JP6720481B2 - Laminated body, conductive laminated body and touch panel - Google Patents

Description

The present invention relates to a laminate, a conductive laminate and a touch panel.

At present, a touch panel is widely used as an input unit in various devices including a display device having a display panel such as a liquid crystal display panel, for example, PDA (Personal Digital Assistants), personal digital assistants, car navigation systems and the like.
The touch panel has a transparent conductive film in which a transparent conductive layer containing ITO (indium tin oxide), metal fibers, carbon nanotubes, etc. is provided on a base film, and is usually separated from a display panel. It is manufactured and arranged on the front surface of the display panel.

Here, all or a part of the transparent conductive layer or the optical adjustment layer containing ITO or the like is generally provided on the base material film through a sputtering process. This sputtering process uses a roll of the base material film. It is performed in the roll-to-roll state used, and at this time, the surface of the base material film is heated to 90° C. or higher by secondary electrons from the plasma during the sputtering process. Therefore, in the sputtering process, there is a problem that wrinkles and wrinkles occur in the base material film during transportation.
For such a problem, for example, by attaching a protective film to the surface of the base film that contacts the guide roll (the surface opposite to the surface on which the sputtering process is performed), there is a method of improving wrinkles and wrinkles that occur during transportation. It is known (for example, refer to Patent Document 1).
Then, the transparent conductive film on which such a transparent conductive layer is formed, after peeling the protective film, on the surface of the side of the base film where the protective film was attached, other functionalities via the adhesive layer. A member (polarizing plate or the like) is attached.

By the way, the transparent conductive layer formed by the sputtering process is crystallized by heat treatment at a high temperature of about 150° C. in order to lower the resistance, improve the transparency, and improve the durability, if necessary. There is something to do.
Further, as a conductive material other than ITO, in order to reduce the cost by eliminating the vacuum process in the manufacturing process and to improve the bendability of the transparent conductive film, for example, metal fiber, carbon nanotube, etc. Also in the case of using, by performing the heat treatment under the condition of about 110 to 150° C., the portions where the conductive materials overlap each other are melted and brought into close contact with each other, and the resistance can be extremely reduced. It is generally known to be possible.

Moreover, since the wiring around the transparent conductive film is formed by baking the silver paste, the transparent conductive film is heated under the condition of about 120 to 140° C. when the wiring around the transparent conductive film is formed.
Further, in the transparent conductive film, the transparent conductive film is heated under the condition of about 150° C. before the patterning to prevent the shrinkage of the base material in order to prevent the gap between the wirings from being displaced due to the dimensional change due to the heating after the patterning. The rate may be adjusted.

However, during the heating, a low molecular component derived from the pressure-sensitive adhesive layer of the protective film may move to the surface of the conductive laminate on which the protective film is attached. When such migration of low-molecular components occurs, the contact angle of water on the surface from which the protective film has been peeled off increases (that is, wettability decreases), and the adhesion during subsequent attachment with other optical members There have been problems such as a decrease in adhesiveness through the member and difficulty in spreading and spreading the liquid pressure-sensitive adhesive or liquid adhesive.

For example, Patent Document 2 discloses that a hard coat film in which a contact angle of water is controlled is used on a base material film for a capacitive touch panel. However, contact of water after heat treatment is performed. No consideration was given to the horn.

JP 2012-194644 A JP, 2011-177938, A

In view of the above-mentioned present situation, the present invention is a case where a film with an adhesive layer is attached to the side opposite to the transparent conductive layer side of a substrate film and subjected to heat treatment, and then the film with an adhesive layer is peeled off. Also, it is an object of the present invention to provide a laminate, a conductive laminate and a touch panel, which can suitably prevent the contact angle of water on the surface to which the film with the adhesive layer is attached from increasing and the adhesiveness from decreasing. Is.

The present invention has one or more optical functional layers on one surface of a base film, has a low contact angle layer on the other surface of the base film, and has the above-mentioned base of the optical functional layer. A laminate used for forming a patterned transparent conductive layer on the side opposite to the material film side, wherein a film with an adhesive layer is attached to the surface of the low contact angle layer, and the conditions are 150° C. and 60 minutes. After the heating with, the wetting tension defined by JIS K6768 (1999) of the surface of the low contact angle layer when the film with the adhesive layer is peeled off is 30 mN/m or more, and as the one or more optical functional layers. The high refractive index layer and the low refractive index layer are laminated on the base material film in this order , the film with an adhesive layer is one in which an adhesive layer is formed on the film, and the adhesive layer is A laminate comprising an acrylic adhesive and an isocyanate crosslinking agent .
The laminate of the present invention has the above-mentioned adhesive layer after being heated under the conditions of the wet tension of the surface of the low contact angle layer specified by JIS K6768 (1999) and the temperature of 150° C. for 60 minutes before the film with the adhesive layer is attached. It is preferable that the difference between the surface of the low contact angle layer and the wetting tension defined by JIS K6768 (1999) after peeling off the adhesive film is 20 mN/m or less.
Further, it is preferable that a hard coat layer, a high refractive index layer and a low refractive index layer are laminated on the base film in this order as one or more optical functional layers.
The low contact angle layer is preferably made of an uncured (meth)acrylic resin alone or a composition containing the uncured (meth)acrylic resin.
Further, it is preferable that a hard coat performance is imparted to the low contact angle layer side of the base film.
The low contact angle layer preferably has hard coat performance.
Further, it is preferable to have a hard coat layer between the low contact angle layer and the substrate film.
The transparent conductive layer preferably contains indium tin oxide or a conductive fibrous filler.

Further, the present invention is also a conductive laminated body characterized in that a patterned transparent conductive layer is formed on the side opposite to the substrate film side of the optical functional layer of the above laminated body.
Further, the present invention is also a touch panel including the above-mentioned conductive laminate.
The present invention will be described in detail below.

As a result of diligent studies on the conventional problems, the present inventors have shown that a low contact angle layer and a film with an adhesive layer are formed in this order on the side opposite to the side on which the transparent conductive layer of the base film is formed. When the film with an adhesive layer is subjected to a treatment and peeled off, the wetting tension defined by JIS K6768 (1999) on the surface to which the film with an adhesive layer of the low contact angle layer is bonded falls within a specific range. It was found that the decrease in adhesiveness can be suitably prevented by controlling in this way, and completed the present invention.
In addition, when the film with the adhesive layer is peeled off after the laminate heat treatment in which the film with the adhesive layer is pasted on the conventional substrate film via the adhesive layer, the low contact that the film with the adhesive layer is stuck. The problem that the contact angle of water increases on the surface of the stratum corneum is a problem first discovered by the study by the present inventors.
Further, in the present specification, “transparent” in the “transparent conductive film” means having a region for transmitting visible light in the plane, and may be substantially semitransparent. Further, “transparent” specifically means that the light transmittance at a wavelength of 550 nm is 50% or more.

The laminate of the present invention has a low contact angle layer on one surface of the base film.
By having the low contact angle layer, after heating for crystallizing the transparent conductive layer described later, even when the film with the adhesive layer is peeled off, the low contact angle with which the film with the adhesive layer is attached. An increase in the contact angle of water on the surface of the layer can be suppressed, and a decrease in adhesiveness on the surface can be prevented.
That is, the increase in the contact angle of water in the laminate in which the film with the adhesive layer is pasted on the conventional substrate film via the adhesive layer, the low-molecular component of the adhesive layer is due to the heat treatment of the laminate. It is considered to occur by moving to the surface of the base film.
On the other hand, in the laminate of the present invention, a low contact angle layer is provided on the surface of the base film opposite to the transparent conductive layer side, and a film with an adhesive layer is further attached on the low contact angle layer. .. The film with the pressure-sensitive adhesive layer is usually attached on the low contact angle layer via the pressure-sensitive adhesive layer, but even if the low-molecular component of the pressure-sensitive adhesive layer moves to the low contact angle layer side like a conventional laminate, The component constituting the low contact angle layer covers the low molecular weight component, or a part of the low contact angle layer peels off the surface layer at the time of peeling the film with the adhesive layer, whereby the film with the adhesive layer is peeled off. It is presumed that it is possible to suppress the increase of the contact angle of water on the raised surface.

The low contact angle layer is a low contact angle layer when the film with an adhesive layer is attached to the surface of the low contact angle layer and heated at 150° C. for 60 minutes, and then the film with an adhesive layer is peeled off. The wetting tension specified by JIS K6768 (1999) on the surface is 30 mN/m or more. If it is less than 30 mN/m, the adhesiveness of the surface of the low contact angle layer on which the adhesive layer-attached film is adhered to other optical members becomes insufficient, and the spread of the liquid adhesive or the liquid adhesive is also insufficient. Becomes
The wetting tension of the surface of the low contact angle layer defined by JIS K6768 (1999) is preferably 35 mN/m or more, and more preferably 40 mN/m or more.
In the present invention, heating is performed to reduce the resistance in the transparent conductive layer containing metal fibers, heating during wiring formation around the transparent conductive film, and to adjust the shrinkage ratio of the base material. Since the heating conditions (150° C., 60 minutes) performed for crystallizing the transparent conductive layer containing ITO are the most severe compared to heating, etc., the heating conditions (150° C., 60 minutes) should be adopted. did.

