JP2009042648A - Hard coat film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hard coat film excellent in saponification resistance while maintaining scratch resistance. <P>SOLUTION: The hard coat film is characterized in that a hard coat layer of the film comprises a cured product of a curable resin composition for the hard coat layer containing reactive inorganic fine particles (A) which have an average particle diameter of 30 to 100 nm, at least a part of the surfaces of which are covered with an organic component, and which have reactive functional groups (a) introduced by the organic component on the surface, and a curable binder system having a curing reactivity in the system and containing a binder component (B) having a reactive functional group (b) having crosslinking reactivity with the reactive functional groups (a) of the reactive inorganic fine particles (A), wherein the density of the reactive inorganic fine particles (A) is lowest on the interface of the hard coat layer on the opposite side to a transparent base film, and the density of the reactive inorganic fine particles (A) is highest on the interface or the near the interface of the hard coat layer close to the transparent base film. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a hard coat film provided with a hard coat layer on a transparent substrate film, which is 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.

  Further, as a method for improving the hardness of the hard coat layer, there is a method of adding inorganic fine particles, and generally, a hard coat film in which a hard coat layer added with inorganic fine particles is provided on a base film is manufactured.

  In the production of the image display device, it is difficult to directly bond the surface of the hard coat film on the base film side to the polarizing plate using an adhesive (including an adhesive). It is necessary to chemically perform surface treatment (saponification treatment) with alkali.

However, when the hard coat film described above is used, when the hard coat film is immersed in an alkaline solution, the inorganic fine particles present in the interface opposite to the base film side of the hard coat layer and in the vicinity of the interface are There is a problem of elution or dropping into the solution. Further, when the amount of the inorganic fine particles contained in the hard coat layer is increased, the hardness of the hard coat film is improved, but at the same time, the hard coat layer is present at the interface opposite to the base film side and near the interface. There is a problem that the amount of the inorganic fine particles to be increased also increases, and the amount of the inorganic fine particles eluted or dropped into the alkaline solution during the saponification treatment also increases.
Therefore, conventionally, a saponification treatment is performed after providing a protective film on the surface of the hard coat layer provided on the base film for the purpose of protecting the hard coat layer from the alkaline solution.

  However, in order to further reduce the manufacturing cost, a hard coat film that can withstand the saponification treatment without providing the protective film is required.

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

As a result of intensive studies, the present inventors have included a reactive inorganic fine particle A having a specific particle diameter in the curable binder system used in the hard coat layer, while having high scratch resistance, The inventors have found that a hard coat film having excellent saponification properties can be obtained, and have completed the present invention.
That is, the present invention is a hard coat film provided with a hard coat layer on a transparent substrate film,
Reactive inorganic fine particles A in which the hard coat layer has an average particle diameter of 30 nm or more and 100 nm or less, at least a part of the surface is coated with an organic component, and has a reactive functional group a introduced by the organic component on the surface. And a hard binder containing a binder component B having a reactive functional group b having a crosslinking reactivity with the reactive functional group a of the reactive inorganic fine particles A, and also having a curing reactivity in the system It consists of a cured product of a curable resin composition for a coat layer, has a density distribution of the reactive inorganic fine particles A in the thickness direction of the hard coat layer, and is on the side opposite to the transparent substrate film side of the hard coat layer. The density of the reactive inorganic fine particles A is the lowest at the interface, and the reactive inorganic fine particles A are present at or near the transparent substrate film side interface of the hard coat layer. Degrees, wherein the highest, it provides a hard coat film.

  Since the reactive inorganic fine particles A have high hardness, they are not easily crushed by pressure (external pressure) applied to the particles from the outside, and are excellent in pressure resistance. Moreover, since the reactive inorganic fine particle A has the reactive functional group b having the crosslinking reactivity with the reactive functional group b of the binder component B, it can be crosslinked with the binder component B. Therefore, since the hard coat layer according to the present invention contains the reactive inorganic fine particles A having high hardness, the hard coat layer has high hardness, and further, the reactive inorganic fine particles A and the binder component B form a large number of crosslinking points. The film strength is improved and excellent scratch resistance is exhibited.

  By setting the particle diameter of the reactive inorganic fine particles A within the above range, the diffusion coefficient of the reactive inorganic fine particles A becomes small, and the number of the reactive inorganic fine particles A present in the thickness direction of the hard coat layer ( Different density distributions are possible. Specifically, at the interface opposite to the transparent substrate film side of the hard coat layer and in the vicinity thereof, the density of the reactive inorganic fine particles A is the smallest, and the interface of the hard coat layer on the transparent substrate film side Alternatively, the density can be maximized in the vicinity thereof. Therefore, the hard coat film using the hard coat layer can reduce the number of the reactive inorganic fine particles A that are eluted or dropped from the surface of the hard coat layer into the alkaline solution during the saponification treatment, and is resistant to saponification. Can be improved. Thereby, the protective film at the time of saponifying the said hard coat film becomes unnecessary, and it becomes possible to reduce the number of processes and material costs.

In the hard coat film according to the present invention, the cross section of the hard coat layer in the thickness direction of the hard coat layer is P1, and the vertical density of the reactive inorganic fine particles A in the cross section P1 is the unit area of the cross section P1. When the number of reactive inorganic fine particles A present per unit (number / μm ² ) is determined, in any part of the region from the interface on the side opposite to the transparent substrate film side of the cross section P1 to a depth of 500 nm. It is preferable that the density of the reactive inorganic fine particles A is 150 / μm ² or less.
Furthermore, it is preferable that the number of the reactive inorganic fine particles A partially protruding from the interface opposite to the transparent base film side of the hard coat layer is 150 or less per unit area of the interface.
By setting the density and number of the reactive inorganic fine particles A within the above ranges, the number of the reactive inorganic fine particles A that are eluted or removed from the hard coat layer surface during the saponification treatment can be reduced. Therefore, the saponification resistance of the hard coat film according to the present invention can be improved.

In the hard coat film according to the present invention, the cross section of the hard coat layer in the plane direction of the hard coat layer is P2, and the planar density of the reactive inorganic fine particles A in the cross section P2 is the unit area of the cross section P2. When the number of reactive inorganic fine particles A present per unit (number / μm ² ) is determined, the density of the reactive inorganic fine particles A at two arbitrary positions in the cross section P2 at an arbitrary height of the hard coat layer. The difference is preferably 30 pieces / μm ² or less from the viewpoint of improving the hardness of the cured film.

In the hard coat film according to the present invention, the organic component covering the reactive inorganic fine particles A is contained in an amount of 1.00 × 10 ⁻³ g / m ² or more per unit area of the inorganic fine particles before coating. Is preferable from the viewpoint of improving the hardness of the cured film.

  In the hard coat film according to the present invention, the reactive inorganic fine particle A is a saturated or unsaturated carboxylic acid, an acid anhydride corresponding to the carboxylic acid, an acid chloride, an ester and an acid amide, an amino acid, an imine, a nitrile, In the presence of one or more surface modification compounds having a molecular weight of 500 or less selected from the group consisting of isonitriles, epoxy compounds, amines, β-dicarbonyl compounds, silanes, and functional metal compounds, water as a dispersion medium and It is preferable that it is obtained by dispersing inorganic fine particles in an organic solvent from the viewpoint of improving the film strength even if the organic component content is small.

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

  In the hard coat film according to the present invention, it is preferable that at least one of the surface modification compounds has a polymerizable unsaturated group. In this case, since the introduced reactive inorganic fine particles A easily form a cross-linked bond, the hardness of the cured film can be improved.

In the hard coat film according to the present invention, the reactive inorganic fine particle A is a reactive functional group introduced into the surface of the inorganic fine particle before coating, a group represented by the following chemical formula (1), and a silanol group or silanol by hydrolysis. It is preferable from the viewpoint of improving dispersibility in organic components and film strength that it is obtained by bonding a compound containing a group that generates a group and metal oxide fine particles.
Chemical formula (1)
^{-Q 1 -C (= Q 2)} -NH-
(In the chemical formula (1), Q ¹ represents NH, O (oxygen atom), or S (sulfur atom), and Q ² represents O or S.)

