JP6405883B2 - LAMINATE, CONDUCTIVE LAMINATE, AND TOUCH PANEL - Google Patents

Description

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

At present, a touch panel is widely used as an input means in various devices including a display device having a display panel such as a liquid crystal display panel, such as a PDA (Personal Digital Assistants), a portable information terminal, a car navigation system, and the like.
The touch panel is a transparent conductive film in which a transparent conductive layer made of ITO (indium tin oxide) or the like is provided on a base film through optical functional layers such as a hard coat layer, a high refractive index layer, and a low refractive index layer. In general, the display panel is manufactured separately from the display panel and disposed on the front surface of the display panel.

Here, all or some of the optical functional layers such as the transparent conductive layer and the low refractive index layer are generally provided on the base film through a sputtering process to form a laminate. However, in this sputtering treatment, the laminate may be charged due to contact between the laminate and a production facility such as a metal roll or friction, and this charging may cause a decrease in the transportability of the laminate, a transparent conductive layer, etc. There has been a problem in that defects (defects) such as pinholes and dents and foreign matters are likely to occur.
In addition, when the sputtering process is performed in a vacuum, the above-described problem caused by charging of the laminate is not effective even if a static eliminator such as an ionizer is installed even though the laminate is more easily charged. It was easy to happen.

On the other hand, as a method for preventing charging of the laminate, a method of imparting antistatic performance to the laminate can be considered.
For example, Patent Document 1 discloses a laminate in which a high refractive index layer is provided between a base material and a conductive layer, and antistatic performance is imparted to the high refractive index layer.
For example, Patent Document 2 discloses a laminate in which a hard coat layer is provided between a base material and a conductive layer, and the antistatic performance is imparted to the hard coat layer.

However, in such a layer structure of the conventional laminate, since the layer having antistatic performance does not exist on the outermost surface, the effect of preventing the laminate from being charged is small. In addition, when heat treatment is performed to reduce the resistance of the formed transparent conductive layer, the conductive layer and the layer having antistatic performance are close to each other. There is a possibility that the antistatic component of the layer having a contact with the conductive layer causes a short circuit, resulting in poor conductivity.

JP 2004-322380 A JP 2010-177194 A

In view of the present situation, the present invention can suitably prevent charging by vacuum film formation (sputtering treatment, etc.) for forming all or part of an optical functional layer such as a transparent conductive layer and a low refractive index layer, and is transparent. When a conductive layer is formed, an object is to provide a laminate, a conductive laminate, and a touch panel that are excellent also in the conductive performance of the transparent conductive layer.

The present invention has one or more optical functional layers on one surface of the base film, a transparent layer on the other surface of the base film, and the base film of the optical functional layer. A laminate used for forming a transparent conductive layer patterned on the side opposite to the side, wherein the transparent layer has antistatic performance on the side opposite to the base film side , and the charging The prevention performance is a method in which the transparent layer contains an electron conductive antistatic agent, or an electron conductive antistatic agent and a resin component on the side of the transparent layer opposite to the base film side. The laminate is provided by a method of forming an antistatic layer .

In the laminate of the present invention, the transparent layer is a hard coat layer, and the hard coat layer preferably contains an electron conduction type antistatic agent.
In addition, the transparent layer has one or more laminated structures including a hard coat layer, and a charge containing an electron conductive antistatic agent and a resin component on the side surface opposite to the base film side of the transparent layer. It is preferable to have a prevention layer.
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 function layers.
Moreover, it is preferable that the high refractive index layer and the low refractive index layer are laminated | stacked on the base film in this order as one or more optical function layers.
In addition, as the one or more optical function layers, a hard coat layer, a high refractive index layer, and a low refractive index layer are preferably laminated on the base film in this order .
The transparent conductive layer is preferably made of indium tin oxide.

In addition, the present invention is also a conductive laminate in which a patterned transparent conductive layer is formed on the side opposite to the base film side of the optical functional layer of the laminate.
Moreover, this invention is also a touch panel provided with the said electroconductive laminated body.
The present invention is described in detail below.

As a result of intensive studies on the conventional problems, the present inventors have provided a transparent layer having an antistatic property on the side surface opposite to the side on which the transparent conductive layer is formed of the base film, thereby charging the laminate by sputtering. The inventors have found that a laminate that can be suitably prevented and is excellent in the conductive performance of the formed transparent conductive layer is obtained, and the present invention has been completed.
In the present specification, “transparent” in the “transparent conductive layer” means having a region that transmits visible light in the plane, and may be substantially translucent. “Transparent” specifically means that, for example, the light transmittance at a wavelength of 550 nm is 50% or more.

The laminate of the present invention has a transparent layer on one surface of the base film.
The transparent layer preferably has a pencil hardness of F or higher, more preferably H or higher, according to a pencil hardness test (load 4.9 N) according to JIS K5600-5-4 (1999).
The transparent layer is preferably a hard coat layer that ensures the hard coat properties of the laminate of the present invention. For example, a hard layer containing an ionizing radiation curable resin that is a resin curable by ultraviolet rays and a photopolymerization initiator. It is preferable that it is formed using the composition for coat layers.
The hard coat layer preferably has a pencil hardness of H or higher, more preferably 2H or higher, according to a pencil hardness test (load 4.9 N) according to JIS K5600-5-4 (1999).

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

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

The ionizing radiation curable resin can be used in combination with a solvent-drying resin. By using the solvent-drying resin in combination, film defects on the coated surface can be effectively prevented. In addition, the said solvent dry type resin means resin which becomes a film only by drying the solvent added in order to adjust solid content at the time of coating, such as a thermoplastic resin.
The solvent-drying resin that can be used in combination with the ionizing radiation curable resin is not particularly limited, and a thermoplastic resin can be generally used.
The thermoplastic resin is not particularly limited. For example, a styrene resin, a (meth) acrylic resin, a vinyl acetate resin, a vinyl ether resin, a halogen-containing resin, an alicyclic olefin resin, a polycarbonate resin, or a polyester resin. Examples thereof include resins, polyamide-based resins, cellulose derivatives, silicone-based resins, rubbers, and elastomers. The thermoplastic resin is preferably amorphous and soluble in an organic solvent (particularly a common solvent capable of dissolving a plurality of polymers and curable compounds). In particular, from the viewpoints of film forming properties, transparency, and weather resistance, styrene resins, (meth) acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (cellulose esters, etc.) and the like are preferable.