The low contact angle layer has a wet tension defined by JIS K6768 (1999) on the surface of the low contact angle layer before sticking a film with an adhesive layer to be described later, and after heating at 150° C. for 60 minutes, It is preferable that the difference between the surface of the low contact angle layer and the wetting tension defined by JIS K6768 (1999) after peeling off the film with the adhesive layer is 20 mN/m or less.
When the difference in the wetting tension is 20 mN/m or less, it is possible to preferably suppress an increase in the contact angle of water on the surface from which the film with the adhesive layer is peeled off.
The difference in the wetting tension is more preferably 10 mN/m or less.

In the laminate of the present invention, examples of the low contact angle layer include styrene resin, (meth)acrylic resin, vinyl acetate resin, vinyl ether resin, halogen-containing resin, alicyclic olefin resin, and polycarbonate resin. Examples thereof include resins, polyester resins, polyamide resins, cellulose derivatives, silicone resins and rubbers or elastomers. Above all, it is preferable that the composition comprises an uncured (meth)acrylic resin alone or a composition containing the uncured (meth)acrylic resin. Such a low contact angle layer can preferably prevent a decrease in adhesiveness.
The term "uncured" means that the resin forming the low contact angle layer is not cured, but the low contact angle layer has no tackiness.
In addition, the “state without tackiness” specifically means that when the finger is brought into contact with the low contact angle layer, the finger sticks to the low contact angle layer or the finger is slid on the low contact angle layer. Sometimes I say there is no catch.
In addition, in this specification, "(meth)acryl" refers to methacrylate and acrylate, and "resin" is a concept including monomers, oligomers, polymers and the like, unless otherwise specified.

The resin forming the low contact angle layer preferably has a weight average molecular weight of 5,000 to 500,000. When it is less than 5,000, the low contact angle layer may have a tackiness when uncured, and when it exceeds 500,000, the viscosity of the composition for forming the low contact angle layer becomes too high and uniform. May not be applied to The more preferable lower limit of the weight average molecular weight is 7,000, and the more preferable upper limit thereof is 200,000.
In addition, in this specification, the said weight average molecular weight is the value calculated|required by polystyrene conversion by gel permeation chromatography (GPC).

The resin forming the low contact angle layer preferably has a double bond equivalent of 100 or more. When it is less than 100, it becomes difficult to synthesize the polymer, and not only the glass transition point (Tg) may be lowered, but even if the polymer can be synthesized, the above low contact angle when uncured The layer may have a tacky feel.
Incidentally, the double bond equivalent of the resin constituting the low contact angle layer,
(Molecular weight of one molecule of compound)/(Number of double bonds contained in one molecule of compound)
It is a value defined by.

The resin forming the low contact angle layer is preferably a solvent-drying resin.
The solvent-drying type resin means a resin that forms a film only by drying the solvent when a composition containing the resin and the solvent is applied.
The resin forming the low contact angle layer preferably does not have a reactive functional group in one molecule. If the resin constituting the low contact angle layer has a reactive functional group in one molecule, a tackiness may be produced when the composition containing the resin is applied to form the low contact angle layer. is there.
In addition, the above-mentioned "having no reactive functional group in one molecule" means that the reactive functional group is not contained in the molecule of the resin constituting the above low contact angle layer at all, or a low contact angle layer. A reactive functional group may be contained in one molecule within a range in which a tack-free state can be maintained.

The low contact angle layer is a composition containing a resin and a solvent constituting the low contact angle layer (hereinafter, also referred to as a composition for low contact angle layer), the side forming the transparent conductive layer of the base film. It can be formed by drying the coating film formed by applying on the opposite side.
The solvent may be selected and used according to the type and solubility of the resin component used, and examples thereof include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, etc.), ethers ( Dioxane, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), aliphatic hydrocarbons (hexane etc.), alicyclic hydrocarbons (cyclohexane etc.), aromatic hydrocarbons (toluene, xylene etc.), Halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.) ), cellosolve acetates, sulfoxides (dimethylsulfoxide, etc.), amides (dimethylformamide, dimethylacetamide, etc.), and the like, and a mixed solvent thereof may be used.

The low contact angle layer may be added with known additives such as an antiblocking agent, a leveling agent and an antistatic agent, as long as the effects of the present invention are not impaired.

The composition for a low contact angle layer preferably has a viscosity of 0.5 to 5.0 mPa·s (25°C). If it is less than 0.5 mPa·s (25° C.), a low contact angle layer having a sufficient thickness cannot be formed, and the adhesion of the low contact angle layer may not be improved. If it exceeds, the uniform low contact angle layer may not be formed.
A more preferable lower limit of the viscosity is 0.7 mPa·s (25°C), and a more preferable upper limit thereof is 3.0 mPa·s (25°C).

The low contact angle layer preferably has a thickness of 1 to 1000 nm. If the thickness is less than 1 nm, the low contact angle layer may have an insufficient thickness and the adhesion of the low contact angle layer may not be improved. If the thickness exceeds 1000 nm, cracks may easily occur in the low contact angle layer, resulting in adhesion. When the layered film is peeled off, planar peeling may occur. The more preferable lower limit of the thickness of the low contact angle layer is 5 nm, and the more preferable upper limit thereof is 500 nm. When the low contact angle layer is provided with a hard coat performance as described below, the low contact angle layer may have a thickness of more than 1000 nm.

The method for coating the composition for a low contact angle layer on a substrate film is not particularly limited, and examples thereof include spin coating, dipping, spraying, die coating, bar coating, roll coater, meniscus coater. Examples of known methods include a method, a flexographic printing method, a screen printing method, and a speed coater method.
Also, when a hard coat layer is provided between a low contact angle layer and a substrate film described later, the low contact angle layer can be formed on the hard coat layer by the same method.

It is preferable to attach a film with an adhesive layer on the side opposite to the base film side of the low contact angle layer formed by the above method. The film with the pressure-sensitive adhesive layer is preferably used as a protective film, and by sticking the film with the pressure-sensitive adhesive layer, during the sputtering treatment for forming the transparent conductive layer described later, wrinkles that occur from the problem of transportability. It is possible to improve the twist.

The film with an adhesive layer is preferably composed of at least a base material and an adhesive layer, has smoothness, heat resistance, and is excellent in hardness and toughness.
The base material is not particularly limited, and examples thereof include polyester resin, polypropylene resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin, and the like. Among them, polyester resin and polypropylene resin are preferably used.
The pressure-sensitive adhesive layer is a layer containing at least a pressure-sensitive adhesive, and examples of the pressure-sensitive adhesive include urethane-based, rubber-based, silicone-based, and acrylic-based pressure-sensitive adhesives. Of these, acrylic pressure-sensitive adhesives are preferable from the viewpoints of high heat resistance and low cost.
Examples of the acrylic pressure-sensitive adhesive include acrylic acid ester copolymers obtained by copolymerizing acrylic acid ester with other monomers.

Examples of the other monomer include, for example, methyl acrylate, methyl methacrylate, styrene, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, itaconic acid, hydroxylethyl acrylate, hydroxylethyl methacrylate, propylene glycol acrylate, Examples thereof include acrylamide, methacrylamide, glycidyl acrylate, glycidyl methacrylate, dimethylaminoethyl methacrylate, -tert-butylaminoethyl methacrylate, and nethylhexyl methacrylate. Among them, n-ethylhexyl methacrylate is preferably used.
The above-mentioned other monomers may be used alone or in combination of two or more.

As the unit ratio (acrylic acid ester/other monomer) between the acrylic acid ester and the other monomer contained in the acrylic acid ester copolymer, the acrylic acid ester copolymer has a desired adhesive force. There is no particular limitation as long as the above can be exhibited.

The weight average molecular weight (Mw) of the acrylic acid ester copolymer is not particularly limited as long as the acrylic pressure-sensitive adhesive exhibits a desired adhesive force.

The pressure-sensitive adhesive layer may further contain a crosslinking agent.
The cross-linking agent is not particularly limited, and examples thereof include epoxy-based and isocyanate-based cross-linking agents.

Examples of the epoxy crosslinking agent include polyfunctional epoxy compounds.
Examples of the polyfunctional epoxy compound include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl glycol diglyceride. Examples thereof include glycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polybutadiene diglycidyl ether.

Examples of the above-mentioned isocyanate-based cross-linking agent include polyisocyanate compounds, trimers of polyisocyanate compounds, urethane prepolymers having an isocyanate group at the end obtained by reacting a polyisocyanate compound and a polyol compound, or such a Examples include urethane trimers such as trimers.
The polyisocyanate compound is not particularly limited and, for example, 2,4-tolylene diisocyanate, 2,5-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4, 4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, lysine isocyanate and the like can be mentioned.

The content of the cross-linking agent varies depending on the type of the cross-linking agent, but may be, for example, in the range of 0.5 to 10.0 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive.

