JP5824398B2 - Transparent conductive laminate - Google Patents

Description

  The present invention relates to a transparent conductive laminate having extremely high visibility.

  Liquid crystal display devices (liquid crystal displays) have advantages such as thinness, light weight, and low power consumption, and are used in various fields such as computers, word processors, televisions, mobile phones, and portable information terminal devices. In these liquid crystal display devices, so-called touch panels having a mechanism for operating devices by holding down the display on the screen are rapidly spreading. Such a touch panel has, for example, a mobile phone such as a smartphone, a tablet PC, a personal digital assistant device, a bank ATM, a vending machine, a personal digital assistant (PDA), a copier, a facsimile machine, and a game machine due to its excellent operability. It is widely used in guidance display devices installed in facilities such as museums and department stores, car navigation systems, multimedia stations (multifunctional terminals installed in convenience stores), monitoring devices for railway vehicles, and the like.

  Generally in the touch panel, the transparent conductive laminated body which has the transparent conductive layer provided on the transparent base material is generally used. As a base film constituting a film having a transparent conductive layer, a film such as a PET film or a polycarbonate film is often used from the viewpoint of high transparency and price. These base films may be provided with a transparent hard coat layer for the purpose of improving scratch resistance and durability.

  The transparent conductive layer of the transparent conductive laminate is made of a base film by performing processing such as vacuum deposition, sputtering, CVD, ion plating, and spraying using a metal oxide such as ITO. A transparent conductive layer is formed thereon. Further, in order to cope with the multi-point input method that has become mainstream in recent years, further patterning processing is required. On the other hand, by patterning the transparent conductive layer, there is a problem that a portion where a transparent conductive layer such as ITO is present can be visually distinguished from a portion where the transparent conductive layer is not present. This greatly reduces the visibility of the touch panel.

  By the way, when a hard coat layer is provided on a thermoplastic film such as a PET film, it may be stored in a manufacturing process such as being wound into a roll. When another layered body is stacked on a base material layer such as a PET film on which a hard coat layer is formed, the adhesive force or chemical force is applied between the layers, resulting in an adhering state, and when using each layered body In addition, a force for peeling off each layered body may be necessary, it may become difficult to peel off due to strong adhesion, or the layered body may be destroyed when it is peeled off. In order to prevent such problems, an uneven layer may be provided to reduce the contact area between the layers, thereby preventing adhesion between layered bodies. A layer having a function of preventing adhesion between layered bodies is called an anti-blocking layer.

JP 2011-76932 A (Patent Document 1) discloses a transparent conductive film in which a first transparent dielectric layer and a transparent conductive layer are formed in this order on a transparent substrate, The pattern portion and the pattern opening portion are formed by patterning, and the hue a * value and the hue b * value of the reflected light when the pattern portion is irradiated with white light are represented by a * _P and b, respectively. When * _P is set to * _O immediately below the pattern opening, the relationship 0 ≦ | a * _P− a * _O | ≦ 4.00 is satisfied, and 0 ≦ | b * _P− b * _O | ≦ A transparent conductive film characterized by satisfying the relationship of 5.00 is described (claim 1). And in this patent document 1, the adjustment which satisfy | fills the said characteristic is made | formed by adjusting the film thickness and refractive index of a 1st transparent dielectric material layer and a 2nd transparent dielectric material layer. Description [0012] paragraph, etc.).

  JP 2011-76802 A (Patent Document 2) discloses a transparent substrate, a first transparent conductive layer formed on at least one surface of the transparent substrate, a second transparent conductive layer, and an insulating property. The second transparent conductive layer and the insulating color difference adjusting layer are formed in that order on the transparent substrate, and the first transparent conductive layer is the second of the insulating color difference adjusting layer. A conductive surface formed by patterning on the upper surface opposite to the transparent conductive layer, the conductive surface forming the upper surface opposite to the insulating color difference adjusting layer of the first transparent conductive layer, and the insulating surface forming the upper surface of the insulating color difference adjusting layer A transparent conductive film is described (claim 1). Here, it is described that the provision of the second transparent conductive layer has achieved a reduction in the difference between high transmittance and visibility ([0014] paragraph, etc.).

JP 2011-76932 A JP 2011-76802 A

  An object of the present invention is to solve the above-described problems of the prior art. More specifically, an object of the present invention is to provide a transparent conductive laminate having extremely high visibility.

