TW201536560A - Hard coat film, transparent conductive film, and capacitive touch panel - Google Patents

Abstract

The present invention aims to provide a hard coat film having excellent adhesiveness by preventing hard coat films from blocking each other, provide a transparent conductive film having the same, and provide a capacitive touch panel. Thus, the present invention is directed to a hard coat film having a hard coat layer on at least one surface of a substrate film, wherein the hard coat layer comprises cured products of materials forming a hard coat layer including at least (A) a energy curing resin, (B) a hydrophobic silica sol, and (C) a silicone based leveling agent, (B) a hydrophobic silica sol being distributed unevenly on the other surface of the hard coat layer opposite to the substrate film after the materials forming a hard coat layer are cured, and in a region from the outermost surface to 5 nm deep, a concentration of silicon atoms being set to a value within the range of 0.2 to 1.95 percent by atom, which is relative to the total amount of carbon atoms, oxygen atoms, and silicone atoms measured by XPS analysis in the direction of thickness.

Description

Hard coating film, transparent conductive film and capacitive touch panel

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

In the past, as a liquid crystal display device having a liquid crystal display, for example, an electronic notebook for carrying or an information terminal has been used. However, in recent years, a liquid crystal display device equipped with a touch panel that can be directly contacted with a display unit and can be input is widely used.

The touch panel is exemplified by a static capacitance method, a resistive film method, an electromagnetic induction method, and the like. Among them, a capacitive touch panel that detects a weak current generated when a finger or the like is in contact, that is, a change in electrostatic capacitance and detects an input position, is becoming widespread.

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

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

For example, a hard coat film for display which is formed by laminating a slip-prone adhesive layer, a hard coat layer, and an antireflection layer on one surface or both surfaces of a transparent polyester film has been disclosed (see, for example, Patent Document 1).

In other words, Patent Document 1 discloses, as a hard coat layer, a hard coat film for display having a specific surface hardness, a specific thickness, and a water contact angle of 40 to 80° on the surface and containing inorganic fine particles.

On the other hand, the film having a hard coatability is stored in a roll form after application of the hard coat layer from the viewpoint of productivity or workability. When stored in a roll state for a long period of time, the surface of the film adheres to each other (adhesion), and scratches or the like are formed on the surface of the hard coat layer, and when a hard coat film which causes adhesion is used, a problem of occurrence of spots on the surface is observed.

Therefore, for example, in the production step, when the hard coat film is wound by a roll, the productivity is lowered in order to prevent the hard coat films from sticking to each other and peeling off, so that it is proposed to have a specific hard coat layer on both sides of the light-transmitting substrate. A laminate, a transparent conductive film, and a capacitive touch panel (see, for example, Patent Document 2).

More specifically, the optical laminate is disclosed, and the hard coat layer is a layer formed of a composition for a hard coat layer containing a binder resin, a flat agent, and a slip agent, and the slip agent is composed of cerium oxide particles and cerium. At least one selected from the group consisting of oxygen particles is preferably used as a flattening agent with a rhodium-based flattening agent.

In addition, a hard coat film, a polarizing plate, and an image display device which are formed of a specific composition for a hard coat layer are proposed for the purpose of suppressing a decrease in yield due to adhesion and improving flatness (see, for example, a patent) Document 3).

More specifically, a composition for a hard coat layer containing a flat agent, cerium oxide fine particles, and a composition for a hard coat layer of a binder resin, and a flat agent containing a specific fluorine-based flat agent are disclosed.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2001-109388 (Patent Patent Application, etc.)

[Patent Document 2] Japanese Laid-Open Patent Publication No. 2012-66409 (Application Patent Range, etc.)

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2012-252275 (Application Patent No., etc.)

However, the hard coat film for display disclosed in Patent Document 1 is hydrophilic because of the surface of the hard coat layer. However, although it has a specific pencil hardness, it is found that the slipperiness is insufficient, and the film cannot be effectively prevented from adhering to each other. problem.

Further, the optical layering system described in Patent Document 2 prevents the optical laminates from sticking to each other by using the larger cerium oxide particles as a slipping agent. Thereby, although the films can be prevented from adhering to each other to a certain extent, since the slip agent is a large particle, there is a problem that the transparency of the optical laminate is insufficient.

Further, the composition for a hard coat layer described in Patent Document 3 uses a large ceria particle as a slip agent, and a fluorine-based flat agent is required as a flat agent. According to this, although it is seen that the adhesion is suppressed to some extent or the smoothness is improved, the water repellency of the fluorine-based flat agent is improved when the conductive layer or the like is further laminated on the hard coat film. The problem.

Therefore, the present inventors have actively reviewed the results of the above problems and found that by providing a hard coat layer on at least one side of the base film, a specific hydrophobized dioxide is formulated in the hard coat forming material forming the hard coat layer. The ruthenium sol and the specific flat agent, and the concentration of the ruthenium atom on the surface is set to a value within a specific range, which can effectively prevent the hard coat films from sticking to each other, and obtain a good surface when forming a surface layer (conductive layer or the like). The hard coating film is thus completed.

That is, the object of the present invention is to provide an effect of effectively preventing adhesion (attachment) of the hard coat films to each other (anti-adhesiveness) and forming a surface layer (conductive layer or the like) with a good surface layer. A hard coating film, a transparent conductive film having the hard coating film, and a capacitive touch panel.

According to the present invention, the above problem can be solved by providing a hard coat film which is a hard coat film having a hard coat layer on at least one side of a base film, and is characterized in that the hard coat layer is at least contained (A An energy ray-curable resin, (B) a hydrophobized cerium oxide sol, and (C) a hardened coating material of a hard coat layer forming material, and (B) a hydrophobized cerium oxide sol is biased to exist Hard coating for hardening the hard coat forming material The surface side opposite to the substrate film, the area of the hard coating film from the outermost surface to the 5 nm position, and the carbon atom, oxygen atom, and ytterbium atom atomic amount measured by XPS analysis in the depth direction (100 atomic %) The value of the germanium atom concentration is in the range of 0.2 to 1.95 atomic %.

That is, by using the hydrophobized cerium oxide sol as a hard coat forming material, hydrophobized dioxide is present in phase separation on the surface side opposite to the base film of the hard coat layer after hardening the hard coat forming material. Since the ruthenium sol is formed, fine irregularities are formed on the surface of the hard coat film, and the hard coat films can be prevented from sticking to each other.

In addition, since the antimony-based flat agent contains the hydrophobized cerium oxide sol on the outermost surface of the hard coat layer, the surface layer (conductive layer or the like) can be effectively prevented from being formed. Stripping of layers, etc.

Further, by setting the concentration of the ruthenium atom in the region from the outermost surface to the position of 5 nm from the outermost surface of the hard coat film, deformation or buckling of the coating film can be suppressed.

Further, when constituting the hard coat film of the present invention, the (C) oxime-based flat agent is preferably a hydroxy-containing polymer modified by oxime-modified acrylic acid, polyether-modified polydimethyl siloxane, or polyether ester. At least one selected from the group consisting of dimethyl methoxy alkane, a polyester-modified polyhydroxy methoxy alkane having a hydroxyl group, and a polydimethyl methoxide modified with a polyether.

According to this configuration, the concentration of germanium atoms in the region from the outermost surface to the position of 5 nm of the hard coat film can be easily adjusted to a value within a specific range.

In addition, when the hard coat film of the present invention is used, the amount of the (C) antimony-based flat agent is preferably in the range of 0.045 to 5 parts by weight in terms of solid content per 100 parts by weight of the (A) energy ray-curable resin. Inside value.

According to this configuration, the adhesion of the hard coat film can be effectively improved.

Further, when the hard coat film of the present invention is formed, the average particle diameter of the (B) hydrophobized cerium oxide sol is preferably in the range of 10 to 100 nm.

According to this configuration, the transparency of the hard coat film can be maintained or effectively improved, and sufficient light transmittance can be obtained.

In the case of the hard coat film of the present invention, the contact angle of water measured in accordance with JIS R 3257 for the coating film when the (B) hydrophobized cerium oxide sol is coated is preferably 100 or more.

With this configuration, adhesion of the hard coat films to each other can be effectively prevented.

