JP5343338B2 - Anti-glare film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antiglare film which is excellent in visibility and scratch resistance, and installed on a front surface used, mainly, in a display device like an LCD or a PDP. <P>SOLUTION: The antiglare film has a hard coat layer and an antiglare layer provided on a transparent base film, and the antiglare layer comprises fine light-transmissive particles A, fine reactive inorganic particles B which have an average particle size of 30 to 100 nm and have surfaces partially coated with an organic component and have a reactive function group b, and a hardened material of a resin composition for forming the antiglare layer, which contains a binder component C having a reactive functional group c. The antiglare layer has a thickness of 1 to 5 &mu;m, and a skin layer wherein the average number of fine reactive inorganic particles is smaller is provided on the interface side of the antiglare layer, and the hard coat layer comprises a hardened material of a resin composition for forming the hard coat layer, which contains fine reactive inorganic particles D having a reactive functional group d and a binder component E having a reactive functional group e. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to an antiglare film installed on the front surface of a display (image display device) such as a liquid crystal display (LCD), a cathode ray tube display (CRT), or a plasma display (PDP).

In the display as described above, an anti-glare film having a fine uneven surface is provided on the display surface in order to prevent reflection of light irradiated from the outside on the display surface.
For such an antiglare film, a type in which an antiglare layer having a concavo-convex shape is formed on the surface by coating a resin composition containing a large particle size or cohesive particles on the surface of the transparent substrate, the particles In this type, a phase separation structure is formed by spinodal decomposition, and a curable resin is cured to form an antiglare layer having an uneven shape on the surface, or a film having an uneven surface is laminated. There is a type in which an antiglare layer having an uneven shape is formed on the surface by transferring the uneven shape (Patent Document 1).

  However, the conventional antiglare film is provided with an antiglare layer on a transparent substrate, and the surface irregularities are made dense for the purpose of improving the sharpness, that is, in addition to improving the antiglare property, In order to ensure the hardness of the layer, that is, to impart scratch resistance, the film thickness of the antiglare layer was thick. Since the film thickness is thick, the amount of the light-transmitting fine particles contained in the anti-glare layer is increased for the purpose of imparting anti-glare properties, thereby causing the problem that internal scattering more than necessary occurs and the contrast is lowered. there were.

JP 2006-103070 A

  The present invention has been made to solve the above problems, and an object of the present invention is to provide an antiglare film having good visibility and excellent scratch resistance.

As a result of intensive studies on the above problems, the present inventors have found that even if the film thickness of the antiglare layer is an extremely thin film, the antiglare property is not lost, and the problem that the contrast is lowered can be solved. By providing a hard coat layer adjacent to the anti-glare layer in the spatial space of the film thickness generated by the anti-glare layer becoming an ultra-thin film, the hard coat layer is responsible for the expression of scratch resistance, The present inventors have found that an antiglare film can be obtained that prevents deterioration of contrast, is excellent in visibility, and is excellent in scratch resistance, and has completed the present invention.
That is, the features of the present invention that solve the above problems are as follows.

The antiglare film according to the present invention is
On one side of the transparent substrate film, an antiglare film provided with an antiglare layer having a concavo-convex shape on the surface adjacent to the hard coat layer and the hard coat layer from the side close to the transparent substrate film,
The antiglare layer is
Translucent fine particles A having an average particle size of 1 μm or more and 10 μm or less, defined as the most existing particle size in either the volume distribution or the number distribution of particle diameters measured by the Coulter counter method,
Reactive inorganic fine particles B having at least a part of the surface coated with an organic component and having a reactive functional group b introduced by the organic component on the surface; and
Anti-glare layer comprising a binder component C having a reactive functional group c having cross-linking reactivity with the reactive functional group b of the reactive inorganic fine particle B, and containing a curable binder system also having curing reactivity in the system It consists of the hardened | cured material of the resin composition for formation, and the film thickness of the said glare-proof layer is 1 micrometer or more and 5 micrometers or less,
The reactivity per unit area in the cross section in the thickness direction of the antiglare layer compared to the region on the transparent substrate film side in the surface layer region on the opposite side to the transparent substrate film of the antiglare layer and in the vicinity thereof It has a skin layer with a small average number of inorganic fine particles B,
The average number of the reactive inorganic fine particles B per unit area in the thickness direction cross section of the skin layer is 50% of the average number of the reactive inorganic fine particles B per unit area in the thickness direction cross section of the antiglare layer. And not more than 80%,
The average distance between particles of the reactive inorganic fine particles B to be dispersed in the region of the transparent substrate film side of the skin layer is not less 30nm or more,
The hard coat layer is
Reactive inorganic fine particles D having at least a part of the surface coated with an organic component and having a reactive functional group d introduced by the organic component on the surface; and
A hard coat layer containing a binder component E having a reactive functional group e having cross-linking reactivity with the reactive functional group d of the reactive inorganic fine particle D, and containing a curable binder system having curing reactivity in the system It consists of a cured product of the forming resin composition,
It is an anti-glare film characterized by having a hardness of 3H or more when a pencil hardness test specified in JIS K5600-5-4 (1999) is performed with a load of 500 g on the surface of the anti-glare layer.

  The translucent fine particles A form surface irregularities and impart antiglare properties to the antiglare layer.

  The antiglare layer and the hard coat layer according to the present invention have high hardness because they contain reactive inorganic fine particles having high hardness, and furthermore, the reactive inorganic fine particles and the binder component form a number of cross-linking points. Strength is improved and excellent scratch resistance is exhibited.

  In the antiglare layer of the present invention, the average particle diameter of the translucent fine particles A and the reactive inorganic fine particles B is in the above range, and the film thickness of the antiglare layer is 1 μm or more and 5 μm or less. Thus, an excessive internal scattering effect of the antiglare layer is suppressed, and a decrease in contrast is prevented while securing an appropriate internal scattering effect.

  In the antiglare layer of the present invention, the average number of the reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer is the reactive inorganic per unit area in the cross section in the thickness direction of the antiglare layer. Compared to the average number of particles B, it is less than 80%. When the average number of particles in the skin layer is small, the number of the reactive inorganic fine particles B partially protruding from the interface of the antiglare layer on the side opposite to the transparent substrate film is also reduced. Therefore, when the anti-glare layer is saponified, the number of the reactive inorganic fine particles B eluted or dropped from the interface of the anti-glare layer into the alkaline solution is reduced. Thereby, the anti-glare film which concerns on this invention can acquire the outstanding saponification resistance.

  The reason why the antiglare layer has such a skin layer is not certain, but by setting the particle size of the reactive inorganic fine particles B to 30 nm or more and 100 nm or less, the diffusion coefficient of the reactive inorganic fine particles B is reduced, It is presumed that the reactive inorganic fine particles B are more likely to stay on the transparent substrate film side than the interface opposite to the transparent substrate film of the antiglare layer.

  In the antiglare film which concerns on this invention, it is preferable that the film thickness of the said hard-coat layer is 2 micrometers or more and 20 micrometers or less from the point which ensures the abrasion resistance of an antiglare film.

By using the antiglare film according to the present invention, it is also possible to obtain a hard coat layer having a hardness of 3H or more when a pencil hardness test specified in JIS K5600-5-4 (1999) is performed at a load of 500 g. It is.

  In the antiglare film according to the present invention, it is preferable that the inorganic fine particles serving as the core of the translucent fine particles A and the reactive inorganic fine particles B are made of silica from the viewpoint that the antiglare property can be improved.

In the antiglare film according to the present invention, at least a part of the surface of the reactive inorganic fine particle B and the reactive inorganic fine particle D is coated with an organic component, and the reactive functional group b is formed by the organic component. Introduced on the surface of the reactive inorganic fine particle B, the organic component is contained in an amount of 1.00 × 10 ⁻³ g / m ² or more per unit surface area of the inorganic fine particle before coating, and the reactive functional group d is Curing that the organic component is introduced into the surface of the reactive inorganic fine particle D and the organic component is contained in an amount of 1.00 × 10 ⁻³ g / m ² or more per unit surface area of the inorganic fine particle before coating. This is preferable from the viewpoint of improving the hardness of the film.

  In the antiglare film according to the present invention, the reactive functional group b of the reactive inorganic fine particle B, the reactive functional group c of the binder component C, the reactive functional group d of the reactive inorganic fine particle D, and the binder The reactive functional group e of Component E can have a polymerizable unsaturated group, can improve the film strength, and forms a cross-linking bond at the layer interface between the antiglare layer and the hard coat layer. This is preferable because the adhesion between the layers can be improved.

  In the antiglare film according to the present invention, the reactive inorganic fine particle B and the reactive inorganic fine particle D are saturated or unsaturated carboxylic acid, acid anhydride, acid chloride, ester and acid corresponding to the carboxylic acid. Presence of one or more surface modification compounds having a molecular weight of 500 or less selected from the group consisting of amides, amino acids, imines, nitriles, isonitriles, epoxy compounds, amines, β-dicarbonyl compounds, silanes, and functional metal compounds It is preferable that the inorganic fine particles are dispersed in water and / or an organic solvent as a dispersion medium from the viewpoint of improving the film strength even if the organic component content is small.

  In the anti-glare film according to the present invention, the surface modification compound is preferably a compound having a hydrogen bond-forming group from the viewpoint that the organic component can be surface modified efficiently.

  In the antiglare film according to the present invention, at least one of the surface modification compounds has a polymerizable unsaturated group that becomes the reactive functional group b and the reactive functional group d, thereby improving the film strength. It is preferable from the point of making it.

  In the antiglare film according to the present invention, the reactive inorganic fine particles B are formed by reactive functional groups b introduced into the surface of the inorganic fine particles before coating, groups represented by the following chemical formula (1), and silanol groups or hydrolysis. A reactive functional group d obtained by bonding a compound containing a group that generates a silanol group and metal oxide fine particles, wherein the reactive inorganic fine particles D are introduced to the surface of the inorganic fine particles before coating, the following chemical formula Dispersibility in organic components and film strength can be obtained by combining the group shown in (1) and a compound containing a silanol group or a group that generates a silanol group by hydrolysis with metal oxide fine particles. It is preferable from the point of improving.

  In the antiglare film according to the present invention, the binder component C is a reactive functional group b of the reactive inorganic fine particle B, a reactive functional group d of the reactive inorganic fine particle D, and a reactivity of the binder component E. A compound having three or more reactive functional groups c that can be bonded to the functional group e, the binder component E being a reactive functional group b of the reactive inorganic fine particle B, and a reactive functional group of the reactive inorganic fine particle D The compound having three or more reactive functional groups e capable of binding to the group d and the reactive functional group c of the binder component C can improve the film strength, and the antiglare layer It is preferable from the viewpoint that adhesion between the layers can be improved by forming a cross-linking bond at the layer interface of the hard coat layer.

  In the antiglare film according to the present invention, the content of the reactive inorganic fine particles B is 2 to 30% by weight based on the total solid content of the resin composition for forming an antiglare layer. This is preferable because sufficient scratch resistance can be obtained while suppressing the content of the inorganic fine particles B.

  In the antiglare film according to the present invention, it is preferable that the transparent base film is mainly composed of cellulose acylate, cycloolefin polymer, acrylate polymer, or polyester.

  The antiglare film according to the present invention has a very thin antiglare layer, a hard coat layer is provided adjacent to the antiglare layer, and the hard coat layer provides scratch resistance. While ensuring the dazzling property, it is possible to obtain an antiglare film that prevents a decrease in contrast and is excellent in scratch resistance.

The antiglare film according to the present invention has a hard coat layer on the one surface side of the transparent base film from the side close to the transparent base film, and an antiglare layer having an uneven shape on the surface adjacent to the hard coat layer. An anti-glare film provided,
The antiglare layer is
Translucent fine particles A having an average particle diameter of 1 μm or more and 10 μm or less,
Reactive inorganic fine particles B having an average particle size of 30 nm to 100 nm, at least a part of the surface of which is coated with an organic component, and having a reactive functional group b introduced by the organic component on the surface;
Anti-glare layer comprising a binder component C having a reactive functional group c having cross-linking reactivity with the reactive functional group b of the reactive inorganic fine particle B, and containing a curable binder system also having curing reactivity in the system It consists of the hardened | cured material of the resin composition for formation, and the film thickness of the said glare-proof layer is 1 micrometer or more and 5 micrometers or less,
The unit area in the cross section in the thickness direction of the antiglare layer compared to the region on the transparent substrate film side of the surface layer region on the surface layer region on the side opposite to the transparent substrate film of the antiglare layer A skin layer having a small average number of particles of the reactive inorganic fine particles B per contact,
The average number of the reactive inorganic fine particles B per unit area in the thickness direction cross section of the skin layer is 80% of the average number of the reactive inorganic fine particles B per unit area in the thickness direction cross section of the antiglare layer. And
The hard coat layer is
Reactive inorganic fine particles D having at least a part of the surface coated with an organic component and having a reactive functional group d introduced by the organic component on the surface; and
A hard coat layer containing a binder component E having a reactive functional group e having cross-linking reactivity with the reactive functional group d of the reactive inorganic fine particle D, and containing a curable binder system having curing reactivity in the system It consists of hardened | cured material of the resin composition for formation, It is characterized by the above-mentioned.

  The translucent fine particles A form surface irregularities and impart antiglare properties to the antiglare layer.

  Since the reactive inorganic fine particles B and the reactive inorganic fine particles D have high hardness, they are not easily crushed by pressure (external pressure) applied to the particles from the outside, and are excellent in pressure resistance. Further, since the inorganic fine particle B has a reactive functional group b having a crosslinking reactivity with a reactive functional group c of the binder component C, it can be crosslinked with the binder component C. Further, since the inorganic fine particle D has the reactive functional group e of the binder component E and the reactive functional group d having crosslinking reactivity, it can be crosslinked with the binder component E. Accordingly, the antiglare layer and the hard coat layer according to the present invention have high hardness because they contain reactive inorganic fine particles having high hardness, and furthermore, the reactive inorganic fine particles and the binder component form a number of crosslinking points. Therefore, the film strength is improved and excellent scratch resistance is exhibited.

  In the antiglare layer according to the present invention, the average particle diameters of the translucent fine particles A and the reactive inorganic fine particles B are in the above range, and the film thickness of the antiglare layer is 1 μm or more and 5 μm or less. Thereby, the quantity of the said translucent fine particle A contained in the said glare-proof layer can be reduced. Thereby, the excessive internal scattering effect of the said glare-proof layer is suppressed, and the fall of contrast is prevented, ensuring the desired internal scattering effect. In addition, a hard coat layer having a scratch-resistant function is provided adjacent to the anti-glare layer in the space of the film thickness generated when the anti-glare layer becomes an extremely thin film, thereby obtaining excellent scratch resistance. ing. Therefore, it is possible to obtain an antiglare film that prevents a decrease in contrast, is excellent in visibility, and is excellent in scratch resistance.

  In the antiglare layer formed by curing the resin composition for forming the antiglare layer, the average number of particles in the unit area of the cross section in the thickness direction of the antiglare layer is the SEM (scanning electron microscope) photograph or TEM of the antiglare layer. (Transmission electron microscope) Observed using a photograph, the number of reactive inorganic fine particles B present in the cross section of the antiglare layer (region having a width of 1 μm) is the area of the cross section of the antiglare layer (region having a width of 1 μm) It is obtained by dividing. Similarly, in the skin layer of the antiglare layer formed by curing the resin composition for forming the antiglare layer, the average number of particles per unit area of the skin layer in the layer thickness direction is the SEM photograph or TEM photograph of the skin layer. And the number of reactive inorganic fine particles B present in the skin layer cross section (1 μm width region) is divided by the area of the skin layer cross section (1 μm width region).