The present invention
A transparent conductive laminate in which a high refractive index antiblocking layer, a color difference adjusting layer and a transparent conductive layer are sequentially laminated on at least one surface of a transparent polymer substrate,
(1) The high refractive index antiblocking layer is a layer formed of an antiblocking layer forming composition containing a first component and a second component,
The first component is an unsaturated double bond-containing acrylic copolymer,
The second component is
(A) A phenol novolak acrylate having 2 or more acrylate groups, and (B) an aromatic group-containing mono- or poly (meth) having 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule. Acrylate,
Including
The phenol novolac acrylate (A) is included in an amount of 60 to 85 parts by mass and the (meth) acrylate (B) in an amount of 15 to 30 parts by mass with respect to 100 parts by mass of the second component.
The difference ΔSP between the SP value (SP1) of the first component and the SP value (SP2) of the second component is in the range of 1 to 4,
The mass ratio of the first component and the second component contained in the composition is: first component: second component = 0.5: 99.5 to 20:80,
After coating the anti-blocking layer forming composition, the first component and the second component cause layer separation, and an anti-blocking layer having fine irregularities on the surface is formed,
(2) The color difference adjustment layer
A cured resin component (i), and metal oxide particles (ii) having an average primary particle diameter of 100 nm or less and / or metal fluoride particles (iii) having an average primary particle diameter of 100 nm or less, and in the color difference adjusting layer The total mass of the particles (ii) and (iii) is 0 to 200 parts by mass with respect to 100 parts by mass of the cured resin component (i).
(3) Reflectivity (R1) when the transparent conductive laminate is irradiated with a light source having a wavelength in the range of 500 to 750 nm, and the transparent conductive laminate is 12N hydrochloric acid, 16N nitric acid, and water is 12N hydrochloric acid: 16N nitric acid: water = 3.3: 1.0: In a transparent conductive laminate after being dipped in a strong acid aqueous solution obtained by mixing at a mass ratio of 3: 1.0: 7.6 at 40 ° C. for 3 minutes and then dried. On the other hand, in the reflectance (R2) when the light source in the wavelength range of 500 to 750 nm is irradiated, the difference ΔR between R1 and R2 is 1 or less.
A transparent conductive laminate is provided, whereby the above-described problems are solved.

The cured resin component (i) of the color difference adjusting layer is an ultraviolet curable resin, the haze value (H1) of the transparent conductive laminate and the transparent conductive laminate are 12N hydrochloric acid, 16N nitric acid and water are 12N hydrochloric acid. : 16N nitric acid: water = 3.3: 1.0: 7.6 transparent conductive laminate after being dipped in a strong acid aqueous solution obtained at 40 ° C. for 3 minutes and then dried. The difference [Delta] H in the haze value (H2) is preferably 0.3% or less.

  The phenol novolac acrylate (A) is represented by the following formula (I):

（Ｉ）

(I)

[In Formula (I), R ¹ is H or CH ₂ OH, R ² is H or OH, n is 2 to 5, and m is 0 to 5. ]
It is preferable that it is a compound shown by these.

  The (meth) acrylate (B) is preferably an aromatic group-containing (meth) acrylate having a refractive index in the range of 1.56 to 1.64.

The total content of ZnO, TiO ₂ , CeO ₂ , SnO ₂ , ZrO ₂ and indium-tin oxide contained in the high refractive index anti-blocking layer is 0.0001% by mass or less in the anti-blocking layer. Is preferred.

  The high refractive index antiblocking layer has a refractive index of 1.565 to 1.620, and the high refractive index antiblocking layer has an arithmetic average roughness (Ra) of 0.001 to 0.09 μm. The point average roughness (Rz) is preferably 0.01 to 0.5 μm.

  It is preferable that the high refractive index antiblocking layer has a thickness of 0.05 to 10 μm.

  It is preferable that the transparent conductive layer is a crystalline layer containing indium oxide and the thickness of the transparent conductive layer is 5 to 50 nm.

  An embodiment in which a metal oxide layer is present between the color difference adjusting layer and the transparent conductive layer and the thickness of the metal oxide layer is 0.5 to 5.0 nm is also preferable.

On one surface of the transparent polymer substrate, a high refractive index anti-blocking layer, a color difference adjusting layer and a transparent conductive layer are sequentially laminated, and
An embodiment in which an antiblocking layer is formed on the other surface of the transparent polymer substrate is also preferable.

The anti-blocking layer is a layer formed by an anti-blocking layer forming composition containing a first component and a second component,
The first component includes an unsaturated double bond-containing acrylic copolymer, the second component includes a polyfunctional acrylate,
The difference ΔSP between the SP value (SP1) of the first component and the SP value (SP2) of the second component is in the range of 1 to 2,
After coating the anti-blocking layer forming composition, it is preferable that the first component and the second component undergo phase separation and an anti-blocking layer having fine irregularities on the surface is formed.