In the case of the hard coat film of the present invention, the amount of the (B) hydrophobized cerium oxide sol is preferably from 0.3 to 55 parts by weight, based on 100 parts by weight of the (A) energy ray-curable resin. The value in the range.

With this configuration, although it is added in a small amount, it can be effectively biased on the surface side in the hard coat layer, and the transparency of the hard coat film can be effectively improved.

Further, when the hard coat film of the present invention is formed, the haze value of the hard coat film measured in accordance with JIS K 7105 is preferably 1.0% or less.

According to this configuration, the transparent conductive film excellent in transparency can be used for an electronic device such as a capacitive touch panel.

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

With this configuration, fine irregularities can be obtained on the surface of the obtained hard coat film. The adhesion of the hard coat films to each other can be preferably prevented.

Further, if the arithmetic mean roughness of the surface of the hard coat layer is a value within the range, a hard coat film having excellent optical characteristics can be obtained.

Further, another aspect of the present invention is a transparent conductive film comprising a transparent conductive layer on at least one surface of the hard coat film.

In other words, by using such a hard coat film which is excellent in blocking resistance and excellent in adhesion to a transparent conductive layer, it is possible to prevent the films from sticking to each other without using a protective film, and to obtain transparency excellent in durability. Conductive film.

Furthermore, another aspect of the present invention is a capacitive touch panel comprising a cover glass having a film for preventing scattering of glass, a first transparent conductive film, a second transparent conductive film, and a static capacitance of the liquid crystal display. The touch panel is characterized in that the first transparent conductive film and the second transparent conductive film or any one of the hard coating layers having a hard coating layer has a transparent conductive layer on the substrate. The hard coating layer is provided on at least one side of the film, and the hard coat layer is formed of a hard coat layer containing at least (A) energy ray-curable resin, (B) hydrophobized cerium oxide sol, and (C) argon-based flattening agent. The hardened material of the material is composed of (B) the hydrophobized cerium oxide sol is biased on the surface side opposite to the substrate film of the hard coat layer after hardening the hard coat layer forming material, and the hard coat film is from the outermost surface to 5 nm. In the region of the position, the concentration of the ruthenium atom is in the range of 0.2 to 1.95 atom% with respect to the total amount of carbon atoms, oxygen atoms, and ruthenium atoms (100 atom%) measured by XPS analysis in the depth direction.

That is, if a hard coating film having good adhesion and blocking resistance when forming a surface layer (conductive layer) is used, transparent conductive layer having a transparent conductive layer is used. A capacitive touch panel with a thin film can obtain a capacitive touch panel with excellent durability.

Further, another aspect of the present invention provides a method for producing a hard coat film which is a method for producing a hard coat film having a hard coat layer on at least one side of a base film, and the method comprises the following steps (1). (3): (1) a step of preparing a hard coat forming material containing at least (A) an energy ray-curable resin, (B) a hydrophobized cerium oxide sol, and (C) a cerium-oxygen flattening agent, (2) a step of coating a hard coat forming material on at least one side of the base film, (3) a step of hardening the hard coat layer forming material to form a hard coat film having a hard coat layer, wherein the hard coat layer (B) hydrophobized cerium oxide sol is biased to be hard after hardening the hard coat layer forming material The surface side of the coating opposite to the substrate film, and the area of the hard coating film from the outermost surface to the position of 5 nm, relative to the carbon atom, oxygen atom, and ruthenium atomium measured by XPS analysis in the depth direction ( 100 atom%), the value of the germanium atom concentration in the range of 0.2 to 1.95 atom%.

That is, by doing so, it is possible to efficiently produce the hard coat film in which the cerium oxide particles are biased on the opposite surface side of the base film.

Therefore, even when a hard coat film is produced by a roll-to-roller, the hard coat films can be effectively prevented from sticking to each other, and productivity can be improved.

10‧‧‧Substrate film

12, 12'‧‧‧ Hard coating

14‧‧‧flat film

16‧‧‧ Hydrophobized cerium oxide sol

18‧‧‧Hydrophilic cerium oxide sol

20, 20', 20" ‧ ‧ hard coating

30, 30', 30" ‧ ‧ transparent conductive layer

40‧‧‧Transparent conductive film

50, 50', 50" ‧ ‧ optical adhesives

60‧‧‧A film that prevents glass from scattering

70‧‧‧Liquid crystal display device

80‧‧‧ Covering glass

100‧‧‧Static Capacitive Touch Panel

1(a) to (b) are diagrams for explaining the state of the hard coat film of the present invention.

Figure 2 is a diagram for conceptually illustrating the hard coat film of the present invention.

Fig. 3 is a view for explaining a distribution of a ruthenium atom concentration in a hard coat layer measured by XPS analysis in the depth direction.

4(a) to 4(b) are views for explaining the state of the transparent conductive film of the present invention.

Fig. 5 is a view for explaining the state of the touch panel for electrostatic capacitance of the present invention.

Fig. 6 is a view for explaining a conventional hard coat film containing a hydrophilic cerium oxide sol on the surface.

[First Embodiment]

The first embodiment is a hard coat film comprising a hard coat film having at least one surface of a base film, wherein the hard coat layer contains at least (A) energy ray-curable resin, (B) The hydrophobized cerium oxide sol is composed of a hardened material of a hard coat layer forming material of (C) a bismuth oxide flat agent, and (B) the hydrophobized cerium oxide sol is biased to be present after hardening the hard coat forming material. The surface side of the hard coat layer opposite to the base film, and the total amount of carbon atoms, oxygen atoms, and helium atoms measured by XPS analysis in the depth direction from the outermost surface to the 5 nm position of the hard coat film (100 atom%), the concentration of germanium atoms is in the range of 0.2 to 1.95 atomic % The value inside.

Hereinafter, the hard coat film of the first embodiment will be specifically described with reference to the appropriate drawings.

Hard coating forming material (1) (A) energy ray curable resin (1)-1. Type

The type of the energy ray-curable resin (A) constituting the hard coat layer forming material is not particularly limited, and may be selected from conventional ones, and is exemplified as an energy ray hardening monomer, an oligomer, a resin, or the like. Composition, etc.

Specific examples are polyfunctional (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and oxime (methyl) A single one or a combination of two or more of acrylates and the like.

Polyfunctional (meth) acrylates are exemplified as 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylic acid. Ester, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, trimethylolethane tri(meth)acrylate, trishydroxyl Pentaerythritol polyfunctional (meth) acrylate such as propane tri(meth) acrylate, pentaerythritol tri(meth) acrylate, or pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate or Dipentaerythritol polyfunctional (meth) acrylate such as dipentaerythritol hexa(meth) acrylate, glycerol tri(meth) acrylate, triallyl (meth) propylene Acid esters, etc.

Among these, pentaerythritol polyfunctional (meth) acrylate or dipentaerythritol polyfunctional (meth) acrylate is preferable in terms of imparting moderate hardness to the hard coat layer.

Further, the polyfunctional (meth) acrylate also preferably contains an EO (ethylene oxide) or PO (propylene oxide) addition-molded polyfunctional (meth) acrylate.

The EO (ethylene oxide) or PO (propylene oxide)-added polyfunctional (meth) acrylate is a compound obtained by esterifying a EO or PO-molded polyol with an acrylate, and more specifically Glycerol triacrylate modified with EO or PO, trimethylolpropane acrylate modified with EO or PO, pentaerythritol tetraacrylate modified with EO or PO, dipentaerythritol hexaacrylate modified with EO or PO Wait.

Among these, based on imparting moderate flexibility to the hard coat layer to prevent cracking or cracking of the hard coat layer, it is preferably EO or PO modified dipentaerythritol hexaacrylate, EO or PO modified tris. Propane tetraacrylate.

Further, in the EO or PO addition molding polyfunctional (meth) acrylate, in order to impart moderate flexibility to the hard coat layer, the amount of EO or PO added per 1 mol of the polyfunctional (meth) acrylate is preferably 6~ The value within the range of 18 moles is preferably 8 to 16 moles.

(1)-2. Quantity

Further, (A) an energy ray hardening tree constituting a hard coat forming material The fat contains (a1) a polyfunctional (meth) acrylate compound, (a2) an ethylene oxide or a propylene oxide addition polyfunctional (meth) acrylate compound, and (a1) a polyfunctional (meth) acrylate The weight of the compound (a2) ethylene oxide or propylene oxide-added polyfunctional (meth) acrylate compound is preferably in the range of from 100:0 to 20:80.

