JP2010120991A - Curable resin composition for hard coat layer and hard coat film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition for a hard coat layer forming a hard coat layer having high hardness even if thinned, and a hard coat film using the curable resin composition. <P>SOLUTION: The hard coat film includes a hard coat layer disposed on one side of a base material, wherein the hard coat layer comprises a cured product of the curable resin composition containing specific spherical reactive silica fine particles (A1) and/or reactive deformed silica fine particles (A2) formed by inorganic chemical bonding of 3-20 specific spherical silica fine particles as reactive silica fine particles (A), a polyfunctional monomer (B) having ≥3 reactive functional groups in one molecule and a molecular weight of ≤1,000, and a reactive polymer (C) having a specific structure and a weight-average molecular weight of 10,000-70,000. The same and/or different reactive functional groups contained in the respective components have crosslinking reactivity between the reactive functional groups. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is used for the purpose of protecting the surface of a display or the like, a hard coat film provided with a hard coat layer on a base material, and a curable resin composition for a hard coat layer for forming the hard coat layer Related to things.

  An image display surface in an image display device such as a liquid crystal display, a CRT display, a projection display, a plasma display, or an electroluminescence display is required to be provided with scratch resistance so as not to be damaged during handling. On the other hand, by using a hard coat film in which a hard coat (HC) layer is provided on a base film, and a hard coat film (optical laminate) having optical functions such as antireflection and antiglare properties. Generally, the scratch resistance of the image display surface of the image display device is improved.

  The hard coat layer is usually formed on the base film using a photopolymerizable resin such as a thermosetting resin or an ultraviolet curable resin. The film thickness is appropriately adjusted according to the performance required for the hard coat film, and is preferably about 3 to 25 μm. However, when the film thickness is as thin as about 3 to 25 μm, a sufficiently high mechanical strength (pencil hardness) cannot be obtained due to the influence of deformation of the underlying base material.

  As a method for improving the hardness of the hard coat layer, it is conceivable to simply increase the thickness of the hard coat layer. However, when the thickness is increased, the hardness is improved, but the hard coat layer is likely to be cracked or the entire laminate is warped (so-called curl) due to curing shrinkage of the components of the hard coat layer. There is a problem that workability is remarkably impaired when the body is attached to the display.

Further, as a method for improving the hardness of the hard coat layer, there is a method of adding inorganic fine particles, and generally, a hard coat film in which a hard coat layer having inorganic fine particles added is provided on a base film is manufactured (patent) Reference 1).
However, even when inorganic fine particles are added to the hard coat layer, it is difficult to achieve a mechanical strength of 4H or more in pencil hardness with a film thickness of the hard coat layer that can meet the required performance of the hard coat film. It was.

JP 2002-107503 A

  The present invention has been made in view of the above problems, and a curable resin composition for a hard coat layer that can form a hard coat layer having a high hardness even if it is thinned, and a hard that uses the curable resin composition. The object is to provide a coated film.

The hard coat film according to the present invention is a hard coat film provided with a hard coat layer on one side of a substrate, and the hard coat layer is
As the reactive silica fine particles (A), spherical reactive silica fine particles (A1) having a reactive functional group a on the particle surface having an average primary particle diameter of 1 to 100 nm and / or a sphere having an average primary particle diameter of 1 to 100 nm. Reactive deformed silica fine particles (A2) having 3 to 20 silica fine particles bonded by an inorganic chemical bond and having a reactive functional group a ′ on the surface,
A polyfunctional monomer (B) having 3 or more reactive functional groups b in one molecule and a molecular weight of 1000 or less, and
Reactive polymer (C) represented by the following general formula (I) and having a weight average molecular weight of 10,000 to 70,000,
The ethylenically unsaturated bonds contained in the reactive functional groups a, a ′, b and the reactive polymer (C) are curable having cross-linking reactivity between the same and / or different reactive functional groups, respectively. It consists of the hardened | cured material of a resin composition, It is characterized by the above-mentioned.

（式（Ｉ）において、Ｒ^１〜Ｒ^４はそれぞれ独立に、水素又はメチル基を表す。Ａは、直鎖状に連なる原子の数が１〜１５の連結基を表す。Ｘ、Ｙ、Ｚは、各重合単位の平均繰り返し数を表し、Ｘは０〜２０００、Ｙは１０〜１０００、及びＺは０〜２０００である。）

(In Formula (I), R ^{1 to} R ⁴ each independently represents hydrogen or a methyl group. A represents a linking group having 1 to 15 atoms in a straight chain. X, Y, Z Represents the average number of repeating units of each polymer unit, X is 0 to 2000, Y is 10 to 1000, and Z is 0 to 2000.)

Moreover, the curable resin composition for hard coat layers of the present invention is a reactive silica fine particle (A), which is a spherical reactive silica fine particle having a reactive functional group a on the particle surface having an average primary particle diameter of 1 to 100 nm. (A1) and / or reactive deformed silica fine particles (A2) having 3 to 20 spherical silica fine particles having an average primary particle diameter of 1 to 100 nm bonded by an inorganic chemical bond and having a reactive functional group a ′ on the surface,
A polyfunctional monomer (B) having 3 or more reactive functional groups b in one molecule and a molecular weight of 1000 or less, and
Reactive polymer (C) represented by the following general formula (I) and having a weight average molecular weight of 10,000 to 70,000,
The ethylenically unsaturated bonds contained in the reactive functional groups a, a ′, b and the reactive polymer (C) have cross-linking reactivity between the same and / or different reactive functional groups, respectively. Features.

（式（Ｉ）において、Ｒ^１〜Ｒ^４はそれぞれ独立に、水素又はメチル基を表す。Ａは、直鎖状に連なる原子の数が１〜１５の連結基を表す。Ｘ、Ｙ、Ｚは、各重合単位の平均繰り返し数を表し、Ｘは０〜２０００、Ｙは１０〜１０００、及びＺは０〜２０００である。）

(In Formula (I), R ^{1 to} R ⁴ each independently represents hydrogen or a methyl group. A represents a linking group having 1 to 15 atoms in a straight chain. X, Y, Z Represents the average number of repeating units of each polymer unit, X is 0 to 2000, Y is 10 to 1000, and Z is 0 to 2000.)

  According to the present invention, the hard coat layer has a specific reactive silica fine particle (A) capable of crosslinking reaction between the same and / or different reactive functional groups of each component, a specific molecular weight and three or more. Because it is formed by curing a curable resin composition comprising a combination of a polyfunctional monomer (B) having a reactive functional group of (1) and a reactive polymer (C) having a specific average molecular weight and a specific structure. Even if the hard coat layer is made thin, a hard coat film with high hardness can be provided.

  In the hard coat film and curable resin composition of the present invention, the reactive silica fine particles (A) are contained in an amount of 35 to 65% by weight based on the total solid content of the curable resin composition, and the reactive polymer (C ) And the polyfunctional monomer (B) in a weight ratio (reactive polymer (C) / polyfunctional monomer (B)) of 0.2 to 10. When the reactive silica fine particles (A) are contained in an amount of 35 to 65% by weight with respect to the total solid content of the curable resin composition, the adhesiveness to the base material is improved while realizing a hard coating layer with high hardness. Excellent and good transparency. When the weight ratio of the reactive polymer (C) to the polyfunctional monomer (B) (reactive polymer (C) / polyfunctional monomer (B)) is 0.2 to 10, While realizing a hard coat layer, it has excellent adhesion to the substrate and curl can be reduced.

  In the hard coat film and the curable resin composition of the present invention, at least 50% by weight or more of the reactive silica fine particles (A) are inorganic and 3 to 20 spherical silica fine particles having an average primary particle size of 1 to 100 nm are inorganic. The reactive deformed silica fine particles (A2) having a reactive functional group a ′ on the surface bonded by the chemical bond are preferable from the standpoint that a hard coat layer having a particularly high hardness can be realized even if the thickness is reduced. The reactive irregular shaped silica fine particles (A2) are bonded to the hard coat layer during the pencil hardness test (500 g load) specified in JIS K5600-5-4 (1999) because the silica fine particles are bonded to each other by inorganic chemical bonds. Even if a load is applied, it is assumed that the bond does not break and works to reinforce the network in the hard coat layer. Therefore, from the viewpoint of improving the pencil hardness of the hard coat layer, the inorganic chemical bond of the reactive irregularly shaped silica fine particles (A2) is preferably a covalent bond.

  In the hard coat film of the present invention, the hardness by the pencil hardness test (500 g load) specified in JIS K5600-5-4 (1999) of the hard coat layer can be 5H or more.

  In the hard coat film of the present invention, even if the film thickness of the hard coat layer is in the range of 5 to 20 μm, the pencil hardness test (500 g load) defined in JIS K5600-5-4 (1999) of the hard coat layer. The hardness by can be 5H or more.

The hard coat film of the present invention comprises a specific reactive silica fine particle (A) in which the hard coat layer can undergo a crosslinking reaction between the same and / or different reactive functional groups of each component, a specific molecular weight and 3 It is formed by curing a curable resin composition comprising a combination of a polyfunctional monomer (B) having at least one reactive functional group and a reactive polymer (C) having a specific average molecular weight and a specific structure. Therefore, even if the hard coat layer is thinned, there is an effect that the hardness can be increased.
Further, the curable resin composition for a hard coat layer of the present invention comprises a specific reactive silica fine particle (A) capable of a crosslinking reaction between the same and / or different reactive functional groups of each component, and a specific By including a combination of a polyfunctional monomer (B) having a molecular weight and three or more reactive functional groups and a reactive polymer (C) having a specific average molecular weight and a specific structure, a cured film (hard coat layer) Even if the film thickness is reduced, it is possible to provide a hard coat film with high hardness.

The present invention is described in detail below.
In the present invention, (meth) acrylate represents acrylate and / or methacrylate.
In the present invention, the “hard coat layer” generally indicates a hardness of “H” or higher in a pencil hardness test (500 g load) defined by JIS K5600-5-4 (1999).
The light of the present invention includes not only electromagnetic waves having wavelengths in the visible and non-visible regions, but also particle beams such as electron beams, and radiation or ionizing radiation that collectively refers to electromagnetic waves and particle beams.
In this invention, a film thickness means the film thickness at the time of drying (dry film thickness).
In the present invention, the molecular weight means a weight average molecular weight which is a polystyrene equivalent value measured by gel permeation chromatography (GPC) when having a molecular weight distribution, and when having no molecular weight distribution, Mean molecular weight.

<Hard coat film>
The hard coat film according to the present invention is a hard coat film provided with a hard coat layer on one side of a substrate, and the hard coat layer is
As the reactive silica fine particles (A), spherical reactive silica fine particles (A1) having a reactive functional group a on the particle surface having an average primary particle diameter of 1 to 100 nm and / or a sphere having an average primary particle diameter of 1 to 100 nm. Reactive deformed silica fine particles (A2) having 3 to 20 silica fine particles bonded by an inorganic chemical bond and having a reactive functional group a ′ on the surface,
A polyfunctional monomer (B) having 3 or more reactive functional groups b in one molecule and a molecular weight of 1000 or less, and
Reactive polymer (C) represented by the following general formula (I) and having a weight average molecular weight of 10,000 to 70,000,
The ethylenically unsaturated bonds contained in the reactive functional groups a, a ′, b and the reactive polymer (C) are curable having cross-linking reactivity between the same and / or different reactive functional groups, respectively. It consists of the hardened | cured material of a resin composition, It is characterized by the above-mentioned.

（式（Ｉ）において、Ｒ^１〜Ｒ^４はそれぞれ独立に、水素又はメチル基を表す。Ａは、直鎖状に連なる原子の数が１〜１５の連結基を表す。Ｘ、Ｙ、Ｚは、各重合単位の平均繰り返し数を表し、Ｘは０〜２０００、Ｙは１０〜１０００、及びＺは０〜２０００である。）

(In Formula (I), R ^{1 to} R ⁴ each independently represents hydrogen or a methyl group. A represents a linking group having 1 to 15 atoms in a straight chain. X, Y, Z Represents the average number of repeating units of each polymer unit, X is 0 to 2000, Y is 10 to 1000, and Z is 0 to 2000.)

  In the hard coat film of the present invention, the hard coat layer has specific reactive silica fine particles (A) capable of crosslinking reaction between the same and / or different reactive functional groups of each component, and a specific molecular weight. Formed by curing a curable resin composition containing a combination of a polyfunctional monomer (B) having three or more reactive functional groups and a reactive polymer (C) having a specific average molecular weight and a specific structure Therefore, a hard coating layer with high hardness can be formed even if the film thickness is reduced.

  In the hard coat layer of the hard coat film of the present invention, as the reactive silica fine particles (A), spherical reactive silica fine particles (A1) having a reactive functional group a on the particle surface having an average primary particle size of 1 to 100 nm. And / or reactive deformed silica fine particles (A2) having 3 to 20 spherical silica fine particles having an average primary particle diameter of 1 to 100 nm bonded by an inorganic chemical bond and having a reactive functional group a ′ on the surface are used. The reactive silica fine particle (A) is a binder component around the silica fine particles (A) and the silica fine particles (A) by having the reactive functional group a or a ′ on the surface of the silica fine particles. A curing reaction that crosslinks with the polyfunctional monomer (B) and / or the reactive polymer (C) is possible, and imparts scratch resistance and hardness to the hard coat layer. Further, the reactive silica fine particles (A) have the above specific particle size and shape, so that they have excellent dispersibility, and when the hard coat layer curable resin composition is cured to form a hard coat layer, The transparency of the coat film can be secured.