Moreover, the said composition for hard-coat layers may contain the thermosetting resin.
The thermosetting resin is not particularly limited. For example, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation Examples thereof include resins, silicon resins, polysiloxane resins, and the like.

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

As the photopolymerization initiator, when the ionizing radiation curable resin is a resin system having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, etc. may be used alone or in combination. It is preferable to use it. When the ionizing radiation curable resin is a resin system having a cationic polymerizable functional group, the photopolymerization initiator may be an aromatic diazonium salt, aromatic sulfonium salt, aromatic iodonium salt, metallocene compound, benzoin sulfone. It is preferable to use acid esters alone or as a mixture.
As the photopolymerization initiator used in the present invention, in the case of an ionizing radiation curable resin having a radical polymerizable unsaturated group, 1-hydroxy-cyclohexyl-phenyl-ketone is compatible with the ionizing radiation curable resin, and It is preferable because of less yellowing.

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

The said composition for hard-coat layers may contain the solvent.
As said solvent, it can select and use according to the kind and solubility of the resin component to be used, for example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol etc.), ethers ( Dioxane, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), Halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (methyl cello) Lube, ethyl cellosolve), cellosolve acetates, sulfoxides (dimethyl sulfoxide), amides (dimethylformamide, dimethylacetamide, etc.) and the like can be exemplified, it may be a mixed solvent thereof.
Among them, it is preferable that at least one of methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or a mixture thereof is included in the ketone solvent because of excellent compatibility with the resin and coating properties.

Although it does not specifically limit as a content rate (solid content) of the raw material in the said composition for hard-coat layers, Usually, it is preferable to set it as 5-70 mass%, especially 15-60 mass%.

The above hard coat layer composition increases the hardness of the transparent layer (hard coat layer), suppresses curing shrinkage, prevents blocking, controls the refractive index, imparts antiglare properties, particles and hard coat Depending on the purpose such as changing the properties of the layer surface, conventionally known organic, inorganic fine particles, dispersants, surfactants, silane coupling agents, thickeners, anti-coloring agents, coloring agents (pigments, dyes), A foaming agent, a leveling agent, a flame retardant, an ultraviolet absorber, an adhesion-imparting agent, a polymerization inhibitor, an antioxidant, a surface modifier, and the like may be added.

Moreover, the said composition for hard-coat layers may mix and use a photosensitizer, As a specific example, n-butylamine, a triethylamine, poly-n-butylphosphine etc. are mentioned, for example.

The method for preparing the hard coat layer composition is not particularly limited as long as each component can be uniformly mixed. For example, the composition can be performed using a known apparatus such as a paint shaker, a bead mill, a kneader, or a mixer.
Moreover, also when making the said hard-coat layer contain the antistatic agent mentioned later, the composition for hard-coat layers can be adjusted with the same method.

The method for applying the hard coat layer composition onto the base film is not particularly limited. For example, spin coating, dipping, spraying, die coating, bar coating, roll coater, meniscus coater And publicly known methods such as a flexographic printing method, a screen printing method, and a pea coater method.

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

Examples of the active energy ray irradiation include irradiation with ultraviolet rays or electron beams. 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 light fluorescent lamp, and a metal halide lamp. Moreover, as a wavelength of an ultraviolet-ray, the wavelength range of 190-380 nm can be used. Specific examples of the electron beam source include various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type.

In addition, since the preferable thickness (at the time of hardening) of the said transparent layer is 0.5-15.0 micrometers, More preferably, it is 0.8-10.0 micrometers, Since curl prevention property and crack prevention property are especially excellent, Most preferably, it is 1.5. It is in the range of ˜8.0 μm. The thickness of the transparent layer is an average value (μm) obtained by observing a cross section with an electron microscope (SEM, TEM, STEM) and measuring any 10 points. As for the thickness of the hard coat layer, as an alternative method, an arbitrary value may be obtained by measuring any 10 points using a Digimatic Indicator IDF-130 manufactured by Mitutoyo Corporation.

The transparent layer has antistatic performance on the side surface opposite to the base film side.
Since the transparent layer has antistatic performance on the side opposite to the side on which the transparent conductive layer is formed of the base film, it is possible to suitably prevent the laminate from being charged by the sputtering treatment and to prevent a short circuit of the transparent conductive layer. A laminate having excellent conductivity can be obtained.
As a method for imparting the antistatic property, for example, a method of adding an antistatic agent to the transparent layer, or a method of forming an antistatic layer on the side surface of the transparent layer opposite to the base film side is preferable. Can be mentioned.
When the method of imparting antistatic properties is a method of adding an antistatic agent to the transparent layer, the transparent layer is the hard coat layer described above, and the hard coat layer may contain an antistatic agent. preferable.
Further, when the method for imparting antistatic properties is a method for forming an antistatic layer on the side surface opposite to the base film side of the transparent layer, the transparent layer comprises one or more laminated layers including a hard coat layer. It is preferable to have an antistatic layer on the side opposite to the base film side of the transparent layer.

As the antistatic agent, there are an ion conduction type and an electron conduction type, and the electron conduction type is preferable because it has a large antistatic effect in vacuum.
Examples of the ion conduction type antistatic agent include various cationic antistatic agents having first to third amino groups such as quaternary ammonium salt and pyridium salt, sulfonate group, sulfate ester base, and phosphoric acid. Anionic antistatic agents having anionic groups such as ester bases and phosphonic acid bases, amphoteric antistatic agents such as amino acids and amino acid sulfate esters, nonionic antistatic agents such as amino alcohols, glycerols, and polyethylene glycols Examples of the electron conduction type antistatic agent include conductive polymers such as polyacetylene and polythiophene, and conductive fine particles such as metal fine particles and metal oxide fine particles.
Of these, antistatic agents, metal fine particles, and metal oxide fine particles in which a dopant is combined with a conductive polymer such as polyacetylene and polythiophene are preferable.
The conductive polymer may contain conductive fine particles.

