TWI656038B - Laminate, conductive laminate and touch panel - Google Patents

Abstract

The present invention provides a case in which a film with an adhesive layer is preferably applied even when the film with an adhesive layer is adhered to the surface of the base film opposite to the transparent conductive layer side and the film is peeled after the heat treatment is performed. The laminated body which prevents the contact angle of water from increasing on the surface to which the film with the adhesive layer is attached and the adhesiveness thereof is reduced.

The laminated body of the present invention has one or more optical functional layers on one side of the base film, and a low contact angle layer on the other side of the base film. The laminated system is used for connecting the optical functional layer to the base. The film side is a patterned transparent conductive layer formed on the opposite side, which is characterized in that the film with the adhesive layer is adhered to the surface of the above-mentioned low contact angle layer and is performed at 150 ° C for 60 minutes. When the film with the adhesive layer is peeled off after heating, the wetting tension specified by JIS K6768 (1999) on the surface of the low contact angle layer is 30 mN / m or more.

Description

Laminate, conductive laminate and touch panel

The invention relates to a laminated body, a conductive laminated body and a touch panel.

Currently, touch panels are widely used as input means for various devices including display devices having a display panel such as a liquid crystal display panel, such as PDA (Personal Digital Assistants), portable information terminals, and car navigation systems.

A touch panel is a transparent conductive film provided with a transparent conductive layer including ITO (indium tin oxide), metal fibers, carbon nanotubes, etc. on a base film, and is usually manufactured separately from a display panel, and It is arranged on the front surface of the display panel.

Here, the entire layer or a part of a transparent conductive layer or an optical adjustment layer containing ITO or the like is usually provided on a substrate film by a sputtering process, which is performed on a roll-to-roll using a roll It is carried out in a state of roll), and the roll is wound with a base film. At this time, the surface of the base film is heated to 90 ° C. or higher due to secondary electrons from the plasma during the sputtering process. Therefore, in the sputtering process, there is a problem that the base film is wrinkled or twisted during transportation. For such a problem, for example, it is known to improve the wrinkles or distortion generated during transportation by bonding the protective film to the surface of the base film that is in contact with the guide roller (the surface opposite to the surface on which the sputtering process is performed). Twist method (for example, refer to Patent Document 1).

In addition, for a transparent conductive film having such a transparent conductive layer formed thereon, after the protective film is peeled off, another functional member (polarizing plate, etc.) is attached to the base film through a protective layer, and the protective film is bonded. Side face.

However, the transparent conductive layer formed by the sputtering process has the following cases: In order to reduce the resistance, improve the transparency, and improve the durability, if necessary, heat treatment at a high temperature of about 150 ° C to crystallize it.

In addition, it is generally known to use metal fibers, carbon nanotubes, etc. as materials other than ITO in order to reduce costs by eliminating the vacuum process in the manufacturing steps, and to improve the bendability of transparent conductive films. In the case of conductive materials, heat treatment is performed at a temperature of about 110 to 150 ° C, and the portions where the conductive materials overlap are also melted, adhered, and turned on, thereby achieving excellent resistance reduction.

The wiring around the transparent conductive film is made by firing a silver paste. Therefore, when making wiring around the transparent conductive film, the transparent conductive film is heated at about 120 to 140 ° C.

Furthermore, in the transparent conductive film, in order to suppress the gap between the wirings from being shifted due to dimensional changes caused by heating after patterning, the transparent conductive film may be heated at about 150 ° C before patterning. And adjust the shrinkage of the substrate.

However, at the time of the above-mentioned heating, there is a low score of the adhesive layer derived from the above-mentioned protective film. The sub-component may move on the surface of the conductive laminated body to which the protective film is attached. If such a movement of the low-molecular component occurs, there is an increase in the contact angle of water on the surface after the protective film is peeled off (that is, the wettability is reduced), and thereafter, when it is attached to other optical members, the adhesive member is separated through the adhesive member. The adhesiveness is lowered, or the liquid adhesive or the liquid adhesive is difficult to spread.

For example, Patent Document 2 discloses that water contact is controlled on a substrate film. The corner hard coating film is used for a capacitive touch panel, but there has not been any research on the contact angle of water after heat treatment.

[Patent Document 1] Japanese Patent Application Publication No. 2012-194644

[Patent Document 2] Japanese Patent Application Laid-Open No. 2011-177938

The present invention has been made in view of the foregoing circumstances, and an object thereof is to provide a case where the film of the adhesive layer is peeled off after the film of the adhesive layer is bonded to the surface of the base film opposite to the transparent conductive layer side and the heat treatment is performed. In this case, a laminated body, a conductive laminated body, and a touch panel in which the contact angle of water on the surface to which the film with the adhesive layer is attached is increased and the adhesion is reduced can be better prevented.

The present invention is a laminated body having one or more optical functional layers on one side of a base film and a low contact angle layer on the other side of the base film. The laminated system is used for the combination of the optical functional layers. The substrate film side is a patterned transparent conductive layer formed on the opposite side, which is characterized in that the film with an adhesive layer is adhered to the surface of the low contact angle layer at 150 ° C for 60 minutes. When the film with the adhesive layer is peeled off after heating under conditions, the surface of the low contact angle layer has a wetting tension of 30 mN / m or more as specified by JIS K6768 (1999).

The laminated body of the present invention is preferably such that the surface of the low contact angle layer before laminating the film with the adhesive layer is adhered to the wetting tension specified by JIS K6768 (1999) and heated at 150 ° C for 60 minutes to heat the above. After the film with the adhesion layer is peeled off, the difference in the wetting tension of the surface of the low contact angle layer specified by JIS K6768 (1999) is 20 mN / m or less.

Moreover, it is preferable to have 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 as one or more optical functional layers.

In addition, it is preferable that the high refractive index layer and the low refractive index layer are sequentially laminated on the base film to serve as one or more optical functional layers.

In addition, it is preferable that the hard coat layer, the high refractive index layer, and the low refractive index layer are sequentially laminated on the substrate film as one or more optical functional layers.

In addition, it is preferable that a hard coat layer, a high refractive index layer, and a low refractive index layer are sequentially laminated on a base film to serve as one or more optical functional layers.

The low contact angle layer is preferably composed of an uncured (meth) acrylic resin alone or a composition containing the uncured (meth) acrylic resin.

Moreover, it is preferable that the low-contact-angle-layer side of the said base film is given hard-coating property.

Moreover, it is preferable that the said low contact angle layer has a hard-coating property.

Moreover, it is preferable to have a hard-coat layer between the said low contact angle layer and a base film.

The transparent conductive layer preferably contains indium tin oxide or a conductive fibrous filler.

In addition, the present invention is also a conductive laminated body characterized in that a patterned transparent conductive layer is formed on a surface of the optical functional layer of the laminated body opposite to the substrate film side.

The present invention is also a touch panel including the above-mentioned conductive laminate.

Hereinafter, the present invention will be described in detail.

The present inventors have made diligent research on the previous subject, and as a result, have found that a laminate of a low contact angle layer and a film with an adhesion layer is sequentially formed on the surface of the base film opposite to the side where the transparent conductive layer is formed. In the body, the film with the adhesive layer is peeled by performing a heat treatment. When the above-mentioned low contact angle layer is adhered to the surface of the film with the adhesive layer, the wetting tension specified by JIS K6768 (1999) is controlled in a specific range, which can better prevent the decrease in adhesiveness. Thus, the present invention has been completed.

In addition, the research by the inventors of the present case found the following problem for the first time: after heating the laminated body with a film with an adhesive layer attached to the substrate film through the adhesive layer, the film with the adhesive layer was heated. During peeling, the contact angle of water will increase on the surface of the low contact angle layer to which the film with the adhesive layer is attached.

In addition, in the present specification, "transparent" in the "transparent conductive film" means that there is a region in a plane that transmits visible light, and it may be substantially translucent. The term "transparent" specifically refers to, for example, a light transmittance of 50% or more at a wavelength of 550 nm.

The laminated body of the present invention has a low contact angle layer on one surface of the base film.

By having the above-mentioned low contact angle layer, even when the film with an adhesive layer is peeled off after the heating for crystallizing the transparent conductive layer described below, the level of the film with the adhesive layer can be suppressed. The contact angle of water on the surface of the contact angle layer is increased, so that the adhesion of the surface can be prevented from decreasing.

That is, it is considered that the increase in the contact angle of water of the laminated body to which the film with the adhesive layer was attached on the substrate film through the adhesive layer was caused by the heat treatment of the laminated body to make the adhesive layer low. Caused by molecular components moving on the surface of the substrate film.

In contrast, in the laminated body of the present invention, a low contact angle layer is provided on the surface of the substrate film opposite to the transparent conductive layer side, and a film with an adhesion layer is further attached to the low contact angle layer. . The film with the adhesive layer is usually attached to the low contact angle layer through the adhesive layer. It is speculated that even if the low molecular component of the adhesive layer is moved to the low contact angle layer side like the previous laminated body, it can also be constituted by When the component of the low contact angle layer covers the above-mentioned low-molecular component or when the film with the adhesive layer is peeled off A part of the low contact angle layer is peeled off from the surface layer, and the contact angle at which water is generated on the surface after peeling the film with the adhesion layer is suppressed from increasing.

