorination process of polyvinyl chloride, etc. are mentioned.

As a transparent protective film formed in the single side | surface or both surfaces of the said polarizer, it is preferable that it is excellent in transparency, mechanical strength, thermal stability, moisture shielding property, stability of retardation value, etc. As a material which forms the said transparent protective film, the same thing as the said transparent plastic film base material is mentioned, for example.

As said transparent protective film, the polymer film of Unexamined-Japanese-Patent No. 2001-343529 (WO01 / 37007) is also mentioned. The polymer film described in the publication is, for example, a thermoplastic resin having at least one imide group of a substituted imide group and an unsubstituted imide group in the side chain (A), and a substituted phenyl group and an unsubstituted phenyl group in the side chain (B). The polymer film formed from the resin composition containing the thermoplastic resin which has at least one phenyl group and a nitrile group is mentioned. As a polymer film formed from the said resin composition, the polymer film formed from the resin composition containing the alternating copolymer which consists of isobutylene and N-methyl maleimide, and an acrylonitrile-styrene copolymer is mentioned, for example. The polymer film can be produced by extrusion molding the resin composition into a film shape. Since the said polymer film has a small phase difference and a small photoelastic coefficient, when applied to protective films, such as a polarizing plate, the problem, such as the nonuniformity by a deformation | transformation, can be eliminated. Since the polymer film has a low water vapor transmission rate, the humidification durability is excellent.

As for the said transparent protective film, cellulose resin films, such as TAC, and norbornene-type resin film are preferable from a point of polarization characteristic, durability, etc. As a commercial item of the said transparent protective film, a brand name "Fuji-Tak" (made by Fujifilm Corporation), a brand name "Zenooa" (made by Nippon Xeon), a brand name "Aton" (made by JSR Corporation), etc. are mentioned, for example. .

The thickness of the transparent protective film is not particularly limited. The thickness of the said transparent protective film is a range of 1-500 micrometers from a point of workability, thinness, etc., such as strength and handleability, for example. When the thickness is within the above range, the polarizer is mechanically protected and the polarizer does not shrink even when exposed to high temperature and high humidity, thereby maintaining stable optical characteristics. The thickness is preferably in the range of 5 to 200 µm, more preferably in the range of 10 to 150 µm.

Although the structure of the polarizing plate which laminated | stacked the hard-coat film of this invention is not restrict | limited, For example, the structure which laminated | stacked the transparent protective film, the polarizer, and the transparent protective film in this order on the said hard-coat film may be sufficient, and on a hard-coat film The polarizer and the transparent protective film which were laminated | stacked in this order may be sufficient.

Various optical elements, such as the hard-coat film of this invention using the composition for hard-coat layer formation of this invention, and the polarizing plate using this, can be used suitably for various image display apparatuses, such as a liquid crystal display device. The image display apparatus of this invention is the same structure as the conventional image display apparatus except using the hard coat film of this invention. In the case where the image display device of the present invention is a liquid crystal display device, for example, optical elements such as liquid crystal cells and polarizing plates, and if necessary, each component such as an illumination system (backlight, etc.) is properly assembled to mount a drive circuit. It can manufacture by the thing. The liquid crystal cell is not particularly limited. The said liquid crystal cell can use various types, such as a TN type, STN type, (pi) type, for example.

In this invention, the structure of a liquid crystal display device is not specifically limited, The liquid crystal display device which arrange | positioned the said optical element in the one side or both sides of a liquid crystal cell, the liquid crystal display device which used the backlight or the reflecting plate in the illumination system, etc. are mentioned. . In these liquid crystal display devices, the optical element of this invention can be arrange | positioned at the one side or both sides of a liquid crystal cell. When arrange | positioning the said optical element on both sides of a liquid crystal cell, they may be the same and may differ. Moreover, you may arrange | position various optical members and optical components, such as a diffuser plate, an antiglare layer, an antireflection layer, a protective plate, a prism array, a lens array sheet, a light-diffusion plate, a backlight, for example in a liquid crystal display device.

