JP2010083935A - Manufacturing method of hard coat film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a hard coat film having excellent hardness and capable of preventing generation of interference fringes. <P>SOLUTION: In the manufacturing method of the hard coat film 1, a curable resin composition for a hard coat layer 20 including silica fine particles having 10 to 100 nm average particle diameter, a binder component and a non-permeable solvent and having 30 to 70 wt.% content of the silica fine particles to the total solid content is applied on one surface side of a triacetyl cellulose base material and cured to form the hard coat layer. The silica fine particles are reactive silica fine particles having reactive groups having crosslinking reactivity between the fine particles and/or to the binder component. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a hard coat film in which a hard coat layer is provided 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.

  However, in an optical laminated body in which layers having a large difference in refractive index are laminated, it is often seen that interface reflection and interference fringes occur at the interface between the layers that overlap each other. In particular, it has been pointed out that when black is reproduced on the image display surface of the image display device, interference fringes are conspicuously generated, and as a result, the visibility of the image is lowered and the aesthetic appearance of the image display surface is impaired. Yes. In particular, when the refractive index of the base film is different from the refractive index of the hard coat layer, interference fringes are likely to occur.

  In patent document 1, the hard-coat layer which hardened the coating composition for hard-coat layers containing an acryl-type and / or methacryl-type resin on a base film is provided, Between a base film and a hard-coat layer, A boundary layer in which the resin for forming the base film and the resin for forming the hard coat layer are mixed is provided to improve the hardness and adhesion and prevent the occurrence of interference fringes.

As a method for improving the hardness of the hard coat layer, there is a method of adding silica fine particles. Generally, a hard coat film in which a hard coat layer with silica fine particles added is provided on a base film is manufactured.
Generally, the resin contained in the hard coat layer has a higher refractive index than the resin forming the base film, but the silica fine particles have a lower refractive index than the resin contained in the hard coat layer, and the entire hard coat layer As a result, the refractive index is brought close to the refractive index of the base film, thereby preventing the occurrence of interference fringes.

  However, when the hard coat film has a boundary layer as in Patent Document 1 and silica particles having a low refractive index are included in the hard coat layer in order to improve hardness, the boundary layer contains a resin having a high refractive index. Since the silica fine particles having a low refractive index are not included, the refractive index becomes higher than that of the adjacent base film and hard coat layer. That is, there is a problem that a refractive index difference occurs between the base film and the hard coat layer adjacent to the boundary layer, and interference fringes are generated.

JP 2008-012675 A

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a hard coat film that is excellent in hardness and can prevent generation of interference fringes.

As a result of intensive studies on the above problems, the present inventors have not made the resin (binder component) of the hard coat layer penetrate into the base film, and the base film resin and the hard coat as in the boundary layer described above. The present invention is completed by finding that both the hardness and the prevention of interference fringes can be achieved by not forming a region (layer) that does not contain silica fine particles having the effect of lowering the refractive index, although the resin of the layer is mixed. It came to.
That is, the features of the present invention that solve the above problems are as follows.

  The method for producing a hard coat film according to the present invention comprises silica fine particles having an average particle size of 10 to 100 nm, a binder component and a non-penetrable solvent on one side of a triacetyl cellulose base material. A hard coat layer is formed by applying and curing a curable resin composition for a hard coat layer having a content ratio of 30 to 70% by weight.

  Silica fine particles having an average particle size of 10 to 100 nm have a low refractive index, excellent hardness, and the silica fine particles are contained in an amount of 30 to 70% by weight based on the total solid content of the curable resin composition for hard coat layers. Hardness is imparted to the hard coat layer, and the refractive index of the entire hard coat layer is reduced.

  Since the non-permeable solvent does not penetrate into the triacetyl cellulose base material, which is a base material, the formation of a region having a high refractive index in which triacetyl cellulose and a binder component are mixed is suppressed, and interference fringes are prevented from being generated.

  In the method for producing a hard coat film according to the present invention, the silica fine particles are reactive silica fine particles having a reactive functional group having cross-linking reactivity with the fine particles and / or the binder component. From the point of view, it is preferable.

  In the method for producing a hard coat film according to the present invention, the binder component is pentaerythritol triacrylate and / or dipentaerythritol hexaacrylate from the viewpoint of improving the adhesion between the hard coat layer and the triacetyl cellulose base material. preferable.

  In the method for producing a hard coat film according to the present invention, the non-permeable solvent is a group consisting of methyl isobutyl ketone, propylene glycol monomethyl ether, normal propanol, isopropanol, normal butanol, sec-butanol, isobutanol, and tert-butanol. It is preferable that it is 1 or more types chosen from.

  In the present invention, osmosis means dissolving or swelling a triacetylcellulose base material.

In the present invention, the average particle diameter of the fine particles is a 50% particle diameter (d50 median diameter) when the fine particles in the solution are measured by a dynamic light scattering method and the particle size distribution is represented by a cumulative distribution. means. The said average particle diameter can be measured using the Nikkiso Co., Ltd. Microtrac particle size analyzer or Nanotrac particle size analyzer.
The fine particles may be agglomerated particles, and in the case of agglomerated particles, the secondary particle diameter may be within the above range.
The measurement of the refractive index is not particularly limited, and a conventionally known method can be used. For example, a method of calculating from a reflectance curve measured with a spectrophotometer using a simulation, a method of measuring using an ellipsometer, and an Abbe method can be mentioned.

  In this invention, a hard-coat layer means the thing which shows the hardness more than H by the pencil hardness test (4.9N load) prescribed | regulated to JISK5600-5-4 (1999).

  The present invention has an effect that it is possible to provide a hard coat film that can achieve both excellent hardness and prevention of occurrence of interference fringes.