Specific examples of the antistatic agent composed of the conductive polymer include polyacetylene, polyaniline, polythiophene, polypyrrole, polyphenylene sulfide, poly (1,6-heptadiyne), polybiphenylene (polyparaphenylene), polyparafinylene sulfide, Examples thereof include conductive polymers such as polyphenylacetylene, poly (2,5-thienylene), and derivatives thereof. Preferably, polythiophene-based conductive organic polymers (for example, 3,4-ethylenedioxythiophene ( PEDOT)).
By using the antistatic agent comprising the conductive organic polymer, the antistatic property can be maintained over a long period of time with little humidity dependency, and also has high transparency, low haze, and high hard coat properties, particularly Pencil hardness and scratch resistance against steel wool can be remarkably improved.

The metal constituting the metal fine particles is not particularly limited, and examples thereof include Au, Ag, Cu, Al, Fe, Ni, Pd, and Pt alone or an alloy of these metals.
Further, no particular limitation is imposed on the metal oxide constituting the metal oxide fine particles, for example, tin oxide _(SnO 2), antimony oxide _{(Sb 2 O} 5), antimony tin oxide (ATO), indium tin oxide (ITO), aluminum zinc oxide (AZO), fluorinated tin oxide (FTO), ZnO and the like.

The conductive fine particles preferably have an average primary particle diameter of 6 to 40 nm. If it is less than 6 nm, it is necessary to increase the amount of addition in order to impart sufficient antistatic performance to the laminate of the present invention, and transparency and adhesion between other layers may be inferior. Since the resistance of the conductive fine particles increases rapidly, the conductive performance of the transparent layer may deteriorate. If it exceeds 40 nm, the resistance of the conductive fine particles themselves is low, but the conductive fine particles are scattered in the transparent layer, and there is a possibility that good resistance cannot be obtained. The more preferable lower limit of the average primary particle diameter of the conductive fine particles is 7 nm, and the more preferable upper limit is 20 nm.
The average primary particle size of the conductive fine particles means a value measured using a MICROTRAC particle size analyzer manufactured by Nikkiso Co., Ltd. in the transparent layer composition. It means an average value of 10 particle diameters of conductive fine particles observed by a transmission electron microscope (TEM) photograph or a scanning transmission electron microscope (STEM) photograph of a layer cross section.

The conductive fine particles are preferably chain-like or needle-like. The conductive fine particles having such a shape are difficult to move in the transparent layer, and the surface resistivity of the laminate of the present invention is almost reduced even when the shrinkage of the transparent layer is somewhat caused during the durability test. It can be stably contained in the transparent layer without being changed.
Moreover, in the said transparent layer, the contact of the adjacent chain-like or needle-like electroconductive fine particles is easy to produce, and it can also be set as the transparent layer which has sufficient electroconductivity with a small addition amount.

Examples of commercially available dispersions containing the chain conductive fine particles include ELCOM-V3560, DP1197, DP1203, DP1204, DP1207, and DP1208 manufactured by JGC Catalysts & Chemicals.

By containing the antistatic agent in the hard coat layer composition, antistatic performance can be imparted to the transparent layer.
The content of the antistatic agent is appropriately adjusted according to the type, shape, size, and the like of the antistatic agent to be used. For example, the resin component of 100 mass of the total solid content of the hard coat layer composition It is preferable that it is 1-30 mass parts with respect to a part. If it is less than 1 part by mass, the antistatic performance of the laminate of the present invention may be insufficient, and if it exceeds 30 parts by mass, the adhesion to the substrate film described later may be inferior, In addition to an increase in the probability of being affected by the change, there may be a problem that the hard coat layer is colored.

The antistatic layer is preferably formed using an antistatic layer composition containing the antistatic agent and a resin component.
The content of the antistatic agent in the antistatic layer is appropriately adjusted according to the type, shape, size, and the like of the antistatic agent to be used, and when the antistatic performance is imparted to the transparent layer described above. The same is preferable.

The resin component is at least one selected from the group consisting of acrylic resin, cellulose resin, urethane resin, vinyl chloride resin, polyester resin, polyolefin resin, polycarbonate, nylon, polystyrene, and ABS resin. Preferably there is.
Examples of the acrylic resin include polymethyl methacrylate.
Examples of the cellulose resin include diacetyl cellulose, cellulose acetate propionate (CAP), and cellulose acetate butyrate (CAB).
Moreover, as said urethane type resin, a urethane resin etc. are mentioned, for example.
Examples of the vinyl chloride resin include polyvinyl chloride and vinyl chloride-vinyl acetate copolymers.
Moreover, as said polyester-type resin, a polyethylene terephthalate etc. are mentioned, for example.
Moreover, as said polyolefin resin, polyethylene, a polypropylene, etc. are mentioned, for example.
The resin component in the laminate of the present invention is preferably a thermoplastic resin. Among them, polymethyl methacrylate is preferably used because it is easy to prevent bleeding out of the antistatic agent and has excellent compatibility. It is done.