The image display device of the present invention is used for any suitable purpose. Its uses include, for example, OA devices such as desktop PCs, notebook PCs, copiers, mobile phones, clocks, digital cameras, portable information terminals (PDAs), portable devices such as portable game machines, video cameras, televisions, microwave ovens, and the like. Home appliances, back monitors, car navigation system monitors, car equipment such as car audio, exhibition equipment such as information monitors for commercial stores, security devices such as monitoring monitors, nursing monitors, medical monitors, etc. Nursing care, a medical device, etc. are mentioned.

Example

Next, the Example of this invention is described with a comparative example. However, this invention is not restrict | limited by the following example and a comparative example. In addition, the various characteristics in the following example and the comparative example were evaluated or measured by the following method.

(Thickness of the hard coat layer)

The total thickness of the hard coat film was measured using the micro gauge thickness gauge manufactured by Mitsutoyo Corporation, and the thickness of the hard coat layer was calculated by subtracting the thickness of the transparent plastic film base material from the total thickness.

(Scratch resistance)

The scratch resistance of the hard coat layer was evaluated by the following test contents.

(1) A 150 mm x 50 mm sample was cut out at the center of the hard coat film, and the surface on which the hard coat layer was not formed was placed face down on a glass plate.

(2) After the steel wool # 0000 was uniformly mounted on a smooth end face of a circumference of 11 mm in diameter, and the sample surface was reciprocated at a speed of about 100 mm per second at a load of 1.5 kg, the sample surface was The number of scratches generated in the eye was visually counted and determined by the following indicators.

A: The number of scratches is less than 10

B: The number of scratches is 11 or more and 29 or less

C: the number of scratches more than 30

(Pencil hardness)

The rule of pencil hardness test as described in JIS K 5600-5-4 after cutting out the 100 mm x 50 mm sample from the center of a hard-coat film, and placing it on the glass plate with the surface where a hard-coat layer is not formed down. According to the above, pencil hardness at a load of 500 g was measured. As a pencil, Mitsubishi Pencil Co., Ltd. product "Uni" (for the pencil scratch value test, the inspection paint of the Japan Paint Testing Association) was used.

(Surface free energy)

The contact angle of water and hexadecane was measured using Kyowa Interface Science, Ltd. "Full automatic contact angle meter DM700", and surface free energy was computed by analysis software FAMAS. The calculation method used the two-component analysis by Kaelble Uy theory.

(Atomic Strength Measurement by ESCA)

, X 선 출력은 30 W (15 ㎸), 측정 영역은 200 ㎛Φ, 측정 각도는 시료 표면에 대하여 45°로 하였다. 에너지의 보정은, C1s 스펙트럼의 C-C 결합에서 기인되는 피크를 285.0 eV 로 보정함으로써 실시하였다.Atomic strength was measured using Albak Pi Co., Ltd. "Quantum 2000". X-ray source is monochrome AlK

The X-ray output was 30 W (15 kPa), the measurement region was 200 µm, and the measurement angle was 45 ° with respect to the sample surface. The correction of energy was performed by correcting the peak resulting from CC coupling of the C1s spectrum to 285.0 eV.

Arbitrary two points of the sample were measured by wide scan at 0-1100 eV, and the qualitative analysis was performed. A narrow scan was performed on the detected elements, and an element ratio (atomic%) was calculated. About the Si2p spectrum, waveform analysis is performed at peaks attributed to bifunctional silicon, and polyfunctional silicon and SiOx bonds, and the silicon atomic strength derived from the reactive silicon compound is calculated.

According to the above conditions, each atomic intensity ratio with respect to the area | region from the outermost surface of a sample to about 5-10 nm in depth can be measured.

(Weight Average Particle Size of Particles ((B) Component))

The resin raw material containing (B) component is diluted with methyl ethyl ketone (MEK) to 10% of solid content concentration, and the dynamic light-scattering type particle size distribution measuring apparatus (the Horiba Corporation make, "LB-500") is used. The particle size distribution was measured. The weight average particle diameter was computed from the obtained particle size distribution.