The reason for this is because the hard coat forming material contains a polyfunctional (meth) acrylate compound which is higher in hardness by irradiation with an energy ray at a specific content, and an epoxy which has higher flexibility even when irradiated by an energy ray. Ethane or propylene oxide is added to form a polyfunctional compound, and the hardness of the hard coat layer can be easily adjusted.

In other words, when the weight ratio of the (a1) polyfunctional (meth) acrylate compound is less than 20, the scratch resistance of the hard coat layer after hardening may be lowered.

Therefore, the weight ratio of the (a1) polyfunctional (meth) acrylate compound to the (a2) ethylene oxide or propylene oxide-added polyfunctional (meth) acrylate compound is preferably 95:5~ The value in the range of 30:70 is more preferably in the range of 90:10 to 50:50.

(1)-3. (D) Photopolymerization initiator

Further, the hard coat forming material of the present invention preferably contains (D) a photopolymerization initiator as needed.

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

Here, the photopolymerization initiator refers to an active energy ray such as ultraviolet rays. A compound that generates a radical species upon irradiation.

The photopolymerization initiator is exemplified by, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, Acetophenone, dimethylaminophenethyl copper, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy- 2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane- 1-ketone, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4-diethyl Aminobenzophenone, dichlorobenzophenone, 2-methylindole, 2-ethylhydrazine, 2-tert-butylindole, 2-aminopurine, 2-methylthioxanthene Ketone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylacetal, phenylethyl Ketodimethyl acetal, p-dimethylamino benzoate, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane] These may be used alone or in combination of two or more.

Further, the content of the (D) photopolymerization initiator is preferably in the range of 0.2 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, per 100 parts by weight of the (A) energy ray-curable resin. The value within the range is more preferably in the range of 1 to 13 parts by weight.

(2) (B) Hydrophobized cerium oxide sol (2)-1. Type

Further, the hard coat forming material is characterized by containing (B) a hydrophobized cerium oxide sol.

Here, the type of the cerium oxide sol is exemplified by a cerium oxide microparticle as a raw material such as an alkoxydecane compound or a chlorosilane compound.

The alkoxydecane compound is not particularly limited as long as it has a hydrolyzable alkoxy group, and examples thereof include a compound represented by the formula (1).

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: halogen atom, epoxy group, (meth) propylene decyloxy group, etc.), alkenyl group) , aryl or aralkyl, R ² represents lower alkyl. n is an integer of 0 to 2, and when each of R ¹ and OR ² is plural, plural R ¹ may be the same or different, and plural OR ² may be the same Can be different).

Further, the alkoxydecane compound represented by the formula (1) is preferably tetramethoxydecane, tetraethoxydecane, tetra-n-propoxydecane, tetraisopropoxydecane or tetra-n-butoxydecane. , tetraisobutoxy decane, tetra-butoxy decane, tetra-butoxy decane, trimethoxyhydrogen decane, triethoxyhydrogen decane, tripropoxyhydrogen decane, methyltrimethoxy decane , methyl triethoxy decane, methyl tripropoxy decane, methyl triisopropoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, propyl triethoxy decane, butyl Trimethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, γ-propylene methoxy propyl trimethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, two Methyl dimethoxy decane, methyl phenyl dimethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, divinyl dimethoxy decane, divinyl diethoxy decane A single type or a combination of two or more types.

In this case, as the alkoxydecane compound, if 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 ceria-based cured product is obtained, and if partially hydrolyzed, a polyorganic is obtained. A sulfoxane-based cured product or a mixed-type cured product of an inorganic cerium oxide-based or polyorganosiloxane.

On the other hand, since the compound in which n is 1 to 2 and R ^{1 is a} non-hydrolyzable group has a non-hydrolyzable group, a polyorganosiloxane can be obtained by partial or complete hydrolysis.

The chlorodecane compound is exemplified by ethyl dichlorodecane, ethyl trichlorodecane, dimethyl dichlorodecane, trichlorodecane, trimethylchlorodecane, dimethyldichlorodecane, methyltrichlorodecane or the like.

Further, the cerium oxide sol is such that the cerium oxide fine particles are dispersed in a sol state in water or an organic solvent.

The organic solvent is not particularly limited and is exemplified by methanol, ethanol, isopropanol, ethylene glycol, n-propyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, dimethyl acetamide, propylene glycol. Monomethyl ether, cyclohexane, benzene, toluene, etc., but particularly preferred are methyl isobutyl ketone and propylene glycol monomethyl ether having a relatively high boiling point.

Further, the cerium oxide sol of the present invention is characterized in that a part or all of the stanol group on the surface of the cerium oxide particle is hydrophobized cerium oxide sol treated with a surface modifying agent having a hydrophobic group.

Here, the surface modifier is exemplified by a decane coupling agent having both a functional group and a hydrophobic group which can react with a stanol group on the surface of the cerium oxide particle.

More specifically, for example, SIRPGM manufactured by CIK Nanotech Co., Ltd. 15WT%-E26 or the like as a hydrophobized cerium oxide sol.

(2)-2. Hydrophobicity

Further, the degree of hydrophobicity of the cerium oxide sol is obtained by applying a cerium oxide sol onto a PET film, removing the solvent to form a cerium oxide sol coating film, and measuring the contact angle of the coating film with water.

More specifically, the contact angle of the coating film when water is applied to the cerium oxide sol is preferably 100 or more.

That is, if the contact angle of the water to the coating film of the cerium oxide sol measured in accordance with JIS R 3257 is 100 or more, the surface of the cerium oxide sol can be judged to be hydrophobic.

Here, Fig. 2 shows a diagram for conceptually explaining the hard coat film 20 of the present invention.

More specifically, the hydrophobized cerium oxide sol 16 of the present invention is considered to be separated from other components in the hard coat layer 12 when the hard coat layer forming material is applied to the surface of the substrate and hardened, and is more biased. The surface side opposite to the surface 10 of the substrate is present, and the ratio existing in the vicinity of the surface of the substrate and in the hard coat layer becomes low.

Therefore, by adding a small amount of the hydrophobized cerium oxide sol, a moderate surface roughness can be imparted to the surface of the hard coat layer, so that even if the hard coat films overlap each other and over a period of time, the films are prevented from sticking to each other (pressing ).

That is, it can be understood that since a specific anti-blocking property (sometimes referred to as anti-blocking property) can be exerted in a small amount, a hard coat film having high transparency can be obtained.

Further, when the contact angle of water to the coating film of the hydrophobized cerium oxide sol is too high, when the transparent conductive layer or the like is further laminated on the hard coating film, the adhesion is lowered, so that water is more preferable. The contact angle of the coating film of the hydrophobized cerium oxide sol is set to a value in the range of 100 to 130°.

On the other hand, when the contact angle of water to the coating film of the cerium oxide sol is less than 100, the hydrophilicity becomes high, and as shown in Fig. 6, it is confirmed that the cerium oxide sol 18 is not biased only in existence and The base film is on the opposite surface side, and is present in a state of being dispersed throughout the entire interior of the hard coat layer.

Therefore, it is understood that in order to impart a specific surface roughness to the hard coat layer, a relatively large amount of cerium oxide sol must be formulated.

Further, the method for measuring the contact angle of water to the coating film of the cerium oxide sol can be calculated by preparing a cerium oxide sol coating film as described in the first embodiment and measuring the contact angle of water.

(2)-3. Average particle size

Further, the average particle diameter of the hydrophobized cerium oxide sol of the present invention is preferably in the range of 10 to 100 nm.

The reason for this is that when the average particle diameter of the hydrophobized cerium oxide sol is less than 10 nm, it is difficult to obtain a specific surface roughness, and in particular, when a small amount is blended, it is difficult to prevent the occurrence of adhesion.

On the other hand, when the average particle diameter of the hydrophobized cerium oxide sol is more than 100 nm, the optical characteristics of the hard coat film may be too low.

Therefore, the average particle diameter of the hydrophobized cerium oxide sol is preferably in the range of 10 to 50 nm, more preferably in the range of 15 to 40 nm. value.

