WO2014109407A1

WO2014109407A1 - Hard coat film, curable resin composition for hard coat layers, and method for producing hard coat film

Info

Publication number: WO2014109407A1
Application number: PCT/JP2014/050379
Authority: WO
Inventors: 悟二嶋; 宏之楠川; 渡辺　健一; 敬輔脇田
Original assignee: 大日本印刷株式会社
Priority date: 2013-01-11
Filing date: 2014-01-10
Publication date: 2014-07-17
Also published as: JP2014238614A; JP2014149520A

Abstract

The main purpose of the present invention is to provide a hard coat film which has excellent hardness, scratch resistance and processability. The present invention achieves the above-mentioned purpose by providing a hard coat film which is obtained by forming a hard coat layer on a substrate, and which is characterized in that the hard coat layer contains irregularly shaped fine silica particles, an acrylic polymer having a weight average molecular weight and an acrylic equivalent within specific ranges, and a matrix resin.

Description

Hard coat film, curable resin composition for hard coat layer, and method for producing hard coat film

The present invention relates to a hard coat film used for the purpose of protecting the surface of a display or the like.

Image display surfaces in image display devices such as liquid crystal displays, CRT displays, projection displays, plasma displays, and electroluminescence displays are required to be provided with scratch resistance so that they are not damaged during handling. In response to such demands, it has been common to improve the scratch resistance of the image display surface of an image display device by using a hard coat film having a hard coat layer provided on a substrate. The performance required for hard coat films has been increasing in recent years, and there is a demand for further improved hardness and scratch resistance.

As means for improving the hardness of the hard coat film, for example, in Patent Document 1, a substrate having a specific configuration is used, and the total thickness of the hard coat film, the thickness of the acrylic resin layer constituting the substrate, and the thickness of the hard coat layer are set. A method for making a specific range is disclosed. Patent Document 2 discloses a method of forming a hard coat layer using a curable composition to which inorganic oxide particles are added. Further, Patent Documents 3 to 7 disclose methods for forming a hard coat layer using a curable composition to which reactive irregularly shaped silica fine particles are added.

JP 2009-279806 A JP 2012-148484 A JP 2010-102123 A JP 2010-120182 A International Publication No. 2012/018009 Pamphlet JP 2010-122325 A JP 2010-122991 A

When a hard coat film is used in an image display device or the like, it is required to have excellent workability because it is subjected to punching, router processing, cutting processing, cutting processing, bending processing, and the like.
However, when the thickness of the acrylic resin layer constituting the substrate is increased as in Patent Document 1, the hardness of the hard coat film is improved, but there is a problem that cracks are likely to occur during processing. Further, the hardness can be improved by simply increasing the thickness of the hard coat layer, but in this case, there is a problem that cracks are likely to occur in the hard coat layer during processing. Moreover, even when inorganic oxide particles or reactive irregularly shaped silica fine particles are added as in Patent Documents 2 to 7, high hardness can be achieved, but the workability requirement cannot be met.

Patent Document 5 discloses that good flexibility can be obtained by adding reactive irregular-shaped silica fine particles to a curable resin composition for a hard coat layer and further adding a polymer. However, there is a concern that the hardness is lowered and the scratch resistance is deteriorated simply by adding a polymer, and it is difficult to achieve both high hardness and workability.
Patent Document 7 proposes that a reactive polymer having a specific structure and a weight average molecular weight is contained in a curable resin composition for a hard coat layer in order to improve hardness and reduce curl. However, the workability has not been studied.

The present invention has been made in view of the above problems, and has as its main object to provide a hard coat film that is excellent in hardness, scratch resistance and workability.

As a result of intensive studies to solve the above problems, the present inventors form a hard coat layer using a curable resin composition containing reactive irregularly shaped silica fine particles, a monomer, and a specific polymer. As a result, it was found that a hard coat film having both high hardness and workability was obtained, and the present invention was completed.

That is, the present invention is a hard coat film in which a hard coat layer is formed on a substrate, and the hard coat layer has irregular-shaped silica fine particles and a weight average molecular weight in the range of 30,000 to 110,000. A hard coat film comprising an acrylic polymer having an acrylic equivalent in the range of 200 to 1,200 and a matrix resin is provided.

According to the present invention, the hard coat layer contains irregular shaped silica fine particles, whereby the hardness and scratch resistance can be improved. Further, by using an acrylic polymer having a weight average molecular weight and an acrylic equivalent within a predetermined range for the hard coat layer, it is possible to improve workability while maintaining high hardness.

In the above invention, the hard coat layer may contain a polymerization initiator.

In the present invention, the hard coat layer may contain a blue color material. This is because when the hard coat film of the present invention is used in an image display device, yellowness can be suppressed and visibility and color reproducibility can be improved.

In the present invention, an antiglare layer may be formed on the hard coat layer. Even in the case where the antiglare layer is formed on the hard coat layer, the hard coat layer is excellent in hardness, so that high hardness can be achieved.

Further, the present invention is a hard coat film in which a hard coat layer is formed on a substrate, the hard coat layer is a curable resin composition containing reactive irregular silica fine particles, the acrylic polymer, and a monomer. A hard coat film comprising a cured product is provided.

According to the present invention, hardness and scratch resistance can be improved by using reactive irregularly shaped silica fine particles in the hard coat layer. Further, by using an acrylic polymer having a weight average molecular weight and an acrylic equivalent within a predetermined range for the hard coat layer, it is possible to improve workability while maintaining high hardness.

The present invention also provides reactive irregularly shaped silica fine particles, an acrylic polymer having a weight average molecular weight in the range of 30,000 to 110,000 and an acrylic equivalent in the range of 200 to 1,200, and a monomer. A curable resin composition for a hard coat layer is provided.

According to the present invention, when the curable resin composition for a hard coat layer contains reactive irregularly shaped silica fine particles, a hard coat layer having excellent hardness and scratch resistance can be obtained. Moreover, it is possible to achieve both high hardness and workability by adding an acrylic polymer having a weight average molecular weight and an acrylic equivalent within a predetermined range to the curable resin composition for a hard coat layer.

Moreover, the curable resin composition for a hard coat layer of the present invention may further contain a polymerization initiator.

Further, the curable resin composition for a hard coat layer of the present invention may further contain a blue color material. This is because when used in an image display device, a hard coat film capable of suppressing yellowness and improving visibility and color reproducibility can be obtained.

The present invention also provides a reactive irregularly shaped silica fine particle on a substrate, an acrylic polymer having a weight average molecular weight in the range of 30,000 to 110,000 and an acrylic equivalent in the range of 200 to 1,200. There is provided a method for producing a hard coat film, comprising a hard coat layer forming step of applying a curable resin composition for a hard coat layer containing a monomer and curing to form a hard coat layer.

According to the present invention, it is possible to obtain a hard coat layer having excellent hardness, scratch resistance and workability by using the above-described curable resin composition for hard coat layer.

The present invention also relates to a hard coat film having a hard coat layer formed on a substrate, wherein the hard coat layer has reactive irregularly shaped silica fine particles and a weight average molecular weight in the range of 30,000 to 110,000. Provided is a hard coat film comprising a cured product of a curable resin composition containing an acrylic polymer having an acrylic equivalent in the range of 200 to 1,200, a monomer, and a polymerization initiator To do.

The present invention also includes reactive irregularly shaped silica particles, an acrylic polymer having a weight average molecular weight in the range of 30,000 to 110,000 and an acrylic equivalent in the range of 200 to 1,200, a monomer, A curable resin composition for a hard coat layer comprising a polymerization initiator is provided.

According to the present invention, the hardness and scratch resistance can be improved by including the reactive deformed silica fine particles in the hard coat layer. Further, by using an acrylic polymer having a weight average molecular weight and an acrylic equivalent within a predetermined range for the hard coat layer, it is possible to improve workability while maintaining high hardness.

The present invention has an effect that it is possible to improve any of hardness, scratch resistance and workability.

It is a schematic sectional drawing which shows an example of the hard coat film of this invention. It is a schematic sectional drawing which shows the other example of the hard coat film of this invention. It is a schematic sectional drawing which shows the other example of the hard coat film of this invention. It is a schematic sectional drawing which shows the other example of the hard coat film of this invention.

Hereinafter, the hard coat film, the curable resin composition for the hard coat layer, and the method for producing the hard coat film of the present invention will be described in detail.

A. Hard coat film The hard coat film of the present invention is a hard coat film in which a hard coat layer is formed on a substrate, and the hard coat layer has irregular-shaped silica fine particles and a weight average molecular weight of 30,000 to 110,000. And an acrylic polymer having an acrylic equivalent in the range of 200 to 1,200 and a matrix resin.

In the specification of the present application, terms such as “film”, “sheet”, and “plate” are not distinguished from each other based only on the difference in names. For example, the “hard coat film” is a concept including a member that can also be called a sheet or a plate.

In the present invention, when the hard coat layer contains irregular-shaped silica fine particles, a hard coat layer having excellent hardness and scratch resistance can be obtained. Further, by using an acrylic polymer having a weight average molecular weight and an acrylic equivalent within a predetermined range for the hard coat layer, it is possible to achieve both high hardness and workability.

The hard coat film of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic sectional view showing an example of the hard coat film of the present invention. As illustrated in FIG. 1, the hard coat film 1 includes a substrate 2 and a hard coat layer 3 formed on the substrate 2. The hard coat layer 3 contains irregular-shaped silica fine particles, an acrylic polymer having a weight average molecular weight and an acrylic equivalent within predetermined ranges, and a matrix resin. That is, the hard coat layer 3 is composed of a cured product of a curable resin composition containing reactive irregular shaped silica fine particles, an acrylic polymer having a weight average molecular weight and an acrylic equivalent within a predetermined range, and a monomer. Yes.
Hereafter, each structure in the hard coat film of this invention is demonstrated.

1. Hard coat layer The hard coat layer in this invention is formed on a board | substrate, and has two aspects. The hard coat layer of the first embodiment contains irregular-shaped silica fine particles, an acrylic polymer having a weight average molecular weight and an acrylic equivalent within predetermined ranges, and a matrix resin. The hard coat layer of the second aspect is a cured product of a curable resin composition containing reactive irregularly shaped silica fine particles, an acrylic polymer having a weight average molecular weight and an acrylic equivalent within a predetermined range, and a monomer. Is included.
Hereinafter, the configuration of the hard coat layer will be described.

(1) Curable resin composition The curable resin composition used in the present invention contains reactive irregularly shaped silica fine particles, an acrylic polymer having a weight average molecular weight and an acrylic equivalent within a predetermined range, and a monomer. Is.
Hereinafter, each component in the curable resin composition will be described.

(A) Reactive Modified Silica Fine Particle In the present invention, the reactive deformed silica fine particle is a component that contributes to improving the hardness of the hard coat layer.

The reactive irregular shaped silica fine particles usually have a reactive functional group. As the reactive functional group, a polymerizable unsaturated group is suitably used, preferably a photocurable unsaturated group, and particularly preferably an ionizing radiation curable unsaturated group. Specific examples include ethylenically unsaturated bonds such as (meth) acryloyl groups, vinyl groups, allyl groups, and epoxy groups.

