JP5332558B2 - Hard coat film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hard coat film which is excellent in abrasion resistance and hardness. <P>SOLUTION: In the hard coat film, first and second hard coat layers are placed in turn on one side of a light transmitting base film. The first layer is made of the cured product of a first curable resin composition containing reactive silica particles 10-100 nm in mean primary particle size and a first binder. The second layer is made of the cured product of a second curable resin composition containing a second binder. The thickness of each of the first and second layers is 1-20 &mu;m, and the total thickness of the two layers is 25 &mu;m or below. The Martens' hardness of the first layer is larger than that of the second layer. The recovery rate, when a load in the layer normal direction is canceled, of the second layer is larger than that of the first hard coat layer. The horizontal force when it is cut horizontally at a constant speed while a load in the normal direction is applied to each of the first and second layers of the second layer is greater than that of the first layer. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a hard coat film in which a hard coat layer is provided on a light-transmitting base film used for the purpose of protecting the surface of a display or the like.

  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.

  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 has been produced.

  In Patent Document 1, an intermediate layer obtained by curing a composition containing a photocurable resin and a thermosetting resin is provided on a transparent substrate, and a hard coat layer is further provided on the intermediate layer to improve hardness. ing.

  However, in recent years, a hard coat film having further excellent scratch resistance and hardness has been demanded.

JP 2008-107762 A

  The present invention has been made to solve the above problems, and an object thereof is to provide a hard coat film having excellent scratch resistance and hardness.

The hard coat film according to the present invention is a hard coat film in which a first hard coat layer and a second hard coat layer are provided in order from the light transmissive base film side on one side of the light transmissive base film. There,
The first hard coat layer has an average primary particle size of 10 to 100 nm having an ethylenically unsaturated bond selected from the group consisting of acryloyl group, methacryloyl group, vinyl group and allyl group as the reactive functional group a on the particle surface. First curable resin composition comprising a reactive silica fine particle and a first binder component having an ethylenically unsaturated bond selected from the group consisting of acryloyl group, methacryloyl group, vinyl group and allyl group as reactive functional group b Made of cured products,
The second hard coat layer includes a second binder component selected from the group consisting of pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate having an acryloyl group as the reactive functional group c. Consisting of a cured product of the curable resin composition of
The reactive functional groups a, b, and c have crosslinking reactivity between the same and different reactive functional groups, respectively.
The first and second hard coat layers each have a thickness of 1 to 20 μm, and the total thickness of the first and second hard coat layers is 25 μm or less,
When a load in the normal direction to the first and second hard coat layers is applied to the first and second hard coat layers, the Martens hardness due to the load is greater in the first hard coat layer than in the second hard coat layer. ,
When a normal load of 100 to 500 mN is applied to the first hard coat layer, the Martens hardness by the load is 290 to 425 N / mm ² ,
When a normal load of 100 to 500 mN is applied to the second hard coat layer, the Martens hardness by the load is 215 to 280 N / mm ² ,
The recovery rate of the indentation depth when the load in the normal direction is eliminated, the second hard coat layer is larger than the first hard coat layer,
The indentation depth recovery rate when the normal load of 500 mN is eliminated is 88% or more and less than 94% in the first hard coat layer, and 95% or more in the second hard coat layer. Yes,
While applying a load in the normal direction to each of the first and second hard coat layers, the horizontal force when the layer is cut at a constant speed in the horizontal direction is such that the second hard coat layer is the first hard coat layer. much larger than the hard coat layer,
In the first hard coat layer, a horizontal force when cutting the layer at a speed of 20 nm / sec in the horizontal direction while applying a load of 100 mN in the normal direction is 0.03 N or more and less than 0.08 N, and
The second hard coat layer has a horizontal force of 0.08 N or more when the layer is cut at a speed of 20 nm / sec in the horizontal direction while applying a load of 100 mN in the normal direction .

  The reactive silica fine particles have an average primary particle size of 10 to 100 nm and can be crosslinked with the first binder component and the second binder component by the reactive functional group a on the particle surface. Hardness is imparted to the first hard coat layer while maintaining light transmittance.

  The first hard coat layer on the light transmissive substrate film side is made of a cured product of a first curable resin composition containing reactive silica fine particles and a first binder component, and has a thickness of 1 to 20 μm. Therefore, the first hard coat layer is resistant to a load in the normal direction of the first layer, the Martens hardness of the first hard coat layer is larger than that of the second hard coat layer, and functions as a base layer.

  The second hard coat layer comprises a cured product of the second curable resin composition containing at least a second binder component, and the recovery rate of the indentation depth when the load in the normal direction is eliminated is When the second hard coat layer is larger than the first hard coat layer and the layer is cut at a constant speed in the horizontal direction with respect to the second hard coat layer, the horizontal force is the second hard coat layer. The coat layer becomes larger than the first hard coat layer and becomes a layer having excellent flexibility. Further, when the total thickness of the first and second hard coat layers is 25 μm or less, there is an effect of suppressing curling while maintaining the hardness.

  The hard coat film according to the present invention has a first hard coat layer that is strong against a load in the normal direction and functions as a base layer, and a second hard coat layer that is excellent in flexibility. By having it in this order from the side, it is excellent in hardness and scratch resistance.

When the hard coat film according to the present invention is applied with a load of 100 to 500 mN in the normal direction to the first hard coat layer in the first hard coat layer, the Martens hardness by the load is 290 to 425 N / mm ²
When a normal load of 100 to 500 mN is applied to the second hard coat layer, the Martens hardness by the load is 215 to 280 N / mm ² ,
The indentation depth recovery rate when the normal load of 500 mN is eliminated is 88% or more and less than 94% in the first hard coat layer, and 95% or more in the second hard coat layer. Yes,
In the first hard coat layer, a horizontal force when cutting the layer at a speed of 20 nm / sec in the horizontal direction while applying a load of 100 mN in the normal direction is 0.03 N or more and less than 0.08 N, and
In the second hard coat layer, the horizontal force when the layer is cut at a speed of 20 nm / sec in the horizontal direction while applying a load of 100 mN in the normal direction is 0.08 N or more, hardness and scratch resistance From the viewpoint of improving the properties.

  In the hard coat film according to the present invention, it is preferable that the second binder component is at least one selected from the group consisting of pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate. This is preferable from the viewpoint of improving the recovery rate of the coating layer.

  In the present invention, the Martens hardness is a 10 μm thick first or second hard coat layer formed on a 40 μm thick triacetyl cellulose film as a test sample film. It means the hardness calculated from the indentation depth (μm) at a constant indentation load using a micro hardness tester (PICODETOR HM500, ISO14577-1) manufactured by Fischer Instruments. The indentation load represents the load in the normal direction of the layer, and the indentation depth represents the depth of the hard coat layer interface when a load is applied (at the time of loading) with the hard coat layer interface before being indented as 0.

  In the present invention, the recovery rate represents how much the indentation of the hard coat layer interface has been recovered when the load is eliminated, and is determined by the following formula (1).

  The horizontal force is a hard coat using a die blade wintes Co., Ltd., SAICAS, with a blade angle of 60 °, a rake angle of 20 °, a bald angle of 10 °, a blade material: single crystal diamond, and a blade edge width of 1 mm. It means the horizontal load applied to the blade when the layer is cut at a constant speed while applying a load in the normal direction to the layer. That is, when the horizontal force is low, the hard coat layer is fragile and means a brittle layer.

  FIG. 1 is a diagram schematically illustrating an example of a state of cutting a hard coat layer. The blade 30 cuts the hard coat layer 20 provided on the light transmissive substrate film 10 while applying a load 40 in the normal direction of the layer, and moves to positions 31 and 32. At this time, the force applied horizontally to the blade is the horizontal force 50.

  In a preferred embodiment of the hard coat film according to the present invention, an antistatic layer, a middle refractive index layer, a high refractive index layer, an antiglare layer are provided between the light transmissive substrate film and the first hard coat layer. Also, it is possible to employ a configuration in which one or more layers selected from the group consisting of third hard coat layers that are the same as or different from the first and second hard coat layers are provided.

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

  In the present invention, the “hard coat layer” refers to a layer having a hardness of “H” or higher in a pencil hardness test (4.9 N load) defined in JIS K5600-5-4 (1999).

  The hard coat film of the present invention has a first hard coat layer as a ground layer, which has a Martens hardness by the load larger than that of the second hard coat layer when a load in the normal direction is applied to the layer. When the load in the line direction is eliminated, the indentation depth recovery rate is greater than that of the first hard coat layer, and the horizontal when the layer is cut at a constant speed in the horizontal direction while applying the load in the normal direction. By having a second hard coat layer whose force is greater than that of the first hard coat layer adjacent to the opposite side of the light-transmitting substrate film of the first hard coat layer, it has both strength and flexibility, Excellent hardness and scratch resistance.