  Hereinafter, the manufacturing method of the hard coat film of the present invention will be described first, and then the hard coat film, the transparent base film that is an essential component thereof, and the hard coat layer will be described in order.

In the present invention, (meth) acrylate represents acrylate and / or methacrylate.
In the present invention, the “hard coat layer” generally indicates a hardness of “H” or higher in a pencil hardness test (4.9 N load) defined by JIS K5600-5-4 (1999).
The light of the present invention includes not only electromagnetic waves having wavelengths in the visible and non-visible regions, but also particle beams such as electron beams, and radiation or ionizing radiation that collectively refers to electromagnetic waves and particle beams.
Moreover, in this invention, a film thickness means the film thickness at the time of drying (dry film thickness).
In the present invention, the molecular weight means a weight average molecular weight which is a polystyrene equivalent value measured by gel permeation chromatography (GPC) when having a molecular weight distribution, and when having no molecular weight distribution, Mean molecular weight.
In the present invention, the average particle diameter of the fine particles 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 size distribution is represented by a cumulative distribution. . The said average particle diameter can be measured using the Nikkiso Co., Ltd. Microtrac particle size analyzer or Nanotrac particle size analyzer.
The fine particles may be agglomerated particles, and in the case of agglomerated particles, the secondary particle diameter may be within the above range.
The measurement of the refractive index is not particularly limited, and a conventionally known method can be used. For example, a method of calculating from a reflectance curve measured with a spectrophotometer using a simulation, a method of measuring using an ellipsometer, and an Abbe method can be mentioned.

1. Method for Producing Hard Coat Film A method for producing a hard coat film according to the present invention comprises silica fine particles having an average particle size of 10 to 100 nm, a binder component and a non-permeable solvent on one side of a triacetyl cellulose base material, A hard coat layer is formed by applying and curing a curable resin composition for a hard coat layer in which the content of the silica fine particles is 30 to 70% by weight with respect to the content.

  Silica fine particles having an average particle size of 10 to 100 nm have a low refractive index, excellent hardness, and the silica fine particles are contained in an amount of 30 to 70% by weight based on the total solid content of the curable resin composition for hard coat layers. Hardness is imparted to the hard coat layer, and the refractive index of the entire hard coat layer is reduced.

The average particle diameter of the silica fine particles is 10 to 100 nm, preferably 12 to 50 nm. When the average particle size is less than 10 nm, sufficient hardness cannot be imparted to the hard coat layer, and the triacetyl cellulose substrate adjacent to the hard coat layer and, if necessary, the triacetyl cellulose substrate of the hard coat layer Since the contact area between the other layer provided on the opposite side and the silica fine particles increases, the adhesion to the substrate may be deteriorated.
If it exceeds 100 nm, the transparency of the hard coat layer is lowered, leading to deterioration in transmittance and increase in haze.

  Silica fine particles are contained in an amount of 30 to 70% by weight, preferably 40 to 60% by weight, based on the total solid content of the hard coat layer curable resin composition. If it is less than 30% by weight, sufficient hardness cannot be imparted to the hard coat layer, and the refractive index of the hard coat layer cannot be lowered sufficiently, resulting in a large difference in refractive index from the triacetyl cellulose substrate, resulting in interference. It becomes easy to prevent the generation of stripes. When it exceeds 70% by weight, the filling rate is excessively increased, the adhesion between the silica fine particles and the binder component is deteriorated, and the hardness of the hard coat layer is lowered.

  The binder component is a component that becomes a matrix of the hard coat layer when cured.

  Since the non-permeable solvent does not penetrate into the triacetyl cellulose base material, which is a base material, the formation of a region having a high refractive index in which triacetyl cellulose and a binder component are mixed is suppressed, and interference fringes are prevented from being generated.

  In the method for producing a hard coat film according to the present invention, the silica fine particles are reactive silica fine particles having a reactive functional group having cross-linking reactivity with the fine particles and / or the binder component. From the point of view, it is preferable.

  In the method for producing a hard coat film according to the present invention, the binder component is pentaerythritol triacrylate and / or dipentaerythritol hexaacrylate from the viewpoint of improving the adhesion between the hard coat layer and the triacetyl cellulose base material. preferable.

  In the method for producing a hard coat film according to the present invention, the non-permeable solvent is a group consisting of methyl isobutyl ketone, propylene glycol monomethyl ether, normal propanol, isopropanol, normal butanol, sec-butanol, isobutanol, and tert-butanol. One or more selected from the above is preferable because the permeability is moderate and the dispersibility of the silica fine particles contained in the hard coat layer curable resin composition is excellent.

(Method for forming hard coat layer)
The hard coat layer may be formed by a conventionally known method.
For example, the prepared curable resin composition for a hard coat layer is applied to one side of a triacetyl cellulose substrate, a coating film is formed, and drying is performed as necessary. Hardened by heat to form a hard coat layer.

  The curable resin composition for a hard coat layer is usually prepared by mixing and dispersing a non-permeable solvent in addition to silica fine particles and a binder component, a polymerization initiator, and the like according to a general preparation method. A paint shaker or a bead mill can be used for mixing and dispersing.

The application method is not particularly limited as long as it is a method capable of uniformly applying the curable resin composition for the hard coat layer to the surface of the triacetyl cellulose substrate, and the spin coating method, the dip method, the spray method, Various methods such as a slide coating method, a bar coating method, a roll coater method, a meniscus coater method, a flexographic printing method, a screen printing method, and a speed coater method can be used.
The coating amount of the curable resin composition for the hard coat layer on the triacetyl cellulose substrate varies depending on the performance required of the obtained hard coat film, but the coating amount after drying is different. in the range of ^{1g / m 2 ~30g / m 2} , 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 for the curable resin composition for the hard coat layer, it is usually room temperature to 80 ° C., preferably 40 ° C. to 70 ° C., preferably 20 seconds to 3 minutes, preferably The drying process is performed in a time of about 30 seconds to 1 minute.