(Weight average molecular weight)

The weight average molecular weight was measured using polystyrene as a standard sample from the gel permeation chromatograph (GPC) method. Specifically, it measured according to the following apparatus, apparatus, and measurement conditions.

Analysis apparatus: Tosoh Corporation make, brand name "SC-8020"

Column: Showa Denko Co., Ltd. make, brand name "Shodex"

Column size: 20.0 mmΦ × 500 mm

Column temperature: room temperature

Eluent: Chloroform

Flow rate: 3.5 ml / min

Inlet pressure: 70 kgf / ㎠ (6.9 MPa)

Example 1

(Preparation of the composition for hard coat layer formation)

Resin raw material (JSR Corporation make, brand name "Opsta Z7540) containing the said (A) component in which the particle surface disperse | distributed the nano silica particle (the said (B) component) modified with the organic compound containing a polymerizable unsaturated group. Solid content: 56% by weight, solvent: butyl acetate / methyl ethyl ketone (MEK) = 76/24 (weight ratio)).

The said resin raw material is a fine particle (weight average) which modified the surface by organic molecules as said (A) component (ultraviolet-curable compound), dipentaerythritol and isophorone diisocyanate type polyurethane, and said (B) component. Particle diameter: 100 nm or less) is contained in the weight ratio of (A) component total: (B) component = 2: 3. The refractive index of the cured film of the said resin raw material was 1.485.

Reactive fluorine compound (made by Daikin Industries Co., Ltd., brand name "Offtool (trademark) DAC", solid content 20%, solvent: 1H, 1H, 3H- tetrafluoropropanol with respect to 100 weight part of solid content of this resin raw material) ) 0.2 parts by weight, 0.5 parts by weight of a reactive silicon compound (manufactured by Dainippon Ink and Chemicals, Inc., trade name "GRANDIC PC-4100"), and a photopolymerization initiator (manufactured by Chiba Specialty Chemicals Co., Ltd., trade name "irgacure 127 ") was added and the composition for hard-coat layer formation was prepared by diluting using butyl acetate so that solid content concentration might be 50 weight%. Moreover, the said reactive fluorine compound is represented by the said General formula (1), In R of the said General formula (1), it has one substituent which has a fluoroalkyl group which has a structure represented by the said General formula (2), The compound which has two substituents which have an acrylate group which has a structure represented by General formula (3) is made into a main component. Moreover, the said reactive silicon compound is a mixture containing the component 1, the component 2, and a solvent shown below.

Component 1: Reactive silicone represented by the said General formula (4) (Methyl hydride of the polydimethylsiloxane unit (X1) of the unit (c) of the said General formula (5), and the unit (b) of the said General formula (5)). The oxypropylsiloxane unit (X2), the 6-isocyanate hexyl isocyanuric acid unit (X3) of the said General formula (9), and the substituent (X4) of the unit (d) of the said General formula (7) are X1: X2: X3: X4 (molar ratio) = 187: 39: 100: 57) (6.85 parts by weight)

Component 2: the glycol compound represented by the general formula (8) (3.15 parts by weight)

Solvent: Ethyl Acetate (90 parts by weight)

(Production of a hard coat film)

The composition for hard-coat layer formation was coated on the transparent plastic film base material (40 micrometers in thickness, TAC film with a refractive index of 1.48, the Konica Minolta company make, brand name "KC4UY") using the comma coater, and the coating film was formed. After the said coating, the said coating film was dried by heating at 60 degreeC for 1 minute. The cured process was performed by irradiating the ultraviolet-ray of accumulated light quantity 300mJ / cm <2> with the high pressure mercury lamp by the high pressure mercury lamp, and the hard coat layer of thickness 7micrometer was formed. Thus, the hard coat film of this Example was manufactured.

[Example 2]

A hard coat film of this example was obtained in the same manner as in Example 1 except that the hard coat layer was formed so as to have a thickness of 15 μm.