In the present specification, (meth) acryloyl means at least one of acryloyl and methacryloyl, (meth) acrylate means at least one of acrylate and methacrylate, and (meth) acryl is at least one of acrylic and methacrylic. Means.

Examples of reactive irregularly shaped silica fine particles include reactive irregularly shaped silica fine particles in which a plurality of fine silica particles are bonded by an inorganic chemical bond. Among them, the reactive irregularly shaped silica fine particles are reactive irregularly shaped silica fine particles having 3 to 20 silica fine particles having an average primary particle diameter of 1 nm to 100 nm bonded by an inorganic chemical bond and having a reactive functional group on the surface. Is preferred. The reactive irregularly shaped silica fine particles have a reactive functional group, so that they can undergo a curing reaction that crosslinks with the reactive irregularly shaped silica fine particles and the monomer, and can impart scratch resistance and hardness to the hard coat layer. .

The average primary particle diameter of the silica fine particles constituting the reactive irregularly shaped silica fine particles is preferably in the range of 1 nm to 100 nm, and more preferably in the range of 5 nm to 80 nm. If the average primary particle size of the silica fine particles is small, only reactive irregularly shaped silica fine particles having a small average secondary particle size can be obtained, and sufficient hardness may not be imparted to the hard coat layer. Further, if the average primary particle size of the silica fine particles is large, the average secondary particle size of the reactive irregularly shaped silica fine particles tends to be large, and if the average secondary particle size is large, the transparency of the hard coat layer is lowered and the transmittance Deterioration and haze increase may occur.
The average secondary particle size of the reactive irregularly shaped silica fine particles is preferably in the range of 5 nm to 300 nm, and more preferably in the range of 10 nm to 200 nm. When the average two particle diameters of the reactive irregularly shaped silica fine particles are within the above range, it is easy to impart hardness to the hard coat layer and maintain the transparency of the hard coat layer.

Here, the average primary particle size of the silica fine particles is determined by measuring the silica fine particles in the curable resin composition by a dynamic light scattering method, and the 50% particle size (d50 median) when the particle size distribution is expressed as a cumulative distribution. Diameter). The average primary particle size can be measured using a Microtrac particle size analyzer or a Nanotrac particle size analyzer manufactured by Nikkiso Co., Ltd. In addition, the average secondary particle size of the reactive irregularly shaped silica fine particles can be determined by the same method as the average primary particle size in the curable resin composition. On the other hand, the average secondary particle size of the reactive irregularly shaped silica fine particles is such that, in the hard coat layer, the cross section of the hard coat layer is observed using an SEM photograph or a TEM photograph, and the observed cured reactive irregularly shaped silica fine particles are 100. It can be obtained as an average value of individual selection.

Silica fine particles do not exclude the use of particles having pores or porous structures inside the particles, such as hollow particles, but solid particles having no pores or porous structures inside the particles should be used. It is more preferable from the viewpoint of improving the hardness.

The reactive irregularly shaped silica fine particles are formed by bonding the above-mentioned silica fine particles, preferably 3 to 20, more preferably 3 to 10, by inorganic chemical bonds. When the number of silica fine particles bonded by inorganic chemical bonds is small, it is substantially the same as monodisperse particles, and it is difficult to obtain a hard coat layer excellent in adhesion to the substrate, scratch resistance, and pencil hardness. Moreover, when there are many silica fine particles couple | bonded by the inorganic chemical bond, the transparency of a hard-coat layer will fall, and the deterioration of the transmittance | permeability and the raise of a haze may be caused.

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

As the particle state of the reactive irregularly shaped silica fine particles, 3 to 20 silica fine particles are bonded by an inorganic chemical bond and aggregated particles (aggregated particles), and 3 to 20 silica fine particles are inorganic. Examples thereof include chain particles bonded by chemical bonds and bonded in a chain. Among these, from the viewpoint of increasing the hardness of the hard coat layer, chain particles are preferable as the particle state of the reactive irregularly shaped silica fine particles. Further, it is preferable that the chain particles are contained in at least a part of the reactive irregular shaped silica fine particles.

Here, when the reactive irregularly shaped silica fine particles are chain particles, the average number of bonds of the silica fine particles is determined by observing the cross section of the hard coat layer using an SEM photograph or a TEM photograph and observing the cured reactive irregularly shaped silica fine particles. 100 are selected, the silica fine particles contained in each reactive deformed silica fine particle are counted, and the average value can be obtained.

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

The reactive irregular shaped silica fine particles have at least a part of the surface coated with an organic component, and have a reactive functional group 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 organic component having an isocyanate group is reacted with the hydroxyl group present on the surface of the silica fine particle and the organic component is bonded to a part of the surface, for example, silica Examples include a mode in which an organic component is attached to a hydroxyl group present on the surface of the fine particle by an interaction such as hydrogen bonding, a mode in which silica fine particles are contained in the polymer particle, and the like.

At least a part of the surface is coated with an organic component, and a method for preparing reactive deformed silica fine particles having a reactive functional group introduced by the organic component on the surface is a reactive functional group to be introduced into the reactive deformed silica fine particles. Thus, a conventionally known method can be appropriately selected and used. Among these, from the viewpoint of suppressing aggregation of the reactive deformed silica fine particles and improving the hardness of the hard coat layer, any one of the following reactive deformed silica fine particles (i) and (ii) may be appropriately selected and used. preferable.
(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 the modified silica fine particles are dispersed in at least one of water and an organic solvent as a dispersion medium in the presence of one or more surface modification compounds having a molecular weight of 500 or less selected from the group consisting of metal compounds having functional groups. Reactive deformed silica fine particles having a reactive functional group on the surface, obtained by
(Ii) a compound containing a reactive functional group to be introduced into the deformed silica fine particle before coating, a group represented by the following chemical formula (1), and a silanol group or a group that generates a silanol group by hydrolysis, and metal oxide fine particles: Reactive deformed silica fine particles having a reactive functional group on the surface, obtained by bonding.
-Q ¹ -C (= Q ² ) -Q ^3- (1)
(In formula (1), Q ¹ represents NH, O or S, Q ² represents O or S, and Q ³ represents NH or a divalent or higher organic group.)
Hereinafter, the reactive irregular-shaped silica fine particle used suitably is demonstrated.

(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 the modified silica fine particles are dispersed in at least one of water and an organic solvent as a dispersion medium in the presence of one or more surface modification compounds having a molecular weight of 500 or less selected from the group consisting of metal compounds having functional groups. Reactive deformed silica fine particles having a reactive functional group on the surface, obtained by
When the reactive irregularly shaped silica fine particles (i) are used, there is an advantage that the strength of the hard coat layer can be improved even if the organic component content is small.

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

The surface-modifying compound is usually added to at least one functional group capable of participating in chemical bonding with the surface group of the irregular-shaped silica fine particle, and after binding to the surface-modifying compound via this functional group, the irregular-shaped silica fine particle is newly added. It has molecular residues that give unique properties. Hereinafter, at least one functional group that can participate in chemical bonding with a group on the surface of the irregular shaped silica fine particle is referred to as a first functional group. The molecular residue or a part thereof is hydrophobic or hydrophilic and, for example, stabilizes, integrates, or activates irregular shaped silica fine particles. For example, the hydrophobic molecular residue includes 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 introduced to the surface so that the reactive irregular shaped silica fine particles can react with the monomer described later is appropriately selected according to the monomer. As the reactive functional group, a polymerizable unsaturated group is suitably used, preferably a photocurable unsaturated group, and particularly preferably an ionizing radiation curable unsaturated group. Specific examples thereof include ethylenically unsaturated bonds such as (meth) acryloyl group, vinyl group and allyl group, and epoxy group.

When a reactive functional group capable of reacting with a monomer described later is contained in the molecular residue of the surface modifying compound, the first functional group contained in the surface modifying compound is reacted with the surface of the deformed silica fine particle. By this, it is possible to introduce a reactive functional group capable of reacting with the monomer on the surface of the reactive deformed 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, in the molecular residue of the surface modification compound, a second reactive functional group is contained, and the second reactive functional group is used as a foothold for the reactive deformed silica fine particles of (i). A reactive functional group capable of reacting with the monomer may be introduced on the surface. For example, a hydrogen bond-forming group capable of hydrogen bonding such as a hydroxyl group and an oxy group is introduced as the second reactive functional group, and another surface modification compound is added to the hydrogen bond-forming group introduced on the surface of the fine particles. It is preferable to introduce a reactive functional group capable of reacting with the monomer by the reaction of the hydrogen bond forming group. That is, as a surface modification compound, it is preferable to use a compound having a hydrogen bond forming group and a compound having a reactive functional group capable of reacting with a monomer such as a polymerizable unsaturated group and a compound having a hydrogen bond forming group in combination. As mentioned. 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 term “amide bond” means that the bond unit contains —NHC (O) or> NC (O) —. Among the hydrogen bond forming groups used in the surface modification compound, a carboxyl group, a hydroxyl group, and an amide group are particularly preferable.

The surface-modifying compound used in the reactive irregularly shaped silica fine particles (i) above preferably has a molecular weight of 500 or less, particularly a molecular weight not exceeding 400, and particularly a molecular weight not exceeding 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 reactive irregular shaped silica fine particles can be prevented.

The surface-modifying compound used in the reactive deformed 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 following chemical formula:
Q _3-n NH _n
In the above formula, n is 0, 1 or 2. Residue Q is independently alkyl having 1 to 12, especially 1 to 6, particularly preferably 1 to 4, carbon atoms such as methyl, ethyl, n-propyl, i-propyl and butyl, and 6 to 24 Represents aryl, alkaryl or aralkyl having 5 carbon atoms such as phenyl, naphthyl, tolyl and benzyl. 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, acetoacetate, acetoacetate Acetoacetic acid-C ₁ -C ₄ -alkyl esters such as ethyl esters, diacetyl and acetonyl acetone.
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 or not having a reactive functional group 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-aminopropyl trimer Xysilane, 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 may include known ones such as KBM-502, KBM-503, KBE-502, KBE-503 manufactured by Shin-Etsu Chemical Co., Ltd. be able to.

Examples of the metal compound having a functional group include a metal compound of metal M from at least one of the first group III to V and the second group II to IV of the periodic table. Specific examples include zirconium and titanium alkoxides represented by the following chemical formula.
M (OR) ₄
In the above formula, M is Ti or Zr. A part of the OR group is substituted with a complexing agent such as a β-dicarbonyl compound or a monocarboxylic acid. 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, at least one of water and 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 C 1-6 aliphatic alcohols such as methanol, ethanol, n- and i-propanol and butanol, ketones such as methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, acetone and butanone, acetic acid Esters such as ethyl; ethers such as diethyl ether, tetrahydrofuran and tetrahydropyran; amides such as dimethylacetamide and dimethylformamide; sulfoxides and sulfones such as sulfolane and dimethyl sulfoxide; and optionally, such as pentane, hexane and cyclohexane Aliphatic hydrocarbons which may be halogenated are mentioned. These dispersion media can be used as a mixture.
The dispersion medium preferably has a boiling point that can be easily removed by distillation, optionally under reduced pressure, and a solvent having a boiling point of 200 ° C. or lower, particularly 150 ° C. or lower is preferable.