In the laminate of the present invention, the resin component is a polymer and a material that plays a role as a binder component of the antistatic layer, does not have a reactive functional group in the molecule, and is a solvent described later. Those having a solubility in the above and an antistatic agent are preferred.
When the antistatic layer contains a resin component that is a polymer as a binder component, the laminate of the present invention does not undergo curing shrinkage in the antistatic layer after the durability test, and the surface resistivity does not change. It will be a thing.
For this reason, as said resin component, what does not have a reactive functional group in a molecule | numerator is preferable. Since the resin component does not have a reactive functional group in the molecule, there is no secondary reaction of the resin component, and the performance of the antistatic layer formed after applying and drying the antistatic layer composition Can be maintained. When the resin component has a reactive group in the molecule, the resin component gradually proceeds by a dark reaction in the antistatic layer formed after coating and drying the antistatic layer composition. When the reaction of the resin component proceeds gradually over a long period of time, the resin component may be bound by the reaction, and the physical distance formed by the resin component may shrink. As a result, the physical distance of the antistatic agent in the antistatic layer is also shortened, which may cause a problem that the conductive path is increased, the conductivity of the antistatic layer is improved, and the resistance value is lowered.
Further, when the resin component has a reactive functional group in the molecule, the reactive functional group reacts by a durability test, and curing shrinkage occurs in the antistatic layer, and the surface resistivity may change.
The reactive functional group means a functional group that may react in the durability test, for example, a functional group having an unsaturated double bond such as an acryloyl group or a vinyl group, an epoxy ring, an oxetane ring, or the like. A cyclic ether group, a ring-opening polymerization group such as a lactone ring, an isocyanate group that forms urethane, and the like.
These reactive functional groups are preferably not contained in the resin component at all, but may be contained as long as they do not cause curing shrinkage in the antistatic layer after the durability test.
The level that does not cause curing shrinkage in the antistatic layer means a case where the rate of change in surface resistivity after the durability test is in the range described later.

Further, the resin component preferably has solubility in a solvent described later and compatibility with the antistatic agent.
The antistatic layer using the antistatic layer composition containing such a resin component is excellent in the dispersibility of the antistatic agent and in the stability of the surface resistivity over time.
In the present specification, “having solubility” means that a gel component is not generated in a resin solution obtained by dissolving the resin component in a solvent described later, and the solvent ratio in the resin solution is increased. It means having a characteristic that the viscosity decreases accordingly.
Further, “compatible” means that in the composition for an antistatic layer obtained by mixing the resin solution and the antistatic agent, the antistatic agent is at least 100 to 300 parts by mass with respect to 100 parts by mass of the resin component. Even if they are mixed at an arbitrary ratio in the range of the part, they are uniformly dispersed without forming a gelled product, and the above antistatic layer composition can be applied evenly to form a coating film. It means that appearance deterioration such as an increase in haze does not occur in the antistatic layer obtained by drying the film.

Moreover, it is preferable that the said resin component is what has a side chain.
The resin component having the above side chain may be difficult to move in the antistatic layer due to the steric hindrance of the side chain, and the laminate of the present invention more preferably has excellent surface resistivity stability. it can.

The resin component preferably has a weight average molecular weight of 20,000 to 200,000. If it is less than 20,000, sufficient hardness cannot be obtained for the antistatic layer, and the surface resistivity may become unstable before and after the durability test. On the other hand, when it exceeds 200,000, the viscosity of the composition for an antistatic layer may become too high to be applied.
In addition, the said weight average molecular weight can be calculated | required by polystyrene conversion by gel permeation chromatography (GPC). Tetrahydrofuran or chloroform can be used as the solvent for the GPC mobile phase. The measurement column may be used in combination with a commercially available column such as a column for tetrahydrofuran or a column for chloroform. Examples of the commercial product column include Shodex GPC KF-801, GPC KF-802, GPC KF-803, GPC KF-804, GPC KF-805, and GPC KF-800D (all trade names, manufactured by Showa Denko KK). And the like. As the detector, an RI (differential refractive index) detector and a UV detector may be used. Using such a solvent, column, and detector, the weight average molecular weight can be appropriately measured by a GPC system such as Shodex GPC-101 (manufactured by Showa Denko).

The resin component preferably has a glass transition temperature of 80 to 120 ° C. If it is less than 80 ° C., the resin component becomes soft and the resistance value may become unstable. On the other hand, if it exceeds 120 ° C., the resin component becomes hard and the adhesion to the base film may be reduced. is there. A more preferable lower limit of the glass transition temperature is 90 ° C., and a more preferable upper limit is 110 ° C. By being in this range, it is possible to ensure adhesion to the base film while obtaining a stable resistance value.

The antistatic layer preferably has a thickness of 50 to 5000 nm. If the thickness is less than 50 nm, a sufficient resistance value may not be obtained. If the thickness exceeds 5000 nm, the adhesion to the substrate film is inferior. Depending on the material of the antistatic agent, the laminate may be colored, In addition to a decrease in transmittance, it may affect the invisibility of the transparent conductive layer described later. The more preferable lower limit of the thickness of the antistatic layer is 100 nm, and the more preferable upper limit is 3000 nm.
The thickness of the antistatic layer is a value measured by observing a cross section of the antistatic layer using an electron microscope (for example, SEM, TEM, STEM, etc.).

The antistatic layer is preferably formed of a composition for an antistatic layer containing the antistatic agent, the resin component, a solvent, and the like.

As the solvent, an organic solvent in which the resin component exhibits the above-described solubility is preferably used. For example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), fat Aromatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, acetic acid) Ethyl, butyl acetate, etc.), alcohols (ethanol, isopropanol, butanol, cyclohexanol, propylene glycol monomethyl ether, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (dimethylsulfo) Sid), amides (dimethylformamide, dimethylacetamide, etc.) and the like, may be a mixed solvent.

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

The antistatic layer can be formed by applying the antistatic layer composition onto a substrate film to form a coating film and then drying the coating film.
The coating method is not particularly limited. For example, spin coating method, dip method, spray method, die coating method, bar coating method, roll coater method, meniscus coater method, flexographic printing method, screen printing method, pea coater method, etc. Can be mentioned.

The surface resistivity of the laminate of the present invention on the side opposite to the side on which the transparent conductive layer is formed is determined by the method in which the hard coat layer contains an antistatic agent, the surface of the hard coat layer opposite to the base film side In any case of forming the prevention layer, it is preferably 1 × 10 ¹³ Ω / □ or less.
If the surface resistivity exceeds 1 × 10 ¹³ Ω / □, defects such as a decrease in the transportability of the laminate, pinholes or dents in the transparent conductive layer, and adhesion of foreign matter may occur. There is.
The surface resistivity is more preferably 1 × 10 ¹¹ Ω / □ or less.