Regarding the low contact angle layer, a film with an adhesive layer is bonded to the low contact angle. When the surface of the layer is heated at 150 ° C. for 60 minutes and the film with the adhesive layer is peeled off, the wetting tension specified by JIS K6768 (1999) on the surface of the low contact angle layer is 30 mN / m or more. If it is less than 30 mN / m, the adhesion of the film with the adhesion layer on the low contact angle layer described above to other optical members becomes insufficient, and the spreadability of the liquid adhesive or liquid adhesive also changes. Not enough.

The wetting tension specified by JIS K6768 (1999) on the surface of the low contact angle layer is preferably 35 mN / m or more, and more preferably 40 mN / m or more.

Furthermore, in the present invention, heating with a transparent conductive layer containing a metal fiber or the like to reduce resistance, heating during the production of wiring around the transparent conductive film, and adjustment of the shrinkage of the substrate The heating conditions (150 ° C, 60 minutes) for crystallizing the transparent conductive layer containing ITO are the most severe compared to the heating, etc., so this heating conditions (150 ° C, 60 minutes) are used.

The low-contact-angle layer is preferably a low-contact layer before the following film is attached to the adhesive layer. The surface of the antenna layer has the wetting tension specified by JIS K6768 (1999) and the surface of the low contact angle layer after being peeled off the film with the adhesive layer after heating at 150 ° C for 60 minutes. The surface of the low contact angle layer is formed by JIS K6768 ( The difference in wetting tension specified in 1999) is 20 mN / m or less.

If the difference in the wetting tension is 20 mN / m or less, the increase in the contact angle of water generated on the surface after the film of the adhesive layer is peeled off can be better suppressed.

The difference in the wetting tension is more preferably 10 mN / m or less.

In the laminated body of the present invention, as the low contact angle layer, for example, Styrene resin, (meth) acrylic resin, vinyl acetate resin, vinyl ether resin, halogen-containing resin, alicyclic hydrocarbon resin, polycarbonate resin, polyester resin, polyamide Based resins, cellulose derivatives, silicone resins, and rubber or elastomers. Among these, it is preferable that it is comprised by the uncured (meth) acrylic-type resin alone or by the composition containing the said uncured (meth) acrylic-type resin. Such a low contact angle layer can better prevent a decrease in adhesion.

The "uncured" refers to a state in which the resin constituting the low contact angle layer has not been cured, but the low contact angle layer has no tacky feel.

The "non-tacky state" specifically refers to a state in which a finger is in contact with a low contact angle layer, a state in which a finger is attached to a low contact angle layer, or a finger is slid over a low contact angle layer. Will not be stuck.

In addition, in the present specification, "(meth) acrylate" means methacrylate and acrylate. The so-called "resin" includes monomers, oligomers, polymers, etc., unless otherwise mentioned. Concept.

The resin constituting the above-mentioned low contact angle layer preferably has a weight average molecular weight of 5000 ~ 500,000. If it is less than 5,000, there may be cases where the above-mentioned low contact angle layer is tacky when it is not hardened. If it exceeds 500,000, the viscosity of the composition used to form the low contact angle layer becomes too high to be uniform. Ground coating. The more preferable lower limit of the weight average molecular weight is 7,000, and the more preferable upper limit is 200,000.

In addition, in this specification, the said weight average molecular weight is a value calculated | required by polystyrene conversion by gel permeation chromatography (GPC).

The resin constituting the low contact angle layer preferably has a double bond equivalent of 100 or more. If If it is less than 100, it is not only difficult to synthesize the polymer, but the glass transition point (Tg) may be reduced. Even if the polymer is synthesized, the above-mentioned low contact angle layer may have a tacky feeling when it is not cured.

In addition, the double bond equivalent of the resin constituting the low contact angle layer is determined by

(Molecular weight of one molecule of the compound) / (Number of double bonds contained in the molecule of compound 1).

The resin constituting the low contact angle layer is preferably a solvent-drying resin.

The above-mentioned solvent-drying resin means a resin that becomes a film by drying only the above-mentioned solvent when coating a composition containing the resin and a solvent.

The resin constituting 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 tacky feeling may occur when a composition containing the resin is applied to form a low contact angle layer.

In addition, the above-mentioned "without reactive functional group in one molecule" can also maintain the low contact angle layer in addition to the case where the reactive polymer group is not included in the molecule of the resin constituting the low contact angle layer at all. Within the range of no tackiness state, there is a reactive functional group in one molecule.

The low contact angle layer can be formed by combining a resin containing the low contact angle layer and A composition of a solvent (hereinafter also referred to as a composition for a low contact angle layer) is formed by coating the surface of the substrate film on the side opposite to the side where the transparent conductive layer is formed and drying the formed coating film.

The solvent can 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, and diacetone alcohol). Etc.), ethers (two Alkane, 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, cyclic Hexanol, etc.), Celluloids (methylcellulose, ethylcellulose, etc.), Cellulose Acetate, Sublimines (Dimethylphosphine, etc.), and Amidoamines (Dimethyl Methylamine, dimethylacetamide, etc.) can also be mixed solvents of these.

The above-mentioned low contact angle layer may be appropriately added with a known additive such as an anti-blocking agent, a leveling agent, or an antistatic agent within a range that does not prevent the effect of the present invention.

The above-mentioned composition for the low contact angle layer preferably has a viscosity of 0.5 to 5.0 mPa. s (25 ° C). If it does not reach 0.5mPa. s (25 ° C), there may be cases where a low contact angle layer with sufficient thickness cannot be formed, and it is impossible to improve the adhesion of the low contact angle layer. If it exceeds 5.0 mPa. s (25 ° C), there is a case where a uniform low contact angle layer cannot be formed.

The better lower limit of the above viscosity is 0.7 mPa. s (25 ° C), and a more preferable upper limit is 3.0 mPa · s (25 ° C).

The above-mentioned low contact angle layer preferably has a thickness of 1 to 1000 nm. If it is less than 1 nm, the thickness of the low contact angle layer may be insufficient to improve the adhesion of the low contact angle layer. If it exceeds 1000 nm, the low contact angle layer may be easily cracked and the adhesion layer may be peeled off. When the film is formed, surface peeling may occur. The lower limit of the thickness of the low contact angle layer is more preferably 5 nm, and the more preferable upper limit is 500 nm. In addition, in the case where the above-mentioned low contact angle layer is provided with hard coating performance as described below, the thickness of the low contact angle layer may have a thickness exceeding 1000 nm.

The method for applying the composition for a low contact angle layer to a substrate film is not particularly limited, and examples thereof include a spin coating method, a dipping method, a spray method, a die coating method, and a rod coating method. , A roll coating method, a meniscus coater method, a flexographic printing method, a screen printing method, a droplet coating method, and other known methods.

In addition, even in the case where a hard coat layer is provided between the low contact angle layer and the base film, as described below, The above-mentioned low contact angle layer can also be formed on the hard coat layer by the same method.

It is preferable that the low contact angle layer formed by the method described above is in contact with the substrate. The film side is a film on which the adhesive layer is attached on the surface on the opposite side. The film with an adhesive layer can be preferably used as a protective film. By bonding the film with an adhesive layer, it can be improved due to transportability problems during the sputtering process used to form the transparent conductive layer described below. Wrinkled or crooked.

The film with an adhesive layer is preferably composed of at least a substrate and an adhesive layer, and has a flat surface. Those with excellent sliding properties, heat resistance, and hardness and toughness.

The substrate is not particularly limited, and examples thereof include polyester resins, polypropylene resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, and polyphenylene sulfide resins. Among these, a polyester resin and a polypropylene resin are preferably used.

The adhesive layer is a layer containing at least an adhesive. Examples of the adhesive include urethane-based, rubber-based, silicone-based, and acrylic-based adhesives. Among these, from the viewpoint of high heat resistance and low cost, an acrylic adhesive is preferred.

Examples of the acrylic pressure-sensitive adhesive include an acrylate copolymer obtained by copolymerizing an acrylate with another monomer.

Examples of the other monomer include methyl acrylate and methacrylic acid. Methyl ester, styrene, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, itaconic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, propylene glycol acrylate, acrylamide, methacrylamide, acrylic acid Glycidyl ester, glycidyl methacrylate, dimethylaminoethyl methacrylate, third butylaminoethyl methacrylate, n-ethylhexyl methacrylate, and the like. Among these, n-ethylhexyl methacrylate is preferably used.

These other monomers may be used alone or in combination.

The unit ratio (acrylate / other monomer) of the acrylate and other monomers contained in the acrylate copolymer is not particularly limited as long as the acrylate copolymer can exhibit the required adhesive force.

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

The said adhesive layer may further contain a crosslinking agent.

The crosslinking agent is not particularly limited, and examples thereof include epoxy-based and isocyanate-based crosslinking agents.

Examples of the epoxy-based crosslinking agent include a polyfunctional epoxy-based compound.

Examples of the polyfunctional epoxy-based compound include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, neoglycerol polyglycidyl ether, diglycerol polyglycidyl ether, glycerin polyglycidyl ether, Trimethylolpropane polyglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, poly Propylene glycol diglycidyl ether, polybutadiene diglycidyl ether, and the like.

Examples of the isocyanate-based crosslinking agent include a polyisocyanate compound, a terpolymer of a polyisocyanate compound, an amine ester prepolymer having an isocyanate group obtained by reacting a polyisocyanate compound and a polyol compound at a terminal, or the like Trimers of amine ester prepolymers, etc.

The polyisocyanate compound is not particularly limited, and examples thereof include 2,4-toluene diisocyanate, 2,5-toluene diisocyanate, 1,3-benzenedimethyldiisocyanate, and 1,4-benzenedimethyl Diisocyanate, diphenylmethane-4,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4 ' -Diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, lysine isocyanate, etc.

