KR102285633B1 - Hard coat film, transparent conductive film, and capacitive touch panel - Google Patents

Abstract

This invention prevents blocking of hard-coat films, and makes it a subject to provide the hard-coat film excellent in adhesiveness, the transparent conductive film provided with such a hard-coat film, and a capacitive touch panel.
As a means to solve these challenges. A hard coat film having a hard coat layer on at least one side of a base film, wherein the hard coat layer comprises at least (A) an energy ray curable resin, (B) hydrophobic silica sol, and (C) a silicone-based leveling agent. Formation of a hard coat layer It consists of a hardened|cured material of a material, and (B) hydrophobized silica sol is unevenly distributed on the surface side opposite to the base film of the hard-coat layer after hardening the hard-coat layer forming material, and is 5 nm from the outermost surface of a hard-coat film. In the region up to the position of , the silicon atom concentration is within the range of 0.2 to 1.95 atom% with respect to the total amount of carbon atoms, oxygen atoms, and silicon atoms measured by XPS analysis in the depth direction.

Description

A hard coat film, a transparent conductive film, and a capacitive touch panel TECHNICAL FIELD

The present invention relates to a hard coat film, a transparent conductive film, and a capacitive touch panel, and in particular, when a surface layer (conductive layer, etc.) is formed, a hard coat film having good adhesion and blocking resistance; It relates to a transparent conductive film and a capacitive touch panel provided with such a hard coat film.

Conventionally, as a liquid crystal display device having a liquid crystal display, for example, a portable electronic notebook or information terminal has been used, but in recent years, a liquid crystal display device equipped with a touch panel capable of inputting by direct contact with a display unit is widely used.

As such a touch panel, a capacitive method, a resistive film method, an electromagnetic induction method, etc. are mentioned. Among them, a capacitive touch panel that detects an input position by detecting a weak current generated when a finger or the like touches, that is, a change in capacitance, is popular.

Such a liquid crystal display device WHEREIN: In order to improve abrasion resistance, such as a transparent conductive film, and handling easiness, a hard-coat film is provided on the surface of a transparent conductive film in many cases.

As such a hard coat film, it is known that the surface of a base material is equipped with a hard coat layer.

For example, a hard coating film for a display in which an easily lubricious adhesive layer, a hard coating layer and an antireflection layer are laminated in this order on one or both sides of a transparent polyester film is disclosed (for example, See Patent Document 1).

That is, in patent document 1, it has predetermined surface hardness and predetermined thickness as a hard-coat layer, the water contact angle of the surface is 40-80 degrees, Furthermore, the hard-coat film for displays containing inorganic microparticles|fine-particles is has been disclosed.

On the other hand, after apply|coating a hard-coat layer from a viewpoint of productivity or handleability, the film which has hard-coat property is wound up and stored in roll shape. When storage in a roll state is prolonged, the surfaces of the films stick together (block), and scratches or the like occur on the surface of the hard coat layer, or when a hard coat film in which blocking is used, unevenness occurs on the surface A problem appeared.

So, for example, in a manufacturing process, when a hard-coat film is wound up with a roll, in order to prevent that hard-coat films become difficult to stick or peel off, and productivity falls, on both surfaces of a light-transmissive base material a predetermined|prescribed hard An optical laminate having a coating layer, a transparent conductive film, and a capacitive touch panel have been proposed (for example, refer to Patent Document 2).

More specifically, the hard coat layer is a layer formed using a composition for a hard coat layer containing a binder resin, a leveling agent and a lubricant, and the lubricant is at least selected from the group consisting of silica particles and silicone particles. It is 1 type, and it is disclosed about the optical laminated body which makes a silicone type leveling agent suitable as a leveling agent.

Moreover, for the purpose of suppressing the fall of the yield by blocking and improving leveling performance, the hard-coat film which consists of a composition for predetermined hard-coat layers, a polarizing plate, and an image display apparatus are proposed (for example, patent document) see 3).

More specifically, as a composition for a hard coat layer containing a leveling agent, silica fine particles, and a binder resin, a composition for a hard coat layer in which the leveling agent contains a predetermined fluorine-based leveling agent is disclosed.

Japanese Patent Laid-Open No. 2001-109388 (claims, etc.) Japanese Patent Laid-Open No. 2012-66409 (claims, etc.) Japanese Patent Laid-Open No. 2012-252275 (claims, etc.)

However, the hard coat film for displays disclosed in Patent Document 1 has a predetermined pencil hardness because the surface of the hard coat layer is hydrophilic. seemed

Moreover, the optical laminated body of patent document 2 is preventing that an optical laminated body mutually sticks by using a comparatively large silica particle as a lubricating agent. Thereby, although close_contact|adherence of films could be prevented to some extent, since a lubricant is comparatively large particle|grains, the problem that transparency of an optical laminated body may become inadequate was seen.

Moreover, the composition for hard-coat layers of patent document 3 uses a comparatively large silica particle as a lubricating agent, and makes a fluorine-type leveling agent essential as a leveling agent. Thereby, although suppression of blocking and the improvement of smoothness to a certain extent were confirmed, the problem that adhesiveness may be inferior when a conductive layer etc. were further laminated|stacked on a hard-coat film by the water repellency of a fluorine-type leveling agent was seen.

Then, as a result of earnestly examining these problems, the present inventors provide a hard-coat layer on at least one side of a base film, and a predetermined hydrophobization silica sol and specific leveling in the hard-coat layer forming material which forms the said hard-coat layer. By blending the agent and setting the silicon atom concentration on the surface to a value within a specific range, blocking between hard coat films can be effectively prevented, and when a surface layer (conductive layer, etc.) is formed, good adhesion It finds out that the hard-coat film which has this is obtained, and completes this invention.

That is, the present invention can effectively prevent blocking (sticking) between hard coat films (anti-blocking property), and when a surface layer (conductive layer, etc.) is formed, good adhesiveness with the surface layer It aims at providing the hard-coat film which has, the transparent conductive film provided with such a hard-coat film, and a capacitive touch panel.

According to the present invention, as a hard coat film having a hard coat layer on at least one side of the base film, the hard coat layer comprises at least (A) an energy ray curable resin, (B) a hydrophobized silica sol, and (C) a silicone-based leveling agent. It consists of a hardened|cured material of the hard-coat layer forming material containing, (B) hydrophobized silica sol is unevenly distributed on the surface side opposite to the base film of the hard-coat layer after hardening the hard-coat layer forming material, and of a hard-coat film In the region from the outermost surface to the position of 5 nm, the silicon atom concentration is within the 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. A hard coat film is provided, characterized in that the value, it is possible to solve the above-mentioned problem.

That is, since the hydrophobized silica sol is phase-separated and exists on the surface side opposite to the base film of the hard-coat layer after hardening the hard-coat layer-forming material by using a hydrophobized silica sol as a hard-coat layer forming material. , fine irregularities may be formed on the surface of the hard coat film, and sticking of the hard coat films can be prevented.

In addition, by containing the silicone-based leveling agent, the silicone-based leveling agent is present on the outermost surface of the hard coat layer by covering the hydrophobized silica sol. can be prevented

Furthermore, in the area|region from the outermost surface of a hard-coat film to the position of 5 nm WHEREIN: By making a silicon atom concentration into a value within a predetermined range, deformation|transformation and cissing of a coating film can be suppressed.

Further, in constituting the hard coat film of the present invention, (C) a silicone-based leveling agent, silicone-modified acrylic, polyether-modified polydimethylsiloxane, polyether ester-modified hydroxyl group-containing polydimethylsiloxane, polyester-modified hydroxyl group-containing polydimethylsiloxane, It is preferable that it is at least 1 sort(s) chosen from the group which consists of polyether modified polydimethylsiloxane.

By comprising in this way, the silicon atom density|concentration in the area|region from the outermost surface of a hard-coat film to the position of 5 nm can be easily adjusted to the value within a predetermined range.

Further, in constituting the hard coat film of the present invention, (C) the compounding amount of the silicone-based leveling agent is preferably a value within the range of 0.045 to 5 parts by weight in terms of solid content with respect to 100 parts by weight of the (A) energy ray-curable resin.

By comprising in this way, the adhesiveness of a hard-coat film can be improved effectively.

Moreover, in comprising the hard coat film of this invention, it is preferable that the average particle diameter of (B) hydrophobized silica sol is a value within the range of 10-100 nm.