The pressure-sensitive adhesive layer may further contain a metal chelating agent.
The metal chelating agent used in the pressure-sensitive adhesive layer has a metal element and a salt-forming site, and when used together with the pressure-sensitive adhesive, the metal element and a carboxyl group contained in the pressure-sensitive adhesive form a chelate bond. By doing so, it is possible to crosslink.
Specific examples of such metal chelating agents include, for example, aluminum isopropylate, aluminum butyrate, aluminum ethylate, aluminum ethyl acetoacetate, aluminum acetylacetonate, aluminum acetylacetonate bisethylacetoacenate, aluminum alkylacetoate. Aluminum chelate compounds such as acenate and dipropoxy-bis(acetylacetonato) titanium, dibutoxytitanium-bis(octylene glycolate), dipropoxytitanium-bis(ethylacetoacetate), dipropoxytitanium-bis(lactate), Dipropoxytitanium-bis(triethanolaminate), di-n-butoxytitanium-bis(triethanolaminate), tri-n-butoxytitanium monostearate, butyl titanate dimer, poly(titanium acetylacetonate), etc. Zirconium chelate compounds such as titanium chelate compounds, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate, zirconium acetylacetonate bisethylacetoacetate, zirconium acetate, zinc octylate, zinc laurate, zinc stearate. , Organic carboxylic acid metal salts such as tin octylate, zinc acetylacetone chelates, benzoylacetone zinc chelates, dibenzoylmethane zinc chelates, ethyl acetoacetate zinc chelates and the like. Among them, aluminum chelate compounds such as aluminum isopropylate, aluminum butyrate, aluminum ethylate, aluminum ethyl acetoacetate, aluminum acetylacetonate, aluminum acetylacetonate bisethylacetoacenate, and aluminum alkylacetoacenate are preferably used. .. This is because it is easy to adjust the crosslinking rate for crosslinking the pressure-sensitive adhesive.

The content of the metal chelating agent varies depending on the type of the metal chelating agent, but is preferably in the range of 0.06 to 0.50 parts by mass with respect to 100 parts by mass of the adhesive. When the amount is less than the above range, the crosslinking rate at the time of forming the pressure-sensitive adhesive layer may be low and the productivity may be lowered, while even when the amount is more than the above range, the effect is not changed and the material cost is increased. Becomes

The adhesive layer may contain other additives.
Examples of the above-mentioned other additives include antioxidants and ultraviolet absorbers.
Further, the pressure-sensitive adhesive is a photosensitive pressure-sensitive adhesive obtained by polymerizing a photosensitive monomer component that is cured by light irradiation, such as acrylic acid ester and other monomers that compose an acrylic pressure-sensitive adhesive. In the case of forming the agent layer by applying a pressure-sensitive adhesive containing the above-mentioned photosensitive monomer component, polymerizing by irradiation of ultraviolet rays or visible light, and then curing it, a photopolymerization initiator is added to the pressure-sensitive adhesive. It

The film thickness of the pressure-sensitive adhesive layer is usually in the range of 3 to 200 μm, preferably in the range of 4 to 100 μm, and particularly preferably in the range of 5 to 50 μm.

Examples of the method for forming the pressure-sensitive adhesive layer include, for example, a method of coating a pressure-sensitive adhesive layer forming material on a base material, a method of transferring the pressure-sensitive adhesive layer on the base material, a constituent material of the pressure-sensitive adhesive layer and a constituent material of the substrate. It is possible to use a method of melt-coextruding and forming and a method of adhering the constituent material of the pressure-sensitive adhesive layer and the constituent material of the substrate into a film shape by extrusion or the like and then adhering them. Among them, the method of applying the pressure-sensitive adhesive layer-forming material on the substrate is preferably used because the pressure-sensitive adhesive layer can be formed with good smoothness.

The adhesive layer-containing film is peeled off after the patterned transparent conductive layer described later is formed, and the peel strength is preferably 10 to 500 mN/25 mm. If it is less than 10 mN/25 mm, the film with an adhesive layer may be peeled off in the process of producing the laminate of the present invention, and if it exceeds 500 mN/25 mm, it may not be peeled from the low contact angle layer. In addition, when the transparent conductive layer is crystallized by heat treatment after the sputtering treatment, as described later, the film with the adhesive layer is subjected to the heat treatment to crystallize the conductive layer. It is preferable that the peeling is performed in any of the subsequent steps such as after the heat treatment and after finishing the heat treatment in the subsequent step.
The same applies to the transparent conductive layer containing a conductive fibrous filler described later, and is peeled off at any step after heating for lowering the resistance and after baking the silver paste in the subsequent step. It is preferable.

The sticking of the film with an adhesive layer to the low contact angle layer is preferably performed via the adhesive layer of the film with an adhesive layer. Since the laminate of the present invention has the low contact angle layer described above, the adhesiveness of the surface of the low contact angle layer after peeling off the film with the adhesive layer does not decrease.

The laminate of the present invention has one or more optical functional layers on one surface of the base film.
Examples of the one or more optical functional layer include any conventionally known optical functional layer, and specifically, for example, a hard coat layer, a low refractive index layer, a high refractive index layer, an antifouling layer, an antistatic layer. , And an antiglare layer.
Among them, those having at least one layer selected from the group consisting of a hard coat layer, a high refractive index layer and a low refractive index layer are preferable.
In the layered product of the present invention, the one or more optical functional layers have a high refractive index layer and a low refractive index layer in this order from the viewpoint that the patterned transparent conductive layer can be made invisible as described later. It is more preferable that it is laminated on the base film.
Further, the one or more optical functional layers are more preferably a hard coat layer, a high refractive index layer and a low refractive index layer formed in this order on the base film. By having the optical functional layer having such a configuration, it is possible to make the transparent conductive layer invisible and to impart a hard coat property to the laminate of the present invention.

The hard coat layer preferably has a pencil hardness of F or higher, and more preferably H or higher, according to a pencil hardness test (load 4.9 N) according to JIS K5600-5-4 (1999).
The hard coat layer is a layer for ensuring the hard coat property of the laminate of the present invention, and for example, a composition for a hard coat layer containing an ionizing radiation curable resin which is a resin curable by ultraviolet rays and a photopolymerization initiator. It is preferably formed using a material.

Examples of the ionizing radiation curable resin include compounds having one or more unsaturated bonds such as compounds having an acrylate-based functional group. Examples of the compound having one unsaturated bond include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, methylstyrene, and N-vinylpyrrolidone. Examples of the compound having two or more unsaturated bonds include polymethylolpropane tri(meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetraacrylate. (Meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate and the like and ethylene oxide ( Examples thereof include a polyfunctional compound modified with EO) or the like, or a reaction product of the above polyfunctional compound and (meth)acrylate (for example, poly(meth)acrylate ester of polyhydric alcohol).

In addition to the above compounds, a polyester resin, a polyether resin, an acrylic resin, an epoxy resin, a urethane resin, an alkyd having a relatively low molecular weight (number average molecular weight of 300 to 80,000, preferably 400 to 5000) having an unsaturated double bond. Resins, spiro acetal resins, polybutadiene resins, polythiol polyene resins and the like can also be used as the ionizing radiation curable resin. The resin in this case includes all dimers, oligomers and polymers other than monomers.
Preferred compounds in the present invention include compounds having 3 or more unsaturated bonds. When such a compound is used, the crosslink density of the formed hard coat layer can be increased and the coating hardness can be improved.
Specifically, in the present invention, pentaerythritol triacrylate, pentaerythritol tetraacrylate, polyester polyfunctional acrylate oligomer (3 to 15 functional), urethane polyfunctional acrylate oligomer (3 to 15 functional), and the like are used in appropriate combination. Is preferred.

The ionizing radiation curable resin may be used in combination with a solvent dry resin. By using the solvent-drying resin in combination, it is possible to effectively prevent film defects on the coated surface. The solvent-drying resin refers to a resin such as a thermoplastic resin that forms a film only by drying the solvent added to adjust the solid content during coating.
The solvent drying type resin that can be used in combination with the above ionizing radiation curing type resin is not particularly limited, and generally a thermoplastic resin can be used.
The thermoplastic resin is not particularly limited, and examples thereof include styrene resin, (meth)acrylic resin, vinyl acetate resin, vinyl ether resin, halogen-containing resin, alicyclic olefin resin, polycarbonate resin, polyester resin. Examples thereof include resins, polyamide resins, cellulose derivatives, silicone resins and rubbers or elastomers. The thermoplastic resin is preferably amorphous and soluble in an organic solvent (particularly, a common solvent capable of dissolving a plurality of polymers and curable compounds). Particularly, from the viewpoints of film-forming property, transparency and weather resistance, styrene resins, (meth)acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (cellulose esters, etc.) and the like are preferable.

Moreover, the composition for the hard coat layer may contain a thermosetting resin.
The thermosetting resin is not particularly limited, and examples thereof include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea co-condensation resin. Resin, silicon resin, polysiloxane resin, etc. can be mentioned.

The photopolymerization initiator is not particularly limited, and known ones can be used. For example, as the photopolymerization initiator, specific examples include acetophenones, benzophenones, Michler's benzoylbenzoate, and α-amilo. Examples include oxime esters, thioxanthones, propiophenones, benzyls, benzoins, and acylphosphine oxides. Further, it is preferable to use a mixture of photosensitizers, and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine and the like.

As the photopolymerization initiator, when the ionizing radiation-curable resin is a resin system having a radically polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, etc. may be used alone or in combination. It is preferable to use. When the ionizing radiation curable resin is a resin system having a cationically polymerizable functional group, examples of the photopolymerization initiator include aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, and benzoin sulfone. It is preferable to use acid esters or the like alone or as a mixture.
As the initiator used in the present invention, in the case of an ionizing radiation curable resin having a radically polymerizable unsaturated group, 1-hydroxy-cyclohexyl-phenyl-ketone is compatible with the ionizing radiation curable resin, and yellow. It is preferable because there is little change.

The content of the photopolymerization initiator in the hard coat layer composition is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin. If it is less than 1 part by mass, the hardness of the hard coat layer in the laminate of the first present invention may not be within the above range, and if it exceeds 10 parts by mass, it is ionized to a deep portion of the coated film. This is because the radiation does not reach and the internal curing is not promoted, and the target pencil hardness F or higher of the surface of the hard coat layer may not be obtained.
The more preferable lower limit of the content of the photopolymerization initiator is 2 parts by mass, and the more preferable upper limit thereof is 8 parts by mass. When the content of the photopolymerization initiator is within this range, hardness distribution does not occur in the thickness direction, and uniform hardness is likely to be obtained.