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

For light irradiation, ultraviolet rays, visible light, electron beams, ionizing radiation, etc. are mainly used. In the case of ultraviolet curing, ultraviolet rays 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).

2. Hard Coat Film The hard coat film of the present invention has a hard coat layer provided on one side of a triacetyl cellulose substrate.
The hard coat film of the present invention is added with other layers such as an antistatic layer, an antistatic layer on the surface of the hard coat layer opposite to the triacetyl cellulose base material in consideration of the function or use as the hard coat film. One or more layers selected from the group consisting of a glare layer, a low refractive index layer, an antifouling layer, and a second hard coat layer that is the same as or different from the hard coat layer may be formed.
Further, the hard coat film of the present invention may be provided with an antistatic function or an antiglare function when the hard coat layer contains an antistatic agent or an antiglare agent.

  The hard coat film of the present invention is preferably 4H or more in the pencil hardness test.

FIG. 1 is a cross-sectional view schematically showing an example of the layer structure of the hard coat film 1 of the present invention. A hard coat layer 20 is provided on one side of the triacetyl cellulose substrate 10.
Between the triacetyl cellulose base material 10 and the hard coat layer 20, an osmotic layer into which the binder component of the hard coat layer has penetrated is not formed.
FIG. 2 is a cross-sectional view schematically showing another example of the layer configuration of the hard coat film 1 of the present invention. A hard coat layer 20, an antistatic layer 30, and a low refractive index layer 40 are provided in this order on one side of the triacetyl cellulose substrate 10.

  Hereinafter, the triacetyl cellulose base material, which is an essential component of the hard coat film of the present invention, and the hard coat layer, and an antistatic layer, an antiglare layer, a low refractive index layer, an antistatic layer that can be appropriately provided as necessary. The dirty layer and one or more other layers selected from the group consisting of the second hard coat layer that is the same as or different from the hard coat layer will be described in order.

2-1. Triacetylcellulose base material The triacetylcellulose base material used for this invention is a plastic film or sheet | seat with high transparency (light transmittance).
The material is not particularly limited as long as it satisfies the physical properties that can be used as the transparent substrate of the optical laminate, and can be appropriately selected and used.

  Generally, the refractive index of the triacetyl cellulose base material is 1.465 to 1.485, but it is preferable to use the one of 1.47 to 1.48.

  Usually, the base material used for the optical layered body is transparent, translucent, colorless, or colored, but is required to have optical transparency. In addition, the measurement of light transmittance uses the value measured in room temperature and air | atmosphere using the ultraviolet visible spectrophotometer (For example, Shimadzu Corporation UV-3100PC).

A triacetyl cellulose base material is a light-transmitting base material capable of setting an average light transmittance to 50% or more in a visible light region of 380 to 780 nm. The average light transmittance of the triacetyl cellulose base material is preferably 70% or more, and more preferably 85% or more.
Since the triacetyl cellulose base material has optical isotropy, it can be preferably used even in the case of a liquid crystal display application.

  In addition, as triacetyl cellulose in the present invention, in addition to pure triacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, and the like are used in combination with components other than acetic acid as fatty acids forming cellulose and esters. There may be. These triacetyl celluloses may be added with other cellulose lower fatty acid esters such as diacetyl cellulose or various additives such as a plasticizer, an antistatic agent, and an ultraviolet absorber as required.

  In the present invention, the thickness of the triacetyl cellulose base material can be appropriately selected and used. It is preferable to use a 20-120 μm triacetyl cellulose base material, and it is more preferable that it is 20-80 μm.

2-2. Hard coat layer The hard coat layer of the present invention comprises a cured product of a curable resin composition for a hard coat layer containing at least silica fine particles having an average particle diameter of 10 to 100 nm, a binder component and a non-permeable solvent.
In the present invention, the “hard coat layer” indicates a hardness of H or higher in the pencil hardness test (4.9 N load) defined in JIS K5600-5-4 (1999) as described above.
The hard coat film of the present invention is preferably 4H or more in the pencil hardness test.

  The film thickness of the hard coat layer can be appropriately selected according to the strength and required performance of the substrate, and is not particularly limited, but is preferably in the range of 1 to 100 μm, and more preferably 5 to 30 μm.

(Curable composition for hard coat layer)
The curable composition for hard coat layers of the present invention will be described.
The curable composition for a hard coat layer of the present invention contains fine silica particles, a binder component and a non-permeable solvent, and in addition, for the purpose of imparting functionality, an antiglare agent, an antifouling agent, an antistatic agent, and a coating As appropriate control, a leveling agent, a solvent, and a lubricant may be contained for the purpose of blocking prevention.

(Silica fine particles)
Silica fine particles are a component for imparting hardness to the hard coat layer.
By containing 30 to 70% by weight of silica fine particles having an average particle diameter of 10 to 100 nm in the curable resin composition for hard coat layer with respect to the total solid content of the curable resin composition for hard coat layer, the hard coat layer Can be imparted with excellent hardness.

  The silica fine particles may be agglomerated particles as long as the average particle size is 10 to 100 nm, and in the case of agglomerated particles, the secondary particle size may be within the above range. The average particle size of the silica fine particles is preferably 12 to 50 nm. When the average particle diameter of the silica fine particles is less than 10 nm, sufficient hardness cannot be imparted to the hard coat layer, and when the average particle diameter exceeds 100 nm, the transparency of the hard coat layer is lowered.

  The silica fine particles preferably have a narrow particle size distribution and are monodispersed from the viewpoint of improving hardness while maintaining the restoration rate when only the binder component described later is used without impairing transparency. .