In the hard coat layer of the hard coat film of the present invention, a polyfunctional monomer having 3 or more reactive functional groups b and a molecular weight of 1000 or less as a binder component in the reactive silica fine particles (A). By using (B) in combination with the reactive polymer (C) having an ethylenically unsaturated bond in the side chain portion of the specific main chain structure, high hardness can be realized. The reason why such a combination achieves high hardness is not clear, but is estimated as follows.
The reactive polymer (C) having the above specific structure has a linear structure obtained by reacting an ethylenically unsaturated bond with the main chain, so that the glass transition temperature of the main chain is increased and the hardness is increased. It is estimated that it has a function to increase Since such a main chain structure has a specific side chain containing a reactive functional group at the terminal with a relatively short linking group, the reactive polymer (C) is composed of the reactive polymers (C) and the reaction. The hardness of the hard coat layer can be improved by a curing reaction that crosslinks with the polyfunctional monomer (B) and / or the reactive silica fine particles (A) around the conductive polymer (C). In the reactive polymer (C), if the linking group in the side chain containing a reactive functional group at the terminal is too long, the hardness of the hard coat layer cannot be improved. In addition, by combining the polyfunctional monomer (B) having a specific molecular weight and three or more reactive functional groups, the crosslink density of the cured film can be increased while improving the adhesion to the substrate. Further, scratch resistance and hardness can be imparted to the hard coat layer. Further, when the reactive polymer (C) is appropriately included, curling can be reduced. Originally, there is polymerization shrinkage when it becomes a covalent bond due to the crosslinking curing reaction, but since the reactive polymer (C) has a polymer structure in advance, the polymerization shrinkage due to curing reaction is reduced. It is estimated that this is because of this. In addition to polymerization shrinkage caused by the crosslinking curing reaction, heat of polymerization is generated. In the case of the reactive polymer (C), since it has a polymer structure in advance, generation of polymerization heat generated by a curing reaction that crosslinks can be reduced, so that heat damage to the resin base material is reduced and wrinkles are generated. Even the appearance defects such as can be solved. When the thermal damage to the resin base material is large, the strength of the resin base material itself is lowered, which is not preferable.

  In a preferred embodiment of the hard coat film according to the present invention, the hardness of a pencil hardness test (4.9 N load) defined in JIS K5600-5-4 (1999) of the hard coat layer may be 5H or more. Is possible.

FIG. 1 is a cross-sectional view schematically showing an example of a layer configuration of a hard coat film according to the present invention. In the cross-sectional view shown in FIG. 1, for ease of explanation, the scale in the thickness direction (vertical direction in the figure) is greatly enlarged and exaggerated than the scale in the width direction (horizontal direction in the figure). is there.
The hard coat film 1 is provided with a hard coat layer 20 on one side of the substrate 10.
Hereinafter, each layer which comprises the hard coat film of this invention is demonstrated in order.

1. Base material The base material used for this invention is suitably selected by the use of a hard coat film, and may be a base material which does not have light transmittance, or a base material which has light transmittance. For example, as a hard coat film used for a reflective screen or the like, a substrate having no light transmittance can be used. As a hard coat film used for protecting an image display surface such as a liquid crystal display, a plasma display, and an organic EL display, a light-transmitting substrate is used.

  The light-transmitting substrate may be transparent, translucent, colorless or colored as long as it transmits light, but the average light transmittance in the visible light region of 380 to 780 nm is 50% or more, preferably 70% or more. More preferably, it is 85% or more. In addition, the measurement of light transmittance uses the value measured in room temperature and air | atmosphere using the ultraviolet visible spectrophotometer (For example, Shimadzu Corporation UV-3100PC).

In the present invention, the thickness of the substrate can be appropriately selected and used depending on the application. The concept of the substrate includes a film or a sheet, and the material of the substrate may be glass in addition to resin.
The light transmissive resin substrate is excellent in terms of thinness, lightness, resistance to cracking, flexibility, and the like.

  Among them, as the hard coat film used for protecting the image display surface, it is preferable to use a light-transmitting resin substrate having a thickness of 20 to 120 μm from the viewpoint of hardly breaking the surface of the hard coat film and imparting hardness, More preferably, it is 20-80 micrometers.

  Preferable materials for the light-transmitting resin base material include cellulose acylate, cycloolefin polymer, polycarbonate, acrylate polymer, or polyester. 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, 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 Nippon Zeon Co., Ltd., Sumilite FS-1700 manufactured by Sumitomo Bakelite Co., Ltd., Arton (modified norbornene resin) manufactured by JSR Co., Ltd. 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 polycarbonate include aromatic polycarbonates based on bisphenols (such as bisphenol A) and aliphatic polycarbonates such as diethylene glycol bisallyl carbonate.
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.

As the substrate used in the present invention, the material having the highest light transmittance is cellulose acylate, and triacetyl cellulose is preferably used among them.
A triacetyl cellulose film (TAC film) is a light-transmitting substrate capable of setting an average light transmittance to 50% or more in a visible light region of 380 to 780 nm.
Since the TAC film has optical isotropy, it can be preferably used in the case of a liquid crystal display application.

  In addition, as triacetyl cellulose in the present invention, in addition to pure triacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, and the like are used in combination with components other than acetic acid as fatty acids forming esters with cellulose. Also good. Further, these triacetyl celluloses may be added with other additives such as other cellulose lower fatty acid esters such as diacetyl cellulose, or plasticizers, antistatic agents, ultraviolet absorbers and the like, if necessary.

  In addition, as a base material having no light transmittance, for example, for a white board of a reflective screen or an electronic blackboard, for example, a base material having a reflective diffusivity having a coating layer of a white pigment on one surface such as a vinyl chloride film. For transmissive screens, there is a base material in which black stripes are patterned with light-absorbing ink on the non-condensing part of the lenticular lens on one surface of a light-transmitting base material such as acrylic resin. For louvers, for example, transparent resins such as polyethylene, polypropylene, and acrylic resins and thin layers kneaded with light-absorbing pigments are alternately laminated and sliced in a direction perpendicular to the transparent and light-absorbing thin layer surfaces. Examples of the base material in which the light transmission part and the light absorption part obtained are provided alternately, and for touch panels, for example, the periphery of the image display part of a polyester film. Light absorbent substrate light shielding frame is printed and icons frame or symbol has been patterned substrates, and the like in.

  In the present invention, the base material may be subjected to surface treatment such as saponification treatment, glow discharge treatment, corona discharge treatment, ultraviolet (UV) treatment, or flame treatment.

2. Hard coat layer The hard coat layer of the present invention comprises, as reactive silica fine particles (A), spherical reactive silica fine particles (A1) having a reactive functional group a on the particle surface having an average primary particle size of 1 to 100 nm and / or Alternatively, reactive deformed silica fine particles (A2) having 3 to 20 spherical silica fine particles having an average primary particle diameter of 1 to 100 nm bonded by an inorganic chemical bond and having a reactive functional group a ′ on the surface,
A polyfunctional monomer (B) having 3 or more reactive functional groups b in one molecule and a molecular weight of 1000 or less, and
Reactive polymer (C) represented by the following general formula (I) and having a weight average molecular weight of 10,000 to 70,000,
The ethylenically unsaturated bonds contained in the reactive functional groups a, a ′, b and the reactive polymer (C) are curable having cross-linking reactivity between the same and / or different reactive functional groups, respectively. It consists of a cured product of the resin composition.
The hard coat layer of the present invention is provided on the one surface side of the substrate directly or via another layer, using the curable resin composition according to the present invention.
In the present invention, the “hard coat layer” indicates a hardness of H or higher in the pencil hardness test (500 g load) defined in JIS K5600-5-4 (1999) as described above.
The hard coat layer of the present invention is preferably 5H or more in the pencil hardness test.

  The film thickness of the hard coat layer may be appropriately adjusted according to the required performance of the hard coat film, but is preferably 5 to 20 μm. If it is 5 μm or more, sufficient strength is easily obtained. In order to prevent adhesion and interference fringes and maintain hardness, the thickness of the hard coat layer is preferably 10 μm or more, and more preferably 15 μm or more. On the other hand, when it exceeds 20 μm, the cost becomes high. Further, in the case of a thin film such as a triacetyl cellulose film having a thickness of 100 μm or less, if it exceeds 20 μm, curling and cracking are likely to occur. Moreover, when the film thickness of the hard coat layer exceeds 20 μm, when the hard coat film of the present invention and the polarizing plate are bonded together, it is difficult for the solvent (organic solvent and water) used for both adhesives to come off. Drying efficiency may be significantly deteriorated. Further, if the solvent used in the adhesive remains, a change in the degree of polarization occurs and the performance of the polarizing plate itself deteriorates.

The composition of the curable resin composition for a hard coat layer that is cured to form the hard coat layer of the present invention will be described below.
The curable resin composition for a hard coat layer of the present invention contains the specific reactive silica fine particles (A), the specific polyfunctional monomer (B), and the specific reactive polymer (C) as essential components. Furthermore, it may contain other components such as a polymerization initiator and a solvent.

(Reactive silica fine particles (A))
In the present invention, as the reactive silica fine particles (A), spherical reactive silica fine particles (A1) having a reactive functional group a on the particle surface having an average primary particle size of 1 to 100 nm and / or an average primary particle size. Reactive deformed silica fine particles (A2) having 3 to 20 spherical silica fine particles of 1 to 100 nm bonded by an inorganic chemical bond and having a reactive functional group a ′ on the surface are used.
The reactive silica fine particle (A) is a binder component around the silica fine particles (A) and the silica fine particles (A) by having the reactive functional group a or a ′ on the surface of the silica fine particles. Further, a curing reaction capable of crosslinking with the polyfunctional monomer (B) and / or the reactive polymer (C) is possible, and imparts scratch resistance and hardness to the hard coat layer after curing.
In the case of a substrate having a low refractive index, for example, a resin substrate such as triacetyl cellulose, the reactive silica fine particles (A) have a refractive index of silica (SiO ₂ ) as low as about 1.46. The refractive index of the hard coat layer containing a binder component (polyfunctional monomer (B) and reactive polymer (C)) of about 1.50 is close to the refractive index of the substrate, and the refractive index of the hard coat layer and the substrate In order to reduce the difference, there is an effect of preventing the occurrence of interference fringes.
In the spherical reactive silica fine particles (A1) and the reactive deformed silica fine particles (A2) in which 3 to 20 spherical silica fine particles are bonded by an inorganic chemical bond, “spherical” is not only true spherical, It is a concept that includes a substantially spherical shape that can be approximated to a sphere including a spheroid and a polyhedron.

  The average primary particle diameter of the spherical reactive silica fine particles (A1) having the reactive functional group a on the particle surface is in the range of 1 to 100 nm, preferably in the range of 12 to 50 nm. If the average primary particle size of the reactive silica fine particles (A1) is less than 1 nm, it cannot contribute to the improvement of the hardness of the hard coat layer, and the substrate adjacent to the hard coat layer or, if necessary, the substrate of the hard coat layer. Since the contact area between the other layer provided on the opposite side to the silica particles and the silica fine particles increases, the adhesion with the substrate may be deteriorated. When the average primary particle size exceeds 100 nm, the transparency of the hard coat layer is lowered, and there is a possibility that the transmittance is deteriorated and the haze is increased.

  The spherical reactive silica fine particles (A1) may be used not only having a single average primary particle diameter but also a combination of two or more kinds having different average primary particle diameters. When two or more types are used in combination, the average primary particle size of each particle may be within 1 to 100 nm.

  As the spherical reactive silica fine particles (A1), the restoration rate when only the binder components (polyfunctional monomer (B) and reactive polymer (C)) described later are used is maintained without impairing transparency. From the viewpoint of improving hardness, the particle size distribution is preferably narrow and monodispersed.

  On the other hand, the average primary particle size of the silica fine particles constituting the reactive deformed silica fine particles (A2) having 3 to 20 spherical silica fine particles bonded by an inorganic chemical bond and having a reactive functional group a ′ on the surface is 1 Within a range of -100 nm, preferably within a range of 5-80 nm. If the average primary particle size of the silica fine particles is less than 1 nm, sufficient hardness cannot be imparted to the hard coat layer. On the other hand, if the average primary particle size of the silica fine particles exceeds 100 nm, the transparency of the hard coat layer is lowered, which may lead to deterioration in transmittance and increase in haze.

  Further, the average secondary particle size of the reactive silica fine particles (A) used in the present invention is preferably in the range of 5 to 300 nm, and more preferably in the range of 10 to 200 nm. When the average secondary particle size of the reactive silica fine particles (A) is within the above range, it is easy to impart hardness to the hard coat layer and maintain the transparency of the hard coat layer.

  In the present invention, the average primary particle size of the silica fine particles is a 50% particle size (d50 median size) when the particles in the solution are measured by a dynamic light scattering method and the particle size distribution is expressed as a cumulative distribution. ). The average primary particle size can be measured using a Microtrac particle size analyzer manufactured by Nikkiso Co., Ltd. The average secondary particle size of the reactive silica fine particles (A) can be determined by the same method as the average primary particle size.

  The silica fine particles do not exclude the use of particles having pores or porous structures inside the particles, such as hollow particles, but solid particles having no pores or porous structures inside the particles. It is more preferable to use from the point of hardness improvement.

  The reactive silica fine particles (A) used in the present invention are at least 50% by weight or more, more preferably 80% by weight or more, and 3 to 20 spherical silica fine particles having an average primary particle diameter of 1 to 100 nm. The reactive deformed silica fine particles (A2) bonded by an inorganic chemical bond and having a reactive functional group a ′ on the surface are particularly preferable from the viewpoint of increasing the hardness of the cured film. In such a case, for example, the hardness of the pencil hardness test (500 g load) specified in JIS K5600-5-4 (1999) of the hard coat layer can be 5H or more, and further 6H or more can be achieved.

