KR20150111828A - Hard coat film, transparent conductive film, and capacitive touch panel - Google Patents

Abstract

The purpose of the present invention is to provide a hard coating film, which prevents blocking between hard coating films and has excellent adhesiveness, a transparent conductive film and a capacitive touch panel which have the same. The hard coating film includes a hard coating layer on at least one side of a base film. The hard coating layer is made of a cured product including at least an energy ray curable resin (A), a hydrophobic silica sol (B), and a silicon-based leveling agent (C). The hydrophobic silica sol (B) is placed on the surface, opposite to the base film, of the hard coating layer after curing materials for forming the hard coating layer. In a region from the outermost surface of the coating film to a depth of 5 nm, the concentration of silicon atoms is within a range of 0.2-1.95 atom% with respect to a total amount of carbon atoms, oxygen atoms, and silicon atoms which is measured by XPS analysis in a depth direction.

Description

A hard coat film, a transparent conductive film, and a capacitive touch panel (a hard coat film, a transconductive film, and a capillary touch panel)

The present invention relates to a hard coating film, a transparent conductive film and a capacitive touch panel, and particularly relates to a hard coating film having good adhesion and anti-blocking property when a surface layer (conductive layer or the like) is formed, A transparent conductive film having such a hard coating film, and a capacitive touch panel.

2. Description of the Related Art Conventionally, as a liquid crystal display device having a liquid crystal display, for example, a portable electronic notebook or an information terminal is used. Recently, a liquid crystal display device in which a touch panel that can be directly contacted with the display portion is mounted is widely used.

Examples of such a touch panel include a capacitive type, a resistive type, and an electromagnetic induction type. Among them, capacitive touch panels that detect input positions by detecting a small current that occurs when a finger or the like comes into contact, that is, a change in capacitance, is becoming widespread.

In such a liquid crystal display device, in many cases, a hard coating film is provided on the surface of the transparent conductive film in order to improve the scratch resistance and ease of handling of the transparent conductive film or the like.

As such a hard coating film, it is known that a hard coat layer is provided on the surface of a substrate.

For example, there has been disclosed a hard coat film for display comprising a transparent polyester film laminated on one side or both sides thereof with an adhesive layer (easy-adhesion adhesive layer), a hard coating layer and an antireflection layer in this order (for example, Patent Document 1).

That is, Patent Document 1 discloses a hard coating film for display containing inorganic fine particles having a predetermined surface hardness and a predetermined thickness as a hard coating layer and having a water contact angle of 40 to 80 deg. Lt; / RTI >

On the other hand, from the viewpoints of productivity and handleability, a film having hard coatability is coated with a hard coat layer and then rolled up and stored. When storage in the roll state is prolonged, the surface of the film is pasted (blocked) to each other to cause scratches or the like on the surface of the hard coating layer, or when the hard coating film in which the blocking occurs is used, I saw a problem.

Thus, for example, in order to prevent the hard coating films from sticking or peeling off from each other when the hard coating film is wound up in a roll in the manufacturing process, An optical laminate having a coating layer, a transparent conductive film and a capacitive touch panel have been proposed (for example, see Patent Document 2).

More specifically, the hard coat layer is a layer formed by using a composition for a hard coat layer containing a binder resin, a leveling agent and a lubricant, wherein the lubricant is at least one selected from the group consisting of silica particles and silicon particles And a silicon leveling agent as a leveling agent is favorable.

A hard coating film, a polarizing plate, and an image display device comprising a predetermined composition for a hard coating layer have been proposed for the purpose of suppressing a decrease in yield due to blocking and improving leveling performance (see, for example, 3).

More specifically, as a composition for a hard coat layer containing a leveling agent, silica fine particles, and a binder resin, a leveling agent is disclosed for a composition for a hard coat layer containing a prescribed fluorine leveling agent.

Japanese Patent Application Laid-Open No. 2001-109388 (claims) Japanese Patent Application Laid-Open No. 2012-66409 (claims and the like) Japanese Patent Application Publication No. 2012-252275 (claims)

However, the hard coating film for display disclosed in Patent Document 1 has a problem that since the surface of the hard coating layer is hydrophilic, it has a predetermined pencil hardness, but the adhesiveness is insufficient and the adhesion between the films can not be effectively prevented It looked.

In addition, the optical laminate described in Patent Document 2 prevents the optical laminate from sticking to each other by using relatively large silica particles as a lubricant. As a result, adhesion between the films can be prevented to a certain extent, but there is a problem that transparency of the optical laminate becomes insufficient since the lubricant is a relatively large particle.

The composition for hard coat layer described in Patent Document 3 uses relatively large silica particles as a lubricant and also requires a fluorine leveling agent as a leveling agent. As a result, a certain degree of inhibition of blocking and an improvement in smoothness can be confirmed, but there is a problem that the adhesiveness is lowered when a conductive layer or the like is further laminated on the hard coat film due to the water repellency of the fluorine leveling agent.

The inventors of the present invention have conducted intensive studies to solve the above problems. As a result, they have found that a hard coating layer is provided on at least one side of a base film, and a hard coating layer forming material for forming the hard coating layer is coated with a predetermined hydrophobic silica sol, The hard coat film can be effectively prevented from blocking with each other and the surface layer (conductive layer or the like) is formed, the good adhesion The present invention has been completed.

That is to say, the present invention is to provide an antistatic agent capable of effectively preventing blocking (sticking) between hard coat films and exhibiting good adhesion with a surface layer when a surface layer (conductive layer or the like) is formed A transparent conductive film having such a hard coating film, and a capacitive touch panel.

According to the present invention, there is provided a hard coating film having a hard coating layer on at least one side of a base film, wherein the hard coating layer comprises at least (A) an energy ray curable resin, (B) a hydrophobic silica sol, (C) (B) the hydrophobic silica sol is localized on the surface side opposite to the substrate film of the hard coat layer after curing the hard coat layer forming material, and the hard coat layer (100 atom%) of carbon atoms, oxygen atoms, and silicon atoms measured by XPS analysis in the depth direction in the region from the outermost surface to the 5 nm position, the silicon atom concentration is within the range of 0.2 to 1.95 atom% Value, and the above-mentioned problems can be solved.

That is, since the hydrophobic silica sol is used as the hard coating layer forming material, the hydrophobic silica sol is present on the surface side of the hard coat layer after the hard coat layer forming material is cured and is phase separated , Minute irregularities are formed on the surface of the hard coating film, so that the hard coating films can be prevented from sticking to each other.

In addition, since the silicone leveling agent is contained on the outermost surface of the hard coat layer by covering the hydrophobic silica sol by containing the silicon leveling agent, the surface layer (the conductive layer, etc.) .

In addition, deformation and cissing of the coating film can be suppressed by setting the concentration of silicon atoms within a predetermined range in a region from the outermost surface of the hard coating film to a position of 5 nm.

(C) a silicone-based leveling agent, a silicone-modified acrylic, a polyether-modified polydimethylsiloxane, a polyetherester-modified hydroxyl group-containing polydimethylsiloxane, a polyester-modified hydroxyl group-containing polydimethylsiloxane, And at least one member selected from the group consisting of polyether-modified polydimethylsiloxane.

By such a constitution, the silicon atom concentration in the region from the outermost surface of the hard coat film to the position of 5 nm can be easily adjusted to a value within a predetermined range.

In the construction of the hard coating film of the present invention, it is preferable that the compounding amount of the silicone leveling agent (C) is within a range of 0.045 to 5 parts by weight in terms of solid content relative to 100 parts by weight of the (A) energy ray curable resin.

By such a constitution, the adhesiveness of the hard coating film can be effectively improved.

In forming the hard coat film of the present invention, the average particle diameter of the hydrophobic silica sol (B) is preferably in the range of 10 to 100 nm.

By such a constitution, transparency of the hard coat film can be maintained or effectively improved, and sufficient light transmittance can be obtained.

In forming the hard coat film of the present invention, it is preferable that the contact angle of water measured in accordance with JIS R 3257 with respect to the coating film when (B) the hydrophobic silica sol is used as a coating film is set to a value of 100 DEG or more.

By such a constitution, blocking of the hard coating films can be effectively prevented.