The laminate of the present invention has one or more optical function layers on one surface of the base film.
Examples of the one or more optical functional layers include conventionally known arbitrary optical functional layers, and specifically include, for example, a hard coat layer, a low refractive index layer, a high refractive index layer, an antifouling layer, and an antistatic layer. And an antiglare layer.
In the laminate of the present invention, the one or more optical functional layers are preferably those in which a hard coat layer, a high refractive index layer, and a low refractive index layer are formed on the base film in this order. By having the optical functional layer having such a configuration, the transparent conductive layer patterned as described later can be invisible.

The optical functional layer preferably has a hard coat layer.
By having the said hard-coat layer, when performing the heat processing to the transparent conductive layer mentioned later and crystallizing, it can prevent that the oligomer etc. which comprise a base film precipitate.
It is also possible to prevent the base film from being damaged.
The hard coat layer in the optical functional layer is preferably formed by, for example, the same composition and method as the hard coat layer on the side surface opposite to the optical functional layer side of the base film described above.

The thickness of the hard coat layer in the optical functional layer is preferably the same thickness as the hard coat layer on the side opposite to the optical functional layer side of the substrate film described above, since it can suitably impart anti-curl properties. .
The “similar thickness” means that the difference between the thickness of the hard coat layer in the optical functional layer and the thickness of the hard coat layer on the side opposite to the optical functional layer side of the base film described above is 1.0 μm. Means that it is within

Since the laminated body of the present invention has a transparent conductive layer patterned as will be described later and is a member used for a touch panel, there is a demand for invisibility of the patterned transparent conductive layer. As a means for making the patterned transparent conductive layer invisible, there is a method of laminating a high refractive index layer and a low refractive index layer in this order as the optical functional layer, but it is applicable to the transparent conductive layer and the touch panel. For this purpose, strict optical characteristics are required, and strict control of thickness and refractive index is required. Specifically, the high refractive index layer preferably has a thickness of 10 to 100 nm and a refractive index of 1.55 to 1.75, and the low refractive index layer has a thickness of 10 to 100 nm and a refractive index of 1. It is preferable that it is 35-1.55. The thickness of the high refractive index layer and the low refractive index layer is more preferably 20 to 70 nm.

The methods for forming the high refractive index layer can be roughly classified into a wet method and a dry method. Among these, the wet method is excellent in terms of production efficiency.
Examples of the wet method include a method of forming by a sol-gel method using a metal alkoxide or the like, and a method of forming 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 high refractive index particles described later, and a method of forming by physical vapor deposition or chemical vapor deposition is used.

Methods for forming the low refractive index layer can be broadly classified into a wet method and a dry method. Among these, the wet method is excellent in terms of production efficiency.
As the above-mentioned wet method, as with the high refractive index layer, a method of forming by a sol-gel method using a metal alkoxide or the like, a method of forming by applying a low refractive index binder such as a fluororesin, a low refractive index to the binder resin Examples thereof include a method of coating and forming a composition containing the rate particles.
Examples of the dry method include a method of selecting particles having a desired refractive index from low-refractive index particles described later and forming them by physical vapor deposition or chemical vapor deposition.
In addition, when forming a high refractive index layer and / or a low refractive index layer as the optical functional layer on the above-described base film by a dry method, in a conventional laminate, a patterned transparent conductive layer described later is provided. The same problem as in the case of forming by sputtering processing occurs.

In the laminate of the present invention, the hard coat layer, the high refractive index layer, and the low refractive index layer preferably have a refractive index satisfying the relationship of the following formula (1). By satisfy | filling following formula (1), invisibility of the transparent conductive layer formed on the said low-refractive-index layer can be aimed at suitably.
Refractive index of high refractive index layer> Refractive index of hard coat layer> Refractive index of low refractive index layer (1)

The high refractive index layer is not particularly limited, and may be a conventionally known one. For example, the high refractive index layer can be formed using a composition containing high refractive index fine particles in the resin and solvent described in the hard coat layer.
As the high refractive index fine particles, for example, metal oxide fine particles having a refractive index of 1.50 to 2.80 are preferably used. Specific examples of the metal oxide fine particles include titanium oxide (TiO ₂ , refractive index: 2.71), zirconium oxide (ZrO ₂ , refractive index: 2.10), cerium oxide (CeO ₂ , refraction). rate: 2.20), tin oxide (SnO _2, refractive index: 2.00), antimony tin oxide (ATO, refractive index: 1.75 to 1.95), indium tin oxide (ITO, the refractive index: 1.95 to 2.00), phosphorus tin compound (PTO, refractive index: 1.75 to 1.85), antimony oxide (Sb ₂ O ₅ , refractive index: 2.04), aluminum zinc oxide (AZO, Refractive index: 1.90 to 2.00), gallium zinc oxide (GZO, refractive index: 1.90 to 2.00) and zinc antimonate (ZnSb ₂ O ₆ , refractive index: 1.90 to 2.00) ) And the like. Among them, tin oxide (SnO ₂ ), antimony tin oxide (ATO), indium tin oxide (ITO), phosphorus tin compound (PTO), antimony oxide (Sb ₂ O ₅ ), aluminum zinc oxide (AZO), Gallium zinc oxide (GZO) and zinc antimonate (ZnSb ₂ O ₆ ) are conductive metal oxides, and can impart antistatic performance by controlling the diffusion state of fine particles and forming conductive paths. There are advantages.
Further, zirconium oxide (ZrO ₂ ) is preferable from the viewpoint of high durability stability such as light resistance.

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

As the fluororesin, a polymerizable compound containing a fluorine atom in at least a molecule or a polymer thereof can be used. Although it does not specifically limit as a polymeric compound, For example, what has hardening reactive groups, such as a functional group hardened | cured by ionizing radiation, and a polar group thermally cured, is preferable. Moreover, the compound which has these reactive groups simultaneously may be sufficient. In contrast to this polymerizable compound, a polymer has no reactive groups as described above.