The composition for hard coat layer may contain the same solvent as the composition for forming a low contact angle layer described above.
In particular, in the present invention, it is preferable to include at least one of methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone in a ketone solvent, or a mixture thereof, because the compatibility with the resin and the coating property are excellent. ..

The content ratio (solid content) of the raw materials in the composition for hard coat layer is not particularly limited, but is usually 5 to 70% by mass, and particularly preferably 15 to 60% by mass.

In the composition for the hard coat layer, the hardness of the hard coat layer is increased, the curing shrinkage is suppressed, the blocking is prevented, the refractive index is controlled, the antiglare property is imparted, the properties of the particles and the hard coat layer surface. In accordance with the purpose of changing the, etc., conventionally known organic and inorganic fine particles, dispersants, surfactants, antistatic agents, silane coupling agents, thickeners, anti-coloring agents, colorants (pigments, dyes), erasing agents, A foaming agent, a leveling agent, a flame retardant, an ultraviolet absorber, an adhesion imparting agent, a polymerization inhibitor, an antioxidant, a surface modifier, etc. may be added.

The composition for the hard coat layer may be mixed with a photosensitizer, and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine and the like.

The method for preparing the composition for the hard coat layer is not particularly limited as long as each component can be uniformly mixed, and for example, a known apparatus such as a paint shaker, a bead mill, a kneader or a mixer can be used.

The method for applying the composition for the hard coat layer onto the substrate film is not particularly limited, and examples thereof include a spin coat method, a dip method, a spray method, a die coat method, a bar coat method, a roll coater method, and a meniscus. Known methods such as a coater method, a flexo printing method, a screen printing method and a speed coater method can be mentioned.

The coating film formed by applying the composition for a hard coat layer on the base film is preferably heated and/or dried as necessary and cured by irradiation with active energy rays.

Examples of the irradiation with active energy rays include irradiation with ultraviolet rays or electron beams. Specific examples of the ultraviolet light source include light sources such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, and a metal halide lamp lamp. Further, as the wavelength of ultraviolet rays, a wavelength range of 190 to 380 nm can be used. Specific examples of the electron beam source include various electron beam accelerators such as Cockcroft-Walt type, Van Degraft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type.

The hard coat layer preferably has a thickness (when cured) of 0.5 to 15 μm, more preferably 0.8 to 10 μm, and particularly preferably has a curl prevention property and a crack prevention property. It is a range. The thickness of the hard coat layer is an average value (μm) obtained by observing a cross section with an electron microscope (SEM, TEM, STEM) and measuring arbitrary 10 points. As for the thickness of the hard coat layer, as another method, an average value may be obtained by measuring arbitrary 10 points using a thickness measuring device, Digimatic Indicator IDF-130 manufactured by Mitutoyo.

Since the laminate of the present invention has a transparent conductive layer patterned as described below and is a member used for a capacitance type touch panel, there is a demand for invisibility of the patterned transparent conductive layer. is there. Examples of means for making the patterned transparent conductive layer invisible include a method in which a high refractive index layer and a low refractive index layer are laminated in this order as the optical functional layer, which is suitable for the transparent conductive layer and the touch panel. Therefore, strict optical characteristics are required, and strict control of thickness and refractive index is required. Specifically, the high refractive index layer preferably has a thickness of 10 to 100 nm and a refractive index of 1.55 to 1.75, and the low refractive index layer has a thickness of 10 to 100 nm and a refractive index of 1. It is preferably 35 to 1.55. The thickness of the high refractive index layer and the low refractive index layer is more preferably 10 to 70 nm.

The method of forming the high refractive index layer can be roughly classified into a wet method and a dry method. The wet method is excellent in production efficiency.
Examples of the wet method include a method of forming by a sol-gel method using a metal alkoxide or the like, and a method of applying a composition in which a binder resin contains high refractive index particles to form. Examples of the dry method include a method of selecting a material having a desired refractive index from the high refractive index particles described later and forming the material by physical vapor deposition or chemical vapor deposition.

The method of forming the low refractive index layer can be roughly classified into a wet method and a dry method. The wet method is excellent in production efficiency.
As the wet method, similar to the high refractive index layer, a method of forming by a sol-gel method using a metal alkoxide, a method of applying a low refractive index binder such as a fluororesin, and a low refractive index to the binder resin. A method of applying a composition containing particles to form the composition may be mentioned. Examples of the dry method include a method in which particles having a desired refractive index are selected from particles having a low refractive index, which will be described later, and the particles are formed by a physical vapor deposition method or a chemical vapor deposition method.

In the laminate of the present invention, it is preferable that the hard coat layer, the high refractive index layer, and the low refractive index layer each have a refractive index satisfying the following expression (1). By satisfying the following expression (1), it is possible to preferably make the transparent conductive layer formed on the low refractive index layer invisible.
High Refractive Index Layer Refractive Index> Hard Coat Layer Refractive Index> Low Refractive Index Layer Refractive Index (1)

The high refractive index layer is not particularly limited and may be a conventionally known one. For example, the high refractive index layer can be formed by using a composition containing high refractive index fine particles in the resin and solvent described in the hard coat layer.
As the high refractive index fine particles, for example, metal oxide fine particles having a refractive index of 1.50 to 2.80 are preferably used. Specific examples of the metal oxide fine particles include titanium oxide (TiO ₂ , refractive index: 2.71), zirconium oxide (ZrO ₂ , refractive index: 2.10), cerium oxide (CeO ₂ , refraction). Ratio: 2.20), tin oxide (SnO ₂ , refractive index: 2.00), antimony tin oxide (ATO, refractive index: 1.75 to 1.95), indium tin oxide (ITO, refractive index: 1.95 to 2.00), phosphorus tin compound (PTO, refractive index: 1.75 to 1.85), antimony oxide (Sb ₂ O ₅ , refractive index: 2.04), aluminum zinc oxide (AZO, refractive index: 1.90 to 2.00), gallium zinc oxide (GZO, refractive index: 1.90 to 2.00) and zinc antimonate (ZnSb ₂ O _6, refractive index: 1.90 to 2.00 ) And the like. Among them, tin oxide (SnO ₂ ), antimony tin oxide (ATO), indium tin oxide (ITO), phosphorus tin compound (PTO), antimony oxide (Sb ₂ O ₅ ), aluminum zinc oxide (AZO), Gallium zinc oxide (GZO) and zinc antimonate (ZnSb ₂ O ₆ ) are conductive metal oxides, and it is possible to impart antistatic properties by controlling the diffusion state of fine particles and forming a conductive path. There are advantages.
Further, zirconium oxide (ZrO ₂ ) is preferable from the viewpoint of high durability stability such as light resistance.

The low refractive index layer is preferably 1) a resin containing silica or magnesium fluoride, 2) a fluororesin which is a low refractive index resin, 3) a fluororesin containing silica or magnesium fluoride, 4) It is composed of either a thin film of silica or magnesium fluoride. As the resin other than the fluorine-based resin, the same resin as the resin used for the hard coat layer can be used.
Further, the silica described above is preferably solid silica fine particles or hollow silica fine particles.

As the fluorine-based resin, a polymerizable compound containing at least a fluorine atom in the molecule or a polymer thereof can be used. The polymerizable compound is not particularly limited, but, for example, a compound having a curable reactive group such as a functional group curable by ionizing radiation and a thermosetting polar group is preferable. Further, a compound having these reactive groups simultaneously may be used. In contrast to this polymerizable compound, the polymer is a compound that does not have any of the reactive groups as described above.

As the polymerizable compound having a functional group that is cured by ionizing radiation, a fluorine-containing monomer having an ethylenically unsaturated bond can be widely used. More specifically, exemplify fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluorobutadiene, perfluoro-2,2-dimethyl-1,3-dioxole). You can As those having a (meth)acryloyloxy group, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3-pentafluoropropyl (meth)acrylate, 2-(perfluorobutyl) ) Ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 2-(perfluorooctyl)ethyl (meth)acrylate, 2-(perfluorodecyl)ethyl (meth)acrylate, α-trifluoro A (meth)acrylate compound having a fluorine atom in the molecule, such as methyl methacrylate and α-trifluoroethyl methacrylate; a fluoroalkyl group having 1 to 14 carbon atoms and at least 3 fluorine atoms in the molecule, fluoro There are also fluorine-containing polyfunctional (meth)acrylic acid ester compounds having a cycloalkyl group or fluoroalkylene group and at least two (meth)acryloyloxy groups.

Preferred as the thermosetting polar group are, for example, hydrogen bond-forming groups such as a hydroxyl group, a carboxyl group, an amino group and an epoxy group. These are excellent not only in adhesiveness with a coating film but also in affinity with inorganic ultrafine particles such as silica. Examples of the polymerizable compound having a thermosetting polar group include 4-fluoroethylene-perfluoroalkyl vinyl ether copolymer; fluoroethylene-hydrocarbon vinyl ether copolymer; epoxy, polyurethane, cellulose, phenol, polyimide, and the like. Examples include fluorine-modified products of each resin.
As the polymerizable compound having both a functional group curable by ionizing radiation and a polar group heat-curable, partially or fully fluorinated alkyl, alkenyl, aryl esters of acrylic or methacrylic acid, fully or partially fluorinated vinyl ethers, completely Alternatively, partially fluorinated vinyl esters, completely or partially fluorinated vinyl ketones and the like can be exemplified.