  The present invention also provides a touch panel having the transparent conductive laminate.

  The transparent conductive laminate of the present invention is characterized by having extremely high visibility. The high visibility in the transparent conductive laminate of the present invention is a layer obtained by curing a specific anti-blocking layer forming composition with a high refractive index anti-blocking layer that the transparent conductive laminate has, And it is achieved because the amount of particles in the color difference adjusting layer is in a specific range. In the production of a transparent conductive laminate, a partial load tends to be generated on a base film having a high refractive index antiblocking layer during processing for providing a transparent conductive layer. This partial load causes a reduction in visibility in which a portion where a transparent conductive layer such as ITO is present and a portion where it is not present are visually distinguished. The transparent conductive laminate of the present invention is characterized in that this reduction in visibility is eliminated by providing a specific high refractive index antiblocking layer and color difference adjusting layer.

It is a schematic explanatory drawing which shows the transparent conductive laminated body by which the etching process was carried out.

  The transparent conductive laminate of the present invention is a transparent conductive laminate in which a high refractive index antiblocking layer, a color difference adjusting layer and a transparent conductive layer are laminated in this order on at least one surface of a transparent polymer substrate. It is. Each layer which comprises the transparent conductive laminated body of this invention is demonstrated.

Transparent polymer substrate The transparent polymer substrate used in the transparent conductive laminate of the present invention includes, for example, a polycarbonate film, a polyester film such as polyethylene terephthalate and polyethylene naphthalate; and a cellulose film such as diacetyl cellulose and triacetyl cellulose. Film: Examples thereof include a substrate made of a transparent polymer such as an acrylic film such as polymethyl methacrylate. The transparent polymer substrate used in the transparent conductive laminate of the present invention includes polystyrene, acrylonitrile / styrene copolymer and other styrene films; polyvinyl chloride, polyethylene, polypropylene, polyolefin having a cyclic or norbornene structure, Examples thereof include substrates made of transparent polymers such as olefin films such as ethylene / propylene copolymers; amide films such as nylon and aromatic polyamide.
Furthermore, as the transparent polymer substrate used in the transparent conductive laminate of the present invention, polyimide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polyvinyl alcohol, polyvinylidene chloride, polyvinyl butyral, polyarylate, Examples also include substrates made of transparent polymers such as polyoxymethylene, epoxy resins, and blends of the above polymers. Among these transparent polymers, polycarbonate and polyethylene terephthalate are particularly preferable from the viewpoints of transparency, heat resistance, and versatility.

  In the use in the transparent conductive laminate of the present invention, among these transparent polymer base materials, those having a low optical birefringence, or a phase difference of 1/4 (λ / 4) or wavelength of the wavelength (for example, 550 nm) Can be selected as appropriate according to the intended use, and those having birefringence not controlled at all can be selected. As mentioned here, when selecting appropriately according to the application, for example, by using polarized light such as linearly polarized light, elliptically polarized light, circularly polarized light, etc. A case where the transparent conductive laminate of the present invention is used together with a display exhibiting a function can be given.

  The thickness of the transparent polymer substrate can be appropriately determined, but is generally about 10 to 500 μm, particularly 20 to 300 μm, more preferably 30 to 200 μm from the viewpoint of workability such as strength and handleability. .

High refractive index antiblocking layer The high refractive index antiblocking layer of the transparent conductive laminate of the present invention is a layer obtained by a specific high refractive index antiblocking layer forming composition. The high refractive index anti-blocking layer forming composition includes a first component and a second component. The first component is an unsaturated double bond-containing acrylic copolymer. The second component includes (A) a phenol novolak acrylate having 2 or more acrylate groups, and (B) 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule. Mono or poly (meth) acrylates. The phenol novolac acrylate (A) is contained in an amount of 60 to 85 parts by mass and the (meth) acrylate (B) is contained in an amount of 15 to 30 parts by mass with respect to 100 parts by mass of the second component. Further, the difference ΔSP between the SP value (SP1) of the first component and the SP value (SP2) of the second component is in the range of 1 to 4, and the first component and the second component contained in the composition The mass ratio is on condition that the first component: the second component = 0.5: 99.5 to 20:80. This high refractive index anti-blocking layer forming composition is characterized in that after coating, the first component and the second component cause layer separation, and an anti-blocking layer having fine irregularities on the surface is formed.