In preparing the reactive deformed silica fine particles (i), the concentration of the dispersion medium is usually within the range of 40% by mass to 90% by mass, preferably within the range of 50% by mass to 80% by mass, and particularly 55% by mass to 75%. It is in the range of mass%. The rest 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 particularly preferably 25: 1 to 10: 1.

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

(Ii) a reactive functional group to be introduced into the irregular shaped silica fine particles before coating, a compound represented by the following chemical formula (1), and a silanol group or a group containing a group that generates a silanol group by hydrolysis, and silica fine particles as a core Reactive deformed silica fine particles having a reactive functional group on the surface, obtained by bonding with metal oxide fine particles.
-Q ¹ -C (= Q ² ) -Q ^3- (1)
(In formula (1), Q ¹ represents NH, O or S, Q ² represents O or S, and Q ³ represents NH or a divalent or higher organic group.)
When the reactive irregularly shaped silica fine particles (ii) are used, there are advantages that the amount of organic components is increased, and the dispersibility and the strength of the hard coat layer are further increased.

First, a compound containing a reactive functional group to be introduced into the silica fine particles before coating, a group represented by the chemical formula (1), and a silanol group or a group that generates a silanol group by hydrolysis will be described. Hereinafter, the compound may be referred to as a reactive functional group-modified hydrolyzable silane.
In the reactive functional group-modified hydrolyzable silane, the reactive functional group to be introduced into the silica fine particles is not particularly limited as long as it is appropriately selected so as to be capable of reacting with a monomer 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 )-], [—O—C (═S) —], [—S—C (═O) —], [—NH—C (═O) —], [—NH—C (═S) — ] And [-SC (= S)-]. These groups can be used alone or in combination of two or more. Among them, from the viewpoint of thermal stability, at least one 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 above 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 the substrate, and heat resistance can be imparted.

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

Preferable specific examples of the reactive functional group-modified hydrolyzable silane include, for example, compounds represented by the following chemical formulas (2) and (3), and the compound represented by the following chemical formula (3) is from the point of hardness. More preferably used.

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

In 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 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 An aromatic group; and these alkyl group-substituted and aryl group-substituted products. Further, 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 above formula (1). Can also be included.

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

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

For the synthesis of the reactive functional group-modified hydrolyzable silane, for example, the method described in JP-A-9-100111 can be used. That is, for example, when it is desired to introduce a polymerizable unsaturated group, (A) an addition reaction between a mercaptoalkoxysilane, a polyisocyanate compound, and an active hydrogen group-containing polymerizable unsaturated compound capable of reacting with an isocyanate group is performed. it can. Moreover, it can carry out by (B) direct reaction with the compound which has an alkoxy silyl group and an isocyanate group in a molecule | numerator, and an active hydrogen group containing polymerizable unsaturated compound. Furthermore, it can also be directly synthesized by addition reaction of (C) a compound having a polymerizable unsaturated group and an isocyanate group in the molecule with mercaptoalkoxysilane or aminosilane.

In the production of the reactive deformed silica fine particles of (ii), after separately hydrolyzing the reactive functional group-modified hydrolyzable silane, this is mixed with the deformed silica fine particles, followed by heating and stirring operation, Alternatively, a method of hydrolyzing a reactive functional group-modified hydrolyzable silane in the presence of deformed silica fine particles, and other components such as polyunsaturated organic compounds, monounsaturated organic compounds, radiation polymerization initiators, etc. Although the method of performing the surface treatment of the deformed silica fine particles in the presence of can be selected, a method of hydrolyzing the reactive functional group-modified hydrolyzable silane in the presence of the deformed silica fine particles is preferable. When the reactive deformed 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. Preferable examples of the acid include organic acids and unsaturated organic acids; examples of the base include tertiary amines or quaternary ammonium hydroxides. The addition amount of these acid or base catalysts is within the range of 0.001% by mass to 1.0% by mass, preferably 0.01% by mass to 0.1% by mass with respect to the reactive functional group-modified hydrolyzable silane. Within range.

As the reactive irregular shaped 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.

The hard coat layer may include not only those in which the reactive functional group of the reactive irregular shaped silica fine particles has reacted but also those in which the reactive functional group of the reactive irregular shaped silica fine particles has not reacted.

The content of the reactive irregularly shaped silica fine particles is preferably in the range of 40% by mass to 70% by mass, and in the range of 50% by mass to 60% by mass with respect to the total solid content of the curable resin composition. It is more preferable. When the content is small, there is a possibility that sufficient hardness cannot be imparted to the hard coat layer. When the content is large, the filling rate is excessively increased, the adhesion between the reactive irregularly shaped silica fine particles and the monomer is deteriorated, and the hardness of the hard coat layer may be lowered.
Here, solid content means things other than a solvent among the components contained in curable resin composition.

(B) Acrylic polymer The acrylic polymer used in the present invention has a weight average molecular weight and an acrylic equivalent within predetermined ranges, and is a component that contributes to improving the workability of the hard coat film.

The weight average molecular weight of the acrylic polymer is in the range of 30,000 to 110,000, particularly in the range of 50,000 to 110,000, from the viewpoint of imparting flexibility to the hard coat layer and preventing cracks during processing. It is preferably within the range of 60,000 to 80,000.
Here, the weight average molecular weight refers to a weight average molecular weight which is a polystyrene conversion value measured by gel permeation chromatography.

The acrylic polymer has an acrylic equivalent in the range of 200 to 1,200, and preferably in the range of 200 to 1,000.
Here, the acrylic equivalent indicates a value obtained by dividing the weight average molecular weight of the acrylic polymer by the number of (meth) acrylic groups in one molecule.

The acrylic polymer is not particularly limited as long as it satisfies the above weight average molecular weight and acrylic equivalent, but it is a polymer of glycerol (meth) acrylate or a compound of a compound obtained by addition polymerization of (meth) acrylic acid to glycidyl methacrylate. It is preferably a coalescence. Specifically, a polymer of an acrylic monomer represented by the following chemical formula (4) or (5) is preferably used.

In the above formula (4), R ¹ to R ³ are each independently an acrylate group, a methacrylate group or a hydrogen atom, and one or more of R ¹ to R ³ are an acrylate group or a methacrylate group. That is, the glycerol (meth) acrylate represented by the above formula (4) may be monofunctional, bifunctional, or trifunctional.
In the above formula (5), R is an acrylic acid group or a methacrylic acid group.

An example of such an acrylic polymer is BL-2002 manufactured by Seiko PMC Co., Ltd.
Moreover, as an acrylic polymer, you may use individually by 1 type, and may mix and use 2 or more types suitably.

The content of the acrylic polymer is preferably in the range of 3% by mass to 20% by mass, more preferably in the range of 5% by mass to 10% by mass, based on the total solid content of the curable resin composition. More preferably, it is in the range of 6% by mass to 8% by mass. If the content of the acrylic polymer is within the above range, the workability of the hard coat film can be improved while maintaining the hardness of the hard coat layer.
The content of the acrylic polymer can be set in the range of 5 to 80 parts by weight with respect to 100 parts by weight of the monomer described later, and is in the range of 20 to 40 parts by weight. Preferably, it is in the range of 10 to 30 parts by weight.

(C) Monomer In this invention, a monomer is a component used as the matrix resin of a hard-coat layer.
The monomer usually has a reactive functional group. Monomers crosslink between monomers when cured. In addition, since the reactive functional group of the monomer has cross-linking reactivity with the reactive functional group of the reactive irregularly shaped silica fine particles, the monomer is crosslinked with the reactive irregularly shaped silica fine particles, forming a network structure, and the hardness of the hard coat layer And further improve the scratch resistance. As the reactive functional group, a polymerizable unsaturated group is suitably used, preferably a photocurable unsaturated group, and particularly preferably an ionizing radiation curable unsaturated group. Specific examples include ethylenically unsaturated bonds such as (meth) acryloyl groups, vinyl groups, allyl groups, and epoxy groups. The reactive functional group of the monomer may be the same as or different from the reactive functional group of the reactive deformed silica fine particle.

As the monomer, a curable organic resin is preferable, and a translucent material that transmits light when it is used as a coating film is preferable. An ionizing radiation curable resin that is a resin that is cured by ionizing radiation represented by ultraviolet rays or electron beams, 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 monomer, one type or two or more types of monomers can be used.

The monomer preferably has three or more reactive functional groups from the viewpoint of increasing the crosslinking density. Examples of the polyfunctional monomer having three or more reactive functional groups include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate. , Trimethylolpropane tri (meth) acrylate, trimethylolpropane hexa (meth) acrylate, and modified products thereof. In addition, as a modified body, an ethylene oxide modified body, a propylene oxide modified body, a caprolactone modified body, an isocyanuric acid modified body, etc. are mentioned.
Among them, as the polyfunctional monomer, pentaerythritol triacrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, and dipentaerythritol pentaacrylate are preferably used, and dipentaerythritol hexaacrylate, penta Erythritol tetraacrylate and dipentaerythritol pentaacrylate are particularly preferably used.

In addition, the hard coat layer may contain not only a monomer that is crosslinked but also a monomer that is not crosslinked.

The monomer content is preferably in the range of 25% by mass to 44% by mass and more preferably in the range of 30% by mass to 40% by mass with respect to the total solid content of the curable resin composition. . When the content is small, there is a possibility that sufficient hardness cannot be imparted to the hard coat layer. On the other hand, when the content is large, the hardness of the hard coat layer is excessively increased, and the content of the acrylic polymer is relatively decreased, which may deteriorate the workability of the hard coat film.

(D) Polymerization initiator In the present invention, the curable resin composition may contain a polymerization initiator. A polymerization initiator is used when the curable resin composition is cured by ultraviolet irradiation or heating, but when it is cured by electron beam irradiation, a polymerization initiator is unnecessary.

The polymerization initiator is decomposed by at least one of light and heat to generate radicals or cations to advance radical polymerization and cationic polymerization.
As the polymerization initiator, radical polymerization initiators, cationic polymerization initiators, radicals and cationic polymerization initiators can be appropriately selected and used.

The radical polymerization initiator only needs to be capable of releasing a substance that initiates radical polymerization by at least one of light and heat. For example, photo radical polymerization initiators 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. It is done. Specific examples include those described in JP 2010-102123 A and JP 2010-120182 A.

Moreover, the cationic polymerization initiator should just be able to discharge | release the substance which starts cationic polymerization by at least any one of light and a heat | fever. 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). Enil) iron (II) and the like. Specific examples include those described in JP 2010-102123 A and JP 2010-120182 A.

Examples of radical polymerization initiators and cationic polymerization initiators that can be used include aromatic iodonium salts, aromatic sulfonium salts, aromatic diazonium salts, aromatic phosphonium salts, triazine compounds, and iron arene complexes. Specific examples include those described in JP 2010-102123 A and JP 2010-120182 A.