  In the hard coat film which concerns on this invention, it is preferable that content of the said reactive inorganic fine particle A is 10 to 60 weight% with respect to the total solid.

  In the hard coat film according to the present invention, the binder component B is preferably a compound having three or more reactive functional groups b.

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

  In the hard coat film according to the present invention, the thickness of the hard coat layer is preferably 1 μm or more and 100 μm or less.

  In the hard coat film according to the present invention, the hardness of the pencil hardness test specified in JIS K5600-5-4 (1999) of the hard coat layer is preferably 4H or more from the viewpoint of scratch resistance and scratch prevention. .

The hard coat film of the present invention has the smallest density of the reactive inorganic fine particles A at the interface opposite to the transparent substrate film side of the hard coat layer, or the interface of the hard coat layer on the transparent substrate film side or the In the vicinity, the density is the highest. Therefore, the hard coat film using the hard coat layer can reduce the number of the reactive inorganic fine particles A that are eluted or dropped from the surface of the hard coat layer into the alkaline solution during the saponification treatment, and is resistant to saponification. Can be improved. Thereby, the protective film at the time of saponifying the said hard coat film becomes unnecessary, and it becomes possible to reduce the number of processes and material costs.
Moreover, since the reactive functional group a of the reactive inorganic fine particle A contained in the curable binder system and the reactive functional group b of the curable binder component B form a cross-linking bond, a high hard coat film is formed on the hard coat film. Can have sex.

  The present invention is described in detail below. In the present specification, (meth) acryloyl represents acryloyl and methacryloyl, and (meth) acrylate represents acrylate and methacrylate. The light in this specification includes not only electromagnetic waves having wavelengths in the visible and invisible regions, but also particle beams such as electron beams, and radiation or ionizing radiation that collectively refers to electromagnetic waves and particle beams.

The reactive functional group a and the reactive functional group b in the present specification include a photocurable functional group and a thermosetting functional group. The photocurable functional group means a functional group capable of curing a coating film by proceeding a polymerization reaction or a crosslinking reaction by light irradiation. For example, photo radical polymerization, photo cation polymerization, photo anion polymerization Examples of the polymerization reaction include those in which the reaction proceeds by a reaction mode such as addition polymerization or condensation polymerization that proceeds through photodimerization. In addition, the thermosetting functional group in the present specification is a functional group capable of curing a coating film by causing a polymerization reaction or a crosslinking reaction to proceed between the same functional groups or other functional groups by heating. For example, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group and the like can be exemplified.
As the reactive functional group a and the reactive functional group b used in the present invention, a polymerizable unsaturated group is preferably used from the viewpoint of improving the hardness of the cured film, and 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 hard coat film of the present invention is a hard coat film in which a hard coat layer is provided on a transparent substrate film,
Reactive inorganic fine particles A in which the hard coat layer has an average particle diameter of 30 nm or more and 100 nm or less, at least a part of the surface is coated with an organic component, and has a reactive functional group a introduced by the organic component on the surface. And a hard binder containing a binder component B having a reactive functional group b having a crosslinking reactivity with the reactive functional group a of the reactive inorganic fine particles A, and also having a curing reactivity in the system It consists of a cured product of a curable resin composition for a coat layer, has a density distribution of the reactive inorganic fine particles A in the thickness direction of the hard coat layer, and is on the side opposite to the transparent substrate film side of the hard coat layer. The density of the reactive inorganic fine particles A is the lowest at the interface, and the reactive inorganic fine particles A are present at or near the transparent substrate film side interface of the hard coat layer. Degree is equal to or highest.

FIG. 1 is a cross-sectional view showing an example of a hard coat film according to the present invention. The hard coat film 1 in FIG. 1 is formed by laminating a hard coat layer 2 on one surface side of a transparent substrate film 3. The hard coat layer 2 contains reactive inorganic fine particles A4 for improving the scratch resistance. In the drawings of FIG. 1 and subsequent figures, the thickness direction (vertical direction in the figure) is greatly exaggerated from the scale in the plane direction (left and right direction in the figure) for ease of explanation.
FIG. 2 is a diagram schematically showing an example of the distribution of the reactive inorganic fine particles A4 in the cross section P1 when the cross section P1 in FIG. 1 is viewed from a direction perpendicular to the cross section P1. In FIG. 2, the density of the inorganic fine particles A4 is low in the interface 30 on the side opposite to the transparent base film 3 side in the cross section P1 and the vicinity thereof, and the interface 40 on the transparent base film 3 side in the cross section P1 and its interface In the vicinity region, the density of the inorganic fine particles A4 is high.
FIG. 3 is a diagram schematically showing an example of the distribution of the reactive inorganic fine particles A4 in the cross section P2 when the cross section P2 of FIG. 1 is viewed from a direction perpendicular to the cross section P2. In FIG. 3, the reactive inorganic fine particles A4 are uniformly dispersed, particles in which the reactive inorganic fine particles A4 are aggregated are formed, and a sea-island structure in which the particles are scattered in the cross section P2 is formed. There is nothing.

The cross section of the hard coat layer in the thickness direction of the hard coat layer is P1, and the vertical density of the reactive inorganic fine particles A in the cross section P1 is the density of the reactive inorganic fine particles A present per unit area of the cross section P1. When the number of particles (μm ² ) is determined, the density of the reactive inorganic fine particles A at an arbitrary position in the region from the interface opposite to the transparent substrate film side of the cross section P1 to a depth of 500 nm is 150. preferably pieces / [mu] m is ² or less, more preferably 50 / [mu] m ² or more 100 / [mu] m ² or less. In addition, the density of the reactive inorganic fine particles A at an arbitrary position in the region from the interface on the transparent base film side of the cross section P1 to a height 10 times the average particle diameter is 200 / μm ² or more and 400 / μm ^2. It is preferable that it is below, Furthermore, it is preferable that they are 200 pieces / micrometer < ² > or more and 300 pieces / micrometer < ² > or less. Here, the arbitrary portion means a unit area selected at random from the target region.
Further, the number of the reactive inorganic fine particles A partially protruding from the interface opposite to the transparent base film side of the hard coat layer is preferably 150 or less per unit area of the interface, Further, it is preferably 130 or less.
Further, the cross section of the hard coat layer in the plane direction of the hard coat layer is P2, and the planar density of the reactive inorganic fine particles A in the cross section P2 is the reactive inorganic fine particles present per unit area of the cross section P2. When the number of A (pieces / μm ² ) is determined, the density difference of the reactive inorganic fine particles A at two arbitrary positions in the cross section P2 at an arbitrary height of the hard coat layer is 30 / μm ² or less. It is preferable that the number is 20 / μm ² or less.
The density of the reactive inorganic fine particles A is obtained by the following method.
A cross-sectional photograph of the cross section P1 of the hard coat layer in the thickness direction of the hard coat layer and a cross section P2 of the hard coat layer in the plane direction of the hard coat layer were taken by SEM (Scanning Electron Microscope) photography. Next, the number of reactive inorganic fine particles A existing in the range of 500 nm × 500 nm in the region from the interface opposite to the transparent substrate film side of the cross section P1 to a depth of 500 nm is visually counted, and this value Was converted into the number of the reactive inorganic fine particles A present per 1 μm ^2, and the density in the vertical direction (number / μm ² ) was determined. Similarly, the number of the reactive inorganic fine particles A existing in the range of 600 nm × 600 nm in the cross section P2 is visually counted, and this value is converted into the number of the reactive inorganic fine particles A existing per 1 μm ^2. The planar density (pieces / μm ² ) was determined.