In the construction of the hard coat film of the present invention, it is preferable that the blending amount of the hydrophobic silica sol (B) is in the range of 0.3 to 55 parts by weight in terms of solid content relative to 100 parts by weight of the (A) energy ray curable resin.

By such a constitution, it is possible to effectively localize on the surface side in the hard coating layer and to improve the transparency of the hard coating film, despite the addition of a relatively small amount.

In forming the hard coat film of the present invention, it is preferable that the haze value measured according to JIS K 7105 of the hard coat film is 1.0% or less.

By such a constitution, it can be used for a transparent conductive film having excellent transparency, and it can be used, for example, in an electronic apparatus such as a capacitive touch panel.

In forming the hard coat film of the present invention, it is preferable that the arithmetic mean roughness (Ra) measured on the surface of the hard coat layer in accordance with JIS B 0601-1994 is in the range of 1.5 to 5 nm.

By such a constitution, it is possible to obtain fine irregularities on the surface of the obtained hard coating film, and blocking of the hard coating films can be prevented inevitably.

When the arithmetic mean roughness on the surface of the hard coat layer is within this range, a hard coat film having excellent optical characteristics can be obtained.

Further, another aspect of the present invention is a transparent conductive film having a transparent conductive layer on at least one side of the above-mentioned hard coat film.

That is, by using the hard coating film excellent in blocking resistance and excellent in adhesion to the transparent conductive layer, there is no need to prevent blocking between films using a protective film, and furthermore, A transparent conductive film can be obtained.

Still another aspect of the present invention is a capacitive touch panel including a cover glass having a glass shatterproof film, a first transparent conductive film, a second transparent conductive film, and a liquid crystal display, The conductive film and the second transparent conductive film either have a transparent conductive layer on the hard coat layer of the hard coat film having the hard coat layer and the hard coat film has the hard coat layer on at least one side of the base film , Wherein the hard coating layer comprises a cured product of a hard coat layer forming material comprising at least (A) an energy ray curable resin, (B) a hydrophobic silica sol, and (C) a silicone leveling agent, and (B) , The hard coat layer after curing the hard coat layer forming material is unevenly distributed on the surface side opposite to the substrate film, and is located in the region from the outermost surface of the hard coat film to the position of 5 nm Wherein the silicon atom concentration is within a range of 0.2 to 1.95 atom% with respect to a total amount (100 atom%) of carbon atoms, oxygen atoms and silicon atoms measured by XPS analysis in the depth direction.

That is, in a capacitive touch panel using a transparent conductive film having a transparent conductive layer in a hard coating film having good adhesion and blocking resistance in the case of forming a surface layer (conductive layer), a capacitive touch panel Can be obtained.

According to another aspect of the present invention, there is provided a method for producing a hard coating film having a hard coating layer on at least one side of a base film, which comprises the following steps (1) to (3) to be.

(1) preparing a hard coat layer forming material comprising at least (A) an energy ray-curable resin, (B) a hydrophobic silica sol, and (C)

(2) a step of applying the hard coating layer-forming material to at least one side of the base film

(3) hardening the hard coating layer forming material, (B) subjecting the hydrophobic silica sol to localization on the surface side opposite to the substrate film of the hard coat layer after curing the hard coat layer forming material, In which the silicon atom concentration is within a range of 0.2 to 1.95 atom% with respect to the total amount (100 atom%) of carbon atoms, oxygen atoms and silicon atoms measured by XPS analysis in the depth direction Process for forming a hard coat film having a coating layer

That is, by carrying out the method in this way, it is possible to efficiently produce the hard coat film in which the silica particles are present in a localized manner on the opposite surface side of the base film.

Therefore, even when the hard coating film is produced by a roll-to-roll process, it is possible to effectively prevent the hard coating films from sticking together and to improve the productivity.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 (a) to (b) are diagrams for explaining aspects of the hard coating film of the present invention. Fig.
Fig. 2 is a view for conceptually illustrating a hard coating film of the present invention. Fig.
Fig. 3 is a view for explaining the silicon atom concentration distribution in the hard coat layer measured by XPS analysis in the depth direction; Fig.
4 (a) to 4 (b) are diagrams for explaining aspects of the transparent conductive film of the present invention.
5 is a view for explaining an aspect of a capacitive touch panel according to the present invention;
6 is a diagram provided to illustrate a conventional hard coating film containing a silica sol whose surface is hydrophilic.

[First Embodiment]

(A) an energy ray-curable resin, (B) a hydrophobic silica sol, (C) a silicone leveling agent, and (C) a silicone-based leveling agent. (B) the hydrophobic silica sol is localized on the surface side opposite to the substrate film of the hard coat layer after curing the hard coat layer forming material, and the hard coat layer (100 atom%) of carbon atoms, oxygen atoms and silicon atoms measured by XPS analysis in the depth direction in a region from the outermost surface to the 5 nm position of the silicon atom concentration in the range of 0.2 to 1.95 atom% Lt; 2 >

Hereinafter, the hard coating film of the first embodiment will be described in detail with reference to the accompanying drawings.

1. Hard coating layer forming material

(1) (A) Energy ray curable resin

(1) -1. Kinds

The kind of the energy ray curable resin constituting the hard coat layer forming material is not particularly limited and may be selected from conventionally known ones. Examples thereof include an energy ray curable monomer, an oligomer, a resin, .

As specific examples, there can be used a single type or a combination of two or more kinds of polyfunctional (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) .

Examples of the polyfunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (Meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene glycol di (meth) acrylate, hexanediol di (Meth) acrylate such as pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (metha) (Meth) acrylate, glycerol tri (meth) acrylate, triallyl (meth) acrylate, and the like.

Of these, pentaerythritol polyfunctional (meth) acrylate or dipentaerythritol polyfunctional (meth) acrylate is more preferable in that it can impart appropriate hardness to the hard coat layer.

It is also preferable that the polyfunctional (meth) acrylate contains a polyfunctional (meth) acrylate of EO (ethylene oxide) or PO (propylene oxide) addition type.

The polyfunctional (meth) acrylate of EO (ethylene oxide) or PO (propylene oxide) addition type is a compound obtained by esterifying polyvalent alcohol of EO or PO addition type with acrylic acid, and more specifically, EO or PO modified glycerol Triacrylate, EO or PO-modified trimethylolpropane acrylate, EO or PO-modified pentaerythritol tetraacrylate, EO or PO-modified dipentaerythritol hexaacrylate, and the like.

Of these, EO or PO-modified dipentaerythritol hexaacrylate, EO or PO-modified trimethylolpropane tetraacrylate is preferable because it can prevent cracking and cracking of the hard coat layer by imparting appropriate flexibility to the hard coat layer. desirable.

In order to impart appropriate flexibility to the hard coat layer in the EO or PO addition type polyfunctional (meth) acrylate, the EO or PO addition amount per 1 mol of the polyfunctional (meth) acrylate is preferably in the range of 6 to 18 mol More preferably 8 to 16 moles.

(1) -2. Amount of blending

It is preferable that the energy ray-curable resin (A) constituting the hard coat layer forming material is a mixture of (a1) a polyfunctional (meth) acrylate compound and (a2) a polyfunctional (meth) acrylate compound of ethylene oxide or propylene oxide addition type (Meth) acrylate compound of (a1) a polyfunctional (meth) acrylate compound and (a2) a polyfunctional (meth) acrylate compound of ethylene oxide or propylene oxide addition type in a weight ratio of 100: 0 to 20:80 Value.

The reason is that the hard coat layer forming material is a polyfunctional (meth) acrylate compound which is relatively hardened by irradiation of energy ray and a polyfunctional compound of ethylene oxide or propylene oxide addition type having relatively high flexibility even by energy ray irradiation Is contained at a predetermined content, the hardness of the hard coat layer can be easily adjusted.

That is, when the content by weight of the (a1) polyfunctional (meth) acrylate compound is less than 20, scratch resistance of the hard coat layer after curing may be lowered.

Therefore, it is preferable that the content by weight of the polyfunctional (meth) acrylate compound (a1) and the polyfunctional (meth) acrylate compound of (a2) ethylene oxide or propylene oxide addition type is within the range of 95: 5 to 30:70 And more preferably in the range of 90:10 to 50:50.