The content of the cross-linking agent varies depending on the type of the cross-linking agent. For example, it can be set within a range of 0.5 to 10.0 parts by mass with respect to 100 parts by mass of the adhesive.

The adhesive layer may further contain a metal chelator.

The metal chelating agent used in the adhesive layer has a metal element and a salt-forming site. When used together with the adhesive, the metal element and the carboxyl group of the adhesive can be bonded by chelation. And cross-linking.

Specific examples of such a metal chelate include aluminum isopropylate, aluminum butyrate, aluminum acetate, aluminum ethyl acetate, aluminum ethyl acetone, and ethyl acetonyl bis (ethyl acetate) ) Aluminum, aluminum chelate compounds such as aluminum alkyl acetoacetate; or dipropoxy-bis (acetylacetonato) titanium, dibutoxy titanium-bis (octyl Alcoholate), titanium dipropoxy-bis (ethyl acetate), titanium dipropoxy-bis (lactate), titanium dipropoxy-bis (triethanolamine), di-n-butoxy Titanium chelate compounds such as titanium-bis (triethanolamine), tri-n-butoxytitanium monostearate, butyl titanate dimer, poly (titanium acetate pyruvate); or zirconium tetraacetamate pyruvate, Zirconium chelate compounds such as zirconium monoacetate pyruvate, zirconium diacetam pyruvate, bis (ethylacetate) zirconium, zirconium acetate; zinc octoate, zinc laurate, zinc stearate, tin octoate And other organic carboxylic acid metal salts; and zinc chelate compounds such as acetoacetone zinc chelate, benzamidine zinc acetone chelate, dibenzomethane zinc chelate, and ethyl acetate ethyl acetate chelate. Among these, aluminum isopropylate, aluminum butyrate, aluminum acetate, aluminum ethyl acetate, aluminum ethyl pyruvate, aluminum ethyl pyruvate bis (ethyl acetate) aluminum, and ethyl ethyl acetate are preferably used. Aluminum chelate compounds such as ester aluminum. The reason is that it is easy to adjust the crosslinking speed at which the above-mentioned adhesive is crosslinked.

The content of the above-mentioned metal chelating agent varies according to the type of the above-mentioned metal chelating agent Different, it is preferably in the range of 0.06 to 0.50 parts by mass with respect to 100 parts by mass of the above-mentioned adhesive. If it is less than the above range, the cross-linking speed at the time of forming the above-mentioned adhesive layer may be slowed and productivity may be reduced. On the other hand, even when it is more than the above range, the effect will not change and the material cost increase.

The adhesive layer may contain other additives.

Examples of the other additives include antioxidants and ultraviolet absorbers.

In addition, the above-mentioned adhesive is a photosensitive adhesive obtained by polymerizing an acrylic ester constituting an acrylic adhesive and a photosensitive monomer component that is cured by light irradiation such as other monomers, and is applied by coating. In the case where the adhesive of the photosensitive monomer component is polymerized and hardened by irradiation with ultraviolet rays or visible light to form an adhesive layer, a photopolymerization initiator is added to the adhesive.

The film thickness of the adhesive layer is usually within a range of 3 to 200 μm, and among them, preferably within a range of 4 to 100 μm, and particularly preferably within a range of 5 to 50 μm.

As the method for forming the above-mentioned adhesive layer, for example, a method of applying an adhesive layer-forming material to a substrate, a method of transferring an adhesive layer to a substrate, and a constituent material of the adhesive layer and a substrate may be used. A method of forming the constituent material by melt co-extrusion; a method of forming the constituent material of the adhesive layer and the constituent material of the substrate into a film shape by extrusion or the like, respectively, and the subsequent method. Among them, a method of applying an adhesive layer forming material to a substrate is preferably used in terms of forming an adhesive layer with good smoothness.

In addition, the film with an adhesive layer is peeled after forming a patterned transparent conductive layer described below, and its peel strength is preferably 10 to 500 mN / 25 mm. If it is less than 10mN / 25mm, there may be cases where the film with an adhesive layer is peeled off during the manufacturing process of the laminated body of the present invention. When it exceeds 500mN / 25mm, it may not be able to peel from the low contact angle layer. In addition, as described below, when the transparent conductive layer is crystallized by performing a heat treatment after the sputtering process, the film with an adhesive layer is preferably formed after the conductive layer is crystallized by performing the heat treatment or After the heat treatment is completed in the subsequent steps, it is peeled off in any of the subsequent steps.

The same applies to the following transparent conductive layer containing a conductive fibrous filler and the like, and it is preferably any step after heating to reduce the resistance or firing the silver paste in a subsequent step. Peeling is performed in the middle.

The adhesion of the film with an adhesive layer to the low contact angle layer is preferably a spacer. The adhesion layer of the film with the adhesion layer is performed. Since the laminated body of the present invention has the above-mentioned low contact angle layer, the adhesion of the surface of the low contact angle layer after peeling of the film with the adhesion layer is not generated.

The laminated body of the present invention has more than one layer of optical function on one surface of the substrate film. Energy layer.

As the above-mentioned one or more optical functional layers, any conventionally known optical functional layer may be mentioned. Specifically, for example, a hard coat layer, a low refractive index layer, a high refractive index layer, an antifouling layer, an antistatic layer, And anti-glare layer.

Among them, it is preferable to have 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.

In the laminated body of the present invention, from the viewpoint that the patterned transparent conductive layer can be invisible as described below, it is more preferable that the one or more optical functional layers be a high refractive index layer and a low refractive index layer in this order. Laminated on a base film.

In addition, the one or more optical functional layers are further preferably a hard coat layer, a high refractive index layer, and a low A refractive index layer is sequentially formed on the said base film. With the optical functional layer having such a structure, an invisible transparent conductive layer can be realized, and a hard coat property can be imparted to the laminated body of the present invention.

The hard coating is based on the pencil hardness of JIS K5600-5-4 (1999). The pencil hardness obtained by the degree test (load 4.9N) is preferably F or more, and more preferably H or more. The hard coat layer is a layer that guarantees the hard coatability of the laminate of the present invention. For example, it is preferable to use a composition for a hard coat layer containing a resin that is hardened by ultraviolet rays, that is, a radiation-hardening resin and a photopolymerization initiator. And the former.

Examples of the free radiation-curable resin include acrylates. Compounds having a functional group such as a compound having one or more unsaturated bonds. 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, and diethylene glycol di (meth) acrylate. , Neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dinepentaerythritol penta (meth) acrylate , 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc .; and polyfunctional compounds modified by using ethylene oxide (EO) etc. Or a reaction product of the above-mentioned polyfunctional compound with a (meth) acrylate or the like (for example, a poly (meth) acrylate of a polyol) or the like.

As the above-mentioned free radiation-curable resin, the above-mentioned compound is included, and Polyester resin, polyether resin, acrylic resin, epoxy resin, amine ester resin, alkyd resin, relatively low molecular weight (number average molecular weight 300-80,000, preferably 400-5000) with unsaturated double bonds, Spiro acetal resin, polybutadiene resin, polythiol polyene resin, etc. Also, in this case Resin means all dimers, oligomers and polymers other than monomers.

Preferred compounds in the present invention include compounds having three or more unsaturated bonds. If such a compound is used, the crosslinking density of the formed hard coat layer can be increased, and the degree of hard coat can be made good.

Specifically, in the present invention, neopentaerythritol triacrylate, neopentaerythritol tetraacrylate, polyester multifunctional acrylate oligomer (3 to 15 functions), and amine multifunctional acrylic acid are preferred. Ester oligomers (3 to 15 functions) are used in appropriate combination.

The above-mentioned free radiation hardening resin may be used together with the solvent-drying resin. use. By using a solvent-drying resin in combination, it is possible to effectively prevent coating defects on the coating surface. In addition, the above-mentioned solvent-drying resin refers to, for example, a thermoplastic resin, that is, a resin that forms a film by drying only a solvent added to adjust a solid content during coating.

The solvent-drying resin that can be used together with the above-mentioned free radiation-curable resin is not particularly limited, and a thermoplastic resin can be generally used.

The thermoplastic resin is not particularly limited, and examples thereof include styrene resins, (meth) acrylic resins, vinyl acetate resins, vinyl ether resins, halogen-containing resins, alicyclic hydrocarbon resins, Polycarbonate resin, polyester resin, polyamide resin, cellulose derivative, silicone resin, rubber or elastomer, etc. The thermoplastic resin is preferably amorphous and soluble in an organic solvent (especially a common solvent capable of dissolving a plurality of polymers or curable compounds). In particular, from the viewpoints of film-forming properties, transparency, and weather resistance, styrene resins, (meth) acrylic resins, alicyclic hydrocarbon resins, polyester resins, and cellulose derivatives ( Cellulose esters, etc.).

Moreover, the said composition for hard-coat layers may contain a thermosetting resin.

The thermosetting resin is not particularly limited, and examples thereof include a phenol resin, a urea resin, a diallyl phthalate resin, a melamine resin, a guanamine resin, an unsaturated polyester resin, and a polyurethane resin. , Epoxy resin, amino alkyd resin, melamine-urea co-condensation resin, silicone resin, polysiloxane resin, etc.