Among them, the polymerization initiator preferably has a relatively low absorption rate in the visible light region. This is because if the absorption rate in the visible light region is high, the light transmittance of the hard coat film may be lowered.

The content of the polymerization initiator is preferably in the range of 2% by mass to 5% by mass with respect to the total solid content of the curable resin composition, and is preferably in the range of 2% by mass to 2.5% by mass. It is more preferable. If the content is small, the polymerization reaction of monomers or the like does not proceed sufficiently, and there is a possibility that sufficient hardness cannot be imparted to the hard coat layer. Moreover, when there is much content, polymerization reaction, such as a monomer, advances rapidly, and there exists a possibility that workability | operativity may fall or it may become a non-uniform cured | curing material.

(E) Surfactant The curable resin composition used in the present invention may further contain a surfactant. The surfactant is a component that imparts coating stability, slipperiness, antifouling properties, and scratch resistance.
Examples of the surfactant include a fluorine-based surfactant, a silicon-based surfactant, and a fluorine-silicon-based surfactant. Of these, a fluorosilicone surfactant is preferably used because of its good slipperiness.

As the surfactant, a commercially available one can be used, and for example, leveling agents described in JP 2010-102123 A and JP 2010-120182 A can be used.

Examples of the fluorosilicone surfactant include a compound having a perfluoroalkyl group and a siloxane bond. Specifically, a compound having a perfluoroalkyl group and a copolymer of siloxane and polyether. Is mentioned. The perfluoroalkyl group has, for example, 4 to 10 carbon atoms. The perfluoroalkyl group may be linear or branched. Examples of the polyether group include a polyethylene oxide chain, a polypropylene oxide chain, and a copolymer thereof.

Specific examples of such fluorine silicon surfactants include compounds represented by the following chemical formula (6).

In the above formula (6), R is a perfluoroalkyl group having 4 to 10 carbon atoms, Q is a polyethylene oxide chain or a polypropylene oxide chain, k and m are each 0 or 1, and n is 1, 2 or 3 It is.

Further, the fluorosilicone surfactant may have a reactive functional group. As the reactive functional group, for example, a polymerizable unsaturated group is used, specifically a photocurable unsaturated group, and more specifically an ionizing radiation curable unsaturated group. Specific examples of the reactive functional group include a (meth) acryloyl group.

Specific examples of the fluorosilicone surfactant include X-71-1203M, X-70-090, X-70-091, X-70-092, X-70-093, manufactured by Shin-Etsu Chemical Co., Ltd., DIC Corporation. Examples thereof include Megafac R-08, XRB-4, and the like.

In addition, when an antiglare layer is formed on the hard coat layer as will be described later, the hard coat layer has good surface wettability so that the antiglare layer can be formed on the hard coat layer. It is preferable to use a surfactant capable of obtaining Such a surfactant can be appropriately selected from the above and used.

The content of the surfactant is preferably 0.2% by mass or less, and preferably in the range of 0.08% by mass to 0.1% by mass with respect to the total solid content of the curable resin composition. More preferred.

(F) Blue color material The curable resin composition used in the present invention may further contain a blue color material. This is because when the hard coat film of the present invention is used in an image display device, yellowness can be suppressed and visibility and color reproducibility can be improved.
As the blue color material, general pigments and dyes can be used. Specific examples include phthalocyanine pigments and indanthrene blue pigments.
The content of the blue color material may be an amount such that the transmittance of the hard coat layer described later is 85% or more, and preferably 90% or more, and is appropriately adjusted. For example, the content of the blue color material is preferably 0.05% by mass or less with respect to the total solid content of the curable resin composition.

(G) Urethane acrylate The curable resin composition used in the present invention may further contain urethane acrylate. This is because by adding urethane acrylate, flexibility can be imparted to the hard coat layer and the occurrence of warpage can be suppressed. In particular, when the hard coat layer 3 and the second hard coat layer 4 are formed on both surfaces of the substrate 2 as illustrated in FIG. 3, a curable resin composition to which urethane acrylate is added is used. By forming the hard coat layer 3 and the second hard coat layer 4, it is possible to further suppress the occurrence of warping and improve the impact resistance.

As the urethane acrylate, for example, a general urethane acrylate used for a hard coat layer can be used. Specific examples include those described in JP 2011-31527 A, JP 2009-84328 A, and International Publication No. 2012/8444.

The content of urethane acrylate may be an amount such that the pencil hardness of the hard coat layer, which will be described later, falls within a predetermined range, and is appropriately adjusted. For example, the content of urethane acrylate can be set within the range of 4 to 100 parts by weight with respect to 100 parts by weight of the monomer.

(H) Solvent The curable resin composition used in the present invention usually contains a solvent.
The solvent is not particularly limited, but a non-permeable solvent is preferable from the viewpoint of increasing the hardness of the hard coat film. Here, permeation refers to dissolving or swelling the substrate.
Specific examples of the non-permeable solvent include methyl isobutyl ketone, propylene glycol monomethyl ether, normal propanol, isopropanol, normal butanol, sec-butanol, isobutanol, and tert-butanol.

(I) Other components The curable resin composition used for this invention may contain the antistatic agent, the glare-proof agent, various sensitizers, etc. as needed.

(J) Curable resin composition The curable resin composition is prepared by mixing a dispersion of reactive irregularly shaped silica fine particles, an acrylic polymer, a monomer, a polymerization initiator and the like in a solvent according to a general preparation method, and dispersing the mixture. Can do. For mixing and dispersing, a paint shaker or a bead mill can be used.

(2) Deformed silica fine particles The deformed silica fine particles contained in the hard coat layer in the present invention are obtained by crosslinking the reactive deformed silica fine particles contained in the curable resin composition, or the reactive deformed silica fine particles It is formed by crosslinking with monomers. That is, the hard coat layer contains cross-linked irregular-shaped silica fine particles or irregular-shaped silica fine particles crosslinked with the matrix resin.
In addition, the hard coat layer includes not only the reactive functional group of the reactive irregular shaped silica fine particles reacted but also the reactive functional group of the reactive irregular shaped silica fine particles not reacting as the irregular shaped silica fine particles. It may be.
The content of the irregular shaped silica fine particles in the hard coat layer can be the same as the content of the reactive irregular shaped silica fine particles in the total solid content of the curable resin composition.

(3) Acrylic polymer The acrylic polymer contained in the hard coat layer in the present invention has a weight average molecular weight and an acrylic equivalent within predetermined ranges.
In addition, since it is the same as that of the acryl-type polymer contained in the said curable resin composition about an acryl-type polymer, description here is abbreviate | omitted.
The content of the acrylic polymer in the hard coat layer can be the same as the content of the acrylic polymer in the total solid content of the curable resin composition.

(4) Matrix resin The matrix resin contained in the hard coat layer in the present invention is a resin forming a composite with irregular-shaped silica fine particles and an acrylic polymer. It is considered that the hardness and scratch resistance of the hard coat layer are increased by forming a three-dimensional network structure with the matrix resin, the deformed silica fine particles, and the acrylic polymer.

Examples of such a matrix resin include acrylic resin, silicone resin, and polyether. Among these, an acrylic resin is preferable. This is because the properties of the hard coat layer are improved because of its high affinity with the acrylic polymer.

Further, the matrix resin is preferably formed by crosslinking of monomers contained in the curable resin composition, or by crosslinking of the monomer with reactive deformed silica fine particles. That is, the hard coat layer preferably contains a matrix resin having a cross-linked bond or a matrix resin cross-linked with irregular shaped silica fine particles.

In the above case, the matrix resin is preferably a polymer having a structural unit derived from a monomer. In particular, because of its affinity with acrylic polymers and ease of molecular design, matrix resins are polymers having structural units derived from hydroxy group-containing monomers such as pentaerythritol, dipentaerythritol, and trimethylolpropane. Preferably there is. Among these, the structural unit is preferably a structural unit derived from a monomer of pentaerythritol. For example, the structure obtained when the monomer of pentaerythritol forms chemical bonds, such as an ether bond and an ester bond, is mentioned. More specifically, structures such as pentaerythritol trimethyl ether and pentaerythritol tetramethyl ether, dipentaerythritol hexamethyl ether, and dipentaerythritol pentamethyl ether can be given as the similar skeleton.

The content of the matrix resin in the hard coat layer can be the same as the content of the monomer in the total solid content of the curable resin composition.

(5) Polymerization initiator The hard coat layer in the present invention may contain a polymerization initiator.
In addition, about a polymerization initiator, since it is the same as that of the polymerization initiator contained in the said curable resin composition, description here is abbreviate | omitted.
The content of the polymerization initiator in the hard coat layer can be the same as the content of the polymerization initiator in the total solid content of the curable resin composition.

(6) Surfactant The hard coat layer in the present invention may contain a surfactant.
In addition, about surfactant, since it is the same as that of surfactant contained in the said curable resin composition, description here is abbreviate | omitted.
The content of the surfactant in the hard coat layer can be the same as the content of the surfactant in the total solid content of the curable resin composition.

(7) Blue color material The hard coat layer in the present invention may contain a blue color material.
In addition, about a blue color material, since it is the same as that of the blue color material contained in the said curable resin composition, description here is abbreviate | omitted.
The content of the blue color material in the hard coat layer can be the same as the content of the blue color material in the total solid content of the curable resin composition.

(8) Urethane acrylate The hard coat layer in the invention may contain urethane acrylate.
In addition, since it is the same as that of the urethane acrylate contained in the said curable resin composition about urethane acrylate, description here is abbreviate | omitted.
The urethane acrylate content in the hard coat layer can be the same as the urethane acrylate content in the curable resin composition.

(9) Hard Coat Layer The hardness of the hard coat layer can be evaluated by a pencil hardness test (4.9 N load) specified by JIS K5600-5-4 (1999). The pencil hardness of the hard coat layer is preferably 6H or more, more preferably 7H or more, and particularly preferably 9H or more.

The hard coat layer is light transmissive. Specifically, the transmittance of the hard coat layer in the visible light region is preferably 80% or more, and more preferably 90% or more. This is because when the transmittance is in the above range, a hard coat layer having excellent light transmittance can be formed.
Here, the transmittance of the hard coat layer is the total light transmittance measured by the method defined in JIS K 7105.

Further, the haze value of the hard coat layer is appropriately determined according to the type of reactive irregularly shaped silica fine particles and is not particularly limited. For example, it is 1.0 or less, particularly 0.8 or less, particularly 0. .5 or less is preferable. It is because it can be set as the hard-coat layer with favorable light transmittance because haze value is the said range.
The haze value can be measured by a method according to JIS-K-7136. For example, it can be measured with a direct reading haze meter manufactured by Toyo Seiki Seisakusho using a semi-integrating sphere. The haze value can also be measured by a method according to JIS K-7105, for example, a haze meter HM150 manufactured by Murakami Color Research Laboratory.