(1) -3. (D) a photopolymerization initiator

In the hard coat layer forming material of the present invention, it is preferable that (D) a photopolymerization initiator is contained, if desired.

This is because the hard coat layer can be efficiently formed by irradiating the hard coating layer forming material with an active energy ray by containing a photopolymerization initiator.

Here, the photopolymerization initiator refers to a compound that generates a radical seed by irradiation with active energy rays such as ultraviolet rays.

Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2 , 2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 4- (2-hydroxyethoxy) phenyl- 2- Propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4-diethylaminobenzophenone, dichlorobenzophenone, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2- Anthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, acetophenone dimethylketal, Amine benzoic acid ester, , And [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane], and the like can be used alone or in combination do.

When the photopolymerization initiator (D) is contained, the content of the photopolymerization initiator is preferably within a range of 0.2 to 20 parts by weight, more preferably within a range of 0.5 to 15 parts by weight, relative to 100 parts by weight of the energy ray- By weight, more preferably from 1 to 13 parts by weight.

(2) (B) Hydrophobic silica sol

(2) -1. Kinds

Further, the hard coating layer-forming material is characterized by containing (B) hydrophobic silica sol.

Examples of the silica sol include sols of fine silica particles having an alkoxysilane compound or a chlorosilane compound as a raw material.

The alkoxysilane compound is not particularly limited as long as it is a silicon compound having a hydrolyzable alkoxy group, and examples thereof include compounds represented by the general formula (1).

R ¹ _n Si (OR ² ) _4-n (1)

(Wherein R ¹ represents a hydrogen atom or a non-hydrolyzable group, specifically, an alkyl group, a substituted alkyl group (wherein the substituent is a halogen atom, an epoxy group, a (meth) acryloyloxy group or the like), an alkenyl group, represents a keel, R ² is a represents a lower alkyl group. n is a constant of 0~2, R ¹ and OR ² is a case where each of the plurality, and the plurality of R ¹ may be the same or different, and plural OR ² is , The same or different)

Examples of the alkoxysilane compound represented by the general formula (1) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxy Silane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, trimethoxysilane hydride, triethoxysilane hydride, tripropoxysilane hydride, methyltrimethoxysilane, methyltriethoxysilane , Methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, ? -acryloyloxypropyltrimethoxysilane,? -methacryloyloxypropyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethyl Sisilran, divinyl this alone or in combination of two or more species such as diethoxysilane is preferred.

In this case, as the alkoxysilane compound, when the compound in which n is 0 or n is ¹ to 2 and R ¹ is a hydrogen atom is completely hydrolyzed, an inorganic silica-based cured product is obtained. When partial hydrolysis is performed, the polyorganosiloxane- A mixed cured product of a cargo or inorganic silica system and a polyorganosiloxane system is obtained.

On the other hand, in the case where n is ¹ to 2 and R ¹ is a non-hydrolyzable group, a polyorganosiloxane-based cured product is obtained by partial or complete hydrolysis because of having a non-hydrolyzable group.

Examples of the chlorosilane compound include ethyldichlorosilane, ethyltrichlorosilane, dimethyldichlorosilane, trichlorosilane, trimethylchlorosilane, dimethyldichlorosilane, and methyltrichlorosilane.

The silica sol is obtained by dispersing silica fine particles in water or an organic solvent in a sol state.

The organic solvent is not particularly limited, and examples thereof include methanol, ethanol, isopropanol, ethylene glycol, n-propyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, dimethylacetamide, propylene glycol monomethyl ether, cyclohexane, benzene, toluene And methyl isobutyl ketone and propylene glycol monomethyl ether having relatively high boiling points are particularly preferable.

The silica sol of the present invention is characterized in that part or all of the silanol groups on the surface of the silica particles are hydrophobic silica sols treated with a surface modifier having a hydrophobic group.

Examples of the surface modifier include a silane coupling agent having a functional group capable of reacting with a silanol group on the surface of silica particles and a hydrophobic group.

More specifically, examples of the hydrophobic silica sol include SIRPGM15WT% -E26 manufactured by CIK Nanotech.

(2) -2. Hydrophobicity degree

The degree of hydrophobicity of the silica sol was determined by measuring the contact angle of water with respect to such a coating film by coating the silica sol on the PET film and removing the solvent to prepare a silica sol coating film.

More specifically, it is preferable that the contact angle of water with respect to the coating film when silica sol is used as a coating film is set to a value of 100 DEG or more.

That is, if the contact angle of water measured according to JIS R 3257 for the coating film of silica sol is 100 ° or more, it can be judged that the surface of the silica sol is hydrophobic.

Here, FIG. 2 shows a diagram for providing a conceptual illustration of the hard coating film 20 of the present invention.

More specifically, in the hydrophobic silica sol 16 of the present invention, when the hard coat layer forming material is coated on the surface of the substrate and cured, the hydrophobic silica sol 16 is phase-separated from the other components in the hard coat layer 12, It is believed that a large portion is distributed on the opposite surface side, and the ratio in the vicinity of the substrate surface and in the hard coat layer is lowered.

Therefore, by adding a small amount of the hydrophobic silica sol, a suitable surface roughness can be imparted to the surface of the hard coat layer. Therefore, even when the hard coat films overlap each other and time elapses, Can be prevented.

That is, it can be understood that a hard coat film having high transparency can be obtained because the effect of predetermined blocking resistance (sometimes referred to as anti-blocking property) can be exhibited by the addition of a relatively small amount.

In addition, if the contact angle of water with respect to the coating film of the hydrophobic silica sol is excessively high, there is a possibility that the adhesiveness is lowered when a transparent conductive layer or the like is further laminated on the hard coating film. Therefore, Is set to a value within a range of 100 to 130 DEG.

On the other hand, when the contact angle of water with respect to the coating film of silica sol becomes a value less than 100 ° and hydrophilicity becomes high, the silica sol 18 does not localize only on the surface side opposite to the base film, It is confirmed that the hard coat layer exists in a dispersed state throughout the hard coat layer.

Therefore, in order to impart a predetermined surface roughness to the hard coat layer, it is understood that a relatively large amount of silica sol is required to be blended.

The method of measuring the contact angle of water with respect to the coating film of silica sol can be calculated by preparing a silica sol coating film as described in detail in Example 1 and measuring the contact angle of water.

(2) -3. Average particle size

The average particle diameter of the hydrophobic silica sol of the present invention is preferably in the range of 10 to 100 nm.

The reason is that when the average particle diameter of the hydrophobic silica sol is less than 10 nm, it becomes difficult to obtain a predetermined surface roughness, and in particular, it is difficult to prevent occurrence of blocking with a small amount of the mixture to be.

On the other hand, when the average particle diameter of the hydrophobic silica sol exceeds 100 nm, the optical characteristics of the hard coating film may be excessively lowered.

Therefore, the average particle diameter of the hydrophobic silica sol is more preferably in the range of 10 to 50 nm, and more preferably in the range of 15 to 40 nm.

The average particle size of the silica sol is the particle size (Medic Glasses D50) at an integrated value of 50% in the particle size-based particle size distribution obtained by using a laser diffraction scattering particle size distribution analyzer, and means an average primary particle size.

(2) -4. Amount of blending

The amount of the hydrophobic silica sol of the present invention is in the range of 0.3 to 55 parts by weight based on 100 parts by weight of the energy ray-curable resin (A) in terms of solid content.

The reason is that when the blending amount of the hydrophobic silica sol is less than 0.3 part by weight, it may become difficult to exhibit the effect of preventing the blocking of the hard coating films.

On the other hand, if the blending amount of the hydrophobic silica sol exceeds 55 parts by weight, adhesion and scratch resistance of the hard coating film may be excessively lowered.

In addition, as described above, since the hydrophobic silica sol is liable to be unevenly distributed on the surface side opposite to the substrate surface in the hard coat layer, the amount of the hydrophobic silica sol to be blended is preferably in the range of (A) 100 parts by weight of the energy ray- In the range of 0.3 to 25 parts by weight, it is possible not only to effectively exhibit the anti-blocking effect even when the amount of the hydrophobic silica sol to be blended is relatively small, but also to have excellent transparency, And can be suitably used as a coating film.