Further, examples of the fluorine-based resin include the following.
A polymer of a monomer or a monomer mixture containing at least one fluorine-containing (meth)acrylate compound of the polymerizable compound having an ionizing radiation-curable group; at least one of the fluorine-containing (meth)acrylate compounds, and methyl (meth). Copolymers with (meth)acrylate compounds containing no fluorine atom in the molecule such as acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; fluoroethylene , Vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, 3,3,3-trifluoropropylene, 1,1,2-trichloro-3,3,3-trifluoropropylene, hexafluoropropylene Monomers or copolymers of monomers. A silicone-containing vinylidene fluoride copolymer in which a silicone component is contained in these copolymers can also be used. In this case, the silicone component includes (poly)dimethylsiloxane, (poly)diethylsiloxane, (poly)diphenylsiloxane, (poly)methylphenylsiloxane, alkyl-modified (poly)dimethylsiloxane, azo group-containing (poly)dimethylsiloxane, Dimethyl silicone, phenylmethyl silicone, alkyl/aralkyl modified silicone, fluorosilicone, polyether modified silicone, fatty acid ester modified silicone, methyl hydrogen silicone, silanol group-containing silicone, alkoxy group-containing silicone, phenol group-containing silicone, methacryl modified silicone, acrylic Examples include modified silicone, amino-modified silicone, carboxylic acid-modified silicone, carbinol-modified silicone, epoxy-modified silicone, mercapto-modified silicone, fluorine-modified silicone and polyether-modified silicone. Among them, those having a dimethylsiloxane structure are preferable.

Furthermore, non-polymers or polymers composed of the following compounds can also be used as the fluororesin. That is, by reacting a fluorine-containing compound having at least one isocyanato group in a molecule with a compound having at least one functional group reactive with an isocyanato group such as an amino group, a hydroxyl group and a carboxyl group in a molecule. Compounds obtained: compounds obtained by reacting fluorine-containing polyols such as fluorine-containing polyether polyols, fluorine-containing alkyl polyols, fluorine-containing polyester polyols, fluorine-containing ε-caprolactone modified polyols with compounds having an isocyanato group, etc. Can be used.

Further, each resin as described above can be mixed and used together with the above-mentioned polymerizable compound or polymer having a fluorine atom. Further, various additives and solvents may be appropriately used in order to improve the coating property and the antifouling property, and a curing agent for curing the reactive group and the like.

In the formation of the low refractive index layer, 0.5 to 5 mPa·s (25° C.) at which the viscosity of the composition for the low refractive index layer obtained by adding the low refractive index agent and the resin can be preferably applied is obtained. It is preferably in the range of 0.7 to 3 mPa·s (25° C.). An antireflection layer excellent in visible light can be realized, a uniform thin film having no coating unevenness can be formed, and a low refractive index layer having particularly excellent adhesion can be formed.

The curing means for the resin forming the low refractive index layer may be the same as the curing means for the hard coat layer. When a heating means is used for the curing treatment, it is preferable to add a thermal polymerization initiator to the fluorine-based resin composition to generate radicals and initiate polymerization of the polymerizable compound by heating.

The substrate film is not particularly limited, and examples thereof include polyester resin, acetate resin, polyether sulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth)acrylic resin, Examples thereof include polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin, aromatic polyetherketone resin, and the like. Among them, polyester resins, polycarbonate resins and polyolefin resins are preferably used.

Examples of the polyolefin-based resin used for the base film include bases containing at least one kind of polyethylene, polypropylene, cyclic polyolefin and the like as a constituent component. Examples of the cyclic polyolefin include those having a norbornene skeleton.
Examples of the polycarbonate resin include aromatic polycarbonates based on bisphenols (bisphenol A and the like), aliphatic polycarbonates such as diethylene glycol bisallyl carbonate, and the like.
Examples of the (meth)acrylic resin include methyl poly(meth)acrylate, ethyl poly(meth)acrylate, methyl (meth)acrylate-butyl (meth)acrylate copolymer, and the like.
Examples of the polyester-based resin include a base material containing at least one of polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate (PEN) as a constituent component.
Examples of the aromatic polyether ketone-based resin include polyether ether ketone (PEEK).

In the present invention, the thickness of the base film is not particularly limited and may be 5 to 300 μm, but from the viewpoint of handling property and preventing wrinkles and twists generated in the laminate, The thickness is preferably 10 μm or more, and preferably 200 μm or less from the viewpoint of thinning.
The more preferable lower limit of the thickness of the base film is 15 μm, and the more preferable upper limit thereof is 125 μm.

The surface of the base material film may be previously subjected to etching treatment such as sputtering, corona discharge, ultraviolet ray irradiation, electron beam irradiation, chemical conversion, oxidation, or an undercoating treatment. By performing these treatments in advance, it is possible to improve the adhesion to the hard coat layer or the cured layer of the monofunctional monomer formed on the base film. In addition, before forming the hard coat layer or the cured layer, the surface of the base film may be dust-removed and cleaned by solvent cleaning, ultrasonic cleaning, or the like, if necessary.

The laminate of the present invention has one or more optical functional layers on one surface of the substrate film and a low contact angle layer on the other surface of the substrate film, From the viewpoint of imparting the curl prevention property, the crack prevention property, and the scratch resistance property, it is preferable that the low contact layer side is provided with the hard coat performance.
Examples of the method for imparting the hard coat performance include a method for imparting hard coat performance to the low contact angle layer and a method for forming a hard coat layer between the low contact angle layer and the base film. Suitable examples are:

As a method for imparting hard coat performance to the low contact angle layer, for example, an ionizing radiation curable resin similar to the above hard coat composition, and a photopolymerization initiator are added to the low contact angle layer composition. Then, a method of forming the low contact angle layer by applying active energy rays such as ultraviolet rays to the substrate film after coating and drying.

As a method for forming a hard coat layer between the low contact angle layer and the base film, for example, the same method as forming the hard coat layer as the optical functional layer described above, the base film A method of forming a hard coat layer on the surface of the above and further forming the above low contact angle layer on the side of the hard coat layer opposite to the base film.
The thickness of the hard coat layer formed between the low contact angle and the base material film can appropriately impart the curl preventive property, and thus has the same thickness as the hard coat layer as the optical functional layer described above. Is preferred.
The "similar thickness" means that the difference between the thickness of the hard coat layer between the low contact angle and the substrate film and the thickness of the hard coat layer as the optical functional layer is 1.0 μm or less. Means the case.

The laminate of the present invention is used to form a patterned transparent conductive layer on the side surface of the optical functional layer opposite to the base film side.
The transparent conductive layer is not particularly limited, and examples thereof include a transparent conductive layer containing a metal oxide and a transparent conductive layer containing a conductive fibrous filler.

Examples of the transparent conductive layer containing the metal oxide include indium tin oxide (ITO), zinc oxide (ZnO), aluminum zinc oxide (AZO), gallium zinc oxide (GZO), tin oxide (SnO ₂ ). , Indium oxide (In ₂ O ₃ ), tungsten oxide (WO ₃ ), and the like. Among them, indium tin oxide (ITO) is preferable.

The thickness of the transparent conductive layer containing the metal oxide is not particularly limited, but a certain thickness is required to form a continuous coating having a surface resistance of 200 Ω/□ or less, but the thickness is When the thickness is too large, transparency is deteriorated. Therefore, the preferable lower limit of the thickness is 15 nm, the preferable upper limit is 45 nm, the more preferable lower limit is 20 nm, and the more preferable upper limit is 40 nm. If the thickness is less than 15 nm, the surface electric resistance becomes high and it becomes difficult to form a continuous film. If it exceeds 45 nm, the transparency may be deteriorated.

The transparent conductive layer containing the metal oxide can be formed by a sputtering treatment, and it is preferable that after the sputtering treatment, a heat treatment is performed at 150° C. for 60 minutes to be crystallized.
By crystallizing the transparent conductive layer, the resistance of the transparent conductive layer is lowered, and the transparency and durability are improved.
As a method for patterning the transparent conductive layer formed by the above-mentioned sputtering treatment, a known etching method or the like can be mentioned. The heat treatment of the transparent conductive layer may be performed before or after patterning the transparent conductive layer.
A conductive laminated body in which a patterned transparent conductive layer is formed on the side opposite to the base film side of the optical functional layer of the above laminated body is also one aspect of the present invention.

In the transparent conductive layer containing the conductive fibrous filler, the thickness is not particularly limited as long as the conductive performance can be obtained, but when considering conduction, the conductive fibrous filler is localized in any of the layers. Is preferred. By localizing the conductive fibrous filler in the layer, not only the conductivity is improved, but also the minimum fiber content is required, and the total light transmittance and the haze can be reduced.
In the laminate of the present invention, the preferable upper limit of the haze value is 5%, the more preferable upper limit thereof is 1.5%, the still more preferable upper limit thereof is 1%, and the preferable lower limit of the total light transmittance thereof is 80%, and the more preferable lower limit thereof is 90. %.
The haze value is the sum of the internal haze value and the surface haze value, and is a value measured according to JIS K-7136. As a device used for the measurement, a reflectance/transmittance meter HM-150 (Murakami Color Research Laboratory) can be mentioned.
The total light transmittance is a value measured according to JIS K-7361. As a device used for the measurement, a reflectance/transmittance meter HM-150 (Murakami Color Research Laboratory) can be mentioned.
Further, since the resistance value of the conductive laminate can be further lowered, it is more preferable that the conductive fibrous filler is localized near the surface of the layer.