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

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

Moreover, as a fluorine resin, the following can be mentioned, for example.
Polymer of monomer or monomer mixture containing at least one fluorine-containing (meth) acrylate compound of a polymerizable compound having an ionizing radiation curable group; at least one fluorine-containing (meth) acrylate compound; and methyl (meth) Copolymers with (meth) acrylate compounds that do not contain fluorine atoms in the molecule such as acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; fluoroethylene , Fluorine-containing compounds such as vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, 3,3,3-trifluoropropylene, 1,1,2-trichloro-3,3,3-trifluoropropylene, hexafluoropropylene Monomer homopolymer or Copolymer such as. Silicone-containing vinylidene fluoride copolymers obtained by adding a silicone component to these copolymers can also be used. The silicone components in this case include (poly) dimethylsiloxane, (poly) diethylsiloxane, (poly) diphenylsiloxane, (poly) methylphenylsiloxane, alkyl-modified (poly) dimethylsiloxane, azo group-containing (poly) dimethylsiloxane, Dimethyl silicone, phenylmethyl silicone, alkyl / aralkyl modified silicone, fluorosilicone, polyether modified silicone, fatty acid ester modified silicone, methyl hydrogen silicone, silanol group containing silicone, alkoxy group containing silicone, phenol group containing silicone, methacryl modified silicone, acrylic Modified silicone, amino modified silicone, carboxylic acid modified silicone, carbinol modified silicone, epoxy modified silicone, mercapto modified silicone Over emissions, fluorine-modified silicones, polyether-modified silicone and the like. Of these, those having a dimethylsiloxane structure are preferred.

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

In addition to the above-described polymerizable compound or polymer having a fluorine atom, the above-described resins can be mixed and used. Furthermore, various additives and solvents can be used as appropriate in order to improve the curing agent for curing reactive groups and the like, to improve the coating property, and to impart antifouling properties.

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

The curing means for the resin constituting the low refractive index layer may be the same as the curing means in the hard coat layer described above. When a heating means is used for the curing treatment, it is preferable to add a thermal polymerization initiator that generates, for example, a radical by heating to start polymerization of the polymerizable compound, to the fluororesin composition.

The base film is not particularly limited. For example, polyester resin, acetate resin, polyethersulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth) acrylic resin, Examples thereof include a base material made of a raw material such as polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyacrylate resin, polyphenylene sulfide resin, aromatic polyether ketone and the like. Of these, polyester resins, polycarbonate resins, and polyolefin resins are preferably used.

As a polyolefin base material used for the said base film, the base material which uses at least 1 sort (s), such as polyethylene, a polypropylene, a cyclic polyolefin base material, for example is mentioned. Examples of the cyclic polyolefin substrate include those having a norbornene skeleton.
Examples of the polycarbonate substrate include aromatic polycarbonate substrates based on bisphenols (bisphenol A and the like), aliphatic polycarbonate substrates such as diethylene glycol bisallyl carbonate, and the like.
Examples of the polyacrylate substrate include poly (meth) methyl acrylate substrate, poly (meth) ethyl acrylate substrate, (meth) methyl acrylate- (meth) butyl acrylate copolymer substrate, and the like. Can be mentioned.
Examples of the polyester base material include a base material containing at least one of polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate (PEN) as a constituent component.
As said aromatic polyether ketone base material, a polyether ether ketone (PEEK) base material etc. are mentioned, for example.

In the present invention, the thickness of the substrate film is not particularly limited, and can be 5 to 300 μm. However, from the viewpoint of handling properties and prevention of wrinkles and kinks occurring in the laminate, Is preferably 10 μm or more, and preferably 200 μm or less from the viewpoint of thinning.
The minimum with more preferable thickness of the said base film is 50 micrometers, and a more preferable upper limit is 125 micrometers.

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

The laminate of the present invention is used for forming a patterned transparent conductive layer on the side of the optical functional layer opposite to the base film side.
It does not specifically limit as said transparent conductive layer, For example, the transparent conductive layer which consists of metal oxides is mentioned.
Examples of the transparent conductive layer made of the metal oxide include indium tin oxide (ITO), zinc oxide (ZnO), aluminum zinc oxide (AZO), gallium zinc oxide (GZO), and tin oxide (SnO ₂ ). , Indium oxide (In ₂ O ₃ ), tungsten oxide (WO ₃ ), and the like, and indium tin oxide (ITO) is preferable.

The thickness of the transparent conductive layer is not particularly limited, but a certain degree of thickness is necessary to obtain a continuous film having a surface resistance of 200 Ω / □ or less, but if the thickness is too thick, the transparent conductive layer is transparent. Therefore, the preferable lower limit of the thickness is 15 nm, the preferable upper limit is 55 nm, the more preferable lower limit is 20 nm, and the more preferable upper limit is 40 nm. When the thickness is less than 15 nm, the surface electrical resistance increases and it becomes difficult to form a continuous film. On the other hand, if it exceeds 55 nm, transparency may be lowered.

The transparent conductive layer can be formed by vacuum film formation.
The vacuum film formation is preferably a sputtering treatment, and the transparent conductive layer is preferably crystallized by performing a heat treatment at 130 to 170 ° C. for 5 to 120 minutes after the sputtering treatment. .
By crystallizing the transparent conductive layer, the transparent conductive layer is reduced in resistance, and transparency and durability are improved.
In addition, a well-known etching method etc. are mentioned as a method of patterning the transparent conductive layer formed by the said sputtering process. The heat treatment of the transparent conductive layer may be before or after patterning the transparent conductive layer.
A conductive laminate in which a transparent conductive layer patterned on the side opposite to the base film side of the optical functional layer of the laminate is also one aspect of the present invention.

In any case, the conductive laminate of the present invention can be used for display displays of televisions, computers and the like. In particular, it can be suitably used for the surface of a high-definition image display such as a liquid crystal panel, PDP, ELD, touch panel, and electronic paper.
The conductive laminate of the present invention in which a patterned transparent conductive layer is formed on the side opposite to the substrate film side of the optical functional layer of the laminate can be suitably used for a capacitive touch panel. A touch panel using such a conductive laminate of the present invention is also one aspect of the present invention.
The touch panel of the present invention is preferably a capacitive touch panel.

Since the laminated body of this invention consists of an above-described structure, it can prevent suitably the electrical charging by the sputtering process for forming a transparent conductive layer, and is excellent also in the electroconductivity of the formed transparent conductive layer.

