KR101069569B1 - Composition for forming hard-coat layer, hard-coat film, optical element, and image display - Google Patents

Abstract

(assignment)

Provided are a hard coat layer-forming composition and a hard coat film which have a sufficient hardness, prevent the occurrence of curl and folds due to curing shrinkage, and obtain a hard coat layer excellent in scratch resistance.

(Solution)

On at least one surface of the transparent plastic film base material 11, (A) Component: Curable compound which has at least one group of an acrylate group and a methacrylate group, (B) Component: The surface of an inorganic oxide particle has a polymerizable unsaturated group The hard coat layer 12 was prepared using the composition for hard-coat layer formation containing the particle | grains modified with the organic compound to contain, and (C) component containing the compound represented by following General formula (1). Form.

In the general formula (1), 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.

Composition for hard coat layer formation, hard coat film, optical element, image display device

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.

For the hard coat treatment, a hard coat film having a thin hard coat layer having a thickness of 2 to 10 µm on one or both surfaces of the transparent plastic film substrate is generally used. 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.

With the application of LCDs to home televisions, users of ordinary home televisions can easily assume the same handling as those of conventional TVs using glass CRTs, even though televisions using LCDs. Therefore, the improvement of hardness is calculated | required about the hard coat film used for LCD.

Improvement of the hardness of a hard coat film becomes possible by increasing the layer thickness of a hard coat layer. However, when the layer thickness is increased, curling may occur due to curing shrinkage during hard coat layer formation. Moreover, when forming a hard-coat layer in a roll-shaped transparent plastic film base material, the coating area of the composition for hard-coat layer formation in the width direction of the said transparent plastic film base material, and the part which is not (that is, for hard-coat layer formation) There exists a possibility that a hard coat film may generate | occur | produce in the vicinity of the boundary of the coating part of a composition and the uncoated part of the transparent plastic film base material edge part. If curling or folding of the hard coat film occurs, it will be a result of causing problems in the continuous production process of the hard coat film, the adhesive lamination work for the polarizing plate of the hard coat film, and the like.

Then, the method of making hardening shrinkage force at the time of hard-coat layer formation small by adding inorganic microparticles | fine-particles in hard coat layer, and preventing generation | occurrence | production of the curl and fold of a hard coat film is proposed (refer patent document 1). In the case of adopting this method, the hardness of the hard coat layer is increased by the addition of the fine particles, but it may be weak against scratch, and there is room for improvement in scratch resistance.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2006-106427

Then, an object of this invention is to provide the composition for hard-coat layer formation which has sufficient hardness, the generation | occurrence | production of the curl and folding which arise from hardening shrinkage is prevented, and the hard coat layer which is excellent in abrasion resistance can be obtained. . Moreover, an object of this invention is to provide the hard-coat film which has sufficient hardness, the generation | occurrence | production of the curl and folding which arise from hardening shrinkage, and is excellent in scratch resistance, the optical element using the same, and an image display apparatus using the same.

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, and (C) 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 modified by the organic compound in which the inorganic oxide particle surface contains a polymerizable unsaturated group

(C) component: Reactive silicone containing the compound represented by following General formula (1)

[Formula 7]

In the general formula (1), 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.

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 is an image display device including a hard coat film or an optical element, wherein the hard coat film is the hard coat film of the present invention, and the optical element is the optical element of the present invention. do.

The hard coat film of the present invention formed of the composition for forming a hard coat layer of the present invention has a sufficient hardness as the functions of the three components interact with each other, and prevents the occurrence of curling and folding caused by the curing shrinkage of the hard coat layer. It is also excellent in scratch resistance. The performance improvement of the hard coat film achieved by the present invention may be obtained by a combination of the three components, or may be obtained by each of the three components. For example, when the said composition for hard-coat layer formation contains the said (A) component, the hardness of the hard-coat layer formed, for example becomes high, and elasticity and flexibility (flexibility) are provided, and the said (B) By containing a component, the hardening shrinkage force at the time of hard coat layer formation is made small, for example, the occurrence of curl and fold of a hard coat film is prevented effectively, and the hard coat formed, for example by containing the said (C) component As the layer surface structure becomes rigid, the slipperiness is improved and the scratch resistance is excellent. Moreover, the hard coat film of this invention also shows the side effect that a fingerprint removal property and a pen | covery property become favorable by containing the said (C) component, for example. In addition, description of the function and effect | action of each of these components is an illustration, and does not restrict this invention at all.