By comprising in this way, transparency of a hard-coat film can be maintained or improved effectively, and sufficient light transmittance can be acquired.

Further, in constituting 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) hydrophobized silica sol is used as a coating film is 100° or more.

By comprising in this way, blocking of hard-coat films can be prevented effectively.

Moreover, in constituting the hard coat film of the present invention, (B) the compounding amount of the hydrophobized silica sol is preferably a value within the range of 0.3 to 55 parts by weight in terms of solid content with respect to 100 parts by weight of the (A) energy ray-curable resin.

By configuring in this way, in spite of the addition of a relatively small amount, it is possible to effectively localize the hard coat layer to the surface side, and to effectively improve the transparency of the hard coat film.

Moreover, in comprising the hard coat film of this invention, it is preferable that haze value measured based on JISK7105 of a hard coat film is 1.0 % or less.

By comprising in this way, it can be used for the transparent conductive film excellent in transparency, For example, it can use for electronic devices, such as a capacitive touch panel.

Moreover, in comprising the hard coat film of this invention, it is preferable that arithmetic mean roughness (Ra) measured based on JISB0601-1994 in the surface of a hard-coat layer is a value within the range of 1.5-5 nm.

By comprising in this way, fine unevenness|corrugation can be obtained on the surface of the obtained hard-coat film, and blocking of hard-coat films can be prevented suitably.

Moreover, if the arithmetic mean roughness in the surface of a hard-coat layer is a value within such a range, the hard-coat film which has the outstanding optical characteristic can be obtained.

Moreover, another aspect of this invention is a transparent conductive film provided with the transparent conductive layer on at least single side|surface of the hard-coat film mentioned above.

That is, by using a hard coat film having such excellent blocking resistance and excellent adhesion to the transparent conductive layer, there is no need to prevent blocking between films using a protection film, and also excellent in durability. A transparent conductive film can be obtained.

Further, another aspect of the present invention is a capacitive touch panel comprising a cover glass provided with a glass scattering prevention film, a first transparent conductive film, a second transparent conductive film, and a liquid crystal display, the first transparent The conductive film and the second transparent conductive film or either one is provided with a transparent conductive layer on the hard coating layer of the hard coating film having a hard coating layer, and the hard coating film is provided with a hard coating layer on at least one side of the base film, , the hard coat layer is composed of a cured product of a hard coat layer forming material comprising at least (A) an energy ray-curable resin, (B) a hydrophobized silica sol, and (C) a silicone-based leveling agent, (B) the hydrophobized silica sol , of the hard coat layer after curing the hard coat layer forming material, is unevenly distributed on the surface side opposite to the base film, and in the region from the outermost surface of the hard coat film to the position of 5 nm, by XPS analysis in the depth direction It is a capacitive touch panel characterized in that the silicon atom concentration is a value within the range of 0.2 to 1.95 atom% with respect to the total amount (100 atom%) of carbon atoms, oxygen atoms, and silicon atoms to be measured.

That is, if it is a capacitive touch panel using a transparent conductive film provided with a transparent conductive layer in a hard coat film having good adhesiveness and blocking resistance when a surface layer (conductive layer) is formed, a capacitive touch panel with excellent durability can get

Moreover, another aspect of this invention is a manufacturing method of the hard-coat film provided with the hard-coat layer on at least single side|surface of a base film, The manufacturing method of the hard-coat film characterized by including the following processes (1)-(3) am.

(1) at least (A) energy ray-curable resin, (B) hydrophobized silica sol, and (C) a step of preparing a material for forming a hard coat layer containing a silicone-based leveling agent

(2) Process of apply|coating hard-coat layer forming material to at least single side|surface of a base film

(3) hard coat layer forming material is cured, (B) hydrophobized silica sol is unevenly distributed on the surface side opposite to the base film of the hard coat layer after curing the hard coat layer forming material, the outermost surface of the hard coat film In the region from to 5 nm, with respect to the total amount (100 atom%) of carbon atoms, oxygen atoms, and silicon atoms measured by XPS analysis in the depth direction, the silicon atom concentration is within the range of 0.2 to 1.95 atom%. Process of forming a hard coat film having a coating layer

That is, by carrying out in this way, the hard-coat film which a silica particle is unevenly distributed and exists on the surface side opposite to a base film can be manufactured efficiently.

Therefore, even if it is a case where a hard-coat film is manufactured by roll-to-roll, it can prevent effectively that hard-coat films stick, and productivity can be improved.

1(a)-(b) is a figure provided in order to demonstrate the aspect in the hard-coat film of this invention.
2 is a view provided to conceptually explain the hard coat film of the present invention.
3 is a view provided to explain the silicon atom concentration distribution in the hard coating layer measured by XPS analysis in the depth direction.
Figs. 4(a) to 4(b) are diagrams provided for explaining aspects of the transparent conductive film of the present invention.
Fig. 5 is a diagram provided to explain an aspect of the touch panel for capacitance of the present invention.
6 is a view provided to explain a conventional hard coating film containing a silica sol having a hydrophilic surface.

[First embodiment]

1st Embodiment is a hard-coat film provided with the hard-coat layer on at least one side of a base film, The hard-coat layer is at least (A) energy-beam curable resin, (B) hydrophobic silica sol, (C) silicone leveling agent It consists of a hardened|cured material of the hard-coat layer forming material containing, (B) hydrophobized silica sol is unevenly distributed on the surface side opposite to the base film of the hard-coat layer after hardening the hard-coat layer forming material, The hard-coat film In the region from the outermost surface to the position of 5 nm, the silicon atom concentration is in the 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. It is a hard-coat film characterized by the value inside.

Hereinafter, the hard coat film of 1st Embodiment is demonstrated concretely with reference to appropriate drawing.

1. Hard coating layer forming material

(1) (A) Energy ray curable resin

(1)-1. Kinds

There is no restriction|limiting in particular as a kind of (A) energy-ray-curable resin which comprises the hard-coat layer forming material, It can select from a conventionally well-known thing, An energy-beam curable monomer, an oligomer, resin, or a composition containing them, etc. are mentioned. can

As a specific example, 1 type, such as polyfunctional (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, silicone (meth)acrylate, or a combination of 2 or more types can be heard

Examples of the polyfunctional (meth)acrylate include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and ethylene glycol di(meth)acrylate. Acrylate, propylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate B, pentaerythritol polyfunctional (meth) acrylate such as pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta such as dipentaerythritol hexa (meth) acrylate Erythritol polyfunctional (meth)acrylate, glycerol tri(meth)acrylate, triallyl (meth)acrylate, etc. are mentioned.

Among these, it is more preferable that they are pentaerythritol polyfunctional (meth)acrylate or dipentaerythritol polyfunctional (meth)acrylate at the point which can provide moderate hardness to a hard-coat layer.

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

Polyfunctional (meth)acrylate of EO (ethylene oxide) or PO (propylene oxide) addition type is a compound obtained by esterifying polyhydric alcohol of EO or PO addition type with acrylic acid, More specifically, EO or PO modified glycerol Triacrylate, EO or PO modified|denatured trimethylol propane acrylate, EO or PO modified|denatured pentaerythritol tetraacrylate, EO or PO modified|denatured dipentaerythritol hexaacrylate, etc. are mentioned.

Among these, EO or PO-modified dipentaerythritol hexaacrylate, EO or PO-modified trimethylolpropane tetraacrylate from the viewpoint of preventing cracks or cracking of the hard coat layer by imparting appropriate flexibility to the hard coat layer desirable.

In addition, in the EO or PO addition type polyfunctional (meth)acrylate, in order to give the hard coating layer adequate flexibility, the amount of EO or PO added per 1 mol of this polyfunctional (meth)acrylate is a value within the range of 6 to 18 moles. It is preferable, and it is more preferable that it is 8-16 mol.

(1)-2. compounding amount

In addition, (A) energy ray-curable resin constituting the hard coat layer forming material is (a1) a polyfunctional (meth) acrylate compound, and (a2) an ethylene oxide or propylene oxide addition type polyfunctional (meth) acrylate compound. It contains, and the content weight ratio of (a1) polyfunctional (meth)acrylate compound and (a2) ethylene oxide or propylene oxide addition type polyfunctional (meth)acrylate compound is within the range of 100:0-20:80 It is preferably a value.