  Hereinafter, the hard coat film according to the present invention will be described first, and then the method for producing the hard coat film will be described.

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 (4.9 N 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.
In the present invention, the average primary particle size of the 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. means. The average primary particle size can be measured using a Microtrac particle size analyzer or a Nanotrac particle size analyzer manufactured by Nikkiso Co., Ltd.

  In the present invention, the Martens hardness is a 10 μm thick first or second hard coat layer formed on a 40 μm thick triacetyl cellulose film as a test sample film. It means the hardness calculated from the indentation depth (μm) at a constant indentation load using a micro hardness tester (PICODETOR HM500, ISO14577-1) manufactured by Fischer Instruments. The indentation load represents the load in the normal direction of the layer, and the indentation depth represents the depth of the hard coat layer interface when a load is applied (at the time of loading) with the hard coat layer interface before being indented as 0.

  In the present invention, the recovery rate represents how much the indentation of the hard coat layer interface has been recovered when the load is eliminated, and is determined by the following formula (1).

  For example, the film thickness of the hard coat layer when no load is applied is 100, the film thickness of the hard coat layer is 60 when the load is applied, and the portion of the hard coat layer when the load is released is applied. When the film thickness is 90, the indentation depth at the time of loading is 100-60 = 40, and the indentation depth at the time of releasing the load is 100-90 = 10. When these numerical values are applied to the above formula (1), the recovery rate is (40−10) / 40 × 100 = 75%.

  The horizontal force is a hard coat using a die blade wintes Co., Ltd., SAICAS, with a blade angle of 60 °, a rake angle of 20 °, a bald angle of 10 °, a blade material: single crystal diamond, and a blade edge width of 1 mm. It means the horizontal load applied to the blade when the layer is cut at a constant speed while applying a load in the normal direction to the layer. That is, when the horizontal force is low, the hard coat layer is fragile and means a brittle layer.

I. Hard Coat Film The hard coat film according to the present invention is a hard coat film in which a first hard coat layer and a second hard coat layer are provided in order from the light transmissive substrate film side on one side of the light transmissive substrate film. A coated film,
The first hard coat layer includes a reactive silica fine particle having an average primary particle diameter of 10 to 100 nm having a reactive functional group a on the particle surface and a first binder component having a reactive functional group b. It consists of a cured product of a curable resin composition,
The second hard coat layer comprises a cured product of a second curable resin composition containing a second binder component having a reactive functional group c,
The reactive functional groups a, b, and c have crosslinking reactivity between the same and different reactive functional groups, respectively.
The first and second hard coat layers each have a thickness of 1 to 20 μm, and the total thickness of the first and second hard coat layers is 25 μm or less,
When a load in the normal direction to the first and second hard coat layers is applied to the first and second hard coat layers, the Martens hardness due to the load is greater in the first hard coat layer than in the second hard coat layer. ,
The recovery rate of the indentation depth when the load in the normal direction is eliminated, the second hard coat layer is larger than the first hard coat layer, and
While applying a load in the normal direction to each of the first and second hard coat layers, the horizontal force when the layer is cut at a constant speed in the horizontal direction is such that the second hard coat layer is the first hard coat layer. It is larger than the hard coat layer.

  The hard coat film according to the present invention has a first hard coat layer that is strong against a load in the normal direction and functions as a base layer, and a second hard coat layer that is excellent in flexibility. By having it in this order from the side, it is excellent in hardness and scratch resistance.

When the hard coat film according to the present invention is applied with a load of 100 to 500 mN in the normal direction to the first hard coat layer in the first hard coat layer, the Martens hardness by the load is 290 to 425 N / mm ²
When a normal load of 100 to 500 mN is applied to the second hard coat layer, the Martens hardness by the load is 215 to 280 N / mm ² ,
The indentation depth recovery rate when the normal load of 500 mN is eliminated is 88% or more and less than 94% in the first hard coat layer, and 95% or more in the second hard coat layer. Yes,
In the first hard coat layer, a horizontal force when cutting the layer at a speed of 20 nm / sec in the horizontal direction while applying a load of 100 mN in the normal direction is 0.03 N or more and less than 0.08 N, and
In the second hard coat layer, the horizontal force when the layer is cut at a speed of 20 nm / sec in the horizontal direction while applying a load of 100 mN in the normal direction is 0.08 N or more, hardness and scratch resistance From the viewpoint of improving the properties.

FIG. 2 is a cross-sectional view schematically showing an example of the layer configuration of the hard coat film according to the present invention.
A first hard coat layer 60 and a second hard coat layer 70 are provided in order from the light transmissive base film 10 on one surface side of the light transmissive base film 10.

  Hereinafter, a light-transmitting substrate film, a first hard coat layer, a second hard coat layer, and other layers that can be appropriately provided as necessary, which are essential elements of the hard coat film according to the present invention. An antistatic layer, a middle refractive index layer, a high refractive index layer, an antiglare layer, and a third hard coat layer that is the same as or different from the first and second hard coat layers will be described in detail.

1. Light transmissive substrate film The light transmissive substrate used in the present invention is a highly transparent (light transmissive) plastic film or sheet that satisfies physical properties that can be used as a light transmissive substrate of an optical laminate. If it is, it will not specifically limit, It can select and use suitably.
Usually, the base film used for the optical layered body is transparent, semi-transparent, colorless, or colored, but is required to have light transmittance. 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 light-transmitting substrate film can be appropriately selected and used. However, the surface of the hard coat film is hardly broken and has a light transmittance of 10 to 200 μm from the viewpoint of imparting hardness. A base material is preferably used, and more preferably 30 to 150 μm.

  Preferable materials for the light transmissive substrate film 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 Corporation, Appel (cyclic olefin) manufactured by Mitsui Chemicals 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 light transmissive substrate film used in the present invention, the material having the highest light transmittance is cellulose acylate, and it is preferable to use triacetyl cellulose 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. The average light transmittance of the substrate film is preferably 70% or more, and more preferably 85% or more.
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. These triacetyl celluloses may be added with other cellulose lower fatty acid esters such as diacetyl cellulose or various additives such as a plasticizer, an antistatic agent, and an ultraviolet absorber as required.

  In the present invention, the TAC film may be subjected to surface treatment (eg, saponification treatment, glow discharge treatment, corona discharge treatment, ultraviolet (UV) treatment, flame treatment), and a primer layer (adhesive layer). It may be formed. The light transmissive substrate film in the present invention includes those including the surface treatment and the primer layer. Therefore, the case where the specific resin penetrates only into the primer layer is also included when the specific resin penetrates into the light-transmitting base film.

2. First Hard Coat Layer The first hard coat layer of the present invention is a first hard silica layer having reactive functional groups a on the particle surface and an average primary particle diameter of 10 to 100 nm and reactive functional groups b. It is made of a cured product of the first curable resin composition containing the binder component, has a film thickness of 1 to 20 μm, and when a load in the normal direction is applied to the first hard coat layer, the Martens hardness by the load Is larger than the second hard coat layer described later.

  The reactive silica fine particles have an average primary particle size of 10 to 100 nm and can be crosslinked with the first binder component and the second binder component by the reactive functional group a on the particle surface. Hardness is imparted to the first hard coat layer while maintaining light transmittance.

The first hard coat layer on the light transmissive substrate film side is made of a cured product of a first curable resin composition containing reactive silica fine particles and a first binder component, and has a thickness of 1 to 20 μm. Therefore, the first hard coat layer is resistant to a load in the normal direction of the first layer, the Martens hardness of the first hard coat layer is larger than that of the second hard coat layer, and functions as a base layer.
Since the Martens hardness of the first hard coat layer is larger than that of the second hard coat layer, it prevents the impact and load from being transmitted to the light-transmitting base film, and has the effect of suppressing cracks and scratches on the hard coat film. Have.

In the first hard coat layer of the present invention, when a normal load of 100 to 500 mN is applied to the first hard coat layer, the Martens hardness by the load is 290 to 425 N / mm ² , The recovery rate of the indentation depth when the load of 500 mN in the linear direction is eliminated is 88% or more and less than 94% in the first hard coat layer, and the speed is 20 nm in the horizontal direction while applying a load of 100 mN in the normal direction. The horizontal force when the layer is cut at / sec is preferably 0.03 N or more and less than 0.08 N from the viewpoint of exhibiting excellent hardness as an underlayer.
When the load in the normal direction is 100 to 500 mN, the Martens hardness and the horizontal force are within the above range, and the recovery rate of the indentation depth when the normal load 500 mN is eliminated is within the above range. Thus, a hard coat film excellent in pencil hardness can be obtained. When the load in the normal direction is less than 100 mN, only the surface portion of the hard coat layer opposite to the light transmissive substrate can be measured, and the pencil hardness of the entire hard coat layer cannot be measured. On the other hand, if the load in the normal direction exceeds 500 mN, the load is too large and the hard coat layer is pushed into the light transmissive substrate.