  Silica fine particles are contained in an amount of 30 to 70% by weight, preferably 40 to 60% by weight, based on the total solid content of the hard coat layer curable resin composition. If it is less than 30% by weight, sufficient hardness cannot be imparted to the hard coat layer, and the refractive index of the hard coat layer cannot be lowered sufficiently. When it exceeds 70% by weight, the filling rate is excessively increased, and on the contrary, the hardness of the hard coat layer is lowered.

  The silica fine particles may be used not only with a single material or a single average particle diameter, but also with a combination of two or more types having different materials and average particle diameters. When two or more types are used in combination, the average particle diameter of each particle may be within 10 to 100 nm and the total weight% of each particle may be 30 to 70% by weight.

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

  The silica fine particle is a reactive silica fine particle having a reactive functional group a capable of forming a covalent bond by crosslinking reaction between the silica fine particles on the surface of the silica fine particles or a binder component described later. It is preferable that The hardness of the hard coat layer can be further improved by crosslinking reaction between the reactive silica fine particles or between the reactive silica fine particles and the binder component.

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

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

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

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

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

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

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

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

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

  The reactive functional group a introduced to the surface so that the reactive silica fine particles can react with the binder component described later is appropriately selected according to the binder component. As the reactive functional group a, a polymerizable unsaturated group is suitably used, preferably a photocurable unsaturated group, and particularly preferably an ionizing radiation curable unsaturated group. Specific examples thereof include ethylenically unsaturated bonds such as (meth) acryloyl group, vinyl group and allyl group, and epoxy group.

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

  On the other hand, the surface of the reactive silica fine particles of (i) above is obtained by containing a second reactive functional group in the molecular residue of the surface modifying compound and using the second reactive functional group as a foothold. A reactive functional group a capable of reacting with the binder component may be introduced. For example, a group capable of hydrogen bonding (hydrogen bond forming group) such as a hydroxyl group and an oxy group is introduced as the second reactive functional group, and another hydrogen bond forming group introduced on the surface of the fine particles It is preferable to introduce a reactive functional group a capable of reacting with the binder component when the hydrogen bond forming group of the surface modifying compound reacts. That is, as the surface modification compound, it is preferable to use a compound having a hydrogen bond-forming group and a compound having a reactive functional group a capable of reacting with a binder component such as a polymerizable unsaturated group and a compound having a hydrogen bond-forming group in combination. An example. Specific examples of the hydrogen bond-forming group indicate a functional group such as a hydroxyl group, a carboxyl group, an epoxy group, a glycidyl group, an amide group, or an amide bond. Here, the amide bond indicates that the bond unit contains —NHC (O) or> NC (O) —. Among the hydrogen bond forming groups used in the surface modification compound of the present invention, among them, a carboxyl group, a hydroxyl group, and an amide group are preferable.

  The surface-modifying compound used in the reactive silica fine particles (i) has a molecular weight of 500 or less, more preferably 400, particularly 200. Since it has such a low molecular weight, it is presumed that the surface of the silica fine particles can be rapidly occupied and aggregation of the silica fine particles can be prevented.

  The surface modifying compound used in the reactive silica fine particles (i) is preferably a liquid under the reaction conditions for surface modification, and is preferably soluble or at least emulsifiable in a dispersion medium. Among these, it is preferable that the polymer is dissolved in the dispersion medium and uniformly distributed as discrete molecules or molecular ions in the dispersion medium.

  Saturated or unsaturated carboxylic acids have 1 to 24 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, acrylic acid, methacrylic acid, crotonic acid, citric acid, Examples include adipic acid, succinic acid, glutaric acid, oxalic acid, maleic acid, fumaric acid, itaconic acid and stearic acid, and the corresponding acid anhydrides, chlorides, esters and amides such as caprolactam. Further, when an unsaturated carboxylic acid is used, a polymerizable unsaturated group can be introduced.

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

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

  Preferred silanes are hydrolyzable organosilanes having at least one hydrolyzable group or hydroxy group and at least one non-hydrolyzable residue. Here, examples of the hydrolyzable group include a halogen, an alkoxy group, and an acyloxy group. As the non-hydrolyzable residue, a non-hydrolyzable residue having a reactive functional group a and / or not having a reactive functional group a is used. Silanes having at least partially organic residues substituted with fluorine may also be used.

As the silane used is not particularly limited, for _{example, CH 2 = CHSi (OOCCH 3} ) 3, CH 2 = CHSiCl 3, CH 2 = CHSi (OC 2 H 5) 3, CH 2 = CHSi (OC 2 H _{4 OCH 3) 3, CH 2} = CH-CH 2 -Si (OC 2 H 5) 3, CH 2 = CH-CH 2 -Si (OOCCH 3) 3, γ- glycidyloxypropyltrimethoxysilane (GPTS), γ-glycidyloxypropyldimethylchlorosilane, 3-aminopropyltrimethoxysilane (APTS), 3-aminopropyltriethoxysilane (APTES), N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- [ N '-(2'-aminoethyl) -2-aminoethyl] -3-aminopropyltrimethoxy Sisilane, hydroxymethyltrimethoxysilane, 2- [methoxy (polyethyleneoxy) propyl] trimethoxysilane, bis- (hydroxyethyl) -3-aminopropyltriethoxysilane, N-hydroxyethyl-N-methylaminopropyltriethoxysilane , 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, and the like.
The silane coupling agent is not particularly limited, and examples thereof include known ones. For example, KBM-502, KBM-503, KBE-502, KBE-503 (trade names, all of which are Shin-Etsu Chemical ( And the like).