Further, the average particle diameter of the cerium oxide sol is a particle diameter (median diameter D50) of 50% of the cumulative value in the particle size distribution of the volume reference determined by the laser diffraction scattering type particle size distribution measuring apparatus, and means average Primary particle size.

(2)-4. Quantity

In addition, the amount of the hydrophobized cerium oxide sol of the present invention is a value in the range of 0.3 to 55 parts by weight in terms of solid content, based on 100 parts by weight of the (A) energy ray-curable resin.

The reason for this is that when the amount of the hydrophobized cerium oxide sol is less than 0.3 parts by weight, it may be difficult to exhibit an effect of preventing the hard coat films from sticking to each other.

On the other hand, when the amount of the hydrophobized cerium oxide sol is more than 55 parts by weight, the adhesion of the hard coat film or the scratch resistance may be too low.

Further, as described above, since the hydrophobized cerium oxide sol tends to be biased toward the surface side opposite to the surface of the substrate present in the hard coat layer, the amount of the hydrophobized cerium oxide sol is adjusted relative to (A) the energy ray-curable resin When 100 parts by weight of the solid content is in the range of 0.3 to 25 parts by weight, even if the amount of the hydrophobized cerium oxide sol is small, the adhesion resistance can be effectively exhibited, and the transparency is excellent. Therefore, a hard coat film for a transparent conductive film requiring transparency can be suitably used.

Therefore, the amount of the hydrophobized cerium oxide sol is preferably 0.3 to 25 in terms of solid content based on 100 parts by weight of the (A) energy ray-curable resin. The value in the range of parts by weight is more preferably in the range of from 0.3 to 10 parts by weight, more preferably in the range of from 0.4 to 3.0 parts by weight.

(3) (C) flat agent (3)-1. Composition

Further, the hard coat layer forming material is characterized by containing (C) a rhodium-based flattening agent.

Further, in the region from the outermost surface to the position of 5 nm of the hard coat film, the total atomic concentration (100 atomic %) of the carbon atom, the oxygen atom, and the ruthenium atom measured by XPS analysis in the depth direction is A value in the range of 0.2 to 1.95 atomic %.

It is generally known that the flat agent is present on the outermost surface side in the hard coat layer forming material, and deformation or buckling of the base film by the coating film can be suppressed.

In the present invention, as shown in Fig. 2, the hydrophobized cerium oxide sol is biased toward the surface side opposite to the surface of the substrate in the hard coat layer as described above, and the xenon-based flat agent covers the hydrophobized cerium oxide. The sol is present on the outermost surface in a specific amount range, whereby a hard coat film excellent in blocking resistance and flatness can be obtained by the interaction of the hydrophobized cerium oxide sol and the oxynium-based flat agent.

More specifically, in the hard coat film of the present invention, the results of XPS analysis (X-ray photoelectron spectroscopy) measurement from the outermost surface toward the depth direction of the substrate are shown in Fig. 3 .

Here, it can be understood from Fig. 3 that the area from the outermost surface toward the substrate to 5 nm In the domain, the concentration of germanium atoms is 0.28 atom%, 0.29 atom% in the region to 10 nm, 0.30 atom% in the region to 50 nm, and 0.20 atom% in the region to 100 nm, and the concentration of germanium in the region exceeding 100 nm is imminent. It rises to become 22.01 atom% in the region of 150 nm.

That is, as can be understood from the above, in the present invention, as shown in FIG. 2, the hard coat layer in the region farthest from the substrate is in the form of a thin film in a manner of covering the hydrophobized cerium oxide sol. 14 biased to exist.

Therefore, by specifying the area from the outermost surface of the hard coating film to the position of 5 nm, the total amount of carbon atoms, oxygen atoms, and helium atoms (100 atomic %) measured by XPS analysis in the depth direction, the atomic concentration of germanium The value is in the range of 0.2 to 1.95 atom%, and the flat agent present on the outermost surface is effectively controlled, whereby the flatness and the blocking resistance can be effectively improved.

That is, since the concentration of the germanium atom is less than 0.2 atomic %, when the hard coat layer forming material is applied, since the flat agent cannot form the film on the outermost surface of the coating film of the hard coat layer forming material, It deforms and bounces, and it is difficult to form a uniform film.

On the other hand, when the concentration of the ruthenium atom is more than 1.95 atomic%, the surface energy of the surface of the hard coat layer is lowered. Therefore, even if the conductive layer or the like is laminated, the conductive layer may be peeled off or the like.

Therefore, it is preferable to set the value of the germanium atom in the region from the outermost surface to the position of 5 nm from the outermost surface to the range of 0.21 to 1.95 atomic %, and more preferably in the range of 0.23 to 1.94 atomic %. .

Moreover, the atomic concentration determined by elemental analysis of XPS means hard coating The concentration of germanium atoms at each depth measured by XPS analysis in the depth direction of the entire layer.

(3)-2. Type

Further, as the (C) oxime-based flattening agent, a hydroxyl group-containing polydimethyl siloxane having a modification of oxime-modified acrylic acid, a polyether-modified polydimethyl siloxane or a polyether ester is preferably used. At least one selected from the group consisting of an ester-modified hydroxy group-containing polydimethyl siloxane and a polyether-modified polydimethyl siloxane.

The reason for this is that if the oxygen-containing flattening agent is of such a type, the concentration of the ruthenium atom in the flattening agent film 14 on the surface of the hard coat layer is likely to fall within the above range, and the surface smoothness required for the flat agent can be improved in a balanced manner. And the subsequent adhesion of the conductive layer and the like.

Therefore, in the case of the oxime-based flat agent of the present invention, not only the conductive layer but also the adhesive layer or the printed layer on the hard coat layer can improve the adhesion to the adhesive layer or the like.

Further, among the above-mentioned oxo-based flat agents, a reactive oxime-based flat agent having a vinyl group or the like is particularly preferably contained.

The reason for this is that if the rhodium-based flat agent is a reactive flat agent, it can react with the energy ray-curable resin to form a stronger flat film, which can be reduced, for example, from a flat agent when assembled in an image display device or the like. Pollution, etc.

In addition, in the present invention, the fluorine-based flattening agent is generally used as a flattening agent, and it is effective in suppressing the elastic opening. However, since the water repellency is high, the adhesion of the conductive layer or the like is poor, and it is confirmed that the silicone-based flattening agent cannot be exhibited. The synergistic effect caused by the hydrophobized cerium oxide sol.

(3)-3. Quantity

Further, it is preferred to further mix (C) a flat agent with a value within a range of 0.045 to 5 parts by weight based on 100 parts by weight of the (A) energy ray-curable resin.

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

More specifically, when the amount of the flat agent is less than 0.045 parts by weight, the flatness of the flat agent on the outermost surface of the substrate is insufficient, and the coating film of the hard coat forming material is deformed. It is difficult to form a uniform coating film when it is bounced off.

On the other hand, when the amount of the flat agent is more than 5 parts by weight, the flat agent exceeding the flat effect is localized, the surface energy of the surface of the hard coat layer is lowered, and the conductive layer or the like is laminated on the hard coat layer. Then, there will still be cases where the conductive layer falls off.

Therefore, it is more preferable to set the amount of the (C) leveling agent to a value in the range of 0.05 to 3 parts by weight, and more preferably in the range of 0.05 to 2 parts by weight.

(4) Other additives

Further, other additives may be appropriately contained within the range not impairing the effects of the present invention.

Other additives are listed, for example, as antioxidants, ultraviolet absorbers, and anti-drugs. An electrostatic agent, a polymerization accelerator, a polymerization inhibitor, an infrared ray absorbing agent, a plasticizer, a diluent solvent, and the like.

Further, the content of the other additives is generally preferably in the range of 0.01 to 5 parts by weight, more preferably in the range of 0.02 to 3 parts by weight, based on 100 parts by weight of the (A) energy ray-curable resin, and more preferably It is preferably in the range of 0.05 to 2 parts by weight.

(5) Thickness

Further, the thickness of the hard coat layer 12 exemplified in Fig. 1 is preferably set to a value within a range of 1 to 10 μm.

The reason for this is that the scratch resistance is remarkably lowered when the thickness of the hard coat layer is less than 1 μm.

On the other hand, since the thickness of the hard coat layer is a value exceeding 10 μm, the curl becomes large.