When the hard coat layer contains the reactive irregularly shaped silica fine particles (A2) cross-linked with the matrix of the hard coat layer, the pencil hardness test defined in JIS K5600-5-4 (1999) of the hard coat layer ( The effect of increasing the hardness of the cured film, which can achieve a hardness of 500 g load) of 5H or higher, further 6H or higher, is not yet elucidated, but is due to the following reasons. it is conceivable that.
In other words, the inorganic chemical bond of the irregular shaped silica fine particles has less flexibility and flexibility in the bonding than the bonds between the reactive functional groups that are organic components, and the silica fine particles are strongly bonded to each other. Even when a traction load is applied, the bond is not easily broken, and it is presumed that the hard coat layer can be given excellent hardness by acting in a form that reinforces the network in the film.

  The reactive irregularly shaped silica fine particles (A2) are formed by bonding the silica fine particles by 3 to 20, preferably 3 to 10, by an inorganic chemical bond. When the number of the fine particles in which the fine silica particles are bonded by an inorganic chemical bond is 3 or more, the effect of increasing the hardness of the cured film is particularly high. On the other hand, when the number of the fine particles in which the fine silica particles are bonded by an inorganic chemical bond exceeds 20, the transparency of the hard coat layer is lowered, and the transmittance may be deteriorated and haze may be increased.

  The reactive irregularly shaped silica fine particles (A2) preferably have an aspect ratio, that is, a ratio of the major axis to the minor axis of 3 to 20 because the effect of improving the scratch resistance and hardness of the hard coat layer is high. .

  Examples of the inorganic chemical bond in the reactive deformed silica fine particle (A2) include an ionic bond, a metal bond, a coordination bond, and a covalent bond. Among them, a bond in which the bonded fine particles are not dispersed even when the deformed silica fine particles are added to a polar solvent, specifically, a metal bond, a coordinate bond, and a covalent bond are preferable, and a covalent bond is more preferable. Examples of the polar solvent include water and lower alcohols such as methanol, ethanol and isopropyl alcohol.

  The reactive deformed silica fine particles (A2) are in a particle state in which 3 to 20 silica fine particles are bonded by an inorganic chemical bond and aggregated particles (aggregated particles) and 3 to 20 silica fine particles. Examples thereof include chain-like particles bonded by an inorganic chemical bond and bonded in a chain. In particular, from the viewpoint of increasing the hardness of the cured film, chain particles are preferred as the particle state of the irregular shaped silica fine particles.

  When the reactive irregularly shaped silica fine particles (A2) are chain particles, the average number of bonds of the silica fine particles is determined by observing the cross section of the hard coat layer using an SEM photograph or a TEM photograph and observing the cured irregular shape. One hundred fine silica particles can be selected, and the fine silica particles contained in each irregular-shaped fine silica particle can be counted and obtained as an average value.

  The method for producing irregularly shaped silica fine particles in the reactive irregularly shaped silica fine particles (A2) is not particularly limited as long as the silica fine particles are bonded by inorganic bonds, and a conventionally known method is appropriately selected and used. Can do. For example, it can be obtained by adjusting the concentration or pH of the monodispersed silica fine particle dispersion and performing hydrothermal treatment at a high temperature of 100 ° C. or higher. At this time, if necessary, a binder component can be added to promote the binding of the silica fine particles. Further, ions may be removed by passing the silica fine particle dispersion used through an ion exchange resin. Such ion exchange treatment can promote the binding of silica fine particles. After the hydrothermal treatment, the ion exchange treatment may be performed again.

The reactive silica fine particles (A) have a reactive functional group a or a ′ on the surface of the silica fine particles. The reactive functional group a or a ′ is a polyfunctional monomer (B) and / or a reactive polymer (C) that is a binder component around the silica fine particles (A) or around the silica fine particles (A). It is appropriately selected so that it can be crosslinked. As the reactive functional group a or a ′, 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 ethylenically unsaturated bonds such as (meth) acryloyl group, vinyl group and allyl group, and epoxy group. The reactive functional group a or a ′ is preferably an ethylenically unsaturated bond capable of crosslinking with the reactive polymer (C).
When the spherical reactive silica fine particles (A1) and the reactive modified silica fine particles (A2) are used in combination, the reactive functional group a of the spherical reactive silica fine particles (A1) and the reactive deformed silica fine particles (A2) The reactive functional groups a ′ may be the same or different, but are preferably selected so that they can react with each other.

  As the reactive silica fine particles (A), the spherical reactive silica fine particles (A1) and the reactive deformed silica fine particles (A2) are both coated with an organic component on at least a part of the surface and introduced by the organic component. It has a reactive functional group a or a ′ on the surface. Here, the organic component is a component containing carbon. Moreover, 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 silica fine particles to cause a part of the surface In addition to the mode in which the organic component is bonded to the surface, or the mode in which the organic component having an isocyanate group is reacted with the hydroxyl group present on the surface of the silica fine particle and the organic component is bonded to a part of the surface, for example, silica Examples include an aspect in which an organic component is attached to a hydroxyl group present on the surface of the fine particle by an interaction such as hydrogen bonding, and an aspect in which silica fine particles are contained in the polymer particle.

As a method for preparing reactive silica fine particles (A) having an organic component coated on at least a part of the surface and having a reactive functional group a or a ′ introduced by the organic component on the surface, spherical reactive silica fine particles may be used. Both (A1) and reactive irregularly shaped silica fine particles (A2) can be carried out in the same manner. A conventionally known method can be appropriately selected and used depending on the reactive functional group a or a ′ to be introduced into the silica fine particles. Among them, in the present invention, it is preferable to select and use any one of the following silica fine particles (i) and (ii) from the viewpoint of suppressing aggregation of the silica fine particles and improving the hardness of the film.
(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 silica 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. Silica fine particles having a reactive functional group a or a ′ on the surface.
(Ii) a compound containing a reactive functional group a or a ′ introduced into silica fine particles before coating, 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 oxide Silica fine particles having a reactive functional group a or a ′ on the surface, obtained by bonding with fine particles.
Chemical formula (1)
−Q ¹ −C (= Q ² ) −Q ³ −
In chemical formula (1), Q ¹ represents NH, O (oxygen atom), or S (sulfur atom), Q ² represents O or S, and Q ³ represents NH or a divalent or higher valent organic group. .

Hereinafter, the reactive silica fine particles (A) preferably used 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 silica 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. Silica fine particles having a reactive functional group a or a ′ on the surface.
When the reactive silica fine particles (A) (i) are used, there is an advantage that the film strength can be improved even if the organic component content is small.

  The surface modifying compound used in the reactive silica fine particles (A) 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, Hydroxyl group, thiol group, epoxy group, primary, secondary and tertiary amino group, Si—OH group, hydrolyzable residue of silane, C—H acid group such as β-dicarbonyl compound, etc. And having a functional group capable of chemically bonding with a group present on the surface of the silica 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, acidic / 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 silica fine particle. The said surface modification compound used for the reactive silica fine particle (A) 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 the first functional group) that can participate in chemical bonding with the surface group of the silica fine particles. After binding, it has molecular residues that impart new properties to the silica particles. The molecular residue or a part thereof is hydrophobic or hydrophilic and, for example, stabilizes, integrates or activates silica 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 a or a ′ introduced to the surface so that the reactive silica fine particles (A) can react with the binder component described later is appropriately selected according to the binder component. As the reactive functional group a or a ', 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 ethylenically unsaturated bonds such as (meth) acryloyl group, vinyl group and allyl group, and epoxy group. The reactive functional group a or a 'is preferably an ethylenically unsaturated bond capable of crosslinking with the reactive polymer (C).

  When the molecular residue of the surface modification compound contains a reactive functional group a or a ′ capable of reacting with a binder component (polyfunctional monomer (B) and reactive polymer (C)) described later, The reactive functional group a or a ′ capable of reacting with the binder component on the surface of the reactive silica fine particles (A) of (i) above by reacting the surface of the silica fine particles with the first functional group contained in the surface modifying compound. Can be introduced. 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, the second reactive functional group is contained in the molecular residue of the surface modification compound, and the reactive silica fine particles (A) of (i) are used as a foothold based on the second reactive functional group. The reactive functional group a or a ′ capable of reacting with the binder component may be introduced on the surface of For example, a group capable of hydrogen bonding (hydrogen bond forming group) such as a hydroxyl group and an oxy group is introduced as the second reactive functional group, and another hydrogen bond forming group introduced on the surface of the fine particles It is preferable to introduce a reactive functional group a or a ′ capable of reacting with the binder component by the reaction of the hydrogen bond forming group of the surface modifying compound. That is, as the surface modification compound, a compound having a hydrogen bond forming group and a reactive functional group a or a ′ capable of reacting with a binder component such as a polymerizable unsaturated group and a compound having 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 indicates that the bond unit contains —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 surface modifying compound used in the reactive silica fine particles (A) of (i) above has a molecular weight of 500 or less, more preferably 400, especially 200. Since it has such a low molecular weight, it is presumed that the surface of the silica fine particles can be rapidly occupied and aggregation of the silica fine particles can be prevented.

  The surface modification compound used in the reactive silica fine particles (A) of (i) is preferably a liquid under the reaction conditions for surface modification, and is soluble or at least emulsifiable in a dispersion medium. preferable. 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, Examples include adipic acid, 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. Further, when an unsaturated carboxylic acid is used, a polymerizable unsaturated group can be introduced.

Examples of preferred amines are those having the chemical formula Q _3-n NH _n (n = 0, 1 or 2), wherein the residue Q is independently 1-12, in particular 1-6, particularly preferably 1- Alkyl having 4 carbon atoms (eg, methyl, ethyl, n-propyl, i-propyl and butyl) and aryl, alkaryl or aralkyl having 6-24 carbon atoms (eg, phenyl, naphthyl, tolyl and benzyl) Represents. Examples of preferred 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, particularly 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 a and / or not having a reactive functional group a 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-aminopropyltrimethoxy Sisilane, hydroxymethyltrimethoxysilane, 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilane, bis- (hydroxyethyl) -3-aminopropyltriethoxysilane, N-hydroxyethyl-N-methylaminopropyltriethoxysilane , 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, and the like.

  The silane coupling agent is not particularly limited, and examples thereof include known ones. For example, KBM-502, KBM-503, KBE-502, KBE-503 (trade names, all of which are Shin-Etsu Chemical ( And the like).

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. Zirconium and titanium alkoxides, M (OR) ₄ (M = Ti, Zr), wherein part of the OR group is replaced by a complexing agent such as a β-dicarbonyl compound or a monocarboxylic acid. Can be mentioned. 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 (especially methanol, ethanol, n (normal)-and i (iso) -propanol and butanol), methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, acetone and Ketones such as butanone, esters such as ethyl acetate; ethers such as diethyl ether, tetrahydrofuran and tetrahydropyran; amides such as dimethylacetamide and dimethylformamide; sulfoxides and sulfones such as sulfolane and dimethyl sulfoxide; and pentane; Aliphatic (optionally halogenated) hydrocarbons such as hexane and cyclohexane. 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 the preparation of the reactive silica fine particles (A) 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 remainder of the dispersion is composed of untreated silica fine particles and the surface modifying compound. Here, the weight ratio of silica fine particles / surface modification compound is preferably 100: 1 to 4: 1, more preferably 50: 1 to 8: 1, and further preferably 25: 1 to 10: 1. .

  The preparation of the reactive silica fine particles (A) 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 a few minutes to a few hours, for example 1 to 24 hours.

(Ii) A compound containing a reactive functional group a introduced into the silica fine particles before coating, a group represented by the following chemical formula (1), and a silanol group or a group that generates a silanol group by hydrolysis, and silica fine particles as a core Silica fine particles having a reactive functional group a or a ′ on the surface, obtained by bonding to the metal oxide fine particles.
Chemical formula (1)
−Q ¹ −C (= Q ² ) −Q ³ −
In chemical formula (1), Q ¹ represents NH, O (oxygen atom), or S (sulfur atom), Q ² represents O or S, and Q ³ represents NH or a divalent or higher valent organic group. .
When the reactive silica fine particles (A) of (ii) are used, there are advantages that the amount of organic components is increased, and dispersibility and film strength are further increased.

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

In the reactive functional group-modified hydrolyzable silane, the [—Q ¹ —C (═Q ² ) —] moiety of the group represented by the chemical formula (1) is specifically [—O—C (═O )-], [-OC (= S)-], [-SC (= O)-], [-NH-C (= O)-], [-NH-C (= S)- ] And [-S-C (= S)-]. 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, at least of a [—O—C (═O) —] group, a [—O—C (═S) —] group, and a [—S—C (═O) —] group. It is preferable to use one type in combination. The group [—Q ¹ —C (= Q ² ) —Q ³ —] represented by the chemical formula (1) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical properties when formed into a cured product. It is considered that properties such as strength, adhesion to a 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.

  Specific examples of the reactive functional group-modified hydrolyzable silane include compounds represented by the following chemical formulas (2) and (3). The compound represented by the chemical formula (3) is more preferable in terms of hardness. Preferably used.

In the chemical formulas (2) and (3), R ^a and R ^b may be the same or different, and are a hydrogen atom or a C ₁ to C ₈ alkyl group or aryl group, for example, methyl, ethyl, propyl, Examples thereof include butyl, octyl, phenyl and xylyl groups. 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, and a dimethylmethoxysilyl group. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

In the chemical formulas (2) and (3), 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.

In the chemical formula (2), 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.

In the chemical formulas (2) and (3), R ^e is an (n + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.

  In the chemical formulas (2) and (3), Y ′ represents a monovalent organic group having a reactive functional group a or a ′. The reactive functional group a or a ′ itself as described above may be used. For example, when the reactive functional group a or a ′ 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 it is desired to introduce a polymerizable unsaturated group, (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 silica fine particles (A) of (ii), a method of separately hydrolyzing the reactive functional group-modified hydrolyzable silane, and then mixing this with the silica fine particles, followed by heating and stirring operations Or a method of hydrolyzing a reactive functional group-modified hydrolyzable silane in the presence of silica fine particles, and other components such as polyunsaturated organic compounds, monounsaturated organic compounds, radiation polymerization initiators, etc. A method of performing surface treatment of the silica fine particles in the presence of can be selected, but a method of hydrolyzing the reactive functional group-modified hydrolyzable silane in the presence of silica fine particles is preferable. When the reactive silica fine particles (A) (ii) are produced, 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 bases include tertiary amines or 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 silica fine particles (A), powdery fine particles not containing a dispersion medium may be used. However, it is possible to omit the dispersion step and to use fine particles as a solvent dispersion sol from the viewpoint of high productivity. preferable.