The reason is that the hard-coat layer forming material is a polyfunctional (meth)acrylate compound which becomes relatively high in hardness by energy ray irradiation, and an ethylene oxide or propylene oxide addition type polyfunctional compound which has comparatively high flexibility even by energy ray irradiation. It is because the hardness of a hard-coat layer can be easily adjusted by containing in predetermined content.

That is, it is because the abrasion resistance of the hard-coat layer after hardening may fall when content weight ratio of (a1) polyfunctional (meth)acrylate compound becomes a value less than 20.

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

(1)-3. (D) Photoinitiator

Moreover, in the hard-coat layer forming material in this invention, it is preferable to contain (D) a photoinitiator as needed.

The reason is because a hard-coat layer can be efficiently formed when an active energy ray is irradiated with respect to a hard-coat layer forming material by containing a photoinitiator.

Here, a photoinitiator means the compound which generate|occur|produces a radical seed by irradiation of active energy rays, such as an ultraviolet-ray.

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 Ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2- Propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-amino Anthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethyl amine benzoic acid ester, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane], and the like, may be used alone or in combination of two or more. They may be used in combination.

Moreover, as content in the case of containing (D) a photoinitiator, it is preferable to set it as the value within the range of 0.2-20 weight part with respect to 100 weight part of (A) energy ray-curable resin, The value within the range of 0.5-15 weight part More preferably, it is more preferable to set it as a value within the range of 1 to 13 parts by weight.

(2) (B) Hydrogenated silica sol

(2)-1. Kinds

Moreover, the hard-coat layer forming material contains (B) hydrophobic silica sol, It is characterized by the above-mentioned.

Here, as a kind of silica sol, the sol of the silica fine particle which uses an alkoxysilane compound, a chlorosilane compound, etc. as a raw material is mentioned.

It will not specifically limit, if it is a silicon compound which has a hydrolysable alkoxy group as an alkoxysilane compound, For example, the compound represented by General formula (1) is mentioned.

R ¹ _n Si(OR ² ) _4-n (1)

( ^{Wherein, R 1} is a hydrogen atom or a non-hydrolyzable group, specifically, an alkyl group, a substituted alkyl group (substituent: a halogen atom, an epoxy group, a (meth)acryloyloxy group, etc.), an alkenyl group, an aryl group, or an aral represents a ^{alkyl group, and R 2} represents a lower alkyl group, n is a constant of 0 to ^{2 , and when R 1} and OR 2 are plural, respectively, a plurality of R ¹ may be the same or different, and a plurality of OR ² may be , may be the same or different)

Moreover, as an alkoxysilane compound represented by General formula (1), tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxy Silane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, trimethoxysilanehydride, triethoxysilanehydride, tripropoxysilanehydride, methyltrimethoxysilane, methyltriethoxysilane , methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, divinyldime Single 1 type or a combination of 2 or more types, such as oxysilane and divinyl diethoxy silane, is preferable.

In this case, as an alkoxysilane compound, when n is 0 or n is ¹ to 2 and R 1 is a hydrogen atom, an inorganic silica-based cured product is obtained when completely hydrolyzed, and when partially hydrolyzed, a polyorganosiloxane-based compound is obtained. A cured product of a mixture or a mixture of inorganic silica and polyorganosiloxane is obtained.

On the other hand, in a ^{compound in which n is 1} to 2 and R 1 is a non-hydrolyzable group, it has a non-hydrolyzable group, so that a polyorganosiloxane-based cured product is obtained by partial or complete hydrolysis.

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

In addition, a silica sol is what disperse|distributed silica microparticles|fine-particles in water or an organic solvent in the sol state.

These organic solvents are not particularly limited, but methanol, ethanol, isopropanol, ethylene glycol, n-propyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, dimethyl acetamide, propylene glycol monomethyl ether, cyclohexane, benzene, toluene Although these etc. are mentioned, methyl isobutyl ketone and propylene glycol monomethyl ether with a comparatively high boiling point are especially preferable.

Further, the silica sol of the present invention is characterized in that it is a hydrophobized silica sol in which some or all of the silanol groups on the surface of the silica particles are treated with a surface modifier having a hydrophobic group.

Here, as the surface modifier, a silane coupling agent having both a functional group capable of reacting with a silanol group on the surface of the silica particle and a hydrophobic group may be mentioned.

More specifically, as the hydrophobized silica sol, SIRPGM15WT%-E26 manufactured by CIK Nanotech Co., Ltd., etc. are mentioned, for example.

(2)-2. degree of hydrophobicity

In addition, the hydrophobization degree of the silica sol was judged by coating the silica sol on PET film, removing a solvent, creating a silica sol coating film, and measuring the contact angle of water with respect to this 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 shall be a value of 100 degrees or more.

That is, when the contact angle of water measured according to JIS R 3257 with respect to the coating film of the silica sol is a value of 100° or more, it can be determined that the surface of the silica sol is hydrophobic.

Here, in FIG. 2, a view provided to conceptually explain the hard coat film 20 of the present invention is shown.

More specifically, the hydrophobized silica sol 16 of the present invention is phase-separated from other components in the hard coating layer 12 when a hard coating layer forming material is applied to the substrate surface and cured, and is separated from the substrate surface 10 It is highly localized on the opposite surface side, and it is thought that the ratio which exists in the vicinity of a base material surface and in a hard-coat layer will become low.

Therefore, by the addition of a small amount of hydrophobized silica sol, moderate surface roughness can be imparted to the surface of the hard coat layer, so that blocking (compression bonding) of the films occurs even when the hard coat films overlap and time elapses. it can be prevented

That is, since the effect of predetermined|prescribed blocking resistance (it may be called anti-blocking property) can be exhibited with a comparatively small amount addition, it can be understood that a hard-coat film with high transparency can be obtained.

In addition, when the contact angle of water with respect to the coating film of the hydrophobized silica sol becomes excessively high, there is a risk that adhesion may decrease when a transparent conductive layer is further laminated on the hard coat film. Therefore, the contact angle of water with the coating film of the hydrophobized silica sol It is more preferable to make it into a value within the range of 100 to 130 degrees.

On the other hand, when the contact angle of water with respect to the coating film of the silica sol becomes a value of less than 100 ° and the hydrophilicity increases, as shown in FIG. 6 , the silica sol 18 is not unevenly distributed only on the surface side opposite to the base film, It is confirmed that it exists in the state disperse|distributed to the whole in the hard-coat layer.

Therefore, it can be understood that in order to impart a predetermined surface roughness to the hard coating layer, it is necessary to blend the silica sol in a relatively large amount.

In addition, the measuring method of the contact angle of water with respect to the coating film of a silica sol is computable by creating a coating film of a silica sol as demonstrated concretely in Example 1, and measuring the contact angle of water.

(2)-3. average particle diameter

Moreover, it is preferable that the average particle diameter of the hydrophobization silica sol of this invention is a value within the range of 10-100 nm.

The reason for this is that when the average particle diameter of the hydrophobized silica sol becomes a value of less than 10 nm, it becomes difficult to obtain a predetermined surface roughness, and in particular, with a small amount of blending, it may become difficult to prevent the occurrence of blocking. am.

On the other hand, it is because the optical characteristic of a hard-coat film may fall too much when the average particle diameter of a hydrophobized silica sol becomes a value exceeding 100 nm.

Therefore, it is more preferable that the average particle diameter of the hydrophobized silica sol is a value within the range of 10-50 nm, and it is more preferable that it is a value within the range of 15-40 nm.

In addition, the average particle diameter of the silica sol is the particle diameter (median diameter D50) at 50% of the integrated value in the volume-based particle size distribution calculated|required using the laser diffraction scattering type particle size distribution analyzer, and means the average primary particle diameter.

(2)-4. compounding amount

Moreover, the compounding quantity of the hydrophobization silica sol of this invention is a value within the range of 0.3-55 weight part in conversion of solid content with respect to 100 weight part of (A) energy-beam curable resin, It is characterized by the above-mentioned.

This is because it may become difficult to express the effect which prevents the blocking of hard-coat films, when the compounding quantity of the hydrophobization silica sol becomes a value less than 0.3 weight part.

On the other hand, it is because the adhesiveness and abrasion resistance of a hard-coat film may fall excessively when the compounding quantity of a hydrophobization silica sol will be a value exceeding 55 weight part.