The film thickness of the first hard coat layer is 1 to 20 μm, but 5 μm or more is preferable from the viewpoint of imparting hardness. Moreover, 15 micrometers or less are preferable from the point of curl reduction.
In order to reduce curl while maintaining the hardness, the total thickness of the first and second hard coat layers is 25 μm or less.

  Hereinafter, the 1st curable resin composition which hardens | cures and forms a 1st hard-coat layer is demonstrated.

(First curable resin composition)
The first curable resin composition includes, as essential components, reactive silica fine particles having an average primary particle diameter of 10 to 100 nm having a reactive functional group a on the particle surface and a first binder component having a reactive functional group b. In addition, other components such as an antistatic agent, an antiglare agent, and a solvent may be appropriately included in consideration of antistatic properties, antiglare properties, and coating properties.
Hereinafter, each component will be described.

(Reactive silica fine particles)
The reactive silica fine particles are a component for imparting hardness to the hard coat layer.
By including silica fine particles having an average primary particle size of 10 to 100 nm in the curable resin composition for a hard coat layer, it becomes easy to impart excellent hardness to the hard coat layer.

The reactive silica fine particles may be agglomerated particles as long as the average primary particle size is 10 to 100 nm. In the case of agglomerated particles, the secondary particle size is within the above range and is reactive on the surface of the agglomerated particles. Any functional group a is sufficient.
The average primary particle size of the reactive silica fine particles is preferably 12 to 50 nm. If the average primary particle size of the reactive silica fine particles is less than 10 nm, sufficient hardness cannot be imparted to the hard coat layer, and the triacetyl cellulose base permeation layer adjacent to the hard coat layer and, if necessary, the hard coat layer Since the contact area between the other layer provided on the side opposite to the triacetyl cellulose substrate and the silica fine particles increases, the adhesion to the substrate may be deteriorated. If the average primary particle size exceeds 100 nm, the light transmittance of the hard coat layer is lowered, leading to deterioration in transmittance and increase in haze.

  In addition, the reactive silica fine particles have a narrow particle size distribution from the viewpoint of improving the hardness while maintaining the restoration rate when only the first binder component described later is used without impairing the light transmittance. Dispersion is preferred.

  The amount of the reactive silica fine particles contained in the total solid content of the first curable resin composition is not particularly limited, and may be appropriately adjusted according to the required performance such as hardness and adhesion of the hard coat layer. That's fine. Especially, it is preferable that the amount of the reactive silica fine particles with respect to the total solid content of the first curable resin composition is 30 to 65% by weight, and more preferably 40 to 60% by weight. If it is 30% by weight or more, sufficient strength against the load (indentation load) in the normal direction of the hard coat layer can be obtained. If it exceeds 65% by weight, it is strong against the indentation load, but the filling rate is excessively increased, the adhesion between the silica fine particles and the binder component is deteriorated, on the contrary, the hardness of the hard coat layer is lowered and cracks may occur. The adhesion with the second hard coat layer may also be reduced.

  The reactive silica fine particles may be used not only having a single average primary particle size but also a combination of two or more types having different average primary particle sizes. When two or more types are used in combination, the average primary particle size of each particle may be within 10 to 100 nm.

The reactive silica fine particles include those having two or more silica fine particles as a core per particle. Moreover, the reactive silica fine particle can raise the crosslinking point in the matrix of a hard-coat layer with respect to content by making a particle size small.
The reactive silica fine particles may further impart a function to the hard coat layer, and are appropriately selected and used according to the purpose.

  In addition, since the reactive silica fine particles are used in the crosslinking reaction in the hard coat layer obtained by curing the first curable resin composition, a part or all of the reactive functional group a is used in the first curable resin composition. The reactive silica fine particles contained in the resin composition and the silica fine particles contained in the hard coat layer are strictly different.

In the present invention, deformed silica fine particles in which 3 to 20, preferably 3 to 10 of the silica fine particles are bonded by an inorganic chemical bond may be used in place of or in combination with the silica fine particles. . It is preferable to use deformed silica fine particles because the hard coat layer can be given further hardness.
If the number of the fine particles in which the silica fine particles are bonded by an inorganic chemical bond is 3 or more, the effect of improving scratch resistance and hardness can be obtained. If the number of the fine particles in which the fine silica particles are bonded by inorganic chemical bonds exceeds 20, the light transmittance of the hard coat layer is lowered, which may lead to deterioration in transmittance and increase in haze.

  The size of the reactive deformed silica fine particles in which 3 to 20 silica fine particles are bonded by an inorganic chemical bond, that is, the length of the major axis is not particularly limited, and is preferably 20 to 300 nm. If it is this range, it will be easy to provide abrasion resistance and hardness to a hard-coat layer, and it will be easy to maintain the light transmittance of a hard-coat layer.

Examples of the inorganic chemical bond 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. In a conventional aggregate having no covalent bond, there is a possibility that the aggregate is separated by a physical external force (for example, a shear in stirring at the ink stage, a shear received during application of a doctor knife or the like). Chemically, there is a possibility that the aggregate is separated by an additive such as a solvent that breaks the aggregation, a binder component, or a surfactant. Further, even when a hard coat film is formed, the aggregate is separated by a physical external force (contact by a sharp object or the like), which may be a scratch on the hard coat film, which is not preferable. On the other hand, if it is a covalent bond, decomposition | disassembly by a physical and chemical force does not occur easily, and it is stable.
In addition, as a polar solvent, lower alcohols, such as water, methanol, ethanol, and isopropanol, etc. are mentioned, for example.

  The reactive silica fine particles of the present invention are improved in hardness by using solid particles that do not have pores or porous structure inside the particles, such as hollow particles, rather than particles that have pores or porous structure inside the particles. From the point of view, it is preferable.

  The reactive silica fine particles have at least a part of the surface coated with an organic component, and have a reactive functional group a introduced by the organic component 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 compound containing the organic component having an isocyanate group reacts with the hydroxyl group present on the surface of the silica fine particles, the organic component is bonded to a part of the surface. Examples include an aspect in which an organic component is attached to a hydroxyl group present on the surface of the silica fine particle by an interaction such as hydrogen bonding, and an aspect in which one or two or more silica fine particles are contained in the polymer particle.

The coating organic component suppresses the aggregation of the silica fine particles and introduces many reactive functional groups into the surface of the silica fine particles to improve the hardness of the film (hard coat layer). It is preferable to coat the whole. From such a viewpoint, the organic component covering the silica fine particles is preferably contained in the reactive silica fine particles at 1.00 × 10 ⁻³ g / m ² or more. In an aspect in which an organic component is attached to or bonded to the surface of the silica fine particles, the organic component covering the silica fine particles may be contained in the reactive silica fine particles in an amount of 2.00 × 10 ⁻³ g / m ² or more. More preferably, the reactive silica fine particles are particularly preferably contained in an amount of 3.50 × 10 ⁻³ g / m ² or more. In the aspect in which the silica particles are contained in the polymer particles, it is more preferable that the organic component covering the silica particles is contained in the reactive silica particles in an amount of 3.50 × 10 ⁻³ g / m ² or more. The reactive silica fine particles are particularly preferably contained in an amount of 5.50 × 10 ⁻³ g / m ² or more.

The ratio of the organic component that is coated is usually a constant value of weight loss when the dry powder is completely burned in air, for example, by thermogravimetric analysis from room temperature to 800 ° C. in air. Can be sought.
In addition, the amount of organic components per unit area can be obtained by the following method. First, a value obtained by dividing the organic component weight by the inorganic component weight (organic component weight / inorganic component weight) is measured by differential thermogravimetric analysis (DTG). Next, the volume of the entire inorganic component is calculated from the inorganic component weight and the specific gravity of the silica fine particles used. Further, assuming that the silica fine particles before coating are spherical, the volume per silica fine particle before coating and the surface area are calculated from the average primary particle size of the silica fine particles before coating. Next, the number of reactive silica fine particles is determined by dividing the volume of the entire inorganic component by the volume per silica fine particle before coating. Furthermore, the amount of the organic component per reactive silica fine particle is determined by dividing the weight of the organic component by the number of reactive silica fine particles. Finally, by dividing the organic component weight per reactive silica fine particle by the surface area per silica fine particle before coating, the amount of organic component per unit area can be determined.