Therefore, it is more preferable to set the thickness of the hard coat layer to a value in the range of 1 to 5 μm, and more preferably to a value in the range of 1.5 to 4 μm.

2. Substrate film (1) Category

The resin used in the base film 10 illustrated in (a) to (b) of FIG. 1 is not particularly limited as long as it is excellent in flexibility and transparency, and examples thereof include polyethylene terephthalate and polyparaphenylene. Polyester film such as butylene formate or polyethylene naphthalate, polycarbonate film, polyethylene film, polypropylene film, cellophane, diethyl cellulose film, triethylene glycol cellulose film, acetamidine Base fiber Butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polymethylpentene film, polyfluorene film, polyether ether a ketone film, a polyether ruthenium film, a polyether quinone film, a polyimide film, a fluororesin film, a polyamide film, an acrylic resin film, a polyurethane resin film, a norbornene resin film, Other plastic films such as cycloolefin resin film.

Among these, a transparent resin film made of polyethylene terephthalate or polycarbonate is preferably used because it is excellent in transparency and has wide versatility.

(2) Thickness

Further, the thickness of the base film 10 exemplified in FIGS. 1(a) to (b) is preferably set to a value within a range of 15 to 250 μm.

The reason for this is that when the thickness of the base film is less than 15 μm, wrinkles and the like are likely to occur, and workability is remarkably lowered. On the other hand, when the thickness of the base film exceeds 250 μm, workability is lowered, and in particular, it is difficult to roll. In the case of a roll.

Therefore, the thickness of the base film is preferably set to a value within a range of 25 to 125 μm, based on a better balance between mechanical strength and light transmittance.

(3) Undercoat

Further, although not shown, by providing an undercoat 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, the constituent material of the undercoat layer is exemplified by a urethane resin, an acrylic resin, an epoxy resin, a polyester resin, a silicone resin, or the like, alone or in combination of two or more.

Further, it is preferred to set the thickness of the undercoat layer to a value in the range of 0.01 to 20 μm.

The reason is that when the thickness of the undercoat layer is less than 0.01 μm, the undercoating effect may not be exhibited. On the other hand, when the thickness of the undercoat layer is more than 20 μm, the light transmittance may be lowered when the hard coat film is formed.

Therefore, in order to make the balance between the undercoating effect and the light transmittance better, it is more preferable to set the thickness of the undercoat layer to a value in the range of 0.1 to 15 μm.

3. Characteristics of hard coating film (1) Surface roughness of hard coating

Further, the arithmetic mean roughness (Ra) measured on the surface of the hard coat layers 12, 12' exemplified in Figs. 1(a) to (b) in accordance with JIS B 0601-1994 is preferably in the range of 1.5 to 5 nm. .

The reason for this is that when the arithmetic mean roughness (Ra) is less than 1.5 nm, it is difficult to prevent the so-called adhesion of the adjacent hard coat films to each other when the hard coat film is wound up and overlapped.

On the other hand, when the arithmetic mean roughness (Ra) is a value exceeding 5 nm, the light transmittance may be remarkably lowered.

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

(2) Hard coat pencil hardness

Further, the pencil hardness of the hard coat layer illustrated in FIGS. 1(a) to (b) measured by JIS K 5600-5-4 is preferably HB or more.

The reason is that when the pencil hardness is less than the value of HB, when it is used for a capacitive touch panel, there is a case where the scratch resistance is insufficient.

(3) turbidity value of hard coating film

Further, the turbidity value measured by JIS K 7105 of the hard coat films 20 and 20' exemplified in Figs. 1(a) to (b) is preferably 1.0% or less.

The reason is that when the haze value is more than 1.0%, when it is used in a mobile phone or the like, the display of the liquid crystal display device may be blurred.

[Second Embodiment]

The second embodiment is a method for producing a hard coat film, which is a method for producing a hard coat film having a hard coat layer on at least one side of a base film, and the method includes the following steps (1) to (3): (1) preparing a step of forming a material containing at least (A) an energy ray-curable resin, (B) a hydrophobized cerium oxide sol, and (C) a cerium-oxygen leveling agent, and (2) a substrate film a step of applying a hard coat forming material on at least one side, (3) a step of hardening the hard coat layer forming material to form a hard coat film having a hard coat layer, wherein the hard coat layer (B) hydrophobized cerium oxide sol is biased to be hard after hardening the hard coat layer forming material The surface side of the coating opposite to the substrate film, and the area of the hard coating film from the outermost surface to the position of 5 nm, relative to the carbon atom, oxygen atom, and ruthenium atomium measured by XPS analysis in the depth direction ( 100 atom%), the value of the germanium atom concentration in the range of 0.2 to 1.95 atom%.

In the following, the base film and the hard coat layer to be used are the same as those in the first embodiment, and therefore, the matters relating to the method for producing the hard coat film will be mainly described.

(1) Step 1: Preparation steps of hard coat forming material

The step (1) is a step of preparing a hard coat forming material containing at least (A) an energy ray-curable resin, (B) a hydrophobized cerium oxide sol, and (C) a cerium-oxygen flattening agent.

More specifically, the step of uniformly mixing the aforementioned hard coat layer forming material with a diluent solvent.

The solvent is exemplified by, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, pentanol, ethyl cellosolve, benzene, toluene, xylene, ethylbenzene, cyclohexane, and B. Further, two or more solvents may be combined, such as cyclohexane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, propylene monomethyl ether, and water.

In particular, based on an energy ray-curable resin which can easily dissolve an acrylic monomer, propylene monomethyl ether, toluene, methyl ethyl ketone, and acetic acid B are preferably used. Ester, n-butyl acetate, cyclohexanone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, pentanol, and the like.

Further, the configuration of the specific hard coat layer forming material is omitted as described above.

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

The step (2) is a step of applying a 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 coat layer-forming material adjusted in the step (1) is coated in such a manner that the film thickness of the hard coat layer after hardening is in the range of 1 to 10 μm. The steps above it.

Further, the coating method of the hard coat layer forming material is not particularly limited, and a conventional method such as a bar coating method, a gravure coating method, a knife coating method, a roll coating method, a blade coating method, or the like can be used. Mold coating method, etc.

(3) Step 3: Hardening of hard coating material and hard coating film formation step

The step (3) is a step of hardening the hard coat layer forming material to form a hard coat film, and (B) the hydrophobized cerium oxide sol is biased to exist on the surface side opposite to the base film of the hard coat layer, and is hard. In the region from the outermost surface to the 5 nm position of the coating film, the atomic concentration of germanium atoms is 0.2 to 1.95 atoms with respect to the carbon atom, oxygen atom, and helium atom (100 atom%) measured by XPS analysis in the depth direction. The value in the range of %.

More specifically, it is preferred that the coating of the hard coat forming material that has evaporated the solvent after the drying step is irradiated with an energy ray such as ultraviolet rays or electricity. The bundle is hardened.

In this way, the hard coat layer can be formed quickly, and at the same time, it can be firmly adhered to the substrate film.

Further, the hydrophobized cerium oxide sol can be effectively biased to exist on the surface side opposite to the base film of the hard coat layer.

Further, the xenon-based flat agent can be biased to the outermost surface, and the atomic concentration of the outermost surface can be easily adjusted to the above range.

Therefore, the mechanical strength of the hard coat layer can be improved, and at the same time, the adhesion of the hard coat films to each other can be effectively prevented, and the adhesion at the time of laminating the conductive layer or the like can be improved.

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

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

On the other hand, when the ultraviolet irradiation amount is more than 1000 mJ/cm ² , the hard coat layer and the base film may be deteriorated by the ultraviolet rays.

Further, the type of the energy ray irradiation device to be used is not particularly limited, and for example, an ultraviolet ray irradiation device such as a high pressure mercury lamp, a xenon lamp, a metal halide lamp, or a fused H lamp can be used.

(4) Step (4): a step of forming a hard coat layer on the other side of the base film

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

More specifically, as shown in FIG. 1(a), it is attached to the base film 10 After the hard coat layer 12 is formed on one surface, the hard coat layer 12' is formed on the other side of the base film.

That is, after a hard coat layer is formed on one surface of the base film, the hard coat layer forming material is applied to the other surface of the base film in the same manner, and is hardened to form a hard surface on both sides of the base film. The step of coating.