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 (2), for example. Let the structure represented by following General formula (2) be a 6-isocyanate hexyl isocyanuric acid unit (a).

[Formula 8]

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 siloxane structure may have a structure represented by following General formula (3), for example. The structure represented by following General formula (3) has a polydimethylsiloxane unit (c) at the terminal, the said unit (c) is couple | bonded with the methylhydroxypropylsiloxane unit (b), and 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 9]

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 active hydrogen group may have a substituent represented by following General formula (4), for example. In the substituent represented by following General formula (4), 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 (4), the said carboxyl group may decarboxylate and may be an amino group.

[Formula 10]

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

[Formula 11]

6-isocyanate hexyl isocyanuric acid which contains the unit (a) which is a structure represented by the said General formula (2), and also the substituent represented by the said General formula (3)-(5) 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 (C) 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 (C) 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.

In the composition for forming a hard coat layer of the present invention, the weight average particle diameter of the component (B) is preferably 200 nm or less in terms of preventing scattering of light, preventing transmittance of the hard coat layer, preventing coloring, and transparency. 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. More preferably, it is the range of 1-100 nm.

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).

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

(D) component: The glycol compound represented by following General formula (6)

[Chemical Formula 12]

In said Formula (6), m and n are 1 or more integers, respectively, and may be same or different.

In the composition for forming a hard coat layer of the present invention, the total amount of the component (C) and the component (D) is preferably blended in a range of 0.01 to 10 parts by weight based on 100 parts by weight of the component (A). .

In the hard coat film of this invention, although the thickness in particular of the said hard coat layer is not restrict | limited, For example, it is the range of 10-50 micrometers. 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 10 to 40 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.

The hard coat film of this invention may be an aspect in which the antireflection layer is formed in the outer surface of the said hard coat layer in order to reduce the reflection of the light in the interface of a hard coat layer and air. If the hard coat film in which the antireflection layer was formed is applied, for example to an image display apparatus, it becomes possible to improve the visibility of the image of a display screen.

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, and the said (C) 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. Examples of the monofunctional methacrylate include methacrylates of ethylene oxide-modified phenols, methacrylates of propylene oxide-modified phenols, methacrylates of ethylene oxide-modified nonylphenols, methacrylates of propylene oxide-modified nonylphenols, 2-ethylhexylcarbitol methacrylate, isobornyl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyhexyl methacrylate Acrylate, 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-butanedioldiacrylate, neopentylglycoldiacrylate, 1,6-hexanedioldiacrylate, diacrylate of ethylene oxide modified neopentylglycol, diacrylate of ethylene oxide modified bisphenol A, propylene Diacrylate of oxide modified bisphenol A, Diacrylate of ethylene oxide modified hydrogenated bisphenol A, Trimethylol propane diacrylate, Trimethylol propane allyl ether diacrylate, Trimethylol propane triacrylate, Ethylene oxide modified trimethylol propane tree Acrylic ray And propylene oxide modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate and the like. The polyfunctional methacrylate is, for example, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacryl Dimethacrylate of polypropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 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, trimethylolpropanedimethacrylate, trimethylolpropane allyl ether dimethacrylate Acrylate, trimethylolpropanetrimethacrylate, ethylene oxide Modified 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, the component (B) has a weight average particle diameter in the range of 1 nm to 200 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. It is preferable that it is so-called 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. More 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 polymerizable 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. From these points, 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 blending about 35-45 weight% with respect to the whole, the said refractive index difference can be controlled to 0.02 or less, and generation | occurrence | production of interference fringe can be suppressed.