As a method for preparing reactive silica fine particles having a reactive functional group a introduced on the surface thereof, the organic component being coated on at least a part of the surface, the reactive functional group a to be introduced into the silica fine particles Thus, a conventionally known method can be appropriately selected and used.
Among them, in the present invention, the organic component that is coated can be contained in the reactive silica fine particles in an amount of 1.00 × 10 ⁻³ g / m ² or more per unit area of the silica fine particles before coating. From the viewpoint of suppressing the aggregation of the fine particles and improving the hardness of the film, it is preferable to select and use any of the following reactive silica fine particles (i) and (ii).
(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. Reactive silica fine particles having a reactive functional group a on the surface.
(Ii) a compound containing a reactive functional group 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 metal oxide fine particles Reactive silica fine particles having a reactive functional group a on the surface, obtained by bonding.
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 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. Reactive silica fine particles having a reactive functional group a on the surface.
When the reactive silica fine particles (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 (i) is a carboxyl group, an acid anhydride group, an acid chloride group, an acid amide group, an ester group, an imino group, a nitrile group, an isonitrile group, a hydroxyl group, or a thiol. Groups, epoxy groups, primary, secondary and tertiary amino groups, Si-OH groups, hydrolysable residues of silanes, or CH acid groups such as β-dicarbonyl compounds It has a functional group capable of chemically bonding with a group present on the surface of the silica fine particle under 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 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 introduced to the surface so that the reactive silica fine particles can react with the first binder component described later is appropriately selected according to the first binder component. As the reactive functional group 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.

  When the molecular residue of the surface modification compound contains a reactive functional group a capable of reacting with a first binder component described later, the first functional group contained in the surface modification compound is silica fine particles. By reacting with the surface, it is possible to introduce the reactive functional group a capable of reacting with the first binder component onto the surface of the reactive silica fine particles (i). For example, in addition to the first functional group, a surface modification compound further having a polymerizable unsaturated group is preferable.

  On the other hand, the surface of the reactive silica fine particles of (i) above is obtained by containing a second reactive functional group in the molecular residue of the surface modifying compound and using the second reactive functional group as a foothold. A reactive functional group a capable of reacting with the first binder component may be introduced. 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 capable of reacting with the first 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 compound having a reactive functional group a capable of reacting with the first binder component such as a polymerizable unsaturated group and a hydrogen bond forming group are used in combination. Is a suitable example. Specific examples of the hydrogen bond-forming group indicate a functional group such as a hydroxyl group, a carboxyl group, an epoxy group, a glycidyl group, an amide group, or an amide bond. Here, the amide bond 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 (i) has a molecular weight of 500 or less, more preferably 400, particularly 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 modifying compound used in the reactive silica fine particles (i) is preferably a liquid under the reaction conditions for surface modification, and is preferably soluble or at least emulsifiable in a dispersion medium. 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 (i), the concentration of the dispersion medium is usually 40 to 90, preferably 50 to 80, 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 (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 reactive functional group a introduced into the silica fine particles before coating, a compound represented by the following chemical formula (1), a compound containing a silanol group or a group that generates a silanol group by hydrolysis, and silica fine particles as a core Reactive silica fine particles having a reactive functional group a on the surface, obtained by bonding 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 (ii) are used, there are advantages that the amount of the organic component is increased, and the dispersibility and the film strength are further increased.

First, a compound containing a reactive functional group a to be introduced into silica fine particles before coating, a group represented by the above chemical formula (1), and a silanol group or a group that generates a silanol group by hydrolysis (hereinafter referred to as reactive functional group-modified hydrolysis). The case may be referred to as decomposable silane).
In the reactive functional group-modified hydrolyzable silane, the reactive functional group 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 the first 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. The reactive functional group a itself as described above may be used. For example, when the reactive functional group 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 of (ii), a method in which a reactive functional group-modified hydrolyzable silane is separately hydrolyzed and then mixed with silica fine particles, followed by heating and stirring, or a reaction A method for hydrolyzing a functional functional group-modified hydrolyzable silane in the presence of silica fine particles, and in the presence of other components such as polyunsaturated organic compounds, monounsaturated organic compounds, radiation polymerization initiators, etc. A method of performing surface treatment of silica fine particles can be selected, but a method of hydrolyzing a reactive functional group-modified hydrolyzable silane in the presence of silica fine particles is preferable. When the reactive silica fine particles (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, powdery fine particles not containing a dispersion medium may be used. However, it is preferable to use a fine particle in a solvent-dispersed sol because the dispersion step can be omitted and the productivity is high.

  As a commercial item of the said reactive silica fine particle, Nissan Chemical Industries Ltd. make; MIBK-SD, MIBK-SDMS, MIBK-SDL etc. can be mentioned.

(First binder component)
The 1st binder component used for the curable resin composition for hard-coat layers has the reactive functional group b which has crosslinking reactivity with the reactive functional group a of the said reactive silica fine particle. The reactive functional group a, the reactive functional group b, and the reactive functional group b are cross-linked to form a network structure, further improving the hardness and scratch resistance of the first hard coat layer.

  The first binder component preferably has three or more reactive functional groups b per molecule in order to obtain sufficient crosslinkability.

  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.

  The reactive functional group b may be the same as or different from the reactive functional group a.

  The first binder component is preferably a curable organic resin, preferably a translucent material that transmits light when formed into a coating film, and an ionizing radiation that is a resin that is cured by ionizing radiation represented by ultraviolet rays or electron beams. What is necessary is just to employ | adopt suitably curable resin, other well-known curable resin, etc. according to a required performance. Examples of the ionizing radiation curable resin include acrylate-based, oxetane-based, and silicone-based resins.

  As the first binder component, one or more binder components can be used.

Examples of the first binder component include pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane hexa ( And 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.

  A compound having a skeleton similar to the compound (B) having a molecular weight of less than 10,000 and having two or more reactive functional groups b described later and having a molecular weight of 10,000 or more can also be used. Examples of such a compound include trade name beam set 371 (manufactured by Arakawa Chemical Industries, Ltd.).

  As the first binder component, pentaerythritol triacrylate and / or dipentaerythritol hexaacrylate is preferably used, and pentaerythritol triacrylate is particularly preferably used.

  In addition, in the hard coat layer, from the point of improving the hardness of the hard coat layer, as the first binder component, a polyalkylene oxide chain-containing polymer (A) represented by the following chemical formula (4) and two or more It is preferable to use in combination with a compound (B) having a reactive functional group b and a molecular weight of less than 10,000.

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

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

  The polymer (A), the compound (B), and the reactive silica fine particles can react with each other, and the polymer (A) forms a crosslink with both the compound (B) and the reactive silica fine particles. Therefore, it is estimated that sufficient scratch resistance can be imparted to the hard coat film.

(Polyalkylene oxide chain-containing polymer represented by chemical formula (4) (A))
The polyalkylene oxide chain-containing polymer (A) is a polyalkylene oxide chain-containing polymer represented by the following chemical formula (4) and having a molecular weight of 1000 or more having three or more reactive functional groups b at the terminals.

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

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

In the chemical formula (4), X is a linear, branched, or cyclic hydrocarbon chain, either alone or in combination. The hydrocarbon chain may have a substituent, and between the hydrocarbon chains. Is a trivalent or higher valent organic group having 3 to 10 carbon atoms excluding the substituent. In the polyalkylene oxide chain-containing polymer (A) represented by the chemical formula (4), X has _k branch points from which the polyalkylene oxide chain (O—R _k ) _nk portion which is a linear side chain appears. Corresponds to the short main chain.

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

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

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

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

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

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

In the chemical formula (4), k represents the number of polyalkylene oxide chains (O—R _k ) _{nk in} the molecule, and represents an integer of 3 to 10. If k is less than 3, that is, if there are two polyalkylene oxide chains, sufficient hardness cannot be obtained. On the other hand, if k exceeds 10, the number of flexible parts increases and the hardness of the cured film decreases, which is not preferable. The k is preferably 3-7, more preferably 3-5.

In the chemical formula (4), L _{1 to} L _k are each independently a divalent group including one or more selected from the group consisting of an ether bond, an ester bond, and a urethane bond, or a direct bond. The divalent group containing one or more selected from the group consisting of an ether bond, an ester bond, and a urethane bond is an ether bond (—O—), an ester bond (—COO—), a urethane bond (—NHCOO—). ) Itself. Since these bonds are easy to spread molecular chains and have a high degree of freedom, it is easy to achieve compatibility with other resin components.

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

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

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

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

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

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

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

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

As a commercial item containing the polyalkylene oxide chain containing polymer (A) represented by the above chemical formula (4), for example, trade name Diabeam UK-4153 (manufactured by Mitsubishi Rayon; in chemical formula (4), X is (x -7), k is 3, L _{1 to} L ₃ are each a direct bond, R _{1 to} R ₃ are each ethylene, the total of n1, n2, and n3 is 20, and Y _{1 to} Y ₃ are each an acryloyloxy group. And the like.