Therefore, the blending amount of the hydrophobic silica sol is more preferably in the range of 0.3 to 25 parts by weight, more preferably in the range of 0.3 to 10 parts by weight, based on 100 parts by weight of the energy ray-curable resin (A) , And particularly preferably in the range of 0.4 to 3.0 parts by weight.

(3) (C) Leveling agent

(3) -1. Configuration

Further, the hard coating layer-forming material is characterized by containing (C) a silicone leveling agent.

The silicon atom concentration is 0.2 (atomic percent) based on the total amount (100 atom%) of carbon atoms, oxygen atoms and silicon atoms measured by XPS analysis in the depth direction in the region from the outermost surface of the hard coat film to 5 nm. To 1.95 atom%.

It is generally known that the leveling agent is able to suppress deformation and seeding of the coating film on the base film by being largely localized on the outermost surface side in the hard coat layer formation material.

In the present invention, as shown in Fig. 2, in the hard coat layer, the hydrophobic silica sol is localized on the surface side opposite to the substrate surface as described above, and the silicon leveling agent covers the hydrophobic silica sol, A hard coating film excellent in blocking resistance and leveling performance can be obtained by the interaction of the hydrophobic silica sol and the silicone leveling agent.

More specifically, FIG. 3 shows the results of XPS analysis (X-ray photoelectron spectroscopy) in the depth direction from the outermost surface to the substrate in the hard coating film of the present invention.

3, the silicon atom concentration was 0.28 atom% in the region from the outermost surface to the substrate up to 5 nm, and 0.29 atom% in the region up to 10 nm, 0.30 atom%, 0.20 atom% in the region up to 100 nm, and 22.01 atom% in the region up to 150 nm in the region where the silicon concentration is abruptly increased in the region exceeding 100 nm.

That is, as described above, in the present invention, in the hard coat layer, as exemplified in Fig. 2, the silicon-based leveling agent is coated on the region farthest from the substrate in a state of an extremely thin film (extremely thin film 14).

Therefore, the silicon atom concentration is 0.2 (atomic percent) based on the total amount (100 atom%) of carbon atoms, oxygen atoms and silicon atoms measured by XPS analysis in the depth direction in the region from the outermost surface of the hard coat film to 5 nm. To 1.95 atom%, it is possible to effectively improve the leveling performance and blocking resistance by effectively controlling the leveling agent present on the outermost surface.

That is, when the silicon atom concentration is less than 0.2 atom%, the leveling agent can not form a thin film on the outermost surface of the coating film of the hard coat layer forming material when coating the hard coating layer forming material, This makes it difficult to form a uniform thin film.

On the other hand, when the silicon atom concentration exceeds 1.95 atom%, the surface energy of the hard coat surface is lowered, so that even if a conductive layer or the like is further laminated thereafter, the conductive layer may fall off or the like to be.

Therefore, the silicon element concentration in the region from the outermost surface of the hard coat film to the position of 5 nm is more preferably in the range of 0.21 to 1.95 atom%, more preferably in the range of 0.23 to 1.94 atom% Is more preferable.

The silicon atom concentration by the elemental analysis measurement of XPS means the silicon atom concentration at each depth measured by XPS analysis in the depth direction in the whole hard coating layer.

(3) -2. Kinds

The silicone leveling agent (C) may further contain, as a silicone leveling agent, at least one member selected from the group consisting of silicone modified acrylic, polyether-modified polydimethylsiloxane, polyetherester-modified polydimethylsiloxane, polydimethylsiloxane containing polyester-modified hydroxyl group, and polyether-modified polydimethylsiloxane At least one kind selected from the group consisting of

This is because if the silicon leveling agent is of such a kind, it becomes easy to set the silicon atom concentration in the leveling thin film 14 on the surface of the hard coat layer to the value within the above-mentioned range, and the surface smoothing required for the leveling agent, It is possible to improve the adhesiveness in a well-balanced manner in the case of further lamination.

Therefore, in the case of the silicone leveling agent of the present invention, when the adhesive layer or the print layer is formed not only on the conductive layer but also on the hard coat layer, for example, adhesion with such an adhesive layer or the like can be enhanced.

Among the silicone leveling agents described above, it is more preferable to contain a reactive silicone leveling agent having a vinyl group or the like.

The reason is that since a silicon leveling agent reacts with an energy ray curable resin to form a stronger leveling thin film when the silicone leveling agent is a reactive leveling agent, it is derived from a leveling agent when it is introduced into, for example, And so on.

With respect to the fluorine leveling agent generally regarded as useful as a leveling agent, in the present invention, seeding can be effectively suppressed, but since the water repellency is high, the adhesiveness of the conductive layer or the like is lowered, And the synergistic effect by the hydrophobic silica sol is not exhibited.

(3) -3. Amount of blending

Further, it is preferable that the leveling agent (C) is further blended at a value within a range of 0.045 to 5 parts by weight based on 100 parts by weight of the energy ray-curable resin (A).

The reason for this is that when the leveling agent is set to a value within this range, the adhesion to the transparent conductive layer can be improved when the transparent conductive layer is formed on the hard coat layer.

More specifically, when the blending amount of the leveling agent is less than 0.045 part by weight, the leveling agent becomes unevenly distributed in the outermost surface of the base material, and the coating film of the hard coating layer forming material is deformed and segregated, It may be difficult to form.

On the other hand, when the blending amount of the leveling agent exceeds 5 parts by weight, the leveling agent is localized beyond the leveling effect, the surface energy of the hard coat surface is lowered, and a conductive layer or the like is laminated on the hard coat layer , And thereafter, the conductive layer may fall off or the like.

Therefore, the blending amount of the leveling agent (C) is more preferably in the range of 0.05 to 3 parts by weight, and still more preferably in the range of 0.05 to 2 parts by weight.

(4) Other additives

In addition, it may contain other additives as far as it does not impair the effect of the present invention.

Examples of other additives include antioxidants, ultraviolet absorbers, antistatic agents, polymerization accelerators, polymerization inhibitors, infrared absorbers, plasticizers, diluting solvents and the like.

The content of other additives is preferably within a range of 0.01 to 5 parts by weight, preferably within a range of 0.02 to 3 parts by weight, relative to 100 parts by weight of the energy ray-curable resin (A) And more preferably in the range of 0.05 to 2 parts by weight.

(5) Thickness

It is also preferable that the thickness of the hard coat layer 12 shown in Fig. 1 is set to a value within a range of 1 to 10 mu m.

This is because when the thickness of the hard coat layer is less than 1 占 퐉, scratch resistance may be remarkably lowered.

On the other hand, if the thickness of the hard coat layer exceeds 10 mu m, the curl may become large.

Therefore, the thickness of the hard coat layer is more preferably in the range of 1 to 5 mu m, and more preferably in the range of 1.5 to 4 mu m.

2. Base film

(1) Type

The resin used for the base film 10 exemplified in Figs. 1 (a) and 1 (b) is not particularly limited as long as it is excellent in flexibility and transparency, and examples thereof include polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate But are not limited to, polyester films, polycarbonate films, polyethylene films, polypropylene films, cellophane, diacetylcellulose film, triacetylcellulose film, acetylcellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, A polyimide film, a fluoride resin film, a polyamide film, an acrylic resin film, a polyvinylidene fluoride film, a polyvinylidene fluoride film, a polyvinylidene fluoride film, a polyvinylidene fluoride film, A polyurethane resin film, a norbornene resin film, And other plastic films such as chlo- olefin resin films.

Among them, it is preferable to use a transparent resin film made of polyethylene terephthalate or polycarbonate because of excellent transparency and general versatility.

(2) Thickness

It is also preferable that the thickness of the base film 10 illustrated in Figs. 1 (a) and 1 (b) be within a range of 15 to 250 탆.

The reason for this is that when the thickness of the base film is less than 15 μm, the handling property such as easy wrinkle is remarkably lowered. On the other hand, when the thickness of the base film exceeds 250 μm, In particular, it may be difficult to make a roll.

Therefore, it is more preferable to set the thickness of the base film to a value within the range of 25 to 125 占 퐉 in that the balance between the mechanical strength and the light transmittance becomes better.

(3) Primer layer

Further, although not shown, the primer layer is provided on the surface of the base film to improve the adhesion between the base film and the hard coat layer, thereby further improving the scratch resistance of the hard coat layer.