The said (C) component is as above-mentioned. All of R of the compound represented by the said General formula (1) may differ, and may be the same. It is sufficient as (C) component to contain 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. The blending ratio of the above (C) component is not particularly limited. By use of the said (C) component, for example, the hard-coat layer surface structure formed becomes rigid, slipperiness | lubricacy improves and it is excellent in scratch resistance. From these points, it is preferable that the compounding ratio of the said (C) component is the range of 0.01-5 weight part with respect to 100 weight part of said (A) components, More preferably, it is the range of 0.05-3 weight part, It is further more preferable Preferably it is the range of 0.1-2 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 three components in the solvent, for example, and the said composition for hard-coat layer formation is carried out in 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-hep Tanone, 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. From the viewpoint of improving the adhesion between the transparent plastic film substrate and the hard coat layer, the solvent preferably contains ethyl acetate at a ratio of 20% by weight or more of the whole, and more preferably 25% by weight or more of the whole. Ethyl acetate is contained, and ethyl acetate is optimally contained in the ratio of 30 to 70weight% of the whole. If the ratio of ethyl acetate in the said solvent is 70 weight% or less, the volatilization rate of the said solvent can be made moderate and it becomes possible to prevent coating nonuniformity and dry nonuniformity effectively. The kind of solvent used together with the said ethyl acetate is not specifically limited. The solvent includes, for example, butyl acetate, methyl ethyl ketone, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and the like.

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

The blending ratio of the component (D) is not particularly limited. 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.

When using the said (D) component, in preparation of the said composition for hard-coat layer formation, it is preferable to prepare the said (D) component as a mixture with the said (C) 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.

It is preferable that the compounding quantity of the mixture of the said (C) component and the said (D) component is the range of 0.01-10 weight part with respect to 100 weight part of said (A) component, More preferably, it is the range of 0.05-8 weight part, More preferably, it is the range of 0.1-5 weight part.

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.

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 the schematic cross section of FIG. 2, the other example of the hard-coat film structure of this invention is shown. As shown in the figure, the hard coat film 20 is provided with a hard coat layer 22 on one side of the transparent plastic film base 21, and the antireflection layer 23 is formed on the outer surface of the hard coat layer 22. It is a configuration that is formed. When the light hits the object, the light is repeatedly transmitted to the rear surface of the object by repeating phenomena such as reflection at the interface, absorption in the inside, and scattering. For example, in the case where the hard coat film is attached to the image display device, reflection of light at the interface between the air and the hard coat layer is one of the factors that lower the visibility of the image. The antireflection layer reduces surface reflection. In the hard coat film 20 shown in FIG. 2, the hard coat layer 22 and the antireflection layer 23 are formed on one surface of the transparent plastic film base 21. 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 and the antireflection layer were formed in both surfaces of the transparent plastic film base material. In the hard coat film 20 shown in FIG. 2, the hard coat layer 22 and the antireflection layer 23 are single layers, respectively. However, this invention is not limited to this. In the hard coat film of the present invention, the hard coat layer and the antireflection layer may have a multilayer structure in which two or more layers are laminated, respectively.

In the present invention, the antireflection layer is formed by stacking two or more layers of the optical thin film or the optical thin film in which thickness and refractive index are strictly controlled. In the antireflection layer, the antireflection function is generated by negating the inverted phases of the incident light and the reflected light with each other using the interference effect of light. The wavelength range of visible light which produces the said antireflection function is the range of 380-780 nm, for example, The wavelength range of especially high visibility is 450-650 nm. It is preferable that the said antireflection layer is designed so that the reflectance of 550 nm which is the center wavelength is minimized.

In the design of the antireflection layer based on the interference effect of light, a means for improving the interference effect is, for example, a method of increasing the refractive index difference between the antireflection layer and the hard coat layer. Generally, in the multilayer antireflection layer of the structure which laminated | stacked 2-5 layers of optical thin layers (thin film which strictly controlled the thickness and refractive index), two or more predetermined thicknesses form the component from which refractive index differs. Therefore, the degree of freedom in the optical design of the antireflection layer is increased, so that the antireflection effect can be further improved, and the spectral reflection characteristic can also be made uniform (flat) in the visible light region. In the optical thin film, high thickness precision is required. For this reason, in general, the formation of each layer is carried out by vacuum deposition, sputtering, CVD or the like which is a dry method.

The multilayer antireflection layer is preferably a two-layer structure in which a silicon oxide layer having a low refractive index (refractive index: about 1.45) is laminated on a titanium oxide layer having a high refractive index (refractive index: about 1.8). More preferably, it is a four-layer structure which laminated | stacked the silicon oxide layer on the titanium oxide layer, laminated | stacked the other titanium oxide layer on it, and laminated | stacked the other silicon oxide layer on it. By forming these two-layer antireflection layers or four-layer antireflection layers, the reflection of the wavelength region of visible light (for example, the range of 380-780 nm) can be reduced uniformly.