In addition, as described above, since the hydrophobized silica sol tends to be unevenly distributed on the surface side opposite to the substrate surface in the hard coating layer, the blending amount of the hydrophobized silica sol is (A) with respect to 100 parts by weight of the energy ray-curable resin, in terms of solid content. As a result, when it is in the range of 0.3 to 25 parts by weight, even if the blending amount of the hydrophobized silica sol is relatively small, it is possible not only to effectively express the blocking effect, but also to have excellent transparency. It can be used suitably as a coating film.

Therefore, the blending amount of the hydrophobized 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, in terms of solid content, with respect to 100 parts by weight of the energy ray-curable resin (A). And it is especially preferable that it is a value in the range of 0.4-3.0 weight part.

(3) (C) Leveling agent

(3)-1. Configuration

Moreover, as a hard-coat layer forming material, (C) silicone type leveling agent is contained, It is characterized by the above-mentioned.

In addition, in the region from the outermost surface of the hard coat film to the position of 5 nm, the silicon atom concentration is 0.2 with respect to the total amount (100 atom%) of carbon atoms, oxygen atoms, and silicon atoms measured by XPS analysis in the depth direction. It is characterized in that the value is within the range of ∼1.95 atom%.

Generally, it is known that the deformation|transformation of a coating film and the sheathing can be suppressed with respect to a base film by a leveling agent being abundantly unevenly distributed in the outermost surface side in a hard-coat layer forming material.

In the present invention, as shown in FIG. 2 , in the hard coating layer, as described above, the hydrophobized silica sol is unevenly distributed on the surface side opposite to the substrate surface, and the silicone-based leveling agent covers the hydrophobized silica sol and covers the outermost surface. By being localized in the range of a predetermined amount, by the interaction of the hydrophobized silica sol and the silicone-based leveling agent, it is possible to obtain a hard coat film having excellent blocking resistance and leveling performance.

More specifically, the hard coat film of this invention WHEREIN: The result measured by XPS analysis (X-ray photoelectron spectroscopy analysis) of the depth direction toward a base material from an outermost surface is shown in FIG.

Here, from Fig. 3, from the outermost surface toward the substrate, the silicon atom concentration is 0.28 atom% in the region up to 5 nm, 0.29 atom% in the region up to 10 nm, and in the region up to 50 nm, It can be understood that 0.30 atom% and 0.20 atom% in the region up to 100 nm, and 22.01 atom% in the region up to 150 nm as the silicon concentration rises rapidly in the region exceeding 100 nm.

That is, as described above, in the present invention, in the hard coating layer, as illustrated in FIG. 2 , the silicone-based leveling agent in the region most distant from the substrate is in the state of an ultra-thin film so as to cover the hydrophobized silica sol ( 14), it can be understood that it is ubiquitous.

Therefore, in the region from the outermost surface of the hard coat film to the position of 5 nm, the silicon atom concentration is 0.2 with respect to the total amount (100 atom%) of carbon atoms, oxygen atoms, and silicon atoms measured by XPS analysis in the depth direction. By specifying that it is a value within the range of -1.95 atom%, the leveling performance and blocking resistance can be improved effectively by effectively controlling the leveling agent which exists on the outermost surface.

That is, when the silicon atom concentration becomes a value of less than 0.2 atom%, when the hard coat layer forming material is coated, the leveling agent cannot form a thin film on the outermost surface of the coating film of the hard coat layer forming material. It is because formation of a uniform thin film may become difficult with accompanying it.

On the other hand, when the silicon atom concentration becomes a value exceeding 1.95 atom%, the surface energy of the hard coating surface decreases. am.

Therefore, it is more preferable to set the silicon element concentration in the region from the outermost surface of the hard coat film to the position of 5 nm to a value within the range of 0.21 to 1.95 atom%, and to a value within the range of 0.23 to 1.94 atom%. it is more preferable

In addition, the silicon atom concentration by elemental analysis measurement of XPS means the silicon atom concentration in each depth measured by XPS analysis of a depth direction in the whole hard-coat layer.

(3)-2. Kinds

Further, (C) as a silicone-based leveling agent, 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 It is preferable that it is at least 1 sort(s) chosen.

The reason is that if the silicon leveling agent is of this kind, it becomes easy to make the silicon atom concentration in the leveling agent thin film 14 on the surface of the hard coat layer a value within the range described above, and the surface smoothing required for the leveling agent and the conductive layer It is because the adhesiveness in the case of laminating|stacking a etc. can be improved with good balance.

Therefore, if it is the silicone leveling agent of this invention, when forming an adhesive bond layer or a printing layer on the hard-coat layer as well as a conductive layer, for example, adhesiveness with such an adhesive bond layer etc. can be improved.

Moreover, it is more preferable to contain the reactive silicone type leveling agent which has a vinyl group etc. especially among the silicone type leveling agents mentioned above.

The reason is that, if the silicone-based leveling agent is a reactive leveling agent, it reacts with the energy ray-curable resin to form a stronger leveling agent thin film. This is because it can reduce pollution.

Moreover, about the fluorine-type leveling agent generally considered useful as a leveling agent, in this invention, although sheathing can be suppressed effectively, certainly, since water repellency is high, adhesiveness of a conductive layer etc. is inferior, and a silicone type leveling agent And, it is confirmed that the synergistic effect by hydrophobized silica sol is not expressed.

(3)-3. compounding amount

Moreover, it is preferable to further mix|blend (C) a leveling agent at the value within the range of 0.045-5 weight part with respect to 100 weight part of (A) energy-beam curable resin.

The reason is because adhesiveness with a transparent conductive layer can be improved by making a leveling agent into the value within this range, when forming a transparent conductive layer on a hard-coat layer.

More specifically, when the blending amount of the leveling agent becomes a value of less than 0.045 parts by weight, localization of the leveling agent on the outermost surface of the base material becomes insufficient, and the coating film of the hard coat layer forming material is deformed and accompanied by shedding, resulting in a uniform coating film. It is because formation may become difficult.

On the other hand, when the compounding amount of the leveling agent becomes a value exceeding 5 parts by weight, the leveling agent is localized beyond the leveling effect, the surface energy of the hard coat surface decreases, and even if a conductive layer is laminated on the hard coat layer , and thereafter, the conductive layer may fall off or the like.

Therefore, it is more preferable to make the compounding quantity of (C) leveling agent into the value within the range of 0.05-3 weight part, and it is more preferable to set it as the value within the range of 0.05-2 weight part.

(4) Other additives

In addition, as long as the effect of the present invention is not impaired, other additives may be contained.

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

Moreover, it is preferable to set it as the value within the range of 0.01-5 weight part with respect to 100 weight part of (A) energy ray-curable resin, and, generally, content of another additive generally sets it as the value within the range of 0.02-3 weight part. It is preferable, and it is more preferable to set it as the value within the range of 0.05-2 weight part.

(5) thickness

Moreover, it is preferable to make the thickness of the hard-coat layer 12 illustrated in FIG. 1 into the value within the range of 1-10 micrometers.

The reason is that, when the thickness of such a hard-coat layer becomes a value less than 1 micrometer, abrasion resistance may become remarkably low.

On the other hand, it is because curl may become large when the thickness of a hard-coat layer becomes a value exceeding 10 micrometers.

Therefore, it is more preferable to make the thickness of a hard-coat layer into the value within the range of 1-5 micrometers, and it is more preferable to set it as the range of 1.5-4 micrometers.

2. Base film

(1) Type

The resin used for the base film 10 illustrated in FIGS. Polyester film, polycarbonate film, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene- Vinyl acetate copolymer film, polystyrene film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, polyimide film, fluororesin film, polyamide film, acrylic resin film, Other plastic films, such as a polyurethane resin film, a norbornene-type resin film, and a cycloolefin resin film, are mentioned.

Among these, it is excellent in transparency, and it is preferable to use the transparent resin film which consists of a polyethylene terephthalate or a polycarbonate at a point with versatility.

(2) thickness

Moreover, it is preferable to make the thickness of the base film 10 illustrated to Fig.1 (a)-(b) into the value within the range of 15-250 micrometers.

The reason is that, when the thickness of the base film becomes a value of less than 15 µm, handling properties such as wrinkle tend to occur remarkably decrease. On the other hand, when the thickness of the base film exceeds 250 µm, handleability decreases, It is because it may become difficult to set it as roll shape especially.

Therefore, it is more preferable to make the thickness of a base film into the value within the range of 25-125 micrometers at the point which balance between mechanical strength and light transmittance becomes more favorable.