  FIG. 1 is a schematic view showing a layer structure of an antiglare film according to the present invention. The antiglare film 1 according to the present invention has a configuration in which the hard coat layer 3 and the antiglare layer 2 are provided in this order on the viewer 70 side of the transparent base film 4 from the side close to the transparent base film. ing. In FIG. 1 and subsequent figures, for the sake of easy explanation, the layer thickness direction (vertical direction in the figure) is greatly enlarged and exaggerated from the scale in the plane direction (horizontal direction in the figure).

FIG. 2 is a perspective view schematically showing an example of a cross section of the antiglare film 2 in the thickness direction of the antiglare layer 2 and a region P10 having a width of 1 μm in the cross section. The antiglare layer 2 has an interface 30 on the opposite side to the transparent base film 4 and an interface 40 on the transparent base film 4 side.
FIG. 3 is a diagram schematically showing an example of a cross section of the antiglare layer 2 in FIG. 2 and a region P10 having a width of 1 μm in the cross section viewed from a direction perpendicular to the cross section.
FIG. 4 is a diagram schematically showing an example of the distribution of the reactive inorganic fine particles B20 in the region P10. In FIG. 4, in the region (skin layer 50) in the vicinity of the interface 30 on the side opposite to the transparent substrate film 4 in the region P <b> 10, the average number of the reactive inorganic fine particles B <b> 20 per unit area is greater than that of the skin layer 50. Is less than the region on the transparent substrate film 4 side and 80% or less of the average number of particles of the reactive inorganic fine particles B20 per unit area of the region P10.

  In the antiglare layer according to the present invention, the average number of the reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer is equal to the reactivity per unit area in the cross section in the thickness direction of the antiglare layer. Compared to the average number of inorganic fine particles B, it is as low as 80% or less. When the average number of particles in the skin layer is small, the number of the reactive inorganic fine particles B partially protruding from the interface of the antiglare layer on the side opposite to the transparent substrate film is also reduced. Therefore, when the anti-glare layer is saponified, the number of the reactive inorganic fine particles B eluted or dropped from the interface of the anti-glare layer into the alkaline solution is reduced. Thereby, the anti-glare film which concerns on this invention can acquire the outstanding saponification resistance.

  The reason why the antiglare layer has such a skin layer is not clear, but by setting the average particle size of the reactive inorganic fine particles B to 30 nm or more and 100 nm or less, the diffusion coefficient of the reactive inorganic fine particles B decreases, It is presumed that the reactive inorganic fine particles B are more likely to stay on the transparent substrate film side than the interface of the antiglare layer opposite to the transparent substrate film.

The distribution state of the reactive inorganic fine particles B in the antiglare layer can be confirmed by a TEM photograph, an SEM photograph, etc. of the antiglare layer. Can be clearly discriminated visually.
Further, the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the antiglare layer can be determined as follows. That is, the average number of particles per unit area is obtained by measuring the number of reactive inorganic fine particles B by a TEM photograph of a cross section in the depth direction of the antiglare layer and dividing the number of particles by the area where the particles are present. Can be calculated.

In the antiglare layer according to the present invention, the thickness of the skin layer is 5 times the average particle diameter of the reactive inorganic fine particles B from the interface of the antiglare layer opposite to the transparent substrate. Preferably, in the region closer to the transparent substrate film than the skin layer, the average interparticle distance of the reactive inorganic fine particles B is 30 nm or more, and at least in the region adjacent to the hard coat layer in the region. From the viewpoint of obtaining sufficient scratch resistance, it is preferable that the reactive inorganic fine particles B are uniformly dispersed.
FIG. 5 is a view schematically showing another example of such distribution of the reactive inorganic fine particles B20 in the region P10. In FIG. 5, the thickness of the skin layer 50 is 5 times the average particle diameter of the reactive inorganic fine particles B20, and the reactive inorganic fine particles B20 are 30 nm or more on the transparent base film side of the skin layer 50. It has the area | region 60 disperse | distributed uniformly, taking the average interparticle distance.

In the present invention, the average particle size is:
In the translucent fine particles A, if each contained particle is a monodisperse type particle (particle having a single shape), it means the average, and an irregular type particle having a broad particle size distribution. Then, it means the particle diameter of the most abundant particles by particle size distribution measurement. The particle diameter of the translucent fine particles A can be measured mainly by the Coulter counter method. In addition to this method, it can also be measured by laser diffraction or SEM photography.
In particles other than the light-transmitting fine particles A, that is, the reactive inorganic fine particles B and the reactive inorganic fine particles D, the particles in the solution were measured by a dynamic light scattering method, and the particle size distribution was expressed as a cumulative distribution. Means 50% particle size (d50 median diameter). The average particle size can be measured using a Microtrac particle size analyzer manufactured by Nikkiso Co., Ltd. or a Nanotrac particle size analyzer. The particle size in the cured film can also be measured by observation with an SEM photograph or a TEM photograph. As a measuring method by SEM or TEM photograph, for example, there is a method in which particles are observed at a magnification of 500 to 2,000,000 and the average value of 100 observed particles is used as an average particle size.
Further, the translucent fine particles A and the particles other than the fine particles A may be aggregated particles. In the case of the aggregated particles, the secondary particle diameter may be within the described range.

  The reactive functional group b of the reactive inorganic fine particle B, the reactive functional group c of the binder component C, the reactive functional group d of the reactive inorganic fine particle D, and the reactive functional group e of the binder component E are all relevant. The ability to form a crosslink between functional groups can improve the film strength of the antiglare layer and the hard coat layer, and a crosslink can be formed at the interface between the antiglare layer and the hard coat layer. By doing, it is preferable from the point which can improve the adhesiveness of the said interlayer.

  Further, the reactive inorganic fine particles B do not exhibit anti-glare properties unless translucent fine particles A having an average particle diameter of 1 μm or more are mixed. That is, by mixing the light-transmitting fine particles A and the reactive inorganic fine particles B, the anti-glare property is exhibited in the reactive inorganic fine particles B in addition to the anti-glare properties due to the light-transmitting fine particles A. Furthermore, a function as an antiglare adjusting agent can be imparted to the reactive inorganic fine particles B. Therefore, by adding the reactive inorganic fine particles B, the content of the translucent fine particles A required for obtaining the desired antiglare property can be suppressed, and the reactive inorganic having relatively high hardness. Since the content of the fine particles B is increased, an antiglare layer having high scratch resistance and antiglare properties can be formed.

By using the antiglare film according to the present invention, it is also possible to obtain a hard coat layer having a hardness of 3H or more when a pencil hardness test specified in JIS K5600-5-4 (1999) is performed at a load of 500 g. It is.

  In the antiglare film according to the present invention, the hard coat layer forming resin composition is applied to the one side of the transparent base film, and then the hard coat layer is applied. The antiglare layer may be formed, and the hard coat layer forming resin composition and the antiglare layer forming resin composition are simultaneously coated on one side of the transparent base film, A hard coat layer and the antiglare layer may be formed.

Hereinafter, the transparent base film, the antiglare layer, and the hard coat layer, which are essential elements constituting the antiglare film according to the present invention, will be described in order.
In the present specification, (meth) acryloyl represents acryloyl and / or methacryloyl, (meth) acrylate represents acrylate and / or methacrylate, and (meth) acryl represents acryl and / or methacryl.

<1. Transparent base film>
The material of the transparent substrate film is not particularly limited, but general materials used for anti-glare films can be used, for example, those mainly composed of cellulose acylate, cycloolefin polymer, acrylate polymer, or polyester. Is preferred. Here, “mainly” means a component having the highest content ratio among the constituent components of the base material.

  Specific examples of cellulose acylate include cellulose triacetate (TAC), cellulose diacetate, and cellulose acetate butyrate. Examples of the cycloolefin polymer include a norbornene polymer, a monocyclic olefin polymer, a cyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer resin, and more specifically, ZEONEX and ZEONOR (norbornene resin) manufactured by ZEON CORPORATION, Sumitrite Bakelite Co., Ltd. Sumilite FS-1700, JSR Corporation Arton (modified norbornene resin), Mitsui Chemicals, Inc. Apel (cyclic olefin) Copolymer), Topas (cyclic olefin copolymer) manufactured by Ticona, Optretz OZ-1000 series (alicyclic acrylic resin) manufactured by Hitachi Chemical Co., Ltd., and the like. Specific examples of the acrylate polymer include methyl poly (meth) acrylate, poly (meth) ethyl acrylate, methyl (meth) acrylate-butyl (meth) acrylate, and the like. Specific examples of the polyester include polyethylene terephthalate and polyethylene naphthalate.

  The thickness of the transparent substrate film is 20 μm or more and 300 μm or less, preferably 30 μm or more and 200 μm or less. When forming a hard coat layer on a transparent substrate film, in addition to physical treatment such as corona discharge treatment and oxidation treatment, a coating called an anchor agent or primer is applied in advance to improve adhesion. May be.

<2. Antiglare layer>
The antiglare layer according to the present invention has irregularities on the surface opposite to the transparent substrate,
Translucent fine particles A having an average particle diameter of 1 μm or more and 10 μm or less,
Reactive inorganic fine particles B having an average particle size of 30 nm to 100 nm, at least a part of the surface of which is coated with an organic component, and having a reactive functional group b introduced by the organic component on the surface;
Anti-glare layer comprising a binder component C having a reactive functional group c having cross-linking reactivity with the reactive functional group b of the reactive inorganic fine particle B, and containing a curable binder system also having curing reactivity in the system It consists of the hardened | cured material of the resin composition for formation, and the film thickness of the said glare-proof layer is 1 micrometer or more and 5 micrometers or less,
The unit area in the cross section in the thickness direction of the antiglare layer compared to the region on the transparent substrate film side of the surface layer region on the surface layer region on the side opposite to the transparent substrate film of the antiglare layer A skin layer having a small average number of particles of the reactive inorganic fine particles B per contact,
The average number of the reactive inorganic fine particles B per unit area in the thickness direction cross section of the skin layer is 80% of the average number of the reactive inorganic fine particles B per unit area in the thickness direction cross section of the antiglare layer. It is as follows.

  Hereinafter, the translucent fine particles A, the reactive inorganic fine particles B, and the binder component C, which are essential components of the curable resin composition for forming an antiglare layer, and other components appropriately blended as necessary. These will be described in order.

<2-1. Translucent fine particles A>
The translucent fine particles A have a function of forming irregularities on the surface and imparting antiglare properties to the antiglare layer. Depending on the purpose, the translucent fine particles A can be used not only in one type but also in a mixture of two or more types having different components, different shapes, different particle size distributions, and the like. Preferably, 1-3 types are used, and in particular, 2-3 types are used. However, various kinds of particles can be used for purposes other than forming irregularities.

  The one or two or more kinds of translucent fine particles A used in the present invention may be in the form of an indefinite shape, a rectangular parallelepiped, a cube or the like, and have a spherical shape, for example, a true spherical shape, a spheroid shape, etc. Also good. Each average particle diameter (μm) of the one or more translucent fine particles A is 1 μm or more and 10 μm or less, preferably 1 μm or more and 7 μm or less, and more preferably 2 μm or more and 5 μm or less. When the average particle size is less than 1 μm, it is difficult to provide a concavo-convex shape having a size capable of exhibiting sufficient anti-glare property on the surface of the antiglare layer. Since the addition amount of the fine particles A must be very large, the film properties of the antiglare layer are deteriorated. On the other hand, when the average particle diameter exceeds 10 μm, the surface shape of the antiglare layer becomes rough, and the surface quality may be deteriorated, or whiteness may increase due to an increase in surface haze. The translucent fine particles A may be agglomerated particles, and in the case of agglomerated particles, the secondary particle diameter may be within the above range.

  In the translucent fine particles A, 80% or more (preferably 90% or more) of the whole fine particles A are preferably in the range of each average particle size ± 300 nm. Thereby, the uniformity of the uneven shape of the antiglare layer can be improved.

The translucent fine particles A may be inorganic or organic. In view of improving the film strength of the antiglare layer, inorganic fine particles are preferably used, and silica fine particles are particularly preferably used.
Further, the translucent fine particles A according to the present invention and the reactive inorganic fine particles B described later are both made of silica, and the translucent particles having a larger particle diameter than the reactive inorganic fine particles B in the antiglare layer are used. The reactive inorganic fine particles B tend to aggregate on the surface of the fine particles A, and the antiglare property of the antiglare layer can be improved.

  Examples of the organic fine particles include plastic beads. Specific examples of the plastic beads include polystyrene beads (refractive index 1.60), melamine resin beads (refractive index 1.57), acrylic beads (refractive index 1.50 to 1.53), acrylic-styrene beads ( Refractive index 1.54-1.58), benzoguanamine beads, benzoguanamine / formaldehyde condensation beads, polycarbonate beads, polyethylene beads and the like. The plastic beads preferably have a hydrophobic group on the surface, and examples thereof include styrene beads.

  Examples of the inorganic fine particles include amorphous silica and inorganic silica beads. As the amorphous silica, it is preferable to use silica beads having a particle diameter of 1 to 10 μm with good dispersibility. In order to improve the dispersibility of the amorphous silica without causing an increase in the viscosity of the resin composition for forming an antiglare layer, which will be described in detail below, the amorphous silica obtained by subjecting the particle surface to a hydrophobic treatment is treated with an organic substance. Is preferably used. In the organic treatment, a method of chemically bonding a compound to the bead surface, or a method of allowing a void (pore) in a composition forming the bead to penetrate without being chemically bonded to the bead surface. There are physical methods, either of which can be used.

  In general, a chemical treatment method using an active group on the silica surface such as a hydroxyl group or a silanol group is preferably used from the viewpoint of treatment efficiency. As a compound used for the treatment, a silane-based, siloxane-based, or silazane-based material having high reactivity with the above-described active group is used. For example, linear alkyl monosubstituted silicone materials such as methyltrichlorosilane, branched alkyl monosubstituted silicone materials, linear alkyl polysubstituted silicone compounds such as di-n-butyldichlorosilane and ethyldimethylchlorosilane, Examples include substituted silicone compounds. Similarly, mono-substituted, poly-substituted siloxane materials and silazane materials having a linear alkyl group or a branched alkyl group can also be used effectively.

Depending on the required function, those having a hetero atom, an unsaturated bond group, a cyclic bond group, an aromatic functional group or the like may be used at the terminal or intermediate part of the alkyl chain.
In these compounds, the alkyl group contained is hydrophobic, so that the surface of the material to be treated can be easily converted from hydrophilic to hydrophobic, and both the high-molecular material with poor affinity when untreated is high. Affinity can be obtained.

  The content of the translucent fine particles A is preferably 5% by mass or more and 40% by mass or less with respect to the total mass of the solid content of the antiglare layer. More preferably, they are 5 mass% or more and 20 mass% or less. If it is less than 5% by mass, sufficient antiglare property cannot be imparted, and if it exceeds 40% by mass, the internal scattering effect becomes excessive and the contrast is lowered, which is not preferable.