Usually, when saponifying a hard coat film, a curable resin phase composition having a thickness of several nanometers on the surface of the hard coat layer is dissolved in an alkali solution. At this time, if the reactive inorganic fine particles A partially protrude from the interface opposite to the transparent base film side of the hard coat layer, the curable resin phase around the protruding inorganic fine particles A When the composition is dissolved in the alkaline solution, a slight gap is formed between the inorganic fine particles A and the surrounding curable resin composition, and the inorganic fine particles A are easily eluted or dropped off from the hard coat layer surface.
On the other hand, by setting the density of the reactive inorganic fine particles A in the above range, the number of the reactive inorganic fine particles A existing at the interface opposite to the transparent base film side of the hard coat layer or in the vicinity thereof, that is, It is possible to reduce the number of the inorganic fine particles A that elute or fall off from the hard coat layer surface. Therefore, the hard coat film according to the present invention exhibits excellent saponification resistance, and the use of the hard coat film eliminates the need for a protective film during saponification treatment, thereby enabling reduction in the number of steps and material costs. .

<Transparent substrate film>
The material of the transparent base film is not particularly limited, but general materials used for hard coat films can be used, for example, cellulose acylate, cycloolefin polymer, acrylate polymer, or polyester Is mentioned. 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 ZEON CORPORATION, Sumitrite Bakelite Co., Ltd. Sumilite FS-1700, JSR Corporation Arton (modified norbornene resin), Mitsui Chemicals, Inc. Appel (cyclic olefin) Copolymer), Topas (cyclic olefin copolymer) manufactured by Ticona, Optretz OZ-1000 series (alicyclic acrylic resin) manufactured by Hitachi Chemical Co., Ltd., and the like. Specific examples of the acrylate polymer include methyl poly (meth) acrylate, poly (meth) ethyl acrylate, methyl (meth) acrylate-butyl (meth) acrylate, and the like. Here, (meth) acryl means acryl, methacryl or a mixture of both. Specific examples of the polyester include polyethylene terephthalate and polyethylene naphthalate.

  The thickness of the transparent substrate film is 20 μm or more and 300 μm or less, preferably 30 μm or more and 200 μm or less. In the present invention, in forming a hard coat layer on a transparent substrate film, in order to improve adhesion, in addition to physical treatment such as corona discharge treatment and oxidation treatment, a coating material called an anchor agent or primer is used. Application may be performed in advance.

<Hard coat layer>
The hard coat layer used in the present invention comprises reactive inorganic fine particles A for imparting hard coat properties, and a binder component B for imparting adhesion to a substrate or an adjacent layer as essential components, after curing. It contains a component of a curable binder system that forms a matrix of the hard coat layer, and the hard coat layer is provided on the transparent substrate film directly or via another layer.
The “hard coat layer” means a layer having a hardness of “H” or higher in a pencil hardness test generally defined by JISK5600-5-4 (1999). The hard coat layer used in the present invention is a pencil hardness test. It is preferable that the hardness of the hard coat layer surface by is 4H or more.
The film thickness of the hard coat layer is preferably 1 μm or more and 100 μm or less, and more preferably 5 μm or more and 30 μm or less from the viewpoint of scratch resistance.
Hereinafter, the constituent materials of the hard coat layer according to the present invention will be described.

[Reactive inorganic fine particles A]
In general, by containing inorganic fine particles in a hard coat layer, the hard coat property is improved while maintaining transparency. Moreover, hard coat property can further be improved by carrying out the crosslinking reaction of the inorganic fine particle which has crosslinking reactivity, and a sclerosing | hardenable binder, and forming a crosslinked structure. The reactive inorganic fine particle A is an inorganic fine particle in which an organic component is coated on at least a part of the surface of the inorganic fine particle serving as a core and has a reactive functional group introduced by the organic component on the surface. The reactive inorganic fine particles A include those having two or more inorganic fine particles as cores per particle. Moreover, the reactive inorganic fine particle A can raise the crosslinking point in a matrix with respect to content by making a particle diameter small.
In the present invention, for the purpose of remarkably improving the hardness so as to have sufficient scratch resistance, at least a part of the surface is coated with an organic component, and the reactive functional group a introduced by the organic component is provided on the surface. It is preferable to contain the reactive inorganic fine particles A contained in The reactive inorganic fine particle A may be one that further imparts a function to the hard coat layer, and is appropriately selected and used according to the purpose.

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

From the viewpoint of high hardness, silica and aluminum oxide are preferable. In addition, in order to form a high refractive index layer in phase, fine particles having a high refractive index when a film such as zirconia, titania or antimony oxide is formed can be appropriately selected and used. Similarly, in order to obtain a relatively low refractive index layer, fine particles having a low refractive index during film formation such as fluoride fine particles such as magnesium fluoride and sodium fluoride can be appropriately selected and used. Furthermore, when it is desired to impart antistatic properties and conductivity, indium tin oxide (ITO), tin oxide, or the like can be appropriately selected and used. These can be used alone or in combination of two or more.
The surface of the inorganic fine particles usually has groups that cannot exist in this form in the inorganic fine particles. These surface groups are usually relatively reactive functional groups. For example, a metal oxide has, for example, a hydroxyl group and an oxy group, for example, a metal sulfide, a thiol group and a thio group, or, for example, a nitride, an amino group, an amide group, and an imide group.

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

  The reactive inorganic fine particles A used in the present invention are coated with an organic component on at least a part of the surface, and have a reactive functional group introduced by the organic component on the surface. Here, the organic component is a component containing carbon. Further, 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 metal oxide fine particles, thereby In addition to the mode in which the organic component is bonded to the part, for example, the mode in which the organic component is attached to the hydroxyl group present on the surface of the metal oxide fine particle by the interaction such as hydrogen bond, or one or two or more in the polymer particle An embodiment containing inorganic fine particles is included.

The coating organic component covers almost the entire particle surface from the viewpoint of suppressing aggregation of inorganic fine particles and increasing the number of reactive functional groups on the surface of the inorganic fine particles to improve the hardness of the film. It is preferable. From such a viewpoint, the organic component covering the inorganic fine particles is preferably contained in the reactive inorganic fine particles A in an amount of 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 inorganic fine particles, the organic component covering the inorganic fine particles is included in the reactive inorganic fine particles A in an amount of 2.00 × 10 ⁻³ g / m ² or more. Is more preferable, and it is particularly preferable that the reactive inorganic fine particles A contain 3.50 × 10 ⁻³ g / m ² or more. In an aspect in which the polymer particles contain inorganic fine particles, it is more preferable that the organic component covering the inorganic fine particles is contained in the reactive inorganic fine particles A in an amount of 3.50 × 10 ⁻³ g / m ² or more. It is particularly preferable that 5.50 × 10 ⁻³ g / m ² or more is contained in the reactive inorganic fine particles A.
The ratio of the organic component to be coated is usually determined by a thermogravimetric analysis from room temperature to normal 800 ° C. in air, for example, as a constant value of weight reduction when the dry powder is completely burned in air. be able to.
The amount of organic component per unit area is determined by the following method. First, the value obtained by dividing the organic component weight by the inorganic component weight (organic component weight / inorganic component weight) is measured by differential thermogravimetry (DTG). Next, the volume of the whole inorganic component is calculated from the inorganic component weight and the specific gravity of the used inorganic fine particles. Further, assuming that the inorganic fine particles before coating are spherical, the volume and surface area per inorganic fine particle before coating are calculated from the average particle diameter of the inorganic fine particles before coating. Next, the number of reactive inorganic fine particles A is determined by dividing the volume of the entire inorganic component by the volume per inorganic fine particle before coating. Further, by dividing the organic component weight by the number of reactive inorganic fine particles A, the amount of organic component per reactive inorganic fine particle A is obtained. Finally, by dividing the organic component weight per reactive inorganic fine particle A by the surface area per inorganic fine particle before coating, the amount of organic component per unit area can be obtained.