  The compounding amount of the reactive silica fine particles (A) is preferably 35 to 65% by weight, more preferably 40 to 60 parts by weight, based on the total solid content of the curable resin composition. If it is less than 35 parts by weight, there is a possibility that sufficient hardness cannot be imparted to the hard coat layer. When the amount exceeds 65 parts by weight, the filling rate is excessively increased, the adhesion between the reactive silica fine particles (A) and the binder component is deteriorated, and the hardness of the hard coat layer may be lowered.

(Polyfunctional monomer (B))
The polyfunctional monomer (B) used in the present invention is one of binder components that are cured to form a matrix of the hard coat layer, and the reactive functional group a or a ′ of the reactive silica fine particles (A), and / Or 3 or more reactive functional groups b having crosslink reactivity with an ethylenically unsaturated bond of the reactive polymer (C) described later, and a molecular weight of 1000 or less. Moreover, it is preferable that the reactive functional group b has cross-linking reactivity with other reactive functional groups b. When cured, the reactive functional groups b and different types of reactive functional groups are cross-linked to form a network structure, which further increases the hardness of the hard coat film. Moreover, since the polyfunctional monomer (B) has a molecular weight as small as 1000 or less and has 3 or more reactive functional groups b, it has a function of increasing the crosslinking density in the hard coat layer and imparting hardness to the hard coat layer. In addition, since the curing speed is high, the production line speed can be improved. It is also effective in improving the adhesion between adjacent layers. When the substrate is triacetyl cellulose (TAC), the adhesion with the TAC substrate can also be improved.

  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 ethylenically unsaturated bonds such as (meth) acryloyl group, vinyl group and allyl group, and epoxy group. Among these, the reactive functional group b is preferably an ethylenically unsaturated bond from the viewpoint that it has crosslinking reactivity with the ethylenically unsaturated bond of the reactive polymer (C) described later and contributes to improvement in hardness.

  The reactive functional group b may be the same as or different from the reactive functional group a. Although the reactive functional group b of the polyfunctional monomer (B) is 3 or more, it is preferable to have 6 or more. In the case of 2 or less, the hardness of the hard coat film becomes insufficient, and the adhesion with the adjacent second hard coat layer is poor, and even if closely adhered, such as heat resistance test, moist heat resistance test, light resistance test, etc. It is not preferable because the adhesion deteriorates in the environmental test.

  The molecular weight of the polyfunctional monomer (B) is 1000 or less. When the molecular weight exceeds 1000, the hardness of the hard coat layer is undesirably lowered.

1 type (s) or 2 or more types can be used as a polyfunctional monomer (B).
Examples of the polyfunctional monomer (B) include pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane hexa. Examples include (meth) acrylates and modified products thereof.
Examples of modified products include EO (ethylene oxide) modified products, PO (propylene oxide) modified products, CL (caprolactone) modified products, and isocyanuric acid modified products.
In the polyfunctional monomer (B), acrylate is preferable to methacrylate from the viewpoint of curing reactivity.

  As the polyfunctional monomer (B), pentaerythritol triacrylate (PETA) and dipentaerythritol hexaacrylate (DPHA) are particularly preferably used.

(Reactive polymer (C))
The reactive polymer (C) used in the present invention is represented by the following general formula (I) and has a weight average molecular weight of 10,000 to 70,000.

（式（Ｉ）において、Ｒ^１〜Ｒ^４はそれぞれ独立に、水素又はメチル基を表す。Ａは、直鎖状に連なる原子の数が１〜１５の連結基を表す。Ｘ、Ｙ、Ｚは、各重合単位の平均繰り返し数を表し、Ｘは０〜２０００、Ｙは１０〜１０００、及びＺは０〜２０００である。）

(In Formula (I), R ^{1 to} R ⁴ each independently represents hydrogen or a methyl group. A represents a linking group having 1 to 15 atoms in a straight chain. X, Y, Z Represents the average number of repeating units of each polymer unit, X is 0 to 2000, Y is 10 to 1000, and Z is 0 to 2000.)

  The reactive polymer (C) having the above specific structure has a linear structure obtained by reacting an ethylenically unsaturated bond with the main chain, so that the glass transition temperature of the main chain is increased and the hardness is increased. It is estimated that it has a function to increase For example, when a binder component containing a urethane bond, an ether bond, an ester bond, a cyclic bond, or the like is included in the main chain, the hardness can be obtained only when the pencil is pressed with a pencil. Since the linear structure as described above has a specific side chain including a reactive functional group at the terminal with a relatively short linking group, the reactive polymer (C) is composed of the reactive polymers (C) and The hardness of the hard coat layer can be improved by a curing reaction that crosslinks with the polyfunctional monomer (B) and / or the reactive silica fine particles (A) around the reactive polymer (C). In the reactive polymer (C), if the linking group in the side chain containing a reactive functional group at the terminal is too long, the hardness of the hard coat layer cannot be improved.

Furthermore, since the reactive polymer (C) having the above specific structure has the above specific molecular weight and structure, the hard coat film according to the present invention warps to the hard coat layer side while achieving high hardness (so-called , Curl) and the effect of suppressing cracks in the hard coat layer.
Originally, there is polymerization shrinkage when it becomes a covalent bond due to the crosslinking curing reaction, but since the reactive polymer (C) has a polymer structure in advance, the polymerization shrinkage due to curing reaction is reduced. Therefore, it is estimated that there is an effect of reducing curl. In addition to polymerization shrinkage caused by the crosslinking curing reaction, heat of polymerization is generated. In the case of the reactive polymer (C), since it has a polymer structure in advance, generation of polymerization heat generated by a curing reaction that crosslinks can be reduced, so that heat damage to the resin base material is reduced and wrinkles are generated. Even the appearance defects such as can be solved. When the thermal damage to the resin base material is large, the strength of the resin base material itself is lowered, which is not preferable.

In the formula (I), A represents a linking group having 1 to 15 atoms connected in a straight chain. Here, the number of atoms connected in a straight chain represents the number of atoms constituting a straight chain skeleton connecting two oxygen atoms to which A is bonded. For example, in the case of a methylene group (—CH ₂ —), the straight-chain continuous atom is —C—, and the straight-chain continuous atom is counted as one. In the case of an amide group (—C (═O) —N (—H) —), the linearly linked atoms are —C—N—, and the number of linearly linked atoms is counted as two. In the case of —CH ₂ CH (OH) CH ₂ —, the atoms connected in a straight chain form —C—C—C—, and the number of atoms connected in a straight chain is counted as three.
In formula (I), the hardness is increased by connecting the (meth) acryloyloxy group and the main chain of the polymer with a relatively short linking group such as 1 to 15 atoms connected in a straight chain. It has a function. If the linking group is too long, the function of increasing the hardness is reduced. Among these, the number of atoms connected in a straight chain is preferably 1 to 10, and more preferably 1 to 7 from the viewpoint of increasing the hardness.

Examples of the unit constituting the linking group include a methylene group (—CR ₂ — (R is hydrogen, fluorine, or a substituent) which may have a substituent, and —O—, —S. -, -NQ- (Q is hydrogen or an alkyl group), -NHCO-, -S (= O)-, -S (= O) _2- , a carbonyl group (-C (= O)-),- COO—, —CH═CH—, —Si (CH 3) ₂ —O—, —Si (CH 3) ₂ — and the like can be mentioned. Examples of the linking group include a structure in which the units constituting the linking group are used as they are in one type of structure, or a combination of two or more types.
Examples of the substituent include a hydroxyl group, carboxyl group, amino group, halogen atom, or alkyl group, mercapto group, cyano group, silyl group, silanol group, nitro group, acetyl group, acetoxy group, and sulfone group. It is not limited. Among these, a hydroxyl group, a carboxyl group, an amino group, or an alkyl group is preferably used.

Examples of the linking group A include an alkylene group having 1 to 15 carbon atoms which may have a substituent, various polyoxyalkylene groups, and the like. More specifically, an ethylene group, a propylene group, various butylene groups, various pentylene groups, various hexylene groups, various octylene groups, —CH ₂ CH ₂ CONQCH ₂ CH ₂ — (Q, which may have a substituent. Is hydrogen or an alkyl group), —CH ₂ CONQCH ₂ — (Q is hydrogen or an alkyl group), —CH ₂ CH ₂ OCONQCH ₂ CH ₂ OCH ₂ CH ₂ — (Q is hydrogen or an alkyl group) , —CH ₂ CH ₂ OCONQCH ₂ CH ₂ — (Q is hydrogen or an alkyl group) —CH ₂ CH ₂ OCH ₂ CH ₂ —, —CH ₂ OCH ₂ —, — (CH ₂ CH ₂ O) _n CH _{2 CH 2 -, - CH 2 CH} 2 COOCH 2 CH 2 - and the like.

Suitable linking groups A include —CH ₂ CH (OH) CH ₂ —, ethylene group, —CH ₂ CH ₂ CONQCH ₂ CH ₂ — (Q is hydrogen or an alkyl group), —CH ₂ CONQCH ₂ — ( Q is hydrogen or an alkyl group), —CH ₂ CH ₂ OCH ₂ CH ₂ —, —CH ₂ CH ₂ OCONQCH ₂ CH ₂ OCH ₂ CH ₂ — (Q is hydrogen or an alkyl group), —CH ₂ CH ₂ OCONQCH ₂ CH ₂ — (Q is hydrogen or an alkyl group) and the like.

In polymerized units having an average repeat number Y, R ¹ is hydrogen or a methyl group. Either may be used, but hydrogen is preferable from the viewpoint of curing speed. R ² is hydrogen or a methyl group. Either may be used, but hydrogen is preferable from the viewpoint of curing speed.

In the polymerized unit having an average repeating number Z, R ³ is hydrogen or a methyl group, and R ⁴ is hydrogen or a methyl group.

  In the formula (I), X, Y and Z represent the average number of repeating units of each polymer unit, X is 0 to 2000, Y is 10 to 1000, and Z is 0 to 2000. X, Y, and Z are not particularly limited as long as the reactive polymer (C) satisfies the weight average molecular weight of 10,000 to 70,000, and are appropriately selected from various viewpoints such as hardness, solubility in a solvent, and transparency. be able to. Among them, X is preferably 0 to 1000, Y is 10 to 800, and Z is 0 to 1000. The reactive polymer (C) may be a homopolymer of polymerized units having an average repeating number Y. When the reactive polymer (C) is a copolymer, each polymer unit may be bonded at random or may be bonded with regularity. Among these, it is preferable to have a structure represented by the formula (I ′).

（式（Ｉ’）において、Ｒ^１〜Ｒ^４はそれぞれ独立に、水素又はメチル基を表す。Ａは、直鎖状に連なる原子の数が１〜１５の連結基を表す。ｘ、ｙ、ｚは、各重合単位の平均繰り返し数を表し、ｘは０〜１０、ｙは１〜１０、及びｚは０〜１０であり、ｎは、平均繰り返し数を表し、３０〜３００である。）

(In Formula (I ′), R ^{1 to} R ⁴ each independently represents hydrogen or a methyl group. A represents a linking group having 1 to 15 atoms in a straight chain. X, y, z represents the average number of repetitions of each polymer unit, x is 0 to 10, y is 1 to 10, and z is 0 to 10, and n is the average number of repetitions and is 30 to 300.)

  The weight average molecular weight of the reactive polymer (C) is 10,000 to 70,000, more preferably 10,000 to 40,000 from the viewpoint of realizing high hardness. If the weight average molecular weight is too low or too high, high hardness may not be realized. When the weight average molecular weight is too high, the viscosity becomes high, so that the coated surface is deteriorated and the quality may be lowered. If the weight average molecular weight is too high, it can be diluted with a solvent in order to lower the viscosity, but in that case, the desired film thickness may not be obtained, and it may be dried in the drying step by increasing the solvent. It may be insufficient.

  As the reactive polymer (C), commercially available products may be used. Examples of the commercially available products include Arakawa Chemical Industries, Ltd., Beam Set 371, Beam Set 371MLV, Beam Set DK1, Beam Set DK2, Beamset DK3; Hitachi Chemical 795D series (Hitaroid 7975D5, 7975D12), etc.

  The weight ratio of the reactive polymer (C) to the polyfunctional monomer (B) (reactive polymer (C) / polyfunctional monomer (B)) is preferably 0.2 to 10, more preferably 0.5 to 4 is preferable, and 0.5 to 3 is more preferable. In the case of such a weight ratio, among others, curl is reduced while achieving high hardness, and a hard coat layer having excellent adhesion to the substrate is obtained. If the amount of the reactive polymer (C) is too small, the curl reduction effect may be reduced. If the amount of the polyfunctional monomer (B) is too small, the effect of improving the hardness may be insufficient or the adhesion to the substrate may be reduced. May be insufficient.

In the curable resin composition of the present invention, the binder component is preferably contained in an amount of 35 to 65% by weight, more preferably 40 to 60% by weight, based on the total solid content.
In addition to the polyfunctional monomer (B) and the reactive polymer (C), which are the main components, the binder component includes a polymerization initiator described later and other binder components as long as the effects of the present invention are not impaired. You can leave.

(Other ingredients)
In addition to the above essential components, a solvent, a polymerization initiator, an antistatic agent, and an antiglare agent can be appropriately added to the curable resin composition of the present invention. Furthermore, various additives, such as a reactive or non-reactive leveling agent and various sensitizers, may be mixed. In the case of containing an antistatic agent and / or an antiglare agent, antistatic properties and / or antiglare properties can be further imparted to the hard coat layer of the present invention.