First component As the first component, an unsaturated double bond-containing acrylic copolymer is used. An unsaturated double bond-containing acrylic copolymer is, for example, a resin obtained by copolymerizing a (meth) acrylic monomer and another monomer having an ethylenically unsaturated double bond, a (meth) acrylic monomer and another ethylenically unsaturated Acrylic acid or glycidyl acrylate for resins reacted with monomers having double bonds and epoxy groups, resins made by reacting (meth) acrylic monomers with other monomers having ethylenically unsaturated double bonds and isocyanate groups, etc. And those having an unsaturated double bond and other functional groups added thereto. One of these unsaturated double bond-containing acrylic copolymers may be used alone, or two or more thereof may be mixed and used. The unsaturated double bond-containing acrylic copolymer preferably has a weight average molecular weight of 2,000 to 100,000, more preferably 5,000 to 50,000.

Second component The second component is:
(A) A phenol novolak acrylate having 2 or more acrylate groups, and (B) an aromatic group-containing mono- or poly (meth) having 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule. Acrylate,
including. Hereinafter, each component (A) and (B) is explained in full detail.

(A) Phenol novolac acrylate having 2 or more acrylate groups The second component includes (A) a phenol novolac acrylate having 2 or more acrylate groups. When the anti-blocking layer-forming composition contains the phenol novolak acrylate (A), the resulting high-refractive index anti-blocking layer becomes a high-refractive index layer that is transparent and has high hardness. Thereby, generation | occurrence | production of an interference fringe can be prevented effectively.

  The phenol novolac acrylate (A) has the following formula (I)

（Ｉ）

(I)

[In Formula (I), R ¹ is H or CH ₂ OH, R ² is H or OH, n is 2 to 5, and m is 0 to 5. ]
It is preferable that it is a phenol novolak-type acrylate shown by these. In said formula (I), it is more preferable that n is 2-4 and m is 0-3, n is 2-4, and it is still more preferable that m is 0-1.

  The weight average molecular weight of the phenol novolac acrylate (A) is preferably 400 to 2500, and more preferably 450 to 2000. The hydroxyl value of the phenol novolac acrylate (A) is preferably 100 to 180 mgKOH / g, and more preferably 120 to 160 mgKOH / g.

  In this specification, the weight average molecular weight of each component can be measured by a gel permeation chromatography method. In the measurement of the weight average molecular weight, a high-speed GPC apparatus such as HLC-8220 GPC (manufactured by Tosoh Corporation) can be used. As a specific measurement condition of weight average molecular weight using HLC-8220GPC (manufactured by Tosoh Corporation), 2 g of a test sample was weighed and treated in a vacuum dryer at 40 ° C. for 2 hours to remove moisture, and then a THF solution. And a measurement is performed under the conditions of a column injection amount: 10 μl and a flow rate: 0.35 ml / min.

  The said phenol novolak-type acrylate (A) is on condition that 60-85 mass parts is contained with respect to 100 mass parts of 2nd components. When the amount of the phenol novolac acrylate (A) is less than 60 parts by mass and when the amount of the phenol novolac acrylate (A) exceeds 85 parts by mass, the hardness of the obtained anti-blocking layer is low. There is a bug.

(B) Aromatic group-containing mono- or poly (meth) acrylate having an alkylene oxide structure of 2 or 3 carbon atoms in the molecule and having the above-mentioned high refractive index anti-blocking layer is composed of (B) 2 carbon atoms. Or an aromatic group-containing mono- or poly (meth) acrylate having 1 to 2 mol of 3 alkylene oxide structures in the molecule. This (meth) acrylate (B) preferably has a viscosity of less than 300 mPa · s and a refractive index in the range of 1.56 to 1.64.

  In the component (B) (meth) acrylate, the alkylene oxide structure having 2 or 3 carbon atoms is contained in the molecule in an amount of 1 to 2 mol, whereby the viscosity of the component (B) can be designed to be less than 300 mPa · s. Become. Moreover, in the (meth) acrylate of the component (B), the extensibility of the obtained high refractive index antiblocking layer is improved by including 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule. Become. Here, examples of the “alkylene structure having 2 or 3 carbon atoms” include an ethylene oxide structure and a propylene oxide structure.

  The (meth) acrylate of component (B) is further characterized by having an aromatic group. When the (meth) acrylate of the component (B) has an aromatic group, a high refractive index such as a refractive index in the range of 1.56 to 1.64 is achieved.