The photopolymerization initiator is not particularly limited, and a known one can be used. For example, specific examples of the photopolymerization initiator include acetophenones, benzophenones, and michell benzamidine. Michler's benzoyl benzoate, α-amyloxime, 9-oxosulfur Thioxanthone, phenylacetone, benzoin, benzoin, fluorenyl phosphine oxide. In addition, it is preferable to use a mixture of a photosensitizer, and specific examples thereof include n-butylamine, triethylamine, and poly-n-butylphosphine.

As the photopolymerization initiator, when the free-radiation-curable resin is a resin system having a radically polymerizable unsaturated group, acetophenones, benzophenones, 9- Oxygen sulfur Category, benzoin, benzoin methyl ether, etc. When the above-mentioned free-radiation-curable resin is a resin system having a radical polymerizable functional group, it is preferable to use an aromatic diazonium salt or an aromatic diazonium salt alone or as a mixture as the photopolymerization initiator. Onium salts, aromatic onium salts, metallocene compounds, benzoin sulfonates, and the like.

As the initiator used in the present invention, in the case of a free radiation-curable resin having a radically polymerizable unsaturated group, it is because the compatibility with the free radiation-curable resin and the yellowing are small. In other words, 1-hydroxy-cyclohexyl-phenyl-one is preferred.

The content of the photopolymerization initiator in the composition for a hard coat layer is relative to 100 parts by mass of the above-mentioned free radiation curable resin is preferably 1 to 10 parts by mass. The reason is that if it is less than 1 part by mass, the hardness of the hard coat layer in the laminated body of the first invention cannot be set. In the case of the above range, if it exceeds 10 parts by mass, the free radiation may not reach the deep portion of the applied film without promoting internal hardening, and the pencil hardness F or more of the surface of the target hard coat layer may not be obtained. A more preferable lower limit of the content of the photopolymerization initiator is 2 parts by mass, and a more preferable upper limit is 8 parts by mass. When the content of the photopolymerization initiator is in this range, hardness distribution does not occur in the thickness direction, and it is easy to achieve uniform hardness.

The composition for a hard coat layer may contain the same solvent as the composition for forming a low contact angle layer.

Especially in the present invention, for reasons of excellent compatibility with the resin and coating properties, among them, a ketone-based solvent is preferred and it contains at least methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Any one or a mixture of these.

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

In the above-mentioned composition for a hard coat layer, it can also be added for the purpose of improving the hardness of the hard coat layer, suppressing hardening shrinkage, preventing blocking, controlling refractive index, imparting anti-glare properties, changing the properties of particles or the surface of the hard coat layer, and the like. Previously known organic, inorganic fine particles, dispersants, surfactants, antistatic agents, silane coupling agents, tackifiers, anti-colorants, colorants (pigments, dyes), defoamers, leveling agents, flame retardants , UV absorbers, adhesives, polymerization inhibitors, antioxidants, surface modifiers, etc.

Moreover, the said composition for hard-coat layers can also be mixed with a photosensitizer, and as a specific example, n-butylamine, triethylamine, poly-n-butylphosphine, etc. are mentioned, for example.

The method for preparing the above-mentioned composition for a hard coat layer is not particularly limited as long as the components can be uniformly mixed. For example, a paint shaker, a bead mill, a kneader, and agitator can be used. It is performed by a known device such as a mixer.

In addition, as a method of applying the composition for a hard coat layer to the base film, The method is not particularly limited, and examples thereof include a spin coating method, a dipping method, a spray method, a die coating method, a bar coating method, a roll coating method, a meniscus coating method, and a flexographic printing method. Well-known methods, such as a method, a screen printing method, and a droplet coating method.

Formed by coating the composition for a hard coat layer on the substrate film The coating film is preferably heated and / or dried as necessary, and hardened by irradiation with active energy rays or the like.

Examples of the active energy ray irradiation include irradiation with ultraviolet rays or electron beams. Shoot. Specific examples of the ultraviolet light source include light sources such as an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc lamp, a black fluorescent lamp, and a metal halide lamp. 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 a Cockcroft Walton type, a Van de Graaff type, a resonance transformer type, an insulated core transformer type, or a linear type, Various electron beam accelerators such as high-frequency high-voltage (Dynamitron) and high-frequency types.

In addition, the preferred thickness of the hard coating layer (when hardened) is 0.5 to 15 μm. It is more preferably 0.8 to 10 μm, and for the reason that curl resistance or crack resistance is particularly excellent, it is most preferably in a range of 1.5 to 8 μm. 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 an arbitrary 10 points. As another method, the thickness of the hard coating layer may be measured at an arbitrary ten points using a digital indicator IDF-130 manufactured by Mitutoyo, a thickness measuring device, and an average value may be determined.

As described below, the laminated body of the present invention has a patterned transparent conductive layer, and It is a component used in the touch panel of the electrostatic capacitance method, so there is a requirement such that the above-mentioned patterned transparent conductive layer is invisible. As a means for making the patterned transparent conductive layer invisible, a method of sequentially stacking a high refractive index layer and a low refractive index layer as the optical function layer may be mentioned, but in order to be suitable for the transparent conductive layer and the touch panel, And strict optical characteristics are required, and strict control of thickness or 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 preferably has a thickness of 10 to 100 nm and a refractive index of 1.35 to 1.55. The thickness of the high refractive index layer and the low refractive index layer is more preferably 10 to 70 nm.

As a method for forming the high refractive index layer, it can be roughly classified into a wet method and a dry method. The wet method is excellent in terms of production efficiency.

Examples of the wet method include a method formed by a sol-gel method using a metal alkoxide or the like; and a method formed by applying a composition containing a high refractive index particle in a binder resin. Examples of the dry method include a method in which a material having a desired refractive index is selected from the following high-refractive index particles and formed by a physical vapor deposition method or a chemical vapor deposition method.

As a method of forming the low refractive index layer, it can be roughly classified into a wet method and a dry method. The wet method is excellent in terms of production efficiency.

As the wet method, as with the high-refractive index layer, a method using a metal alkoxide or the like and forming it by a sol-gel method; a method using a low-refractive-index adhesive such as a fluororesin; And a method of coating and forming a composition containing low refractive index particles in the binder resin. Examples of the dry method include a method in which a material having a desired refractive index is selected from the following low-refractive index particles and formed by a physical vapor deposition method or a chemical vapor deposition method.

In the laminated body of the present invention, the hard coat layer, the high refractive index layer, and the low refractive index The layers preferably have a refractive index satisfying the relationship of the following formula (1). By satisfying the following formula (1), the transparent conductive layer formed on the low refractive index layer can be made invisible.

Refractive index of high refractive index layer> Refractive index of hard coating layer> Refractive index of low refractive index layer

(1)

The high-refractive index layer is not particularly limited, and examples thereof include conventionally known ones. For example, the resin and the solvent described in the hard coat layer described above can be formed by containing a composition having high-refractive-index fine particles.

As the high refractive index fine particles, for example, metal oxide fine particles having a refractive index of 1.50 to 2.80 can be preferably used. Specific examples of the metal oxide fine particles include titanium oxide (TiO ₂ , refractive index: 2.71), zirconia (ZrO ₂ , refractive index: 2.10), and cerium oxide (CeO ₂ , refractive index: 2.20). , Tin oxide (SnO ₂ , refractive index: 2.00), tin antimony oxide (ATO, refractive index: 1.75 to 1.95), indium tin oxide (ITO, refractive index: 1.95 to 2.00), phosphorus tin compound (PTO, refraction Ratio: 1.75 ~ 1.85), antimony oxide (Sb ₂ O ₅ , refractive index: 2.04), zinc aluminum oxide (AZO, refractive index: 1.90 ~ 2.00), zinc gallium oxide (GZO, refractive index: 1.90 ~ 2.00), and antimony Zinc acid (ZnSb ₂ O ₆ , refractive index: 1.90 ~ 2.00), etc. Among them, tin oxide (SnO ₂ ), tin antimony oxide (ATO), indium tin oxide (ITO), phosphorus tin compound (PTO), antimony oxide (Sb ₂ O ₅ ), zinc aluminum oxide (AZO), gallium oxide Zinc (GZO) and zinc antimonate (ZnSb ₂ O ₆ ) are conductive metal oxides, and have the advantage that antistatic properties can be imparted by forming conductive paths by controlling the diffusion state of fine particles.

From the viewpoint of high durability such as light resistance, zirconia (ZrO ₂ ) is preferred.

The low refractive index layer is preferably composed of 1) a resin containing silicon dioxide or magnesium fluoride, 2) a fluorine-based resin containing low-refractive index resin, and 3) a fluorine-based resin containing silicon dioxide or magnesium fluoride. 4) A thin film of silicon dioxide or magnesium fluoride. About other than fluorine resin As the resin, the same resin as that used for the above-mentioned hard coat layer can be used. The silicon dioxide is preferably solid silicon dioxide fine particles or hollow silicon dioxide fine particles.

As the above-mentioned fluorine-based resin, a polymerization including a fluorine atom at least in a molecule can be used Sex compounds or polymers. Although it does not specifically limit as a polymerizable compound, For example, it is preferable to have a hardening reactive group, such as a functional group hardened by a free radiation, and a polar group thermally hardened. It may also be a compound having both of these reactive groups. With respect to the polymerizable compound, the polymer system does not have any of the above-mentioned reactive groups and the like.