(solvent)
Specific examples of the solvent include methanol, ethanol, normal propanol, isopropanol (IPA), normal butanol, sec-butanol, isobutanol, tert-butanol, methyl glycol, propylene glycol monomethyl ether (PGME), methyl glycol acetate, methyl cellosolve. Alcohols such as ethyl cellosolve and butyl cellosolve; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone and diacetone alcohol; methyl formate, methyl acetate, ethyl acetate, ethyl lactate, butyl acetate, etc. Esters; nitrogen-containing compounds such as nitromethane, N-methylpyrrolidone, N, N-dimethylformamide; diisopropyl ether, tetrahydrofuran , Dioxane, dioxolane and the like; methylene chloride, chloroform, trichloroethane, halogenated hydrocarbons such as tetrachloroethane; dimethylsulfoxide, other objects, such as propylene carbonate; or mixtures thereof.
It is one or more impermeable solvents selected from the group consisting of MIBK, PGME, normal propanol, isopropanol, normal butanol, sec-butanol, isobutanol, and tert-butanol from the viewpoint of improving the hardness of the hard coat film. It is preferable. By using a non-permeable solvent, the polyfunctional monomer (B) and the reactive polymer (C) do not penetrate into the resin substrate, so that the hardness of the hard coat layer can be increased.
In the present invention, permeation refers to dissolving or swelling the resin base material.

(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 name Irgacure 651, Ciba Japan Co., Ltd.) 1-hydroxy-cyclohexyl-phenyl- T (trade name Irgacure 184, manufactured by Ciba Japan Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (trade names Irgacure 369, Ciba Japan ( Co., Ltd.), bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium) (trade name Irgacure 784, manufactured by Ciba Japan 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. Examples of the cationic polymerization initiator include sulfonic acid ester, imide sulfonate, dialkyl-4-hydroxysulfonium salt, arylsulfonic acid-p-nitrobenzyl ester, silanol-aluminum complex, (η ⁶ -benzene) (η ⁵ -cyclopentadidiene). Enyl) iron (II) and the like are exemplified, and more specifically, benzoin tosylate, 2,5-dinitrobenzyl tosylate, N-tosiphthalimide and the like are exemplified, but not limited thereto.

Examples of radical polymerization initiators 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, bromide, borofluoride, 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.
When a polymerization initiator is used, it is desirable that it is contained so as to be 1 to 10% by weight, more preferably 3 to 6% by weight, based on the total solid content of the curable resin composition.

(Antistatic agent)
Specific examples of the antistatic agent include quaternary ammonium salts, pyridinium salts, various cationic compounds having cationic groups such as primary to tertiary amino groups, sulfonate groups, sulfate ester bases, and phosphate ester bases. , Anionic compounds having an anionic group such as phosphonate group, amphoteric compounds such as amino acid series and aminosulfate ester series, nonionic compounds such as amino alcohol series, glycerin series and polyethylene glycol series, and alkoxides of tin and titanium And metal chelate compounds such as acetylacetonate salts thereof, and compounds obtained by increasing the molecular weight of the compounds listed above. In addition, it has a tertiary amino group, a quaternary ammonium group, or a metal chelate portion, and has a monomer or oligomer that can be polymerized by ionizing radiation, or a polymerizable functional group that can be polymerized by ionizing radiation, and Polymerizable compounds such as organometallic compounds such as coupling agents can also be used as antistatic agents.

Moreover, electroconductive fine particles are mentioned as another example of the said antistatic agent. Specific examples of the conductive fine particles include those made of a metal oxide. Examples of such metal oxides include ZnO (refractive index 1.90, the numerical value in parentheses below represents the refractive index), CeO ₂ (1.95), Sb ₂ O ₂ (1.71), SnO. ₂ (1.997), indium tin oxide (1.95) often referred to as ITO, In ₂ O ₃ (2.00), Al ₂ O ₃ (1.63), antimony-doped tin oxide (abbreviation) ATO, 2.0), aluminum-doped zinc oxide (abbreviation: AZO, 2.0), and the like. The conductive fine particles preferably have an average particle size of 0.1 nm to 0.1 μm. By being within such a range, when the conductive fine particles are dispersed in a binder, a composition capable of forming a highly transparent film having almost no haze and good total light transmittance can be obtained.

(Anti-glare agent)
Examples of the antiglare agent include fine particles, and the shape of the fine particles may be a true sphere or an ellipse, and preferably a true sphere. The fine particles may be inorganic or organic, but those formed of an organic material are preferred. The fine particles exhibit anti-glare properties and are preferably transparent. Specific examples of the fine particles include plastic beads, and more preferably those having transparency. Specific examples of plastic beads include styrene beads (refractive index 1.59), melamine beads (refractive index 1.57), acrylic beads (refractive index 1.49), acrylic-styrene beads (refractive index 1.54), Examples thereof include polycarbonate beads and polyethylene beads. The addition amount of the fine particles is about 2 to 30 parts by weight, preferably about 10 to 25 parts by weight with respect to 100 parts by weight of the resin composition.
The measurement of the refractive index is not particularly limited, and a conventionally known method can be used. For example, a method of calculating from a reflectance curve measured with a spectrophotometer using a simulation, a method of measuring using an ellipsometer, and an Abbe method can be mentioned.
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. A group, an acetyl group, an acetoxy group, a sulfone group and the like, but are 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, A branched or cyclic hydrocarbon chain), an alkyl ester group (RCOO-, where R is a saturated or unsaturated linear, branched, or cyclic hydrocarbon chain). .

(Leveling agent)
A leveling agent can be added to the curable resin composition for a hard coat layer of the present invention, and among them, it is preferable to add a leveling agent such as a fluorine type or a silicone type. The curable resin composition for a hard coat 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.
The addition amount of the leveling agent is preferably 0 to 0.5% by weight, more preferably 0 to 0.2% by weight, based on the total solid content of the curable resin composition for hard coat layers.

  As a commercial item of the leveling agent, DIC Corporation, Megafac F443, F444, F445 and the like can be mentioned.

3. Other layers The hard coat film is basically composed of the base material and the hard coat layer as described above. However, in consideration of the function or application as a hard coat film, the following one further is provided on the surface of the hard coat layer on the substrate side or the side opposite to the substrate within the scope of the present invention. Alternatively, two or more layers may be provided.

(Antistatic layer)
The antistatic layer is made of a cured product of a curable resin composition for an antistatic layer containing an antistatic agent and a curable resin. The thickness of the antistatic layer is preferably about 30 nm to 3 μm.

  As the antistatic agent, the same materials as those mentioned above for the antistatic agent for the hard coat layer can be used.

  As a curable resin contained in the curable resin composition for an antistatic layer, a known resin can be appropriately selected and used alone or in combination of two or more.

(Anti-glare layer)
The antiglare layer is made of a cured product of a curable resin composition for an antiglare layer containing an antiglare agent and a curable resin. As the curable resin, a known resin can be appropriately selected, and one kind or two or more kinds can be used.

(Anti-glare agent)
As the antiglare agent, the same antiglare agents as those described above for the hard coat layer can be used.

(Anti-fouling layer)
According to a preferred embodiment of the present invention, an antifouling layer may be provided for the purpose of preventing dirt on the outermost surface of the hard coat film. The antifouling layer can further improve the antifouling property and scratch resistance of the hard coat film. The antifouling layer comprises a cured product of a curable resin composition for an antifouling layer comprising an antifouling agent and a curable resin composition.

  The antifouling agent and curable resin contained in the curable resin composition for the antifouling layer can be appropriately selected from known antifouling agents and curable resins, and one or more can be used.

(Low refractive index layer)
A low refractive index layer is a layer whose refractive index is lower than the layer adjacent to the base film side of the said layer, and consists of hardened | cured material of the curable resin composition for low refractive index layers. In the curable resin composition for a low refractive index layer, a known low refractive index curable resin or fine particles can be appropriately used so that the refractive index is lower than that of the adjacent layer.

(Second hard coat layer)
From the viewpoint of further improving the hardness of the hard coat film, a second hard coat layer having a smooth surface may be provided on the substrate side of the hard coat layer.
The second hard coat layer may be the same as the hard coat layer, and the composition of the two hard coat layers may be the same or different.

(Method for forming hard coat layer)
The hard coat layer may be formed by a conventionally known method.
For example, the prepared curable resin composition for a hard coat layer is applied to one side of the substrate, a coating film is formed, drying is performed as necessary, and then the coating film is irradiated with light, and further if necessary And cured by heating to form a hard coat layer.

  The curable resin composition for a hard coat layer is generally prepared by a general method of preparing a polymerization initiator and the like in addition to the reactive silica fine particles (A), the polyfunctional monomer (B), and the reactive polymer (C). According to the above, it is prepared by mixing and dispersing. A paint shaker or a bead mill can be used for mixing and dispersing.

The application method is not particularly limited as long as it can uniformly apply the curable resin composition for the hard coat layer to the surface of the base material. The spin coating method, the dip method, the spray method, the slide coating method. Various methods such as a bar coating method, a roll coater method, a meniscus coater method, a flexographic printing method, a screen printing method, and a speed coater method can be used.
Moreover, as a coating amount of the curable resin composition for a hard coat layer on a substrate, although it differs depending on the performance required for the obtained hard coat film, the film thickness after drying is 5 to 20 μm. so as to be appropriately adjusted, it is preferable coating amount in the range of ^{5g / m 2 ~35g / m 2} , in particular in the range of ^{10g / m 2 ~30g / m 2} .

  Examples of the drying method include reduced-pressure drying or heat drying, and a method combining these drying methods. Moreover, when drying at normal pressure, it is preferable to dry at 30-110 degreeC. For example, when methyl isobutyl ketone is used as the solvent of the curable resin composition for the hard coat layer, it is usually room temperature to 80 ° C., preferably 40 ° C. to 70 ° C., preferably 20 seconds to 3 minutes, preferably The drying process is performed in a time of about 30 seconds to 1 minute.

  Next, the reactive silica fine particles (A) and the polyfunctional monomer (B) contained in the curable resin composition are applied to the coating film obtained by applying the curable resin composition for the hard coat layer and drying it as necessary. Curable resin composition for hard coat layer by curing the coating film by irradiation with light and further heating as necessary according to the reactive functional group of and the ethylenically unsaturated bond of the reactive polymer (C) A hard coat layer made of the cured product is formed.

For light irradiation, ultraviolet rays, visible light, electron beams, ionizing radiation, etc. are mainly used. In the case of ultraviolet curing, ultraviolet rays or the like emitted from light such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp are used. The irradiation amount of the energy ray source is about 50 to 5000 mJ / cm ² as an integrated exposure amount at an ultraviolet wavelength of 365 nm.
When heating, it processes at the temperature of 40 to 120 degreeC normally. Moreover, you may react by leaving it to stand for 24 hours or more at room temperature (25 degreeC).

In the above-described method for forming a hard coat layer, the curable resin composition for a hard coat layer is applied to one side of the substrate, a coating film is formed, and drying is performed as necessary. The film is brought into contact with a smooth surface having a surface roughness Ra of 10 nm or less, then the coating film is irradiated with light, and further cured by heating as necessary, and then the smooth surface is peeled off to form a hard coat layer. May be.
Specifically, after forming a coating film of the curable resin composition for hard coat layer on one surface side of the substrate, the surface roughness Ra is 10 nm or less on the surface opposite to the substrate of the coating film. Touch the smooth surface.
The smooth surface to be brought into contact with the coating film has a surface roughness Ra of 10 nm or less, but those having such a smooth surface are not particularly limited, and are appropriately selected in consideration of workability, strength of the smooth surface, economy, and the like. You can choose. For example, a smooth surface made of glass or metal such as chromium and iron can be used. Chromium is preferred in terms of strength and resistance to wear during repeated use, and from the viewpoint of economy, a steel roller surface plated with chromium is preferred.
Next, the reactivity of the reactive silica fine particles (A) and the polyfunctional monomer (B) contained in the curable resin composition with respect to the coating film of the curable resin composition for the hard coat layer in contact with the smooth surface. Cured product of curable resin composition for hard coat layer by curing with light irradiation and further heating as necessary according to the ethylenically unsaturated bond of functional group and reactive polymer (C) A hard coat layer is formed. Then, by removing the smooth surface brought into contact with the surface of the hard coat layer opposite to the substrate, the surface of the hard coat layer is given a smoothness with a surface roughness of 1 nm or less, and has scratch resistance. Can be improved.

In the method for forming a hard coat layer, a curable resin composition for a hard coat layer is applied to one side of a substrate, a coating film is formed, and drying is performed as necessary. The film is cured with light of 5 to 300 mJ / cm ² as an integrated exposure amount when the irradiation amount of the energy ray source is an ultraviolet wavelength of 365 nm, and an expander or the like is used before and after forming the hard coat layer. By stretching the laminated body in the width direction with a tension of 1/100 or more, the undulation of the obtained hard coat film can be reduced.
Further, the tensile in the width direction is preferably within 700 mm before and after the irradiation apparatus, and a place where the tension is reduced to the ambient temperature within the range is preferable.

Moreover, the hard coat film obtained by the above process is heated at 60 to 150 ° C. and passed between two rolls that are in contact with each other in the major axis direction while being pressed. Curling of the hard coat film can be reduced while maintaining the hardness.
When the heating temperature is less than 60 ° C., curling cannot be sufficiently reduced, and when the heating temperature is higher than 150 ° C., the base material contracts.
Further, the pressure of pressurization may be appropriately adjusted according to the cured resin, but it is preferable that the pressurization is 300 to 2000 kg / cm because curling can be further reduced. If the pressurization is 300 kg / cm or more, curling can be sufficiently reduced, and if the pressurization exceeds 2000 kg / cm, there is a risk of breakage, which is not preferable.
In the above process, the method of passing the hard coat film is not particularly limited as long as it can pass between two rolls that are in contact with each other in the major axis direction while being heated and pressurized as described above. The well-known method used by etc. can be used. For example, a press system and a calendar system are mentioned.