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

(Compound (B) having two or more reactive functional groups b and a molecular weight of less than 10,000)
The compound (B) having a molecular weight of less than 10,000 having two or more reactive functional groups b improves the hardness of the first hard coat layer in combination with the reactive silica fine particles described above, and is sufficient. It imparts scratch resistance. In addition, what has the structure of the said polymer (A) is remove | excluded from the compound (B) which has two or more reactive functional groups b and whose molecular weight is less than 10,000.
In the present invention, the compound (B) is a wide range of compounds having reactive functional groups b capable of reacting with each other in the combination of the polymer (A) and the reactive silica fine particles, and having sufficient scratch resistance. Can be appropriately selected and used. As the said compound (B), you may use individually by 1 type, but may mix and use 2 or more types suitably.
In the compound (B) having a molecular weight of less than 10,000 having two or more reactive functional groups b, the number of reactive functional groups b contained in one molecule is three or more, which increases the crosslinking density of the cured film. From the viewpoint of imparting hardness. Here, when the compound (B) is an oligomer having a molecular weight distribution, the number of reactive functional groups b is represented by an average number.
Moreover, it is preferable that the molecular weight of a compound (B) is less than 5,000 from the point of a hardness improvement.

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

  Commercially available products can be used as the trifunctional or higher acrylate resin. Specifically, KAYARAD and KAYAMER series (for example, DPHA, PET30, GPO303, TMPTA, THE330, TPA330, manufactured by Nippon Kayaku Co., Ltd.) D310, D330, PM2, PM21, DPCA20, DPCA30, DPCA60, DPCA120); Aronix series manufactured by Toagosei Co., Ltd. (for example, M305, M309, M310, M315, M320, M327, M350, M360, M402, M408, M450, M7100, M7300K, M8030, M8060, M8100, M8530, M8560, M9050); NK ester series (for example, TMPT, A-TMPT, A-TMM-) manufactured by Shin-Nakamura Chemical Co., Ltd. A-TMM3L, A-TMMT, A-TMPT-6EO, A-TMPT-3CL, A-GLY-3E, A-GLY-6E, A-GLY-9E, A-GLY-11E, A-GLY-18E , A-GLY-20E, A-9300, AD-TMP-4CL, AD-TMP); NK Economer series manufactured by Shin-Nakamura Chemical Co., Ltd. (for example, ADP51, ADP33, ADP42, ADP26, ADP15); New Frontier series (for example, TMPT, TMP3, TMP15, TMP2P, TMP3P, PET3, TEICA) manufactured by Ichi Kogyo Seiyaku Co., Ltd .; Ebecryl series (for example, TMPTA, TMPTAN, 160, manufactured by Daicel UCB) TMPEOTA, OTA480, 53, PETIA, 2047, 40, 1 0, 1140, PETAK, DPHA); CD501, CD9021, CD9052, SR351, SR351HP, SR351LV, SR368, SR368D, SR415, SR444, SR454, SR454HP, SR492, SR499, SR502, SR9008, SR9020, SR9020 SR9035, CD9051, SR350, SR9009, SE9011, SR295, SR355, SR399, SR399LV, SR494, SR9041 and the like.

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

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

  Moreover, as the compound (B) used in the present invention, a polymer represented by the following chemical formula (5) having a molecular weight of less than 100,000 can also be used.

化学式（５）中、Ｄは炭素数１〜１０の連結基を表し、ｑは０又は１を表す。Ｒは水素原子又はメチル基を表す。Ｅは任意のビニルモノマーの重合単位を表し、単一成分であっても複数の成分で構成されていてもよい。ｏ、ｐは各重合単位のモル％である。ｐは０であっても良い。

In chemical formula (5), D represents a linking group having 1 to 10 carbon atoms, and q represents 0 or 1. R represents a hydrogen atom or a methyl group. E represents a polymerization unit of an arbitrary vinyl monomer, and may be composed of a single component or a plurality of components. o and p are mol% of each polymerized unit. p may be 0.

  D in the chemical formula (5) represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, which is linear. May have a branched structure, may have a ring structure, and may have a heteroatom selected from O, N, and S.

Preferred examples of the linking group D in the chemical formula (5) include * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * — (CH ₂ ) ₄ —O. _{- **, * - (CH 2} ) 6 -O - **, * - (CH 2) 2 -O- (CH) 2 -O - **, * - CONH- (CH 2) 3 -O- * *, * —CH ₂ CH (OH) CH ₂ —O — **, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — ** and the like. Here, * represents a connecting site on the polymer main chain side, and ** represents a connecting site on the (meth) acryloyl group side.

  In chemical formula (5), R represents a hydrogen atom or a methyl group, and is more preferably a hydrogen atom from the viewpoint of curing reactivity.

  In the chemical formula (5), o may be 100 mol%, that is, a single polymer. Moreover, even if o is 100 mol%, the copolymer in which 2 or more types of polymerization units containing the (meth) acryloyl group represented by o mol% were used may be used. The ratio of o and p is not particularly limited, and can be appropriately selected from various viewpoints such as hardness, solubility in a solvent, and light transmittance.

  In chemical formula (5), E represents a polymerization unit of an arbitrary vinyl monomer, and is not particularly limited, and can be appropriately selected from various viewpoints such as hardness, solubility in a solvent, and light transmittance. It may be composed of a single or a plurality of vinyl monomers.

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

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

  Commercially available products can be used for the above compounds. As urethane acrylate having a weight average molecular weight of less than 10,000 and having two or more polymerizable unsaturated groups, Kyoeisha Chemical Co., Ltd. trade names AH-600, AT-600, UA-306H, UA- 306T, UA-306I, etc. are mentioned. As the urethane (meth) acrylate suitably used in combination with the polymer (A) of the present invention, a monomer or multimer of isophorone diisocyanate, a pentaerythritol polyfunctional acrylate, and a dipentaerythritol polyfunctional acrylate are reacted. And urethane (meth) acrylate obtained in this way. As a commercial item of the said urethane (meth) acrylate, brand name UV-1700B (made by Nippon Synthetic Chemical Industry Co., Ltd.) is mentioned, for example.

  A commercially available product can be used as the urethane (meth) acrylate resin, and specific examples include the purple light series manufactured by Nippon Synthetic Chemical Industry Co., Ltd., such as UV1700B, UV6300B, UV765B, UV7640B, and UV7600B; Art Resin series manufactured by Kogyo Co., Ltd., for example, Art Resin HDP, Art Resin UN 9000H, Art Resin UN 3320HA, Art Resin UN 3320HB, Art Resin UN 3320HC, Art Resin UN 3320HS, Art Resin UN901M, Art Resin UN902MS, Art Resin UN903, etc. And UA100H, U4H, U6H, U15HA, UA32P, U6LPA, U324A, U9HAMI, etc. manufactured by Shin-Nakamura Chemical Co., Ltd .; Ebecryl series manufactured by, for example, 1290, 5129, 254, 264, 265, 1259, 1264, 4866, 9260, 8210, 204, 205, 6602, 220, 4450, etc .; Arakawa Chemical Industries, Ltd. For example, 371, 371MLV, 371S, 577, 577BV, 577AK, etc .; Mitsubishi Rayon Co., Ltd. RQ series, etc .; DIC Corporation, Unidic series, etc. are mentioned. DPHA40H (manufactured by Nippon Kayaku Co., Ltd.), CN9006, CN968 (manufactured by Thermer), and the like. Among these, UV1700B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), DPHA40H (manufactured by Nippon Kayaku Co., Ltd.), Art Resin HDP (manufactured by Negami Kogyo Co., Ltd.), beam set 371, beam set 577 (Arakawa) Chemical Industry Co., Ltd.), U15HA (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

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

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

(Other ingredients)
In addition to the above components, a polymerization initiator, an antistatic agent, an antiglare agent, and the like can be appropriately added to the first curable resin composition. Further, various additives such as a reactive or non-reactive leveling agent and various sensitizers may be mixed, and a solvent may be contained in order to improve the coatability and hardness. When an antistatic agent and / or an antiglare agent are included, antistatic properties and / or antiglare properties can be further imparted to the hard coat layer.

(Polymerization initiator)
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 may be appropriately selected and used as necessary. . 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.

  In addition to the above, commercially available products can be used. Specifically, Irgacure 907, Irgacure 379, Irgacure 819, Irgacure 127, Irgacure 500, Irgacure 754, Irgacure 250, Irgacure 1800, Irgacure 1870 manufactured by Ciba Japan Co., Ltd. , Irgacure OXE01, DAROCUR TPO, DAROCUR1173, Japan Siber Hegner Co., Ltd. of SpeedcureMBB, SpeedcurePBZ, SpeedcureITX, SpeedcureCTX, SpeedcureEDB, Esacure ONE, Esacure KIP150, Esacure KTO46, manufactured by Nippon Kayaku Co., of (stock) KAYACURE DETX-S, KAYACURE CTX , KAYACURE BMS, K YACURE DMBI, and the like.