The hard coat layer preferably has antifouling properties. The antifouling property can be evaluated by wettability. Specifically, the wettability of the hard coat layer surface is appropriately determined according to the components used in the curable resin composition, and is not particularly limited. However, the contact angle of water droplets on the hard coat layer surface is preferably 90 ° or more, more preferably 100 ° or more, and even more preferably 110 ° or more. This is because if the wettability is as described above, the hard coat layer can exhibit good antifouling properties. On the other hand, the contact angle of the water droplet is usually 120 ° or less.
The contact angle of the water droplet is obtained by measuring the contact angle with water 30 seconds after dropping the water droplet from the microsyringe using a contact angle measuring device CA-Z type manufactured by Kyowa Interface Science Co., Ltd. be able to.

Moreover, when the hard coat film of this invention is used for a touch panel etc., it is preferable that a hard coat layer has slipperiness. The slipperiness can be evaluated by a dynamic friction coefficient. The smaller the dynamic friction coefficient, the better the slipperiness. The coefficient of dynamic friction on the surface of the hard coat layer is, for example, 0.300 or less, preferably 0.200 or less, and more preferably 0.100 or less. This is because if the dynamic friction coefficient is too large, it may be difficult to perform a good touch operation on the surface of the hard coat layer.
The dynamic friction coefficient can be measured by a method in accordance with JIS K7125. For example, a dynamic friction tester HEIDON Type HHS2000 manufactured by Shinto Kagaku Co., Ltd. is used, a stainless hard ball having a diameter of 10 mm, a load of 200 g, and a speed. The dynamic friction coefficient can be measured at 5 mm / sec.

The thickness of the hard coat layer is not particularly limited as long as the desired hardness and workability can be exhibited. For example, the thickness can be about 5 μm to 40 μm, and particularly within the range of 10 μm to 30 μm. In particular, it is preferably in the range of 18 μm to 22 μm. This is because if the hard coat layer is thin, sufficient hardness cannot be exhibited, and if it is thick, cracks and warpage may occur.

The method for forming the hard coat layer is not particularly limited as long as the hard coat layer can be formed using the curable resin composition, and the curable resin composition is applied onto the substrate, A method of curing the coating film can be used.
The coating method of the curable resin composition is not particularly limited as long as the curable resin composition can be uniformly coated on the substrate, and is not limited to spin coating, dipping, spraying, slide coating. Various methods such as a method, a bar coat method, a roll coater method, a meniscus coater method, a flexographic printing method, a screen printing method, and a speed coater method can be used. Moreover, it is preferable to adjust as the coating amount of the curable resin composition on a board | substrate so that the hard-coat layer of a desired film thickness may be obtained.
Examples of the method for drying the coating film include reduced-pressure drying, heat drying, and combinations thereof. When drying at normal pressure, it is preferable to dry in a temperature range in which the substrate does not deteriorate, for example, in the range of 30 ° C. to 110 ° C.

As a method for curing the coating film, at least one of light irradiation and heating can be used.
For light irradiation, ultraviolet rays, visible light, electron beams, ionizing radiation, etc. are mainly used, and among these, ultraviolet rays are preferably used. In the case of ultraviolet curing, ultraviolet rays emitted from light such as an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp are used. The amount of irradiation with the energy radiation source of accumulative exposure at an ultraviolet wavelength of 365 nm, is preferably in the range of, for example, ^{50mJ / cm 2 ~ 5000mJ / cm} 2.
In addition, when heating, it is preferable to heat in a temperature range in which the substrate does not deteriorate, for example, in the range of 40 ° C. to 120 ° C. Moreover, you may react by leaving it to stand for 24 hours or more at room temperature of about 25 degreeC.

2. Substrate The substrate used in the present invention is not particularly limited as long as it has optical transparency and satisfies physical properties that can be used as a substrate for a hard coat film. Usually, the substrate used for the hard coat film may be transparent, translucent, colorless or colored, but is required to have light transmittance.

Examples of the material for the substrate include acrylate polymers, polycarbonates, polyesters, cellulose acylates, cycloolefin polymers, and the like. Specific examples of the acrylate polymer include methyl poly (meth) acrylate, poly (meth) ethyl acrylate, methyl (meth) acrylate-butyl (meth) acrylate, and the like. Specific examples of the polycarbonate include aromatic polycarbonates based on bisphenols such as bisphenol A, and aliphatic polycarbonates such as diethylene glycol bisallyl carbonate. Specific examples of the polyester include polyethylene terephthalate and polyethylene naphthalate. Specific examples of cellulose acylate include cellulose triacetate, cellulose diacetate, and cellulose acetate butyrate. Specific examples of the cycloolefin polymer include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymer resins, and the like.

The substrate may be a single layer or a laminate of a plurality of layers. In the case of a single layer, the substrate material is preferably an acrylate polymer, more preferably polymethyl methacrylate. This is because the transparency is high. On the other hand, in the case of a plurality of layers, the substrate has a plurality of resin layers. The number of resin layers may be two or more, preferably in the range of 3 to 5 layers, more preferably 3 layers.

When the substrate has three or more resin layers, the outermost two layers are the outermost resin layers and the innermost resin layer is the innermost resin layer. As shown in FIG. 2, for example, when the substrate 2 has three resin layers 2a to 2c, the two outermost resin layers 2b and 2c are defined as the two outermost resin layers 2b and 2c, The layer located inside 2c is referred to as an inner resin layer 2a. The inner resin layer 2a may be a single layer or a plurality of layers.

When the substrate has three or more resin layers, it is preferable that the pencil hardness of the two outermost resin layers positioned on both sides of the substrate is higher than the pencil hardness of the inner resin layer. By increasing the hardness of the outermost resin layer, it becomes easier to form a hard coat film with high hardness, and by reducing the hardness of the inner resin layer, the stress caused by the difference in thermal expansion coefficient, etc. can be relieved, that is, the inner side This is because the resin layer becomes a cushion layer, and for example, impact resistance such as ball drop resistance is improved. The difference in hardness between the outermost resin layer and the inner resin layer is preferably two or more steps, more preferably three or more steps, on the basis of pencil hardness. For example, the pencil hardness of the outermost resin layer is preferably HB or higher, and more preferably H or higher and 5H or lower. The pencil hardness of the inner resin layer is preferably H or less, for example, and more preferably 3B or more and HB or less.

When the substrate has a plurality of resin layers, the pencil hardness of the substrate is preferably 2H or more, and more preferably 3H or more. This is because the hardness of the hard coat film can be further improved. The pencil hardness of the substrate is preferably high, but is usually 4H or less.
On the other hand, even when the substrate is a single layer, the pencil hardness of the substrate is preferably 2H or more.

Further, as illustrated in FIG. 2, when the substrate 2 has three resin layers 2a to 2c, the inner resin layer 2a is polycarbonate, and the two outermost resin layers 2b and 2c are acrylate polymers. Is preferred. This is because the impact resistance is improved. In this case, the thickness of one outermost resin layer is preferably in the range of 60 μm to 110 μm.

In addition, the substrate may contain a blue color material. Instead of adding a blue color material to the hard coat layer, a hard coat film capable of suppressing yellowishness and improving visibility and color reproducibility when used in an image display device is obtained by adding to a substrate. be able to. In addition, about a blue color material, it can be the same as that of what was described in the said hard-coat layer.

It is preferable that the substrate transmits more light. The total light transmittance in the visible light region is preferably 80% or more, and more preferably 90% or more. The total light transmittance is a value measured by the method defined in JIS K 7105.

Further, the substrate may or may not have flexibility.
The thickness of the substrate is not particularly limited, but in the case of a substrate that does not have flexibility, it is preferably 0.3 mm or more, more preferably in the range of 0.3 mm to 5 mm. . It is because sufficient impact resistance can be maintained within the above range. On the other hand, in the case of a flexible substrate, the thickness of the substrate varies depending on the material, configuration, etc., but can be set within a range of 10 μm to 500 μm, for example.
Further, the substrate may be subjected to surface treatment such as saponification treatment, glow discharge treatment, corona discharge treatment, ultraviolet treatment, flame treatment and the like.

3. Second Hard Coat Layer In the present invention, as illustrated in FIG. 3, the second hard coat layer 4 may be formed on the surface of the substrate 2 opposite to the surface on which the hard coat layer 3 is formed. . By forming the second hard coat layer, the hardness of the hard coat film can be further improved.

The curable resin composition used for the second hard coat layer is the same as the curable resin composition used for the hard coat layer.
Especially, it is preferable that the curable resin composition used for a 2nd hard-coat layer contains urethane acrylate. In this case, it is preferable that the curable resin composition used for the hard coat layer also contains urethane acrylate. As described above, by adding urethane acrylate, flexibility can be imparted to the hard coat layer and the second hard coat layer, occurrence of warpage can be suppressed, and impact resistance can be improved. Because.
The curable resin composition used for the second hard coat layer may be the same as or different from the curable resin composition used for the hard coat layer. Especially, it is preferable that the curable resin composition used for a 2nd hard-coat layer is the same as the curable resin composition used for the said hard-coat layer. This is because warpage can be further suppressed.

Further, the thickness of the second hard coat layer is the same as the thickness of the hard coat layer. The thickness of the second hard coat layer may be the same as or different from the thickness of the hard coat layer. Especially, it is preferable that the thickness of a 2nd hard-coat layer is the same as the thickness of the said hard-coat layer. It is because generation | occurrence | production of curvature can further be suppressed similarly to said case.

The characteristics and formation method of the second hard coat layer are the same as those of the hard coat layer.

4). Antiglare Layer In the present invention, the antiglare layer 5 may be formed on the hard coat layer 3 as illustrated in FIG. By forming the antiglare layer, reflection of light on the surface of the hard coat film of the present invention can be suppressed, and when the hard coat film of the present invention is used for an image display device, it reflects external light. Can suppress glare and glare. In addition, since the hard coat layer in the present invention is excellent in hardness, high hardness can be achieved even when an antiglare layer is formed on the hard coat layer.

The antiglare layer is not particularly limited as long as it has an antiglare property, but among them, a layer containing a resin and fine particles is preferable. Antiglare property can be exhibited by forming irregularities on the surface of the antiglare layer by the fine particles.

The fine particles are not particularly limited as long as they exhibit antiglare properties, but are preferably translucent fine particles. As the fine particles, both inorganic and organic can be used.
Examples of the inorganic fine particles include amorphous silica particles and inorganic silica particles.
Examples of the organic fine particles include plastic beads, and specific examples include polystyrene beads, melamine resin beads, acrylic beads, acrylic-styrene beads, benzoguanamine beads, benzoguanamine formaldehyde condensation beads, polycarbonate beads, polyethylene beads, and the like. The plastic beads preferably have a hydrophobic group on the surface, and examples thereof include styrene beads.
The fine particles may be used alone or in combination of two or more. The fine particles may be primary particles or secondary particles.
Among these, inorganic fine particles are preferably used from the viewpoint of improving the film strength of the antiglare layer, and silica fine particles are particularly preferably used.
In the case of amorphous silica particles, in order to obtain good dispersibility, it is preferable to use amorphous silica particles that have been subjected to organic treatment on the surface of the particles to make them hydrophobic. The organic matter treatment can be the same as the organic matter treatment described in JP2009-86361A.

Examples of the shape of the fine particles include a true spherical shape, an elliptical shape, an indefinite shape, a rectangular parallelepiped shape, and a cubic shape.