  When many translucent fine particles A as described above are added, the translucent fine particles A easily settle in the resin composition. Therefore, an inorganic filler such as silica may be added to prevent sedimentation. In addition, although the addition amount of an inorganic filler is more effective in preventing sedimentation of the translucent fine particles A, depending on the particle size and the amount used, the transparency of the coating film is adversely affected. Therefore, it is preferable that an inorganic filler having a particle size of 0.5 μm or less is contained so as not to impair the transparency of the coating film with respect to the binder.

In the present invention, when two or more kinds of translucent fine particles A are mixed and used, the average particle size of the first fine particles is R ₁ (μm), and the average particle size of the second fine particles is R ₂ (μm). ), The following formula (I):
0.25R ₁ (preferably 0.50R ₁ ) ≦ R ₂ ≦ 1.0R ₁ (preferably 0.75R ₁ ) (I)
Those satisfying these conditions are preferred.
When R ₂ is 0.25R ₁ or more, the resin composition (coating liquid) is easily dispersed and the particles are not aggregated. Moreover, a uniform uneven | corrugated shape can be formed, without receiving to the influence of the wind at the time of floating in the drying process after application | coating. This relationship holds true for the third fine particles relative to the second fine particles. When the third fine particles are R ₃ , those satisfying 0.25R ₂ ≦ R ₃ ≦ 1.0R ₂ are preferable.
When two or more kinds of fine particles composed of different components are mixed and used, the two or more kinds of fine particles preferably have different average particle diameters as described above, but those having the same average particle diameter are also suitable. Used for.

<2-2. Reactive inorganic fine particles B>
In general, the anti-glare layer contains inorganic fine particles to improve scratch resistance. Scratch resistance can be further improved by cross-linking the reactive inorganic fine particles having cross-linking reactivity and a curable binder to form a cross-linking bond. The reactive inorganic fine particle B is an inorganic fine particle in which at least a part of the surface of the inorganic fine particle serving as a core is coated with an organic component and the surface has a reactive functional group introduced by the organic component. The reactive inorganic fine particles B include those having two or more inorganic fine particles as a core per particle.

  The antiglare layer according to the present invention contains the reactive inorganic fine particles B for the purpose of improving the hardness so as to have scratch resistance. The reactive inorganic fine particles B may be those that further impart a function to the antiglare layer, and are appropriately selected and used according to the purpose.

The average particle size of the reactive inorganic fine particles B according to the present invention is 30 nm to 100 nm, preferably 30 nm to 70 nm, and more preferably 40 nm to 60 nm. When the average particle size of the reactive inorganic fine particles B is 30 nm or more, the skin layer is obtained. In addition, by setting the average particle size of the reactive inorganic fine particles B to 100 nm or less, the crosslinking point in the matrix can be increased with respect to the content, and an uneven layer having high film strength can be obtained.
In addition, the reactive inorganic fine particles B have a narrow particle size distribution and are monodispersed from the viewpoint of significantly improving hardness while maintaining the restoration rate when using only a resin without impairing transparency. Is preferred.

  The reason why the antiglare layer has the skin layer is not clear, but by setting the average particle diameter of the reactive inorganic fine particles B to 30 nm or more and 100 nm or less, the diffusion coefficient of the inorganic fine particles B is reduced, and the antiglare is reduced. It is presumed that the reactive inorganic fine particles B easily stay on the transparent base film side rather than the interface on the opposite side of the transparent base film of the layer.

Examples of the inorganic fine particles include metal oxides such as silica (SiO ₂ ), aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide. Examples thereof include fine particles, fine metal fluoride particles such as magnesium fluoride and sodium fluoride. Metal fine particles, metal sulfide fine particles, metal nitride fine particles and the like may be used.

  From the viewpoint of high hardness, silica and aluminum oxide are preferable. Further, in order to obtain a high refractive index layer relative to the hard coat layer adjacent to the antiglare layer, fine particles such as zirconia, titania, antimony oxide and the like having a high refractive index during film formation are appropriately selected and used. be able to. Similarly, in order to make the refractive index layer relatively low with respect to the hard coat layer, fine particles such as fluoride fine particles such as magnesium fluoride and sodium fluoride whose refractive index is lowered during film formation are appropriately selected. Can be used. Furthermore, when it is desired to impart antistatic properties and conductivity, indium tin oxide (ITO), tin oxide, or the like can be appropriately selected and used. These can be used alone or in combination of two or more.

  The reactive inorganic fine particle B according to the present invention uses solid particles having no voids or porous structure inside the particles, rather than particles having voids or porous structure inside the particles such as hollow particles. preferable. Since hollow particles have pores and porous structure inside the particles, the hardness is lower than that of solid particles, and the hollow particles have an apparent specific gravity (mass per unit volume averaged including the hollow part). ) Is smaller than solid particles, and hollow particles present at the interface on the side opposite to the transparent base film side of the antiglare layer are likely to increase. Therefore, the reactive inorganic fine particles B are preferably solid particles having a high hardness and a specific gravity larger than that of the hollow particles.

  The surface of the inorganic fine particles usually has groups that cannot exist in this form in the inorganic fine particles. These surface groups are usually relatively reactive functional groups. For example, in the case of metal oxides, for example, hydroxyl groups and oxy groups, for example in the case of metal sulfides, thiol groups and thio groups, or in the case of nitrides, for example, amino groups, amide groups and imides. Has a group.

  The reactive inorganic fine particles B used in the present invention are coated with an organic component on at least a part of the surface, and have a reactive functional group b introduced by the organic component on the surface. Here, the organic component is a component containing carbon. In addition, as an aspect in which at least a part of the surface is coated with an organic component, for example, a compound containing an organic component such as a silane coupling agent reacts with a hydroxyl group present on the surface of the inorganic fine particles to cause a part of the surface An aspect in which an organic component is bonded to an organic particle, an aspect in which an organic component is attached to a hydroxyl group present on the surface of an inorganic fine particle by an interaction such as a hydrogen bond, or an aspect in which one or more inorganic fine particles are contained in a polymer particle Etc. are included.

The coated organic component covers almost the entire particle surface from the viewpoint of suppressing aggregation of inorganic fine particles and increasing the number of reactive functional groups on the surface of the inorganic fine particles to improve the hardness of the film. It is preferable. From such a viewpoint, the organic component covering the reactive inorganic fine particles B is contained in the reactive inorganic fine particles B in an amount of 1.00 × 10 ⁻³ g / m ² or more per unit area of the inorganic fine particles before coating. It is preferable that In an aspect in which an organic component is attached to or bonded to the surface of the inorganic fine particles, the organic component covering the reactive inorganic fine particles B is included in the reactive inorganic fine particles B per unit area of the inorganic fine particles before coating. More preferably, it is contained at least 00 × 10 ⁻³ g / m ^{2, and} particularly preferably at least 3.50 × 10 ⁻³ g / m ² . In the aspect in which the polymer particles contain inorganic fine particles, the organic component covering the reactive inorganic fine particles B is 3.50 × 10 per unit area of the inorganic fine particles before coating in the reactive inorganic fine particles B. ^-3 g / m ² or more is more preferable, and 5.50 × 10 ⁻³ g / m ² or more is particularly preferable.
The ratio of the organic component to be coated is usually a constant weight value of weight loss% when the dry powder is completely burned in air, for example, thermogravimetric analysis from room temperature to normal 800 ° C. in air. It can ask for.
The amount of organic component per unit area is determined by the following method. First, the organic component weight / inorganic component weight is measured by differential thermogravimetry (DTG). Next, the volume of the entire inorganic component is calculated from the weight and the specific gravity of the used inorganic fine particles. Further, assuming that the inorganic fine particles before coating are spherical, the volume per inorganic fine particle before coating is calculated from the average particle diameter of the inorganic fine particles before coating. From the volume of the whole inorganic component and the volume per inorganic fine particle before coating, the number of inorganic fine particles before coating is obtained. Next, by dividing the organic component weight per reactive inorganic fine particle B by the surface area per inorganic fine particle before coating, the amount of organic component per unit area of the inorganic fine particle before coating can be obtained.

  In addition, as the reactive functional group b of the reactive inorganic fine particle B, particularly from the viewpoint of improving the hardness of the cured film, a polymerizable unsaturated group is preferably used, preferably a photocurable unsaturated group, Particularly preferred are ionizing radiation curable unsaturated groups. Specific examples thereof include an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group, and an epoxy group.

As a method for preparing reactive inorganic fine particles B having a reactive functional group b introduced by the organic component on at least a part of the surface and introduced on the surface, the kind of inorganic fine particles used as a core and the introduction thereof are introduced. A conventionally known method can be appropriately selected and used depending on the reactive functional group.
Among them, in the present invention, the organic component to be coated can be contained in the reactive inorganic fine particles B in an amount of 1.00 × 10 ⁻³ g / m ² or more per unit area of the inorganic fine particles before coating, From the viewpoint of suppressing aggregation of inorganic fine particles and improving the hardness of the film, it is preferable to select and use the following inorganic fine particles (i) or (ii) as appropriate.
(I) saturated or unsaturated carboxylic acid, acid anhydride, acid chloride, ester and acid amide corresponding to the carboxylic acid, amino acid, imine, nitrile, isonitrile, epoxy compound, amine, β-dicarbonyl compound, silane, And by dispersing inorganic fine particles in water and / or an organic solvent as a dispersion medium in the presence of one or more surface modification compounds having a molecular weight of 500 or less selected from the group consisting of metal compounds having functional groups. Inorganic fine particles having a reactive functional group b on the surface.
(Ii) Bonding a compound containing a reactive functional group b introduced into the inorganic fine particles, a group represented by the following chemical formula (1), and a silanol group or a group that generates a silanol group by hydrolysis with metal oxide fine particles Inorganic fine particles having a reactive functional group b on the surface, obtained by
Chemical formula (1)
^{-Q 1 -C (= Q 2)} -NH-
(In the chemical formula (1), Q ¹ represents NH, O (oxygen atom), or S (sulfur atom), and Q ² represents O or S).

  The reactive functional group b of the reactive inorganic fine particle B includes, in addition to the reactive functional group c of the binder component C, the reactive functional group d of the reactive inorganic fine particle D contained in the resin composition for forming a hard coat layer described later, And the reactive functional group e of the binder component E can form a cross-linked bond, the film strength is improved, and the cross-linking bond is formed at the layer interface between the antiglare layer and the hard coat layer. It is preferable from the point which can improve the adhesiveness between layers.

Hereinafter, the reactive inorganic fine particles B preferably used in the present invention will be described in order.
(I) saturated or unsaturated carboxylic acid, acid anhydride, acid chloride, ester and acid amide corresponding to the carboxylic acid, amino acid, imine, nitrile, isonitrile, epoxy compound, amine, β-dicarbonyl compound, silane, And by dispersing inorganic fine particles in water and / or an organic solvent as a dispersion medium in the presence of one or more surface modification compounds having a molecular weight of 500 or less selected from the group consisting of metal compounds having functional groups. Inorganic fine particles having a reactive functional group b on the surface.
The use of the reactive inorganic fine particles B of (i) has an advantage that the film strength can be improved even if the organic component content is small.

  The surface modifying compound used for the reactive inorganic fine particle B of (i) is a carboxyl group, an acid anhydride group, an acid chloride group, an acid amide group, an ester group, an imino group, a nitrile group, an isonitrile group, a hydroxyl group, Thiol groups, epoxy groups, primary, secondary and tertiary amino groups, Si-OH groups, hydrolyzable residues of silanes, or CH acid groups such as β-dicarbonyl compounds, etc. It has a functional group capable of chemically bonding with a group present on the surface of the inorganic fine particle under dispersion conditions. The chemical bond here preferably includes a covalent bond, an ionic bond or a coordinate bond, but also includes a hydrogen bond. The coordination bond is considered to be complex formation. For example, an acid-base reaction, complex formation or esterification according to Bronsted or Lewis occurs between the functional group of the surface modifying compound and the group on the surface of the inorganic fine particle. The said surface modification compound used for the reactive inorganic fine particle B of said (i) can be used 1 type or in mixture of 2 or more types.

The surface modifying compound is usually added to the surface modifying compound via the functional group in addition to at least one functional group (hereinafter referred to as a first functional group) capable of participating in chemical bonding with the surface group of the inorganic fine particles. After linking, it has molecular residues that impart new properties to the inorganic particulates. The molecular residue or a part thereof is hydrophobic or hydrophilic and, for example, stabilizes, integrates or activates inorganic fine particles.
For example, examples of the hydrophobic molecular residue include an alkyl, aryl, alkaryl, aralkyl, or fluorine-containing alkyl group that causes inactivation or repulsion. Examples of the hydrophilic group include a hydroxy group, an alkoxy group, and a polyester group.

The reactive functional group b introduced to the surface so that the reactive inorganic fine particles B can react with at least the binder component C is appropriately selected according to the binder component C. As the reactive functional group b, a polymerizable unsaturated group is suitably used, preferably a photocurable unsaturated group, and particularly preferably an ionizing radiation curable unsaturated group. Specific examples thereof include an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group, and an epoxy group.
When a reactive functional group b capable of reacting with the binder component C is contained in the molecular residue of the surface modifying compound, the first functional group contained in the surface modifying compound is reacted with the surface of the inorganic fine particles. It is possible to introduce the reactive functional group b capable of reacting with the binder component C onto the surface of the reactive inorganic fine particle B of (i). For example, in addition to the first functional group, a surface modification compound further having a polymerizable unsaturated group is preferable.

  On the other hand, a second reactive functional group is contained in the molecular residue of the surface modification compound, and the reactive inorganic fine particle B of (i) is used as a foothold based on the second reactive functional group. A reactive functional group b capable of reacting with the binder component C may be introduced on the surface. For example, a group capable of hydrogen bonding (hydrogen bonding group) such as a hydroxyl group and an oxy group is introduced as the second reactive functional group, and another hydrogen bonding group introduced on the surface of the inorganic fine particles It is preferable that the reactive functional group b capable of reacting with the binder component C is introduced by the reaction of the hydrogen bond forming group of the surface modification compound. That is, as the surface modification compound, a compound having a hydrogen bond forming group and a compound having a reactive functional group b capable of reacting with the binder component C such as a polymerizable unsaturated group and a hydrogen bond forming group are used in combination. Is a suitable example. Specific examples of the hydrogen bond-forming group indicate a functional group such as a hydroxyl group, a carboxyl group, an epoxy group, a glycidyl group, an amide group, or an amide bond. Here, the amide bond means a bond unit containing —NHC (O) or> NC (O) —. Among the hydrogen bond forming groups used in the surface modification compound of the present invention, among them, a carboxyl group, a hydroxyl group, and an amide group are preferable.

The molecular weight of the surface modifying compound used for the reactive inorganic fine particle B of (i) is preferably 500 or less, more preferably 400 or less, and particularly preferably 200 or less. By setting it as such a low molecular weight, it is estimated that the inorganic fine particle surface can be occupied rapidly and aggregation of inorganic fine particles can be prevented.
The surface modifying compound used in the reactive inorganic fine particle B of (i) is preferably a liquid under the reaction conditions for surface modification, and can be dissolved or at least emulsifiable in a dispersion medium. Is preferred. Among these, it is preferable that the polymer is dissolved in the dispersion medium and uniformly distributed as discrete molecules or molecular ions in the dispersion medium.