Further, since the coating step and the hardening step are the same as described above, the details are omitted.

[Third embodiment]

The third embodiment is a transparent conductive film in which at least one of the masks of the hard coat film is a transparent conductive layer.

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.

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

Further, since the transparent conductive film using the hard coat film of the present invention is excellent in blocking resistance, it is not necessary to use a protective film for preventing the films from sticking to each other, and an adhesive for bonding the protective film is not required.

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

Further, since the hard coat film and the transparent conductive layer are excellent in adhesion, a 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 is exemplified by metals such as platinum, gold, silver, and copper; graphene and carbon nanotubes. Carbon materials such as tubes; organic conductive materials such as polyaniline, polyacetylene, polythiophene, polyparaphenylene extended ethylene, polyethylene dioxythiophene, polypyrrole; inorganic conductive materials such as copper iodide and copper sulfide; chalcogen compounds Non-participating compounds such as (chalcogenide), antimony hexafluoride, titanium nitride, titanium carbide, etc.; zinc oxide, zinc dioxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, zinc oxide doped indium oxide (IZO) , tin oxide, indium oxide, cadmium oxide, tin-doped indium oxide (ITO), doped tin and gallium indium oxide (IGZO), fluorine-doped indium oxide, antimony-doped tin oxide, doped fluorine A conductive metal oxide such as tin oxide (FTO).

Among these, a transparent conductive film having excellent transparent conductivity is more easily obtained, and a conductive metal oxide is preferable.

(2) Forming method

The transparent conductive layer can be formed by conventional methods. For example, a sputtering method, an ion plating method, a vacuum vapor deposition method, a chemical vapor phase growth method, a coating method such as a bar coater or a micro gravure coater, and the like are exemplified.

Among these, it is preferable to form a transparent conductive layer by a sputtering method.

(3) Thickness

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

(4) Graphicalization

The formed transparent conductive layer may be patterned as shown in Fig. 4(b) as needed. The method of patterning is exemplified by chemical etching by photolithography or the like, physical etching using a laser or the like, vacuum vapor deposition using a mask, sputtering, lift off, printing, or the like.

[Fourth embodiment]

The fourth embodiment is a capacitive touch panel including a cover glass having a film for preventing scattering of glass, a first transparent conductive film, a second transparent conductive film, and a capacitive touch panel of a liquid crystal display. The first transparent conductive film and the second transparent conductive film are either provided with a transparent conductive layer on the hard coat layer having a hard coat film, and the hard coat film is on at least one side of the base film. A hard coat layer is provided, and the hard coat layer is a cured product of a hard coat layer containing at least (A) an energy ray-curable resin, (B) a hydrophobized cerium oxide sol, and (C) a cerium-oxygen flattening agent. The (B) hydrophobized cerium oxide sol is biased toward the surface side of the hard coat layer which is hardened by the hard coat layer forming material, and the surface of the hard coat film from the outermost surface to the position of 5 nm. In the case of a carbon atom, an oxygen atom, or a ruthenium atom (100 atom%) measured by XPS analysis in the depth direction, the ruthenium atom concentration is in the range of 0.2 to 1.95 atom%.

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. For example, as shown in FIG. 5, the capacitive touch panel 100 is provided with a hard coat film 20 having a hard coat layer, a transparent conductive layer 30 (first electrode), and an optical adhesive 50, which are provided through the optical adhesive 50. Hard coating film 20, transparent conductive layer 30" (second electrode), optical adhesive 50", film 60 for preventing scattering of glass with optical adhesive layer, and cover glass 80 laminated to liquid crystal display A capacitive touch panel on device 70.

Further, in addition to the above layers, the present invention may be provided with other layers as needed.

Moreover, the capacitive touch panel of the present invention can be a surface type static capacitance type or a projection type static capacitance type.

In particular, when the surface layer (conductive layer or the like) is formed, the electrostatic capacitance touch panel of the present invention has a hard coat film having excellent adhesion, and thus can be a static capacitance touch panel excellent in durability.

[Examples]

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

[Example 1] 1. Production of hard coating film (1) Preparation steps of hard coat forming material

As shown in Table 1, the energy ray-curable resin as the component (A), the hydrophobized cerium oxide sol as the component (B), the oxime-based flat agent as the component (C), and the component (D) The photopolymerization initiator was adjusted to adjust the hard coat forming material of Example 1.

More specifically, (a1) pentaerythritol triacrylate (NK Ester, A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.), 100 parts by weight of (a2) dipentaerythritol hexaacrylate (EO12 Mo) 10 parts by weight of a photopolymerization initiator (Irgacure 184, manufactured by Kabart Chemicals Co., Ltd.), which is a component (D), 100 parts by weight of an ear-additive (A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd.) Hydrophobized cerium oxide sol A (manufactured by CIK Nanotech Co., Ltd., SIRPGM 15 WT%-E26, average particle diameter: 30 nm), 0.8 parts by weight, and oxime-based flattening agent as a component (C) 0.1 parts by weight of acrylic acid a (BYK-3550, manufactured by BYK Chemical Co., Ltd.) was diluted with 492.1 parts by weight of propylene monomethyl ether as a diluent solvent to adjust a hard coat layer forming material (solid content concentration: 30% by weight).

(2) Coating step of hard coat forming material

Next, a Mayer bar was used on one side of a PET film (LUMIROR U48, film thickness: 100 μm, manufactured by Toray Co., Ltd.) which was applied as an adhesive film on both sides of the substrate film. The hard coat layer forming material was applied so that the film thickness after drying became 3 μm.

(3) Drying step

Next, the dilution solvent contained in the hard coat layer forming material coated on the base film is removed.

That is, it was dried by heating at 70 ° C for 1 minute using a hot air drying device to sufficiently remove the dilution solvent.

(4) Hardening step

Next, ultraviolet rays were irradiated at 300 mJ/cm ² using a high pressure mercury lamp to photoharden the hard coat layer forming material to obtain a hard coat film.

Further, although not shown, a section of the hard coat film produced in Example 1 was imaged under the conditions of an acceleration voltage of 10 kV and a magnification of 20,000 times using a scanning electron microscope (SEM) (manufactured by Hitachi, Ltd., Model S-4700). Thereafter, it was confirmed that the hydrophobized cerium oxide sol was present on the surface side of the hard coat layer opposite to the substrate film.

2. Evaluation of hard coating film (1) Analysis of germanium atom concentration

Elemental analysis of carbon atoms, oxygen atoms, and ruthenium atoms measured by XPS analysis in the depth direction of the hard coat layer in the obtained hard coat film was carried out using an XPS measurement analyzer (Quantum 2000, manufactured by Ulvac-Phi Co., Ltd.). The obtained atomic concentration distribution obtained by XPS measurement is shown in Fig. 3.

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

(2) Determination of hydrophobization degree

Hydrophobized cerium oxide sol A (solid content concentration: 15%) dispersed in methyl isobutyl ketone was applied to a PET film (manufactured by Toray Co., Ltd., LUMIRROR U48, film thickness: 100 μm).

Subsequently, it was dried in an oven at 90 ° C for 1 minute to obtain a cerium oxide sol coating film having a thickness of 1 μm after drying.

Next, the contact angle of the water measured on the cerium oxide sol coating film measured in accordance with JIS R 3257 was measured, and the degree of hydrophobization was evaluated.

That is, the PET film on which the cerium oxide sol-coated film is formed is placed on a flat glass substrate, and when the glass substrate is tilted to 0 degrees, 2 μL of water droplets are dropped, and after the droplets are still, the Young formula is obtained. Water contact angle. The results obtained are shown in Table 1.

(3) Adhesion evaluation of hard coating

An ultraviolet curable ink (UVPAL911 ink manufactured by Imperial Ink Co., Ltd.) was applied onto the surface of the obtained hard coat film, and the ink was cured by irradiation with ultraviolet rays to form a printed layer having a film thickness of 1 μm. A 1 mm-wide cross cut is applied to the surface of the printed layer, and an adhesive tape (Cellotape (registered trademark), manufactured by Nichiban Co., Ltd.) is attached to the surface of the cross-cut printed layer of the checkerboard pattern, according to JIS K 5600- The Cellotape (registered trademark) peeling test was carried out by the checkerboard tape method of 5-6 (cross cutting method), and the printing adhesiveness of the curable resin layer was evaluated based on the following criteria. The results obtained are shown in Table 1.