The thickness of the transparent conductive layer containing the conductive fibrous filler is preferably less than the fiber diameter of the conductive fibrous filler. When the thickness of the transparent conductive layer is equal to or larger than the fiber diameter of the conductive fibrous filler, the amount of the binder resin entering the contact point of the conductive fibrous filler becomes large and conduction deteriorates, and the target resistance value cannot be obtained. Sometimes.
Specifically, the thickness of the transparent conductive layer containing the conductive fibrous filler is preferably about 10 to 200 nm. When the thickness of the transparent conductive layer is less than 10 nm, an uncoated region is generated when the transparent conductive layer composition is applied when the transparent conductive layer is formed, and the transparent conductive layer is formed by the transfer method described below. In this case, the transparent conductive layer may not be transferred. On the other hand, if it exceeds 200 nm, the fiber diameter of the conductive fibrous filler needs to be thicker than the preferable range described later, so that the haze of the conductive laminate increases and the total light transmittance decreases. And is optically unsuitable.
The thickness of the transparent conductive layer containing the conductive fibrous filler is more preferably 50 nm or less, further preferably 30 nm or less.
The thickness of the transparent conductive layer is, for example, using an electron microscope such as SEM, STEM, TEM, etc., and the cross-section of the transparent conductive layer is observed at a magnification of 1,000 to 500,000 times to measure the average thickness at 10 locations. Can be asked as

The conductive fibrous filler preferably has a fiber diameter of 200 nm or less and a fiber length of 1 μm or more.
When the fiber diameter is more than 200 nm, the haze value of the conductive laminate may be increased or the light transmission performance may be insufficient. The preferable lower limit of the fiber diameter of the conductive fibrous filler is 10 nm from the viewpoint of the conductivity of the transparent conductive layer, and the more preferable range of the fiber diameter is 15 to 180 nm.
If the fiber length of the conductive fibrous filler is less than 1 μm, a transparent conductive layer having sufficient conductivity may not be formed, and agglomeration may occur to increase haze value and decrease light transmission performance. Therefore, the preferable upper limit of the fiber length is 500 μm, the more preferable range of the fiber length is 3 to 300 μm, and the further preferable range is 10 to 30 μm.
The fiber diameter and fiber length of the conductive fibrous filler are, for example, using an electron microscope such as SEM, STEM, and TEM, and the fiber diameter and fiber length of the conductive fibrous filler are set to 1,000 to 500,000 times. It can be calculated as an average value of 10 measured points.

Such conductive fibrous filler is preferably at least one selected from the group consisting of conductive carbon fibers, metal fibers and metal-coated synthetic fibers.
Examples of the conductive carbon fiber include vapor grown carbon fiber (VGCF), carbon nanotube, wire cup, and wire wall. These conductive carbon fibers may be used alone or in combination of two or more.

As the above-mentioned metal fiber, for example, a fiber produced by a wire-drawing method for making stainless steel, iron, gold, silver, aluminum, nickel, titanium, etc. thin and long, or a cutting method can be used. Such metal fibers may be used alone or in combination of two or more. Among these metal fibers, the metal fiber using silver is preferable because it has excellent conductivity.
Examples of the method for producing a metal fiber using silver include a method of reducing a silver compound such as silver nitrate and silver sulfate in a solution, and the like. Examples of the method of reducing silver sulfate in a solution include Y. Sun, B.I. Gates, B.A. Mayers, & Y. Xia, "Crystalline silver nanowares by soft solution processing", Nanoletters, (2002), 2(2) 165-168, followed by the "polyol" method, followed by dissolution in ethylene glycol in the presence of polyvinylpyrrolidone (PVP). And a method of synthesizing the obtained silver sulfate by reduction.

Examples of the metal-coated synthetic fibers include fibers obtained by coating acrylic fibers with gold, silver, aluminum, nickel, titanium and the like. One kind or two or more kinds of such metal-coated synthetic fibers can be used. Among these metal-coated synthetic fibers, a metal-coated synthetic fiber using silver is preferable because it has excellent conductivity.

The content of the conductive fibrous filler is preferably, for example, 20 to 3000 parts by mass with respect to 100 parts by mass of the resin component forming the transparent conductive layer. If it is less than 20 parts by mass, a transparent conductive layer having sufficient conductivity may not be formed, and if it exceeds 3000 parts by mass, the haze of the conductive laminate may be high or the light transmission performance may be insufficient. There is something to do. In addition, since the amount of the binder resin that enters the contact points of the conductive fibrous filler increases, the conductivity of the transparent conductive layer may deteriorate, and the conductive laminate of the present invention may not obtain the target resistance value. The more preferable lower limit of the content of the conductive fibrous filler is 50 parts by mass, and the more preferable upper limit thereof is 1000 parts by mass.

It is preferable that a part of the conductive fibrous filler projects from the surface of the transparent conductive layer.
When the electroconductive laminate of the present invention is produced by a transfer method using a transfer film, the electroconductive fibrous filler is laminated by laminating the transparent electroconductive layer side surface and the transferred material so as to face each other and applying pressure. Is projected from the surface of the transparent conductive layer opposite to the base film side (that is, the surface of the transparent conductive layer which is pressed by the transfer target), and the protruding conductive fibrous filler is a transfer target. In the state of being embedded in, the resulting conductive laminate has improved solvent resistance, and a conductive pattern can be suitably formed by an etching method or the like. Further, the scratch resistance of the conductive laminate is also excellent.

It is preferable that a part of the conductive fibrous filler projects from the surface of the transparent conductive layer in the range of 5 to 600 nm. In the present invention, it is preferable that the range of the vertical distance from the flat portion on the surface of the transparent conductive layer where the conductive fibrous filler does not project to the tip of the projected conductive fibrous filler is 5 to 600 nm. If the vertical distance is less than 5 nm, the solvent resistance of the conductive laminate may not be improved, and if it exceeds 600 nm, the conductive fibrous filler may fall off from the transparent conductive layer. The more preferable lower limit of the vertical distance is 10 nm, and the more preferable upper limit thereof is 200 nm.
The vertical distance of the conductive fibrous filler protruding from the surface of the transparent conductive layer is, for example, using an electron microscope such as SEM, STEM, or TEM, and the surface of the transparent conductive layer is observed at 1000 to 500,000 times. Then, the vertical distance from the flat portion of the surface of the transparent conductive layer to the tip of the conductive fibrous filler protruding can be obtained as an average value of 10 measured points.

In the electroconductive laminate of the present invention, the transparent electroconductive layer has a ratio of electroconductive material elements constituting the electroconductive fibrous filler on the surface of 0.15 to 5.00 at% in atomic composition percentage. If it is less than 0.15 at %, the electroconductivity of the electroconductive laminate of the present invention may be insufficient in conductivity or the etching rate may be slow. When it exceeds 5.00 at %, the light transmittance of the electroconductive laminate of the present invention is lowered and the scratch resistance is deteriorated. The preferable lower limit of the ratio of the conductive material elements constituting the conductive fibrous filler present on the surface of the transparent conductive layer is 0.20 at%, the preferable upper limit is 2.00 at%, and the more preferable lower limit is 0.30 at%. A more preferable upper limit is 1.00 at %.
The ratio of the conductive material element forming the conductive fibrous filler present on the surface of the transparent conductive layer can be measured by the following conditions using X-ray photoelectron spectroscopy.
Accelerating voltage: 15kV
Emission current: 10mA
X-ray source: Al dual anode Measurement area: 300×700 μmφ
A depth of 10 nm was measured from the surface, and an average value of n=3 times. The transparent conductive layer having such a surface was caused by the conductive fibrous filler on the surface, and thus had low solvent resistance and scratch resistance, and further low resistance. It is preferable that an uneven shape is formed to such an extent that an extremely high light transmittance can be achieved with a haze value.

The method for producing the conductive laminate of the present invention includes, for example, a method of laminating a transparent conductive layer on a substrate film by a usual coating method, and further, an overcoat at a level at which a target resistance value is obtained. Examples thereof include a method of laminating layers, a method including a transfer step of transferring the conductive layer to a transfer target by using a transfer film having at least the conductive layer on a base film. In the case of lowering the resistance value of the electroconductive laminate, it is preferably produced by a method having a transfer step of transferring the electroconductive layer to an object to be transferred.
In the transfer step, a transfer film having at least a conductive layer on the base film is used.
The transfer target is not particularly limited as long as it is a member that can be provided with a conductive layer, for example, a substrate made of any material such as glass, resin, metal, ceramic, or on these substrates. Examples of the formed transfer layer such as a resin layer and an adhesive layer.

The laminate of the present invention can be used for display on televisions, computers and the like. In particular, it can be suitably used for a high-definition image display such as LCD, organic/inorganic LED, PDP, electronic paper, and the surface of a touch panel.
Among them, the conductive laminate of the present invention in which a patterned transparent conductive layer is formed on the side opposite to the base film side of the optical functional layer of the laminate is preferably used for a capacitance type touch panel. You can A touch panel provided with such a conductive laminate of the present invention is also one aspect of the present invention. The touch panel of the present invention is preferably a capacitance type touch panel.