  Saturated or unsaturated carboxylic acids have 1 to 24 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, acrylic acid, methacrylic acid, crotonic acid, citric acid, adipine Examples include acids, succinic acid, glutaric acid, oxalic acid, maleic acid, fumaric acid, itaconic acid and stearic acid, and the corresponding acid anhydrides, chlorides, esters and amides such as caprolactam. The carboxylic acid includes those in which the carbon chain is blocked by an O-group, S-group or NH-group. Particularly preferred are carboxylic acid ethers such as carboxylic acid monoethers and carboxylic acid polyethers, and the corresponding acid hydrates, esters and amides (eg, methoxyacetic acid, 3,6-dioxaheptanoic acid and 3,6,6 9-trioxadecanoic acid) and the like. Further, when an unsaturated carboxylic acid is used, a polymerizable unsaturated group can be introduced.

Examples of preferred amines are those having the general formula Q _3-n NH _n (n = 0, 1 or 2), wherein the residue Q is independently 1-12, more preferably 1-6, particularly preferably Are alkyls having 1 to 4 carbon atoms (eg methyl, ethyl, n-propyl, i-propyl and butyl) and aryl, alkaryl or aralkyl having 6 to 24 carbon atoms (eg phenyl, naphthyl, tolyl) And benzyl). Examples of preferable amines include polyalkyleneamines, and specific examples are methylamine, dimethylamine, trimethylamine, ethylamine, aniline, N-methylaniline, diphenylamine, triphenylamine, toluidine, ethylenediamine, and diethylenetriamine. .

Preferred β-dicarbonyl compounds are those having 4 to 12, especially 5 to 8 carbon atoms, such as diketones (such as acetylacetone), 2,3-hexanedione, 3,5-heptanedione, acetoacetic acid, acetoacetate Examples include acetic acid-C ₁ -C ₄ -alkyl esters (such as acetoacetic acid ethyl ester), diacetyl and acetonylacetone.
Examples of amino acids include β-alanine, glycine, valine, aminocaproic acid, leucine and isoleucine.

Preferred silanes are hydrolyzable organosilanes having at least one hydrolyzable group or hydroxy group and at least one non-hydrolyzable residue. Here, examples of the hydrolyzable group include a halogen, an alkoxy group, and an acyloxy group. As the non-hydrolyzable residue, a non-hydrolyzable residue having a reactive functional group b and / or not having a reactive functional group b is used. Silanes having at least partially organic residues substituted with fluorine may also be used.
As the silane used is not particularly limited, for _{example, CH 2 = CHSi (OOCCH 3} ) 3, CH 2 = CHSiCl 3, CH 2 = CHSi (OC 2 H 5) 3, CH 2 = CHSi (OC _{2 H 4 OCH 3) 3,} CH 2 = CH-CH 2 -Si (OC 2 H 5) 3, CH 2 = CH-CH 2 -Si (OOCCH 3) 3, γ- glycidyloxypropyltrimethoxysilane (GPTS ), Γ-glycidyloxypropyldimethylchlorosilane, 3-aminopropyltrimethoxysilane (APTS), 3-aminopropyltriethoxysilane (APTES), N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N -[N '-(2'-Aminoethyl) -2-aminoethyl] -3-aminopropyltrimeth Xysilane, hydroxymethyltrimethoxysilane, 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilane, bis- (hydroxyethyl) -3-aminopropyltriethoxysilane, N-hydroxyethyl-N-methylaminopropyltriethoxysilane Examples include 3- (meth) acryloxypropyltriethoxysilane and 3- (meth) acryloxypropyltrimethoxysilane.

As a metal compound which has a functional group, the metal compound of the metal M from 1st group III-V and / or 2nd group II-IV of an element periodic table is mentioned. Examples of such metal compounds include alkoxides of zirconium and titanium, M (OR) ₄ (M = Ti, Zr), wherein a part of the OR group is a complex such as a β-dicarbonyl compound or a monocarboxylic acid. Substituted by the generating agent). When a compound having a polymerizable unsaturated group (such as methacrylic acid) is used as a complexing agent, a polymerizable unsaturated group can be introduced.

As the dispersion medium, water and / or an organic solvent is preferably used. A particularly preferred dispersion medium is distilled (pure) water. As the organic solvent, polar, nonpolar and aprotic solvents are preferred. Examples thereof include alcohols such as aliphatic alcohols having 1 to 6 carbon atoms (particularly methanol, ethanol, n- and i-propanol and butanol), ketones such as acetone and butanone, esters such as ethyl acetate; , Ethers such as tetrahydrofuran and tetrahydropyran; amides such as dimethylacetamide and dimethylformamide; sulfoxides and sulfones such as sulfolane and dimethyl sulfoxide; and aliphatics (optionally halogenated) such as pentane, hexane and cyclohexane And hydrocarbons. These dispersion media can be used as a mixture.
The dispersion medium preferably has a boiling point that can be easily removed by distillation (optionally under reduced pressure), and a solvent having a boiling point of 200 ° C. or lower, particularly 150 ° C. or lower is preferable.

  In preparing the reactive inorganic fine particles B of (i), the concentration of the dispersion medium is usually 40 to 90% by weight, preferably 50 to 80% by weight, particularly 55 to 75% by weight. The rest of the dispersion is composed of untreated inorganic fine particles and the surface modifying compound. Here, the weight ratio of the inorganic fine particles / surface modification compound is preferably 100: 1 to 4: 1, more preferably 50: 1 to 8: 1, and particularly preferably 25: 1 to 10: 1. .

  The preparation of the reactive inorganic fine particles B of (i) is preferably performed at room temperature (about 20 ° C.) to the boiling point of the dispersion medium. Particularly preferably, the dispersion temperature is 50 to 100 ° C. The dispersion time depends in particular on the type of material used, but is generally from a few minutes to a few hours, for example 1 to 24 hours.

(Ii) a compound containing a reactive functional group b to be introduced into the inorganic fine particles, a group represented by the following chemical formula (1), and a silanol group or a group that generates a silanol group by hydrolysis, and a metal as the inorganic fine particles serving as a core Inorganic fine particles having reactive functional groups b on the surface, obtained by bonding with oxide fine particles.
Chemical formula (1)
^{-Q 1 -C (= Q 2)} -NH-
(In the chemical formula (1), Q ¹ represents NH, O (oxygen atom), or S (sulfur atom), and Q ² represents O or S.)
When the reactive inorganic fine particle B (ii) is used, there is an advantage that the dispersibility and the film strength are further increased from the viewpoint of improving the amount of organic components.

First, a compound containing a reactive functional group b introduced into inorganic fine particles, a group represented by the above chemical formula (1), and a silanol group or a group that generates a silanol group by hydrolysis (hereinafter, reactive functional group-modified hydrolyzable) (Sometimes referred to as silane).
In the reactive functional group-modified hydrolyzable silane, the reactive functional group introduced into the inorganic fine particles is not particularly limited as long as it is appropriately selected so as to be able to react with the binder component C. Suitable for introducing polymerizable unsaturated groups as described above.

In the reactive functional group-modified hydrolyzable silane, the group [—Q ¹ —C (═Q ² ) —NH—] represented by the chemical formula (1) is specifically [—O—C (═O ) —NH—], [—O—C (═S) —NH—], [—S—C (═O) —NH—], [—NH—C (═O) —NH—], [— NH-C (= S) -NH-] and [-S-C (= S) -NH-]. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use at least one NH-] group in combination. The group [—Q ¹ —C (= Q ² ) —NH—] represented by the chemical formula (1) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength when formed into a cured product. It is considered that properties such as adhesion to the substrate and heat resistance can be imparted.

  Examples of the group that generates a silanol group by hydrolysis include groups having an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom, etc. on the silicon atom. An oxysilyl group is preferred. A silanol group or a group that forms a silanol group by hydrolysis can be combined with the metal oxide fine particles by a condensation reaction or a condensation reaction that occurs following hydrolysis.

  Preferable specific examples of the reactive functional group-modified hydrolyzable silane include, for example, compounds represented by the following chemical formula (2).

化学式（２）中、Ｒ^ａ、Ｒ^ｂは同一でも異なっていてもよいが、水素原子、Ｃ_１からＣ_８のアルキル基、又はアリール基であり、例えば、メチル、エチル、プロピル、ブチル、オクチル、フェニル、キシリル基等を挙げることができる。ここでｍは、１、２又は３である。
［（Ｒ^ａＯ）_ｍＲ^ｂ _３−ｍＳｉ‐］で示される基としては、例えば、トリメトキシシリル基、トリエトキシシリル基、トリフェノキシシリル基、メチルジメトキシシリル基、ジメチルメトキシシリル基等を挙げることができる。斯かる基のうち、トリメトキシシリル基又はトリエトキシシリル基等が好ましい。

In the chemical formula (2), R ^a and R ^b may be the same or different, and are a hydrogen atom, a C ₁ to C ₈ alkyl group, or an aryl group, for example, methyl, ethyl, propyl, butyl, octyl , Phenyl, xylyl group and the like. Here, m is 1, 2 or 3.
Examples of the group represented by [(R ^a O) _m R ^b _3-m Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, and the like. Can be mentioned. Of such groups, a trimethoxysilyl group or a triethoxysilyl group is preferred.

R ^c is a divalent organic group having a C ₁ to C ₁₂ aliphatic or aromatic structure and may contain a chain, branched or cyclic structure. Examples of such an organic group include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, and dodecamethylene. Among these, preferred examples are methylene, propylene, cyclohexylene, phenylene and the like.
R ^d is a divalent organic group and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. For example, chain polyalkylene groups such as hexamethylene, octamethylene, dodecamethylene; alicyclic or polycyclic divalent organic groups such as cyclohexylene and norbornylene; divalent groups such as phenylene, naphthylene, biphenylene and polyphenylene Aromatic group; and these alkyl group-substituted and aryl group-substituted products. In addition, these divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, and a group represented by the chemical formula (1). Can also be included.

R ^e is an (n + 1) -valent organic group, preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
Y ′ represents a monovalent organic group having a reactive functional group. The reactive functional group itself as described above may be used. For example, when the reactive functional group b is selected from a polymerizable unsaturated group, a (meth) acryloyl (oxy) group, a vinyl (oxy) group, a propenyl (oxy) group, a butadienyl (oxy) group, a styryl (oxy) group Ethynyl (oxy) group, cinnamoyl (oxy) group, maleate group, (meth) acrylamide group and the like. N is preferably a positive integer of 1 to 20, more preferably 1 to 10, particularly preferably 1 to 5.

  For the synthesis of the reactive functional group-modified hydrolyzable silane used in the present invention, for example, a method described in JP-A-9-100111 can be used. That is, for example, when a polymerizable unsaturated group is introduced, (i) it is carried out by an addition reaction of a mercaptoalkoxysilane, a polyisocyanate compound, and an active hydrogen group-containing polymerizable unsaturated compound capable of reacting with an isocyanate group. it can. Further, (b) the reaction can be carried out by a direct reaction between a compound having an alkoxysilyl group and an isocyanate group in the molecule and an active hydrogen group-containing polymerizable unsaturated compound. Furthermore, (c) it can also be directly synthesized by an addition reaction of a compound having a polymerizable unsaturated group and an isocyanate group in the molecule with mercaptoalkoxysilane or aminosilane.

  In the production of the reactive inorganic fine particle B of (ii), a reactive functional group-modified hydrolyzable silane is separately hydrolyzed, then mixed with the inorganic fine particle, and heated and stirred. A method of hydrolyzing a functional functional group-modified hydrolyzable silane in the presence of inorganic fine particles, or in the presence of other components such as a polyunsaturated organic compound, a monounsaturated organic compound, a radiation polymerization initiator, etc. A method of performing surface treatment of inorganic fine particles can be selected, but a method of hydrolyzing a reactive functional group-modified hydrolyzable silane in the presence of inorganic fine particles is preferable. When producing the reactive inorganic fine particles B of (ii), the temperature is usually 20 ° C. or higher and 150 ° C. or lower, and the treatment time is in the range of 5 minutes to 24 hours.

  In order to accelerate the hydrolysis reaction, an acid, salt or base may be added as a catalyst. Suitable acids include organic acids and unsaturated organic acids; examples of suitable bases include tertiary amines and quaternary ammonium hydroxides. The amount of the acid or base catalyst added is 0.001 to 1.0% by weight, preferably 0.01 to 0.1% by weight, based on the reactive functional group-modified hydrolyzable silane.

  As the reactive inorganic fine particles B, powdery fine particles not containing a dispersion medium may be used. However, it is preferable to use a fine particle in a solvent-dispersed sol from the viewpoint of high productivity because the dispersion step can be omitted.

  While the content of the reactive inorganic fine particles B is 2 to 30% by weight with respect to the total solid content of the resin composition for forming an antiglare layer, while suppressing the content of the reactive inorganic fine particles B, This is preferable because sufficient scratch resistance can be obtained. Furthermore, it is preferable that it is 2-15 weight part. When the amount is less than 2 parts by weight, the hardness of the surface of the antiglare layer may be insufficient. When the amount exceeds 30 parts by weight, the filling rate may increase excessively, and the film strength may decrease.

  The content of the reactive inorganic fine particles B is preferably 70 to 1000 parts by weight, more preferably 80 to 750 parts by weight, particularly preferably 100 parts by weight of the total amount of the light transmissive fine particles A. 150 to 500 parts by weight. When the content of the reactive inorganic fine particles B is less than 70 parts by weight, a desired uneven shape cannot be formed on the uneven layer of the antiglare layer, and the antiglare property is lowered and the film strength is increased. Can not. On the other hand, when the amount exceeds 1000 parts by weight, the cost of the reactive inorganic fine particles B is increased, and the inorganic fine particles B tend to aggregate, leading to a decrease in contrast.

<2-3. Curing binder system for antiglare layer>
In the present specification, the constituent component of the curable binder system of the antiglare layer is, in addition to the binder component C, if necessary, after curing of a curable binder component other than the binder component C, a polymer component, a polymerization initiator, and the like. Represents a matrix component of the antiglare layer.

<2-3-1. Binder component C>
In the resin composition for forming an antiglare layer according to the present invention, the binder component C has a reactive functional group c having cross-linking reactivity with the reactive functional group b of the reactive inorganic fine particle B, and the reactive functional group. The group b and the reactive functional group c are cross-linked to form a network structure. The binder component C preferably has three or more reactive functional groups c per molecule in order to obtain sufficient crosslinkability. As the reactive functional group c, a polymerizable unsaturated group is suitably used, preferably a photocurable unsaturated group, and particularly preferably an ionizing radiation curable unsaturated group. Specific examples thereof include an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group, and an epoxy group.

  In addition to the reactive functional group b of the reactive inorganic fine particle B, the reactive functional group c of the binder component C is a reactive functional group of the reactive inorganic fine particle D contained in the hard coat layer forming resin composition to be described later. The group d and the reactive functional group e of the binder component E can form a cross-linked bond, which improves the film strength and forms a cross-linked bond at the layer interface between the antiglare layer and the hard coat layer. This is preferable from the viewpoint of improving the adhesion between the layers.