Polymerization as the functional group having the above-mentioned functional group hardened by free radiation As the compound, a fluorine-containing monomer having an ethylenically unsaturated bond can be widely used. More specifically, fluoroolefins (e.g., fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluorobutadiene, perfluoro-2,2-dimethyl-1,3 -Dioxolene, etc.). As those having (meth) acrylic acid, there are also the following: 2,2-2-trifluoroethyl (meth) acrylate, and 2,2,3,3,3-pentafluoropropane (meth) acrylate Ester, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, ( 2- (perfluorodecyl) ethyl meth) acrylate, α-trifluoromethyl methacrylate, α-trifluoroethyl methacrylate (meth) acrylate compounds having a fluorine atom in the molecule ; And fluorine-containing fluoroalkyl, fluorinated cycloalkyl or fluorinated alkyl groups having at least 3 fluorine atoms in the molecule and having 1 to 14 carbon atoms and at least 2 (meth) acryloxy groups Polyfunctional (meth) acrylate compounds and the like.

As the thermally-curable polar group, for example, a hydroxyl group, a carboxyl group, an amine group, Hydrogen-bonding groups such as epoxy groups. These are not only excellent in adhesion to the coating film, but also excellent in affinity with inorganic ultrafine particles such as silicon dioxide. Examples of the polymerizable compound having a thermosetting polar group include a 4-fluoroethylene-perfluoroalkyl vinyl ether copolymer; and a fluoroethylene-hydrocarbon-based ethylene. Ether copolymer; and fluorine modified products of epoxy, polyurethane, cellulose, phenol, polyimide and other resins.

Examples of the polymerizable compound having a functional group that is hardened by free radiation and a polar group that is thermally hardened include the following: partially or completely fluorinated alkyl, alkenyl, and aryl esters of acrylic acid or methacrylic acid; completely or Partially fluorinated vinyl ethers; fully or partially fluorinated vinyl esters; and fully or partially fluorinated vinyl ketones.

Examples of the fluorine-based resin include the following.

A monomer or a polymer of a monomer mixture containing at least one fluorine-containing (meth) acrylate compound of the polymerizable compound having the above-mentioned free radiation-curable group; at least one of the above-mentioned fluorine-containing (meth) acrylate compound It is not as good in the molecule as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Copolymers of (meth) acrylate compounds containing fluorine atoms; and fluoroethylene, vinylidene fluoride, trifluoroethylene, trifluorochloroethylene, 3,3,3-trifluoropropylene, 1,1,2-tri Homopolymers or copolymers of fluorine-containing monomers such as chloro-3,3,3-trifluoropropylene and hexafluoropropylene. Polysiloxane-containing vinylidene fluoride copolymers in which these copolymers contain a polysiloxane component can also be used. Examples of the polysiloxane component in this case include (poly) dimethylsiloxane, (poly) diethylsiloxane, (poly) diphenylsiloxane, and (poly) methylphenyl) Siloxane, alkyl modified (poly) dimethylsiloxane, (poly) dimethylsiloxanes containing azo groups, dimethylpolysiloxane, phenylmethylpolysiloxane, alkyl ． Aralkyl modified polysiloxane, fluorosilicone, polyether modified polysiloxane, fatty acid ester modified polysiloxane, methylhydrogen polysiloxane, silanol containing silanol group, alkoxy group Polysiloxane, phenol-containing polysiloxane, methacrylic modified polysiloxane, acrylic modified polysiloxane, amine modified polysiloxane, carboxylic acid modified polysiloxane, methanol modified polysiloxane Oxygen, epoxy-modified polysiloxane, mercapto-modified polysiloxane, fluorine-modified polysiloxane, polyether-modified polysiloxane, etc. Among them, it is preferable to have Dimethylsiloxane structure.

Furthermore, non-polymers or polymers composed of the following compounds can also be used as fluorine Department of resin. That is, the following can be used: a compound obtained by reacting a fluorine-containing compound having at least one isocyanate group in a molecule with a compound having at least one functional group reacting with an isocyanate group such as an amine group, a hydroxyl group, and a carboxyl group in the molecule; And the fluorine-containing polyols such as fluorine-containing polyether polyols, fluorine-containing alkyl polyols, fluorine-containing polyester polyols, fluorine-containing ε-caprolactone modified polyols, and those having isocyanate groups Compounds obtained by reacting compounds.

In addition, each of the resins described above and the above-mentioned polymerizable polymer having a fluorine atom may be used. Compounds or polymers are used together. Further, a hardening agent for hardening a reactive group or the like, various additives and a solvent for improving coatability or imparting antifouling properties can be appropriately used.

In the formation of the above-mentioned low refractive index layer, it is preferable to add a low refractive index agent and a tree The viscosity of the composition for a low refractive index layer made of a grease or the like is set to 0.5 to 5 mPa to obtain better coating properties. s (25 ℃), more preferably 0.7 ~ 3mPa. s (25 ° C) range. It can realize an excellent anti-reflection layer for visible light, and it can form a uniform and non-uniform thin film, and it can form a low refractive index layer with particularly excellent adhesion.

The hardening means of the resin constituting the low refractive index layer may also be the same as that of the hard coat layer. The hardening method is the same. When a heating means is used for hardening treatment, it is preferred to add a thermal polymerization initiator that initiates polymerization of a polymerizable compound by heating to the fluorine-based resin composition by heating.

The base film is not particularly limited, and examples thereof include polyester resins, Acetate resin, Polyether resin, Polycarbonate resin, Polyamide resin, Polyimide resin, Polyolefin resin, (Meth) acrylic resin, Polyvinyl chloride resin, Poly partial Vinyl chloride-based resins, polystyrene-based resins, polyvinyl alcohol-based resins, polyarylate-based resins, polyphenylene sulfide-based resins, aromatic polyetherketone-based resins, and the like. Among them, polyester-based resins, polycarbonate-based resins, and polyolefin-based resins can be preferably used.

Examples of the polyolefin-based resin used in the substrate film include polyethylene At least one of olefin, polypropylene, and cyclic polyolefin is used as the base material of the constituents. Examples of the cyclic polyolefin include those having a norbornene skeleton.

Examples of the polycarbonate-based resin include an aromatic polycarbonate having a bisphenol (bisphenol A) as a matrix, an aliphatic polycarbonate such as diethylene glycol bis (allyl carbonate), and the like. .

Examples of the (meth) acrylic resin include poly (meth) acrylate, poly (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, and the like. .

Examples of the polyester-based resin include polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate (PEN At least one of) is used as a base material of a constituent.

Examples of the aromatic polyetherketone-based resin include polyetheretherketone (PEEK).

In the present invention, the thickness of the substrate film is not particularly limited, and may be set to 5 to 300 μm. The thickness is preferably 10 μm or more in terms of operability or prevention of wrinkles or distortions generated in the laminated body. From the viewpoint of thinning, the thickness is preferably 200 μm or less.

The more preferable lower limit of the thickness of the substrate film is 15 μm, and the more preferable upper limit is 125 μm.

The substrate film may be subjected to an etching treatment or a primer treatment such as sputtering, corona discharge, ultraviolet irradiation, electron beam irradiation, chemical treatment, or oxidation in advance on the surface thereof. By performing these processes in advance, the adhesion with the hard coat layer or the hardened layer of the monofunctional monomer formed on the substrate film can be improved. Alternatively, before forming a hard coat layer or a hardened layer, Agent cleaning or ultrasonic cleaning can be used to remove dust and clean the surface of the substrate film.

The laminated body of the present invention has the following structure: a layer is provided on one surface of the base film The above optical functional layer has a low contact angle layer on the other side of the base film; from the viewpoint of imparting curl resistance, crack resistance, and damage resistance at the time of manufacturing, it is preferable that the above-mentioned low contact is The corner layer side imparts hard coating performance.

Examples of the method for imparting the hard-coating performance include a method for imparting a hard-coating performance to the low-contact-angle layer or a method for forming a hard-coat layer between the low-contact-angle layer and the substrate film.

Examples of the method for imparting hard coating performance to the low contact angle layer include, for example, Method: Add the same radiation-hardenable resin and photopolymerization initiator as the composition for the hard coat layer to the composition for the low contact angle layer, apply to the substrate film to dry, and then perform ultraviolet rays The above-mentioned low contact angle layer is formed by irradiation of active energy rays.

As a method for forming a hard coat layer between the above-mentioned low contact angle layer and the substrate film, an example For example, it is possible to form a hard coat layer on the surface of the above-mentioned substrate film by the same method as that of forming the above-mentioned hard coat layer as the optical functional layer, and then to form the hard coating layer on the side opposite to the substrate film. Method for forming the above-mentioned low contact angle layer.

The thickness of the hard coat layer formed between the above-mentioned low contact angle and the base film is preferably the same as that of the above-mentioned hard coat layer as the optical functional layer in terms of giving the curl resistance better. .

In addition, the "thickness of the same degree" means a case where the difference between the thickness of the hard coat layer between the low contact angle and the base film and the thickness of the hard coat layer as the optical functional layer is 1.0 μm or less.

The laminated system of the present invention is used for the optical functional layer and the substrate film. A patterned transparent conductive layer is formed on the opposite side.

The transparent conductive layer is not particularly limited, and examples thereof include a transparent conductive layer containing a metal oxide or 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), zinc aluminum oxide (AZO), gallium zinc oxide (GZO), tin oxide (SnO ₂ ), A film made of indium oxide (In ₂ O ₃ ), tungsten oxide (WO ₃ ), or the like is preferred. Among them, indium tin oxide (ITO) is preferred.