The average particle size of the reactive inorganic fine particles A according to the present invention is 30 nm or more and 100 nm or less, and particularly preferably 40 nm or more and 60 nm or less. By setting the average particle size of the reactive inorganic fine particles A to 30 nm or more, not only can the hard coat layer be given scratch resistance, but also the diffusion coefficient of the reactive inorganic fine particles A can be reduced, and the transparent group of the hard coat layer can be reduced. The density of the reactive inorganic fine particles A at the interface opposite to the material film and in the vicinity thereof can be reduced. Further, by setting the average particle size of the reactive inorganic fine particles A to 100 nm or less, the crosslinking point in the matrix can be increased with respect to the content, and a hard coat layer having high film strength can be obtained.
In addition, the reactive inorganic fine particles A have a narrow particle size distribution and are monodispersed from the viewpoint of significantly improving the hardness while maintaining the restoration rate when using only a resin without impairing the transparency. Is preferred.
The average particle diameter of the reactive inorganic fine particles A means a 50% particle diameter (d50 median diameter) when the particles in the solution are measured by a dynamic light scattering method and the particle diameter distribution is represented by a cumulative distribution. The average particle size can be measured using a Microtrac particle size analyzer manufactured by Nikkiso Co., Ltd.
The reactive inorganic fine particles A may be agglomerated particles, and in the case of agglomerated particles, not only the primary particle size but also the secondary particle size may be within the above range.

As a method for preparing the reactive inorganic fine particles A having at least a part of the surface coated with an organic component and having a reactive functional group introduced by the organic component on the surface, the reactive functional group a to be introduced into the inorganic fine particle Thus, a conventionally known method can be appropriately selected and used.
Among them, in the present invention, the organic component to be coated can be contained in the reactive inorganic fine particles A in an amount of 1.00 × 10 −3 g / m ² or more per unit area of the inorganic fine particles before coating. From the viewpoint of suppressing aggregation of the fine particles and improving the hardness of the film, it is preferable to select and use any one of the following inorganic 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 inorganic fine particles in water and / or an organic solvent as a dispersion medium in the presence of one or more surface modification compounds having a molecular weight of 500 or less selected from the group consisting of metal compounds having functional groups. Inorganic fine particles having a reactive functional group on the surface.
(Ii) A compound containing a reactive functional group to be introduced into inorganic 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 is combined with metal oxide fine particles. Inorganic fine particles having reactive functional groups on the surface, obtained by
Chemical formula (1)
^{-Q 1 -C (= Q 2)} -NH-
(In the chemical formula (1), Q ¹ represents NH, O (oxygen atom), or S (sulfur atom), and Q ² represents O or S.)

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

  The surface modifying compound used for the reactive inorganic fine particles A of (i) is a carboxyl group, an acid anhydride group, an acid chloride group, an acid amide group, an ester group, an imino group, a nitrile group, an isonitrile group, a hydroxyl group, Such as thiol groups, epoxy groups, primary, secondary and tertiary amino groups, Si-OH groups, hydrolyzable residues of silanes, or C-H 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 inorganic fine particle under dispersion conditions. The chemical bond here preferably includes a covalent bond, an ionic bond or a coordinate bond, but also includes a hydrogen bond. The coordination bond is considered to be complex formation. For example, 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 inorganic fine particle. The surface modifying compound used in the reactive inorganic fine particles A of (i) can be used alone or in combination of two or more.

The surface modifying compound is usually added to the surface modifying compound via the functional group in addition to at least one functional group (hereinafter referred to as a first functional group) capable of participating in chemical bonding with the surface group of the inorganic fine particles. After linking, it has molecular residues that impart new properties to the inorganic particulates. The molecular residue or a part thereof is hydrophobic or hydrophilic, and stabilizes, integrates, or activates the inorganic fine particles, for example.
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 inorganic fine particles A can react with the binder component B described later is appropriately selected according to the binder component B. 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 a reactive functional group a capable of reacting with the binder component B is contained in the molecular residue of the surface modifying compound, the first functional group contained in the surface modifying compound is reacted with the surface of the inorganic fine particles. By doing so, it is possible to introduce the reactive functional group a capable of reacting with the binder component B onto the surface of the reactive inorganic fine particle A of (i). For example, in addition to the first functional group, a surface modification compound further having a polymerizable unsaturated group is preferable.
On the other hand, a second reactive functional group is contained in the molecular residue of the surface modification compound, and the second reactive functional group is used as a foothold for the reactive inorganic fine particles A of (i) above. A reactive functional group a capable of reacting with the binder component B may be introduced on the surface. For example, a group capable of hydrogen bonding (hydrogen bonding group) such as a hydroxyl group and an oxy group is introduced as the second reactive functional group, and another hydrogen bonding group introduced on the surface of the fine particles It is preferable that a reactive functional group a capable of reacting with the binder component B is introduced 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 binder component B 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 inorganic fine particles A of (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 inorganic fine particles can be rapidly occupied and aggregation of the inorganic fine particles can be prevented.
The surface modifying compound used for the reactive inorganic fine particles A of (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, adipine Examples include acids, succinic acid, glutaric acid, oxalic acid, maleic acid, fumaric acid, itaconic acid and stearic acid, and the corresponding acid anhydrides, chlorides, esters and amides such as caprolactam. 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.

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 (particularly methanol, ethanol, n- and i-propanol and butanol), ketones such as acetone and butanone, esters such as ethyl acetate; , Ethers such as tetrahydrofuran and tetrahydropyran; amides such as dimethylacetamide and dimethylformamide; sulfoxides and sulfones such as sulfolane and dimethylsulfoxide; and aliphatic (optionally halogenated) such as pentane, hexane and cyclohexane And hydrocarbons. These dispersion media can be used as a mixture.
The dispersion medium preferably has a boiling point that can be easily removed by distillation (optionally under reduced pressure), and a solvent having a boiling point of 200 ° C. or lower, particularly 150 ° C. or lower is preferable.

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

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

(Ii) a compound containing a reactive functional group to be introduced into inorganic 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; Inorganic fine particles having reactive functional groups on the surface, obtained by bonding with metal oxide fine particles.
Chemical formula (1)
^{-Q 1 -C (= Q 2)} -NH-
(In the chemical formula (1), Q ¹ represents NH, O (oxygen atom), or S (sulfur atom), and Q ² represents O or S.)
When the reactive inorganic fine particles A (ii) are used, there are advantages that the amount of organic components is increased, and dispersibility and film strength are further increased.

First, a compound containing a reactive functional group to be introduced into inorganic 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, reactive functional group-modified hydrolysis) In some cases, it may be referred to as a functional silane).
In the reactive functional group-modified hydrolyzable silane, the reactive functional group a to be introduced into the inorganic fine particles is not particularly limited as long as it is appropriately selected so as to be able to react with the binder component B. Suitable for introducing polymerizable unsaturated groups as described above.

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

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

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

In the chemical formula (2), 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, butyl, octyl, Examples thereof include 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, a dimethylmethoxysilyl group, and the like. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

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

R ^e is an (n + 1) -valent organic group, preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
Y ′ represents a monovalent organic group having a reactive functional group. The reactive functional group itself as described above may be used. For example, when the reactive functional group 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, Examples include 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 can be 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. . 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.

  (Ii) In the production of the reactive inorganic fine particles A, a method in which a reactive functional group-modified hydrolyzable silane is separately hydrolyzed and then mixed with the inorganic fine particles, followed by heating and stirring, or A method of hydrolyzing a reactive functional group-modified hydrolyzable silane in the presence of inorganic 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 inorganic fine particles can be selected, but a method of hydrolyzing a reactive functional group-modified hydrolyzable silane in the presence of inorganic fine particles is preferable. When the reactive inorganic fine particles A of (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. Preferable examples of the acid include organic acids and unsaturated organic acids; examples of the base 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 inorganic fine particles A, 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.
The content of the reactive inorganic fine particles A is preferably 10 to 60% by weight, more preferably 20 to 40% by weight, based on the total solid content. If it is less than 10% by weight, the hardness of the hard coat layer surface may be insufficient, and if it exceeds 60% by weight, the adhesion at the interface between the hard coat layer and the transparent substrate film may be insufficient. .