Moreover, when using a TAC film as a base material, 1 or more types of main solvents chosen from acetone, hexane, dimethylglycol, and methyl acetate are provided in the surface on the opposite side to the surface which formed the hard-coat layer of the TAC film. In addition, it is preferable to apply a solvent in which the total amount of the main solvent is a ratio of 70% by weight or more of the whole solvent within a range of 4 to ²⁰ g / m ² . By applying the solvent to the surface of the TAC film opposite to the surface on which the hard coat layer is formed, curling of the hard coat film can be reduced while maintaining the hardness of the hard coat film.
When the total amount of the main solvent is less than 70% by weight of the total solvent, the hardness of the hard coat layer cannot be maintained.
Further, the coating amount of the solvent is in the range of 4~20g / ^{m 2,} preferably in the range of 5 to 10 g / ^{m 2.} When the application amount of the solvent is less than 4 g / m ² , curling cannot be sufficiently reduced, and when the application amount of the solvent exceeds 20 g / m ² , the hardness of the hard coat film is lowered.
Here, maintaining the hardness means that the hard coat film in a state where the solvent is not applied and the hard coat after the solvent is applied and dried in an oven at 80 ° C. for 1 minute. Comparison of the hardness of the pencil hardness test (using 2H pencil, 500 g load) specified in JIS K5600-5-4 (1999) on the hard coat layer surface of the film, and the evaluation of the pencil hardness test when a solvent is applied is the solvent It means that it has not fallen from evaluation of the state which has not apply | coated.

(Formation of other layers)
When other layers are formed on the substrate, before applying the curable resin composition for the hard coat layer, for example, the curable resin composition of the other layers is applied, dried, irradiated with light and / or Alternatively, heating or the like may be performed to form another layer, and then the hard coat layer curable resin composition may be applied and cured to form a hard coat layer.
When other layers are formed on the hard coat layer, the curable resin composition for the hard coat layer is applied and cured to form the hard coat layer, and then, for example, the curable resin composition of the other layer is applied. And then drying, irradiating with light and / or heating, and providing other layers.

  The hard coat film of the present invention thus obtained has a pencil hardness specified in JIS K5600-5-4 (1999) of the hard coat layer even when the thickness of the hard coat layer is in the range of 5 to 20 μm. It is possible to achieve a hardness of 5H or more in the test (500 g load).

  Hereinafter, the present invention will be described more specifically with reference to examples. These descriptions do not limit the present invention.

Example 1
(1) Preparation of curable resin composition for hard coat layer The components of the composition shown below were blended to prepare a curable resin composition for hard coat layer.
<Composition of curable resin composition for hard coat layer>
Reactive unusual shape silica fine particles (A2) (manufactured by JGC Catalysts & Chemicals, product name DP1039SIV; average primary particle size 20 nm, average number of connections 3.5, average secondary particle size 55 nm, solid content 40%, MIBK solvent, reactivity Functional group is methacrylate group): 100 parts by weight (solid content: 40 parts by weight)
・ Polyfunctional monomer (B) (manufactured by Nippon Kayaku Co., Ltd., product name DPHA; dipentaerythritol hexaacrylate, hexafunctional, molecular weight 524): 30 parts by weight ・ Reactive polymer (C) (product name, manufactured by Arakawa Chemical Co., Ltd.) Beam set DK1; weight average molecular weight of about 20000, X = 0, Y = 50, Z = 0, A is —CH ₂ CH (OH) CH ₂ —, the number of atoms linked in a straight chain is 3, and R ¹ is Methyl group, R ² is hydrogen, solid content 75%, MIBK solvent): 40 parts by weight (solid content 30 parts by weight)
Polymerization initiator (Ciba Japan Co., Ltd., trade name Irgacure 184): 4 parts by weight Leveling agent (DIC, MegaFuck MCF350-5): 0.2 parts by weight (solid content)
MIBK (methyl isobutyl ketone): 80 parts by weight

(2) Production of hard coat film A 40 μm triacetyl cellulose film (TAC film) was used as a substrate, and the curable resin composition for hard coat layer prepared in (1) was applied to one side of the TAC film, and the temperature was The film is dried in a 70 ° C. heat oven for 60 seconds, the solvent in the coating film is evaporated, and the coating film is cured by irradiating ultraviolet rays so that the integrated light quantity becomes 200 mJ / cm ^2. A coat layer was formed to produce a hard coat film.

(Example 2)
In Example 1, the hard coat film of Example 2 was produced in the same manner as in Example 1 except that the curable resin composition for hard coat layer was prepared by blending the components shown below. did.
<Composition of curable resin composition for hard coat layer>
Reactive unusual shape silica fine particles (A2) (manufactured by JGC Catalysts & Chemicals, product name DP1039SIV; average primary particle size 20 nm, average number of connections 3.5, average secondary particle size 55 nm, solid content 40%, MIBK solvent, reactivity Functional group is methacrylate group): 100 parts by weight (solid content: 40 parts by weight)
Polyfunctional monomer (B) (Nippon Kayaku Co., Ltd., product name DPHA; dipentaerythritol hexaacrylate, hexafunctional, molecular weight 524): 20 parts by weight Reactive polymer (C) (product name, manufactured by Arakawa Chemical) Beam set DK1; weight average molecular weight of about 20000, X = 0, Y = 50, Z = 0, A is —CH ₂ CH (OH) CH ₂ —, the number of atoms linked in a straight chain is 3, and R ¹ is methyl group, ^{R 2} is hydrogen, solids 75%, MIBK solvent): 53 parts by weight (solid content 40 parts by weight)
Polymerization initiator (Ciba Japan Co., Ltd., trade name Irgacure 184): 4 parts by weight Leveling agent (DIC, MegaFuck MCF350-5): 0.2 parts by weight (solid content)
MIBK (methyl isobutyl ketone): 77 parts by weight

(Example 3)
In Example 1, a hard coat film of Example 3 was produced in the same manner as in Example 1 except that a curable resin composition for a hard coat layer was prepared by blending the components shown below. did.
<Composition of curable resin composition for hard coat layer>
Reactive unusual shape silica fine particles (A2) (manufactured by JGC Catalysts & Chemicals, product name DP1039SIV; average primary particle size 20 nm, average number of connections 3.5, average secondary particle size 55 nm, solid content 40%, MIBK solvent, reactivity Functional group is methacrylate group): 100 parts by weight (solid content: 40 parts by weight)
Polyfunctional monomer (B) (Nippon Kayaku Co., Ltd., product name DPHA; dipentaerythritol hexaacrylate, hexafunctional, molecular weight 524): 40 parts by weight Reactive polymer (C) (Arakawa Chemical, product name Beam set DK1; weight average molecular weight of about 20000, X = 0, Y = 50, Z = 0, A is —CH ₂ CH (OH) CH ₂ —, the number of atoms linked in a straight chain is 3, and R ¹ is Methyl group, R ² is hydrogen, solid content 75%, MIBK solvent): 27 parts by weight (solid content 20 parts by weight)
Polymerization initiator (Ciba Japan Co., Ltd., trade name Irgacure 184): 4 parts by weight Leveling agent (DIC, MegaFuck MCF350-5): 0.2 parts by weight (solid content)
MIBK (methyl isobutyl ketone): 83 parts by weight

Example 4
In Example 1, the hard coat film of Example 4 was prepared in the same manner as in Example 1 except that the curable resin composition for hard coat layer was prepared by blending the components having the following composition. did.
<Composition of curable resin composition for hard coat layer>
Reactive unusual shape silica fine particles (A2) (manufactured by JGC Catalysts & Chemicals, product name DP1039SIV; average primary particle size 20 nm, average number of connections 3.5, average secondary particle size 55 nm, solid content 40%, MIBK solvent, reactivity Functional group is methacrylate group): 125 parts by weight (solid content: 50 parts by weight)
Polyfunctional monomer (B) (Nippon Kayaku Co., Ltd., product name DPHA; dipentaerythritol hexaacrylate, hexafunctional, molecular weight 524): 25 parts by weight Reactive polymer (C) (product name, Arakawa Chemical) Beam set DK1; weight average molecular weight of about 20000, X = 0, Y = 50, Z = 0, A is —CH ₂ CH (OH) CH ₂ —, the number of atoms linked in a straight chain is 3, and R ¹ is Methyl group, R ² is hydrogen, solid content 75%, MIBK solvent): 33 parts by weight (solid content 25 parts by weight)
Polymerization initiator (Ciba Japan Co., Ltd., trade name Irgacure 184): 4 parts by weight Leveling agent (DIC, MegaFuck MCF350-5): 0.2 parts by weight (solid content)
MIBK (methyl isobutyl ketone): 67 parts by weight

(Example 5)
In Example 1, the hard coat film of Example 5 was produced in the same manner as in Example 1 except that the curable resin composition for hard coat layer was prepared by blending the components shown below. did.
<Composition of curable resin composition for hard coat layer>
Reactive unusual shape silica fine particles (A2) (manufactured by JGC Catalysts & Chemicals, product name DP1039SIV; average primary particle size 20 nm, average number of connections 3.5, average secondary particle size 55 nm, solid content 40%, MIBK solvent, reactivity Functional group is methacrylate group): 150 parts by weight (solid content: 60 parts by weight)
Polyfunctional monomer (B) (Nippon Kayaku Co., Ltd., product name DPHA; dipentaerythritol hexaacrylate, hexafunctional, molecular weight 524): 10 parts by weight Reactive polymer (C) (product name, manufactured by Arakawa Chemical) Beam set DK1; weight average molecular weight of about 20000, X = 0, Y = 50, Z = 0, A is —CH ₂ CH (OH) CH ₂ —, the number of atoms linked in a straight chain is 3, and R ¹ is Methyl group, R ² is hydrogen, solid content 75%, MIBK solvent): 40 parts by weight (solid content 30 parts by weight)
Polymerization initiator (Ciba Japan Co., Ltd., trade name Irgacure 184): 4 parts by weight Leveling agent (DIC, MegaFuck MCF350-5): 0.2 parts by weight (solid content)
MIBK (methyl isobutyl ketone): 50 parts by weight

(Example 6)
In Example 1, the hard coat film of Example 6 was produced in the same manner as in Example 1 except that the curable resin composition for hard coat layer was prepared by blending the components shown below. did.
<Composition of curable resin composition for hard coat layer>
Reactive unusual shape silica fine particles (A2) (manufactured by JGC Catalysts & Chemicals, product name DP1039SIV; average primary particle size 20 nm, average number of connections 3.5, average secondary particle size 55 nm, solid content 40%, MIBK solvent, reactivity Functional group is methacrylate group): 150 parts by weight (solid content: 60 parts by weight)
Polyfunctional monomer (B) (Nippon Kayaku Co., Ltd., product name DPHA; dipentaerythritol hexaacrylate, hexafunctional, molecular weight 524): 25 parts by weight Reactive polymer (C) (product name, Arakawa Chemical) Beam set DK1; weight average molecular weight of about 20000, X = 0, Y = 50, Z = 0, A is —CH ₂ CH (OH) CH ₂ —, the number of atoms linked in a straight chain is 3, and R ¹ is Methyl group, R ² is hydrogen, solid content 75%, MIBK solvent): 33 parts by weight (solid content 25 parts by weight)
Polymerization initiator (Ciba Japan Co., Ltd., trade name Irgacure 184): 4 parts by weight Leveling agent (DIC, MegaFuck MCF350-5): 0.2 parts by weight (solid content)
MIBK (methyl isobutyl ketone): 42 parts by weight

(Example 7)
In Example 1, a hard coat film of Example 7 was produced in the same manner as in Example 1 except that the curable resin composition for hard coat layer was prepared by blending the components having the following composition. did.
<Composition of curable resin composition for hard coat layer>
Reactive unusual shape silica fine particles (A2) (manufactured by JGC Catalysts & Chemicals, product name DP1039SIV; average primary particle size 20 nm, average number of connections 3.5, average secondary particle size 55 nm, solid content 40%, MIBK solvent, reactivity Functional group is methacrylate group): 163 parts by weight (solid content: 65 parts by weight)
Polyfunctional monomer (B) (Nippon Kayaku Co., Ltd., product name DPHA; dipentaerythritol hexaacrylate, hexafunctional, molecular weight 524): 17.5 parts by weight Reactive polymer (C) (Arakawa Chemical, Product name beam set DK1; weight average molecular weight about 20,000, X = 0, Y = 50, Z = 0, A is —CH ₂ CH (OH) CH ₂ —, the number of atoms linked in a straight chain is 3, R ¹ is methyl group, R ² is hydrogen, solid content 75%, MIBK solvent): 23 parts by weight (solid content 17.5 parts by weight)
Polymerization initiator (Ciba Japan Co., Ltd., trade name Irgacure 184): 4 parts by weight Leveling agent (DIC, MegaFuck MCF350-5): 0.2 parts by weight (solid content)
MIBK (methyl isobutyl ketone): 47 parts by weight

(Example 8)
In the preparation of the curable resin composition for the hard coat layer of Example 1, 40 parts by weight (30 parts by weight of solid content) of the reactive polymer (C) (product name Beam Set DK1 manufactured by Arakawa Chemical Co., Ltd.) (C) (manufactured by Hitachi Chemical Co., Ltd., product name Hitaroid 7975D10M; weight average molecular weight of about 11000, X = 30, Y = 30, Z = 30, A is 1 to 15 atoms linked in a straight chain, R ¹ is Hydrogen, R ² is hydrogen, R ³ is a methyl group, R ⁴ is a methyl group, solid content is 70%, butyl acetate solvent): Except for 43 parts by weight (solid content 30 parts by weight) Similarly, the hard coat film of Example 8 was produced.