  As the binder component C, a curable organic resin is preferable, and a light-transmitting material that transmits light when formed into a coating film is preferable. Specific examples include ionizing radiation curable resins that are cured by ionizing radiation typified by ultraviolet rays or electron beams, ionizing radiation curable resins and solvent-drying resins (such as thermoplastic resins). A resin with which a film is formed by simply drying a solvent for adjustment, or a thermosetting resin, preferably an ionizing radiation curable resin.

Specific examples of the ionizing radiation curable resin include a compound having a radical polymerizable functional group such as a (meth) acrylate group, for example, a (meth) acrylate oligomer, a prepolymer, or a monomer (monomer). . More specifically, (meth) acrylate oligomers or prepolymers include relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiols. Examples include oligomers or prepolymers composed of (meth) allyllic acid esters of polyfunctional compounds such as polyene resins and polyhydric alcohols. Examples of the (meth) acrylate monomer include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1, Examples include 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
Examples other than (meth) acrylate compounds include monofunctional or polyfunctional monomers such as styrene, methylstyrene, N-vinylpyrrolidone, or bisphenol type epoxy compounds, novolac type epoxy compounds, aromatic vinyl ethers, aliphatic vinyl ethers. And compounds having a cationically polymerizable functional group such as an oligomer or a prepolymer.

When the ionizing radiation curable resin is used as an ultraviolet curable resin, a sensitizer can be added as a photopolymerization initiator or a photopolymerization accelerator.
As specific examples of the photopolymerization initiator, in the case of a resin system having a radical polymerizable functional group, acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, tetramethylchuram monosulfide, benzoins, Examples include benzoin methyl ether, thioxanthones, propiophenones, benzyls, acylphosphine oxides, 1-hydroxy-cyclohexyl-phenyl-ketone, and the like, which are used alone or in combination. 1-hydroxy-cyclohexyl-phenyl-ketone is available, for example, under the trade name Irgacure 184 (manufactured by Ciba Specialty Chemicals). As α-aminoalkylphenones, for example, trade names Irgacure 907 and 369 are available.
In the case of a resin system having a cationic polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metatheron compound, a benzoin sulfonic acid ester or the like is used alone or as a mixture as a photopolymerization initiator.
Further, it is preferable to use a mixture of photosensitizers, and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine and the like.
The addition amount of a photoinitiator is 0.1-10 weight part with respect to 100 weight part of ionizing radiation-curable compositions.

  The solvent-drying resin used by mixing with the ionizing radiation curable resin mainly includes a thermoplastic resin. As the thermoplastic resin, those generally exemplified are used. By adding the solvent-drying resin, coating film defects on the coated surface can be effectively prevented. Specific examples of preferable thermoplastic resins include, for example, styrene resins, (meth) acrylic resins, organic acid vinyl ester resins, vinyl ether resins, halogen-containing resins, and olefin resins (including alicyclic olefin resins). ), Polycarbonate resin, polyester resin, polyamide resin, thermoplastic polyurethane resin, polysulfone resin (eg, polyethersulfone, polysulfone), polyphenylene ether resin (eg, polymer of 2,6-xylenol), cellulose Derivatives (eg, cellulose esters, cellulose carbamates, cellulose ethers), silicone resins (eg, polydimethylsiloxane, polymethylphenylsiloxane), rubbers or elastomers (eg, polybutadiene, polyisoprene) Diene rubber, styrene - butadiene copolymer, acrylonitrile - butadiene copolymer, acrylic rubber, urethane rubber, silicone rubber) and the like are preferable.

  Specific examples of the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin, silicon resin. And polysiloxane resin. When a thermosetting resin is used, a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier and the like can be further added as necessary.

<2-3-2. Other ingredients>
In the antiglare layer according to the present invention, additives may be mixed in addition to the above essential components in order to impart a function without departing from the spirit of the present invention. Examples of the additive include a leveling agent, a solvent, an antistatic agent, a polymerization initiator, and an antifouling agent.

<2-3-2-1. Leveling agent>
A leveling agent can be added to the resin composition for forming an antiglare layer of the present invention, and among them, a leveling agent such as fluorine or silicone is preferably added. The resin composition for forming an antiglare layer to which a leveling agent is added can impart coating stability, slipperiness, antifouling property, and scratch resistance to the coating film surface during application or drying.

<2-3-2-2. Solvent>
Depending on the type and amount of the binder component C, it may function as a liquid medium, so that the antiglare layer-forming resin composition may be applied without using a solvent. Therefore, a solvent may be used in order to prepare a resin composition for forming an antiglare layer having excellent coating properties by appropriately dissolving and dispersing solid components and adjusting the concentration.

  Examples of the solvent include alcohols such as isopropyl alcohol, methanol, ethanol, butanol, and isobutyl alcohol; ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, and the like. Esters: Halogenated hydrocarbons such as chloroform, methylene chloride, and tetrachloroethane; aromatic hydrocarbons such as toluene and xylene, or mixtures thereof.

<2-3-2-2-3. Antistatic agent>
The antiglare layer may contain an antistatic agent as necessary in order to prevent the generation of static electricity and prevent the adhesion of dust, and to prevent external static electricity damage when incorporated in a liquid crystal display or the like. It may be added. In this case, as the antistatic performance, the surface resistance after forming the antiglare film is preferably 10 ¹² Ω / □ or less. However, even when the surface resistance is 10 ¹² Ω / □ or more, the addition of the antistatic agent makes it easier to suppress the adhesion of dust than the antiglare film without the addition of the antistatic agent.

  Examples of the antistatic agent include various cationic antistatic agents having a cationic group such as a quaternary ammonium salt, a pyridinium salt, and first to third amino groups; a sulfonate group, a sulfate ester base, and a phosphate ester. Anionic antistatic agents having anionic groups such as bases and phosphonic acid groups; amphoteric antistatic agents such as amino acids and aminosulfate esters; nonionic antistatic agents such as amino alcohols, glycerols, and polyethylene glycols A conductive polymer in which a dopant is combined with a conductive polymer such as polyacetylene, polyaniline, or polythiophene (for example, 3,4-ethylenedioxythiophene (PEDOT)); organometallic compounds such as tin and titanium alkoxides, and the like Various metal chelate compounds such as acetylacetonate salts Surface active agents antistatic agents; and the above-mentioned antistatic agent increasing the molecular weight of the polymeric antistatic agent and the like. In addition, a tertiary amino group, a quaternary ammonium group, a monomer or oligomer having a metal chelate portion and polymerizable by ionizing radiation, and an organometallic compound such as a coupling agent having a functional group polymerizable by ionizing radiation And other polymerizable antistatic agents.

  Other antistatic agents include fine particles having a particle size of 100 nm or less, such as tin oxide, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), indium-doped zinc oxide (AZO), antimony oxide, and indium oxide. be able to. In particular, when the particle diameter is 100 nm or less, which is equal to or less than the wavelength of visible light, the transparency of the antistatic layer can be easily secured and the transparency of the antiglare film is hardly impaired.

<2-4. Preparation of Antiglare Layer Forming Resin Composition>
The resin composition for forming an antiglare layer according to the present invention is prepared by mixing and dispersing the above components according to a general preparation method. A paint shaker or a bead mill can be used for mixing and dispersing. When the translucent fine particles A and the reactive inorganic fine particles B are obtained in a dispersed state in a solvent, the curable binder system and other components including the solvent are appropriately added and mixed in the dispersed state. It is prepared by dispersion treatment.

<3. Hard coat layer>
The hard coat layer according to the present invention is
Reactive inorganic fine particles D having at least a part of the surface coated with an organic component and having a reactive functional group d introduced by the organic component on the surface; and
Curing in the system includes a binder component E having a reactive functional group b of the reactive inorganic fine particle B and a reactive functional group e having a crosslinking reactivity with the reactive functional group d of the reactive inorganic fine particle D. It consists of the hardened | cured material of the resin composition for hard-coat layer formation containing the curable binder type | system | group which also has reactivity. Since the reactive inorganic fine particles D are excellent in hardness and can form a crosslink with the binder component E, the hard coat layer has excellent scratch resistance.

  Hereinafter, the reactive inorganic fine particles D, the binder component E, which are essential components of the curable resin composition for forming a hard coat layer, and other components appropriately blended as necessary will be described in order.

<3-1. Reactive inorganic fine particles D>
The hard coat layer according to the present invention contains the reactive inorganic fine particles D for the purpose of improving the hardness so as to have scratch resistance. The reactive inorganic fine particle D may be one that further imparts a function to the hard coat layer, and is appropriately selected and used according to the purpose.
As the reactive inorganic fine particles D, those having the same material, shape, and surface treatment as the reactive inorganic fine particles B described in the antiglare layer can be used.
The reactive inorganic fine particles D have an average particle size of preferably 5 nm to 120 nm, more preferably 10 nm to 80 nm.

  Like the reactive inorganic fine particle B in the antiglare layer, the hard coat layer according to the present invention has a constant average particle diameter of the reactive inorganic fine particle D so that the hard coat layer has a constant value. The distribution of the reactive inorganic fine particles D can also be controlled. When the average particle size of the reactive inorganic fine particles D is 5 nm or more and less than 30 nm, the region where the average number of the reactive inorganic fine particles D is large in the vicinity of the interface of the hard coat layer on the side opposite to the transparent substrate. When the average particle size of the reactive inorganic fine particles D is 30 nm or more and 100 nm or less, the average particle size of the reactive inorganic fine particles D is near the interface opposite to the transparent substrate of the hard coat layer. A region having a small number is formed.

  The reactive functional group d of the reactive inorganic fine particle D can form a crosslink with the reactive functional group e of the binder component E. In addition, the reactive functional group d can further form a cross-linked bond with the reactive functional group b of the reactive inorganic fine particle B and the reactive functional group c of the binder component C, thereby improving the film strength. And it is preferable from the point which can improve the adhesiveness between the said layers by forming a bridge | crosslinking bond in the layer interface of the said glare-proof layer and the said hard-coat layer.

<3-2. Hard coat layer curable binder system>
In the present specification, the constituent components of the curable binder system of the hard coat layer include, in addition to the binder component E, after curing of a curable binder component other than the binder component E, a polymer component, a polymerization initiator, and the like. This represents a matrix component of the hard coat layer.

<3-2-1. Binder component E>
In the resin composition for forming a hard coat layer according to the present invention, the binder component E has a reactive functional group e having a crosslinking reactivity with a reactive functional group d of the reactive inorganic fine particle D, and the reactive functional group The group d and the reactive functional group e are cross-linked to form a network structure. In addition, the binder component E preferably has three or more reactive functional groups e per molecule in order to obtain sufficient crosslinkability. As the reactive functional group e, a polymerizable unsaturated group is suitably used, preferably a photocurable unsaturated group, and particularly preferably an ionizing radiation curable unsaturated group. Specific examples thereof include an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group, and an epoxy group.

  Further, the reactive functional group e of the binder component E includes the reactive functional group d of the reactive inorganic fine particle D, and the reactive functional group d of the reactive inorganic fine particle B contained in the above-described resin composition for forming an antiglare layer. The group b and the reactive functional group c of the binder component C can form a cross-linked bond, which improves the film strength and forms a cross-linked bond at the layer interface between the antiglare layer and the hard coat layer. This is preferable from the viewpoint of improving the adhesion between the layers.

  The binder component E is preferably a curable organic resin, preferably a translucent material that transmits light when formed into a coating film, and an ionizing radiation curable resin that is cured by ionizing radiation represented by ultraviolet rays or electron beams. Resins, other known curable resins, and the like may be appropriately employed according to required performance. Examples of the ionizing radiation curable resin include acrylate-based, oxetane-based, and silicone-based resins.

  In the hard coat layer according to the present invention, the binder component E may be the same as the binder component C of the antiglare layer. In addition, in terms of improving the hardness of the hard coat layer, a compound having a molecular weight of less than 10,000 having a polyalkylene oxide chain-containing polymer (F) represented by the following chemical formula (3) and two or more reactive functional groups e (G) is preferably used in combination.

化学式（３）において、Ｘは直鎖、分枝、若しくは環状の炭化水素鎖が単独又は組み合わされてなり、当該炭化水素鎖は置換基を有していても良く、また当該炭化水素鎖間には異種原子が含まれていても良い、前記置換基を除いた炭素数が３〜１０の３価以上の有機基である。ｋは３〜１０の整数を表す。Ｌ_１〜Ｌ_ｋはそれぞれ独立に、エーテル結合、エステル結合、及びウレタン結合よりなる群から選択される１種以上を含む２価の基、又は、直接結合である。Ｒ_１〜Ｒ_ｋはそれぞれ独立に、炭素数１〜４の直鎖又は分岐の炭化水素基である。ｎ１、ｎ２・・・ｎｋはそれぞれ独立の数である。Ｙ_１〜Ｙ_ｋはそれぞれ独立に、１つ以上の反応性官能基ｅを有する化合物残基を示す。

In the chemical formula (3), X is a linear, branched, or cyclic hydrocarbon chain, which is used alone or in combination, and the hydrocarbon chain may have a substituent, and between the hydrocarbon chains. Is a trivalent or higher valent organic group having 3 to 10 carbon atoms, excluding the substituent, which may contain different atoms. k represents an integer of 3 to 10. L _{1 to} L _k are each independently a divalent group containing one or more selected from the group consisting of an ether bond, an ester bond, and a urethane bond, or a direct bond. R _{1 to} R _k are each independently a linear or branched hydrocarbon group having 1 to 4 carbon atoms. n1, n2,... nk are independent numbers. Y _{1 to} Y _k each independently represent a compound residue having one or more reactive functional groups e.

  The polymer (F), the compound (G), and the reactive inorganic fine particle D can react with each other, and the polymer (F) is cross-linked with both the compound (G) and the reactive inorganic fine particle D. Therefore, it is presumed that the hard coat layer can have sufficient scratch resistance.

<3-2-1-1. Polyalkylene oxide chain-containing polymer represented by chemical formula (3) (F)>
The polyalkylene oxide chain-containing polymer (F) is a polyalkylene oxide chain-containing polymer represented by the following chemical formula (3) and having a molecular weight of 1000 or more having three or more reactive functional groups e at the terminals.

化学式（３）において、Ｘは直鎖、分枝、若しくは環状の炭化水素鎖が単独又は組み合わされてなり、当該炭化水素鎖は置換基を有していても良く、また当該炭化水素鎖間には異種原子が含まれていても良い、前記置換基を除いた炭素数が３〜１０の３価以上の有機基である。ｋは３〜１０の整数を表す。Ｌ_１〜Ｌ_ｋはそれぞれ独立に、エーテル結合、エステル結合、及びウレタン結合よりなる群から選択される１種以上を含む２価の基、又は、直接結合である。Ｒ_１〜Ｒ_ｋはそれぞれ独立に、炭素数１〜４の直鎖又は分岐の炭化水素基である。ｎ１、ｎ２・・・ｎｋはそれぞれ独立の数である。Ｙ_１〜Ｙ_ｋはそれぞれ独立に、１つ以上の反応性官能基ｅを有する化合物残基を示す。

In the chemical formula (3), X is a linear, branched, or cyclic hydrocarbon chain, which is used alone or in combination, and the hydrocarbon chain may have a substituent, and between the hydrocarbon chains. Is a trivalent or higher valent organic group having 3 to 10 carbon atoms, excluding the substituent, which may contain different atoms. k represents an integer of 3 to 10. L _{1 to} L _k are each independently a divalent group containing one or more selected from the group consisting of an ether bond, an ester bond, and a urethane bond, or a direct bond. R _{1 to} R _k are each independently a linear or branched hydrocarbon group having 1 to 4 carbon atoms. n1, n2,... nk are independent numbers. Y _{1 to} Y _k each independently represent a compound residue having one or more reactive functional groups e.