(3) Primer layer

In addition, although not shown, by providing a primer layer on the surface of the base film, the adhesion between the base film and the hard coat layer can be improved, and the scratch resistance of the hard coat layer can be further improved.

Here, as a constituent material of a primer layer, single 1 type, or a combination of 2 or more types, such as a urethane resin, an acrylic resin, an epoxy resin, a polyester resin, a silicone resin, is mentioned.

Moreover, it is preferable to make the thickness of a primer layer into the value within the range of 0.01-20 micrometers.

The reason is that the primer effect may not be expressed when the thickness of the primer layer is set to a value of less than 0.01 µm. On the other hand, when the thickness of a primer layer becomes a value exceeding 20 micrometers, when a hard-coat film is comprised, it is because light transmittance may fall.

Therefore, since the balance between a primer effect and light transmittance becomes more favorable, it is more preferable to make the thickness of a primer layer into the value within the range of 0.1-15 micrometers.

3. Characteristics of hard coating film

(1) Surface roughness of the hard coating layer

Moreover, arithmetic mean roughness Ra measured based on JISB0601-1994 in the surface of the hard-coat layers 12 and 12' illustrated by Fig.1 (a)-(b) is 1.5-5 nm Preferably, it is a value within the range of .

The reason for this is that when such arithmetic mean roughness (Ra) becomes a value of less than 1.5 nm, when winding a hard coat film or stacking it, the so-called blocking that adjacent hard coat films stick together is prevented. Because it is sometimes difficult to do.

On the other hand, when arithmetic mean roughness Ra becomes a value exceeding 5 nm, it is because light transmittance may fall remarkably.

Therefore, it is more preferable that arithmetic mean roughness Ra in the surface of a hard-coat layer is a value within the range of 2.0-4 nm, It is more preferable that it is a value within the range of 2.5-3.5 nm.

(2) Pencil hardness of the hard coating layer

Moreover, it is preferable that the pencil hardness measured according to JISK5600-5-4 of the hard-coat layer illustrated to Fig.1 (a)-(b) is HB or more.

The reason is that, when such a pencil hardness becomes a value less than HB, when it uses for a capacitive touchscreen, it is because abrasion resistance may become inadequate.

(3) Haze value of hard coat film

Moreover, it is preferable that the haze value measured based on JISK7105 of the hard-coat films 20 and 20' illustrated by Fig.1 (a)-(b) is a value of 1.0 % or less.

The reason is that when such a haze value becomes a value exceeding 1.0%, the display of the liquid crystal display device may look blurry when used for a mobile phone or the like.

[Second embodiment]

2nd Embodiment is a manufacturing method of the hard-coat film provided with the hard-coat layer on at least single side|surface of a base film, Comprising: The following process (1)-(3) is included, It is a manufacturing method of the hard-coat film characterized by the above-mentioned.

(1) at least (A) energy ray-curable resin, (B) hydrophobized silica sol, and (C) a step of preparing a material for forming a hard coat layer containing a silicone-based leveling agent

(2) Process of apply|coating hard-coat layer forming material to at least single side|surface of a base film

(3) hard coat layer forming material is cured, (B) hydrophobized silica sol is unevenly distributed on the surface side opposite to the base film of the hard coat layer after curing the hard coat layer forming material, the outermost surface of the hard coat film In the region from to 5 nm, with respect to the total amount (100 atom%) of carbon atoms, oxygen atoms, and silicon atoms measured by XPS analysis in the depth direction, the silicon atom concentration is within the range of 0.2 to 1.95 atom%. Process of forming a hard coat film having a coating layer

Hereinafter, since it can be set as the content similar to 1st Embodiment about the base film and hard-coat layer to be used, it demonstrates mainly about the matter regarding the manufacturing method of a hard-coat film.

(1) Process 1: Preparation process of hard-coat layer forming material

A process (1) is a process of preparing the hard-coat layer forming material containing at least (A) energy-beam curable resin, (B) hydrophobized silica sol, and (C) a silicone-type leveling agent.

More specifically, it is a process of uniformly mixing the above-mentioned hard-coat layer forming material and a diluent solvent.

Examples of the solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, pentyl alcohol, ethyl cellosolve, benzene, toluene, xylene, ethylbenzene, cyclo Hexane, ethylcyclohexane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, propylene monomethyl ether, water, etc. are mentioned, You may combine 2 or more types of solvents.

In particular, 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, etc. are preferably used.

In addition, since it is as having already described about the structure of a predetermined|prescribed hard-coat layer forming material, it abbreviate|omits.

(2) Process 2: Application|coating process to the base film of a hard-coat layer forming material

A process (2) is a process of apply|coating a hard-coat layer forming material to at least single side|surface of a base film.

More specifically, the base film 10 is prepared, and the hard coat layer forming material adjusted in step (1) is coated thereon so that the film thickness of the hard coat layer after curing becomes a value within the range of 1 to 10 µm. it is fair

In addition, the coating method of the hard coat layer forming material is not particularly limited, and a known method, for example, a bar coating method, a gravure coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, etc. can be used

(3) Step 3: Hard coat layer forming material curing and hard coating film forming step

Process (3) hardens the hard-coat layer forming material mentioned above, (B) hydrophobized silica sol is unevenly distributed on the surface side opposite to the base film of a hard-coat layer, and 5 from the outermost surface of a hard-coat film In the region up to the nm position, the silicon atom concentration is a value within the 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. Hard coating film is the process of forming

More specifically, it is preferable to irradiate and harden|cure the coated object of the hard-coat layer forming material which evaporated the solvent through the drying process, for example, an energy beam, for example, an ultraviolet-ray or an electron beam.

When it carries out in this way, while being able to form a hard-coat layer quickly, it can closely_contact|adhere firmly to a base film.

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

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

Therefore, while being able to improve the mechanical strength of a hard-coat layer, blocking of hard-coat films can be prevented effectively, and adhesiveness in the case of laminating|stacking a conductive layer etc. further can be improved.

Moreover, when forming a hard-coat layer, for example, when irradiating an ultraviolet-ray, it is preferable to make the irradiation amount (accumulated light amount) with respect to a hard-coat layer forming material into the value within the range of 100-1000 mJ/cm<2>.

The reason is that hardening of a hard-coat layer may become inadequate when this ultraviolet irradiation amount will be a value of less than 100 mJ/cm<2>.

On the other hand, it is because a hard-coat layer and a base film may deteriorate with an ultraviolet-ray when this ultraviolet irradiation amount will be a value exceeding 1000 mJ/cm<2>.

Moreover, there is no restriction|limiting in particular with respect to the kind of energy-beam irradiation apparatus to be used, For example, the ultraviolet irradiation apparatus using a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fusion H lamp, etc. can be used.

(4) Process 4: Hard coating layer formation process on the other side of a base film

A process (4) is a process employ|adopted in manufacture of the hard-coat film provided with the hard-coat layer on both surfaces of a base film.

More specifically, as shown in FIG. is a process that

That is, after forming a hard coat layer on one surface of the above-described base film, in the same manner, a hard coat layer forming material is applied to the other surface of the base film, cured to form a hard coat layer on both surfaces of the base film am.

In addition, since an application|coating process and a hardening process are the same as the above-mentioned, the detail is abbreviate|omitted.

[Third embodiment]

3rd Embodiment is a transparent conductive film provided with the transparent conductive layer on at least single side|surface of the hard-coat film mentioned above.

Hereinafter, a transparent conductive film is demonstrated concretely with reference to drawings, centering on the point different from the content described in 1st and 2nd embodiment.

That is, the transparent conductive film of this invention is the transparent conductive film 40 provided with the transparent conductive layer 30 on at least single side|surface of the hard-coat film 20, as shown to Fig.4 (a).

In addition, since the transparent conductive film using the hard coat film of the present invention has excellent blocking resistance, it is not necessary to use a protection film for preventing blocking between films, and an adhesive used for bonding with the protection film is also required. does not exist.

Therefore, productivity is high and an inexpensive transparent conductive film can be obtained.

Furthermore, since it is excellent in the adhesiveness of a hard-coat film and a transparent conductive layer, the transparent conductive film excellent in durability can be obtained.