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

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

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

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

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

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

In the reactive functional group-modified hydrolyzable silane, the [—Q ¹ —C (═Q ² ) —] moiety of the group represented by the chemical formula (1) is specifically [—O—C (═O )-], [-OC (= S)-], [-SC (= O)-], [-NH-C (= O)-], [-NH-C (= S)- ] And [-S-C (= S)-]. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, at least of a [—O—C (═O) —] group, a [—O—C (═S) —] group, and a [—S—C (═O) —] group. It is preferable to use one type in combination. The group [—Q ¹ —C (= Q ² ) —Q ³ —] represented by the chemical formula (1) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical properties when formed into a cured product. It is considered that properties such as strength, adhesion to a substrate and heat resistance can be imparted.

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

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

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

In the chemical formulas (2) and (3), R ^c is a divalent organic group having a C ₁ to C ₁₂ aliphatic or aromatic structure, and may contain a chain, branched or cyclic structure. . Examples of such an organic group include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, and dodecamethylene. Among these, preferred examples are methylene, propylene, cyclohexylene, phenylene and the like.

In the chemical formula (2), R ^d is a divalent organic group and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. For example, chain polyalkylene groups such as hexamethylene, octamethylene, dodecamethylene; alicyclic or polycyclic divalent organic groups such as cyclohexylene and norbornylene; divalent groups such as phenylene, naphthylene, biphenylene and polyphenylene Aromatic group; and these alkyl group-substituted and aryl group-substituted products. In addition, these divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, and a group represented by the chemical formula (1). Can also be included.

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

  In the chemical formulas (2) and (3), Y ′ represents a monovalent organic group having a reactive functional group a. The reactive functional group a itself as described above may be used. For example, when the reactive functional group a is selected from a polymerizable unsaturated group, a (meth) acryloyl (oxy) group, a vinyl (oxy) group, a propenyl (oxy) group, a butadienyl (oxy) group, a styryl (oxy) group Ethynyl (oxy) group, cinnamoyl (oxy) group, maleate group, (meth) acrylamide group and the like. N is preferably a positive integer of 1 to 20, more preferably 1 to 10, particularly preferably 1 to 5.

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

  In the production of the reactive silica fine particles of (ii), a method in which a reactive functional group-modified hydrolyzable silane is separately hydrolyzed and then mixed with silica fine particles, followed by heating and stirring, or a reaction A method for hydrolyzing a functional functional group-modified hydrolyzable silane in the presence of silica fine particles, and in the presence of other components such as polyunsaturated organic compounds, monounsaturated organic compounds, radiation polymerization initiators, etc. A method of performing surface treatment of silica fine particles can be selected, but a method of hydrolyzing a reactive functional group-modified hydrolyzable silane in the presence of silica fine particles is preferable. When the reactive silica fine particles (ii) are produced, the temperature is usually 20 ° C. or higher and 150 ° C. or lower, and the treatment time is in the range of 5 minutes to 24 hours.

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

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

(Binder component)
The binder component used in the hard coat layer curable resin composition has a reactive functional group a having a crosslinking reactivity and a reactive functional group a of the reactive silica fine particles. The reactive functional group a and the reactive functional group b are cross-linked to form a network structure, which further increases the hardness and scratch resistance of the hard coat layer. The binder component preferably has three or more reactive functional groups b per molecule in order to obtain sufficient crosslinkability. As the reactive functional group b, a polymerizable unsaturated group is suitably used, preferably a photocurable unsaturated group, and particularly preferably an ionizing radiation curable unsaturated group. Specific examples thereof include ethylenically unsaturated bonds such as (meth) acryloyl group, vinyl group and allyl group, and epoxy group.

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

  The binder component is preferably a curable organic resin, preferably a translucent material that transmits light when formed into a coating film, and an ionizing radiation curable resin that is cured by ionizing radiation represented by ultraviolet rays or electron beams. In addition, 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.

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

Examples of the binder component include pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), dipentaerythritol pentaacrylate (DPPA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane hexaacrylate, and these The modified body is mentioned.
Examples of modified products include EO (ethylene oxide) modified products, PO (propylene oxide) modified products, CL (caprolactone) modified products, and isocyanuric acid modified products.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The content of the polymer (A) is preferably 5 to 100 parts by weight and more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the compound (B) described later. If the content of the polymer (A) is 5 parts by weight or more with respect to 100 parts by weight of the compound (B) described later, flexibility and restorability can be imparted to the cured film, and if it is 100 parts by weight or less, The hardness of the cured film can be maintained.

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

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

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

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

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

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

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

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

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

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

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

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

  In chemical formula (5), E represents a polymerized unit of an arbitrary vinyl monomer, and is not particularly limited, and can be appropriately selected from various viewpoints such as hardness, solubility in a solvent, and transparency. 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 acid and derivatives thereof.

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

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

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

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

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

(Non-permeable solvent)
Since the non-permeable solvent does not penetrate into the triacetyl cellulose base material which is the base material, it has an effect of suppressing the formation of interference fringes by suppressing the formation of a high refractive index region in which triacetyl cellulose and a binder component are mixed. .
For example, when a permeable solvent such as methyl ethyl ketone is used, the binder component of the curable resin composition for the hard coat layer penetrates into the triacetyl cellulose substrate together with the permeable solvent. However, at this time, the reactive silica fine particles do not penetrate into the triacetyl cellulose base material.
For this reason, in the region where the binder component of the triacetyl cellulose base material and the penetrating solvent have permeated, the effect of lowering the refractive index by the reactive silica fine particles cannot be obtained, and the refractive index is lower than that of the triacetyl cellulose base material or the reactive silica fine particles. A region with a high refractive index is formed by a high binder component, and the region is refracted because the refractive index is higher than that of a hard coat layer containing a triacetyl cellulose base material portion and reactive silica fine particles that are not penetrated by the binder component. A rate difference is generated and interference fringes are generated.
On the other hand, by using a non-permeable solvent, it is possible to suppress the formation of a region through which the binder component penetrates and to prevent generation of interference fringes.
In addition, in this invention, osmosis | permeation means dissolving or swelling a triacetylcellulose base material.