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

(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.
Examples of the antistatic agent include conductive polymers. The conductive polymer is not particularly limited. For example, aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, aliphatic conjugated polyacetylene, heteroatom-containing polyaniline, mixed type Conjugated poly (phenylene vinylene), a double chain conjugated system that has a plurality of conjugated chains in the molecule, and a conductive polymer that is a polymer obtained by grafting or block-copolymerizing the conjugated polymer chain to a saturated polymer. And the like.

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 average primary particle size of the conductive fine particles is preferably 0.1 nm to 0.1 μm. By being within this range, when the conductive fine particles are dispersed in a binder, a composition capable of forming a film having high light transmittance with little 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 preferably have light-transmitting properties. Specific examples of the fine particles include plastic beads, and more preferably those having optical 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.

(Solvent of the first curable resin composition)
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, butyl cellosolve; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, 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 the non-permeable solvent, the first binder component does not penetrate into the light-transmitting substrate film, so that the hardness of the first hard coat layer can be increased.
In the present invention, the term “penetration” refers to dissolving or swelling the light transmissive substrate film.

3. 2nd hard-coat layer The 2nd hard-coat layer of this invention consists of hardened | cured material of the 2nd curable resin composition containing a 2nd binder component, and is 1-20 micrometers in film thickness, The said 2nd hard-coat layer When a normal direction load is applied to the hard coat layer, the Martens hardness due to the load is smaller than that of the first hard coat layer, and the indentation depth recovery rate when the normal direction load is eliminated is The second hard coat layer is larger than the first hard coat layer, and
The horizontal force when the layer is cut at a constant speed in the horizontal direction while applying a load in the normal direction to each of the first and second hard coat layers, the second hard coat layer has the first hard coat layer. By being larger than the coat layer, the layer has excellent flexibility.

  The hard coat film according to the present invention is the first hard coat layer having a high Martens hardness and functioning as a base layer, and the second hard coat layer having excellent flexibility, in this order from the light-transmitting substrate film side. It has excellent hardness and scratch resistance.

The second hard coat layer is made of a cured product of the second curable resin composition containing the second binder component, and has a film thickness of 1 to 20 μm, so that it has excellent resilience to impact and a large horizontal force. Have excellent flexibility.
Due to the flexibility of the second hard coat layer, compared to the case without the second hard coat layer, the impact and load transmitted to the layer on the light transmissive substrate film side are reduced, and when the impact and load are eliminated It has the effect of recovering and reducing quality deterioration of the appearance due to scratches and the like.

In the second hard coat layer of the present invention, when a normal load of 100 to 500 mN is applied to the second hard coat layer, the Martens hardness by the load is 215 to 280 N / mm ² , The recovery rate of the indentation depth when the load of 500 mN in the linear direction is eliminated is 95% or more in the second hard coat layer, and at a speed of 20 nm / sec in the horizontal direction while applying a load of 100 mN in the normal direction. The horizontal force when the layer is cut is preferably 0.08 N or more from the viewpoint of exhibiting excellent flexibility as a surface layer.
The small horizontal force means that the hard coat layer is broken even with a small load, that is, the hard coat layer is easily broken and brittle.
When the load in the normal direction is 100 to 500 mN, the Martens hardness and the horizontal force are within the above range, and the recovery rate of the indentation depth when the normal load 500 mN is eliminated is within the above range. Thus, a hard coat film excellent in pencil hardness can be obtained. When the load in the normal direction is less than 100 mN, only the surface portion of the hard coat layer opposite to the light transmissive substrate can be measured, and the pencil hardness of the entire hard coat layer cannot be measured. On the other hand, if the load in the normal direction exceeds 500 mN, the load is too large and the hard coat layer is pushed into the light transmissive substrate.

The film thickness of the second hard coat layer is 1 to 20 μm, but since there is the first hard coat layer, 1.5 μm or more is preferable from the viewpoint of imparting hardness. Moreover, 15 micrometers or less are preferable from the point of curl reduction.
In order to reduce curl while maintaining the hardness, the total thickness of the first and second hard coat layers is 25 μm or less.

  Hereinafter, the 2nd curable resin composition for hard-coat layers which hardens | cures and forms a 2nd hard-coat layer is demonstrated.

(Second curable resin composition)
The second curable resin composition for the hard coat layer contains the second binder component as an essential component. In addition, the second reaction is appropriately performed in consideration of hardness, antistatic property, antiglare property, and coating property. May contain components such as fine silica particles, an antistatic agent, an antiglare agent, and a solvent.
Hereinafter, each component will be described.

(Second binder component)
The second binder component has a reactive functional group c capable of crosslinking reaction with the first binder component and the reactive silica fine particles, and the first binder component described in the first curable resin composition and The same can be used. The second binder component may be the same as or different from the first binder component.

  As the second binder component, one or more binder components can be used.

  The reactive functional group c may be the same as or different from the reactive functional group a and the reactive functional group b.

  As the second binder component, pentaerythritol triacrylate and / or dipentaerythritol hexaacrylate is preferably used, and dipentaerythritol hexaacrylate is particularly preferably used.

(Other components of the second curable resin composition)
In the second curable resin composition for hard coat layer, the hardness, polymerization initiator, antistatic property, antiglare property, antifouling property, coating property, etc. are considered without departing from the spirit of the present invention. The second fine particles, antistatic agent, antiglare agent, antifouling agent, and other components such as a solvent may be contained.

(Second reactive silica fine particles)
Examples of the second reactive silica fine particles that may be contained in the second curable resin composition include the same reactive silica fine particles contained in the first curable resin composition.
The content of the second reactive silica fine particles in the second curable resin composition is preferably 0% by weight or more and less than 30% by weight with respect to the total solid content of the second curable resin composition. More preferably, the content is 1% by weight or more and less than 30% by weight. By being less than 30% by weight, it is easy to ensure the recoverability of the second binder component, the adhesiveness with the first hard coat layer can be improved, and the horizontal force of the second hard coat layer can be increased.

(Polymerization initiator of second curable resin composition)
Examples of the polymerization initiator include those similar to those mentioned in the first curable resin composition, and the polymerization initiator and the first curable resin composition contained in the second curable resin composition. These polymerization initiators may be the same or different.

(Antistatic agent for second curable resin composition)
Examples of the antistatic agent are the same as those mentioned in the first curable resin composition, and the antistatic agent contained in the second curable resin composition and the first curable resin composition. These antistatic agents may be the same or different.

(Anti-glare agent for the second curable resin composition)
Examples of the antiglare agent are the same as those mentioned in the first curable resin composition, and the antiglare agent and the first curable resin composition contained in the second curable resin composition. These anti-glare agents may be the same or different.

(Solvent of second curable resin composition)
The solvent which is the other component of the second curable resin composition may be non-permeable or permeable, and may be used in combination.

4). Other Layers The hard coat film is basically composed of the light transmissive substrate film, the first hard coat layer, and the second hard coat layer as described above. However, within the range not departing from the gist of the present invention, in consideration of the function or application as a hard coat film, the following one or two are further provided on the light transmissive substrate film side of the first hard coat layer. The above layers may be provided.

4-1. Antistatic layer The antistatic layer comprises 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 antistatic agents as those mentioned for the antistatic agent of the first 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.

4-2. Medium Refractive Index Layer and High Refractive Index Layer The medium refractive index layer and the high refractive index layer usually contain mainly a binder component and refractive index adjusting particles. As the binder component, those similar to the hard coat layer can be used. Moreover, what is necessary is just to make it the same as a hard-coat layer also about the photoinitiator used as needed, various additives, a formation method, etc.

  Examples of the particles for adjusting the refractive index include fine particles having a particle diameter of 100 nm or less. Examples of such fine particles include zinc oxide (refractive index: 1.90), titania (refractive index: 2.3 to 2.7), ceria (refractive index: 1.95), and tin-doped indium oxide (refractive index: 1). .95), at least one selected from the group consisting of antimony-doped tin oxide (refractive index: 1.80), yttria (refractive index: 1.87), and zirconia (refractive index: 2.0). it can.

4-3. Antiglare layer The antiglare layer comprises 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 first hard coat layer can be used.

4-4. Third Hard Coat Layer From the viewpoint of further improving the hardness of the hard coat film, a third hard coat layer which is the same as or different from the first hard coat layer and the second hard coat layer may be provided.
The third hard coat layer can be the same as the first and second hard coat layers, and the compositions of the first and third or second and third hard coat layers are the same. May be good or different.

FIG. 3 is a cross-sectional view schematically showing another example of the layer configuration of the hard coat film according to the present invention.
On one surface side of the light transmissive substrate film 10, an antistatic layer 80, a first hard coat layer 60, and a second hard coat layer 70 are provided in order from the light transmissive substrate film 10.