In the polyalkylene oxide chain-containing polymer (F) represented by the chemical formula (3), X has _k branch points from which the polyalkylene oxide chain (O—R _k ) _nk portion, which is a linear side chain, appears. Corresponds to the short main chain.

The hydrocarbon chain includes a saturated hydrocarbon such as —CH ₂ — or an unsaturated hydrocarbon such as —CH═CH—. The cyclic hydrocarbon chain may be composed of an alicyclic compound or may be composed of an aromatic compound. Further, different atoms such as O and S may be contained between the hydrocarbon chains, and ether bonds, thioether bonds, ester bonds, urethane bonds, etc. may be contained between the hydrocarbon chains. In addition, the hydrocarbon chain branched via a different atom with respect to a linear or cyclic hydrocarbon chain is counted as the carbon number of the substituent mentioned later.

  Specific examples of the substituent that the hydrocarbon chain may have include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, a mercapto group, a cyano group, a silyl group, a silanol group, and a nitro group. Group, acetyl group, acetoxy group, sulfone group and the like are mentioned, but not particularly limited. Substituents that may be present in the hydrocarbon chain include hydrocarbon chains that are branched via a hetero atom with respect to a linear or cyclic hydrocarbon chain as described above. A group (RO-, where R is a saturated or unsaturated linear, branched, or cyclic hydrocarbon chain), an alkylthioether group (RS-, where R is a saturated or unsaturated linear chain, Branched or cyclic hydrocarbon chains), alkyl ester groups (RCOO-, where R is a saturated or unsaturated linear, branched, or cyclic hydrocarbon chain). .

X is a trivalent or higher valent organic group having 3 to 10 carbon atoms excluding the substituent. When the number of carbon atoms excluding the substituent of X is less than 3, it is difficult to have three or more polyalkylene oxide chain (O—R _k ) _nk moieties which are linear side chains. On the other hand, when the number of carbon atoms excluding the substituent of X exceeds 10, the flexible portion increases and the hardness of the cured film decreases, which is not preferable. The number of carbon atoms excluding the substituent is preferably 3-7, and more preferably 3-5.

  X is not particularly limited as long as the above conditions are satisfied. For example, what has the following structure is mentioned.

  Among them, preferable structures include the above structures (x-1), (x-2), (x-3), (x-7) and the like.

  Among the raw materials for X, among others, 1,2,3-propanetriol (glycerol), trimethylolpropane, pentaerythritol, dipentaerythritol and the like are polyvalent having 3 to 10 carbon atoms having 3 or more hydroxyl groups in the molecule. Alcohols, polyvalent carboxylic acids having 3 to 10 carbon atoms having 3 or more carboxyl groups in the molecule, polyvalent amine acids having 3 to 10 carbon atoms having 3 or more amino groups in the molecule, etc. Preferably used.

In the chemical formula (3), k represents the number of polyalkylene oxide chains (O—R _k ) _{nk in} the molecule, and represents an integer of 3 to 10. If k is less than 3, that is, if there are two polyalkylene oxide chains, sufficient hardness cannot be obtained. On the other hand, if k exceeds 10, the number of flexible parts increases and the hardness of the cured film decreases, which is not preferable. The k is preferably 3-7, more preferably 3-5.

In the chemical formula (3), L _{1 to} L _k are each independently a divalent group including one or more selected from the group consisting of an ether bond, an ester bond, and a urethane bond, or a direct bond. The divalent group containing one or more selected from the group consisting of an ether bond, an ester bond, and a urethane bond is an ether bond (—O—), an ester bond (—COO—), a urethane bond (—NHCOO—). ) Itself. Since these bonds are easy to spread molecular chains and have a high degree of freedom, it is easy to achieve compatibility with other resin components.

  Examples of the divalent group containing one or more selected from the group consisting of an ether bond, an ester bond, and a urethane bond include —O—R—O— and —O (C═O) —R—O—. -O (C = O) -R- (C = O) O-,-(C = O) O-R-O-,-(C = O) O-R- (C = O) O-, — (C═O) O—R—O (C═O) —, —NHCOO—R—O—, —NHCOO—R—O (C═O) NH—, —O (C═O) NH—R —O—, —O (C═O) NH—R—O (C═O) NH—, —NHCOO—R—O (C═O) NH—, —NHCOO—R— (C═O) O— , —O (C═O) NH—R— (C═O) O—, —NHCOO—R—O (C═O) —, —O (C═O) NH—R—O (C═O) -Etc. are mentioned. Here, R represents a saturated or unsaturated, linear, branched or cyclic hydrocarbon chain.

  Specific examples of the divalent group include, for example, diols such as (poly) ethylene glycol and (poly) propylene glycol, dicarboxylic acids such as fumaric acid, maleic acid, and succinic acid, tolylene diisocyanate, hexamethylene diisocyanate, Although the residue remove | excluding active hydrogen, such as diisocyanates, such as isoboron diisocyanate, is mentioned, It is not limited to these.

In the chemical formula (3), (O—R _k ) _nk is a polyalkylene oxide chain in which the alkylene oxide is a linear side chain of a repeating unit. Here, R _{1 to} R _k are each independently a linear or branched hydrocarbon group having 1 to 4 carbon atoms. Examples of the alkylene oxide include methylene oxide, ethylene oxide, propylene oxide, isobutylene oxide, and the like, and ethylene oxide and propylene oxide which are linear or branched hydrocarbon groups having 2 to 3 carbon atoms are preferably used.

N1, n2... Nk, which are the number of repeating units of alkylene oxide R _k —O, are independent numbers. n1, n2,... nk are not particularly limited as long as the weight average molecular weight as a whole molecule is 1000 or more. n1, n2... nk may be different from each other, but it is preferable that the chain lengths are substantially the same from the viewpoint of suppressing cracks while maintaining the hardness when the hard coat layer is formed. Therefore, the difference between n1, n2,... Nk is preferably about 0 to 100, more preferably about 0 to 50, and particularly preferably about 0 to 10.
From the viewpoint of suppressing cracks while maintaining the hardness when the hard coat layer is formed, n1, n2... Nk are each preferably a number of 2 to 500, and more preferably a number of 2 to 300. preferable.

Y _{1 to} Y _k each independently represent a reactive functional group e or a compound residue having one or more reactive functional groups e. This provides three or more reactive functional groups e at the ends of the polyalkylene oxide chain-containing polymer.
When Y _{1 to} Y _k are the reactive functional group e itself, examples of Y _{1 to} Y _k include polymerizable unsaturated groups such as a (meth) acryloyl group.

Examples of the reactive functional group e in the case where Y _{1 to} Y _k are a compound residue having one or more reactive functional groups e include, for example, a (meth) acryloyl group, a (meth) acryloyloxy group, and a vinyl group. _{(CH 2 = CH -),} CH 2 = CR- ( wherein R represents a hydrocarbon group) include polymerizable unsaturated group such as. The compound residue is not particularly limited as long as the reactive functional group e is appropriately selected so that it can react with the compound (G) and the reactive inorganic fine particles D described later. When Y _{1 to} Y _k are compound residues, the number of reactive functional groups e possessed by Y _{1 to} Y _k may be one, but two or more can increase the crosslinking density. From the viewpoint of hardness when a hard coat layer is obtained.

When Y _{1 to} Y _k are compound residues having one or more reactive functional groups e, the compound residues are separated from at least one or more reactive functional groups e and the reactive functional groups e. Furthermore, it is a residue obtained by removing the reactive substituent or a part of the reactive substituent (such as hydrogen) from the compound having the reactive substituent.
For example, as a compound residue having an ethylenically unsaturated group, specifically, for example, a reactive substituent other than the ethylenically unsaturated group of the following compound or a part of the reactive substituent (such as hydrogen) is removed. Residue. Examples include (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and pentaerythritol tri (meth) acrylate, but are not limited thereto.

  The molecular weight of the polyalkylene oxide chain-containing polymer (F) used in the present invention is 1000 or more, more preferably 5000 or more, particularly preferably 10,000, from the viewpoint of imparting flexibility to the cured film and preventing cracks. That's it.

Commercially available products containing the polyalkylene oxide chain-containing polymer (F) represented by the chemical formula (3) include, for example, trade name beam set 371 (manufactured by Arakawa Chemical Industries), trade name Diabeam UK-4153 (Mitsubishi Rayon). Manufactured; in chemical formula (3), X is (x-7), k is 3, L _{1 to} L ₃ are direct bonds, R _{1 to} R ₃ are ethylene, and the total of n1, n2, and n3 is 20 Y _{1 to} Y ₃ are each an acryloyloxy group.) And the like.

  The content of the polymer (F) is preferably 5 to 100 parts by weight, and more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the compound (G) described later. If content of the said polymer (F) is 5 weight part or more with respect to 100 weight part of said compound (G) mentioned later, a softness | flexibility and a restoring property can be provided to a cured film, If it is 100 weight part or less The hardness of the cured film can be maintained.

<3-2-1-2.2 Compound (G) having a molecular weight of less than 10,000 having two or more reactive functional groups e>
The compound (G) having a molecular weight of less than 10,000 having two or more reactive functional groups e improves the hardness of the cured film of the resin composition in combination with the reactive inorganic fine particles A described above, and provides sufficient resistance. It has a function of imparting scratch resistance. In addition, what has the structure of the said polymer (F) is remove | excluded from the compound (G) which has two or more reactive functional groups e and whose molecular weight is less than 10,000.
In the present invention, the compound (G) has a reactive functional group e that can react with each other in a combination of the polymer (F) and the reactive inorganic fine particles A, and has a wide range of scratch resistance. It can be used by appropriately selecting from compounds. As the said compound (G), you may use individually by 1 type, but may mix and use 2 or more types suitably.
The compound (G) having a molecular weight of less than 10,000 having two or more reactive functional groups e has three or more reactive functional groups e contained in one molecule, which increases the crosslinking density of the cured film. From the viewpoint of imparting hardness. Here, when the compound (G) is an oligomer having a molecular weight distribution, the number of reactive functional groups e is represented by an average number.
Moreover, it is preferable that the molecular weight of a compound (G) is less than 5000 from the point of a hardness improvement.

Specific examples are given below, but the compound (G) used in the present invention is not limited thereto.
As a specific example having a polymerizable unsaturated group, as a polyfunctional (meth) acrylate monomer having two or more polymerizable unsaturated groups in one molecule, for example, 1,6-hexanediol di (meth) acrylate, Bifunctional (meth) acrylate compounds such as neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate; trimethylolpropane tri (meth) acrylate, and its EO, PO, epichlorohydrin modified product, pentaerythritol tri (meth) acrylate, glycerol tri (meth) acrylate and its EO, PO, epichlorohydrin modified product, isocyanuric acid EO modified tri (meth) acrylate (Aronix M-31 manufactured by Toagosei Co., Ltd.) Etc.), tris (meth) acryloyloxyethyl phosphate, hydrogen phthalate- (2,2,2-tri- (meth) acryloyloxymethyl) ethyl, glycerol tri (meth) acrylate, and its EO, PO, epichlorohydrin modification Trifunctional (meth) acrylate compounds such as products; pentaerythritol tetra (meth) acrylate and its EO, PO, epichlorohydrin modified products, tetrafunctional (meth) acrylate compounds such as ditrimethylolpropane tetra (meth) acrylate; dipentaerythritol Penta (meth) acrylate and pentafunctional (meth) acrylate compounds such as EO, PO, epichlorohydrin, fatty acid, alkyl and urethane modified products thereof; dipentaerythritol hexa (meth) acrylate and EO and P thereof , Epichlorohydrin, fatty acids, alkyl, urethane-modified products, sorbitol hexa (meth) acrylate, and EO, PO, epichlorohydrin, fatty acids, alkyl, hexafunctional (meth) acrylate compound of the urethane modified products are exemplified.

  Examples of (meth) acrylate oligomers (or prepolymers) include epoxy (meth) acrylates obtained by addition reaction of glycidyl ether and a monomer having (meth) acrylic acid or a carboxylate group; polyols and polyisocyanates; (Meth) acrylates obtained by an addition reaction between a reaction product of (1) and a hydroxyl group-containing (meth) acrylate; polyesters obtained by esterification of a polyester polyol comprising a polyol and a polybasic acid and (meth) acrylic acid Examples of acrylates include polybutadiene (meth) acrylate, which is a (meth) acrylic compound having a polybutadiene or hydrogenated polybutadiene skeleton. When the reactive functional group e which the essential component in this invention has is a polymerizable unsaturated group, especially urethane (meth) acrylate is used suitably from the point which gives hardness and a softness | flexibility to a cured film.

Examples of the glycidyl ether used in the epoxy (meth) acrylates include 1,6-hexane diglycidyl ether, polyethylene glycol glycidyl ether, bisphenol A type epoxy resin, naphthalene type epoxy resin, cardo epoxy resin, and glycerol triglycidyl ether. And phenol novolac type epoxy resins.
Examples of the polyol used in the urethane (meth) acrylates include 1,6-hexane diglycidyl ether, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone diol, polycarbonate diol, polybutadiene polyol, and polyester diol. Etc. Examples of the polyisocyanate used in the urethane (meth) acrylates include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylene diisocyanate, hexamelletin diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and the like. Examples of the (meth) acrylate containing a hydroxyl group used in the urethane (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and pentaerythritol. (Meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate and the like.
Examples of the polyol for forming the polyester polyol used in the polyester acrylates include ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, neopentyl glycol, 1,4-butanediol, trimethylolpropane, and pentaerythritol. Examples of the polybasic acid include succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid.

  Moreover, as a compound (G) used for this invention, the polymer represented by following Chemical formula (4) whose molecular weight is less than 10,000 can also be used.

化学式（４）中、Ｌ’は炭素数１〜１０の連結基を表し、ｑは０又は１を表す。Ｒは水素原子又はメチル基を表す。Ｊは任意のビニルモノマーの重合単位を表し、単一成分であっても複数の成分で構成されていてもよい。ｏ、ｐは各重合単位のモル％である。ｐは０であっても良い。

In chemical formula (4), L ′ represents a linking group having 1 to 10 carbon atoms, and q represents 0 or 1. R represents a hydrogen atom or a methyl group. J represents a polymerized unit of an arbitrary vinyl monomer, and may be composed of a single component or a plurality of components. o and p are mol% of each polymerized unit. p may be 0.

L ′ in the chemical formula (4) represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, which is linear. Alternatively, it may have a branched structure, may have a ring structure, or may have a heteroatom selected from O, N, and S.
Preferred examples of the linking group L ′ in the chemical formula (4) include * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * — (CH ₂ ) ₄ —. _{O - **, * - (CH} 2) 6 -O - **, * - (CH 2) 2 -O- (CH) 2 -O - **, * - CONH- (CH 2) 3 -O- **, * —CH ₂ CH (OH) CH ₂ —O — **, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — **, and the like. Here, * represents a connecting site on the polymer main chain side, and ** represents a connecting site on the (meth) acryloyl group side.