○: There was no print layer peeled off from the hard coat film and transferred to the adhesive tape.

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

×: The number of printed layers transferred to the adhesive tape was 50% or more.

(4) Evaluation method of coating property (bounce)

A hard coat film was applied to a single surface of a PET film having an adhesion layer by using a Maa bar so that the film thickness after drying became 3 μm, and the fluorescent lamp was cured before curing. The visual inspection was carried out to confirm the presence or absence of bounce, and the coatability was evaluated according to the following criteria. The results obtained are shown in Table 1. Further, the area for visual inspection was 0.5 m ² .

○: There is no bounce

×: The bounce is one or more

(5) Pencil hardness evaluation

The pencil hardness of the obtained hard coat film was measured by a pencil drawing hardness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd., No. 553-M) in accordance with JIS K 5600-5-4. Also, the pulling speed is 1 mm/sec. The results obtained are shown in Table 1.

(6) Evaluation of adhesion resistance

The obtained hard coat film was cut into a size of 100 × 100 mm, and two hard coat films were superposed (this state was made into an initial stage).

Next, in a state where a load of 10 kg/m ² was applied, the film which was superposed at the initial stage of peeling and after 5 days in a storage environment of 23° C. and 50% RH (this state was set as the elapsed time) was visually observed under a fluorescent lamp. The state was observed, and adhesion was evaluated according to the following criteria. The results obtained are shown in Table 1.

○: No adhesion occurred at the beginning and after the passage, and no film surface was attached to each other.

△: Although adhesion did not occur in the initial stage, adhesion occurred after the passage of time (the bonding area of the film faces did not reach 30%).

X: Adhesion occurred from the initial stage (the bonding area of the film faces was 30% or more).

(7) Turbidity value

The haze value of the obtained hard coat film was measured using a turbidimeter (Nippon Denshoku Industries Co., Ltd., NDH-2000) in accordance with JIS K7105. The results obtained are shown in Table 1.

[Embodiment 2]

In the second embodiment, a hard coat film was prepared and evaluated in the same manner as in Example 1 except that the amount of the (C) oxime-based flat agent a was changed from 0.1 part by weight to 0.16 part by weight. The results obtained 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 (C) the oxygen-based flat agent a was changed from 0.1 part by weight to 0.2 part by weight. The results obtained are shown in Table 1.

[Example 4]

In Example 4, except that the (C) oxime-based flattening agent was changed to the oxime-modified acrylic acid a, 0.1 part by weight of the polyether-modified polydimethyl siloxane (b) was prepared by BYK Chemical Co., Ltd., BYK- A hard coat film was prepared and evaluated in the same manner as in Example 1 except for 300). The results obtained are shown in Table 1.

Further, although not shown, the cross section of the hard coat film produced in Example 4 was imaged by a scanning electron microscope (SEM) in the same manner as in Example 1, and it was confirmed that the hydrophobized cerium oxide sol was present in the hard coat layer. The surface side opposite to the substrate film.

[Example 5]

In Example 5, in addition to changing (C) the oxygen-modified acrylic acid a of the xenon-based flat agent, 0.1 part by weight of the polyether ester-modified hydroxyl group-containing polydimethyloxane c (Japanese BYK Chemical) was formulated. A hard coat film was prepared and evaluated in the same manner as in Example 1 except for BYK-375. The results obtained are shown in Table 1.

Further, although not shown, the cross section of the hard coat film produced in Example 5 was imaged by a scanning electron microscope (SEM) in the same manner as in Example 1, and it was confirmed that the hydrophobized cerium oxide sol was present in the hard coat layer. The surface side opposite to the substrate film.

[Embodiment 6]

In Example 6, except that the (C) oxime-based flat agent was changed. The acrylic acid a was prepared in the same manner as in Example 1 except that 0.1 part by weight of a polyester-modified hydroxy group-containing polydimethyl siloxane d (manufactured by BYK Chemical Co., Ltd., BYK-370) was blended. Hard film was evaluated and evaluated. The results obtained are shown in Table 1.

Further, although not shown, the cross section of the hard coat film produced in Example 6 was imaged by a scanning electron microscope (SEM) in the same manner as in Example 1, and it was confirmed that the hydrophobized cerium oxide sol was present in the hard coat layer. The surface side opposite to the substrate film.

[Embodiment 7]

In Example 7, except that the (C) oxime-based flattening agent was changed to the oxime-modified acrylic acid a, 0.1 part by weight of the polyether-modified polydimethyl siloxane (e.g., BYK Chemical Co., Ltd., BYK) was blended. A hard coat film was prepared and evaluated in the same manner as in Example 1 except for -331). The results obtained are shown in Table 1.

Further, although not shown, the cross section of the hard coat film produced in Example 7 was imaged by a scanning electron microscope (SEM) in the same manner as in Example 1, and it was confirmed that the hydrophobized cerium oxide sol was present in the hard coat layer. The surface side opposite to the substrate film.

[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 the amount of the (C) oxime-based flat agent a was changed from 0.1 part by weight to 0.08 part by weight. The results obtained are shown in Table 1.

Further, although not shown, the cross section of the hard coat film produced in Comparative Example 1 was imaged by a scanning electron microscope (SEM) in the same manner as in Example 1, and it was confirmed that the hydrophobized cerium oxide sol was present in the hard coat layer. The surface side opposite to the substrate film.

[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 (C) antimony-based flat agent a was changed from 0.1 part by weight to 0.04 part by weight. The results obtained are shown in Table 1.

[Comparative Example 3]

In Comparative Example 3, except that the (C) oxime-based flattening agent was changed to oxime-modified acrylic acid a, 0.1 part by weight of a polyether-modified polymethylalkyl decane f (manufactured by BYK Chemical Co., Ltd., A hard coat film was prepared and evaluated in the same manner as in Example 1 except for BYK-325). The results obtained are shown in Table 1.

Further, although not shown, the cross section of the hard coat film produced in Comparative Example 3 was imaged by a scanning electron microscope (SEM) in the same manner as in Example 1, and it was confirmed that the hydrophobized cerium oxide sol was present in the hard coat layer. The surface side opposite to the substrate film.

[Comparative Example 4]

In Comparative Example 4, in addition to changing (C) the oxygen-modified acrylic acid a of the oxime-based flat agent, 0.1 part by weight of the polyether-modified polydimethyl hydrazine was formulated. A hard coat film was prepared and evaluated in the same manner as in Example 1 except that oxyalkylene g (manufactured by BYK Chemical Co., Ltd., BYK-378) was used. The results obtained are shown in Table 1.

Further, although not shown, the cross section of the hard coat film produced in Comparative Example 4 was imaged by a scanning electron microscope (SEM) in the same manner as in Example 1, and it was confirmed that the hydrophobized cerium oxide sol was present in the hard coat layer. The surface side opposite to the substrate film.

[Comparative Example 5]

In Comparative Example 5, except that the (C) oxime-based flattening agent was changed to the oxime-modified acrylic acid a, 0.1 part by weight of the polyether-modified polydimethyl methoxy hydride h (manufactured by BYK Chemical Co., Ltd., BYK) was blended. A hard coat film was prepared and evaluated in the same manner as in Example 1 except for -UV3510. The results obtained are shown in Table 1.

Further, although not shown, the cross section of the hard coat film produced in Comparative Example 5 was imaged by a scanning electron microscope (SEM) in the same manner as in Example 1, and it was confirmed that the hydrophobized cerium oxide sol was present in the hard coat layer. The surface side opposite to the substrate film.

[Comparative Example 6]

In Comparative Example 6, a hard coat film was prepared in the same manner as in Example 1 except that cerium oxide sol I (SIRMIBK 15 WT%-K18, manufactured by CIK Nanotech Co., Ltd., average particle diameter: 100 nm) was used as the component (B). Evaluation. The results obtained are shown in Table 1.