[Curable binder system]
In the present specification, the constituent component of the curable binder system refers to the hard coat layer after curing of the curable binder component other than the binder component B, the polymer component, the polymerization initiator, etc., as required, in addition to the binder component B. Represents a matrix component.
(Binder component B)
The binder component B used in the present invention has a reactive functional group b having cross-linking reactivity with the reactive functional group a of the reactive inorganic fine particle A, and the reactive functional group a and the reactive functional group b. Are crosslinked to form a network structure. In addition, the binder component B 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 binder component B is preferably a curable organic resin, preferably a translucent material that transmits light when formed into a coating film, and an ionizing radiation curable resin that is cured by ionizing radiation represented by ultraviolet rays or electron beams. Resins, other known curable resins, and the like may be appropriately employed according to required performance. Examples of the ionizing radiation curable resin include acrylate-based, oxetane-based, and silicone-based resins.

  The hard coat layer according to the present invention has a polyalkylene oxide chain-containing polymer (A) represented by the following chemical formula (3) and two or more reactive functional groups from the viewpoint of improving the hardness of the hard coat layer. It is preferable to use in combination with the compound (B) having a molecular weight of less than 10,000.

（化学式（３）において、Ｘは直鎖、分枝、または環状の炭化水素鎖が単独また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。Ｌ₁〜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 (3), X is a linear, branched, or cyclic hydrocarbon chain, either alone or in combination, and the hydrocarbon chain may have a substituent, and between the hydrocarbon chains. Is a trivalent or higher valent organic group having 3 to 10 carbon atoms, excluding the substituent, which may contain a heteroatom, k represents an integer of 3 to 10. L _{1 to} L _k are R _{1 to} R _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. to 4 of a straight-chain or branched hydrocarbon group .n1, n2 ··· nk is the number of independent _.Y 1 to Y _k are each independently have one or more reactive functional groups b Compound residues are indicated.)

  The polymer (A), the compound (B), and the reactive inorganic fine particles A can react with each other, and the polymer (A) is cross-linked with both the compound (B) and the reactive inorganic fine particles A. Therefore, it is presumed that the hard coat film can have sufficient scratch resistance.

[Polyalkylene oxide chain-containing polymer represented by chemical formula (3) (A)]
The polyalkylene oxide chain-containing polymer (A) is represented by the following chemical formula (3), and is a polyalkylene oxide chain-containing polymer having a molecular weight of 1000 or more having three or more reactive functional groups b at the terminals.

（化学式（３）において、Ｘは直鎖、分枝、または環状の炭化水素鎖が単独また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。Ｌ₁〜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 (3), X is a linear, branched, or cyclic hydrocarbon chain, either alone or in combination, and the hydrocarbon chain may have a substituent, and between the hydrocarbon chains. Is a trivalent or higher valent organic group having 3 to 10 carbon atoms, excluding the substituent, which may contain a heteroatom, k represents an integer of 3 to 10. L _{1 to} L _k are R _{1 to} R _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. to 4 of a straight-chain or branched hydrocarbon group .n1, n2 ··· nk is the number of independent _.Y 1 to Y _k are each independently have one or more reactive functional groups b Compound residues are indicated.)

In the chemical formula (3), X is a linear, branched, or cyclic hydrocarbon chain, which is used 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 (3), X has _k branch points from which the polyalkylene oxide chain (O—R _k ) nk portion which is a linear side chain appears. Corresponds to the short main chain.

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

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

X is a trivalent or higher valent organic group having 3 to 10 carbon atoms excluding the substituent. When the number of carbon atoms excluding the substituent of X is less than 3, it is difficult to have three or more polyalkylene oxide chain (O—R _k ) nk moieties which are linear side chains. On the other hand, if 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 above substituent is preferably 3-7, more preferably 3-5.

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

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

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

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

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

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

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

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

N1, n2... Nk, which are the number of repeating units of alkylene oxide R _k —O, are independent numbers. n1, n2... nk are not particularly limited as long as the weight average molecular weight as a whole molecule is 1000 or more. n1, n2... nk may be different from each other, but it is preferable that the chain lengths are substantially the same from the viewpoint of suppressing cracks while maintaining the hardness when the hard coat layer is formed. Therefore, the difference between n1, n2,... Nk is preferably about 0 to 100, more preferably about 0 to 50, particularly 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 compound (B) and the reactive inorganic fine particles A 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 a compound residue having an ethylenically unsaturated group, specifically, for example, a reactive substituent other than the ethylenically unsaturated group of the following compound or a part of the reactive substituent (such as hydrogen) is removed. Residue. Examples include (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and pentaerythritol tri (meth) acrylate, but are not limited thereto.

  The molecular weight of the polyalkylene oxide chain-containing polymer (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.

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

  The content of the polymer (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 two or more reactive functional groups b and having a molecular weight of less than 10,000 improves the hardness of the cured film of the resin composition in combination with the reactive inorganic fine particles A described above, and provides sufficient resistance. It has a function of imparting scratch resistance. In addition, what has the structure of the said polymer (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) has a reactive functional group b capable of reacting with each other in a combination of the polymer (A) and the reactive inorganic fine particles A, and has a wide range of scratch resistance. It can be used by appropriately selecting from compounds. As the said compound (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 point of imparting hardness, it is preferable. 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 5000 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, urethane modified product thereof; dipentaerythritol hexa (meth) acrylate, and EO, PO, Pikuroruhidorin, fatty acids, alkyl, urethane-modified products, sorbitol hexa (meth) acrylate, and EO, PO, epichlorohydrin, fatty acids, alkyl, hexafunctional (meth) acrylate compound of the urethane modified products are exemplified.

  Examples of (meth) acrylate oligomers (or prepolymers) include epoxy (meth) acrylates obtained by addition reaction of glycidyl ether and a monomer having (meth) acrylic acid or a carboxylate group; polyols and polyisocyanates; (Meth) acrylates obtained by an addition reaction between a reaction product of (1) and a hydroxyl group-containing (meth) acrylate; polyesters obtained by esterification of a polyester polyol comprising a polyol and a polybasic acid and (meth) acrylic acid Examples of acrylates include polybutadiene (meth) acrylate, which is a (meth) acrylic compound having a polybutadiene or hydrogenated polybutadiene skeleton. When the reactive functional group 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 a compound (B) used for this invention, the polymer represented by following Chemical formula (4) whose molecular weight is less than 10,000 can also be used.

（化学式（４）中、Ｌは炭素数１〜１０の連結基を表し、ｑは０又は１を表す。Ｒは水素原子又はメチル基を表す。Ａ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 the chemical formula (4), L represents a linking group having 1 to 10 carbon atoms, q represents 0 or 1, R represents a hydrogen atom or a methyl group, A represents a polymerization unit of any vinyl monomer, It may be composed of a single component or a plurality of components. O and p are mol% of each polymerized unit. P may be 0.)

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

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

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

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

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

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

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

  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.

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

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

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

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

[Other ingredients]
In addition to the above essential components, an antistatic agent and an antiglare agent can be appropriately added to the hard coat layer according to the present invention. Furthermore, various additives, such as a reactive or non-reactive leveling agent and various sensitizers, may be mixed. 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 according to the present invention.

Hereinafter, the manufacturing method of the hard coat film of this invention is demonstrated.
(Preparation of curable resin composition for hard coat layer)
The curable resin composition for a hard coat layer according to the present invention is usually prepared by mixing and dispersing the above components in a solvent according to a general preparation method. A paint shaker or a bead mill can be used for mixing and dispersing.

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

(Formation of hard coat layer)
The curable resin composition for a hard coat layer is applied onto a transparent substrate film and dried.
The application method is not particularly limited as long as it is a method that can uniformly apply the curable resin composition to the surface of the transparent substrate film, and includes a spin coating method, a dip method, a spray method, a slide coating method, Various methods such as a bar coat method, a roll coater method, a meniscus coater method, a flexographic printing method, a screen printing method, and a speed coater method can be used.
The coating amount on the transparent substrate film varies depending on the performance required for the obtained hard coat film, but the coating amount after drying ranges from 1 g / m ^{2 to} 30 g / m ² . among them, particularly preferably in the range of ^{5g / m 2 ~25g / m 2} .