Example 3

A hard coat film of this example was obtained in the same manner as in Example 1 except that 0.1 parts by weight of the reactive fluorine compound and 0.5 parts by weight of the reactive silicon compound were used.

Example 4

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 part by weight and the reactive silicon compound was 0.2 part by weight.

Example 5

A hard coat film of this example was obtained in the same manner as in Example 1 except that 0.1 parts by weight of the reactive fluorine compound and 1 part by weight of the reactive silicon compound were used.

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 part by weight and the reactive silicon compound was 1 part by weight.

Example 7

A hard coat film of this example was obtained in the same manner as in Example 1 except that 0.1 parts by weight of the reactive fluorine compound and 0.2 parts by weight of the reactive silicon compound were used.

Example 8

A hard coat film of this example was obtained in the same manner as in Example 1 except that 0.1 parts by weight of the reactive fluorine compound and 0.1 parts by weight of the reactive silicon compound were used.

Example 9

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 part by weight and the reactive silicon compound was 0.1 part by weight.

Comparative Example 1

A hard coat film of the present comparative example was obtained in the same manner as in Example 1 except that the reactive fluorine compound and the reactive silicon compound were not added.

Comparative Example 2

The hard coat film of the present comparative example was obtained in the same manner as in Example 1 except that the reactive fluorine compound was not added and the reactive silicon compound was 0.2 part by weight.

Comparative Example 3

The hard coat film of this comparative example was obtained by the method similar to Example 1 except not having added the said reactive fluorine compound and making the said reactive silicon compound 1 weight part.

[Comparative Example 4]

A hard coat film of the present comparative example was obtained in the same manner as in Example 1 except that 0.2 part by weight of the reactive fluorine compound and the reactive silicon compound were not added.

[Comparative Example 5]

A hard coat film of the present comparative example was obtained in the same manner as in Example 1 except that 1 part by weight of the reactive fluorine compound and the reactive silicon compound were not added.

Thus, various characteristics were measured or evaluated about each hard coat film of the obtained Example and the comparative example. The results are shown in Table 1 below.

As shown in the said Table 1, the hard coat film of an Example had favorable antifouling property represented by abrasion resistance and surface free energy value. In particular, in Examples 1 to 6, very excellent scratch resistance was shown. Moreover, the hard coat film of the Example had high pencil hardness and the curl characteristic was favorable. On the other hand, the hard coat film of the comparative example did not have enough scratch resistance. The hard coat films of Comparative Examples 1-3 have large surface free energy values and cannot be said to have good antifouling properties. Although the hard-coat films of Comparative Example 4 and Comparative Example 5 had small surface free energy values, scratch resistance was not sufficient.

The hard coat film of this invention using the composition for hard-coat layer formation of this invention has sufficient hardness, is excellent in abrasion resistance, and is also excellent in antifouling property. Therefore, the hard coat film of this invention can be used suitably for various image display apparatuses, such as optical elements, such as a polarizing plate, CRT, LCD, PDP, and ELD, for example, The use is not restrict | limited, It is applicable to a wide field. can do.

BRIEF DESCRIPTION OF THE DRAWINGS The schematic cross section which shows an example of the hard-coat film of this invention.

* Description of the symbols for the main parts of the drawings *

10: hard coat film

11: transparent plastic base material

12: hard coat layer

Claims (23)

As a composition for hard-coat layer formation used for formation of a hard-coat layer, The following (A) component, (B) component, (C) component, and (D) component are contained, The composition for hard-coat layer formation characterized by the above-mentioned. (A) component: Curable compound which has at least one group of an acrylate group and a methacrylate group (B) component: The particle | grains whose surface of an inorganic oxide particle is modified by the organic compound containing a polymerizable unsaturated group, and whose weight average particle diameter is 200 nm or less (C) component: a reactive fluorine compound (D) Component: Reactive Silicon Compound The method of claim 1, The composition for hard-coat layer formation in which the said (C) component has a structure represented by following General formula (1). [Formula 10]