[Comparative Example 7]

In Comparative Example 7, a hard coat film was prepared in the same manner as in Comparative Example 1, except that cerium oxide sol J (OSCAL-1632, manufactured by Nippon Chemical Co., Ltd., average particle diameter: 30 nm) was used as the component (B). Evaluation. The results obtained 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 cerium oxide sol K (MIBK-ST, manufactured by Nissan Chemical Industries, Ltd., average particle diameter: 15 nm) was used as the component (B). Evaluation. The results obtained are shown in Table 1.

[Comparative Example 9]

In Comparative Example 9, except that the (C) oxime-based flattening agent was changed to the oxime-modified acrylic acid a, and 0.1 part by weight of the perfluoro-modified acrylic resin (MEGAFAC RS75, manufactured by DIC Corporation) was blended, the remainder and the implementation were carried out. In the same manner as in Example 1, a hard coat film was prepared and evaluated. The results obtained are shown in Table 1.

Further, although not shown, the cross section of the hard coat film produced in Comparative Example 9 was imaged by a scanning electron microscope (SEM) in the same manner as in Example 1, and it was confirmed that the hydrophobized cerium oxide sol was present in the hard coat layer. The surface side opposite to the substrate film.

[Comparative Example 10]

In Comparative Example 10, in addition to changing (C) the oxygen-modified acrylic acid a of the xenon-based flattening agent, 0.1 part by weight of the polyether-modified polydimethyloxane j (manufactured by Dow Corning Toray Co., Ltd., SH) was blended. A hard coat film was prepared and evaluated in the same manner as in Example 1 except for -28). The results obtained are shown in Table 1.

Further, although not shown, the cross section of the hard coat film produced in Comparative Example 10 was imaged by a scanning electron microscope (SEM) in the same manner as in Example 1, and it was confirmed that the hydrophobized cerium oxide sol was present in the hard coat layer. The surface side opposite to the substrate film.

Type of flattening agent:

a: 矽 oxygen modified acrylic

b: polyether modified polydimethyl methoxy oxane

c: polyether ester modified hydroxyl-containing polydimethyloxane

d: polyester modified hydroxyl-containing polydimethyloxane

e: polyether modified polydimethyl methoxy oxane

f: polyether modified polymethylalkyl sulfoxane

g: polyether modified polydimethyl methoxy oxane

h: polyether modified polydimethyl methoxy oxane

i: containing perfluoro-modified acrylic resin

j: polyether modified polydimethyl methoxy oxane

In the specific hydrophobized cerium oxide sol, and in the region from the outermost surface to the 5 nm position of the hard coat film, the concentration of the ruthenium atom determined by XPS analysis in the depth direction is a value within a specific range, and Examples 1 to 7 are used. It is excellent in blocking resistance and excellent in coatability and adhesion.

However, in Comparative Examples 1 to 2 in which the atomic concentration of germanium on the surface was lower than the specific range, the adhesion resistance was poor, but the coating property was poor, and it was difficult to apply the hard coat layer forming material smoothly.

Further, in Comparative Examples 3, 4, 5, and 10 in which the concentration of germanium atoms was higher than the specific range, the adhesion resistance was poor, but the adhesion of the surface layer to the hard coat film was inferior.

Further, in Comparative Examples 6 to 8 in which the specific hydrophobized cerium oxide sol was not used, the coating property and the like were good, but the blocking resistance could not be obtained.

Further, in Comparative Example 9 using a fluorine-based flat agent, since the surface became smooth, And the water repellency is high, so the adhesion resistance and adhesion are poor.

[Industrial availability]

As described in detail above, the hard coat film according to the present invention is a hard coat film having a hard coat layer on at least one side of the base film, and the hard coat layer is composed of a specific hydrophobized cerium oxide sol and a specific hydrazine. A hardened coating material such as an oxygen-based flat agent is formed by a hardened cerium oxide sol which is present on the surface side opposite to the substrate film in the hard coat layer, and is formed on the surface of the hard coat film. Since the atomic concentration has a value within a specific range, it is possible to prevent the films from sticking to each other and to obtain a hard coat film excellent in coatability.

Further, when the surface layer or the like is further laminated on the hard coat film of the present invention, a hard coat film excellent in adhesion is obtained.

In addition, by having such a hard coat film, a transparent conductive film which is excellent in transparency and excellent in adhesion is effectively obtained.

Therefore, since the hard coat film of the present invention can be effectively used for a capacitive touch panel or the like, it can be expected to be efficiently mounted in an action information device such as a mobile phone that particularly requires mechanical strength or the like.

Claims (11)

A hard coat film comprising a hard coat film having a hard coat layer on at least one side of a base film, wherein the hard coat layer contains at least (A) an energy ray-curable resin, and (B) a hydrophobized cerium oxide sol And (C) the hydrophobized cerium oxide sol is biased toward the hard coat layer after curing the hard coat layer forming material. The surface side opposite to the base film, the carbon atom, oxygen atom, and ruthenium atomium measured by XPS analysis in the depth direction from the outermost surface to the 5 nm position of the hard coat film (100) Atomic %), a value in which the concentration of germanium atoms is in the range of 0.2 to 1.95 atomic %. The hard coating film of claim 1, wherein the (C) oxime-based flat agent is a hydroxy-containing poly(ethylene) modified by oxime-modified acrylic acid, polyether modified polydimethyl siloxane, or polyether ester. At least one selected from the group consisting of methyl siloxane, polyester-modified polydimethyl methoxy oxane, and polyether modified polydimethyl methoxy hydride. The hard coat film of claim 1, wherein the amount of the (C) oxygen-based flattening agent is in the range of 0.045 to 5 parts by weight based on 100 parts by weight of the energy ray-curable resin (A) The value. The hard coat film of claim 1, wherein the (B) hydrophobized cerium oxide sol has an average particle diameter in a range of from 10 to 100 nm. A hard coat film according to claim 1, wherein the (B) is hydrophobic The coating film when the cerium oxide sol is coated is a value in which the contact angle of water measured according to JIS R 3257 is 100 or more. The hard coat film of claim 1, wherein the amount of the (B) hydrophobized cerium oxide sol is from 0.3 to 55 parts by weight in terms of solid content based on 100 parts by weight of the energy ray-curable resin (A). The value inside. The hard coat film of claim 1, wherein the hard coat film has a haze value of 1.0% or less as measured according to JIS K 7105. The hard coat film of claim 1, wherein the surface of the hard coat layer has an arithmetic mean roughness Ra measured in accordance with JIS B 0601-1994 of a range of 1.5 to 5 nm. A transparent conductive film characterized in that a transparent conductive layer is provided on at least one side of the hard coat film of claim 1. A capacitive touch panel comprising: a cover glass having a film for preventing scattering of glass, a first transparent conductive film, a second transparent conductive film, and a capacitive touch panel of a liquid crystal display, wherein: The first transparent conductive film and the second transparent conductive film or any one of the hard coat layers having a hard coat layer is provided with a transparent conductive layer on at least one side of the base film. The hard coat layer is provided, and the hard coat layer is hardened by a hard coat layer containing at least (A) an energy ray-curable resin, (B) a hydrophobized cerium oxide sol, and (C) a cerium-oxygen flattening agent. The composition of the above (B) hydrophobized cerium oxide sol is present in the above-mentioned hard a surface side of the hard coat layer which is hardened by the coating forming material opposite to the base film, and a region of the hard coat film from the outermost surface to a position of 5 nm with respect to XPS analysis by depth direction A carbon atom, an oxygen atom, a helium atom (100 atom%), and a germanium atom concentration of 0.2 to 1.95 atom%. A method for producing a hard coat film, which is a method for producing a hard coat film having a hard coat layer on at least one side of a base film, and the method comprises the following steps (1) to (3): (1) preparing at least a step of forming a material comprising a (A) energy ray-curable resin, (B) a hydrophobized cerium oxide sol, and (C) a cerium-oxygen flattening agent, and (2) on at least one side of the base film a step of applying the hard coat layer forming material, (3) a step of hardening the hard coat layer forming material to form a hard coat film having a hard coat layer, the hard coat layer being the (B) hydrophobized cerium oxide sol The surface side opposite to the base film of the hard coat layer after the hard coat layer forming material is hardened, and the depth of the hard coat film from the outermost surface to a position of 5 nm with respect to the depth direction The carbon atom, oxygen atom, and ruthenium atom (100 atom%) measured by XPS analysis, and the ytterbium atom concentration is in the range of 0.2 to 1.95 atom%.