  The non-permeable solvent may be appropriately selected in consideration of the permeability and the dispersibility of the silica fine particles. In particular, methyl isobutyl ketone, propylene glycol monomethyl ether, normal propanol, isopropanol, normal butanol, sec-butanol, isopropanol One or more types selected from the group consisting of butanol and tert-butanol are preferable because the permeability is moderate and the dispersibility of the silica fine particles contained in the hard coat layer curable resin composition is excellent.

  The curable resin composition for a hard coat layer may contain a permeable solvent in addition to the non-permeable solvent without departing from the gist of the present invention. In that case, it is preferable that the ratio of the impermeable solvent is 80% by weight or more based on the total amount of the solvent. It is particularly preferred to use only a non-permeable solvent.

(Other ingredients)
In addition to the above components, a polymerization initiator, an antistatic agent, an antiglare agent and the like can be appropriately added to the hard coat layer curable resin composition. 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.

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

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

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

Moreover, the cationic polymerization initiator should just be able to discharge | release the substance which starts cationic polymerization by light irradiation and / or a heating. Examples of the cationic polymerization initiator include sulfonic acid ester, imide sulfonate, dialkyl-4-hydroxysulfonium salt, arylsulfonic acid-p-nitrobenzyl ester, silanol-aluminum complex, (η ⁶ -benzene) (η ⁵ -cyclopentadidiene). Enyl) iron (II) and the like are exemplified, and more specifically, benzoin tosylate, 2,5-dinitrobenzyl tosylate, N-tosiphthalimide and the like are exemplified, but not limited thereto.

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

(Antistatic agent)
Specific examples of the antistatic agent include quaternary ammonium salts, pyridinium salts, various cationic compounds having cationic groups such as primary to tertiary amino groups, sulfonate groups, sulfate ester bases, and phosphate ester bases. , Anionic compounds having an anionic group such as phosphonate group, amphoteric compounds such as amino acid series and aminosulfate ester series, nonionic compounds such as amino alcohol series, glycerin series and polyethylene glycol series, and alkoxides of tin and titanium And metal chelate compounds such as acetylacetonate salts thereof, and compounds obtained by increasing the molecular weight of the compounds listed above. In addition, it has a tertiary amino group, a quaternary ammonium group, or a metal chelate portion, and has a monomer or oligomer that can be polymerized by ionizing radiation, or a polymerizable functional group that can be polymerized by ionizing radiation, and Polymerizable compounds such as organometallic compounds such as coupling agents can also be used as antistatic agents.
Examples of the antistatic agent include conductive polymers. The conductive polymer is not particularly limited, for example, aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, aliphatic conjugated polyacetylene, heteroatom-containing polyaniline, mixed type Conjugated poly (phenylene vinylene), a double chain conjugated system that has a plurality of conjugated chains in the molecule, and a conductive polymer that is a polymer obtained by grafting or block-copolymerizing the conjugated polymer chain to a saturated polymer. And the like.

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

(Anti-glare agent)
Examples of the antiglare agent include fine particles, and the shape of the fine particles may be a true sphere or an ellipse, and preferably a true sphere. The fine particles may be inorganic or organic, but those formed of an organic material are preferred. The fine particles exhibit anti-glare properties and are preferably transparent. Specific examples of the fine particles include plastic beads, and more preferably those having transparency. Specific examples of plastic beads include styrene beads (refractive index 1.59), melamine beads (refractive index 1.57), acrylic beads (refractive index 1.49), acrylic-styrene beads (refractive index 1.54), Examples thereof include polycarbonate beads and polyethylene beads. The addition amount of the fine particles is about 2 to 30 parts by weight, preferably about 10 to 25 parts by weight with respect to 100 parts by weight of the resin composition.
3. Other Layers The hard coat film is basically composed of the triacetyl cellulose base material and the hard coat layer as described above. However, in consideration of the function or use as a hard coat film, one or more layers as described below may be further provided on the surface of the hard coat layer opposite to the triacetyl cellulose substrate.

3-1. Antistatic layer The antistatic layer comprises a cured product of a curable resin composition for an antistatic layer containing an antistatic agent and a curable resin. The thickness of the antistatic layer is preferably about 30 nm to 3 μm.

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

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

3-2. Antiglare layer The antiglare layer comprises a cured product of a curable resin composition for an antiglare layer containing an antiglare agent and a curable resin. As the curable resin, a known resin can be appropriately selected, and one kind or two or more kinds can be used.

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

3-3. Antifouling layer According to a preferred embodiment of the present invention, an antifouling layer may be provided for the purpose of preventing dirt on the outermost surface of the hard coat film. The antifouling layer can further improve the antifouling property and scratch resistance of the hard coat film. The antifouling layer comprises a cured product of a curable resin composition for an antifouling layer comprising an antifouling agent and a curable resin composition.

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

3-4. Low Refractive Index Layer The low refractive index layer is a layer having a lower refractive index than the layer adjacent to the base film side of the layer, and is made of a cured product of the curable resin composition for the low refractive index layer. In the curable resin composition for a low refractive index layer, a known low refractive index curable resin or fine particles can be appropriately used so that the refractive index is lower than that of the adjacent layer.

3-5. Second Hard Coat Layer From the viewpoint of further improving the hardness of the hard coat film, a second hard coat layer may be provided on the surface of the hard coat layer opposite to the triacetyl cellulose substrate.
The second hard coat layer may be the same as the hard coat layer, and the composition of the two hard coat layers may be the same or different.