Since the laminate of the present invention has the above-mentioned constitution, the adhesive layer-attached film was attached to the side opposite to the transparent conductive layer side of the substrate film and subjected to heat treatment, and then the adhesive layer-attached film was peeled off. Even in such a case, the contact angle of water on the surface to which the film with the pressure-sensitive adhesive layer is attached is increased, and the decrease in adhesiveness can be preferably prevented.

The contents of the present invention will be explained by the following examples, but the contents of the present invention should not be construed as being limited to these embodiments. In this example, “parts” and “%” represent “parts by mass” and “% by mass”, respectively, unless otherwise specified.

(Example 1)
1. On one surface (on the primer layer) of a biaxially stretched polyester film having a thickness of 100 μm (manufactured by Toyobo Co., Ltd., A4300; with a primer layer), using a hard coat layer composition having the following formulation, the thickness after drying was 2. It was applied so as to have a thickness of 0 μm to form a hard coat layer.
Then, using the composition for the high refractive index layer and the composition for the low refractive index layer having the following formulations, the high refractive index layer (thickness 50 nm, refractive index 1.68) and the low refractive index layer (thickness 30 nm, refraction) The rate of 1.48) was sequentially formed on the hard coat layer of the biaxially stretched polyester film.
The drying conditions of the optical functional layer including the hard coat layer, the high refractive index layer and the low refractive index layer were 70° C. and 60 seconds. Further, after drying the coating film of the composition for the hard coat layer, the coating film of the composition for the high refractive index layer, and the coating film of the composition for the low refractive index layer, each is irradiated with ultraviolet rays (150 mJ/cm ² ) Went.

On the other surface of the biaxially stretched polyester film, a low contact angle layer composition 1 having the following formulation is applied to form a coating film, and the coating film is dried at 70° C. for 60 seconds. A laminated body in which a low contact angle layer having a thickness of 20 nm was provided on the other surface of the biaxially stretched polyester film was obtained.

<Composition for hard coat layer>
Dipentaerythritol hexaacrylate (weight average molecular weight 580, double bond equivalent 100) 50 parts Photoinitiator (BASF Corporation, Irgacure 184) 2 parts Methyl isobutyl ketone 200 parts

<Composition for high refractive index layer>
Dipentaerythritol hexaacrylate (weight average molecular weight 580, double bond equivalent 100) 10 parts Photopolymerization initiator (BASF Corporation, Irgacure 127) 0.7 parts High refractive index particle-containing liquid (zirconia having an average particle size of 10 to 15 nm) Particles dispersed in methyl ethyl ketone to give a solid content of 30%) 65 parts Methyl isobutyl ketone 1000 parts

<Composition for low refractive index layer>
Dipentaerythritol hexaacrylate (weight average molecular weight 580, double bond equivalent 100) 3.5 parts Photopolymerization initiator (BASF Corporation, Irgacure 127) 1 part Low refractive index particle-containing liquid (silica having an average particle size of 10 to 15 nm) Particles dispersed in methyl isobutyl ketone to a solid content of 30%) 21.7 parts Methyl isobutyl ketone 1000 parts

<Composition 1 for low contact angle layer>
Acrylic polymer solution (weight average molecular weight 160,000, double bond equivalent 1,000, solid content 25%)
16 parts Methyl isobutyl ketone 1000 parts

(Example 2)
The composition 1 for low contact angle layer of Example 1 was changed to the composition 2 for low contact angle layer having the following formulation, the composition 2 for low contact angle layer was applied, and the thickness after drying was 2.0 μm. After forming a coating film as described above, drying was performed at 70° C. for 60 seconds, and ultraviolet irradiation (150 mJ/cm ² ) was performed to form a low contact angle layer, and in the same manner as in Example 1, A laminated body was obtained.

<Composition 2 for low contact angle layer>
Acrylic polymer solution (weight average molecular weight 160,000, double bond equivalent 1,000, solid content 25%)
16 parts Dipentaerythritol hexaacrylate (weight average molecular weight 580, double bond equivalent 100) 4 parts Photopolymerization initiator (BASF Corporation, Irgacure 127) 0.8 parts Methyl isobutyl ketone 30 parts

(Example 3)
After forming the optical functional layer in the same manner as in Example 1, the composition for the hard coat layer was applied onto the other surface of the biaxially stretched polyester film, and the thickness after drying was 2.0 μm. After forming the coating film, the coating film was dried and irradiated with ultraviolet rays to form a hard coat layer (refractive index 1.52). The drying conditions of the coating film were 70° C. and 60 seconds, and the irradiation amount of ultraviolet rays was 150 mJ/cm ² . Then, the low contact angle layer composition 1 was used to form a low contact angle layer on the hard coat layer formed on the other surface of the biaxially stretched polyester film so as to have a thickness of 20 nm. The coating film formed by applying the composition 1 for low contact angle layer was dried at 70° C. for 60 seconds to obtain a laminate.

(Example 4)
A laminate was obtained in the same manner as in Example 1 except that the composition 1 for low contact angle layer of Example 1 was changed to the composition 3 for low contact angle layer having the following formulation.

<Composition 3 for low contact angle layer>
Acrylic polymer (weight average molecular weight 9100, double bond equivalent 1000) 16 parts Methyl isobutyl ketone 1000 parts

(Example 5)
A laminate was obtained in the same manner as in Example 1 except that the composition 1 for low contact angle layer of Example 1 was changed to the composition 4 for low contact angle layer having the following formulation.

<Composition 4 for low contact angle layer>
Acrylic polymer (weight average molecular weight 59400, double bond equivalent 425) 16 parts Methyl isobutyl ketone 1000 parts

(Example 6)
A laminate was obtained in the same manner as in Example 1 except that the composition 1 for low contact angle layer of Example 1 was changed to the composition 5 for low contact angle layer having the following formulation.

<Composition 5 for low contact angle layer>
Acrylic polymer (weight average molecular weight 15400, double bond equivalent 265) 16 parts Methyl isobutyl ketone 1000 parts

(Example 7)
A laminate was obtained in the same manner as in Example 1 except that the composition 1 for low contact angle layer of Example 1 was changed to the composition 6 for low contact angle layer having the following formulation.

<Composition 6 for low contact angle layer>
Acrylic polymer (weight average molecular weight 75800, double bond equivalent 230) 16 parts Methyl isobutyl ketone 1000 parts

(Example 8)
A laminate was obtained in the same manner as in Example 1 except that the composition 1 for low contact angle layer of Example 1 was changed to the composition 7 for low contact angle layer having the following formulation.

<Composition 7 for low contact angle layer>
Acrylic polymer (weight average molecular weight 63000, double bond equivalent 200) 16 parts Methyl isobutyl ketone 1000 parts

(Example 9)
The composition 1 for low contact angle layer of Example 1 was changed to the composition 8 for low contact angle layer having the following formulation, the coating film was dried under the same conditions as in Example 1, and the coating after the drying was performed. A laminate was obtained in the same manner as in Example 1 except that the film was irradiated with ultraviolet rays (150 mJ/cm ² ) to form a low contact angle layer.

<Composition 8 for low contact angle layer>
Dipentaerythritol hexaacrylate (weight average molecular weight 580, double bond equivalent 100) 50 parts Photoinitiator (BASF Corporation, Irgacure 184) 2 parts Methyl isobutyl ketone 3000 parts

(Comparative Example 1)
The composition 1 for low contact angle layer of Example 1 was changed to the composition 9 for low contact angle layer having the following formulation, and the composition 9 for low contact angle layer was applied and the thickness after drying was 20 nm. A laminated body was formed in the same manner as in Example 1 except that after the coating film was formed on the film, it was dried at 70° C. for 60 seconds, and ultraviolet irradiation (150 mJ/cm ² ) was performed to form a low contact angle layer. Got

<Composition 9 for low contact angle layer>
Dipentaerythritol hexaacrylate (weight average molecular weight: 580, double bond equivalent: 100) 50 parts Photopolymerization initiator (BASF, Irgacure 184) 2 parts Silicone leveling agent (Dainichi Seika Kogyo, Seika Beam 10-28, Solid content 10%) 1 part Methyl isobutyl ketone 3000 parts

(Comparative example 2)
A laminate was obtained in the same manner as in Example 2 except that the composition 2 for low contact angle layer of Example 2 was changed to the composition 10 for low contact angle layer having the following formulation.

<Composition 10 for low contact angle layer>
Dipentaerythritol hexaacrylate (weight average molecular weight: 580, double bond equivalent: 100) 50 parts Photopolymerization initiator (BASF, Irgacure 184) 2 parts Silicone leveling agent (Dainichi Seika Kogyo, Seika Beam 10-28, Solid content 10%) 1 part Methyl isobutyl ketone 200 parts

(Comparative example 3)
A laminate was obtained in the same manner as in Example 3 except that the composition 1 for low contact angle layer was changed to the composition 9 for low contact angle layer.

(Reference example 1)
A laminate was obtained in the same manner as in Example 1 except that the composition 1 for low contact angle layer was changed to the composition 9 for low contact angle layer.

The physical properties of the laminates obtained in Examples, Comparative Examples and Reference Examples were measured and evaluated as follows. The respective results are shown in Table 1.