(In the said General formula (1), at least 1 R is a substituent which has a fluoroalkyl group, and at least 1 R is a substituent which has at least one of an acrylate group and a methacrylate group.) The method of claim 2, The composition for hard-coat layer formation in R of the said General formula (1) in which the substituent which has the said fluoroalkyl group has a structure represented by following General formula (2). [Formula 11]

(In the said General formula (2), n is an integer of 1 or more.) The method of claim 2, The composition for hard-coat layer formation in R of the said General formula (1) in which the substituent which has the said acrylate group has a substituent represented by following General formula (3). [Formula 12]

The method of claim 1, The composition for hard-coat layer formation in which the said (D) component has a structure represented by following General formula (4). [Formula 13]

(In the said General formula (4), R is a substituent selected from the substituent which has a siloxane structure, the substituent which has at least one of an acrylate group, and a methacrylate group, and the substituent which has an active hydrogen group, and each R is the same. Or different.) The method of claim 5, The composition for hard-coat layer formation in R of the said General formula (4) in which the substituent which has the said siloxane structure has a structure represented by following General formula (5). [Formula 14]

(In the said General formula (5), n is an integer of 1 or more.) The method of claim 5, In R of the said General formula (4), the composition for hard-coat layer formation in which the substituent which has the said active hydrogen group has a substituent represented by following General formula (6). [Formula 15]

The method of claim 5, In R of the said General formula (4), the composition for hard-coat layer formation in which the substituent which has the said acrylate group has a substituent represented by following General formula (7). [Formula 16]

(In the said General formula (7), m and n are the integers of 1-10, respectively, and may be same or different. L is an integer of 1-5.) The method of claim 1, The composition for hard-coat layer formation whose weight average particle diameter of the said (B) component is the range of 1-100 nm. The method of claim 1, The composition for hard coat layer formation in which the said (B) component contains at least 1 sort (s) of microparticles | fine-particles selected from the group which consists of a titanium oxide, a silicon oxide, aluminum oxide, zinc oxide, tin oxide, and zirconium oxide. The method of claim 1, The composition for hard-coat layer formation in which the said (B) component is mix | blended in the range of 100-200 weight part with respect to 100 weight part of said (A) component. The method of claim 1, For hard coat layer formation, the said (C) component is mix | blended in the range of 0.05-0.4 weight part with respect to 100 weight part of said (A) component, and the said (D) component is mix | blended in the range of 0.05-1 weight part. Composition. The method of claim 1, Furthermore, the composition for hard-coat layer formation containing the following (E) component. (E) component: The glycol compound represented by following General formula (8) [Formula 17]

(In General Formula (8), m and n are each an integer of 1 or more, and may be the same or different.) The method of claim 13, The said (C) component is mix | blended in the range of 0.05-0.4 weight part with respect to 100 weight part of said (A) component, Furthermore, the said (D) component and the said (E) component mix | blend in the range of 0.1-1 weight part in total. The composition for hard-coat layer formation. As a hard coat film which has a hard-coat layer in at least one surface of a transparent plastic film base material, The hard coat film is formed of the hard coat layer-forming composition according to claim 1. The method of claim 15, The outermost layer of the hard coat layer has a fluorine atom strength derived from a reactive fluorine compound in the range of 5 to 30% in the analysis by ESCA, and a silicon atom strength of 0.2 to 10% derived from a reactive silicon compound. In-scope, hard coat film. The method of claim 15, The hard coat film whose thickness of the said hard coat layer is a range of 12-50 micrometers. The method of claim 15, The hard-coat film whose pencil hardness in the weight 500g based on the specification of JISK5600-5-4 of the said hard-coat layer surface is 4H or more. The method of claim 15, The hard coat film whose surface free energy of the said hard-coat layer surface is 15-25 mJ / m <2>. The method of claim 15, A hard coat film, wherein the hard coat layer further contains fine particles. The hard coat film of Claim 15 is laminated | stacked on at least one surface of an optical member, The optical element characterized by the above-mentioned. The hard coat film of Claim 15 is provided, The image display apparatus characterized by the above-mentioned. An image display device comprising the optical element according to claim 21.

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