Hereinafter, the present invention will be described more specifically with reference to examples. These descriptions do not limit the present invention.
As the silica fine particles (1), Nissan Chemical Industries, Ltd., IPA-ST, average particle size of 12 nm, colloidal silica, and 30% solid content liquid were used.
As the silica fine particles (2), Nissan Chemical Industries, Ltd., IPA-STMS, average particle diameter of 20 nm, colloidal silica, and 30% solid content liquid were used.
As the silica fine particles (3), Nissan Chemical Industries, Ltd., IPA-ST (L), average particle size 44 nm, colloidal silica, 30% solid content solution was used.
As the silica fine particles (4), IPA-STZL, average particle diameter of 80 nm, colloidal silica, and a solid content 30% solution manufactured by Nissan Chemical Industries, Ltd. were used.
Silica fine particles having an average particle diameter of 200 nm were used as the silica particles (5).
As reactive alumina fine particles, CAI Kasei Co., Ltd. (trade name: ALMIBK15WT% -20), an average particle size of 30 nm, and a refractive index of 1.76 were used.
As pentaerythritol triacrylate, Nippon Kayaku Co., Ltd. product, PET30 was used.
DPHA manufactured by Nippon Kayaku Co., Ltd. was used as dipentaerythritol hexaacrylate.
As a silane coupling agent, 3-methacryloxypropyltrimethoxysilane, KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd., was used.
As the polyfunctional urethane acrylate, UV1700B manufactured by Nippon Synthetic Chemical Industry Co., Ltd. was used.
As a polymerization initiator, Irgacure 184 manufactured by Ciba Japan Co., Ltd. was used.
As the transparent substrate film, a TAC film (thickness 80 μm, triacetyl cellulose resin film, trade name: TF80UL, manufactured by Fuji Film Co., Ltd.) was used.
Abbreviations for each compound are as follows.
PETA: pentaerythritol triacrylate DPHA: dipentaerythritol hexaacrylate MIBK: methyl isobutyl ketone MEK: methyl ethyl ketone IPA: isopropanol

(Preparation of reactive silica fine particles (1))
The silica fine particles (1) were solvent-substituted from IPA to MIBK using a rotary evaporator to obtain a MIBK dispersion having 30% by weight of silica particles. By adding 5 parts by weight of 3-methacryloxypropylmethyldimethoxysilane to 100 parts by weight of this MIBK dispersion and subjecting it to a heat treatment at 50 ° C. for 1 hour, the solid content of the surface-treated reactive silica fine particles having an average particle diameter of 12 nm is obtained. A 30 wt% MIBK dispersion was obtained.

(Preparation of reactive silica fine particles (2))
In the preparation of the reactive silica fine particles (1), except that the silica fine particles (1) are replaced with the silica fine particles (2), the solid content of the surface-treated reactive silica fine particles (2) having an average particle diameter of 20 nm is the same. A 30 wt% MIBK dispersion was obtained.

(Preparation of reactive silica fine particles (3))
In the preparation of the reactive silica fine particles (1), the solid content of the surface-treated reactive silica fine particles (3) having an average particle diameter of 44 nm was similarly obtained except that the silica fine particles (1) were replaced with the silica fine particles (3). A 30 wt% MIBK dispersion was obtained.

(Preparation of reactive silica fine particles (4))
In the preparation of the reactive silica fine particles (1), the solid content of the surface-treated reactive silica fine particles (4) having an average particle diameter of 80 nm was similarly obtained except that the silica fine particles (1) were replaced with the silica fine particles (4). A 30 wt% MIBK dispersion was obtained.

(Preparation of curable resin composition)
Components of the composition shown below were blended to prepare curable resin compositions 1 to 13, respectively. Table 1 shows the mixing ratio (wt%) of reactive silica fine particles or silica fine particles of each curable resin composition relative to the total solid content of the curable resin composition, the type of binder component, and the solvent.

(Curable resin composition 1)
Reactive silica fine particles (3): 133 parts by mass (solid content: 40 parts by mass)
DPHA: 60 parts by mass Irgacure 184: 4 parts by mass MIBK: 57 parts by mass

(Curable resin composition 2)
Reactive silica fine particles (2): 133 parts by mass (solid content: 40 parts by mass)
DPHA: 60 parts by mass Irgacure 184: 4 parts by mass MIBK: 57 parts by mass

(Curable resin composition 3)
Reactive silica fine particles (1): 133 parts by mass (solid content: 40 parts by mass)
DPHA: 60 parts by mass Irgacure 184: 4 parts by mass MIBK: 57 parts by mass

(Curable resin composition 4)
Reactive silica fine particles (4): 133 parts by mass (solid content: 40 parts by mass)
DPHA: 60 parts by mass Irgacure 184: 4 parts by mass MIBK: 57 parts by mass

(Curable resin composition 5)
Reactive silica fine particles (3): 117 parts by mass (solid content: 35 parts by mass)
DPHA: 60 parts by mass Irgacure 184: 4 parts by mass MIBK: 68 parts by mass

(Curable resin composition 6)
Reactive silica fine particles (3): 167 parts by mass (solid content: 50 parts by mass)
DPHA: 50 parts by mass Irgacure 184: 4 parts by mass MIBK: 33 parts by mass

(Curable resin composition 7)
Reactive silica fine particles (3): 200 parts by mass (solid content: 60 parts by mass)
DPHA: 50 parts by mass Irgacure 184: 4 parts by mass MIBK: 10 parts by mass

(Curable resin composition 8)
Reactive silica fine particles (3): 133 parts by mass (solid content: 40 parts by mass)
DPHA: 60 parts by mass Irgacure 184: 4 parts by mass IPA: 57 parts by mass

(Curable resin composition 9)
Reactive silica fine particles (3): 133 parts by mass (solid content: 40 parts by mass)
DPHA: 60 parts by mass Irgacure 184: 4 parts by mass n-butanol: 57 parts by mass