The thickness of the transparent conductive layer containing the above metal oxide is not particularly limited. It is necessary to make a continuous film with good conductivity with a surface resistance of 200Ω / □ or less. If the thickness becomes too thick, it will lead to a reduction in transparency, etc., so the lower limit of the above thickness is preferred. It is 15 nm, a preferable upper limit is 45 nm, a more preferable lower limit is 20 nm, and a more preferable upper limit is 40 nm. If the thickness is less than 15 nm, the surface resistance increases and it becomes difficult to form a continuous film. Moreover, when it exceeds 45 nm, transparency may fall, etc. may exist.

The transparent conductive layer containing the above-mentioned metal oxide can be formed by a sputtering process, and it is preferable to perform a heat treatment at 150 ° C. for 60 minutes after the sputtering process to crystallize it.

By crystallizing the transparent conductive layer, the transparent conductive layer is reduced in resistance, and transparency and durability are also improved.

Moreover, as a method of patterning the transparent conductive layer formed by the said sputtering process, a well-known etching method etc. are mentioned. The heat treatment of the transparent conductive layer may be performed before the transparent conductive layer is patterned, or may be performed after the transparent conductive layer is patterned.

In addition, the optical functional layer of the laminated body is formed on a surface opposite to the substrate film side. The conductive laminated body of the patterned transparent conductive layer is also one of the present invention.

Regarding the thickness of the transparent conductive layer containing the conductive fibrous filler, The conductive properties are not particularly limited. In consideration of conduction, it is preferable that the conductive fibrous filler is locally present in any part of the layer. By making the conductive fibrous filler locally in the layer, not only the conduction becomes good, but also the minimum fiber content is required, and the total light transmittance can be increased and the haze can be reduced.

The preferred upper limit of the haze value of the laminated body of the present invention is 5%, the more preferred upper limit is 1.5%, and the further preferred upper limit is 1%. The preferred lower limit of the total light transmittance is 80%, and the preferred lower limit is 90%. .

The haze value is the total of the internal haze value and the surface haze value, and is a value measured in accordance with JISK-7136. Examples of the measurement device include a reflection-transmittance meter HM-150 (Murakami Color Technology Research Institute).

The total light transmittance is a value measured in accordance with JIS K-7361. Examples of the measurement device include a reflection-transmittance meter HM-150 (Murakami Color Technology Research Institute).

Moreover, from the point which can further reduce the electric resistance value of a conductive laminated body, it is more preferable that the said conductive fibrous filler exists locally in the vicinity of the surface of a layer.

In the transparent conductive layer containing the conductive fibrous filler, the thickness is preferably Reach the fiber diameter of conductive fibrous filler. If the thickness of the transparent conductive layer is greater than the fiber diameter of the conductive fibrous filler, the amount of the adhesive resin entering the contact point of the conductive fibrous filler may increase and the conduction may deteriorate, and the target resistance value may not be obtained.

As the thickness of the transparent conductive layer containing the conductive fibrous filler, specifically, it is preferably about 10 to 200 nm. If the thickness of the transparent conductive layer is less than 10 nm, there are cases in which an uncoated region is generated when the transparent conductive layer is formed while coating the composition for a transparent conductive layer. In the case where the transparent conductive layer is formed by the following transfer method, the transparent conductive layer is not transferred. On the other hand, if it exceeds 200 nm, the fiber diameter of the conductive fibrous filler must be made thicker than the preferable range described below, so that the haze of the conductive laminate may increase and the total light transmittance may decrease. Not optically appropriate. The thickness of the transparent conductive layer containing the conductive fibrous filler is more preferably 50 nm or less, and even more preferably 30 nm or less.

In addition, the thickness of the transparent conductive layer can be obtained, for example, by using an electron microscope such as SEM, STEM, or TEM to determine the thickness of the transparent conductive layer by observing the cross section of the transparent conductive layer at 1000 to 500,000 times. Average of 10 locations.

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 exceeds 200 nm, the haze value of the conductive laminate may increase or the light transmission performance may become insufficient. From the viewpoint of the conductivity of the transparent conductive layer, the preferable lower limit of the fiber diameter of the conductive fibrous filler is 10 nm, and the more preferable range of the fiber diameter is 15 to 180 nm.

In addition, if the fiber length of the above-mentioned conductive fibrous filler is less than 1 μm, a transparent conductive layer having sufficient conductive properties may not be formed, and agglomeration may occur, resulting in an increase in haze value or a decrease in light transmission performance. Therefore, the preferable upper limit of the fiber length is 500 μm, and the more preferable range of the fiber length is 3 to 300 μm, and the more preferable range is 10 to 30 μm.

In addition, the fiber diameter and fiber length of the conductive fibrous filler can be determined, for example, as follows: using an electron microscope such as SEM, STEM, and TEM, the fiber diameter of the conductive fibrous filler can be determined by 1,000 to 500,000 times. And the fiber length was measured and averaged at 10 locations.

The conductive fibrous filler is preferably selected from conductive carbon fibers, At least one of the group consisting of metal fibers and metal-coated synthetic fibers.

Examples of the conductive carbon fiber include a vapor deposition carbon fiber (VGCF), a nano carbon tube, a wire cup, and a wire wool. These conductive carbon fibers may be used alone or in combination of two or more.

As the metal fiber, for example, stainless steel, iron, gold, silver, Fibers made of aluminum, nickel, titanium, etc., which are drawn into a thin and long drawing method or cutting method. Such metal fibers can be used alone or in combination of two or more. Among these metal fibers, a metal fiber using silver is preferred in terms of excellent electrical conductivity.

Examples of the method for producing the metal fiber using the silver include a method of reducing silver compounds such as silver nitrate and silver sulfate in a solution. As a method of reducing silver sulfate in a solution, following Y.Sun, B.Gates, The "polyol" method described in B. Mayers, & Y. Xia, "Crystalline silver nanowires by soft solution processing", Nanoetters, (2002), 2 (2) 165-168, can be cited by polyvinylpyrrolidone ( A method for synthesizing by reducing silver sulfate dissolved in ethylene glycol in the presence of PVP).

Examples of the metal-coated synthetic fibers include acrylic fiber coatings. Fabrics made of gold, silver, aluminum, nickel, titanium, etc. Such metal-coated synthetic fibers may be used alone or in combination of two or more. Among these metal-coated synthetic fibers, a metal-coated synthetic fiber using silver is preferred in terms of excellent electrical conductivity.

As the content of the conductive fibrous filler, for example, the content of The resin component of the electric layer is 100 parts by mass, preferably 20 to 3000 parts by mass. If it is less than 20 parts by mass, there may be cases where a transparent conductive layer having sufficient conductivity cannot be formed, and if it exceeds 3000 parts by mass The amount may increase the haze of the conductive laminated body or the light transmission performance may be insufficient. In addition, there is a case where the amount of the adhesive resin entering the conductive fibrous filler increases, which leads to deterioration of the conduction of the transparent conductive layer, and the conductive laminated body of the present invention may not be able to obtain a target resistance value. A more preferable lower limit of the content of the conductive fibrous filler is 50 parts by mass, and a more preferable upper limit is 1000 parts by mass.

A part of the conductive fibrous filler is preferably from the transparent conductive layer. The surface is prominent. When the conductive laminated body of the present invention is manufactured by a transfer method using a transfer film, the transparent conductive layer is laminated and pressurized so that the side of the transparent conductive layer faces the object to be transferred, so that The conductive fibrous filler protrudes from the surface of the transparent conductive layer that is opposite to the substrate film side (that is, the surface of the transparent conductive layer that is pressed against the transferee), whereby the protruding conductive fibers The filler is transferred in a state of being embedded in the transferred body. As a result, the obtained conductive laminated body has improved solvent resistance, and the conductive pattern can be formed by an etching method or the like. In addition, the conductive laminate has excellent scratch resistance.

A part of the conductive fibrous filler is preferably away from the transparent conductive layer. The surface protrudes from 5 to 600 nm. In the present invention, the range of the vertical distance from the flat portion of the surface of the transparent conductive layer that does not protrude from the conductive fibrous filler to the front end of the protruded conductive fibrous filler is preferably 5 to 600 nm. If the vertical distance is less than 5 nm, the solvent resistance of the conductive laminate may not be improved. 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 is 200 nm.

In addition, the vertical distance of the conductive fibrous filler protruding from the surface of the transparent conductive layer can be obtained, for example, by using an electron microscope such as SEM, STEM, and TEM at 1000 Observe the surface of the transparent conductive layer by ~ 500,000 times, and determine the 10 points obtained by measuring the vertical distance from the flat part of the surface of the transparent conductive layer to the front end of the protruding conductive fibrous filler. Site average.

In the conductive laminated body of the present invention, the constitution of the transparent conductive layer is as described in the above table. The ratio of the conductive material elements of the above-mentioned conductive fibrous filler is 0.15 to 5.00 at% in terms of atomic composition percentage. If it is less than 0.15 at%, there will be a problem that the conductivity of the conductive laminated body of the present invention becomes insufficient or the etching rate is reduced. If it exceeds 5.00 at%, the light transmittance of the conductive laminate of the present invention is reduced, and the scratch resistance is poor. A preferable lower limit of the ratio of the conductive material elements constituting the conductive fibrous filler existing on the surface of the transparent conductive layer is 0.20at%, a preferable upper limit is 2.00at%, a more preferable lower limit is 0.30at%, and a more preferable upper limit is 1.00at%.

In addition, the ratio of the conductive material elements constituting the conductive fibrous filler existing on the surface of the transparent conductive layer can be measured using X-ray photoelectron spectrometry under the following conditions.