Examples of the drying method include reduced-pressure drying or heat drying, and a method combining these drying methods. For example, when a ketone solvent is used as the solvent, it is usually dried at a temperature in the range of room temperature to 80 ° C., preferably 40 ° C. to 60 ° C., for 20 seconds to 3 minutes, preferably 30 seconds to 1 minute. A process is performed.
In addition, the reactive inorganic fine particles A uniformly dispersed in the curable resin composition for hard coat layer are unevenly distributed in the vicinity of the interface on the transparent substrate film side in the drying step.

Next, the coating film obtained by applying and drying the curable resin composition for a hard coat layer is applied by light irradiation and / or heating depending on the reactive functional group contained in the curable resin composition. By curing the film, the reactive functional group a of the reactive inorganic fine particle A and the reactive functional group b of the binder component B contained in the constituent components of the curable resin composition are cross-linked, A hard coat layer made of a cured product of the curable resin composition is formed, and the hard coat film of the present invention is obtained.
For light irradiation, ultraviolet rays, visible light, electron beams, ionizing radiation, etc. are mainly used. In the case of ultraviolet curing, ultraviolet rays or the like emitted from light such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, or a metal halide lamp are used. The irradiation amount of the energy ray source is about 50 to 5000 mJ / cm ² as an integrated exposure amount at an ultraviolet wavelength of 365 nm.
When heating, it processes at the temperature of 40 to 120 degreeC normally. Moreover, you may react by leaving it to stand for 24 hours or more at room temperature (25 degreeC).

<Other layers>
The hard coat film according to the present invention is basically constituted by the transparent base film and the hard coat layer as described above. However, in consideration of the function or use as a hard coat film, in addition to the hard coat layer according to the present invention, one or more layers as described below may be further contained. Furthermore, you may form including a middle refractive index layer and a high refractive index layer.

(1) Antistatic layer The antistatic layer comprises an antistatic agent and a resin. The thickness of the antistatic layer is preferably about 30 nm to 1 μm.

  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. Further, it has a tertiary amino group, a quaternary ammonium group, or a metal chelate portion, and has a monomer or oligomer that can be polymerized by ionizing radiation, or a polymerizable functional group that can be polymerized by ionizing radiation, and Polymerizable compounds such as organometallic compounds such as coupling agents can also be used as antistatic agents.

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

As specific examples of the resin contained in the antistatic layer, a thermoplastic resin, a thermosetting resin, a photocurable resin, or a photocurable compound (including an organic reactive silicon compound) can be used. As the resin, a thermoplastic resin can also be used, but it is more preferable to use a thermosetting resin, and more preferably a photocurable composition containing a photocurable resin or a photocurable compound.
As a photocurable composition, the prepolymer, oligomer, and / or monomer which have a polymerizable unsaturated group or an epoxy group in a molecule | numerator are mixed suitably.
Examples of the prepolymer, oligomer, and monomer in the photocurable composition may be the same as those mentioned for the hard coat layer.

  Usually, as the monomer in the photocurable composition, one or two or more types are mixed and used as necessary. In order to give the photocurable composition with a usual coating suitability, the above prepolymer is used. Alternatively, it is preferable that the oligomer is 5% by weight or more and the monomer and / or polythiol compound is 95% by weight or less.

(2) Antiglare layer The antiglare layer may be formed between the transparent resin substrate and the hard coat layer or the low refractive index layer. The antiglare layer comprises a resin and an antiglare agent, and the resin may be the same as that described in the section of the antistatic layer.

According to a preferred embodiment of the present invention, the antiglare layer has an average particle diameter of R (μm), and the maximum value from the substrate surface in the vertical direction of the convex and concave portions of the antiglare layer is Hmax (μm). And the average interval between the irregularities of the antiglare layer is Sm (μm), and the average inclination angle of the irregularities is θa, the following formula:
8R ≦ Sm ≦ 30R
R <Hmax <3R
1.3 ≦ θa ≦ 2.5
1 ≦ R ≦ 8
What satisfies all simultaneously is preferable.

  According to another preferred embodiment of the present invention, when the refractive indexes of the fine particles and the transparent resin composition are n1 and n2, respectively, Δn = | n1−n2 | <0.1 is satisfied, And the anti-glare layer whose haze value inside an anti-glare layer is 55% or less is preferable.

(Anti-glare agent)
Examples of the antiglare agent include fine particles, and the shape of the fine particles may be a true sphere or an ellipse, and preferably a true sphere. The fine particles may be inorganic or organic, but those formed of an organic material are preferred. The fine particles exhibit anti-glare properties and are preferably transparent. Specific examples of the fine particles include plastic beads, and more preferably those having transparency. Specific examples of plastic beads include styrene beads (refractive index 1.59), melamine beads (refractive index 1.57), acrylic beads (refractive index 1.49), acrylic-styrene beads (refractive index 1.54), Examples thereof include polycarbonate beads and polyethylene beads. The addition amount of the fine particles is about 2 to 30 parts by weight, preferably about 10 to 25 parts by weight with respect to 100 parts by weight of the resin composition.

It is preferable to add an antisettling agent when adjusting the composition for the antiglare layer. This is because, by adding an anti-settling agent, precipitation of the anti-glare agent can be suppressed and the anti-glare agent can be uniformly dispersed in the solvent. Specific examples of the anti-settling agent include silica beads having an average particle size of 0.5 μm or less, preferably about 0.1 to 0.25 μm.
The film thickness (when cured) of the antiglare layer is 0.1 to 100 μm, preferably 0.8 to 20 μm. When the film thickness is within this range, the function as an antiglare layer can be sufficiently exhibited.

(3) Low refractive index layer The low refractive index layer is composed of a resin containing silica or magnesium fluoride, a fluorine resin which is a low refractive index resin, silica or a fluorine resin containing magnesium fluoride, It can be composed of a thin film having a refractive index of 1.46 or less, which is also about 30 nm to 1 μm, or a thin film formed by chemical vapor deposition or physical vapor deposition of silica or magnesium fluoride. The resin other than the fluororesin is the same as the resin used for constituting the antistatic layer.

  More preferably, the low refractive index layer can be composed of a silicone-containing vinylidene fluoride copolymer. This silicone-containing vinylidene fluoride copolymer is specifically a monomer containing 30 to 90% vinylidene fluoride and 5 to 50% hexafluoropropylene (including percentages below, all in terms of weight). It is obtained by copolymerization using the composition as a raw material, and comprises 100 parts of a fluorine-containing copolymer having a fluorine content of 60 to 70% and 80 to 150 parts of a polymerizable compound having an ethylenically unsaturated group. A low refractive index having a refractive index of less than 1.60 (preferably 1.46 or less) which is a thin film having a film thickness of 200 nm or less and is provided with scratch resistance by using this resin composition. Form a layer.

In addition, the low refractive index layer also can be formed of a thin film made of SiO _2, an evaporation method, a sputtering method, or a plasma CVD method or the like, or to form a SiO ₂ gel film from the sol solution containing SiO ₂ sol It may be formed by a method. The low refractive index layer, in addition to SiO ₂ also, the or a thin film MgF _2, but may be configured in other materials, in terms of high adhesion to the lower layer, it is preferable to use a SiO ₂ thin film.

According to a preferred embodiment of the low refractive index layer of the present invention, it is preferable to use “fine particles having voids”.
The “fine particles having voids” can reduce the refractive index while maintaining the layer strength of the low refractive index layer. “Fine particles with voids” means a structure in which fine particles are filled with gas and / or a porous structure containing gas, and is inversely proportional to the gas occupancy in the fine particles compared to the original refractive index of the fine particles. Thus, it means a fine particle having a reduced refractive index. The present invention also includes fine particles capable of forming a nanoporous structure inside and / or at least part of the surface depending on the form, structure, aggregation state, and dispersion state of the fine particles inside the coating film. It is.