In chemical formula (4), R represents a hydrogen atom or a methyl group, and is more preferably a hydrogen atom from the viewpoint of curing reactivity.
In chemical formula (4), o may be 100 mol%, that is, a single polymer. Moreover, even if o is 100 mol%, the copolymer in which 2 or more types of polymerization units containing the (meth) acryloyl group represented by o mol% were used may be used. The ratio of o and p is not particularly limited and can be appropriately selected from various viewpoints such as hardness, solubility in a solvent, and transparency.

  In chemical formula (4), J represents a polymerization unit of an arbitrary vinyl monomer, and is not particularly limited, and can be appropriately selected from various viewpoints such as hardness, solubility in a solvent, transparency, and the like. You may be comprised by the single or several vinyl monomer.

  For example, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, allyl vinyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, etc. (Meth) acrylates such as vinyl esters, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane, Styrene derivatives such as styrene and p-hydroxymethyl styrene, and unsaturated hydrocarbons such as crotonic acid, maleic acid and itaconic acid. Mention may be made of carbon acids and derivatives thereof.

  Moreover, the reactive oligomer which has an ethylenically unsaturated bond in the terminal and side chain whose weight average molecular weight is less than 10,000 can also be used. As the reactive oligomer, the skeleton component is poly (meth) acrylate methyl, polystyrene, poly (meth) butyl acrylate, poly (acrylonitrile / styrene), poly ((meth) acrylate 2-hydroxymethyl / (meth) Methyl acrylate), poly (2-hydroxymethyl (meth) acrylate / butyl (meth) acrylate), and copolymers of these resins and silicone resins.

  Commercially available products can be used for the above compounds. As urethane acrylate having a weight average molecular weight of less than 10,000 and having two or more polymerizable unsaturated groups, Kyoeisha Chemical Co., Ltd. trade names AH-600, AT-600, UA-306H, UA-306T, UA-306I, etc .; manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Trade names UV-1700B, UV-3000B, UV-3200B, UV-6300B, UV-6330B, UV-7000B, etc .; Arakawa Chemical Industries, Ltd., trade name beam Set 500 series (502H, 504H, 550B, etc.); Shin-Nakamura Chemical Co., Ltd. trade names U-6HA, U-15HA, UA-32P, U-324A, etc .; Toagosei Co., Ltd. trade names M-9050 Etc. Among them, as the urethane (meth) acrylate suitably used in combination with the polymer (F) of the present invention, a monomer or multimer of isophorone diisocyanate, a pentaerythritol polyfunctional acrylate, and a dipentaerythritol polyfunctional acrylate are used. The urethane (meth) acrylate obtained by reaction is mentioned. As a commercial item of the said urethane (meth) acrylate, brand name UV-1700B (made by Nippon Synthetic Chemical Industry Co., Ltd.) is mentioned, for example.

  Moreover, as an epoxy acrylate having a weight average molecular weight of less than 10,000 and having two or more polymerizable unsaturated groups, trade name SP series (SP-4060, 1450, etc.), VR series (VR- 60, 1950; VR-90, 1100, etc.); Nippon Synthetic Chemical Industry Co., Ltd., trade names UV-9100B, UV-9170B, etc .; Shin-Nakamura Chemical Co., Ltd., trade names EA-6320 / PGMAc, EA- 6340 / PGMAc and the like.

  Moreover, as a reactive oligomer having a weight average molecular weight of less than 10,000 and having two or more polymerizable unsaturated groups, trade name Macromonomer Series AA-6, AS-6, AB- manufactured by Toagosei Co., Ltd. 6, AA-714SK and the like.

<3-2-2. Other ingredients>
In addition to the above essential components, additives may be mixed in the hard coat layer according to the present invention in addition to the above essential components without departing from the spirit of the present invention. Examples of the additive include a polymerization initiator, a leveling agent, a solvent, an antistatic agent, and an antifouling agent.

<3-2-2-1. Polymerization initiator>
In the present invention, in order to initiate or promote the radical polymerizable functional group or the cationic polymerizable functional group, a radical polymerization initiator, a cationic polymerization initiator, a radical and a cationic polymerization initiator are appropriately selected as necessary. May be used. These polymerization initiators are decomposed by light irradiation and / or heating to generate radicals or cations to advance radical polymerization and cationic polymerization.

  Any radical polymerization initiator may be used as long as it can release a substance that initiates radical polymerization by light irradiation and / or heating. For example, examples of the photo radical polymerization initiator include imidazole derivatives, bisimidazole derivatives, N-aryl glycine derivatives, organic azide compounds, titanocenes, aluminate complexes, organic peroxides, N-alkoxypyridinium salts, thioxanthone derivatives, and the like. More specifically, 1,3-di (tert-butyldioxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetrakis (tert-butyldioxycarbonyl) benzophenone, 3-phenyl-5- Isoxazolone, 2-mercaptobenzimidazole, bis (2,4,5-triphenyl) imidazole, 2,2-dimethoxy-1,2-diphenylethane-1-one (trade names: Irgacure 651, Ciba Specialty Chemicals ( 1-hydroxy-cyclo Xyl-phenyl-ketone (trade name Irgacure 184, manufactured by Ciba Specialty Chemicals), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (trade name Irgacure) 369, manufactured by Ciba Specialty Chemicals), bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl ) Titanium) (trade name: Irgacure 784, manufactured by Ciba Specialty Chemicals Co., Ltd.), etc., but is not limited thereto.

  Moreover, the cationic polymerization initiator should just be able to discharge | release the substance which starts cationic polymerization by light irradiation and / or a heating. As cationic polymerization initiators, sulfonic acid esters, imide sulfonates, dialkyl-4-hydroxysulfonium salts, arylsulfonic acid-p-nitrobenzyl esters, silanol-aluminum complexes, (η6-benzene) (η5-cyclopentadienyl) Iron (II) and the like are exemplified, and more specifically, benzoin tosylate, 2,5-dinitrobenzyl tosylate, N-tosicphthalimide and the like are exemplified, but not limited thereto.

  Examples of radical polymerization initiators that can be used as cationic polymerization initiators include aromatic iodonium salts, aromatic sulfonium salts, aromatic diazonium salts, aromatic phosphonium salts, triazine compounds, iron arene complexes, and the like. More specifically, iodonium chloride such as diphenyliodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bromide, borofluoride, hexafluorophosphate salt, hexafluoro Iodonium salts such as antimonate salts, chlorides of sulfonium such as triphenylsulfonium, 4-tert-butyltriphenylsulfonium, tris (4-methylphenyl) sulfonium, bromides, borofluorides, hexaf Sulfonium salts such as orophosphate salts and hexafluoroantimonate salts, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1, 2,4,6-substituted-1,3,5 triazine compounds such as 3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, etc. It is not limited to these.

<3-2-2-2. Solvent>
Depending on the type and amount of the binder component E, it may function as a liquid medium, so that the hard coat layer forming resin composition may be applied without using a solvent. Therefore, a solvent may be used in order to prepare a resin composition for forming a hard coat layer having excellent coating properties by appropriately dissolving and dispersing solid components and adjusting the concentration.

  Specific examples of the solvent include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, isobutyl alcohol, methyl glycol, methyl glycol acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone Ketones such as alcohol; esters such as methyl formate, methyl acetate, ethyl acetate, ethyl lactate and butyl acetate; nitrogen-containing compounds such as nitromethane, N-methylpyrrolidone and N, N-dimethylformamide; diisopropyl ether, tetrahydrofuran and dioxane Ethers such as dioxolane; halogenated hydrocarbons such as methylene chloride, chloroform, trichloroethane, and tetrachloroethane; Kishido, other objects, such as propylene carbonate; or mixtures thereof. More preferred solvents include methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone and the like.

<3-2-2-3. Leveling agent>
A leveling agent can be added to the resin composition for forming a hard coat layer of the present invention, and among them, it is preferable to add a fluorine or silicone leveling agent. The resin composition for forming a hard coat layer to which a leveling agent has been added can impart coating stability, slipperiness, antifouling properties, and scratch resistance to the coating film surface during application or drying.

<3-3. Preparation of resin composition for forming hard coat layer>
The resin composition for forming a hard coat layer according to the present invention is prepared by mixing and dispersing the above components according to a general preparation method. A paint shaker or a bead mill can be used for mixing and dispersing. When the reactive inorganic fine particle D is obtained in a state dispersed in a solvent, it is prepared by adding the curable binder system and other components including the solvent as appropriate in the dispersed state, and mixing and dispersing the mixture. Is done.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and has the same operational effects can be used. Included in the technical scope.

  Hereinafter, the present invention will be described more specifically with reference to examples. These descriptions do not limit the present invention. In addition, in an Example, a part means a weight part, when there is no separate description. Further, the thickness of the antiglare layer (the thickness from the hard coat layer side interface of the antiglare layer to the concave surface of the antiglare layer opposite to the hard coat layer) is 5 in the TEM photograph of the cross section of the antiglare film. The location was measured and taken as the average value. Similarly, the thickness of the hard coat layer (thickness from the transparent base film side interface of the hard coat layer to the antiglare layer side interface of the hard coat layer) was also measured at five locations in the TEM photograph of the cross section of the antiglare film. The average value was used.

<Production Example 1. Preparation of reactive inorganic fine particles B (1)>
(1) Removal of surface adsorbed ions Water-dispersed colloidal silica having a particle size of 30 nm (trade name: Snowtex 50, manufactured by Nissan Chemical Industries, Ltd., pH 9 to 10) is replaced with a cation exchange resin (trade name: Diaion SK1B, Mitsubishi Chemical). After performing ion exchange for 3 hours using 400 g of anion exchange resin (trade name: Diaion SA20A, manufactured by Mitsubishi Chemical Corporation) for 3 hours using 400 g, Washed to obtain an aqueous dispersion of silica fine particles having a solid content concentration of 20% by weight.
At this time, the Na ₂ O content of the aqueous dispersion of silica fine particles was 7 ppm for each silica fine particle.
(2) Surface treatment (introduction of monofunctional monomer)
150 mL of isopropanol, 4.0 g of 3,6,9-trioxadecanoic acid, and 4.0 g of methacrylic acid are added to 10 g of the silica fine particle aqueous dispersion subjected to the treatment (1), and the mixture is stirred for 30 minutes. Mixed.
The obtained mixed liquid was stirred while heating at 60 ° C. for 5 hours to obtain a silica fine particle dispersion in which a methacryloyl group was introduced on the surface of the silica fine particles. Distilled water and isopropanol were distilled off using a rotary evaporator, and the resulting silica fine particle dispersion was added with methyl ethyl ketone so as not to dry, while finally making the remaining water and isopropanol 0.1% by weight, A silica-dispersed methyl ethyl ketone solution having a solid content of 50% by weight was obtained.
The silica fine particles (reactive inorganic fine particles B (1)) thus obtained had an average particle size of d ₅₀ = 30 nm as a result of measurement using a Nanotrac particle size analyzer manufactured by Nikkiso Co., Ltd. . The amount of the organic component covering the surface of the silica fine particles was 2.73 × 10 ⁻³ g / m ² as a result of measurement by thermogravimetric analysis. Further, the specific gravity of the obtained reactive inorganic fine particles B (1) was 2.1. In the examples, the surface modification method of the fine particles in Production Example 1 is referred to as Modification Method 1.

<Production Example 2. Preparation of reactive inorganic fine particles B (2)>
(1) Removal of surface adsorbed ions Using water-dispersed colloidal silica having a particle size of 90 nm (trade name: Snowtex ZL, manufactured by Nissan Chemical Industries, Ltd., pH 9 to 10), surface adsorbed ions were removed in the same manner as in Production Example 1. An aqueous dispersion of the removed silica fine particles was obtained.
(2) Surface treatment (introduction of polyfunctional monomer)
Surface treatment was performed in the same manner as in Production Example 1 except that methacrylic acid was changed to dipentaerythritol pentaacrylate (trade name: SR399, manufactured by Sartomer Co., Ltd.) in Production Example 1.
The reactive inorganic fine particles B (2) thus obtained had an average particle diameter of d ₅₀ = 90 nm as a result of measurement by the particle size analyzer. The amount of the organic component covering the surface of the silica fine particles was 2.15 × 10 ⁻³ g / m ² as a result of measurement by thermogravimetric analysis. Further, the specific gravity of the obtained reactive inorganic fine particles B (2) was 2.1. In the examples, the surface modification method for fine particles in Production Example 2 is referred to as Modification Method 2.

<Production Example 3. Preparation of reactive inorganic fine particles B (3)>
To a solution consisting of 7.8 parts by weight of mercaptopropyltrimethoxysilane and 0.2 parts by weight of dibutyltin dilaurate in dry air, 20.6 parts by weight of isophorone diisocyanate was added dropwise at 50 ° C. over 1 hour with stirring. Stir at 60 ° C. for 3 hours. To this was added dropwise 71.4 parts by weight of pentaerythritol triacrylate at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 3 hours to obtain Compound (1).
Under a nitrogen stream, methanol silica sol having a particle diameter of 60 nm (trade name: OSCAL series, manufactured by Catalytic Chemical Industry Co., Ltd.) 88.5 parts by weight (solid content 26.6 parts by weight), compound (1) synthesized above 8. A mixed solution of 5 parts by weight and 0.01 parts by weight of p-methoxyphenol was stirred at 60 ° C. for 4 hours. Subsequently, 3 parts by weight of methyltrimethoxysilane was added to this mixed solution, and after stirring for 1 hour at 60 ° C., 9 parts by weight of methyl orthoformate was added, and the reaction was continued by heating and stirring at the same temperature for 1 hour. Inorganic fine particles B (3) were obtained.
The reactive inorganic fine particles B (3) thus obtained had an average particle size of d ₅₀ = 60 nm as a result of measurement by the particle size analyzer. Moreover, the amount of organic components covering the surface was 7.08 × 10 ⁻³ g / m ² as a result of measurement by thermogravimetric analysis. Further, the specific gravity of the obtained reactive inorganic fine particles B (3) was 2.1. In the examples, the surface modification method of the fine particles in Production Example 3 is referred to as Modification Method 3.

<Production Example 4. Preparation of reactive inorganic fine particles B (4)>
(1) Removal of surface adsorbed ions Using water-dispersed colloidal silica having a particle size of 200 nm (trade name: Snowtex MP, manufactured by Nissan Chemical Industries, Ltd., pH 9 to 10), surface adsorbed ions were removed in the same manner as in Production Example 1. An aqueous dispersion of the removed silica fine particles was obtained.
(2) Surface treatment (introduction of monofunctional monomer)
Surface treatment was performed in the same manner as in Production Example 1.
The reactive inorganic fine particles B (4) thus obtained had an average particle size of d ₅₀ = 200 nm as a result of measurement by the particle size analyzer. The amount of the organic component covering the surface of the silica fine particles was 1.90 × 10 ⁻³ g / m ² as a result of measurement by thermogravimetric analysis. Further, the specific gravity of the obtained reactive inorganic fine particles B (4) was 2.1.

<Production Example 5. Preparation of inorganic fine particles having no reactive functional group>
(1) Removal of surface adsorbed ions In Production Example 1, only the surface adsorbed ions were removed, and the surface treatment was not performed, and inorganic fine particles (1) were obtained.
The inorganic fine particles thus obtained had an average particle diameter of d ₅₀ = 30 nm as a result of measurement using the particle size analyzer. Further, the specific gravity of the obtained inorganic fine particles was 2.1.