Examples of the constituent material of the primer layer include a urethane resin, an acrylic resin, an epoxy resin, a polyester resin, a silicone resin and the like, or a combination of two or more thereof.

It is also preferable that the thickness of the primer layer is within a range of 0.01 to 20 占 퐉.

The reason is that if the thickness of the primer layer is less than 0.01 탆, the primer effect may not be developed. On the other hand, when the thickness of the primer layer exceeds 20 탆, the light transmittance may be lowered when the hard coating film is formed.

Therefore, since the balance between the primer effect and the light transmittance is better, it is more preferable that the thickness of the primer layer is within the range of 0.1 to 15 占 퐉.

3. Characteristics of hard coating film

(1) Surface roughness of hard coat layer

The arithmetic mean roughness (Ra) measured in accordance with JIS B 0601-1994 on the surfaces of the hard coat layers 12 and 12 'shown in Figs. 1 (a) and 1 (b) Of the total amount of water.

The reason is that when the arithmetic mean roughness (Ra) is less than 1.5 nm, it is possible to prevent the so-called blocking that the adjacent hard coating films adhere to each other when the hard coating film is wound or stacked This is because it is sometimes difficult to carry out the present invention.

On the other hand, when the arithmetic mean roughness (Ra) exceeds 5 nm, the light transmittance may remarkably decrease.

Therefore, the arithmetic mean roughness (Ra) on the surface of the hard coat layer is more preferably in the range of 2.0 to 4 nm, and more preferably in the range of 2.5 to 3.5 nm.

(2) Pencil hardness of the hard coat layer

It is also preferable that the pencil hardness measured in accordance with JIS K 5600-5-4 of the hard coat layer exemplified in Figs. 1 (a) to 1 (b) is equal to or higher than HB.

The reason for this is that when the pencil hardness is less than HB, scratch resistance may become insufficient when used in a capacitive touch panel.

(3) Haze value of hard coating film

The haze value measured according to JIS K 7105 of the hard coating films 20 and 20 'illustrated in Figs. 1 (a) and 1 (b) is preferably 1.0% or less.

This is because when the haze value exceeds 1.0%, the display of the liquid crystal display device may appear blurry when used in a mobile phone or the like.

[Second Embodiment]

The second embodiment is a method for producing a hard coating film having a hard coating layer on at least one side of a base film, which comprises the following steps (1) to (3).

(1) preparing a hard coat layer forming material comprising at least (A) an energy ray-curable resin, (B) a hydrophobic silica sol, and (C)

(2) a step of applying the hard coating layer-forming material to at least one side of the base film

(3) hardening the hard coating layer forming material, (B) subjecting the hydrophobic silica sol to localization on the surface side opposite to the substrate film of the hard coat layer after curing the hard coat layer forming material, In which the silicon atom concentration is within a range of 0.2 to 1.95 atom% with respect to the total amount (100 atom%) of carbon atoms, oxygen atoms and silicon atoms measured by XPS analysis in the depth direction Process for forming a hard coat film having a coating layer

Hereinafter, the base film and the hard coat layer to be used can be made the same as those in the first embodiment. Therefore, the description will focus on the manufacturing method of the hard coat film.

(1) Step 1: Preparation of hard coating layer forming material

Step (1) is a step of preparing a hard coat layer forming material comprising at least (A) an energy ray curable resin, (B) a hydrophobic silica sol, and (C) a silicone leveling agent.

More specifically, it is a step of uniformly mixing the hard coat layer forming material and the diluting solvent.

Examples of the solvent include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, pentyl alcohol, ethyl cellosolve, benzene, toluene, Examples of the solvent include hexane, ethylcyclohexane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, propylene monomethyl ether and water.

Particularly, from the viewpoint of easily dissolving an energy ray curable resin such as an acrylic monomer, propylene monomethyl ether, toluene, methyl ethyl ketone, ethyl acetate, n-butyl acetate, cyclohexanone, methyl alcohol, ethyl alcohol, Propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, pentyl alcohol and the like are preferably used.

The constitution of the predetermined hard coat layer forming material is the same as described above, and therefore will not be described.

(2) Step 2: Coating of the material for forming the hard coat layer on the base film

Step (2) is a step of applying the hard coat layer forming material to at least one side of the base film.

More specifically, the base film 10 is prepared, and the hard coating layer forming material adjusted in the step (1) is coated thereon so that the hard coating layer after curing has a thickness within a range of 1 to 10 占 퐉 Process.

The coating method of the material for forming the hard coat layer is not particularly limited and a known method such as a bar coating method, a gravure coating method, a knife coating method, a roll coating method, a blade coating method, Can be used.

(3) Step 3: Curing of hard coating layer forming material and hard coating film forming process

The step (3) is a step of curing the above-mentioned hard coating layer-forming material so that the hydrophobic silica sol (B) is localized on the surface side opposite to the base film of the hard coat layer, (100 atom%) of carbon atoms, oxygen atoms and silicon atoms measured by XPS analysis in the depth direction in the region up to the position of the silicon atom concentration of 0.2 to 1.95 atom% .

More specifically, it is preferable to cure the coating material of the hard coat layer-forming material evaporated from the solvent through a drying step by irradiation with an energy ray, for example, ultraviolet rays or electron rays.

By doing so, the hard coat layer can be formed quickly and firmly adhered to the base film.

In addition, the hydrophobic silica sol can be effectively localized on the surface side opposite to the base film of the hard coat layer.

In addition, the silicon leveling agent can be localized on the outermost surface, and it becomes easy to adjust the silicon atom concentration on the outermost surface in the above-mentioned range.

Accordingly, it is possible to improve the mechanical strength of the hard coat layer, effectively prevent blocking between the hard coat films, and improve the adhesion in the case of further laminating the conductive layer or the like.

Further, in forming the hard coat layer, for example, when irradiated with ultraviolet rays, it is preferable to set the irradiation amount (accumulated light amount) of the hard coat layer forming material to a value within the range of 100 to 1000 mJ / cm 2.

The reason for this is that if the ultraviolet irradiation amount is less than 100 mJ / cm 2, hardening of the hard coat layer may be insufficient.

On the other hand, when the ultraviolet ray irradiation amount exceeds 1000 mJ / cm 2, the hard coat layer and the base film may deteriorate due to ultraviolet rays.

There is no particular limitation on the type of the energy ray irradiating apparatus to be used, and for example, an ultraviolet ray irradiating apparatus using a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fusion H lamp, or the like can be used.

(4) Step 4: A step of forming a hard coating layer on the other side of the substrate film

Step (4) is a step employed in the production of a hard coat film having a hard coat layer on both sides of a base film.

More specifically, as shown in Fig. 1A, after a hard coat layer 12 is formed on one surface of a base film 10, a hard coat layer 12 'is formed on the other surface of the base film .

That is, after a hard coating layer is formed on one surface of the above-mentioned base film, a hard coating layer forming material is coated on the other surface of the base film in the same manner and cured to form a hard coating layer on both surfaces of the base film to be.

Since the application step and the curing step are the same as described above, the details are omitted.

[Third embodiment]

The third embodiment is a transparent conductive film having a transparent conductive layer on at least one surface of the above-mentioned hard coating film.

Hereinafter, the transparent conductive film will be specifically described with reference to the drawings, focusing on differences from the contents described in the first and second embodiments.

That is, the transparent conductive film of the present invention is a transparent conductive film 40 having a transparent conductive layer 30 on at least one side of the hard coat film 20 as shown in Fig. 4 (a).

Further, since the transparent conductive film using the hard coating film of the present invention is excellent in blocking resistance, it is not necessary to use a protective film for preventing blocking between the films, and a pressure sensitive adhesive to be used for bonding with the protective film is also required none.

Therefore, a transparent conductive film having high productivity and low cost can be obtained.

In addition, since the adhesion between the hard coating film and the transparent conductive layer is excellent, a transparent conductive film having excellent durability can be obtained.