The antireflection effect can also be expressed by forming a single optical thin film (antireflection layer) on the hard coat layer. In general, a coating method such as a fountain coat, a die coat, a spin coat, a spray coat, a gravure coat, a roll coat, a bar coat, etc., which is a wet method, is employed to form a single layer antireflection layer.

The material for forming the single-layer antireflection layer is, for example, a resin material such as an ultraviolet curable acrylic resin, a hybrid material in which inorganic fine particles such as colloidal silica is dispersed in the resin, metal such as tetraethoxysilane, titanium tetraethoxide and the like. Sol-gel materials using alkoxides and the like. It is preferable that the said forming material contains a fluorine group in order to provide the antifouling property of the surface. The forming material is preferably a forming material having a high inorganic component content for reasons such as scratch resistance, and more preferably the sol-gel material. The sol-gel material may be used by partial condensation.

As said antireflection layer (low refractive index layer), the siloxane oligomer of the range of ethylene glycol conversion number average molecular weights 500-10000, the polystyrene conversion number average molecular weight 5000 or more, and contain the fluorine compound which has a fluoroalkyl structure and a polysiloxane structure. What is formed of the material (the material of Unexamined-Japanese-Patent No. 2004-167827) is preferable by the point which is compatible with abrasion resistance and low reflection.

The antireflection layer (low refractive index layer) may contain an inorganic sol in order to improve film strength. The inorganic sol is not particularly limited. The said inorganic sol contains silica, alumina, magnesium fluoride, etc., for example. Among these, silica sol is preferable. The compounding ratio of the said inorganic sol is the range of 10-80 weight part with respect to 100 weight part of total solids of the said antireflection layer forming material, for example. The weight average particle diameter of the inorganic fine particles in the inorganic sol is preferably in the range of 2 to 50 nm, more preferably in the range of 5 to 30 nm.

It is preferable that the formation material of the said antireflection layer contains the hollow, spherical silicon oxide fine particles. It is preferable that the weight average particle diameters are about 5-300 nm, and, as for the said silicon oxide fine particle, the range of 10-200 nm is more preferable. The silicon oxide fine particles have a hollow sphere shape in which a cavity is formed inside an outer shell having pores. The cavity contains at least one of a solvent and a gas at the time of preparing the silicon oxide fine particles. It is also preferred that a precursor material for forming the cavity of the silicon oxide fine particles remains in the cavity. The thickness of the outer shell is preferably in the range of about 1 to 50 nm, and preferably in the range of about 1/50 to 1/5 of the weight average particle diameter of the silicon oxide fine particles. It is preferable that the said outer shell is formed by the some coating layer. In the silicon oxide fine particles, the pores are preferably closed, and the cavity is sealed by the outer shell. This is because the porous or voids of the silicon oxide fine particles are held in the antireflection layer, and the refractive index of the antireflection layer can be further reduced. As a manufacturing method of such hollow, spherical silicon oxide fine particles, the manufacturing method of the silica type microparticles | fine-particles disclosed by Unexamined-Japanese-Patent No. 2001-233611, for example is employ | adopted preferably.

The drying and curing temperatures at the time of forming the antireflection layer (low refractive index layer) are not particularly limited. The said drying and hardening temperature is the range of 60-150 degreeC, for example, Preferably it is the range of 70-130 degreeC. The said drying and hardening time is the range of 1 to 30 minutes, for example, and when considering productivity, the range of 1 to 10 minutes is preferable. Moreover, the hard coat film of the high hardness which has an antireflection layer is obtained by heat-processing further after the said drying and hardening. The heat treatment temperature is not particularly limited. The said heat processing temperature is 40-130 degreeC, for example, Preferably it is 50-100 degreeC. The heat treatment time is not particularly limited. The said heat processing time is a range of 1 minute-100 hours, for example, and it is more preferable to carry out 10 hours or more from a viewpoint of abrasion resistance improvement. The heat treatment can be performed by a method using a hot plate, an oven, a belt furnace or the like.