<Production Example 6. Preparation of reactive inorganic fine particles D (1)>
In the same manner as in Production Example 1, reactive inorganic fine particles D (1) were obtained. The reactive inorganic fine particles D (1) thus obtained had an average particle diameter of d ₅₀ = 30 nm as a result of measurement by the particle size analyzer. The amount of the organic component covering the surface of the silica fine particles was 2.73 × 10 ⁻³ g / m ² as a result of measurement by thermogravimetric analysis. Further, the specific gravity of the obtained reactive inorganic fine particles B (1) was 2.1.

<Production Example 7. Preparation of Antiglare Layer Forming Resin Composition (1)>
Pentaerythritol triacrylate (PETA): 42.5 parts by weight Irgacure 184 (photopolymerization initiator): 0.25 parts by weight Silicone (leveling agent): 0.1 parts by weight Reactive inorganic fine particles B (1) : 7.5 parts by weight Silica (translucent fine particles A) (average particle size 1 μm): 12 parts by weight Toluene: 34 parts by weight The above materials were sufficiently mixed to prepare a composition.

<Production Example 8. Preparation of Antiglare Layer Forming Resin Composition (2)>
A resin composition (2) for forming an antiglare layer was prepared in the same manner as in Production Example 7 except that the reactive inorganic fine particles B (1) were changed to reactive inorganic fine particles B (2) in Production Example 7.

<Production Example 9. Preparation of Antiglare Layer-Forming Resin Composition (3)>
A resin composition (3) for forming an antiglare layer was prepared in the same manner as in Production Example 7 except that the reactive inorganic fine particles B (1) were changed to reactive inorganic fine particles B (3) in Production Example 7.

<Production Example 10. Preparation of Antiglare Layer-Forming Resin Composition (4)>
A resin composition (4) for forming an antiglare layer was prepared in the same manner as in Production Example 7 except that the reactive inorganic fine particles B (1) were changed to reactive inorganic fine particles B (4) in Production Example 7.

<Production Example 11. Preparation of Antiglare Layer Forming Resin Composition (5)>
In Production Example 7, the anti-glare layer was formed in the same manner as in Production Example 7, except that the reactive inorganic fine particles B (1) were changed to the inorganic fine particles (1) having no reactive functional group obtained in Production Example 5. Resin composition (5) was prepared.

<Production Example 12. Preparation of Antiglare Layer-Forming Resin Composition (6)>
In Production Example 7, a resin composition for forming an antiglare layer (6) was prepared in the same manner as in Production Example 7 except that the particle size of the translucent fine particles A was changed to 0.5 μm.

<Production Example 13. Preparation of Hard Coat Layer Forming Resin Composition (1)>
UV1700B (trade name, manufactured by Nippon Synthetic Chemical Co., Ltd., urethane acrylate, 10 functional, molecular weight 2000): 70 parts by weight (converted into solid content)
Reactive inorganic fine particles D (1): 30 parts by weight (in terms of solid content)
-Methyl ethyl ketone: 100 parts by weight-Irgacure 184 (trade name, manufactured by Ciba Specialty Chemicals, radical polymerization initiator): 0.4 parts by weight The above materials were sufficiently mixed to prepare a composition.

<Example 1. Production of antiglare film>
On one side of a triacetylcellulose (TAC) film (transparent substrate film) having a thickness of 80 μm, the hard coat layer forming resin composition (1) prepared in Production Example 13 was coated with 3.5 g / After coating m ² and evaporating and drying the solvent, a hard coat layer is formed by irradiating twice at a rate of 10 m / min with an 80 W / cm ultraviolet irradiation device while keeping the oxygen concentration at 0.1% or less. Then, the antiglare layer-forming resin composition (1) prepared in Production Example 7 was applied with a Miya bar coat at 3.5 g / m ² , and after evaporating and drying the solvent, the oxygen concentration was 0.1%. The antiglare layer was formed by irradiating twice at a rate of 10 m / min with an 80 W / cm ultraviolet irradiation device while maintaining the following, to obtain an antiglare film.
The resulting antiglare film had an antiglare layer thickness of 1 μm and a hard coat layer thickness of 2 μm. The average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer of the antiglare layer is the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the antiglare layer. It was 72%.

<Example 2. Production of antiglare film>
In Example 1, an antiglare film having a hard coat layer thickness of 2 μm was prepared in the same manner as in Example 1 except that the film thickness of the antiglare layer was changed to 5 μm. The average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer of the antiglare layer is the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the antiglare layer. It was 60%.

<Example 3. Production of antiglare film>
The film thickness of the antiglare layer was 1 μm in the same manner as in Example 1 except that the resin composition for forming an antiglare layer (1) was replaced with the resin composition for forming an antiglare layer (2). An antiglare film having a hard coat layer thickness of 2 μm was prepared. The average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer of the antiglare layer is the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the antiglare layer. It was 57%.

<Example 4. Production of antiglare film>
In Example 1, the resin composition for forming an antiglare layer (1) was changed to the resin composition for forming an antiglare layer (2), and the film thickness of the antiglare layer was 5 μm. Thus, an antiglare film having a hard coat layer thickness of 2 μm was produced. The average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer of the antiglare layer is the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the antiglare layer. It was 50%.

<Example 5. Production of antiglare film>
In Example 1, an antiglare film having an antiglare layer thickness of 1 μm was produced in the same manner as in Example 1 except that the hard coat layer thickness was 20 μm. The average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer of the antiglare layer is the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the antiglare layer. It was 72%.

<Example 6. Production of antiglare film>
In Example 1, an antiglare film was produced in the same manner as in Example 1 except that the film thickness of the antiglare layer was 5 μm and the film thickness of the hard coat layer was 20 μm. The average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer of the antiglare layer is the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the antiglare layer. It was 60%.

<Example 7. Production of antiglare film>
In Example 1, the resin composition for forming an antiglare layer (1) was changed to the resin composition for forming an antiglare layer (2), and the film thickness of the hard coat layer was 20 μm. Thus, an antiglare film having an antiglare layer thickness of 1 μm was produced. The average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer of the antiglare layer is the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the antiglare layer. It was 57%.

<Example 8. Production of antiglare film>
In Example 1, the antiglare layer-forming resin composition (1) was the antiglare layer-forming resin composition (2), the antiglare layer thickness was 5 μm, and the hard coat layer thickness was 20 μm. Except for this, an antiglare film was produced in the same manner as in Example 1. The average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer of the antiglare layer is the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the antiglare layer. It was 50%.

<Example 9. Production of antiglare film>
In Example 1, the resin composition for forming an antiglare layer (1) was changed to the resin composition for forming an antiglare layer (3), and the film thickness of the hard coat layer was set to 20 μm. Thus, an antiglare film having an antiglare layer thickness of 1 μm was produced. The average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer of the antiglare layer is the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the antiglare layer. 62%.

<Example 10. Production of antiglare film>
In Example 1, a triacetyl cellulose (TAC) film (transparent substrate film) having a thickness of 80 μm was used as a cycloolefin polymer (COP) film having a thickness of 80 μm, and the film thickness of the antiglare layer was 5 μm. An antiglare film was produced in the same manner as in Example 1 except that the film thickness was 20 μm. The average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer of the antiglare layer is the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the antiglare layer. It was 60%.

<Example 11. Production of antiglare film>
In Example 1, a 80 μm thick triacetyl cellulose (TAC) film (transparent substrate film) is a 80 μm thick polyethylene terephthalate (PET) film, the antiglare layer is 5 μm thick, and the hard coat layer is a film. An antiglare film was produced in the same manner as in Example 1 except that the thickness was 20 μm. The average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer of the antiglare layer is the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the antiglare layer. It was 60%.

<Example 12. Production of antiglare film>
In Example 1, a triacetyl cellulose (TAC) film (transparent substrate film) having a thickness of 80 μm is an acrylic resin film having a thickness of 80 μm, the film thickness of the antiglare layer is 5 μm, and the film thickness of the hard coat layer is An antiglare film was produced in the same manner as in Example 1 except that the thickness was 20 μm. The average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer of the antiglare layer is the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the antiglare layer. It was 60%.

<Comparative Example 1. Production of antiglare film>
In Example 1, an antiglare film was produced in the same manner as in Example 1 except that the film thickness of the antiglare layer was 10 μm and the film thickness of the hard coat layer was 20 μm. The average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer of the antiglare layer is the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the antiglare layer. It was 55%.

<Comparative Example 2. Production of antiglare film>
In Example 1, the antiglare layer-forming resin composition (1) was the antiglare layer-forming resin composition (4), the antiglare layer thickness was 5 μm, and the hard coat layer thickness was 20 μm. Except for this, an antiglare film was produced in the same manner as in Example 1. The average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer of the antiglare layer is the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the antiglare layer. 45%.

<Comparative Example 3. Production of antiglare film>
In Example 1, the antiglare layer-forming resin composition (1) was the antiglare layer-forming resin composition (5), the antiglare layer thickness was 5 μm, and the hard coat layer thickness was 20 μm. Except for this, an antiglare film was produced in the same manner as in Example 1. The average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer of the antiglare layer is the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the antiglare layer. 120%.

<Comparative Example 4. Production of antiglare film>
In Example 1, the particle size of the light-transmitting fine particles was 0.5 μm, the film thickness of the antiglare layer was 5 μm, and the film thickness of the hard coat layer was 20 μm. A film was prepared. The average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the skin layer of the antiglare layer is the average number of reactive inorganic fine particles B per unit area in the cross section in the thickness direction of the antiglare layer. It was 72%.

〔Evaluation method〕
The following 1 thru | or 3 evaluation was performed about the anti-glare film obtained by the said each Example and each comparative example. The results are shown in Table 1.

Evaluation 1. Pencil hardness test The pencil hardness of the antiglare layer surface of the obtained antiglare film was evaluated according to JIS K5600-5-4 (1999). Using a 3H pencil, 5 lines were drawn with a load of 500 g, and then the presence or absence of scratches on the antiglare layer was visually observed and evaluated according to the following criteria.
Evaluation criteria evaluation A: 0 to 1 scratch was found.
Evaluation (triangle | delta): There were 2-3 scratches.
Evaluation x: There were 4 to 5 scratches.

Evaluation 2. Front contrast reduction rate (preparation of polarizing plate)
The obtained antiglare film was saponified with 55 ° C., 2N aqueous sodium hydroxide (NaOH) solution for 2 minutes, and then applied to the polarizing plate with the transparent substrate film bonded to one side, which was not the coated surface of the antiglare film. The side was bonded to the polarizer surface to produce a polarizing plate (A).
(Measurement of front contrast (C / R) reduction rate)
Sony BRAVIA 27-inch panel with a polarizing plate (A) on the liquid crystal cell surface side and a polarizing plate with triacetyl cellulose bonded on both sides of the polarizer on the back surface of the liquid crystal cell Then, the contrast was measured using a BM-5 luminance meter manufactured by Topcon Techno House.

Evaluation 3. Cracking property When the obtained antiglare film was wound around a metal roll having a diameter of 0.5 cm, the presence or absence of cracks was confirmed by visual observation and evaluated according to the following criteria.
Evaluation criteria Evaluation ○: No crack evaluation ×: Crack present

FIG. 1 is a diagram schematically showing a layer configuration of an antiglare film according to the present invention. FIG. 2 is a perspective view schematically showing an example of a cross section in the layer thickness direction of the antiglare film according to the present invention and an area having a width of 1 μm in the cross section. FIG. 3 is a diagram schematically showing an example of a cross section in the layer thickness direction of the antiglare film according to the present invention and a region having a width of 1 μm in the cross section. FIG. 4 is a view schematically showing an example of a state of distribution of the reactive inorganic fine particles B in a region having a width of 1 μm in a cross section in the layer thickness direction of the antiglare film according to the present invention. FIG. 5 is a diagram schematically showing another example of the distribution of the reactive inorganic fine particles B in a region having a width of 1 μm in the cross section in the layer thickness direction of the antiglare film according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Anti-glare film 2 Anti-glare layer 3 Hard-coat layer 4 Transparent base film 10 Section P
20 Reactive inorganic fine particles B
30 Interface 40 opposite to the transparent substrate of the antiglare layer 40 Interface 50 of the antiglare layer on the transparent substrate side Skin layer 60 Region in which the reactive inorganic fine particles B are uniformly distributed with an average inter-particle distance of 30 nm or more 70 observer

Claims (5)

On one side of the transparent substrate film, an antiglare film provided with an antiglare layer having a concavo-convex shape on the surface adjacent to the hard coat layer and the hard coat layer from the side close to the transparent substrate film,
The antiglare layer is
Translucent fine particles A having an average particle size of 1 μm or more and 10 μm or less, defined as the most existing particle size in either the volume distribution or the number distribution of particle diameters measured by the Coulter counter method,
Reactive inorganic fine particles B having at least a part of the surface coated with an organic component and having a reactive functional group b introduced by the organic component on the surface; and
Anti-glare layer comprising a binder component C having a reactive functional group c having cross-linking reactivity with the reactive functional group b of the reactive inorganic fine particle B, and containing a curable binder system also having curing reactivity in the system It consists of the hardened | cured material of the resin composition for formation, and the film thickness of the said glare-proof layer is 1 micrometer or more and 5 micrometers or less,
The reactivity per unit area in the cross section in the thickness direction of the antiglare layer compared to the region on the transparent substrate film side in the surface layer region on the opposite side to the transparent substrate film of the antiglare layer and in the vicinity thereof It has a skin layer with a small average number of inorganic fine particles B,
The average number of the reactive inorganic fine particles B per unit area in the thickness direction cross section of the skin layer is 50% of the average number of the reactive inorganic fine particles B per unit area in the thickness direction cross section of the antiglare layer. And not more than 80%,
The average distance between particles of the reactive inorganic fine particles B to be dispersed in the region of the transparent substrate film side of the skin layer is not less 30nm or more,
The hard coat layer is
Reactive inorganic fine particles D having at least a part of the surface coated with an organic component and having a reactive functional group d introduced by the organic component on the surface; and
A hard coat layer containing a binder component E having a reactive functional group e having cross-linking reactivity with the reactive functional group d of the reactive inorganic fine particle D, and containing a curable binder system having curing reactivity in the system It consists of a cured product of the forming resin composition,
An antiglare film characterized by having a hardness of 3H or more when a pencil hardness test specified in JIS K5600-5-4 (1999) is performed with a load of 500 g on the surface of the antiglare layer.   The reactive inorganic fine particle B is an average defined as a 50% particle size when the particle size distribution measured by a dynamic light scattering method using a nanotrack particle size analyzer manufactured by Nikkiso Co., Ltd. is expressed as a cumulative distribution. The antiglare film according to claim 1, wherein the particle size is 30 nm or more and 100 nm or less.   3. The antiglare film according to claim 1, wherein the inorganic fine particles serving as cores of the translucent fine particles A and the reactive inorganic fine particles B are made of silica. 4. The content of the reactive inorganic fine particles B is the total solid content of the antiglare layer forming resin composition, characterized in that 2 to 30 wt%, any one of claims 1 to 3 An antiglare film as described in the item. The antiglare film according to any one of claims 1 to 4 , wherein the transparent base film is mainly composed of cellulose acylate, cycloolefin polymer, acrylate polymer, or polyester.

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