  The average particle diameter of the “fine particles having voids” is 5 nm or more and 300 nm or less, preferably the lower limit is 8 nm or more and the upper limit is 100 nm or less, more preferably the lower limit is 10 nm or more and the upper limit is 80 nm or less. When the average particle diameter of the fine particles is within this range, excellent transparency can be imparted to the low refractive index layer.

(4) Antifouling layer According to a preferred embodiment of the present invention, an antifouling layer may be provided for the purpose of preventing contamination on the outermost surface of the low refractive index layer. The antifouling layer can further improve the antifouling property and scratch resistance of the hard coat film.

  Specific examples of the antifouling agent include fluorine compounds and / or silicon that have low compatibility with the photocurable resin composition having fluorine atoms in the molecule and are difficult to add to the low refractive index layer. And a fluorine-based compound and / or a siliceous compound having compatibility with fine particles, a photocurable resin composition having a fluorine atom in the molecule, and fine particles.

  Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention. In the examples, parts represent parts by weight unless otherwise specified.

(Production Example 1: Preparation of reactive inorganic fine particles A (1))
(1) Surface adsorbed ion removal Water-dispersed colloidal silica (Snowtex ZL, trade name, manufactured by Nissan Chemical Industries, Ltd., pH 9 to 10) having a particle diameter of 90 nm is converted to a cation exchange resin (Diaion SK1B, Mitsubishi Chemical Corporation). The product was ion-exchanged for 3 hours using 400 g, and then ion-exchanged for 3 hours using 200 g of an anion exchange resin (Diaion SA20A, manufactured by Mitsubishi Chemical Corporation), followed by washing and solid content concentration of 20 An aqueous dispersion of wt% inorganic fine particles was obtained.
At this time, the Na ₂ O content of the aqueous dispersion of inorganic fine particles was 7 ppm for each inorganic fine particle.
(2) Surface treatment (introduction of monofunctional monomer)
150 g of isopropanol, 4.0 g of 3,6,9-trioxadecanoic acid, and 4.0 g of methacrylic acid are added to 10 g of the aqueous dispersion of inorganic fine particles subjected to the treatment of (1) above and stirred for 30 minutes. Mixed.
The obtained mixed liquid was stirred while being heated at 60 ° C. for 5 hours to obtain an inorganic fine particle dispersion liquid in which methacryloyl groups were introduced on the surface of the inorganic fine particles. Distilled water and isopropanol were distilled off using a rotary evaporator to the obtained inorganic fine particle dispersion, and while adding methyl ethyl ketone so as not to dry, the final residual water and isopropanol were 0.1% by weight, A silica-dispersed methyl ethyl ketone solution having a solid content of 50% by weight was obtained.
The reactive inorganic fine particles A (1) thus obtained had an average particle size of d ₅₀ = 93 nm as a result of measurement with a Microtrac particle size analyzer manufactured by Nikkiso Co., Ltd. The amount of the organic component covering the surface of the inorganic fine particles was 4.05 × 10 ⁻³ g / m ² as a result of measurement by thermogravimetric analysis.

(Production Example 2: Preparation of reactive inorganic fine particles A (2))
(1) Removal of surface adsorbed ions As in Production Example 1, an aqueous dispersion of inorganic fine particles from which surface adsorbed ions were removed was obtained.
(2) Surface treatment (introduction of polyfunctional monomer)
Surface treatment was performed in the same manner as in Production Example 1 except that methacrylic acid was changed to dipentaerythritol pentaacrylate (SR399, trade name, manufactured by Sartomer Co., Ltd.) in Production Example 1.
The reactive inorganic fine particles A (2) thus obtained had an average particle diameter of d ₅₀ = 93 nm as a result of measurement using the particle size analyzer. The amount of the organic component covering the surface of the inorganic fine particles was 3.84 × 10 ⁻³ g / m ² as a result of measurement by thermogravimetric analysis.

(Production Example 3: Preparation of reactive inorganic fine particles A (3))
To a solution consisting of 7.8 parts of mercaptopropyltrimethoxysilane and 0.2 part of dibutyltin dilaurate in dry air, 20.6 parts of isophorone diisocyanate was added dropwise at 50 ° C. over 1 hour and then at 60 ° C. Stir for 3 hours. To this, 71.4 parts of pentaerythritol triacrylate was added dropwise at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 3 hours to obtain Compound (1).

Under a nitrogen stream, methanol silica sol (manufactured by Catalyst Chemicals Co., Ltd., trade name, OSCAL series, methanol dispersion, number average particle size 45 nm) 88.5 parts (solid content 26.6 parts), compound synthesized above (1 ) A mixed solution of 8.5 parts and 0.01 part of p-methoxyphenol was stirred at 60 ° C. for 4 hours. Subsequently, 3 parts of methyltrimethoxysilane as compound (2) is added to this mixed solution, and after stirring for 1 hour at 60 ° C., 9 parts of methyl orthoformate is added, and further heated and stirred at the same temperature for 1 hour. Thus, crosslinkable inorganic fine particles were obtained. The reactive inorganic fine particles A (3) thus obtained had an average particle diameter of d ₅₀ = 49 nm as a result of measurement by the particle size analyzer. Moreover, the amount of organic components covering the surface was 7.08 × 10 ⁻³ g / m ² as a result of measurement by thermogravimetric analysis.

<Example 1>
(1) Preparation of curable resin composition for hard coat layer The following components were mixed and adjusted to a solid content of 50% by weight with a solvent to prepare a curable resin composition for a hard coat layer.
<Composition of curable resin composition for hard coat layer>
UV1700B (trade name, manufactured by Nippon Synthetic Chemical, urethane acrylate, 10 functional, molecular weight 2000): 70 parts by weight (converted into solid content)
Reactive inorganic fine particles A (1) of Production Example 1 (average particle diameter 93 nm): 30 parts by weight (in terms of solid content)
・ Methyl ethyl ketone: 100 parts by weight ・ Irgacure 184 (trade name, manufactured by Ciba Specialty Chemicals, radical polymerization initiator): 0.4 parts by weight

(2) Production of Hard Coat Film Using a 80 μm cellulose triacetate film as a transparent substrate film, the hard coat layer curable resin composition prepared in (1) was applied on the substrate with a WET weight of 40 g / m ² ( A dry weight of 20 g / m ² ) was applied. It dried at 50 degreeC for 30 ^second, and irradiated the ultraviolet-ray 200mJ / cm < ² >, and produced the hard coat film of Example 1. FIG.

<Example 2>
In the production of the hard coat film of Example 1, 30 parts by weight of the reactive inorganic fine particles A (2) obtained in Production Example 2 were used instead of the reactive inorganic fine particles A (1) obtained in Production Example 1. A hard coat film was obtained in the same manner as in Example 1 except that.

<Example 3>
In the production of the hard coat film of Example 1, instead of the reactive inorganic fine particles A (1) obtained in Production Example 1, the reactive inorganic fine particles A (3) obtained in Production Example 3 were used for 30 parts by weight. A hard coat film was obtained in the same manner as in Example 1 except that.

<Example 4>
In the production of the hard coat film of Example 1, the average particle size of the reactive inorganic fine particles A (1) obtained in Production Example 1 was d ₅₀ = 63 nm, and the binder component B was dipentaerythritol hexaacrylate (DPHA). A hard coat film was obtained in the same manner as in Example 1 except that 70 parts by weight was used.

<Example 5>
Example 3 except that in the production of the hard coat film of Example 3, 90 parts by weight of UV1700B and 10 parts by weight of the reactive inorganic fine particles A (3) obtained in Production Example 3 were used as the binder component B. In the same manner, a hard coat film was obtained.

<Example 6>
Example 3 except that 40 parts by weight of UV1700B and 60 parts by weight of reactive inorganic fine particles A (3) obtained in Production Example 3 were used as binder component B in the production of the hard coat film of Example 3. In the same manner as above, a hard coat film was obtained.