Accelerating voltage: 15kV

Emission current: 10mA

X-ray source: Al Dual Anode

Measurement area: 300 × 700μmΦ

Measurement from the surface to a depth of 10 nm

n = 3 times average

Furthermore, it is preferable that the transparent conductive layer having such a surface is derived from a conductive fibrous filler and formed on the surface to such an extent that solvent resistance and abrasion resistance can be achieved, and further a low haze value and extremely high light transmittance are formed. The uneven shape.

Examples of the method for producing the conductive laminated body of the present invention include the following: Method: a method of laminating a transparent conductive layer on a substrate film by a general coating method; further a method of laminating a protective layer thereon at a level capable of obtaining a target resistance value; and having at least a substrate film A transfer film having the above-mentioned conductive layer, a method for transferring the above-mentioned conductive layer to a transfer target, and the like. In the case where the electrical resistance of the conductive laminate is lowered, it is preferably produced by a method having a transfer step of transferring the conductive layer to a transfer target.

In the above transfer step, a transfer film having at least a conductive layer on a base film is used.

The transfer target is not particularly limited as long as it is a member capable of providing a conductive layer, and examples thereof include a substrate made of any material such as glass, resin, metal, ceramic, or the like. Transferred layers such as resin layers or adhesive layers.

The laminated body of the present invention can be used for display display of televisions, computers and the like. Coyo It is best used on the surface of high-definition imaging displays or touch panels such as LCD, organic, inorganic LED, PDP, and electronic paper.

Among them, the conductive laminated body of the present invention, in which the patterned transparent conductive layer is formed on the side of the optical functional layer of the laminated body opposite to the substrate film side, can be preferably used for the capacitive touch. Control panel. In addition, a touch panel using the conductive laminated body of the present invention is also one of the present invention. The touch panel of the present invention is preferably a touch panel of an electrostatic capacitance method.

The laminated system of the present invention is composed of the above-mentioned structure. Therefore, even if the film with an adhesive layer is bonded to the surface of the base film opposite to the transparent conductive layer side and the heat treatment is performed, the film with the adhesive layer is heated. In the case of peeling, it is also possible to prevent the contact angle of water from increasing on the surface of the film to which the adhesive layer is attached, and the adhesion to be lowered.

The contents of the present invention will be described by the following examples, but the contents of the present invention are not limited to the embodiments. In addition, as long as it is not specifically limited, in this embodiment, "part" and "%" represent "mass part" and "mass%", respectively.

(Example 1)

The hard-coating composition with the following formula was applied on one side of a biaxially-stretched polyester film (manufactured by Toyobo Co., Ltd., A4300; with undercoating) having a thickness of 2.0 μm so that the thickness after drying became 2.0 μm Coating)) to form a hard coating.

Next, using the composition for the high refractive index layer and the composition for the low refractive index layer described below, the high refractive index layer (thickness 50 nm, refractive index 1.68) and the low refractive index layer (thickness 30 nm, refractive index 1.48) were used. Sequentially formed on the hard coat of a biaxially stretched polyester film.

In addition, the drying conditions of the optical functional layer composed of the hard coat layer, the high refractive index layer, and the low refractive index layer were all set to 70 ° C. and 60 seconds. In addition, after drying each of 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, ultraviolet irradiation (150 mJ / cm ² ).

In addition, a coating film was formed by coating the composition 1 for a low contact angle layer with the following formula on the other surface of the above-mentioned biaxially stretched polyester film, and drying was performed at 70 ° C and 60 seconds to obtain a biaxially-oriented polyester film. A laminated body of a low contact angle layer with a thickness of 20 nm is provided on the other side of the axially-stretched polyester film.

<Composition for Hard Coating>

Dipentaerythritol hexaacrylate (weight average molecular weight 580, double bond equivalent 100) 50 parts

Photopolymerization initiator (manufactured by BASF, 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 (Irgacure 127, manufactured by BASF Corporation) 0.7 part

Liquid containing high refractive index particles (a dispersion of zirconia particles having an average particle size of 10 to 15 nm in methyl ethyl ketone and 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 (manufactured by BASF, Irgacure 127) 1 part

Liquid containing low-refractive-index particles (one obtained by dispersing silica particles with an average particle size of 10 to 15 nm in methyl isobutyl ketone and setting the solid content to 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 for low contact angle layer 1 of Example 1 was changed to the composition for low contact angle layer 2 of the following formula, and the composition 2 for low contact angle layer was applied so that the thickness after drying became 2.0 μm. A laminated body was obtained in the same manner as in Example 1 except that a coating film was formed, followed by drying at 70 ° C. for 60 seconds, and irradiating with ultraviolet rays (150 mJ / cm ² ) to form a low contact angle layer.

<Composition 2 for Low Contact Angle Layer>

16 parts of acrylic polymer (weight average molecular weight 160,000, double bond equivalent 1,000, solid content 25%)

Dinepentaerythritol hexaacrylate (flat weight 580, double bond equivalent 100) 4 parts

Photopolymerization initiator (Irgacure 127, manufactured by BASF) 0.8 part

30 parts of methyl isobutyl ketone

(Example 3)

After the optical functional layer was formed in the same manner as in Example 1, the composition for the hard coat layer was coated on the other surface of the biaxially stretched polyester film so that the thickness after drying became 2.0 μm to form a coating. The film is then 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, using the composition 1 for a low contact angle layer, a low contact angle layer was formed on the hard-coat layer formed on the other surface of the biaxially stretched polyester film so that thickness might be 20 nm. The coating film formed by applying the composition 1 for a low contact angle layer was dried at 70 ° C. for 60 seconds to obtain a laminated body.

(Example 4)

A laminated body was obtained in the same manner as in Example 1 except that the composition 1 for a low contact angle layer of Example 1 was changed to the composition 3 for a low contact angle layer of the following formula.

<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

A laminated body was obtained in the same manner as in Example 1 except that the composition 1 for a low contact angle layer of Example 1 was changed to the composition 4 for a low contact angle layer of the following formula.

<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 laminated body was obtained in the same manner as in Example 1 except that the composition 1 for a low contact angle layer of Example 1 was changed to the composition 5 for a low contact angle layer of the following formula.

<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 laminated body was obtained in the same manner as in Example 1 except that the composition 1 for a low contact angle layer of Example 1 was changed to the composition 6 for a low contact angle layer of the following formula.

<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)

The composition 1 for the low contact angle layer of Example 1 was changed to the composition for the low contact angle layer of the following formula Except for the composition 7, a laminated body was obtained in the same manner as in Example 1.

<Composition 7 for Low Contact Angle Layer>

Acrylic polymer (weight average molecular weight 63,000, double bond equivalent 200) 16 parts

Methyl isobutyl ketone 1000 parts

(Example 9)

The composition 1 for a low contact angle layer of Example 1 was changed to the composition 8 for a low contact angle layer of the following formula, the coating film was dried under the same conditions as in Example 1, and the dried coating film was then dried. A laminated body was obtained in the same manner as in Example 1 except that ultraviolet irradiation (150 mJ / cm ² ) was performed 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

Photopolymerization initiator (manufactured by BASF, Irgacure 184) 2 parts

Methyl isobutyl ketone 3000 parts

(Comparative example 1)

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

<Composition 9 for Low Contact Angle Layer>

Dipentaerythritol hexaacrylate (weight average molecular weight 580, double bond equivalent 100) 50 parts

Photopolymerization initiator (manufactured by BASF, Irgacure 184) 2 parts

Silicone-based leveling agent (manufactured by Daiichi SEIKI, SEIKA BEAM 10-28, solid Ingredients 10%) 1 serving

Methyl isobutyl ketone 3000 parts

(Comparative example 2)

A laminated body was obtained in the same manner as in Example 2 except that the composition 2 for a low contact angle layer of Example 2 was changed to the composition 10 for a low contact angle layer of the following formula.

<Composition 10 for Low Contact Angle Layer>

Dipentaerythritol hexaacrylate (weight average molecular weight 580, double bond equivalent 100) 50 parts

Photopolymerization initiator (manufactured by BASF, Irgacure 184) 2 parts

Silicone leveling agent (manufactured by Dainichi Seika Co., Ltd. SEIKA BEAM 10-28, solid content 10%) 1 part

Methyl isobutyl ketone 200 parts

(Comparative example 3)

A laminated body was obtained in the same manner as in Example 3 except that the composition 1 for a low contact angle layer was changed to the composition 9 for a low contact angle layer described above.

(Reference example 1)

A laminated body was obtained in the same manner as in Example 1 except that the composition 1 for a low contact angle layer was changed to the composition 9 for a low contact angle layer described above.

As described below, the physical properties of the laminated bodies obtained in the examples, comparative examples, and reference examples were measured and evaluated. Each result is shown in Table 1.

[Wetting tension]

An adhesive layer was formed on the above-mentioned biaxially stretched polyester film having a thickness of 125 μm to obtain a film with an adhesive layer.

The following adhesive solution was used. As the adhesive for forming the above-mentioned adhesive layer, an acrylic adhesive (manufactured by Soken Chemical Co., Ltd .: SK-Dyne 1811L (solid content: 23%)) and an isocyanate-based crosslinking agent (manufactured by Kenken Chemical Co., Ltd.) were used: TD75 (solid content 75%)), mixed with an acrylic adhesive: isocyanate-based crosslinking agent = 100: 1 (mass ratio), and dissolved in a solvent such that the solid content becomes 20% (mass basis) Ethyl acetate). This adhesive solution was applied on 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 is attached to the surface of the adhesive layer for protection.