The average particle diameter of the fine particles is not particularly limited as long as the antiglare property can be imparted, but it is preferable that irregularities can be formed on the surface of the antiglare layer. The thickness is preferably in the range of 1 μm to 10 μm, more preferably in the range of 1 μm to 7 μm, and particularly preferably in the range of 2 μm to 5 μm. If the average particle size is small, it is difficult to provide the surface of the antiglare layer with irregularities large enough to exhibit antiglare properties, and even if irregularities can be provided, the amount of fine particles added is very large. Therefore, the film physical properties of the antiglare layer may be deteriorated. On the other hand, if the average particle size is large, the surface shape of the antiglare layer becomes rough, and the surface quality may be deteriorated, or whiteness may increase due to an increase in surface haze. The fine particles may be agglomerated particles. In the case of agglomerated particles, the secondary particle size may be in the above range.

Further, it is preferable that the particle size of fine particles of 80% or more, especially 90% or more of the whole fine particles is in the range of average particle size ± 300 nm. Thereby, the uniformity of the uneven shape on the surface of the antiglare layer can be improved.

The average particle size of the fine particles means the average when each fine particle is a monodispersed fine particle, that is, a fine particle having a single shape, and is an irregular fine particle having a broad particle size distribution. Means the particle size of fine particles present most abundantly by particle size distribution measurement. The particle size of the fine particles can be measured mainly by the Coulter counter method. In addition to this method, measurement can also be performed by laser diffraction or SEM photography.

The content of the fine particles in the antiglare layer may be adjusted as long as it is an amount capable of exhibiting antiglare properties. The content of the fine particles in the antiglare layer is, for example, preferably in the range of 2 to 35 parts by weight with respect to 100 parts by weight of the resin, and more preferably in the range of 5 to 25 parts by weight. preferable. If the content of the fine particles is small, sufficient antiglare properties may not be imparted. In addition, if the content of fine particles is large, the strength and hardness may decrease, or the internal scattering effect may be excessive and the contrast may decrease. The haze and gloss of the antiglare layer can be adjusted by adjusting the ratio of the resin and fine particle content in the antiglare layer.

As the resin, a curable resin is preferably used. For example, a thermosetting resin or an ionizing radiation curable resin that is cured by an ionizing radiation such as an ultraviolet ray or an electron beam can be used. As curable resin, what is generally used for a glare-proof layer can be used. Examples thereof include those used for the antiglare layer described in JP-A-2009-86361.

The antiglare layer may contain a surfactant. As the surfactant, those used for the hard coat layer can be used.
Further, the antiglare layer may contain a polymerization initiator, an antistatic agent, an antifouling agent, and the like as necessary.

The antiglare layer may contain a blue color material. Hard coat film that can suppress yellowishness and improve visibility and color reproducibility when used in an image display device by adding a blue color material to the antiglare layer instead of adding it to the hard coat layer Can be obtained. In addition, about a blue color material, it can be the same as that of what was described in the said hard-coat layer.

The hardness of the antiglare layer can be evaluated by a pencil hardness test (4.9 N load) defined in JIS K5600-5-4 (1999). The pencil hardness of the antiglare layer can be the same as the pencil hardness of the hard coat layer.

The antiglare layer is light transmissive. The transmittance of the antiglare layer in the visible light region can be the same as the transmittance of the hard coat layer.

Further, the haze value of the antiglare layer is appropriately determined according to the use of the hard coat film of the present invention, and is not particularly limited, and is set within a range of 3% to 30%, for example. can do.
The haze value can be measured according to JIS K-7105. As an apparatus used for the measurement, for example, there is a haze meter HM150 manufactured by Murakami Color Research Laboratory.

The antiglare layer preferably has antifouling properties. The antifouling property can be evaluated by wettability. The wettability of the antiglare layer surface can be the same as the wettability of the hard coat layer surface.

In addition, when the hard coat film of the present invention is used for a touch panel or the like, the antiglare layer preferably has slipperiness. The slipperiness can be evaluated by a dynamic friction coefficient. The dynamic friction coefficient of the surface of the antiglare layer can be the same as the dynamic friction coefficient of the surface of the hard coat layer.

The thickness of the antiglare layer is not particularly limited as long as the desired antiglare property can be exhibited, but it is preferably in the range of 1 μm to 5 μm, for example. By setting the thickness of the antiglare layer within the above range, the amount of fine particles contained in the antiglare layer can be reduced. Thereby, the excessive internal scattering effect in an anti-glare layer can be suppressed, and the fall of contrast can be suppressed, ensuring the desired internal scattering effect. Furthermore, when the antiglare layer is an extremely thin film, high hardness can be obtained by the hard coat layer formed in contact with the antiglare layer.

As a method for forming the antiglare layer, a method of applying a curable resin composition on the hard coat layer and curing the coating film can be used.
In addition, since it forms in the below-mentioned "C. manufacturing method of a hard coat film" about the formation method of an anti-glare layer, description here is abbreviate | omitted.

5. Other Configurations The hard coat film of the present invention may have a substrate and a hard coat layer, but may further have another layer depending on the use of the hard coat film. Examples of other layers include a primer layer, an antistatic layer, an antiglare layer, and a low refractive index layer.

In the present invention, a colored layer containing a blue color material may be formed on the surface of the substrate opposite to the surface on which the hard coat layer is formed. Instead of adding a blue color material to the hard coat layer, by forming a colored layer containing a blue color material, it is possible to suppress yellowness and improve visibility and color reproducibility when used in an image display device. A hard coat film can be obtained.
The colored layer contains a blue color material and a binder resin. In addition, about a blue color material, it can be the same as that of what was described in the said hard-coat layer. As the binder resin, a general one can be used. For example, a resin used for a colored layer described in JP-A-2000-57976 can be used.

Moreover, the hard coat film of the present invention may or may not have flexibility.

6). Uses The use of the hard coat film of the present invention is not particularly limited. For example, contact-type image display devices such as touch panels, non-contact types such as liquid crystal displays, CRT displays, projection displays, plasma displays, and electroluminescence displays. Examples include image display device applications and solar cell applications such as dye-sensitized solar cells. Especially, it is preferable that the hard coat film of this invention is used as a front plate of a touch panel. This is because the front plate of the touch panel is a member in direct contact with a finger, and high hardness and scratch resistance are required.

B. Curable resin composition for hard coat layer The curable resin composition for hard coat layer of the present invention comprises reactive irregularly shaped silica fine particles, an acrylic polymer having a weight average molecular weight and an acrylic equivalent within a predetermined range, a monomer, It is characterized by containing.

In the present invention, a hard coat layer having excellent hardness and scratch resistance can be obtained when the curable resin composition for a hard coat layer contains reactive deformed silica fine particles. Moreover, it is possible to achieve both high hardness and workability by adding an acrylic polymer having a weight average molecular weight and an acrylic equivalent within a predetermined range to the curable resin composition for a hard coat layer.

Since the curable resin composition for the hard coat layer was described in detail in the above section “A. Hard coat film 1. Hard coat layer”, description thereof is omitted here.

Further, the curable resin composition for a hard coat layer of the present invention can be used as an ink. When preparing the ink, for example, the viscosity and solid content concentration may be adjusted. Specifically, the viscosity and solid content concentration can be adjusted by adding a solvent or heating. As a solvent, the solvent used for the curable resin composition described in the above-mentioned item of “A. Hard coat film 1. Hard coat layer” can be used.

C. Method for producing hard coat film The method for producing a hard coat film of the present invention comprises a reactive irregularly shaped silica fine particle on a substrate, a weight average molecular weight in the range of 30,000 to 110,000, and an acrylic equivalent of 200 to A hard coat layer forming step of forming a hard coat layer by applying and curing a curable resin composition for a hard coat layer containing an acrylic polymer in the range of 1,200 and a monomer. And
Hereinafter, each process in the manufacturing method of the hard coat film of this invention is demonstrated.

1. Hard coat layer forming step In the present invention, on the substrate, hardened layer hardenability containing reactive irregular silica fine particles, an acrylic polymer having a weight average molecular weight and an acrylic equivalent within a predetermined range, and a monomer. A hard coat layer forming step is performed in which the resin composition is applied and cured to form a hard coat layer.
In addition, since it described in the said "A. hard-coat film 1. hard-coat layer" about the curable resin composition for hard-coat layers, and the formation method of a hard-coat layer, description here is abbreviate | omitted.

Moreover, when forming a glare-proof layer on a hard-coat layer so that it may mention later, it is preferable to semi-harden the coating film of the curable resin composition for hard-coat layers at a hard-coat layer formation process. The adhesion of the hard coat layer and the anti-glare layer can be improved by applying and curing the curable resin composition for the anti-glare layer on the semi-cured coating film of the curable resin composition for the hard coat layer. Because it can.
In the case of semi-curing the coating film of the curable resin composition for the hard coat layer, for example, the irradiation amount of the energy ray source may be reduced.

2. Antiglare layer forming step In the present invention, an antiglare layer forming step of forming an antiglare layer by applying a curable resin composition for an antiglare layer on the hard coat layer and curing it may be performed.
In the hard coat layer forming step and the antiglare layer forming step, the hard coat layer resin composition was applied onto the substrate, the coating film of the hard coat layer curable resin composition was semi-cured, and then semi-cured. The curable resin composition for the antiglare layer is applied onto the coating film of the curable resin composition for the hard coat layer, and the curable resin composition for the hard coat layer and the curable resin composition for the antiglare layer are coated. It is preferable to cure the coating film to form a hard coat layer and an antiglare layer. This is because an antiglare layer having good adhesion to the hard coat layer can be obtained.

In addition, about the formation method of a glare-proof layer, since it can be made to be the same as the formation method of the said hard-coat layer, description here is abbreviate | omitted.

The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

Hereinafter, the present invention will be described in more detail with reference to examples.

[Example 1]
(Preparation)
As a substrate, a laminate in which polymethyl methacrylate (PMMA), polycarbonate (PC), and polymethyl methacrylate (PMMA) were laminated in this order was prepared. The laminate had an overall thickness of 1.0 mm, a PMMA thickness of 100 μm, and a pencil hardness of 3H.
As reactive irregularly shaped silica fine particles, 3 to 10 silica fine particles having an average primary particle size of 55 nm are bonded by an inorganic chemical bond and have an average secondary particle size of 100 to 300 nm, and having a photocurable unsaturated group as a reactive functional group. A dispersion of propylene glycol-1-methyl ether acetate (PGMEA) solvent with a solid content concentration of 40.0% by mass was prepared using reactive irregular shaped silica fine particles.
Pentaerythritol triacrylate (PETA) was prepared as a monomer. As a polymerization initiator, Irgacure 184 manufactured by Ciba Japan Co., Ltd. was prepared. As the surfactant, a fluorosilicone surfactant X-71-1203M manufactured by Shin-Etsu Chemical Co., Ltd. was prepared. Propylene glycol-1-methyl ether acetate (PGMEA) was prepared as a solvent.
As polymers, acrylic polymers and urethane acrylates having different weight average molecular weights and acrylic equivalents as shown in Table 1 below were prepared. As the acrylic polymer, BL-2002 and BL-2184 manufactured by Seiko PMC Co., Ltd. were used. The composition of BL-2002 manufactured by Seiko PMC Co., Ltd. is 30 to 40 parts by weight of acrylic resin, 60 to 70 parts by weight of methyl ethyl ketone, less than 1 part by weight of acetic acid, 2,6-di-tert-butyl-4-cresol. Less than 1 part by weight. In Table 1, the difference in physical properties refers to a material having a changed weight average molecular weight or acrylic equivalent. Further, as urethane acrylate, UV75550 manufactured by Nippon Synthetic Chemical Industry Co., Ltd., U15HA manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and UN904 manufactured by Negami Industrial Co., Ltd. were used.