Example 9
In the preparation of the curable resin composition for the hard coat layer of Example 1, 30 parts by weight of the polyfunctional monomer (B) (product name DPHA) manufactured by Nippon Kayaku Co., Ltd. Name PET30; pentaerythritol triacrylate, trifunctional, molecular weight 298): A hard coat film of Example 9 was produced in the same manner as in Example 1 except that the amount was changed to 30 parts by weight.
(Example 10)
In the preparation of the curable resin composition for the hard coat layer of Example 1, 40 parts by weight (30 parts by weight of solid content) of the reactive polymer (C) (product name Beam Set DK1 manufactured by Arakawa Chemical Co., Ltd.) (C) (manufactured by Arakawa Chemical Co., Ltd., product name beam set 371; weight average molecular weight of about 40,000, X = 0, Y = 100, Z = 0, A is linearly linked by —CH ₂ CH (OH) CH ₂ —. 3 atoms, R ¹ is a methyl group, R ² is hydrogen, solid content 65%, butyl acetate solvent): The same as in Example 1 except that it is changed to 47 parts by weight (solid content 30 parts by weight) Thus, a hard coat film of Example 10 was produced.

(Example 11)
In the preparation of the hard coat layer curable resin composition of Example 1, 30 parts by weight of the polyfunctional monomer (B) (product name DPHA manufactured by Nippon Kayaku Co., Ltd.) Name M406; dipentaerythritol hexaacrylate, hexafunctional, molecular weight 524, product name DPHA manufactured by Nippon Kayaku Co., Ltd. is different in hydroxyl value): Same as Example 1 except for changing to 30 parts by weight A hard coat film of Example 11 was produced.

Example 12
In the preparation of the curable resin composition for the hard coat layer of Example 1, 30 parts by weight of the polyfunctional monomer (B) (product name DPHA manufactured by Nippon Kayaku Co., Ltd.) Name M315; isocyanuric acid EO-modified triacrylate, trifunctional, molecular weight 423): A hard coat film of Example 12 was produced in the same manner as in Example 1 except that the amount was changed to 30 parts by weight.

(Example 13)
In the preparation of the curable resin composition for the hard coat layer of Example 1, 30 parts by weight of the polyfunctional monomer (B) (product name DPHA manufactured by Nippon Kayaku Co., Ltd.) Name M450; pentaerythritol tetraacrylate, tetrafunctional, molecular weight 352): A hard coat film of Example 13 was produced in the same manner as in Example 1 except that the amount was changed to 30 parts by weight.

(Example 14)
In the preparation of the curable resin composition for the hard coat layer of Example 1, 30 parts by weight of the polyfunctional monomer (B) (product name DPHA manufactured by Nippon Kayaku Co., Ltd.) Name DCPA20; caprolactone-modified dipentaerythritol hexaacrylate, hexafunctional, molecular weight 807): A hard coat film of Example 14 was produced in the same manner as in Example 1 except that the weight was changed to 30 parts by weight.

(Example 15)
In the preparation of the hard coat layer curable resin composition of Example 1, 30 parts by weight of the polyfunctional monomer (B) (product name DPHA manufactured by Nippon Kayaku Co., Ltd.) Name DCPA30; caprolactone-modified dipentaerythritol hexaacrylate, hexafunctional, molecular weight 921): A hard coat film of Example 15 was produced in the same manner as in Example 1 except that the weight was changed to 30 parts by weight.

(Example 16)
In the preparation of the curable resin composition for the hard coat layer of Example 1, 40 parts by weight (30 parts by weight of solid content) of the reactive polymer (C) (product name Beam Set DK1 manufactured by Arakawa Chemical Co., Ltd.) (C) (Polymer 1, weight average molecular weight of about 41000, X = 100, Y = 100, Z = 0, A is —CH ₂ CH (OH) CH ₂ — having 3 atoms connected in a straight chain, R ¹ is a methyl group, R ² is hydrogen, solid content 75%, MIBK solvent): The hard of Example 16 is the same as Example 1 except that 40 parts by weight (solid content 30 parts by weight) is used. A coated film was produced.

(Example 17)
In the preparation of the curable resin composition for the hard coat layer of Example 1, 40 parts by weight (30 parts by weight of solid content) of the reactive polymer (C) (product name Beam Set DK1 manufactured by Arakawa Chemical Co., Ltd.) (C) (Polymer 2, weight average molecular weight of about 50,000, X = 0, Y = 100, Z = 100, A is —CH ₂ CH (OH) CH ₂ — having 3 atoms connected in a straight chain, R ¹ is a methyl group, R ² is hydrogen, R ³ is a methyl group, R ⁴ is a methyl group, solid content is 75%, MIBK solvent): the same as the above except that it is replaced with 40 parts by weight (solid content 30 parts by weight) In the same manner as in Example 1, a hard coat film of Example 17 was produced.

(Example 18)
In the preparation of the curable resin composition for the hard coat layer of Example 1, 40 parts by weight (30 parts by weight of solid content) of the reactive polymer (C) (product name Beam Set DK1 manufactured by Arakawa Chemical Co., Ltd.) (C) (Polymer 3, weight average molecular weight of about 10,000, X = 0, Y = 30, Z = 30, A is 10 atoms linked in a straight chain, R ¹ is a methyl group, R ² is hydrogen, R ³ is a methyl group, R ⁴ is a methyl group, solid content 75%, MIBK solvent): Except that it is replaced with 40 parts by weight (solid content 30 parts by weight), A hard coat film was produced.

(Example 19)
In Example 1, the hard coat film of Example 19 was produced in the same manner as in Example 1 except that the curable resin composition for hard coat layer was prepared by blending the components shown below. did.
<Composition of curable resin composition for hard coat layer>
Reactive silica fine particles (A1) (manufactured by Nissan Chemical Co., Ltd., product name MIBK-SD; average primary particle size 12 nm, solid content 30%, MIBK solvent, reactive functional groups are methacrylate groups): 33 parts by weight (solid content: 10 Parts by weight)
Reactive unusual shape silica fine particles (A2) (manufactured by JGC Catalysts & Chemicals, product name DP1039SIV; average primary particle size 20 nm, average number of connections 3.5, average secondary particle size 55 nm, solid content 40%, MIBK solvent, reactivity Functional group is methacrylate group): 125 parts by weight (solid content: 50 parts by weight)
Polyfunctional monomer (B) (Nippon Kayaku Co., Ltd., product name DPHA; dipentaerythritol hexaacrylate, hexafunctional, molecular weight 524): 20 parts by weight Reactive polymer (C) (product name, manufactured by Arakawa Chemical) Beam set DK1; weight average molecular weight of about 20000, X = 0, Y = 50, Z = 0, A is —CH ₂ CH (OH) CH ₂ —, the number of atoms connected in a straight chain is 3, and R ¹ is Methyl group, R ² is hydrogen, solid content 75%, MIBK solvent): 27 parts by weight (solid content 20 parts by weight)
Polymerization initiator (Ciba Japan Co., Ltd., trade name Irgacure 184): 4 parts by weight Leveling agent (DIC, MegaFuck MCF350-5): 0.2 parts by weight (solid content)
MIBK (methyl isobutyl ketone): 45 parts by weight

(Example 20)
In the preparation of the hard coat layer curable resin composition of Example 1, reactive irregularly shaped silica fine particles (A2) (manufactured by JGC Catalysts & Chemicals, product name DP1039SIV): 100 parts by weight (solid content: 40 parts by weight) Reactive silica fine particles (A1) (manufactured by Nissan Chemical Co., Ltd., product name MIBK-SD; average primary particle size 12 nm, solid content 30%, MIBK solvent, reactive functional groups are methacrylate groups): 133 parts by weight (solid content: 40 weights) A hard coat film of Example 20 was produced in the same manner as in Example 1 except that the part was changed to (Part).

(Example 21)
In the preparation of the hard coat layer curable resin composition of Example 1, reactive irregularly shaped silica fine particles (A2) (manufactured by JGC Catalysts & Chemicals, product name DP1039SIV): 100 parts by weight (solid content: 40 parts by weight) Reactive silica fine particles (A1) (manufactured by JGC Catalysts & Chemicals, product name DP1117SIV; average primary particle size 25 nm, solid content 40%, MIBK solvent, reactive functional group is methacrylate group): 100 parts by weight (solid content: 40 parts by weight The hard coat film of Example 21 was produced in the same manner as in Example 1 except that the above was replaced.

(Example 22)
In the preparation of the curable resin composition for hard coat layer of Example 1, reactive irregularly shaped silica fine particles (A2) (manufactured by JGC Catalysts & Chemicals, product name DP1039SIV): 100 parts by weight (solid content: 40 parts by weight) Reactive silica fine particles (A1) (manufactured by Nissan Chemical Co., Ltd., product name MIBK-SDL; average primary particle size 44 nm, solid content 30%, MIBK solvent, reactive functional groups are methacrylate groups): 133 parts by weight (solid content: 40 weights) A hard coat film of Example 22 was produced in the same manner as in Example 1 except that the part was changed to (Part).

(Example 23)
In the preparation of the curable resin composition for hard coat layer of Example 1, reactive irregularly shaped silica fine particles (A2) (manufactured by JGC Catalysts & Chemicals, product name DP1039SIV): 100 parts by weight (solid content: 40 parts by weight) Reactive silica fine particles (A1) (manufactured by Nissan Chemical Co., Ltd., product name MIBK-SDZL; average primary particle size 80 nm, solid content 30%, MIBK solvent, reactive functional groups are methacrylate groups): 133 parts by weight (solid content: 40 weights) A hard coat film of Example 23 was produced in the same manner as in Example 1 except that the part was changed to (Part).

(Comparative Example 1)
In the preparation of the curable resin composition for the hard coat layer of Example 1, the polyfunctional monomer (B) (product name DPHA manufactured by Nippon Kayaku Co., Ltd.): 30 parts by weight, 2 reactive functional groups in the molecule Monomer (product name M215 manufactured by Toagosei Co., Ltd., bifunctional, molecular weight 369): A hard coat film of Comparative Example 1 was produced in the same manner as in Example 1 except that the amount was changed to 30 parts by weight.

(Comparative Example 2)
In the preparation of the hard coat layer curable resin composition of Example 1, reactive irregularly shaped silica fine particles (A2) (manufactured by JGC Catalysts & Chemicals, product name DP1039SIV): 100 parts by weight (solid content: 40 parts by weight) Silica fine particles having no reactive functional group on the fine particle surface (manufactured by Nissan Chemical Co., Ltd., product name IPA-ST-UP; average particle size 20 nm, solid content 15%, IPA solvent, no reactive functional group): 200 parts by weight (solid A hard coat film of Comparative Example 2 was prepared in the same manner as in Example 1 except that MIBK: 80 parts by weight was replaced with MIBK: 1 part by weight instead of 40 parts by weight.

(Comparative Example 3)
In the preparation of the hard coat layer curable resin composition of Example 1, 30 parts by weight of the polyfunctional monomer (B) (product name DPHA manufactured by Nippon Kayaku Co., Ltd.) has 6 reactive functional groups in the molecule. Is a polyfunctional monomer having a molecular weight exceeding 1000 (product name: DCPA120; hexafunctional, molecular weight: 1947, manufactured by Nippon Kayaku Co., Ltd.): The hard coat film of Comparative Example 3 in the same manner as in Example 1 except that 30 parts by weight was used. Was made.

(Comparative Example 4)
In the preparation of the curable resin composition for the hard coat layer of Example 1, 40 parts by weight of the reactive polymer (C) (product name Beam Set DK1 manufactured by Arakawa Chemical Co., Ltd.) Manufactured by Negami Kogyo Co., Ltd., product name UN5507; 15 functional, weight average molecular weight of about 17000) The same as Example 1 except that the solid content was changed to 30 parts by weight, and MIBK: 80 parts by weight was changed to MIBK: 90 parts by weight. A hard coat film of Comparative Example 4 was produced.

(Comparative Example 5)
In the preparation of the curable resin composition for the hard coat layer of Example 1, 40 parts by weight of the reactive polymer (C) (product name Beam Set DK1 manufactured by Arakawa Chemical Co., Ltd.) (solid content 30 parts by weight) was added to polymethyl methacrylate. (Soken Chemicals, product name M116A; no reactive functional group, weight average molecular weight of about 500 to 1,000,000, solid content 10%, toluene solvent) instead of 300 parts by weight (solid content 30 parts by weight), MIBK: 80 parts by weight A hard coat film of Comparative Example 5 was produced in the same manner as in Example 1 except that MIBK was replaced with 1 part by weight.

(Comparative Example 6)
In the preparation of the curable resin composition for the hard coat layer of Example 1, 40 parts by weight of the reactive polymer (C) (product name Beam Set DK1 manufactured by Arakawa Chemical Co., Ltd.) with a molecular weight of 10,000 less linear reactive polymer (Osaka organic chemical Co., product name SPBDA30; 2 _{functionality, CH 2 = CHCOO - [(} CH (CH 2 CH 3) CH 2) - (CH 2 CH 2)] n-OCOCH = CH ₂ , weight average molecular weight of about 1000) Hard coat film of Comparative Example 6 in the same manner as in Example 1 except that MIBK: 80 parts by weight was replaced with MIBK: 90 parts by weight instead of 30 parts by weight of solid content. Was made.

(Comparative Example 7)
In the preparation of the curable resin composition for hard coat layer of Example 1, 40 parts by weight (solid content 30 parts by weight) of the reactive polymer (C) (product name Beam Set DK1 manufactured by Arakawa Chemical Co., Ltd.) Reactive polymer (produced by Osaka Organic Chemical Co., Ltd., product name STAR501; weight average molecular weight of about 15000, polymer having a three-dimensional network structure) Instead of 30 parts by weight of solid content, MIBK: 80 parts by weight and MIBK: 90 parts by weight A hard coat film of Comparative Example 7 was produced in the same manner as in Example 1 except for the above.