(1) Transparent conductive layer

The material constituting the transparent conductive layer of the present invention is not particularly limited as long as the visible light transmittance at 550 nm of the transparent conductive layer is 70% or more, and examples thereof include 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, polyethylenedioxythiophene, and polypyrrole; inorganic conductive materials such as copper iodide and copper sulfide; non-oxidizing compounds such as chalcogenide, lanthanum hexaboride, titanium nitride, and titanium carbide; Zinc oxide, zinc dioxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, zinc-doped indium oxide (IZO), tin oxide, indium oxide, cadmium oxide, tin-doped indium oxide (ITO), tin and gallium-doped indium oxide (IGZO) ), conductive metal oxides such as fluorine-doped indium oxide, antimondoped tin oxide, and fluorine-doped tin oxide (FTO); and the like.

Among these, an electroconductive metal oxide is preferable at the point which can obtain the transparent electroconductive film which has the outstanding transparent electroconductivity more simply.

(2) Formation method

A transparent conductive layer can be formed by a conventionally well-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 and a micro gravure coater, etc. are mentioned.

Among these, the sputtering method is preferable at the point which can form a transparent conductive layer simply.

(3) thickness

The value within the range of 5 nm - 500 nm is preferable, as for the thickness of a transparent conductive layer, the value within the range of 5-200 nm is more preferable, The value within the range of 10-100 nm is still more preferable.

(4) patterning

As shown in Fig. 4B, the formed transparent conductive layer may be subjected to patterning 30' as needed. As a method of patterning, chemical etching by photolithography etc., physical etching using a laser etc., the vacuum deposition method using a mask, a sputtering method, a lift-off method, a printing method, etc. are mentioned.

[Fourth embodiment]

A fourth embodiment is a capacitive touch panel comprising a cover glass provided with a glass scattering prevention film, a first transparent conductive film, a second transparent conductive film, and a liquid crystal display, the first transparent conductive film and the second 2 The transparent conductive film or any one is equipped with a transparent conductive layer on the hard-coat layer of the hard-coat film which has a hard-coat layer, The said hard-coat film is provided with a hard-coat layer on at least one side of a base film, A hard-coat layer At least (A) an energy ray-curable resin, (B) a hydrophobized silica sol, and (C) a cured product of a hard coat layer forming material containing a silicone-based leveling agent, (B) the hydrophobized silica sol is a hard coat layer It is unevenly distributed on the surface side opposite to the base film of the hard-coat layer after hardening a forming material, and in the area|region from the outermost surface of a hard-coat film to the position of 5 nm WHEREIN: Carbon measured by XPS analysis of the depth direction. A capacitive touch panel characterized in that the silicon atom concentration is within the range of 0.2 to 1.95 atom% with respect to the total amount of atoms, oxygen atoms, and silicon atoms (100 atom%).

Hereinafter, a capacitive touch panel is specifically demonstrated with reference to drawings, centering on the point different from the content described in 1st - 3rd embodiment.

That is, the basic configuration of the capacitive touch panel is not particularly limited. For example, the capacitive touch panel 100 is, as shown in FIG. 5, on the liquid crystal display device 70, through the adhesive 50 for optics, the hard-coat film 20 provided with the hard-coat layer, transparent Conductive layer 30 (first electrode), optical adhesive 50, hard coating film 20 having a hard coating layer, transparent conductive layer 30'' (second electrode), optical adhesive 50' '), the glass scattering prevention film 60 provided with the adhesive layer for optics, and the capacitive touch panel on which the cover glass 80 is laminated|stacked is mentioned.

In addition, in this invention, you may provide other layers other than an above-mentioned layer as needed.

Further, the capacitive touch panel of the present invention may be a surface type capacitive type or a projected type capacitance type.

Since the capacitive touch panel of this invention is equipped with the hard-coat film which has favorable adhesiveness especially when a surface layer (conductive layer etc.) is formed, it can be set as the capacitive touch panel excellent in durability.

[Example]

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

[Example 1]

1. Preparation of hard coating film

(1) Preparation process of hard-coat layer forming material

As shown in Table 1, an energy ray-curable resin as a component (A), a hydrophobized silica sol as a component (B), a silicone-based leveling agent as a component (C), and a photoinitiator as a component (D) of Example 1 The hard-coat layer forming material was adjusted.

More specifically, as component (A), (a1) 100 parts by weight of pentaerythritol triacrylate (NK ester manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMM-3L), (a2) dipentaerythritol hexaacryl 100 parts by weight of the rate (EO12 mole adduct) (manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH-12E), and 10 parts by weight of a photopolymerization initiator (Chiba Specialty Chemicals, Irgacure 184) as component (D), ( B) 0.8 parts by weight of hydrophobized silica sol A (manufactured by CIK Nanotech, SIRPGM15WT%-E26, average particle diameter of 30 nm) as component (C), silicone-modified acryl a as a silicone-based leveling agent as component (C) (manufactured by Bikchemi Japan, BYK-3550) ) 0.1 parts by weight and 492.1 parts by weight of propylene monomethyl ether as a diluting solvent to prepare a hard-coat layer forming material (solid content concentration: 30% by weight).

(2) Application process of hard-coat layer forming material

Next, using the hard coat layer forming material as a base film, on one side of a PET film with an easily adhesive layer (manufactured by Toray Corporation, Lumira U48, film thickness 100 μm) subjected to an easily adhesive treatment on both sides, Meyer Using a bar, it applied so that the film thickness after drying might be set to 3 micrometers.

(3) drying process

Next, the diluting solvent contained in the hard-coat layer forming material apply|coated to the base film was removed.

That is, it heat-dried on 70 degreeC and conditions for 1 minute using the hot air drying apparatus, and the dilution solvent was fully removed.

(4) curing process

Next, using a high-pressure mercury lamp, ultraviolet rays were irradiated at 300 mJ/cm 2 , the hard-coat layer forming material was photocured, and the hard-coat film was obtained.

Moreover, although not shown in figure, the cross section of the hard coat film manufactured in Example 1 was used for the scanning electron microscope (SEM) (The Hitachi Seisakusho company make, S-4700 type|mold), acceleration voltage 10 kV, 20,000 times magnification. When photographed under the conditions of , it was confirmed that the hydrophobized silica sol was unevenly distributed on the surface side of the hard coating layer opposite to the base film.

2. Evaluation of Hard Coating Films

(1) Silicon atom concentration analysis

Elemental analysis of a carbon atom, an oxygen atom, and a silicon atom measured by XPS analysis of the depth direction of the hard-coat layer in the obtained hard-coat film was performed using the XPS measurement and analysis apparatus (made by Aruba Pai, Quantum2000). The silicon atom concentration distribution by the obtained XPS measurement is shown in FIG.

In addition, from these measurements, the silicon atom concentration with respect to the total amount (100 atom%) of a carbon atom, an oxygen atom, and a silicon atom in the area|region from the outermost surface to the position of 5 nm was computed. The obtained results are shown in Table 1.

(2) Measurement of hydrophobicity

Hydrophobized silica sol A (solid content concentration: 15%) dispersed in methyl isobutyl ketone was coated on PET film (manufactured by Toray Corporation, Lumira U48, film thickness of 100 µm) with Meyer Bar #8.

Next, it dried in 90 degreeC oven for 1 minute, and obtained the silica sol coating film whose thickness after drying is 1 micrometer.

Next, the contact angle of water measured based on JIS R 3257 with respect to this silica sol coating film was measured, and the hydrophobization degree was evaluated.

That is, the PET film formed with such a silica sol coating film is left still on a flat glass substrate, and when the inclination of the glass substrate is set to 0 degrees, 2 μl of water drops are added dropwise, and at the place where the droplets stop, according to Young's formula The water contact angle was obtained. The obtained results are shown in Table 1.

(3) Evaluation of the adhesiveness of the hard coat layer

On the surface of the obtained hard coat film, an ultraviolet curable ink (made by Tikoku Ink Seijo Co., Ltd., UVPAL911 ink) was apply|coated, the ink was irradiated by ultraviolet-ray, and the ink was hardened, and the printed layer with a film thickness of 1 micrometer was formed. The surface of the print layer is crosscut with a width of 1 mm in a checkerboard pattern, and an adhesive tape (manufactured by NichiReflective, CelloTape (registered trademark)) is applied to the surface of the printed layer crosscut in a checkerboard pattern. The cellotape (registered trademark) peel test was performed in accordance with the checkered tape method of JIS K 5600-5-6 (cross skirt method), and the print adhesiveness of the curable resin layer was evaluated according to the following criteria. The obtained results are shown in Table 1.