(Wetting tension)
An adhesive layer was formed on the above biaxially stretched polyester film having a thickness of 125 μm to obtain a film with an adhesive layer.
As the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer, an acrylic pressure-sensitive adhesive (manufactured by Soken Chemical Industry Co., Ltd.: SK Dyne 1811L (solid content 23%)) and an isocyanate-based crosslinking agent (manufactured by Soken Chemical Industry Co., Ltd.: TD75 (solid content 75%)) Acrylic adhesive: Isocyanate cross-linking agent = 100:1 (mass ratio) is used, and the adhesive solution is dissolved in a solvent (ethyl acetate) so that the solid content is 20% (mass standard). I was there. The adhesive solution was applied onto the biaxially stretched polyester film and dried at 100° C. for 1 minute to form an adhesive layer (thickness 15 μm). Further, a releasable release film was attached to the surface of the adhesive layer for protection.
The film with the adhesive layer was used after peeling off the release film.
Regarding the laminates obtained in Examples and Comparative Examples, the wetting tension (initial) of the surface of the low contact angle layer before sticking the film with the pressure-sensitive adhesive layer, and after heating at 150° C. for 60 minutes, the pressure-sensitive adhesive layer The wetting tension (after heating) after peeling off the attached film was measured based on JIS K6768 (1999).
A wet tension of 22.6 to 73.0 mN/m was prepared as the test mixture.

(Stickiness)
Regarding the laminates obtained in Examples and Comparative Examples, after heating at 150° C. for 60 minutes, the adhesiveness of the surface of the low contact angle layer after peeling off the film with the adhesive layer is described below. It was measured by the method and evaluated according to the following criteria.
A 1 mm thick stainless steel plate (width of 25 mm or more) is attached to one adhesive surface of a double-sided adhesive tape (VHB double-sided tape Y-4920, manufactured by Sumitomo 3M Limited), and a width of 25 mm is applied to the other adhesive surface of the double-sided adhesive tape. The laminates obtained in Examples and Comparative Examples, which were cut into a size of 150 mm in length, were stuck together by reciprocating a 2 kg roller twice, to prepare a measurement sample.
The measurement sample was left for 72 hours in a room temperature environment, and then, using a peeling tester (device name: small bench tester “EZ-LX” manufactured by Shimadzu Corporation), according to JIS Z 0237, pulling speed The peel strength (N/25 mm width) was measured under the conditions of 300 mm/min and peel angle of 180 degrees.
⊚: Peel strength is 10 N/25 mm or more ◯: Peel strength is 5 N/25 mm or more, less than 10 N/25 mm ×: Peel strength is less than 5 N/25 mm

(Steel wool resistance (SW resistance))
Regarding the laminates obtained in Examples and Comparative Examples, the surface of the low contact angle layer before the film with the pressure-sensitive adhesive layer was stuck was subjected to a predetermined friction load (150 g/cm ² ) using #0000 steel wool. After rubbing back and forth 10 times, the state of scratches on the coating film was visually observed and evaluated according to the following criteria.
⊚: No scratches (0 scratches)
◯: Almost no scratches (about 1 to 9 scratches)
X: Clearly scratched (10 or more scratches and numerous scratches in a band) or the coating film was peeled off

(Tackiness)
The tackiness (tackiness) of the surface of the low contact corner layer before sticking the film with the adhesive layer of the laminates obtained in Examples and Comparative Examples was evaluated by touching with fingers according to the following criteria.
○: No tackiness (when the finger does not stick, the finger does not stick, and the finger does not get stuck even if the finger slides)
×: Tacky (not touching or touching even if it moves)

As shown in Table 1, regarding the sticking property after heating, the laminates according to Examples 1 to 5 have a peel strength of 10 N/25 mm or more, which is a good result, and the laminates according to Examples 6 to 9 are good. Then, the peel strength was 5 N/25 mm or more and less than 10 N/25 mm, which was a little good result, whereas the laminates according to Comparative Examples 1 to 3 had a peel strength of less than 5 N/25 mm, and thus the double-sided pressure-sensitive adhesive tape was used. It was inferior in sticking property with.
In addition, in the laminates according to the examples, the SW resistance was obtained in Example 2 in which the low contact angle layer was provided with the hard coat performance, and the hard coat layer was provided between the base film and the low contact angle layer. The laminate according to Example 3 was particularly good without being scratched, and the laminates according to Examples 1, 4 to 9 were hardly scratched.
Moreover, the tackiness was excellent in the laminates according to all the examples.
In addition, the laminates according to Examples 1 to 8 had a small difference in wet tension before and after heating, which was 6 mN/m or less. In the laminates according to Examples 1 to 8 having such a small difference in wetting tension, the components of the adhesive layer did not migrate to the low contact angle layer, and the adhesive components of the adhesive layer migrate to the low contact angle layer. As a result, it was possible to suppress not only the deterioration of the sticking property but also the adverse effects on the optical properties such as the light transmittance of the optical film. Further, the laminate according to Example 9 had a larger difference in wetting tension than the laminates according to Examples 1 to 8, but the wetting tension after heating was 30 mN/m or more, and the difference in wetting tension was Was 20 mN/m or less, the desired sticking performance could be secured.
The laminates according to the examples all had a haze value of 5% or less and a total light transmittance of 80% or more.
On the other hand, the laminate according to Reference Example 1 had a good wettability after heating of 30 mN/m or more, so that the stickiness was evaluated well, but the stickiness of the low contact angle layer before heating was large and the wettability was high. Could not be measured accurately. Further, since the difference in the wetting tension is a large value exceeding 20 mN/m, not only the migration of the pressure-sensitive adhesive component of the pressure-sensitive adhesive layer to the low contact angle layer was large, but also the initial wetting tension was high, so that the low contact angle layer This resulted in the problem of poor SW resistance and tackiness, which was not preferable in practice.
In addition, in the laminated body according to the example, the transparent conductive layer containing ITO (thickness 20 to 30 μm) is formed by the sputtering process, and the patterned transparent conductive layer is invisible, so that there is no problem in optical characteristics. confirmed.
Furthermore, Example 3 in which the hard coat layer as the optical functional layer and the hard coat layer between the base film and the low contact angle layer had the same thickness was cut into 100 mm×100 mm, and sputtering was performed. After the transparent conductive layer was formed by the treatment, it was placed on a flat table and the distance of the four corners farthest from the table was measured.
On the other hand, in the laminates according to Comparative Examples 1 to 3, the wetting tension was less than 30 mN/m, and sufficient sticking property could not be imparted.
In addition, in the laminate according to Reference Example 1, when the sputtering treatment for forming the transparent conductive layer was performed, the laminate had a tacky feeling and was blocked, and thus the laminate could not be wound up and thus the transparent body was transparent. The conductive layer could not be formed.
Further, by comparing the layered product of Example 9 and the layered product of Comparative Example 1, it was found that when the low contact angle layer did not contain a leveling agent, the sticking property was excellent.
Further, in the same manner as in Example 1, a coating film was formed using the composition for hard coat layer on one surface of a biaxially stretched polyester film having a thickness of 100 μm, and after half-cure, a silver nano film was formed by a transfer method. A transparent conductive layer using a wire was formed. Then, the hard coat layer was cured, and a low contact angle layer was formed on the other surface of the biaxially stretched polyester film by the same method as in Example 1 to obtain a conductive laminate. When heating the conductive laminate to reduce the resistance of the transparent conductive layer, the wetting tension after heating was 30 N/m or more, and the difference in wetting tension was 20 mN/m or less, The desired sticking performance could be secured. Also, there was no problem in the optical characteristics.

The present invention, even if the adhesive layer-attached film is peeled off after the adhesive layer-attached film is adhered to the side opposite to the transparent conductive layer side of the substrate film and subjected to heat treatment. It is possible to provide a laminate capable of suitably preventing a decrease in adhesiveness due to an increase in the contact angle of water on the surfaces to which the films are attached.

Claims (10)

On one surface of the base film, having one or more optical functional layers, on the other surface of the base film, having a low contact angle layer, with the base film side of the optical functional layer. A stack used to form a patterned transparent conductive layer on an opposite side, comprising:
A film with an adhesive layer is attached to the surface of the low contact angle layer, heated at 150° C. for 60 minutes, and then the film with the adhesive layer is peeled off. JIS K6768 (1999) The wetting tension specified by is 30 mN/m or more,
As the one or more optical functional layers, a high refractive index layer and a low refractive index layer are laminated on the base film in this order ,
The film with an adhesive layer has an adhesive layer formed on the film, and the adhesive layer contains an acrylic adhesive and an isocyanate crosslinking agent . Before the film with the adhesive layer is attached, the wet tension of the surface of the low contact angle layer specified by JIS K6768 (1999) and after heating at 150° C. for 60 minutes, the film with the adhesive layer is peeled off. The laminate according to claim 1, wherein a difference between the surface of the low contact angle layer and the wetting tension defined by JIS K6768 (1999) is 20 mN/m or less. The laminate according to claim 1 or 2, wherein a hard coat layer, a high refractive index layer, and a low refractive index layer are laminated on the base film in this order as one or more optical functional layers. The laminated body according to claim 1, 2 or 3, wherein the low contact angle layer is composed of an uncured (meth)acrylic resin alone or a composition containing the uncured (meth)acrylic resin. The laminate according to claim 1, 2, 3 or 4, wherein a hard coat performance is imparted to the low contact angle layer side of the base film. The laminate according to claim 5, wherein the low contact angle layer has hard coat performance. The laminate according to claim 5, further comprising a hard coat layer between the low contact corner layer and the base film. The laminate according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the transparent conductive layer contains indium tin oxide or a conductive fibrous filler. A patterned transparent conductive layer is formed on the side opposite to the substrate film side of the optical functional layer of the laminate according to claim 1, 2, 3, 4, 5, 6, 7, or 8. Conductive laminate. A touch panel comprising the conductive laminate according to claim 9.