(Comparative Example 8)
In the preparation of the curable resin composition for the hard coat layer of Example 1, 40 parts by weight (30 parts by weight of solid content) of the reactive polymer (C) (product name Beam Set DK1 manufactured by Arakawa Chemical Co., Ltd.) Reactive polymer of ester skeleton (manufactured by Daicel Cytec, product name Ebecryl 524; 10 functional or less, main chain is ester skeleton, weight average molecular weight about 10,000) Solid content is changed to 30 parts by weight, MIBK: 80 parts by weight MIBK: 90 parts by weight A hard coat film of Comparative Example 8 was produced in the same manner as in Example 1 except that.

(Comparative Example 9)
In the preparation of the curable resin composition for the hard coat layer of Example 1, 40 parts by weight of the reactive polymer (C) (product name Beam Set DK1 manufactured by Arakawa Chemical Co., Ltd.) and the molecular weight of 70000 are used. In place of 46 parts by weight (solid content 30 parts by weight) instead of 46 parts by weight (solid content 30 parts by weight) A hard coat film of Comparative Example 9 was produced in the same manner as in Example 1 except that the weight part was changed to 74 parts by weight of MIBK.

(Reference Example 1)
In Example 1, the hard coat film of Reference Example 1 was produced in the same manner as in Example 1 except that the curable resin composition for hard coat layer was prepared by blending the components shown below. did.
<Composition of curable resin composition for hard coat layer>
Reactive unusual shape silica fine particles (A2) (manufactured by JGC Catalysts & Chemicals, product name DP1039SIV; average primary particle size 20 nm, average number of connections 3.5, average secondary particle size 55 nm, solid content 40%, MIBK solvent, reactivity Functional group is methacrylate group): 188 parts by weight (solid content 75 parts by weight)
Polyfunctional monomer (B) (Nippon Kayaku Co., Ltd., product name DPHA; dipentaerythritol hexaacrylate, hexafunctional, molecular weight 524): 12.5 parts by weight Reactive polymer (C) (Arakawa Chemical, Product name beam set DK1; weight average molecular weight about 20,000, X = 0, Y = 50, Z = 0, A is —CH ₂ CH (OH) CH ₂ —, the number of atoms linked in a straight chain is 3, R ¹ is a methyl group, R ² is hydrogen, solid content 75%, MIBK solvent): 17 parts by weight (solid content 12.5 parts by weight)
Polymerization initiator (Ciba Japan Co., Ltd., trade name Irgacure 184): 4 parts by weight Leveling agent (DIC, MegaFuck MCF350-5): 0.2 parts by weight (solid content)
MIBK (methyl isobutyl ketone): 1 part by weight

(Reference Example 2)
In Example 1, a hard coat film of Reference Example 2 was produced in the same manner as in Example 1 except that the curable resin composition for hard coat layer was prepared by blending the components having the following composition. did.
<Composition of curable resin composition for hard coat layer>
Reactive unusual shape silica fine particles (A2) (manufactured by JGC Catalysts & Chemicals, product name DP1039SIV; average primary particle size 20 nm, average number of connections 3.5, average secondary particle size 55 nm, solid content 40%, MIBK solvent, reactivity Functional group is methacrylate group): 75 parts by weight (solid content 30 parts by weight)
Polyfunctional monomer (B) (Nippon Kayaku Co., Ltd., product name DPHA; dipentaerythritol hexaacrylate, hexafunctional, molecular weight 524): 35 parts by weight Reactive polymer (C) (product name, manufactured by Arakawa Chemical Co., Ltd.) Beam set DK1; weight average molecular weight of about 20000, X = 0, Y = 50, Z = 0, A is —CH ₂ CH (OH) CH ₂ —, the number of atoms linked in a straight chain is 3, and R ¹ is Methyl group, R ² is hydrogen, solid content 75%, MIBK solvent): 47 parts by weight (solid content 35 parts by weight)
Polymerization initiator (Ciba Japan Co., Ltd., trade name Irgacure 184): 4 parts by weight Leveling agent (DIC, MegaFuck MCF350-5): 0.2 parts by weight (solid content)
MIBK (methyl isobutyl ketone): 93 parts by weight

(Reference Example 3)
In Example 1, a hard coat film of Reference Example 3 was produced in the same manner as in Example 1 except that the curable resin composition for hard coat layer was prepared by blending the components having the following composition. did.
<Composition of curable resin composition for hard coat layer>
Reactive unusual shape silica fine particles (A2) (manufactured by JGC Catalysts & Chemicals, product name DP1039SIV; average primary particle size 20 nm, average number of connections 3.5, average secondary particle size 55 nm, solid content 40%, MIBK solvent, reactivity Functional group is methacrylate group): 100 parts by weight (solid content 40 parts by weight)
Polyfunctional monomer (B) (Nippon Kayaku Co., Ltd., product name DPHA; dipentaerythritol hexaacrylate, hexafunctional, molecular weight 524): 55 parts by weight Reactive polymer (C) (product name, manufactured by Arakawa Chemical) Beam set DK1; weight average molecular weight of about 20000, X = 0, Y = 50, Z = 0, A is —CH ₂ CH (OH) CH ₂ —, the number of atoms linked in a straight chain is 3, and R ¹ is Methyl group, R ² is hydrogen, solid content 75%, MIBK solvent): 7 parts by weight (solid content 5 parts by weight)
Polymerization initiator (Ciba Japan Co., Ltd., trade name Irgacure 184): 4 parts by weight Leveling agent (DIC, MegaFuck MCF350-5): 0.2 parts by weight (solid content)
MIBK (methyl isobutyl ketone): 88 parts by weight

(Reference Example 4)
In Example 1, a hard coat film of Reference Example 4 was produced in the same manner as in Example 1 except that the curable resin composition for hard coat layer was prepared by blending the components having the following composition. did.
<Composition of curable resin composition for hard coat layer>
Reactive unusual shape silica fine particles (A2) (manufactured by JGC Catalysts & Chemicals, product name DP1039SIV; average primary particle size 20 nm, average number of connections 3.5, average secondary particle size 55 nm, solid content 40%, MIBK solvent, reactivity Functional group is methacrylate group): 100 parts by weight (solid content 40 parts by weight)
Polyfunctional monomer (B) (Nippon Kayaku Co., Ltd., product name DPHA; dipentaerythritol hexaacrylate, hexafunctional, molecular weight 524): 5 parts by weight Reactive polymer (C) (Arakawa Chemical, product name Beam set DK1; weight average molecular weight of about 20000, X = 0, Y = 50, Z = 0, A is —CH ₂ CH (OH) CH ₂ —, the number of atoms linked in a straight chain is 3, and R ¹ is Methyl group, R ² is hydrogen, solid content 75%, MIBK solvent): 73 parts by weight (solid content 55 parts by weight)
Polymerization initiator (Ciba Japan Co., Ltd., trade name Irgacure 184): 4 parts by weight Leveling agent (DIC, MegaFuck MCF350-5): 0.2 parts by weight (solid content)
MIBK (methyl isobutyl ketone): 72 parts by weight

(Evaluation methods)
The following points were evaluated with respect to each of the above Examples and Comparative Examples. The results are shown in Table 1.
(1) Pencil hardness Pencil hardness test: The hardness of the pencil scratch test is for the test specified by JIS-S-6006 after the prepared hard coat film is conditioned for 2 hours at a temperature of 25 ° C. and a relative humidity of 60%. Using a pencil, a pencil hardness test (500 g load) defined in JIS K5600-5-4 (1999) was performed, and the highest hardness that was not damaged was measured.
(2) Curl property The degree of curl (curl width) of the hard coat film was raised by placing a sample piece obtained by cutting the hard coat film into 10 cm × 10 cm with the TAC film facing down on a horizontal base (plane). The average value (mm) of the distance between the end points of the hard coat layer was evaluated.
<Evaluation criteria>
A: 1 to 85 mm.
X: It was less than 1 mm or a roll-shaped object.
(3) Adhesiveness Application adhesiveness (JIS K 5600): Put a total of 100 grids in 1 mm square, and perform 5 continuous peel tests using Nichiban Co., Ltd. industrial 24 mm cello tape (registered trademark). The quantity of the remaining squares was measured, and the adhesion was evaluated by measuring the degree of adhesion based on the following criteria.
Adhesion degree (%) = (number of cells not peeled / total number of cells 100) × 100
<Evaluation criteria>
○: 90% or more ×: Less than 90% (4) Haze The haze value (%) of the produced hard coat film was measured according to JIS K- using a haze meter (manufactured by Murakami Color Research Laboratory, product number: HM-150). Measured according to 7136.
<Evaluation criteria>
○: 0.5% or less ×: Greater than 0.5%

(Summary of results)
From Table 1, in Examples 1 to 23 using the curable resin composition for hard coat of the present invention, pencil hardness of 6H or 5H and excellent hardness were obtained, curl was further reduced, and It was revealed that the adhesion was good and the haze value was also good at 0.5% or less. Among them, in Examples 1 to 19 containing the reactive irregularly shaped silica fine particles (A2) in a specific amount, it has been clarified that the pencil hardness is as excellent as 6H.
On the other hand, from Table 2, it was found that Comparative Examples 1 to 9 that did not contain all the specific components combined in the curable resin composition for hard coat of the present invention had low hardness.

It is sectional drawing which showed typically an example of the layer structure of the hard coat film which concerns on this invention.

Explanation of symbols

1 Hard Coat Film 10 Base Material 20 Hard Coat Layer

Claims (10)

A hard coat film provided with a hard coat layer on one side of the substrate, the hard coat layer,
As the reactive silica fine particles (A), spherical reactive silica fine particles (A1) having a reactive functional group a on the particle surface having an average primary particle diameter of 1 to 100 nm and / or a sphere having an average primary particle diameter of 1 to 100 nm. Reactive deformed silica fine particles (A2) having 3 to 20 silica fine particles bonded by an inorganic chemical bond and having a reactive functional group a ′ on the surface,
A polyfunctional monomer (B) having 3 or more reactive functional groups b in one molecule and a molecular weight of 1000 or less, and
Reactive polymer (C) represented by the following general formula (I) and having a weight average molecular weight of 10,000 to 70,000,
The ethylenically unsaturated bonds contained in the reactive functional groups a, a ′, b and the reactive polymer (C) are curable having cross-linking reactivity between the same and / or different reactive functional groups, respectively. A hard coat film comprising a cured product of a resin composition.

(In Formula (I), R ^{1 to} R ⁴ each independently represents hydrogen or a methyl group. A represents a linking group having 1 to 15 atoms in a straight chain. X, Y, Z Represents the average number of repeating units of each polymer unit, X is 0 to 2000, Y is 10 to 1000, and Z is 0 to 2000.)   The reactive silica fine particles (A) are contained in an amount of 35 to 65% by weight based on the total solid content of the curable resin composition, and the weight ratio of the reactive polymer (C) and the polyfunctional monomer (B) (reactivity). The hard coat film according to claim 1, wherein the polymer (C) / polyfunctional monomer (B)) is 0.2 to 10.   At least 50% by weight or more of the reactive silica fine particles (A) are bonded with 3 to 20 spherical silica fine particles having an average primary particle diameter of 1 to 100 nm by an inorganic chemical bond, and have a reactive functional group a ′ on the surface. The hard-coated film according to claim 1, wherein the hard-coated film is a reactive deformed silica fine particle (A2).   The hard coat film according to claim 3, wherein the inorganic chemical bond in the reactive deformed silica fine particles (A2) is a covalent bond.   The hard according to any one of claims 1 to 4, wherein a hardness of a pencil hardness test (500 g load) defined in JIS K5600-5-4 (1999) of the hard coat layer is 5H or more. Coat film.   The hard coat film according to claim 1, wherein a film thickness of the hard coat layer is in a range of 5 to 20 μm. As the reactive silica fine particles (A), spherical reactive silica fine particles (A1) having a reactive functional group a on the particle surface having an average primary particle diameter of 1 to 100 nm and / or a sphere having an average primary particle diameter of 1 to 100 nm. Reactive deformed silica fine particles (A2) having 3 to 20 silica fine particles bonded by an inorganic chemical bond and having a reactive functional group a ′ on the surface,
A polyfunctional monomer (B) having 3 or more reactive functional groups b in one molecule and a molecular weight of 1000 or less, and
Reactive polymer (C) represented by the following general formula (I) and having a weight average molecular weight of 10,000 to 70,000,
The reactive functional groups a, a ′, b, and the ethylenically unsaturated bond contained in the reactive polymer (C) each have a crosslinking reactivity between the same and / or different reactive functional groups. Curable resin composition for coat layer.

(In Formula (I), R ^{1 to} R ⁴ each independently represents hydrogen or a methyl group. A represents a linking group having 1 to 15 atoms in a straight chain. X, Y, Z Represents the average number of repeating units of each polymer unit, X is 0 to 2000, Y is 10 to 1000, and Z is 0 to 2000.)   The reactive silica fine particles (A) are contained in an amount of 35 to 65% by weight based on the total solid content of the curable resin composition, and the weight ratio of the reactive polymer (C) and the polyfunctional monomer (B) (reactivity). The curable resin composition for a hard coat layer according to claim 7, wherein the polymer (C) / polyfunctional monomer (B)) is 0.2 to 10.   At least 50% by weight or more of the reactive silica fine particles (A) are bonded with 3 to 20 spherical silica fine particles having an average primary particle diameter of 1 to 100 nm by an inorganic chemical bond, and have a reactive functional group a ′ on the surface. The curable resin composition for a hard coat layer according to claim 7 or 8, wherein the curable resin composition is a reactive deformed silica fine particle (A2).   The curable resin composition for a hard coat layer according to claim 9, wherein the inorganic chemical bond in the reactive irregularly shaped silica fine particles (A2) is a covalent bond.

Images