<Example 7>
In the production of the hard coat film of Example 3, the hard coat film was prepared in the same manner as in Example 3 except that the average particle size of the reactive inorganic fine particles A (3) obtained in Production Example 3 was d ₅₀ = 32 nm. A film was obtained.

<Example 8>
In the production of the hard coat film of Example 3, the hard coat film was prepared in the same manner as in Example 3 except that the average particle size of the reactive inorganic fine particles A (3) obtained in Production Example 3 was set to d ₅₀ = 100 nm. A film was obtained.

<Example 9>
In the production of the hard coat film of Example 3, 50 parts by weight of UV1700B and 20 parts by weight of beam set 371 (trade name, manufactured by Arakawa Chemical Industries, Ltd., polymer acrylate, molecular weight 30000) were used as binder component B. Obtained a hard coat film in the same manner as in Example 3.

<Comparative Example 1>
In the production of the hard coat film of Example 1, in place of the reactive inorganic fine particles A, average particle size _d 50 = 60 nm colloidal silica: 30 weight (MEK-ST trade name, manufactured by Nissan Chemical Industries, Ltd.) was A hard coat film was obtained in the same manner as in Example 1 except for using a part.

<Comparative example 2>
In the production of the hard coat film of Example 3, the hard coat film was prepared in the same manner as in Example 3 except that the average particle diameter of the reactive inorganic fine particles A (3) obtained in Production Example 3 was set to d ₅₀ = 20 nm. A film was obtained.

〔Evaluation methods〕
The following points were evaluated with respect to the above examples and comparative examples. The results are listed in Table 1.
(1) Saponification resistance The obtained hard coat film (A4: 2 sheets) is immersed in 200 ml of 2N aqueous sodium hydroxide solution at 60 ° C. for 2 minutes, and the hard coat film is washed with pure water to be saponified. Did. Next, a sodium hydroxide aqueous solution after the saponification treatment was collected, concentrated by heating at 100 ° C., added with pure water, and further acidified with nitric acid. Evaluation was made by measuring the Si content in the aqueous sodium hydroxide solution by ICP emission spectroscopy.
<Evaluation criteria>
Evaluation A: The Si content in the aqueous sodium hydroxide solution was less than 2.0 μg / g.
Evaluation (circle): Si content in sodium hydroxide aqueous solution was 2.0-8.0 microgram / g.
Evaluation x: The Si content in the sodium hydroxide aqueous solution exceeded 8.0 μg / g.

(2) Pencil hardness The pencil hardness of the hard coat layer surface of the obtained hard coat film was evaluated according to JISK5600-5-4 (1999). Using a 4H pencil, five lines were drawn with a load of 500 g, and the subsequent hard coat layer was visually checked for scratches and evaluated according to the following criteria.
<Evaluation criteria>
Evaluation A: The number of scratches was 0 to 1.
Evaluation ○: There were 2 to 3 scratches.
Evaluation x: There were 4 to 5 scratches.

It is a figure which shows the basic layer structure of the hard coat film which concerns on this invention. It is the figure which showed typically an example of the mode of distribution of the reactive inorganic fine particle A in the cross section of the layer thickness direction of the hard coat film which concerns on this invention. It is the figure which showed typically an example of the mode of distribution of the reactive inorganic fine particle A in the cross section of the surface direction of the hard coat film which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Hard coat film 2 Hard coat layer 3 Transparent base film 4 Reactive inorganic fine particle A
P1 Cross section in the layer thickness direction of the hard coat layer P2 Cross section in the surface direction of the hard coat layer 30 Interface on the opposite side of the transparent base film side of the hard coat layer 40 Interface on the transparent base film side of the hard coat layer

Claims (14)

A hard coat film provided with a hard coat layer on a transparent substrate film,
Reactive inorganic fine particles A in which the hard coat layer has an average particle diameter of 30 nm or more and 100 nm or less, at least a part of the surface is coated with an organic component, and has a reactive functional group a introduced by the organic component on the surface. And a hard binder containing a binder component B having a reactive functional group b having a crosslinking reactivity with the reactive functional group a of the reactive inorganic fine particles A, and also having a curing reactivity in the system It consists of a cured product of a curable resin composition for a coat layer, has a density distribution of the reactive inorganic fine particles A in the thickness direction of the hard coat layer, and is on the side opposite to the transparent substrate film side of the hard coat layer. The density of the reactive inorganic fine particles A is the lowest at the interface, and the reactive inorganic fine particles A are present at or near the transparent substrate film side interface of the hard coat layer. Degrees, wherein the highest, the hard coat film. The cross section of the hard coat layer in the thickness direction of the hard coat layer is P1, and the vertical density of the reactive inorganic fine particles A in the cross section P1 is the density of the reactive inorganic fine particles A present per unit area of the cross section P1. When the number of particles (μm ² ) is determined, the density of the reactive inorganic fine particles A at an arbitrary position in the region from the interface opposite to the transparent substrate film side of the cross section P1 to a depth of 500 nm is 150. The hard coat film according to claim 1, wherein the hard coat film is ² pieces / μm ² or less.   The number of the reactive inorganic fine particles A partially protruding from the interface opposite to the transparent substrate film side of the hard coat layer is 150 or less per unit area of the interface, The hard coat film according to claim 1 or 2. The cross section of the hard coat layer according to the surface direction of the hard coat layer is P2, and the planar density of the reactive inorganic fine particles A in the cross section P2 is the density of the reactive inorganic fine particles A present per unit area of the cross section P2. When the number (pieces / μm ² ) is determined, the density difference of the reactive inorganic fine particles A at two arbitrary positions in the cross section P2 at an arbitrary height of the hard coat layer is 30 / μm ² or less. The hard coat film according to claim 1, wherein the hard coat film is provided. 5. The organic component covering the reactive inorganic fine particles A is contained in an amount of 1.00 × 10 ⁻³ g / m ² or more per unit area of the inorganic fine particles before coating. Hard coat film as described in any one of these.   The reactive inorganic fine particles A are saturated or unsaturated carboxylic acid, acid anhydride, acid chloride, ester and acid amide, amino acid, imine, nitrile, isonitrile, epoxy compound, amine, β-dicarboxylic acid corresponding to the carboxylic acid. Inorganic fine particles in water and / or an organic solvent as a dispersion medium in the presence of one or more surface modification compounds having a molecular weight of 500 or less selected from the group consisting of carbonyl compounds, silanes, and metal compounds having functional groups It is obtained by making it disperse | distribute, The hard coat film as described in any one of Claims 1 thru | or 5 characterized by the above-mentioned.   The hard coat film according to claim 6, wherein the surface modifying compound is a compound having at least one hydrogen bond-forming group.   The hard coat film according to claim 6 or 7, wherein at least one of the surface modification compounds has a polymerizable unsaturated group. The reactive inorganic fine particles A include a reactive functional group introduced on the surface of the inorganic 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; The hard coat film according to claim 1, wherein the hard coat film is obtained by bonding with metal oxide fine particles.
Chemical formula (1)
^{-Q 1 -C (= Q 2)} -NH-
(In the chemical formula (1), Q ¹ represents NH, O (oxygen atom), or S (sulfur atom), and Q ² represents O or S.)   10. The hard coat film according to claim 1, wherein the content of the reactive inorganic fine particles A is 10 to 60 wt% with respect to the total solid content.   The hard coat film according to any one of claims 1 to 10, wherein the binder component B is a compound having three or more of the reactive functional groups b.   The hard coat film according to any one of claims 1 to 11, wherein the transparent base film is mainly composed of cellulose acylate, cycloolefin polymer, acrylate polymer, or polyester.   The hard coat film according to any one of claims 1 to 12, wherein the hard coat layer has a thickness of 1 µm or more and 100 µm or less.   The hard coat film according to any one of claims 1 to 13, wherein the hardness of the hard coat layer according to JISK5600-5-4 (1999) is 4H or more.

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