The contents of the present invention will be described with reference to the following examples, but the contents of the present invention should not be construed as being limited to these embodiments. Unless otherwise specified, in this example, “part” and “%” represent “part by mass” and “% by mass”, respectively.

Example 1
On one side (on the primer layer) of a 100 μm thick biaxially stretched polyester film (Toyobo Co., Ltd., A4300; with primer layer), the thickness after drying is 2. The hard coat layer was formed by applying to 0 μm.
Next, using the composition for high refractive index layer (1) and the composition for low refractive index layer (1) of the following formulation, a high refractive index layer (thickness after drying, 50 nm, refractive index 1.68) and low refractive index. The rate layer (thickness after drying 30 nm, refractive index 1.48) was formed in order on the hard coat layer of the biaxially stretched polyester film.
In addition, the drying conditions of each coating film were 70 degreeC and 60 second, respectively. Moreover, after drying each of the coating film of the composition for hard-coat layers, the coating film of the composition for high refractive index layers (1), and the coating film of the composition for low refractive index layers (1), each ultraviolet-ray Irradiation (150 mJ / cm ² ) was performed.
Moreover, on the other surface of the biaxially stretched polyester film, using the antistatic layer composition (1) having the following formulation, a coating film is formed by coating so that the thickness after drying is 2000 nm, The coating film was cured by heat drying to form a transparent layer having antistatic performance, thereby obtaining a laminate. The coating film was dried at 70 ° C. for 60 seconds.

<Composition for hard coat layer>
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA, solid content 100%) 50 parts photopolymerization initiator (manufactured by BASF, Irgacure 184) 3 parts leveling agent (manufactured by DIC Corporation, MegaFuck MCF350-5, solid content) 5%) 0.5 part methyl isobutyl ketone 75 parts

<Composition for high refractive index layer (1)>
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA, solid content 100%) 10 parts photopolymerization initiator (manufactured by BASF, Irgacure 127) 1.7 parts leveling agent (manufactured by DIC, Megafac MCF350-5, (Solid content 5%) 0.3 part high refractive index particle-containing liquid (dispersed zirconia particles having an average particle size of 10 to 15 nm in methyl ethyl ketone to give a solid content of 30%) 65 parts methyl isobutyl ketone 1250 parts

<Composition for low refractive index layer (1)>
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA, solid content: 100%) 3.5 parts photopolymerization initiator (manufactured by BASF, Irgacure 127) 0.6 parts leveling agent (manufactured by DIC, Megafac MCF350- 5, 5% solid content) 0.1 part low refractive index particle-containing liquid (silica particles having an average particle size of 10 to 15 nm dispersed in methyl isobutyl ketone to give a solid content of 30%) 21.7 parts methyl isobutyl ketone 1250 parts

<Composition for antistatic layer (1)>
Antistatic agent (manufactured by Shin-Etsu Polymer Co., Ltd., polythiophene, solid content 50%, diluted with isopropyl alcohol) 1.5 parts acrylic polymer solution (weight average molecular weight 160,000, double bond equivalent 1000, solid content 25%, methyl 100 parts leveling agent (manufactured by DIC, Megafac MCF350-5, solid content 5%) 0.3 parts diluted with isobutyl ketone

(Example 2)
The antistatic layer composition (1) in Example 1 was changed to the antistatic layer composition (2) of the following formulation, and the coating film was dried and cured by ultraviolet irradiation to provide antistatic performance. A transparent layer, which is a hard coat layer, was formed to obtain a laminate. In addition, the drying conditions of the coating film were 70 degreeC and 60 second, and the laminated body was obtained like Example 1 except the irradiation amount of the ultraviolet-ray having been 200 mJ / cm < ² >.

<Antistatic layer composition (2)>
Antistatic agent (manufactured by Shin-Etsu Polymer Co., Ltd., polythiophene, solid content 50%, diluted with isopropyl alcohol) 1.5 parts dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA, solid content 100%) 25 parts photopolymerization Initiator (manufactured by BASF, Irgacure 184) 1.5 parts leveling agent (manufactured by DIC, MegaFac MCF350-5, solid content 5%) 0.3 parts methyl isobutyl ketone 75 parts

(Example 3)
The composition for antistatic layer (2) in Example 2 was changed to the composition for hard coat layer in Example 1, and the amount of UV irradiation was changed to 150 mJ / cm ² in the same manner as in Example 2. After forming a hard coat layer, the methyl ethyl ketone of the antistatic layer composition (2) was changed to 700 parts, the photopolymerization initiator was changed to BASF Corporation Irgacure 127, and the thickness after drying and ultraviolet irradiation was changed. A coating film was formed by coating on the hard coat layer so as to be 100 nm, and the conditions for drying and ultraviolet irradiation of the coating film were the same as the conditions for the composition for hard coat layer (drying conditions: 70 ° C., A transparent layer composed of a hard coat layer and an antistatic layer was formed in the same manner as in Example 1 except for 60 seconds and an ultraviolet irradiation condition of 150 mJ / cm ² ) to obtain a laminate.

(Comparative Example 1)
A laminate was obtained in the same manner as in Example 1 except that the composition for antistatic layer (1) in Example 1 was changed to the composition for transparent layer (1) having the following formulation.

<Transparent layer composition (1)>
Acrylic polymer solution (weight average molecular weight 160,000, double bond equivalent 1000, solid content 25%, diluted with isopropyl alcohol) 92 parts leveling agent (manufactured by DIC, Megafac MCF350-5, solid content 5%) 0 .2 parts

(Comparative Example 2)
A laminate was obtained in the same manner as in Example 2, except that the composition for antistatic layer (2) in Example 2 was changed to the composition for hard coat layer in Example 1.

(Comparative Example 3)
Comparative Example 2 except that the composition for high refractive index layer (1) of Example 1 was changed to the composition for high refractive index layer (2) of the following formulation and the film thickness of the high refractive index layer was changed to 100 nm. In the same manner, a laminate was obtained.