II. Production Method of Hard Coat Film The hard coat film according to the present invention may be produced by a conventionally known method and is not particularly limited. For example, the first curable resin composition is applied to one side of the light-transmitting substrate film to form a coating film, semi-cured or completely cured, and then on the coating film of the first curable resin composition. By applying the second curable resin composition to a coating film and curing it completely with the semi-cured coating film of the first curable resin composition or by curing the second curable resin composition A second hard coat layer is formed.

(Method for forming first and second hard coat layers)
The hard coat layer may be formed by a conventionally known method.
For example, the prepared first curable resin composition is applied to one side of a light-transmitting substrate film, a coating film is formed and dried, and then the coating film is cured by light and / or heat. A first hard coat layer is formed.
The second hard coat layer is also applied and cured on the semi-cured coating film of the first curable resin composition or the completely hardened first hard coat layer in the same manner as the first curable resin composition. Just do it.

  The first and second curable resin compositions are usually prepared by mixing and dispersing a reactive silica fine particle, a binder component, a polymerization initiator, and the like in a solvent according to a general preparation method. A paint shaker or a bead mill can be used for mixing and dispersing.

The application method is not particularly limited as long as the method can uniformly apply the curable resin composition to the surface of the light-transmitting base film or the coating film of the first curable resin composition. Various methods such as a coating method, a dip method, a spray method, a slide coating method, a bar coating method, a roll coater method, a meniscus coater method, a flexographic printing method, a screen printing method, and a pea coater method can be used.
Further, the amount of the first and second curable resin compositions to be applied onto the surface of the light transmissive substrate film or the coating film of the first curable resin composition requires an obtained hard coat film. that it is different from the performance, may appropriately be adjusted so that the film thickness after drying becomes 3～25Myuemu, within coated amount of ^{3g / m 2 ~30g / m 2} , in particular 5 g / ^{m 2} It is preferable to be within the range of ˜25 g / 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 from room temperature to 80 ° C., preferably from 40 ° C. to 70 ° C., preferably from 20 seconds to 3 minutes, preferably The drying process is performed in a time of about 30 seconds to 1 minute.

  Next, the reactive functional groups of the reactive silica fine particles and the binder component contained in the curable resin composition are coated on the first and second curable resin compositions and dried as necessary. Accordingly, a hard coat layer made of a cured product of the curable resin composition is formed by curing the coating film by light irradiation and / or heating.

For light irradiation, ultraviolet rays, visible light, electron beams, ionizing radiation, etc. are mainly used. In the case of ultraviolet curing, ultraviolet rays emitted from light such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and 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).

(Formation of other layers)
When forming other layers on the light-transmitting substrate film, before applying the first curable resin composition for hard coat layer, apply and dry the curable resin composition of the other layers. The other layer is formed by light irradiation and / or heating, and then the first curable resin composition for hard coat layer is applied and cured to form the first hard coat layer.

Hereinafter, the present invention will be described more specifically with reference to examples. These descriptions do not limit the present invention.
As the reactive silica fine particles (1), MIBK-SDL (average primary particle size 44 nm, solid content 30% liquid (solvent: MIBK), reactive functional group is a methacrylate group) manufactured by Nissan Chemical Industries, Ltd. was used. .
As reactive silica fine particles (2), MIBK-SDL (average primary particle size 12 nm, solid content 30% liquid (solvent; MIBK), reactive functional group is methacrylate group) manufactured by Nissan Chemical Industries, Ltd. was used. .
As the reactive silica fine particles (3), MIBK-SDL (average primary particle size 20 nm, solid content 30% liquid (solvent: MIBK), reactive functional group is a methacrylate group) manufactured by Nissan Chemical Industries, Ltd. was used. .
As reactive silica fine particles (4), MIBK-SDL (average primary particle size 80 nm, solid content 30% liquid (solvent; MIBK), reactive functional group is methacrylate group) manufactured by Nissan Chemical Industries, Ltd. was used. .
As reactive silica fine particles (5), manufactured by JGC Catalysts & Chemicals Co., Ltd., DP1039SIV (deformed shape, average primary particle size 55 nm, average number of connections 3.5, solid content 40% liquid (solvent: MIBK), reactivity The functional group used was a methacrylate group).
As the reactive silica fine particles (6), MIBK-STD2L (average primary particle size 44 nm, solid content 30% liquid (solvent: MIBK), reactive functional group is an acrylate group) manufactured by Nissan Chemical Industries, Ltd. was used. .
As silica particles (1) having no reactive functional group, silica fine particles having an average primary particle size of 44 nm were used.
As the binder component (1), DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd. was used.
As a binder component (2), Nippon Kayaku Co., Ltd. product, PET30 (pentaerythritol triacrylate) was used.
As the binder component (3), UV1700B (polyfunctional urethane acrylate, 10 functional, molecular weight 2000) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. was used.
As the binder component (4), Arakawa Chemical Industries, Ltd. beam set DK1 (reactive functional group is acrylate group, 30 functional or higher, weight average molecular weight 20000, solid content 75% by weight, MKBK solvent) was used.
M215 (isocyanuric acid EO-modified diacrylate, molecular weight 333, number of reactive functional groups 2) manufactured by Toagosei Co., Ltd. was used as the binder component (5).
As a polymerization initiator, Irgacure 184 manufactured by Ciba Japan Co., Ltd. was used.
As a leveling agent, Megafac MCF350-5 (solid content) manufactured by DIC Corporation was used.
A TAC film (thickness 40 μm, triacetyl cellulose resin film, trade name: KC4UY, manufactured by Konica Corporation) was used as the light-transmitting substrate film.
Abbreviations for each compound are as follows.
DPHA: dipentaerythritol hexaacrylate PETA: pentaerythritol triacrylate MIBK: methyl isobutyl ketone

(Preparation of curable resin composition)
Components of the composition shown below were blended to prepare curable resin compositions 1-1 to 1-12 and 2-1 to 2-2, respectively. Table 1 shows the mixing ratio (wt%) of reactive silica fine particles or silica fine particles of each curable resin composition with respect to the total solid content, the type of binder component, and the number of functional groups of the binder component.

(Curable resin composition 1-1)
Reactive silica fine particles (1): 140 parts by weight (solid content 42 parts by weight)
Binder component (1): 58 parts by weight Irgacure 184: 4 parts by weight MegaFuck MCF350-5: 0.2 parts by weight MIBK: 57 parts by weight

(Curable resin composition 1-2)
Reactive silica fine particles (2): 140 parts by weight (solid content 42 parts by weight)
Binder component (1): 58 parts by weight Irgacure 184: 4 parts by weight MegaFuck MCF350-5: 0.2 parts by weight MIBK: 57 parts by weight

(Curable resin composition 1-3)
Reactive silica fine particles (3): 140 parts by weight (solid content 42 parts by weight)
Binder component (1): 58 parts by weight Irgacure 184: 4 parts by weight MegaFuck MCF350-5: 0.2 parts by weight MIBK: 57 parts by weight

(Curable resin composition 1-4)
Reactive silica fine particles (4): 140 parts by weight (solid content 42 parts by weight)
Binder component (1): 58 parts by weight Irgacure 184: 4 parts by weight MegaFuck MCF350-5: 0.2 parts by weight MIBK: 57 parts by weight

(Curable resin composition 1-5)
Reactive silica fine particles (5): 105 parts by weight (solid content 42 parts by weight)
Binder component (1): 58 parts by weight Irgacure 184: 4 parts by weight MegaFuck MCF350-5: 0.2 parts by weight MIBK: 90 parts by weight

(Curable resin composition 1-6)
Reactive silica fine particles (6): 140 parts by weight (solid content 42 parts by weight)
Binder component (1): 58 parts by weight Irgacure 184: 4 parts by weight MegaFuck MCF350-5: 0.2 parts by weight MIBK: 57 parts by weight

(Curable resin composition 1-7)
Reactive silica fine particles (6): 140 parts by weight (solid content 42 parts by weight)
Binder component (2): 58 parts by weight Irgacure 184: 4 parts by weight MegaFuck MCF350-5: 0.2 parts by weight MIBK: 57 parts by weight

(Curable resin composition 1-8)
Reactive silica fine particles (1): 140 parts by weight (solid content 42 parts by weight)
Binder component (3): 58 parts by weight Irgacure 184: 4 parts by weight MegaFuck MCF350-5: 0.2 parts by weight MIBK: 57 parts by weight

(Curable resin composition 1-9)
Reactive silica fine particles (1): 140 parts by weight (solid content 42 parts by weight)
Binder component (4): 77 parts by weight (solid content 58 parts by weight)
Irgacure 184: 4 parts by weight MegaFuck MCF350-5: 0.2 parts by weight MIBK: 37 parts by weight