(1) Transparent conductive layer

The material for constituting the transparent conductive layer of the present invention is not particularly limited as long as the transparent conductive layer has a visible light transmittance of 70% or more at 550 nm. For example, metals such as platinum, gold, silver and copper; Carbon materials such as graphene and carbon nanotubes; Organic conductive materials such as polyaniline, polyacetylene, polythiophene, polyparaphenylenevinylene, polyethylene dioxythiophene, and polypyrrole; Inorganic conductive materials such as copper iodide and copper sulfide; Non-oxidizing compounds such as chalcogenide, lanthanum pentaboride, titanium nitride, and titanium carbide; (IZO), tin oxide, indium oxide, cadmium oxide, tin doped indium oxide (ITO), tin and gallium doped indium oxide (IGZO), zinc oxide, zinc oxide, zinc oxide, gallium doped zinc oxide, aluminum doped zinc oxide, zinc oxide doped indium oxide ), Conductive metal oxides such as fluorine-doped indium oxide, antimony doped tin oxide, and fluorine-doped tin oxide (FTO); And the like.

Of these, conductive metal oxides are preferable because they can more easily obtain a transparent conductive film having excellent transparent conductivity.

(2) Formation method

The transparent conductive layer can be formed by a conventionally known method. For example, a sputtering method, an ion plating method, a vacuum deposition method, a chemical vapor deposition method, a coating method such as a bar coater or a microgravure coater, and the like can be given.

Among these, a sputtering method is preferable in that a transparent conductive layer can be easily formed.

(3) Thickness

The thickness of the transparent conductive layer is preferably in the range of 5 nm to 500 nm, more preferably in the range of 5 to 200 nm, and more preferably in the range of 10 to 100 nm.

(4) Patterning

The formed transparent conductive layer may be patterned (30 ') as required, as shown in Fig. 4 (b). As a method of patterning, chemical etching using photolithography or the like, physical etching using a laser or the like, vacuum evaporation using a mask, sputtering, lift-off, printing or the like can be given.

[Fourth Embodiment]

The fourth embodiment is a capacitive touch panel including a cover glass having a glass shatterproof film, a first transparent conductive film, a second transparent conductive film, and a liquid crystal display, wherein the first transparent conductive film and the first transparent conductive film Wherein the hard coat film comprises a hard coat layer on at least one side of a base film, and the hard coat layer is formed on at least one surface of the hard coat layer, (C) a hard coating layer forming material comprising at least (A) an energy ray curable resin, (B) a hydrophobic silica sol, and (C) a silicone leveling agent, wherein (B) the hydrophobic silica sol comprises The hard coating layer after the forming material is cured is unevenly distributed on the surface side opposite to the base film and in the region from the top surface of the hard coating film to the position of 5 nm, Based on the total amount (100atom%) of carbon atoms, oxygen atoms, silicon atoms, as measured by XPS analysis of the orientation, the density of silicon atoms is a capacitive touch panel, characterized in that a value in the range 0.2~1.95atom%.

Hereinafter, the capacitive touch panel will be specifically described with reference to the drawings, focusing on differences from the contents described in the first to third embodiments.

That is, the basic configuration of the capacitive touch panel is not particularly limited. 5, the capacitive touch panel 100 includes a hard coating film 20 provided with a hard coating layer, a transparent conductive film (not shown) having a hard coating layer on the liquid crystal display device 70, A hard coat film 20 having a hard coat layer, a transparent conductive layer 30 '' (second electrode), an optical adhesive 50 ', a conductive layer 30 (first electrode) '), A glass scattering prevention film 60 having an optical pressure-sensitive adhesive layer, and a cover glass 80 are stacked.

In the present invention, other layers other than the above-described layers may be provided as necessary.

The capacitive touch panel of the present invention may be a surface-type electrostatic capacitance type or a projection-type electrostatic capacitance type.

The capacitive touch panel of the present invention can provide a capacitive touch panel having excellent durability because a hard coat film having good adhesiveness is provided especially when a surface layer (conductive layer or the like) is formed.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples. However, the following description is illustrative of the present invention, and the present invention is not limited to these descriptions.

[Example 1]

1. Preparation of Hard Coating Film

(1) Preparation process of hard coating layer forming material

As shown in Table 1, the energy ray-curable resin as the component (A), the hydrophobic silica sol as the component (B), the silicon leveling agent as the component (C), and the photopolymerization initiator as the component The hard coating layer forming material was adjusted.

More specifically, 100 parts by weight of (a1) pentaerythritol triacrylate (NK ester manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMM-3L) and 100 parts by weight of (a2) dipentaerythritol hexaacryl , 10 parts by weight of a photopolymerization initiator (Irgacure 184, manufactured by Chiba Specialty Chemicals Co., Ltd.) as a component (D), 100 parts by weight of a photopolymerization initiator (EO12 molar adduct) (Shin- Nakamura Kagaku Kogyo Co., 0.8 parts by weight of hydrophobicized silica sol A (manufactured by CIK Nanotech Co., Ltd., SIRPGM15WT% -E26, average particle diameter 30 nm) as component B), 0.8 part by weight of silicone-modified acrylic a (BYK-3550 ) And 492.1 parts by weight of propylene monomethyl ether as a diluting solvent to prepare a hard coat layer forming material (solid concentration 30% by weight).

(2) Coating process of hard coating layer forming material

Next, on one side of this adhesive layer-attached PET film (Lumirra U48, film thickness 100 mu m) having the hard coating layer forming material as a base film subjected to the adhesion (easy adhesion) treatment on both sides, Using a bar so as to have a thickness of 3 mu m after drying.

(3) Drying process

Next, the diluting solvent contained in the hard coat layer forming material applied to the base film was removed.

That is, the film was heated and dried at 70 ° C for 1 minute using a hot-air drying apparatus to sufficiently remove the diluting solvent.

(4) Curing process

Next, using a high-pressure mercury lamp, ultraviolet rays were irradiated at 300 mJ / cm < 2 > to harden the hard coating layer forming material to obtain a hard coating film.

Although not shown, the cross section of the hard coating film prepared in Example 1 was measured with a scanning electron microscope (SEM) (S-4700, manufactured by Hitachi Seisakusho Co., Ltd.) at an acceleration voltage of 10 kV and a magnification of 20,000 times , It was confirmed that the hydrophobic silica sol was localized on the surface side of the hard coat layer opposite to the substrate film.

2. Evaluation of Hard Coating Film

(1) Analysis of silicon atom concentration

Elemental analysis of carbon atoms, oxygen atoms, and silicon atoms measured by XPS analysis in the depth direction of the hard coat layer in the obtained hard coating film was performed using an XPS measurement analyzer (Quantum2000 manufactured by Arubak Pai). The silicon atom concentration distribution obtained by the XPS measurement is shown in Fig.

From this measurement, the silicon atom concentration was calculated with respect to the total amount (100 atom%) of carbon atoms, oxygen atoms and silicon atoms in the region from the outermost surface to the position of 5 nm. The obtained results are shown in Table 1.

(2) Measurement of hydrophobicity

The hydrophobic silica sol A (solid content concentration: 15%) dispersed in methyl isobutyl ketone was coated on a PET film (manufactured by Toray Industries, Lumirra U48, thickness 100 탆) with Meyer bar # 8.

Next, it was dried in an oven at 90 캜 for 1 minute to obtain a silica sol coating film having a thickness of 1 탆 after drying.

Next, the contact angle of water measured according to JIS R 3257 for this silica sol coating film was measured, and the degree of hydrophobicity was evaluated.

That is, when the PET film on which such a silica sol coating film was formed was allowed to stand on a flat glass substrate and 2 占 퐇 of a water droplet was dropped when the slope of the glass substrate was 0 degree, The water contact angle was obtained. The obtained results are shown in Table 1.

(3) Evaluation of adhesiveness of hard coat layer

An ultraviolet curable ink (UVPAL911, manufactured by DAIKOKU INK SEIKO CO., LTD.) Was applied to the surface of the obtained hard coat film, and the ink was cured by irradiation with ultraviolet rays to form a print layer having a thickness of 1 m. The surface of the printing layer was covered with a 1 mm wide croissant in a checkerboard pattern, and an adhesive tape (Nichia Reflector, Cellotape (registered trademark)) was applied to the surface of the printed layer cross- And a cellotape (registered trademark) peeling test was carried out in accordance with the checkerboard tape method of JIS K 5600-5-6 (cross-cut method), and the print adhesion of the curable resin layer was evaluated according to the following criteria. The obtained results are shown in Table 1.