When attaching the hard coat film including the antireflection layer to an image display device, the frequency at which the antireflection layer becomes the outermost layer is high. For this reason, the antireflection layer is susceptible to contamination from the external environment. The antireflection layer is more likely to be contaminated than a simple transparent plate or the like. The antireflection layer may have a change in surface reflectance due to adhesion of contaminants such as fingerprints, handprints, sweat, hair dressings, or the like, or may cause white matters to appear, resulting in inconspicuous display content. In order to prevent adhesion of the contaminants and to improve the ease of removal of the adhered contaminants, it is preferable that a pollution prevention layer formed of a fluorine group-containing silane compound, a fluorine group-containing organic compound, or the like be laminated on the antireflection layer.

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. Surface treatment of the surface of the hard coat layer further improves adhesion to the antireflection layer, the polarizer or the polarizing plate. 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, In addition, the structure which laminated | stacked the polarizer and a transparent protective film 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 liquid crystal display device of this invention is the same structure as the conventional liquid crystal display device except using the hard coat film of this invention. The liquid crystal display device of the present invention can be manufactured by, for example, attaching a driving circuit by appropriately assembling each component such as an optical element such as a liquid crystal cell, a polarizing plate, and an illumination system (backlight, etc.) as necessary. Can be. 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 the flat end surface of the circumference of 25 mm in diameter, and the sample surface was reciprocated 30 at a speed of about 100 mm per second at a load of 1.5 kg, the sample surface 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.

(Curl value)

A 100 mm × 100 mm sample is cut out at the center of the hard coat film, the width W of the sample after curling is measured using a digital caliper, and the curl value (mm) is obtained by the following formula (I). It was.

Curl value (mm) = 100-W. (Ⅰ)

W: width of the sample after curling (mm)

A: curl value is less than 75 mm

B: curl value is 75 mm or more but less than 80 mm

C: curl value is 80 mm or more

(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

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 / methylethylketone (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 mixture (Dainippon Ink Chemical Industry Co., Ltd. product, brand name "GRANDIC PC-4100") containing (C) component, (D) component, and a solvent shown below were prepared.

(C) component: Reactive silicone represented by the said General formula (1) (The polydimethylsiloxane unit (X1) of the unit (c) of the said General formula (3), and the methyl of the unit (b) of the said General formula (3).) Hydroxypropyl siloxane unit (X2), the 6-isocyanate hexyl isocyanuric acid unit (X3) of the said General formula (2), and the substituent (X4) of the unit (d) of the said General formula (5), X1 : X2: X3: X4 (molar ratio) = 187: 39: 100: 57) (6.85 parts by weight)

(D) component: The glycol compound represented by the said General formula (6) (3.15 weight part)

Solvent: Ethyl Acetate (90 parts by weight)

(Preparation of the composition for hard coat layer formation)

0.5 weight part of said mixture and 0.5 weight part of photoinitiators (Ciba Specialty Chemicals make, brand name "Irgacure 127") are added to 100 weight part of said resin raw materials, and butyl acetate so that solid content concentration may be 50 weight%. By diluting using, the composition for hard-coat layer formation was prepared.

(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 of width 300mm, the Konica Minolta company make, brand name "KC4UYW") using the bar coater, and the coating film was formed. . After the said coating, the said coating film was dried by heating at 100 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 to the coating film after the said drying, and formed the hard-coat layer of thickness 17micrometer. Thus, the hard coat film of this Example was manufactured.

Comparative Example 1

A hard coat film of this comparative example was produced in the same manner as in Example 1, except that the following reactive silicone (manufactured by Dainippon Ink Chemical Co., Ltd., product name "GRANDIC PC-4131") was used instead of the mixture.

Reactive silicone: polydimethylsiloxane unit: 3-acryloyl-2-hydroxy-propoxypropylsiloxane unit: 2-acryloyl-3-hydroxy-propoxypropylsiloxane unit (weight ratio) = 55: 36: 9

Comparative Example 2

A hard coat film of this comparative example was produced in the same manner as in Example 1, except that the following reactive silicone (manufactured by Dainippon Ink Chemical Co., Ltd., product name "GRANDIC PC-4151") was used instead of the mixture.

Reactive silicone: Polydimethylsiloxane Unit: Methyl polyethyleneglycolpropylethersiloxane having an acrylate group at the terminal Unit: Methyl polyethyleneglycolpropylethersiloxane unit having a hydroxyl group at the terminal: An acrylate group, a hydroxyl group, and an arylether group at the terminal Polyethylene glycol having any of the groups (weight ratio) = 64: 15: 8: 13

Comparative Example 3

Instead of the above resin raw material, the following ultraviolet curable resin (manufactured by Dainippon Ink Chemical Co., Ltd., trade name "GRANDIC PC-1070", solid content: 66 wt%), and the thickness of the hard coat layer were changed to 20 µm. A hard coat film of this comparative example was manufactured in the same manner as in Example 1 except for the one.