<Composition for high refractive index layer (2)>
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA, solid content 100%) 7 parts antistatic agent (manufactured by Shin-Etsu Polymer Co., Ltd. polythiophene, solid content 50%, diluted with isopropyl alcohol) 6 parts photopolymerization initiator ( BASF Corp., Irgacure 127) 1.7 parts leveling agent (DIC, MegaFac MCF350-5, solid content 5%) 0.3 parts high refractive index particle-containing liquid (zirconia particles having an average particle size of 10 to 15 nm) 65 parts methyl isobutyl ketone 1250 parts dispersed in methyl ethyl ketone to a solid content of 30%

(Reference Example 1)
A laminate was obtained in the same manner as in Example 3 except that the thickness of the antistatic layer in Example 3 was changed to 30 nm.

(Reference Example 2)
A laminate was obtained in the same manner as in Example 3 except that the antistatic layer composition (2) of Example 3 was changed to the antistatic layer composition (3) having the following formulation.

<Antistatic layer composition (3)>
Antistatic agent (Mitsubishi Chemical Corporation, Iupima-H6100, quaternary ammonium salt, solid content 50%)
20 parts dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DPHA, solid content 100%) 25 parts photopolymerization initiator (manufactured by BASF, Irgacure 127) 1.5 parts leveling agent (manufactured by DIC, MegaFac MCF350- 5, solid content 5%) 0.4 part methyl isobutyl ketone 1250 parts

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

(Surface resistivity)
Based on JIS-K6911, the surface resistivity (Ω / □) of the surface of each laminate having the transparent layer was measured by the following method.
That is, a high resistivity meter Hirestar UP MCP-HT450 (manufactured by Mitsubishi Chemical Corporation) is used, and a URS probe MCP-HTP14 (manufactured by Mitsubishi Chemical Corporation) is used as a probe, temperature 25 ± 4 ° C., humidity 50 ± 10%. The surface resistivity (Ω / □) was measured at an applied voltage of 500 V under the environment of. The results were evaluated according to the following criteria.
○: 1.0 × 10 ¹¹ Ω / □ or less △: 1.0 × 10 ¹² Ω / □ or less ×: 1.0 × 10 ¹³ Ω / □ or more

(Suitable for sputtering)
A tin-doped indium oxide (ITO) layer having a thickness of 25 nm was formed on the surface of the low refractive index layer of each laminate by a sputtering method. Thereafter, spot-like defects were extracted on a black mount under a fluorescent lamp, and the longest diameter spot of the spot-like defects was observed with an optical microscope, and those having a diameter of 0.1 mm or more were counted. Evaluation was made according to the following criteria.
○: No point defects Δ: Point defects 1 to 10 pieces / m ²
×: Over 10 point defects / m ²

As shown in Table 1, in the laminate according to the example, the surface resistivity of the transparent layer is 1 × 10 ¹¹ Ω / □ or less, and even if the transparent conductive layer is formed by sputtering, There were no defects.
Further, in Example 2 in which the transparent layer was a hard coat layer having antistatic performance and in Example 3 in which the transparent layer had a hard coat layer and an antistatic layer, the transparent layer was obtained in accordance with JIS K-5400. The pencil hardness of the laminate (however, a load of 500 g) was H or more.
Moreover, after cutting Example 2 and 3 which has a hard-coat layer as an optical function layer into 100 mm x 100 mm, and forming a transparent conductive layer by sputtering process, it placed on a plane stand and was most distant from the stand among four corners. When the distance was measured, it was within 5 mm, and the curl prevention property was excellent.
On the other hand, in the laminate according to the comparative example, a point defect is generated at a frequency of 10 / m ² or more in the transparent conductive layer formed by the sputtering process, and the surface resistivity of the transparent layer is high. It had no antistatic performance on the side opposite to the material film side.
Since the thickness of the antistatic layer constituting the transparent layer was thin in the laminate according to Reference Example 1, the surface resistivity of the transparent layer was compared with the laminate according to Example 3 provided with the transparent layer having the same layer configuration. The sputtering suitability was slightly inferior.
Moreover, since the antistatic agent was an ion conduction type, the laminate according to Reference Example 2 was compared with the laminate according to Example 3 having the same layer configuration and a transparent layer containing an electron conduction type antistatic agent. Thus, the surface resistivity and sputtering suitability of the transparent layer were slightly inferior.

INDUSTRIAL APPLICABILITY The present invention can provide a laminate, a conductive laminate, and a touch panel that can suitably prevent electrification due to sputtering treatment for forming a transparent conductive layer and that are excellent in the conductive performance of the formed transparent conductive layer. .

Claims (9)

One side of the base film has one or more optical functional layers, the other side of the base film has a transparent layer, and the side of the optical functional layer opposite to the base film side A laminate used to form a transparent conductive layer patterned thereon,
The transparent layer has antistatic performance on the side opposite to the base film side ,
The antistatic performance is determined by a method in which the transparent layer contains an electron conductive antistatic agent, or an electron conductive antistatic agent and a resin component on the side of the transparent layer opposite to the base film side. A laminate characterized by being provided by a method of forming an antistatic layer containing . The laminate according to claim 1, wherein the transparent layer is a hard coat layer, and the hard coat layer contains an electron conduction type antistatic agent. The transparent layer has one or more laminated structures including a hard coat layer, and an antistatic layer containing an electron conductive antistatic agent and a resin component is provided on the side of the transparent layer opposite to the base film side. The laminate according to claim 1. The laminate according to claim 1, 2 or 3, wherein the one or more optical functional layers 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. The laminate according to claim 1, 2, 3, or 4, wherein a high refractive index layer and a low refractive index layer are laminated on the base film in this order as one or more optical function layers. 6. The laminate according to claim 1, wherein a hard coat layer, a high refractive index layer, and a low refractive index layer are laminated on the base film in this order as one or more optical function layers. . Transparent conductive layer, according to claim 2, 3, 4, 5 or 6 laminate according indium tin oxide. 8. A conductive film comprising a patterned transparent conductive layer formed on the side opposite to the substrate film side of the optical functional layer of the laminate according to claim 1, 2, 3, 4, 5, 6 or 7. Laminate. A touch panel comprising the conductive laminate according to claim 8 .