?: No printed layer peeled from the hard coating film and transferred to the adhesive tape

: The number of printed layers to be transferred to the adhesive tape was less than 50%

X: The number of print layers to be transferred to the adhesive tape was 50% or more

(4) Evaluation method of coating (sushi)

The hard coating layer forming material was coated on one side of the PET film with the adhesive layer so that the film thickness after drying became 3 占 퐉 using a Meyer bar, and the hard coating film was visually observed under fluorescent lamps before curing, The coating properties were evaluated according to the following criteria. The obtained results are shown in Table 1. In addition, the area for inspection at the time of municipal inspection is 0.5 m 2.

○: No sushi

X: More than one seething

(5) Evaluation of pencil hardness

The pencil hardness of the obtained hard coat film was measured using a pencil scratch hardness tester (No.553-M, manufactured by Yasuda Seiki Seisakusho Co., Ltd.) according to JIS K 5600-5-4. The scratching speed was 1 mm / sec. The obtained results are shown in Table 1.

(6) Evaluation of blocking resistance

The obtained hard coating film was cut into a size of 100 x 100 mm, and two hard coating films were superimposed (this state was initialized).

Subsequently, the laminated film was peeled off after five days of elapsed time (after the elapsed time) in an initial state and a storage environment of 23 ° C and 50% RH in a state of applying a load of 10 kg / The state was observed with a naked eye under a fluorescent lamp, and the presence or absence of blocking was evaluated according to the following criteria. The obtained results are shown in Table 1.

?: No blocking occurred at the beginning and after the elapse of time, and there was no adherence between the film surfaces

?: No blocking occurred at the initial stage, but blocking occurred after the elapse of time (the sticking area between the film surfaces was less than 30%).

X: Blocking occurred from the beginning (the cross-sectional area between the film sides is at least 30%)

(7) Haze value

The haze value of the obtained hard coat film was measured using a haze meter (NDH-2000 manufactured by Nihon Denshoku Kogyo Co., Ltd.) in accordance with JIS K 7105. The obtained results are shown in Table 1.

[Example 2]

In Example 2, a hard coat film was prepared and evaluated in the same manner as in Example 1, except that the amount of silicone leveling agent (a) was changed from 0.1 part by weight to 0.16 part by weight. The obtained results are shown in Table 1.

[Example 3]

In Example 3, a hard coat film was prepared and evaluated in the same manner as in Example 1, except that the amount of silicone leveling agent (a) was changed from 0.1 part by weight to 0.2 part by weight. The obtained results are shown in Table 1.

[Example 4]

Example 4 was the same as Example 1 except that 0.1 part by weight of polyether-modified polydimethylsiloxane b (BYK-300, manufactured by Big-Chem Japan Co., Ltd.) was used instead of silicone-modified acrylic a of silicone leveling agent (C) , A hard coating film was prepared and evaluated. The obtained results are shown in Table 1.

Although not shown, the cross-section of the hard coat film prepared in Example 4 was photographed by a scanning electron microscope (SEM) in the same manner as in Example 1, and the hydrophobic silica sol was found to have a hard coat layer And it was confirmed that it was localized on the opposite surface side.

[Example 5]

In Example 5, except that 0.1 part by weight of polyether siloxane-containing polydimethylsiloxane c (BYK-375, manufactured by BICKEMI Japan Co., Ltd.) was used instead of silicone-modified acrylic a of silicone leveling agent (C) A hard coat film was prepared and evaluated by the same method as in (1). The obtained results are shown in Table 1.

Although not shown, the cross section of the hard coat film prepared in Example 5 was photographed by a scanning electron microscope (SEM) in the same manner as in Example 1, and the hydrophobic silica sol was found to have a hard coat layer And it was confirmed that it was localized on the opposite surface side.

[Example 6]

Example 6 was the same as Example 1 except that 0.1 part by weight of a polyester-modified hydroxyl group-containing polydimethylsiloxane d (BYK-370 available from Big Chem Japan Co., Ltd.) was used instead of the silicone-modified acrylic a of the silicone leveling agent (C) A hard coating film was prepared and evaluated. The obtained results are shown in Table 1.

Although not shown, the cross-section of the hard coat film prepared in Example 6 was photographed by a scanning electron microscope (SEM) in the same manner as in Example 1, and the hydrophobic silica sol was found to have a hard coat layer And it was confirmed that it was localized on the opposite surface side.

[Example 7]

Example 7 was the same as Example 1 except that 0.1 part by weight of polyether-modified polydimethylsiloxane e (BYK-331 manufactured by Big-Chem Japan Co., Ltd.) was used instead of silicone-modified acrylic a of silicone leveling agent (C) , A hard coating film was prepared and evaluated. The obtained results are shown in Table 1.

Although not shown, the cross section of the hard coat film prepared in Example 7 was photographed by a scanning electron microscope (SEM) in the same manner as in Example 1, and the hydrophobic silica sol was found to have a hard coat layer And it was confirmed that it was localized on the opposite surface side.

[Comparative Example 1]

In Comparative Example 1, a hard coat film was prepared and evaluated in the same manner as in Example 1, except that (C) the amount of silicone leveling agent a was changed from 0.1 part by weight to 0.08 part by weight. The obtained results are shown in Table 1.

Although not shown, the cross-section of the hard coating film prepared in Comparative Example 1 was photographed by a scanning electron microscope (SEM) in the same manner as in Example 1, and the hydrophobic silica sol was found to have a hard coat layer And it was confirmed that it was localized on the opposite surface side.

[Comparative Example 2]

In Comparative Example 2, a hard coat film was prepared and evaluated in the same manner as in Example 1, except that the amount of the silicone leveling agent (a) was changed from 0.1 part by weight to 0.04 part by weight. The obtained results are shown in Table 1.

[Comparative Example 3]

Comparative Example 3 was the same as Example 1 except that 0.1 part by weight of polyether-modified polymethylalkylsiloxane f (BYK-325, manufactured by Big-Chemie Japan) was used instead of silicone-modified acrylic a of silicone leveling agent (C) By the same method, a hard coat film was prepared and evaluated. The obtained results are shown in Table 1.

Although not shown, the cross section of the hard coating film prepared in Comparative Example 3 was photographed by a scanning electron microscope (SEM) in the same manner as in Example 1, and the hydrophobic silica sol was found to have a hard coat layer And it was confirmed that it was localized on the opposite surface side.

[Comparative Example 4]

In Comparative Example 4, in the same manner as in Example 1 except that 0.1 part by weight of polyether-modified polydimethylsiloxane g (BYK-378, manufactured by Big-Chem Japan Co., Ltd.) was used instead of silicone-modified acrylic a of silicone leveling agent , A hard coating film was prepared and evaluated. The obtained results are shown in Table 1.

The cross section of the hard coat film prepared in Comparative Example 4 was photographed by a scanning electron microscope (SEM) in the same manner as in Example 1, although not shown, And it was confirmed that it was localized on the opposite surface side.

[Comparative Example 5]

In Comparative Example 5, in the same manner as in Example 1 except that 0.1 part by weight of polyether-modified polydimethylsiloxane h (BYK-UV3510, manufactured by Big-Chem Japan Co., Ltd.) was used instead of silicone-modified acrylic a of silicone leveling agent , A hard coating film was prepared and evaluated. The obtained results are shown in Table 1.

Although not shown, the cross-section of the hard coat film prepared in Comparative Example 5 was photographed by a scanning electron microscope (SEM) in the same manner as in Example 1, and the hydrophobic silica sol was found to have a hard coat layer And it was confirmed that it was localized on the opposite surface side.

[Comparative Example 6]

In Comparative Example 6, a hard coat film was prepared in the same manner as in Example 1, except that silica sol I (manufactured by CIK Nanotech, SIRMIBK15WT% -K18, average particle diameter 100 nm) was used as the component (B) And evaluated. The obtained results are shown in Table 1.

[Comparative Example 7]

In Comparative Example 7, a hard coat film was obtained in the same manner as in Comparative Example 1, except that silica sol J (manufactured by Nippon Shokubai Co., Ltd., OSCAL-1632, average particle diameter 30 nm) was used as the component (B) And evaluated. The obtained results are shown in Table 1.