(Curable resin composition 1-10)
Reactive silica fine particles (1): 200 parts by weight (solid content 60 parts by weight)
Binder component (1): 40 parts by weight Irgacure 184: 4 parts by weight MegaFuck MCF350-5: 0.2 parts by weight MIBK: 10 parts by weight

(Curable resin composition 1-11)
Silica fine particles (1): 140 parts by weight (solid content 42 parts by weight)
Binder component (1): 58 parts by weight Irgacure 184: 4 parts by weight MegaFuck MCF350-5: 0.2 parts by weight MIBK: 57 parts by weight

(Curable resin composition 1-12)
Silica fine particles (1): 140 parts by weight (solid content 42 parts by weight)
Irgacure 184: 4 parts by weight MegaFuck MCF350-5: 0.2 parts by weight MIBK: 57 parts by weight

(Second curable resin composition 2-1)
Binder component (1): 100 parts by weight Irgacure 184: 4 parts by weight MegaFuck MCF350-5: 0.2 parts by weight MIBK: 150 parts by weight

(Second curable resin composition 2-2)
Binder component (2): 100 parts by weight Irgacure 184: 4 parts by weight MegaFuck MCF350-5: 0.2 parts by weight MIBK: 150 parts by weight

Example 1: Production of a hard coat film The curable resin composition 1-1 was applied as a first curable resin composition to one side of a TAC film and dried in a hot oven at a temperature of 70 ° C for 60 seconds. The first hard coat layer (lower layer) having a thickness of 10 μm was formed by evaporating the solvent in the coating film and curing the coating film by irradiating ultraviolet rays so that the integrated light amount was 100 mJ / cm ² . . Furthermore, the said curable resin composition 2-1 was apply | coated as said 2nd curable resin composition on the said 1st hard-coat layer, and it dried for 60 second in a 70 degreeC hot oven, and a coating film The second hard coat layer (upper layer) having a thickness of 5 μm was formed by evaporating the solvent therein and irradiating ultraviolet rays with an integrated light amount of 200 mJ / cm ² to cure the coating film. 1 hard coat film was produced.

(Examples 2-12 and Comparative Examples 1-7)
Example 1 is different from Example 1 except that the first curable resin composition and the second curable resin composition are replaced with the compositions shown in Table 1 and the film thicknesses are changed as shown in the table. Similarly, hard coat films of Examples 2 to 12 and Comparative Examples 1 to 7 were produced.

(Evaluation of hard coat layer)
For the first hard coat layer and the second hard coat layer of the hard coat films of Examples 1 to 12 and Comparative Examples 1 to 7 that were produced, the first hard coat layer having a thickness of 10 μm was formed on the TAC film as follows. The indentation depth when only the hard coat layer or the second hard coat layer is formed and the Martens hardness (N / mm ² ) by the normal load of 100 mN of the hard coat layer and the normal load of 500 mN are eliminated. The horizontal force (N) when the layer was cut at a speed of 20 nm / sec in the horizontal direction was measured while applying a load of 100 mN in the normal direction. The results are shown in Table 2. Further, the value obtained by subtracting the Martens hardness of the second hard coat layer from the Martens hardness of the first hard coat layer, the value obtained by subtracting the recovery rate of the first hard coat layer from the recovery rate of the second hard coat layer, and the second hard coat layer Table 2 shows the values obtained by subtracting the horizontal force of the first hard coat layer from the horizontal force of the coat layer.

(Evaluation of hard coat film)
Moreover, about the produced Examples 1-12 and the hard coat film of Comparative Examples 1-7, pencil hardness and curl property were evaluated as follows. The results are shown in Table 2.

(Evaluation: Pencil hardness)
Pencil hardness test: The hardness of the pencil scratch test is as follows. After the prepared hard coat film is conditioned at a temperature of 25 ° C. and a relative humidity of 60% for 2 hours, a test pencil specified by JIS-S-6006 is used. A pencil hardness test (4.9 N load) specified in JIS K5600-5-4 (1999) was performed to evaluate the highest pencil hardness without scratching.

(Evaluation: Curl property)
The degree of curl (curl width) of the hard coat film was determined by placing the sample piece, which was cut into 10 cm x 10 cm with the TAC film on the bottom, on a horizontal table (plane), and then the second hard coat was lifted The average value (mm) of the distance between the end points of the layer was evaluated.
<Evaluation criteria>
A: 1 to 85 mm.
X: Less than 1 mm or roll shape.

  The hard coat films of Examples 1 to 12 were excellent in both pencil hardness and curl properties.

In Comparative Example 1 in which the silica fine particles contained in the first curable resin composition do not have reactive functional groups, the recovery rate of the first hard coat layer is as low as 85%, and the base layer is hard and brittle, so the pencil hardness is 2H. It became low.
In Comparative Example 2 in which the binder component was not contained in the first curable resin composition, the recovery rate of the first hard coat layer was as low as 70%, and the pencil hardness was as low as 2H.
In Comparative Example 3, where the first and second hard coat layers were each 15 μm and the total thickness of the two layers was 30 μm, the pencil hardness was high, but the curl property was deteriorated.
In Comparative Example 4 where the first and second hard coat layers were as thin as 0.3 μm, the pencil hardness was as low as H.
In Comparative Example 5 in which the compositions of the first hard coat layer and the second hard coat layer in Example 1 were exchanged, the Martens hardness of the lower first hard coat layer was higher than that of the upper second hard coat layer. Since the horizontal force of the upper second hard coat layer was small, the pencil hardness was as low as 3H.
In Comparative Example 6 having only the first hard coat layer of Example 1, the pencil hardness was as low as 3H because there was no flexibility as the surface layer of the second hard coat layer.
In Comparative Example 7 having only the second hard coat layer of Example 1, since there was no foundation layer excellent in hardness, the pencil hardness was as low as 2H.

FIG. 1 is a diagram schematically illustrating an example of a state of cutting a hard coat film. FIG. 2 is a cross-sectional view schematically showing an example of the layer configuration of the hard coat film according to the present invention. FIG. 3 is a cross-sectional view schematically showing another example of the layer configuration of the hard coat film according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Hard coat film 10 Light-transmitting base film 20 Hard coat layer 30, 31, 32 Blade 40 Load in normal direction 50 Horizontal force 60 First hard coat layer 70 Second hard coat layer 80 Antistatic layer

Claims (2)

A hard coat film provided with a first hard coat layer and a second hard coat layer in order from the light transmissive base film side on one side of the light transmissive base film,
The first hard coat layer has an average primary particle size of 10 to 100 nm having an ethylenically unsaturated bond selected from the group consisting of acryloyl group, methacryloyl group, vinyl group and allyl group as the reactive functional group a on the particle surface. First curable resin composition comprising a reactive silica fine particle and a first binder component having an ethylenically unsaturated bond selected from the group consisting of acryloyl group, methacryloyl group, vinyl group and allyl group as reactive functional group b Made of cured products,
The second hard coat layer includes a second binder component selected from the group consisting of pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate having an acryloyl group as the reactive functional group c. Consisting of a cured product of the curable resin composition of
The reactive functional groups a, b, and c have crosslinking reactivity between the same and different reactive functional groups, respectively.
The first and second hard coat layers each have a thickness of 1 to 20 μm, and the total thickness of the first and second hard coat layers is 25 μm or less,
When a load in the normal direction to the first and second hard coat layers is applied to the first and second hard coat layers, the Martens hardness due to the load is greater in the first hard coat layer than in the second hard coat layer. ,
When a normal load of 100 to 500 mN is applied to the first hard coat layer, the Martens hardness by the load is 290 to 425 N / mm ² ,
When a normal load of 100 to 500 mN is applied to the second hard coat layer, the Martens hardness by the load is 215 to 280 N / mm ² ,
The recovery rate of the indentation depth when the load in the normal direction is eliminated, the second hard coat layer is larger than the first hard coat layer,
The indentation depth recovery rate when the normal load of 500 mN is eliminated is 88% or more and less than 94% in the first hard coat layer, and 95% or more in the second hard coat layer. Yes,
While applying a load in the normal direction to each of the first and second hard coat layers, the horizontal force when the layer is cut at a constant speed in the horizontal direction is such that the second hard coat layer is the first hard coat layer. much larger than the hard coat layer,
In the first hard coat layer, a horizontal force when cutting the layer at a speed of 20 nm / sec in the horizontal direction while applying a load of 100 mN in the normal direction is 0.03 N or more and less than 0.08 N, and
In the second hard coat layer, a horizontal force when the layer is cut at a speed of 20 nm / sec in the horizontal direction while applying a load of 100 mN in the normal direction is 0.08 N or more. Coat film. Same as the antistatic layer, the middle refractive index layer, the high refractive index layer, the antiglare layer, and the first and second hard coat layers between the light transmissive substrate film and the first hard coat layer. The hard coat film according to claim 1 , wherein one or more layers selected from the group consisting of different third hard coat layers are provided.

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