The film with an adhesive layer is used after peeling the said release film.

For the laminates obtained in the examples and comparative examples, based on JIS K6768 (1999), the wetting tension (initial) of the surface of the low contact angle layer before lamination of the film with the adhesive layer was After the condition of minutes, the wetting tension (after heating) after peeling the film with the adhesive layer was measured.

In addition, as a test mixture liquid, a liquid having a wetting tension of 22.6 to 73.0 mN / m was prepared.

[Attachment]

For the laminates obtained in the examples and comparative examples, the surface of the low-contact-angle layer after peeling the film with the above-mentioned adhesive layer after heating at 150 ° C for 60 minutes was performed by the method described below. The adhesiveness was measured and evaluated based on the following criteria.

A 1mm thick stainless steel plate (25mm or more in width) was attached to one of the two sides of an adhesive tape (VHB double-sided tape Y-4920, manufactured by Sumitomo 3M), and a 2kg roller was reciprocated twice to cut the width to 25mm. The laminated body obtained in the examples and comparative examples with a length of 150 mm was adhered to the other adhesive surface of the above two-sided adhesive tape to prepare a measurement sample.

After the measurement sample was left at room temperature for 72 hours, a peel tester (apparatus name: small table tester "EZ-LX" manufactured by Shimadzu Corporation) was used based on JIS Z 0237 at a tensile speed of 300 mm / minute, The peeling strength (N / 25mm width) was measured under the condition of a peeling angle of 180 degrees.

◎: Peel strength is 10N / 25mm or more

○: Peel strength is 5N / 25mm or more and less than 10N / 25mm

×: Peel strength is less than 5N / 25mm

(Steel wool resistance (SW resistance))

For the laminates obtained in the examples and comparative examples, the surface of the low contact angle layer before the film with the above-mentioned adhesion layer was bonded with a specific friction load (150 g / cm ² ) using steel wool of # 0000 with a steel wool of # 0000 It rubbed back and forth 10 times, and the damage state of the subsequent coating film was visually evaluated and evaluated based on the following criteria.

◎: Not damaged (0 scars)

○: Hardly damaged (about 1 to 9 scars)

×: Significantly damaged (10 or more scars or a state with numerous band-shaped scars) or peeling of the coating film

(Tacky)

About the tackiness (tacky feel) of the surface of the low contact angle layer before the above-mentioned film with an adhesion layer was laminated on the laminates obtained in the examples and comparative examples, it was evaluated based on the following criteria by finger contact.

○: No stickiness (even if the fingers are in contact, the fingers will not stick, and the fingers will slide without getting stuck)

×: It has a sticky feel (it will not move if it is in contact with fingers or it will be stuck even if it moves)

As shown in Table 1, the adhesiveness after heating was laminated in Examples 1 to 5. In the body, the peeling strength was 10N / 25mm or more, which is a good result. In the laminates of Examples 6 to 9, the peeling strength was 5N / 25mm or more and less than 10N / 25mm, which is a better result. The peel strength of the laminates of Comparative Examples 1 to 3 was less than 5N / 25mm, and the adhesion to the two-sided adhesive tape was poor.

In the laminated body of the examples, regarding the SW resistance, Example 2 in which the hard contact performance was imparted to the low contact angle layer, and the example in which a hard coat layer was provided between the substrate film and the low contact angle layer. The laminated body of 3 was not damaged and was particularly good. The laminated bodies of Examples 1, 4 to 9 were hardly damaged.

In addition, the tackiness was excellent in the laminates of all the examples.

In addition, the difference in wetting tension between the laminates of Examples 1 to 8 before and after heating was small, and was 6 mN / m or less. In the laminates of Examples 1 to 8 in which the difference in wetting tension was as small as described above, the components of the adhesive layer shifted less to the low contact angle layer, and the adhesive components of the adhesive layer shifted to the low contact angle layer. Suppression can not only suppress the decrease of the adhesion, but also suppress the bad influence on the optical characteristics such as the light transmittance of the optical film. In addition, the difference in wetting tension between the laminates of Example 9 is larger than that of the laminates of Examples 1 to 8, but the wetting tension after heating is 30 mN / m or more, and the difference between the wetting tensions is 20 mN / m or less, successfully securing the required adhesion performance.

Moreover, the haze values of the laminated bodies in the examples are all 5% or less, and the total light transmittances are all 80% or more.

On the other hand, since the laminated body of Reference Example 1 has a wetting tension after heating of 30 mN / m or more, the adhesion evaluation is good, but the low contact angle layer before heating has a large viscosity and cannot accurately measure the wetting. Wet tension. In addition, since the difference in wetting tension is a large value exceeding 20 mN / m, not only the adhesive component of the adhesive layer has a larger migration range to the low contact angle layer, but also the initial wetting tension is larger, so the result Will have low contact angle, poor SW resistance or poor tackiness, etc. Adverse conditions, but not good in actual use.

In the multilayer system of the example, a transparent conductive layer (thickness: 20-30 μm) containing ITO was formed by a sputtering process, and the patterned transparent conductive layer was invisible, and it was confirmed that there were no problems with optical characteristics.

Furthermore, Example 3 was cut into 100 mm × 100 mm, and a transparent conductive layer was formed by sputtering. The transparent conductive layer was then placed on the platform and the distance between the four corners and the platform was measured. As a result, the distance was within 5 mm, and the curl resistance was also excellent. Among them, the above-mentioned Example 3 is a hard coating layer which becomes an optical functional layer and a hard coating layer between the substrate film and the low contact angle layer having the same thickness.

On the other hand, in the laminates of Comparative Examples 1 to 3, the wetting tension was less than 30 mN / m, and sufficient adhesiveness could not be provided.

Also, in the multilayer body of Reference Example 1, when the sputtering process for forming a transparent conductive layer was performed, the wound body of the multilayer body had a tacky feel and stuck, so that the multilayer body could not be rolled up and could not be formed transparent Conductive layer.

In addition, by comparing the laminated body of Example 9 and the laminated body of Comparative Example 1, it was found that those without a leveling agent in the low contact angle layer exhibited excellent adhesion.

In addition, in the same manner as in Example 1, a coating film was formed on one surface of a biaxially stretched polyester film having a thickness of 100 μm using the composition for a hard coat layer, and after the semi-curing, a silver nano-film was formed by a transfer method. Transparent conductive layer of rice noodles. Thereafter, the hard coat layer was hardened, and a low contact angle layer was formed on the other side of the above-mentioned biaxially stretched polyester film by the same method as in Example 1 to obtain a conductive laminate. The conductive laminate is heated to reduce the resistance of the transparent conductive layer. As a result, the wetting tension after heating is 30 mN / m or more, and the difference between the wetting tensions is 20 mN / m or less. Adhesive performance. In addition, there are no problems with optical characteristics.

[Industrial availability]

The present invention can provide a method for attaching a film with an adhesive layer to a substrate film. When the surface opposite to the side of the transparent conductive layer is heated and the film with the adhesive layer is peeled off after heat treatment, the contact angle of water on the surface to which the film with the adhesive layer is attached can also be prevented from increasing. Laminated body with reduced adhesion.

Claims (12)

A laminated body having one or more optical functional layers on one side of a base film and a low contact angle layer on the other side of the base film. The laminated system is used for connecting the optical functional layer to the base. The film side is a patterned transparent conductive layer formed on the opposite side, which is characterized in that the film with the adhesive layer is adhered to the surface of the low contact angle layer and heated at 150 ° C for 60 minutes. When the film with the adhesive layer is peeled off, the wetting tension of the surface of the low-contact-angle layer specified by JIS K6768 (1999) is 30 mN / m or more. For example, the laminated body of item 1 of the scope of patent application, wherein the surface of the low contact angle layer before the film with the adhesive layer is bonded is the condition of wetting tension specified by JIS K6768 (1999) and conditions of 150 ° C and 60 minutes The difference in wetting tension between the surface of the low contact angle layer and the surface of the low contact angle layer after peeling the film with the adhesive layer after heating is 20 mN / m or less. For example, the laminated body of item 1 or 2 of the patent application scope has 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 as one or more optical functional layers. For example, the laminated body according to item 1 or 2 of the scope of patent application, wherein the high refractive index layer and the low refractive index layer are sequentially laminated on the substrate film as one or more optical functional layers. For example, the laminated body according to item 1 or 2 of the scope of patent application, in which a hard coat layer, a high refractive index layer, and a low refractive index layer are sequentially laminated on a substrate film as one or more optical functional layers. For example, the laminated body according to item 1 or 2 of the patent application scope, wherein the low contact angle layer is composed of an uncured (meth) acrylic resin alone or a composition containing the aforementioned uncured (meth) acrylic resin . For example, the laminated body according to item 1 or 2 of the scope of patent application, wherein the low contact angle layer side of the substrate film is given a hard coat property. For example, the laminated body according to item 7 of the patent application scope, wherein the low contact angle layer has hard coating performance. For example, the laminated body according to item 7 of the patent application scope, wherein a hard coating layer is provided between the low contact angle layer and the substrate film. For example, the laminated body according to item 1 or 2 of the patent application scope, wherein the transparent conductive layer contains indium tin oxide or a conductive fibrous filler. A conductive laminated body whose surface on the side opposite to the substrate film side of the optical functional layer of the laminated body according to item 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 of the scope of patent application A patterned transparent conductive layer is formed thereon. A touch panel is provided with a conductive laminated body with the scope of application for item 11.