(Curable resin composition 10)
Reactive silica fine particles (3): 133 parts by mass (solid content: 40 parts by mass)
PET30: 60 parts by mass Irgacure 184: 4 parts by mass MIBK: 57 parts by mass

(Curable resin composition 11)
Reactive silica fine particles (3): 133 parts by mass (solid content: 40 parts by mass)
UV1700B: 60 parts by mass Irgacure 184: 4 parts by mass n-butanol: 57 parts by mass

(Curable resin composition 12)
Reactive silica fine particles (3): 133 parts by mass (solid content: 40 parts by mass)
DPHA: 60 parts by mass Irgacure 184: 4 parts by mass MEK: 57 parts by mass

(Curable resin composition 13)
Silica fine particles (5): 133 parts by mass (solid content: 40 parts by mass)
DPHA: 60 parts by mass Irgacure 184: 4 parts by mass MIBK: 57 parts by mass

(Curable resin composition 14)
Reactive silica fine particles: 0 parts by mass DPHA: 60 parts by mass Irgacure 184: 4 parts by mass MIBK: 57 parts by mass

(Curable resin composition 15)
Reactive silica fine particles (3): 83 parts by mass (solid content: 25 parts by mass)
DPHA: 75 parts by mass Irgacure 184: 4 parts by mass MIBK: 92 parts by mass

(Curable resin composition 16)
Reactive silica fine particles (3): 250 parts by mass (solid content: 75 parts by mass)
DPHA: 25 parts by mass Irgacure 184: 4 parts by mass MIBK: 5 parts by mass

(Curable resin composition 17)
Reactive alumina fine particles (1): 133 parts by mass (solid content: 40 parts by mass)
DPHA: 60 parts by mass Irgacure 184: 4 parts by mass MIBK: 5 parts by mass

Example 1: Preparation of a hard coat film The curable resin composition 1 was applied as a curable resin composition for a hard coat layer on one side of a TAC film, and dried in a hot oven at a temperature of 70 ° C for 60 seconds. By evaporating the solvent in the film and irradiating ultraviolet rays with an integrated light amount of 200 mJ / cm ² to cure the coating film, a hard coat layer having a film thickness of 15 g / cm ² (when dried) is formed. A hard coat film was produced.

  The hard coat of Examples 2 to 11 and Comparative Examples 1 to 6 was the same as Example 1 except that the curable resin composition 1 was changed to the one shown in Table 1 as the curable resin composition for the hard coat layer. A film was prepared.

(Evaluation of hard coat film)
About the produced hard coat film of Examples 1-11 and Comparative Examples 1-6, pencil hardness, haze, and interference fringe were evaluated as follows. The results are shown in Table 1.

(Evaluation: Pencil hardness)
Pencil hardness test: The hardness of the pencil scratch test is as follows. After the prepared hard coat film is conditioned at a temperature of 25 ° C. and a relative humidity of 60% for 2 hours, a test pencil specified by JIS-S-6006 is used. A pencil hardness test (4.9 N load) specified in JIS K5600-5-4 (1999) was performed, and the highest hardness that was not damaged was measured.

(Evaluation: Haze)
The haze value (%) of the prepared hard coat film was measured according to JIS K-7136 using a haze meter (Murakami Color Research Laboratory, product number: HM-150).
○: 1.0% or less ×: larger than 1.0%

After sticking black tape made by Teraoka Seisakusho Co., Ltd. on the entire surface of the hard coat film on the TAC film side, the presence or absence of interference fringes was evaluated by the following criteria using an interference fringe inspection lamp (Funatech Co., Ltd., FNA18 type). did.
○: Interference fringes were generated by visual observation in all directions.
X: Interference fringes were confirmed by visual observation in all directions.

From Table 1, Examples 1-11 obtained pencil hardness 4H and the outstanding hardness, and the evaluation of haze and an interference fringe was also favorable.
However, in Comparative Example 1 using a penetrating solvent, the binder component penetrated into the TAC film, so that the hardness decreased, a region having a high refractive index was formed, and interference fringes were generated.
In Comparative Example 2, since the average particle size of the silica fine particles was as large as 200 nm, the transparency of the hard coat film was lowered and the haze evaluation was poor.
Since Comparative Example 3 did not contain silica fine particles, the hardness was as low as 3H, and the refractive index of the hard coat layer was not lowered, so the occurrence of interference fringes could not be suppressed.
In Comparative Examples 4 and 5, since the content of the reactive silica fine particles exceeds the lower limit value and the upper limit value of the present invention, the hardness is low, and the occurrence of interference fringes was not suppressed in Comparative Example 4.
In Comparative Example 6, since reactive alumina fine particles having a high refractive index of 1.76 were used instead of silica fine particles, generation of interference fringes could not be suppressed.

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

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Hard coat film 10 Transparent base film 20 Hard coat layer 30 Antistatic layer 40 Low refractive index layer

Claims (4)

  A hard coat containing silica fine particles having an average particle size of 10 to 100 nm, a binder component and a non-permeable solvent on one side of the triacetyl cellulose base material, and the content of the silica fine particles relative to the total solid content is 30 to 70% by weight A method for producing a hard coat film, wherein a hard coat layer is formed by applying and curing a curable resin composition for a layer.   2. The production of a hard coat film according to claim 1, wherein the silica fine particles are reactive silica fine particles having a reactive functional group having cross-linking reactivity with the fine particles and / or the binder component. Method.   The method for producing a hard coat film according to claim 1 or 2, wherein the binder component is pentaerythritol triacrylate and / or dipentaerythritol hexaacrylate.   The impermeable solvent is one or more selected from the group consisting of methyl isobutyl ketone, propylene glycol monomethyl ether, normal propanol, isopropanol, normal butanol, sec-butanol, isobutanol, and tert-butanol. The manufacturing method of the hard coat film as described in any one of Claims 1 thru | or 3.

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