(Preparation of curable resin composition)
A curable resin composition was prepared with the following composition.
Reactive deformed silica fine particle dispersion: 60 parts by weight (solid content: 40% by mass)
Monomer: 12.7 parts by weight Polymer: 7.2 parts by weight Polymerization initiator: 0.76 parts by weight Surfactant: 0.905 parts by weight Solvent: 19.2 parts by weight Based on the total solid content of the curable resin composition The content of reactive irregularly shaped silica fine particles is 60% by mass. Further, the content of the reactive irregularly shaped silica fine particles is 60% by mass with respect to the total solid content of the curable resin composition, and the ratio of the ratio of the components other than the polymer and reactive irregularly shaped silica fine particles is constant. The curable resin composition was prepared by changing the addition amount.

(Formation of hard coat layer)
A curable resin composition is applied to one side of the substrate by a spin coating method, dried on a hot plate at a temperature of 80 ° C. for 180 seconds, the solvent in the coating film is evaporated, and ultraviolet light having a central wavelength of 365 nm is applied to an integrated light amount of 3000 mJ. The hard coat layer with a film thickness of 20 μm was formed by curing the coating film by irradiating it to / cm ² . The obtained hard coat layer contained a matrix resin, irregular-shaped silica fine particles, and an acrylic polymer or urethane acrylate having a predetermined weight average molecular weight and acrylic equivalent.

[Evaluation 1]
(Pencil hardness test)
The obtained hard coat film was conditioned for 2 hours under the conditions of a temperature of 25 ° C. and a relative humidity of 60%. Then, using a test pencil specified by JIS-S-6006, JIS K5600-5-4 (1999) was used. The specified pencil hardness test (4.9 N load) was performed to evaluate the highest pencil hardness without scratches.

(Mandrel test)
In accordance with the mandrel test described in JIS-K5600-5-1 (test in which a sample is wound around a metal cylinder), the hard coat layer is wound around the cylinder in the length direction of the hard coat film. The minimum diameter of the bar that did not occur was evaluated. For example, when a crack was generated in a cylinder having a diameter of 150 mm and no crack was generated in a cylinder having a diameter of 160 mm, the thickness was set to 160 mm.
Here, as a result of examining the processability of the hard coat film by the present inventors, there is a correlation between the mandrel test and the processability, and when the bendability by the mandrel test is good, the punching process, the router process, and the cutting process The processability with etc. was good.

In addition, in Table 1, the addition amount of a polymer shows the quantity with respect to the total solid of a curable resin composition, ie, the quantity in a hard-coat layer.
As shown in Table 1, it was confirmed that the workability was improved while maintaining the hardness of the hard coat layer by adding an acrylic polymer having a weight average molecular weight and an acrylic equivalent within a predetermined range. In particular, when the addition amount of the acrylic polymer in which the weight average molecular weights and acrylic equivalents of No. 1-2 and 1-9 are within a predetermined range is 6.3% by mass, the polymer is added. The hardness of the hard coat layer was improved, and both the hardness and workability were excellent.

[Example 2]
(Preparation of curable resin composition)
A curable resin composition was prepared in the same manner as in Example 1 except that BL-2002 made by Seiko PMC Co., Ltd. having a weight average molecular weight of 70,000 and an acrylic equivalent of 265 was used as the acrylic polymer.
Moreover, curable resin compositions were prepared by changing the amount of the acrylic polymer added so that the ratio of the components other than the acrylic polymer was constant. Further, a curable resin composition was prepared by changing the addition amount of the reactive irregular shaped silica fine particles so that the ratio of the components other than the reactive irregular shaped silica fine particles was constant.

(Formation of hard coat layer)
A hard coat layer was formed in the same manner as in Example 1 except that the thickness of the hard coat layer was 17 μm or 20 μm.

[Evaluation 2]
In the same manner as in Example 1, a pencil hardness test and a mandrel test were performed and evaluated.

In addition, in Table 2, content of each component shows the quantity with respect to the total solid of a curable resin composition, ie, the quantity in a hard-coat layer.
As shown in Table 2, it was confirmed that the workability was improved while maintaining the hardness of the hard coat layer by adding an acrylic polymer having a weight average molecular weight and an acrylic equivalent within a predetermined range. In particular, when the amount of acrylic polymer No.2-4 added is 6.3% by mass, the hardness of the hard coat layer is improved despite the addition of the polymer, and both hardness and workability are improved. It was.

[Example 3]
(Preparation of curable resin composition)
A curable resin composition was prepared in the same manner as in Example 1 except that the following reactive silica fine particles, acrylic polymer, and surfactant were used and the following composition was used.
As reactive silica fine particles, a dispersion of reactive irregular shaped silica fine particles used in Example 1 was prepared. This dispersion of reactive irregularly shaped silica fine particles is DP1222 manufactured by JGC Catalysts & Chemicals. Further, as another reactive silica fine particle, a spherical reactive silica fine particle having an average primary particle size of 15 nm, 45 nm or 55 nm and a photocurable unsaturated group as a reactive functional group is used, and the solid content concentration is 40.0 mass. %, A dispersion of methyl isobutyl ketone (MIBK) solvent was prepared. These reactive silica fine particle dispersions are MIBK-SDL and MIBK-DL manufactured by Nissan Chemical Industries, Ltd., and V8803 manufactured by JGC Catalysts & Chemicals, Inc., respectively.
As an acrylic polymer, BL-2002 manufactured by Seiko PMC Co., Ltd. having a weight average molecular weight of 70,000 and an acrylic equivalent of 265 was used.
As the surfactant, a fluorosilicone surfactant X-71-1203M manufactured by Shin-Etsu Chemical Co., Ltd. was prepared.
Reactive silica fine particle dispersion: 60 parts by weight (solid content concentration 40% by mass)
Monomer: 12.7 parts by weight Acrylic polymer: 7.2 parts by weight Polymerization initiator: 0.76 parts by weight Surfactant: 0.905 parts by weight Solvent: 19.2 parts by weight Components other than reactive silica fine particles A curable resin composition was prepared by changing the addition amount of the reactive silica fine particles so that the ratio of the ratio of was constant.

(Formation of hard coat layer)
A hard coat layer was formed in the same manner as in Example 1 except that the thickness of the hard coat layer was changed to 10 μm to 20 μm.

[Evaluation 3]
(Pencil hardness test)
A pencil hardness test was performed and evaluated in the same manner as in Example 1.

(Mandrel test)
A mandrel test was conducted and evaluated in the same manner as in Example 1.

(Abrasion resistance)
The surface of the hard coat layer of the hard coat film was subjected to 20 reciprocating frictions using # 0000 steel wool while applying a load, and then the presence or absence of scratches on the hard coat layer was observed and evaluated according to the following criteria.
A: No damage at 1000 g / cm ² load at 20 reciprocations or more B: 1000 g / cm ² load at 10 reciprocations or more but less than 20 reciprocations C: 1000 g / cm ² load at 10 reciprocations or less flaws

In Table 3, the content of the reactive silica fine particles indicates the amount with respect to the total solid content of the curable resin composition, that is, the amount in the hard coat layer.
As shown in Table 3, it was confirmed that the hardness of the hard coat layer was improved by adding reactive irregular shaped silica fine particles.

[Example 4]
(Preparation)
As a substrate, Technoloy C101 manufactured by Sumitomo Chemical Co., Ltd., in which polymethyl methacrylate (PMMA), polycarbonate (PC), and polymethyl methacrylate (PMMA) were laminated in this order, was prepared. Technoloy C101 had an overall thickness of 0.3 mm to 1 mm, a PMMA thickness of 70 μm, and a pencil hardness of 2H. As another substrate, FX1190 manufactured by Sumitomo Chemical Co., Ltd., in which polymethyl methacrylate (PMMA), polycarbonate (PC), and polymethyl methacrylate (PMMA) were laminated in this order, was prepared. FX1190 had an overall thickness of 1 mm, a PMMA thickness of 100 μm, and a pencil hardness of 3H.
As reactive irregular shaped silica fine particles, a dispersion of reactive irregular shaped silica fine particles used in Example 1 was prepared. As monomers, pentaerythritol triacrylate (PETA), 3-4 functional PETA, SNP Clear 11 made by DNP Fine Chemical Co., Ltd., and acrylate monomers KARAYAD DPCA20 and DPCA120 made by Nippon Kayaku Co., Ltd. were prepared. As an acrylic polymer, BL-2002 manufactured by Seiko PMC Co., Ltd. having a weight average molecular weight of 70,000 and an acrylic equivalent of 265 was used. As a polymerization initiator, Irgacure 184 manufactured by Ciba Japan Co., Ltd. was prepared. As surfactants, fluorosilicone surfactant X-71-1203M manufactured by Shin-Etsu Chemical Co., Ltd., or fluorinated surfactant Megafac MCF350-5 manufactured by DIC Corporation was prepared. Propylene glycol-1-methyl ether acetate (PGMEA) was prepared as a solvent.

(Preparation of curable resin composition)
Curable resin compositions were prepared with the compositions shown in Table 4 below.

(Formation of hard coat layer)
A curable resin composition is applied to one side of the substrate by a spin coating method, dried on a hot plate at a temperature of 80 ° C. for 180 seconds, and the solvent in the coating film is evaporated. A hard coat layer having a film thickness of 10 μm to 22 μm was formed by irradiating ultraviolet rays having a wavelength of 365 nm so that the integrated light amount was 3000 mJ / cm ² to cure the coating film. The obtained hard coat layer contained a matrix resin, irregular-shaped silica fine particles, and an acrylic polymer having a predetermined weight average molecular weight and acrylic equivalent.
As the light source, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a D bulb and an H bulb manufactured by Fusion UV Systems were used.

[Evaluation 4]
(Pencil hardness test)
A pencil hardness test was performed and evaluated in the same manner as in Example 1.

(Abrasion resistance)
Evaluation was performed in the same manner as in Example 1.

(Heat-resistant crack)
The hard coat film was placed in an oven at 80 ° C. for 30 minutes, and the presence or absence of cracks was evaluated.
A: Cracks do not occur even when placed in an oven at 80 ° C. for 30 minutes.
B: Cracks occur after being placed in an oven at 80 ° C. for 30 minutes.

(Contact angle)
The contact angle of water droplets in the hard coat layer of the hard coat film was measured by using a contact angle measuring device CA-Z type manufactured by Kyowa Interface Science Co., Ltd. Was evaluated by measuring.