○: There is not even one printed layer peeled off from the hard coat film and transferred to the adhesive tape

△: The number of printed layers transferred to the adhesive tape is less than 50%

x: the number of printed layers transferred to the adhesive tape is 50% or more

(4) Evaluation method of coatability (sheathing)

The hard coat layer forming material was applied to one side of the PET film with an easily adhesive layer on one side of the PET film with an easily adhesive layer using a Meyer bar so that the film thickness after drying was 3 μm. Then, according to the following reference|standard, coatability was evaluated. The obtained results are shown in Table 1. In addition, the area which visually inspects shall be 0.5 m<2>.

○ : No sheathing

× : There is more than one sheathing

(5) Pencil hardness evaluation

According to JISK5600-5-4, the pencil hardness of the obtained hard-coat film was measured using the pencil scratching hardness tester (The Yasuda Seiki Seisakusho make, No.553-M). In addition, the scraping speed|rate was 1 mm/sec. The obtained results are shown in Table 1.

(6) Blocking resistance evaluation

The obtained hard coat film was cut out in the magnitude|size of 100 x 100 mm, and 2 sheets of hard coat films were superimposed (let this state be an initial stage).

Next, in a state in which a load of 10 kg / m 2 is applied, after 5 days have elapsed at the initial stage and in a storage environment of 23 ° C. and 50% RH (this state is referred to as lapse of time), each overlapped film is peeled off, and the The state was visually observed under a fluorescent lamp, and the presence or absence of blocking was evaluated according to the following reference|standard. The obtained results are shown in Table 1.

(circle): Even after initial stage and time-lapse, blocking did not arise at all, and sticking of film surfaces did not arise

(triangle|delta): In the initial stage, blocking did not arise, but blocking has arisen after time-lapse (the area of sticking between film surfaces is less than 30%).

x: Blocking has arisen from the initial stage (the affixing area between film surfaces is 30% or more)

(7) Haze value

Based on JISK7105, the haze value of the obtained hard-coat film was measured using the haze meter (The Nippon Denshoku Kogyo Co., Ltd. make, NDH-2000). The obtained results are shown in Table 1.

[Example 2]

In Example 2, the method similar to Example 1 created and evaluated the hard-coat film except having changed the compounding quantity of (C) silicone leveling agent a into 0.16 weight part from 0.1 weight part. The obtained results are shown in Table 1.

[Example 3]

In Example 3, the method similar to Example 1 created and evaluated the hard-coat film except having changed the compounding quantity of (C) silicone type leveling agent a into 0.2 weight part from 0.1 weight part. The obtained results are shown in Table 1.

[Example 4]

In Example 4, (C) It is the same as Example 1 except having mix|blended 0.1 weight part of polyether modified polydimethylsiloxane b (made by Bikchemi Japan, BYK-300) instead of silicone modified acryl a of a silicone type leveling agent. A hard coat film was created and evaluated by the method of The obtained results are shown in Table 1.

In addition, although not shown, similarly to Example 1, when the cross section of the hard coating film manufactured in Example 4 was imaged with a scanning electron microscope (SEM), the hydrophobized silica sol is the base film of the hard coating layer and It was confirmed that it was unevenly distributed on the opposite surface side.

[Example 5]

In Example 5, (C) 0.1 parts by weight of polyether ester-modified hydroxyl group-containing polydimethylsiloxane c (BYK-375, manufactured by Bikchemi Japan) was blended in place of the silicone-modified acryl a of the silicone-based leveling agent. By the method similar to 1, the hard-coat film was created and evaluated. The obtained results are shown in Table 1.

In addition, although not shown, similarly to Example 1, when the cross section of the hard coat film manufactured in Example 5 was imaged with a scanning electron microscope (SEM), the hydrophobized silica sol is the base film of the hard coat layer and It was confirmed that it was unevenly distributed on the opposite surface side.

[Example 6]

In Example 6, (C) Example 1 except that 0.1 parts by weight of polyester-modified hydroxyl group-containing polydimethylsiloxane d (BYK-370, manufactured by Bikchemi Japan) was blended in place of (C) silicone-modified acryl a of the silicone-based leveling agent. By the method similar to the above, the hard-coat film was created and evaluated. The obtained results are shown in Table 1.

In addition, although not shown, similarly to Example 1, when the cross section of the hard coat film manufactured in Example 6 was imaged with a scanning electron microscope (SEM), the hydrophobized silica sol is the base film of the hard coat layer and It was confirmed that it was unevenly distributed on the opposite surface side.

[Example 7]

In Example 7, (C) It is the same as Example 1 except mix|blending 0.1 weight part of polyether-modified polydimethylsiloxane e (the Bikchemi Japan company make, BYK-331) instead of the silicone-modified acryl a of a silicone type leveling agent. A hard coat film was created and evaluated by the method of The obtained results are shown in Table 1.

In addition, although not shown, similarly to Example 1, when the cross section of the hard coat film manufactured in Example 7 was imaged with a scanning electron microscope (SEM), the hydrophobized silica sol is the base film of the hard coat layer and It was confirmed that it was unevenly distributed on the opposite surface side.

[Comparative Example 1]

In the comparative example 1, the method similar to Example 1 created and evaluated the hard-coat film except having changed the compounding quantity of (C) silicone leveling agent a into 0.08 weight part from 0.1 weight part. The obtained results are shown in Table 1.

In addition, although not shown, similarly to Example 1, when the cross section of the hard coat film produced in Comparative Example 1 was photographed with a scanning electron microscope (SEM), the hydrophobized silica sol was different from the base film of the hard coat layer. It was confirmed that it was unevenly distributed on the opposite surface side.

[Comparative Example 2]

In the comparative example 2, the method similar to Example 1 created and evaluated the hard-coat film except having changed the compounding quantity of (C) silicone leveling agent a into 0.04 weight part from 0.1 weight part. The obtained results are shown in Table 1.

[Comparative Example 3]

In Comparative Example 3, (C) In place of the silicone-modified acryl a of the silicone-based leveling agent, 0.1 parts by weight of the polyether-modified polymethylalkylsiloxane f (by Bikchemi Japan Co., Ltd., BYK-325) was added, except that 0.1 parts by weight were blended. By the same method, the hard-coat film was created and evaluated. The obtained results are shown in Table 1.

In addition, although not shown, similarly to Example 1, when the cross section of the hard coat film produced in Comparative Example 3 was photographed with a scanning electron microscope (SEM), the hydrophobized silica sol was different from the base film of the hard coat layer. It was confirmed that it was localized on the opposite surface side.

[Comparative Example 4]

In Comparative Example 4, (C) Instead of the silicone-modified acryl a of the silicone-based leveling agent, 0.1 parts by weight of polyether-modified polydimethylsiloxane g (by Bikchemi Japan, BYK-378) was blended in the same manner as in Example 1, except that 0.1 parts by weight were added. A hard coat film was created and evaluated by the method of The obtained results are shown in Table 1.

In addition, although not shown, similarly to Example 1, when the cross section of the hard coat film produced in Comparative Example 4 was photographed with a scanning electron microscope (SEM), the hydrophobized silica sol was different from the base film of the hard coat layer. It was confirmed that it was unevenly distributed on the opposite surface side.

[Comparative Example 5]

In Comparative Example 5, (C) instead of the silicone-modified acryl a of the silicone-based leveling agent, 0.1 parts by weight of polyether-modified polydimethylsiloxane h (by Bikchemi Japan, BYK-UV3510) was blended in the same manner as in Example 1 A hard coat film was created and evaluated by the method of The obtained results are shown in Table 1.

In addition, although not shown, similarly to Example 1, when the cross section of the hard coat film produced in Comparative Example 5 was photographed with a scanning electron microscope (SEM), the hydrophobized silica sol was different from the base film of the hard coat layer. It was confirmed that it was unevenly distributed on the opposite surface side.

[Comparative Example 6]

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

[Comparative Example 7]

In Comparative Example 7, the hard coat film was prepared by the same method as in Comparative Example 1 except that silica sol J (manufactured by Nikkishokubai Co., Ltd., OSCAL-1632, average particle diameter of 30 nm) was used as (B) component. It was written and evaluated. The obtained results are shown in Table 1.