Dipentaerythritol acrylate (18 parts by weight)

Aliphatic urethane acrylate (36 parts by weight)

Pentaerythritol diacrylate (0.5 part by weight)

Pentaerythritol triacrylate (9 parts by weight)

Pentaerythritol tetraacrylate (15 parts by weight)

A mixture of a polymer and a copolymer having a repeating unit represented by the following General Formula (7) (21 parts by weight)

Photoinitiator: Add 3 parts by weight of a brand name "Irgacure 184" (made by Chiba Specialty Chemicals) and a brand name "Lucirine TPO" (made by BASF)

Mixed solvent: butyl acetate: ethyl acetate (weight ratio) = 89: 11

[Formula 13]

In the formula (7), R ¹ is -H or -CH ₃ And, R ² is a group represented by -CH ₂ CH ₂ OX or the following general formula (8), wherein X is an acryloyl group represented by formula (9) or to -H.

[Formula 14]

In the said General formula (8), said X is acryloyl group represented by -H or following General formula (9), and said X may be same or different.

[Formula 15]

[Comparative Example 4]

Except having changed the thickness of the hard-coat layer into 15 micrometers, the hard coat film of this comparative example was produced by the method similar to the comparative example 3.

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 Example 1 had good scratch resistance, the pencil hardness was high, and the curl characteristic was favorable. On the other hand, although the pencil hardness of the hard coat films of Comparative Example 1 and Comparative Example 2 was high, scratch resistance was bad. Moreover, although the hard coat film of the comparative example 3 had favorable scratch resistance, the pencil hardness was slightly low and the curl characteristic was bad. Although the hard-coat film of the comparative example 4 had good scratch resistance, pencil hardness was low and the curl characteristic was slightly bad.

The hard coat film of this invention using the composition for hard-coat layer formation of this invention has sufficient hardness, the generation | occurrence | production of the curl and folding which originate in the cure shrinkage of a hard-coat layer is prevented, and it is excellent in abrasion resistance. 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.

It is a schematic cross section which shows the other example of the hard-coat film of this invention.

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

10, 20: hard coat film

11, 21: transparent plastic substrate

12, 22: hard coat layer

23: antireflection layer

Claims (17)

As a composition for hard-coat layer formation used for formation of a hard-coat layer, The following (A) component, (B) component, and (C) 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 modified by the organic compound in which the inorganic oxide particle surface contains a polymerizable unsaturated group (C) component: Reactive silicone containing the compound represented by following General formula (1) [Formula 1]

(In the said General formula (1), R is a substituent chosen 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 1, The composition for hard-coat layer formation which has a structure represented by the said (C) component with following General formula (2). [Formula 2]

The method of claim 1, The composition for hard-coat layer formation in R of the said General formula (1) in which the substituent which has the said siloxane structure has a structure represented by following General formula (3). (3)

(In the said General formula (3), n is an integer of 1 or more.) The method of claim 1, The composition for hard-coat layer formation in R of the said General formula (1) in which the substituent which has the said active hydrogen group has a substituent represented by following General formula (4). [Formula 4]

The method of claim 1, 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 (5). [Chemical Formula 5]

(In the said General formula (5), 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 200 nm or less. 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, Furthermore, the composition for hard-coat layer formation containing the following (D) component. (D) component: The glycol compound represented by following General formula (6)  [Formula 6]

(In the said General formula (6), m and n are 1 or more integers, respectively and may be the same or different.) The method of claim 9, The composition for hard-coat layer formation in which the said (C) component and the said (D) component are mix | blended in the range of 0.01-10 weight part in total with respect to 100 weight part of said (A) component. 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 11, The hard coat film whose thickness of the said hard-coat layer is the range of 10-50 micrometers. The method of claim 11, 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 11, A hard coat film, wherein an antireflection layer is laminated on an outer surface of the hard coat layer. The hard coat film of Claim 11 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 11 is provided, The image display apparatus characterized by the above-mentioned. An image display device comprising the optical element according to claim 15.

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