(Anti-fouling property)
The hard coat layer of the hard coat film was evaluated by drawing a line on the thin side of the marker Mackie Extra Fine Black Model No .: MO-120-MC · BK manufactured by Zebra Corporation.
A: Smoke within 2 seconds (Hajik)
B: A line can be drawn (not relieved) within 2 seconds.

In addition, in Table 4, content of each component shows the quantity with respect to the total solid of a curable resin composition, ie, the quantity in a hard-coat layer.
From No.4-1 to 4-4, when the content of the reactive irregular shaped silica fine particles is in the range of 50% by mass to 60% by mass with respect to the total solid content of the curable resin composition, the pencil hardness is It was confirmed that the processability was improved. From No. 4-2 and 4-5 to 4-9, when the acrylic polymer content is 7.9% by mass, the hardness of the hard coat layer is the highest and the workability is improved. confirmed. From No. 4-2 and 4-10 to 4-13, it was confirmed that the pencil hardness was further improved when the thickness of the hard coat layer was 20 μm or more. From No.4-14 to 4-16, it was confirmed that the pencil hardness was further improved by changing the configuration of the substrate. From No. 4-2 and 4-17 to 4-19, it was confirmed that the pencil hardness was further improved when the thickness of the substrate was 0.5 mm or more. From No. 4-20 to 4-22, it was confirmed that the pencil hardness was further improved when PETA was used as a monomer. From No.4-23 to 4-26, it was confirmed that good pencil hardness could be obtained even if the curing conditions were changed.

[Example 5]
(Preparation of curable resin composition)
As the surfactant, fluorine-based surfactant X-71-1203M manufactured by Shin-Etsu Chemical Co., Ltd., fluorine-based surfactant MegaFuck MCF350-5 manufactured by DIC Corporation, or silicon-based manufactured by Shin-Etsu Chemical Co., Ltd. A curable resin composition was prepared in the same manner as in Example 1 except that the surfactant X22-163A was used.

(Formation of hard coat layer)
A hard coat layer was formed in the same manner as in Example 1.

[Evaluation 5]
(Dynamic friction coefficient)
With respect to the hard coat layer of the hard coat film, the dynamic friction coefficient was measured with a dynamic friction tester HEIDON Type HHS2000 manufactured by Shinto Kagaku Co., Ltd. using a stainless hard ball having a diameter of 10 mm at a load of 200 g and a speed of 5 mm / sec.

As shown in Table 5, it was confirmed that the lubricity was improved by adding a fluorosilicone surfactant. This hard coat film is useful as a hard coat film used for a touch panel.

[Example 6]
(Preparation)
As a substrate, FX1190 manufactured by Sumitomo Chemical Co., Ltd., in which polymethyl methacrylate (PMMA), polycarbonate (PC), and polymethyl methacrylate (PMMA) were laminated in this order, was prepared. FX1190 had an overall thickness of 0.65 mm, a PMMA thickness of 100 μm, and a pencil hardness of 3H.
As reactive irregular shaped silica fine particles, a dispersion of reactive irregular shaped silica fine particles used in Example 1 was prepared. As a blue color material, a blue pigment PB15: 6 was used. Pentaerythritol triacrylate (PETA) was prepared as a monomer. As an acrylic polymer, BL-2002 manufactured by Seiko PMC Co., Ltd. having a weight average molecular weight of 70,000 and an acrylic equivalent of 265 was used. As a polymerization initiator, Irgacure 184 manufactured by Ciba Japan Co., Ltd. was prepared. As the surfactant, a fluorosilicone surfactant X-71-1203M manufactured by Shin-Etsu Chemical Co., Ltd. was prepared. Propylene glycol-1-methyl ether acetate (PGMEA) was prepared as a solvent.

(Preparation of curable resin composition)
Curable resin compositions were prepared with the compositions shown in Table 6 below.

[Evaluation 6]
(Pencil hardness test)
A pencil hardness test was performed and evaluated in the same manner as in Example 1.

(optical properties)
The obtained hard coat film was measured for spectrum with an ultraviolet-visible near-infrared spectrophotometer MPC-3100 manufactured by Shimadzu Corporation, and using a C light source, chromaticity coordinates x, y in the XYZ color system of CIE In addition, luminance Y, chromaticity b ^* and yellowness YI in CIE L ^* a ^* b ^* color system were measured.
The chromaticity b ^* is an index in color coordinates defined in JIS-Z-8729. The chromaticity b ^* is an index of yellowness. When b ^* is large, the yellowness is strong, and when the value is negative, the yellowness is insufficient and the color becomes blue.

[Example 7]
1. Formation of hard coat layer (Preparation of curable resin composition)
A curable resin composition was prepared with the same composition as in Example 1 except that Megafac F568 manufactured by DIC Corporation was added as a surfactant.
(Formation of hard coat layer)
A hard coat layer was formed in the same manner as in Example 1 except that the exposure amount was 1/8.

2. Formation of anti-glare layer TAC-D105 manufactured by Dainichi Chemical Industries as a clear material, EXG40-77 (D-30M) manufactured by Dainichi Chemical Industries as a mat material containing amorphous silica, and Silicon 10 manufactured by Dainichi Chemical Industries as a surfactant A curable resin composition for an antiglare layer was prepared using -28, methyl isobutyl ketone (MIBK) as a solvent. At this time, 0.6 parts by weight of a surfactant was added to 100 parts by weight of the total amount of the clear material and the mat material, and the clear / mat ratio was changed to prepare a curable resin composition for an antiglare layer.
On one side of the substrate on which the hard coat layer is formed, the anti-glare layer curable resin composition is applied by a spin coating method, dried on a hot plate at a temperature of 80 ° C. for 180 seconds, and the solvent in the coating film is evaporated. An anti-glare layer having a thickness of 5 μm or less was formed by irradiating ultraviolet rays having a central wavelength of 365 nm so that the integrated light amount was 3000 mJ / cm ² to cure the coating film.

[Evaluation 7]
(Pencil hardness test)
A pencil hardness test was performed and evaluated in the same manner as in Example 1.

(Haze and transmittance)
The haze and transmittance of the hard coat film were measured by a method based on JIS-K7105 using a haze meter HM150 manufactured by Murakami Color Research Laboratory.

(Glossy)
Using a gloss meter GM-26PRO manufactured by Murakami Color Research Laboratory, the gloss value of the surface of the hard coat film was measured under the condition of an incident angle of 60 degrees. A higher number indicates higher gloss, and a lower number indicates lower gloss.

(Close contact)
In accordance with JIS K5600-5-6, an adhesive test by cross-cut method was performed using an industrial 24 mm cello tape (registered trademark) manufactured by Nichiban Co., Ltd. as an adhesive tape, and the adhesion was evaluated. Evaluation was made according to the following criteria as (number of squares not peeled) / (total squares).
A: 100/100
B: 50/100 to 99/100
C: less than 50/100

Even when an antiglare layer was formed on the hard coat layer, high hardness was obtained.

[Example 8]
(Preparation of curable resin composition)
A curable resin composition was prepared with the same composition as in Example 1 except that urethane acrylate was further added. At this time, the ratio of the monomer, the acrylic polymer and the urethane acrylate was changed as shown in Table 8. As urethane acrylate, purple light UV-7000B made by Nippon Synthetic Chemical Industry was used. This urethane acrylate has an elongation of 10% to 40% when the elongation is measured with a tensile tester at room temperature of 25 ° C. and speed of 100 mm / min.

(Formation of hard coat layer)
First, a polyethylene terephthalate (PET) substrate having a thickness of 0.35 mm was used as a substrate, and a hard coat layer having a predetermined thickness was formed on one side of the PET substrate in the same manner as in Example 1. Next, for some of the samples, a second hard coat layer having a predetermined film thickness was similarly formed on the surface of the substrate opposite to the surface on which the hard coat layer was formed.

[Evaluation 8]
(Pencil hardness test)
A pencil hardness test was performed and evaluated in the same manner as in Example 1.

(warp)
The obtained hard coat film was set to 1/4 of the A4 size, the hard coat film was placed on a flat surface, and the average value of the height of lifting from the flat surfaces of the four corners and four sides was measured as warpage. Under the present circumstances, it measured about each after a hard coat film preparation (initial stage) and the following weathering test.
The warpage was measured for each of the case where the substrate or the second hard coat layer was on the lower side and the case where the hard coat layer was on the lower side. In Table 8, the warp to the hard coat layer side when the substrate or the second hard coat layer is down is negative, and the substrate or second hard coat layer is when the hard coat layer is down The warp to the side is shown as a positive value.
The weather resistance test was a test in which the hard coat film was allowed to stand for 24 hours at a temperature of 50 ° C. and a relative humidity of 95%, and a test for which the hard coat film was allowed to stand for 24 hours under a temperature of 85 ° C. and a relative humidity of 85%.

(Falling ball test)
A test was conducted in which a steel ball of 36 g was dropped from a predetermined height, and the substrate and the hard coat film were checked for cracks and cracks. At this time, the test was conducted at a height of 5 cm. The values in the table indicate the height at which the appearance was good with no cracks or cracks.

It was confirmed that warpage can be reduced by adding urethane acrylate. In particular, when hard coat layers containing urethane acrylate were formed on both sides of the substrate, warpage after the weather resistance test was reduced.

DESCRIPTION OF SYMBOLS 1 ... Hard coat film 2 ... Board | substrate 3 ... Hard coat layer 4 ... 2nd hard coat layer 5 ... Anti-glare layer

Claims

A hard coat film having a hard coat layer formed on a substrate,
The hard coat layer is
Irregular shaped silica fine particles,
An acrylic polymer having a weight average molecular weight in the range of 30,000 to 110,000 and an acrylic equivalent in the range of 200 to 1,200;
A hard coat film comprising a matrix resin.
The hard coat film according to claim 1, wherein the hard coat layer contains a polymerization initiator.
The hard coat film according to claim 1, wherein the hard coat layer contains a blue color material.
The hard coat film according to any one of claims 1 to 3, wherein an antiglare layer is formed on the hard coat layer.
A hard coat film having a hard coat layer formed on a substrate,
The hard coat layer is
Reactive irregularly shaped silica fine particles;
The acrylic polymer;
A hard coat film comprising a cured product of a curable resin composition containing a monomer.
Reactive irregularly shaped silica fine particles;
An acrylic polymer having a weight average molecular weight in the range of 30,000 to 110,000 and an acrylic equivalent in the range of 200 to 1,200;
A curable resin composition for a hard coat layer, comprising a monomer.
The curable resin composition for a hard coat layer according to claim 6, further comprising a polymerization initiator.
The curable resin composition for a hard coat layer according to claim 6 or 7, further comprising a blue color material.
A reactive irregularly shaped silica particle, an acrylic polymer having a weight average molecular weight in the range of 30,000 to 110,000 and an acrylic equivalent in the range of 200 to 1,200, and a monomer are contained on the substrate. The manufacturing method of the hard coat film characterized by having the hard-coat layer formation process which apply | coats and hardens the curable resin composition for hard-coat layers to form a hard-coat layer.