[Comparative Example 8]

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

[Comparative Example 9]

In Comparative Example 9, (C) A method similar to that of Example 1 except that 0.1 parts by weight of a perfluoro-modified acrylic-containing resin (manufactured by DIC, Megapark RS75) was blended in place of the silicone-modified acryl a of the silicone-based leveling agent. Thus, the hard coat film was created and evaluated. The obtained results are shown in Table 1.

In addition, although not shown, similarly to Example 1, when the cross section of the hard coat film produced in Comparative Example 9 was photographed with a scanning electron microscope (SEM), the hydrophobized silica sol was different from the base film of the hard coat layer. It was confirmed that it was unevenly distributed on the opposite surface side.

[Comparative Example 10]

In Comparative Example 10, (C) instead of the silicone-modified acryl a of the silicone-based leveling agent, 0.1 parts by weight of polyether-modified polydimethylsiloxane j (Sh-28, manufactured by Toledow Corning) was blended in the same manner as in Example 1 A hard coat film was created and evaluated by the method of The obtained results are shown in Table 1.

In addition, although not shown, similarly to Example 1, when the cross section of the hard coat film produced in Comparative Example 10 was photographed with a scanning electron microscope (SEM), the hydrophobized silica sol was different from the base film of the hard coat layer. It was confirmed that it was unevenly distributed on the opposite surface side.

[Table 1]

type of leveling agent;

a: silicone modified acrylic

b: polyether-modified polydimethylsiloxane

c: polyether ester-modified hydroxyl group-containing polydimethylsiloxane

d: polyester-modified hydroxyl group-containing polydimethylsiloxane

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

Example 1 using a predetermined hydrophobized silica sol, and wherein the silicon atom concentration measured by XPS analysis in the depth direction in the region from the outermost surface of the hard coat film to the position of 5 nm is a value within a predetermined range -7 was excellent in blocking resistance, and was excellent also in coatability and adhesiveness.

However, Comparative Examples 1 and 2 in which the surface silicon atom concentration was lower than the predetermined range had blocking resistance, but the coatability was inferior, and it was difficult to coat the hard-coat layer forming material smoothly.

Moreover, although the comparative examples 3, 4, 5, and 10 with a silicon atom concentration higher than the predetermined range had blocking resistance, the adhesiveness at the time of further laminating|stacking the surface layer on the hard-coat film was inferior.

In Comparative Examples 6 to 8 in which a predetermined hydrophobized silica sol was not used, coating properties were good, but blocking resistance was not obtained.

Moreover, since the surface became smooth and the comparative example 9 using the fluorine-type leveling agent was high, both blocking resistance and adhesiveness were inferior.

As described above, according to the hard coat film of the present invention, as a hard coat film having a hard coat layer on at least one side of the base film, the hard coat layer contains a predetermined hydrophobized silica sol and a specific silicone-based leveling agent. It consists of a hardened|cured material of the hard-coat layer forming material containing, this hydrophobized silica sol is unevenly distributed on the surface side opposite to the base film in a hard-coat layer, and the silicon atom concentration of the outermost surface of a hard-coat film is predetermined. By having it in the value within a range, the blocking of films was prevented and the hard-coat film excellent in coatability was obtained.

Moreover, when a surface layer etc. were further laminated|stacked on the hard-coat film of this invention, the hard-coat film excellent in adhesiveness came to be obtained.

Furthermore, by having such a hard-coat film, it was excellent in transparency and the transparent conductive film excellent also in adhesiveness came to be obtained efficiently.

Therefore, since the hard coat film of this invention can be used effectively for a capacitive touch panel etc., it is anticipated that it can mount effectively in portable information devices, such as a mobile phone which mechanical strength etc. are specifically calculated|required.

10: base film
12, 12': hard coating layer
14: leveling agent thin film
16: hydrophobized 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 device
80: cover glass
100: capacitive touch panel

Claims (11)

A hard coat film having a hard coat layer on at least one side of the base film,
The hard coat layer is composed of a cured product of a hard coat layer forming material comprising at least (A) an energy ray-curable resin, (B) a hydrophobized silica sol, and (C) a silicone-based leveling agent,
Said (B) hydrophobized silica sol is unevenly distributed on the surface side opposite to the said base film of the said hard-coat layer after hardening the said hard-coat layer forming material,
(B) The contact angle of water measured in accordance with JIS R 3257 with respect to the coating film when the hydrophobized silica sol is used as the coating film is set to a value of 100° or more,
The compounding amount of the (C) silicone-based leveling agent is a value within the range of 0.045 to 5 parts by weight in terms of solid content with respect to 100 parts by weight of the energy ray-curable resin (A),
In the region from the outermost surface of the hard coat film to the position of 5 nm, the silicon atom concentration is 0.2 to the total amount (100 atom%) of carbon atoms, oxygen atoms and silicon atoms measured by XPS analysis in the depth direction. Hard coating film, characterized in that the value within the range of 1.95 atom%. According to claim 1,
The (C) silicone-based leveling agent 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 It is at least 1 type, The hard-coat film characterized by the above-mentioned. delete According to claim 1,
The average particle diameter of the said (B) hydrophobized silica sol is a value within the range of 10-100 nm, The hard-coat film characterized by the above-mentioned. delete According to claim 1,
(B) The blending amount of the hydrophobized silica sol is a value within the range of 0.3 to 55 parts by weight in terms of solid content with respect to 100 parts by weight of the energy ray-curable resin (A). According to claim 1,
Haze value measured based on JISK7105 of the said hard-coat film is 1.0 % or less, The hard-coat film characterized by the above-mentioned. According to claim 1,
Arithmetic mean roughness Ra measured based on JISB0601-1994 in the surface of the said hard-coat layer is a value within the range of 1.5-5 nm, The hard-coat film characterized by the above-mentioned. A transparent conductive film comprising a transparent conductive layer on at least one side of the hard coat film according to claim 1 . A capacitive touch panel comprising a cover glass provided with a glass shatter prevention film, a first transparent conductive film, a second transparent conductive film, and a liquid crystal display, comprising:
The first transparent conductive film and the second transparent conductive film or either one is provided with a transparent conductive layer on the hard coating layer of the hard coating film having a hard coating layer,
The said hard-coat film is provided by providing the said hard-coat layer on at least single side|surface of a base film,
The hard coat layer is composed of a cured product of a hard coat layer forming material comprising at least (A) an energy ray-curable resin, (B) a hydrophobized silica sol, and (C) a silicone-based leveling agent,
Said (B) hydrophobized silica sol is unevenly distributed on the surface side opposite to the said base film of the said hard-coat layer after hardening the said hard-coat layer forming material,
(B) The contact angle of water measured in accordance with JIS R 3257 with respect to the coating film when the hydrophobized silica sol is used as the coating film is set to a value of 100° or more,
The compounding amount of the (C) silicone-based leveling agent is a value within the range of 0.045 to 5 parts by weight in terms of solid content with respect to 100 parts by weight of the energy ray-curable resin (A),
In the region from the outermost surface of the hard coat film to the position of 5 nm, the silicon atom concentration is 0.2 to the total amount (100 atom%) of carbon atoms, oxygen atoms and silicon atoms measured by XPS analysis in the depth direction. A capacitive touch panel, characterized in that a value within the range of 1.95 atom%. A method for producing a hard coat film having a hard coat layer on at least one side of a base film, the method comprising:
The manufacturing method of the hard-coat film characterized by including the following processes (1)-(3).
(1) at least (A) energy ray-curable resin, (B) hydrophobized silica sol, and (C) a step of preparing a material for forming a hard coat layer containing a silicone-based leveling agent
(2) The process of apply|coating the said hard-coat layer forming material to at least single side|surface of the said base film
(3) curing the hard coat layer forming material, the (B) hydrophobized silica sol is unevenly distributed on the surface side of the hard coat layer after curing the hard coat layer forming material, opposite to the base film,
(B) The contact angle of water measured in accordance with JIS R 3257 with respect to the coating film when the hydrophobized silica sol is used as the coating film is set to a value of 100° or more,
The compounding amount of the (C) silicone-based leveling agent is a value within the range of 0.045 to 5 parts by weight in terms of solid content with respect to 100 parts by weight of the energy ray-curable resin (A),
In the region from the outermost surface of the hard coat film to the position of 5 nm, the silicon atom concentration is 0.2 to the total amount (100 atom%) of carbon atoms, oxygen atoms and silicon atoms measured by XPS analysis in the depth direction. Process of forming a hard coat film having a hard coat layer that is a value within the range of 1.95 atom%

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