[Comparative Example 8]

In Comparative Example 8, a hard coat film was prepared in the same manner as in Comparative Example 1 except that silica sol K (MIBK-ST, manufactured by Nissan Chemical Industries, Ltd., average particle size: 15 nm) was used as the component (B) And evaluated. The obtained results are shown in Table 1.

[Comparative Example 9]

In Comparative Example 9, in the same manner as in Example 1 except that (C) 0.1 part by weight of a perfluoro modified acrylic-containing resin (Mega Park RS75 manufactured by DIC Co., Ltd.) was used instead of the silicone-modified acrylic a of the silicon leveling agent , A hard coating film was prepared and evaluated. The obtained results are shown in Table 1.

Although not shown, the cross section of the hard coating film prepared in Comparative Example 9 was photographed by a scanning electron microscope (SEM) in the same manner as in Example 1, and the hydrophobic silica sol was found to have a hard coat layer And it was confirmed that it was localized on the opposite surface side.

[Comparative Example 10]

Comparative Example 10 was the same as Example 1 except that (C) 0.1 part by weight of polyether-modified polydimethylsiloxane j (SH-28, manufactured by Dow Corning Toray Co., Ltd.) was used in place of silicone-modified acrylic a of silicone leveling agent , A hard coating film was prepared and evaluated. The obtained results are shown in Table 1.

Although not shown, the cross-section of the hard coat film prepared in Comparative Example 10 was photographed by a scanning electron microscope (SEM) in the same manner as in Example 1, and the hydrophobic silica sol was found to have a hard coat layer And it was confirmed that it was localized on the opposite surface side.

[Table 1]

Type of leveling agent;

a: Silicone-modified acrylic

b: Polyether-modified polydimethylsiloxane

c: Polyether ester-modified polydimethylsiloxane containing hydroxyl group

d: a polydimethylsiloxane containing a polyester-modified hydroxyl group

e: polyether-modified polydimethylsiloxane

f: polyether-modified polymethylalkylsiloxane

g: polyether-modified polydimethylsiloxane

h: Polyether-modified polydimethylsiloxane

i: perfluoro-modified acrylic-containing resin

j: Polyether-modified polydimethylsiloxane

In which the silicon atom concentration measured by the XPS analysis in the depth direction is a value within a predetermined range in the region from the outermost surface of the hard coat film to the 5 nm position using a predetermined hydrophobic silica sol, To 7 were excellent in blocking resistance, and were also excellent in coatability and adhesiveness.

However, in Comparative Examples 1 and 2 where the silicon atom concentration on the surface was lower than the predetermined range, although having blocking resistance, the coatability was poor and it was difficult to smoothly coat the material for forming the hard coat layer.

Comparative Examples 3, 4, 5, and 10, in which the silicon atom concentration was higher than the predetermined range, had anti-blocking properties, but had poor adhesion when a surface layer was further laminated on the hard coating film.

In Comparative Examples 6 to 8, which did not use a predetermined hydrophobic silica sol, the coatability and the like were good, but the anti-blocking property was not obtained.

Further, in Comparative Example 9 using a fluorine-based leveling agent, the surface was smoothed and the water repellency was high, so that blocking resistance and adhesiveness were all lowered.

As described above, according to the hard coating film of the present invention, a hard coating film having a hard coating layer on at least one side of a base film, wherein the hard coating layer comprises a predetermined hydrophobic silica sol and a specific silicone leveling agent, And the hydrophobic silica sol is localized on the surface side opposite to the substrate film in the hard coat layer and the silicon atom concentration of the outermost surface of the hard coat film is smaller than a predetermined By virtue of having a value in the range, it is possible to prevent blocking between the films and to obtain a hard coating film excellent in coatability.

Further, when a hard coat film of the present invention is further laminated with a surface layer or the like, a hard coat film having excellent adhesion can be obtained.

Further, by having such a hard coating film, a transparent conductive film excellent in transparency and excellent in adhesion can be efficiently obtained.

Therefore, since the hard coating film of the present invention can be effectively used for capacitive touch panels and the like, it is expected that the hard coating film can be effectively mounted on a portable information device such as a cellular phone in which mechanical strength and the like are particularly required.

10: substrate film
12, 12 ': hard coat layer
14: leveling agent thin film
16: Hydrophobic silica sol
18: Hydrophilic silica sol
20, 20 ', 20'': hard coating film
30, 30 ', 30'': transparent conductive layer
40: transparent conductive film
50, 50 ', 50'': optical adhesive
60: Glass shatterproof film
70: liquid crystal display
80: cover glass
100: Capacitive touch panel

Claims (11)

A hard coating film having a hard coating layer on at least one side of a base film,
Wherein the hard coat layer comprises a hard coat layer forming material comprising at least (A) an energy ray curable resin, (B) a hydrophobic silica sol, and (C) a silicone leveling agent,
Wherein the hydrophobic silica sol (B) is localized on the surface side of the hard coat layer after curing the hard coat layer forming material, opposite to the base film,
(100 atom%) of carbon atoms, oxygen atoms and silicon atoms measured by XPS analysis in the depth direction in a region from the outermost surface of the hard coat film to a position of 5 nm, Lt; RTI ID = 0.0 > 1.95 < / RTI > atom%. The method according to claim 1,
The silicone leveling agent (C) is selected from the group consisting of silicone modified acrylic, polyether-modified polydimethylsiloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, polyester-modified hydroxyl group-containing polydimethylsiloxane and polyether-modified polydimethylsiloxane Lt; RTI ID = 0.0 > 1, < / RTI > The method according to claim 1,
Wherein the compounding amount of the silicone leveling agent (C) is in the range of 0.045 to 5 parts by weight in terms of solid content relative to 100 parts by weight of the energy ray-curable resin (A). The method according to claim 1,
Wherein the average particle diameter of the hydrophobic silica sol (B) is in the range of 10 to 100 nm. The method according to claim 1,
Wherein the contact angle of water measured according to JIS R 3257 with respect to the coating film when the (B) hydrophobic silica sol is used as a coating film is set to a value of 100 DEG or more. The method according to claim 1,
Wherein the blending amount of the hydrophobic silica sol (B) is in the range of 0.3 to 55 parts by weight in terms of solid content relative to 100 parts by weight of the energy ray-curable resin (A). The method according to claim 1,
Wherein the hard coating film has a haze value measured according to JIS K 7105 of 1.0% or less. The method according to claim 1,
Wherein an arithmetic average roughness Ra measured on the surface of the hard coat layer in accordance with JIS B 0601-1994 is within a range of 1.5 to 5 nm. The transparent conductive film according to claim 1, wherein the hard coating film has a transparent conductive layer on at least one side. 1. A capacitive touch panel comprising a cover glass having a glass shatterproof film, a first transparent conductive film, a second transparent conductive film, and a liquid crystal display,
Wherein either one of the first transparent conductive film and the second transparent conductive film has a transparent conductive layer on the hard coat layer of the hard coat film having the hard coat layer,
Wherein the hard coat film comprises a hard coat layer on at least one side of a base film,
Wherein the hard coat layer comprises a hard coat layer forming material comprising at least (A) an energy ray curable resin, (B) a hydrophobic silica sol, and (C) a silicone leveling agent,
Wherein the hydrophobic silica sol (B) is localized on the surface side of the hard coat layer after curing the hard coat layer forming material, opposite to the base film,
(100 atom%) of carbon atoms, oxygen atoms and silicon atoms measured by XPS analysis in the depth direction in a region from the outermost surface of the hard coat film to a position of 5 nm, 1.95 atom%. A method for producing a hard coating film having a hard coating layer on at least one side of a base film,
A process for producing a hard coating film, which comprises the following steps (1) to (3).
(1) preparing a hard coat layer forming material comprising at least (A) an energy ray-curable resin, (B) a hydrophobic silica sol, and (C)
(2) a step of applying the hard coating layer-forming material to at least one surface of the base film
(3) The hard coating layer-forming material is cured so that the hydrophobic silica sol (B) is localized on the surface side of the hard coat layer after curing the hard coat layer-forming material, opposite to the base film,
(100 atom%) of carbon atoms, oxygen atoms and silicon atoms measured by XPS analysis in the depth direction in a region from the outermost surface of the hard coat film to a position of 5 nm, A step of forming a hard coat film having a hard coat layer within a range of 1.95 atom%

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