  As the aromatic group-containing (meth) acrylate that can be preferably used as the component (B) in the present invention, for example, an alkyleneoxylated phenol (meth) having 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule. Examples include acrylate, alkyleneoxylated orthophenylphenol (meth) acrylate, alkyleneoxylated metaphenylphenol (meth) acrylate, alkyleneoxylated paraphenylphenol (meth) acrylate, and alkyleneoxylated cumylphenol (meth) acrylate. Among these, (meth) acrylate having two aromatic groups is more preferable in that it has a high refractive index.

  The refractive index of the component (B) can be measured with an Abbe refractometer by a method based on JIS K0062.

  As described above, the viscosity of the component (B) is preferably less than 300 mPa · s. When the viscosity of a component (B) exceeds 300 mPa * s, there exists a problem that the curing reactivity of a composition will be inferior and the hardness of the high refractive index antiblocking layer obtained will become low. The viscosity of the component (B) is more preferably in the range of 1 to 300 mPa · s, still more preferably in the range of 1 to 200 mPa · s.

  The viscosity of the component (B) can be measured with a B-type viscometer (TVB-22L manufactured by Toki Sangyo Co., Ltd.). Examples of the B-type viscometer include TVB-22L (manufactured by Toki Sangyo Co., Ltd.).

  The component (B) preferably has a weight average molecular weight in the range of 150 to 600, and more preferably in the range of 200 to 400.

  In this invention, it is on condition that a component (B) is contained 15-30 mass parts with respect to 100 mass parts of 2nd components contained in a high refractive index antiblocking layer forming composition. When the (meth) acrylate (B) is contained in the high-refractive index anti-blocking layer forming composition in the above mass range, the obtained anti-blocking layer has an advantage of high hardness and high refractive index. When the amount of the component (B) is less than 15 parts by mass and when the amount of the component (B) exceeds 30 parts by mass, there is a problem that the hardness of the obtained anti-blocking layer is lowered.

Other (meth) acrylates The second component in the high refractive index anti-blocking layer forming composition of the present invention may contain other (meth) acrylates in addition to the components (A) and (B). Examples of such (meth) acrylates include polyfunctional (meth) acrylate monomers and / or oligomer compounds. These polyfunctional (meth) acrylate monomers and / or oligomer compounds undergo a curing reaction based on the reaction of (meth) acryloyl groups upon irradiation with active energy rays after coating the composition for forming a high refractive index antiblocking layer. There is an advantage that an anti-blocking layer having high hardness can be obtained.

  The polyfunctional (meth) acrylate monomer and / or oligomer compound preferably has two or more (meth) acryloyl groups. By having two or more (meth) acryloyl groups, there is an advantage that an anti-blocking layer having high hardness can be obtained after irradiation with active energy rays.

  Specific examples of the polyfunctional (meth) acrylate monomer and / or oligomer compound include, for example, hydroxypropylated trimethylolpropane triacrylate, isocyanuric acid ethylene oxide modified diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, trimethylolpropane tri Examples thereof include acrylate, tris (acryloxyethyl) isocyanurate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and oligomers thereof. These monomers or oligomers may be used alone or in combination of two or more.

  When the second component contained in the high-refractive index anti-blocking layer forming composition contains other (meth) acrylates, 100 parts by mass of the second component contained in the high-refractive index anti-blocking layer forming composition The range of 1 to 30 parts by mass is preferable, and the range of 1 to 25 parts by mass is more preferable.

High refractive index antiblocking layer forming composition The high refractive index antiblocking layer forming composition is composed of a first component and a second component, and addition of a solvent, a photopolymerization initiator, a catalyst, a photosensitizer and the like as required. It is prepared by mixing the agent. The ratio of the first component to the second component in the high refractive index anti-blocking layer forming composition of the present invention is: first component: second component = 0.5: 99.5 to 20:80. As for this ratio, 1st component: 2nd component = 1: 99-20: 80 is more preferable, and it is further more preferable that it is 1: 99-15: 85.

  In the high refractive index anti-blocking layer forming composition, phase separation is caused by the difference in SP value between the first component and the second component. By this phase separation, an anti-blocking layer having fine irregularities on the surface is formed. In the present invention, the difference (ΔSP) between the SP value of the first component and the SP value of the second component is within the range of 1 to 4. When the difference between the SP value of the first component and the SP value of the second component is 1 or more, the compatibility of the resins with each other is low, whereby the first component and the second component are applied after application of the anti-blocking layer forming composition. It is thought that phase separation is brought about. The ΔSP is more preferably in the range of 2.0 to 3.5.

  The SP value is an abbreviation for solubility parameter (solubility parameter) and is a measure of solubility. The SP value indicates that the polarity is higher as the numerical value is larger, and the polarity is lower as the numerical value is smaller.

  For example, the SP value can be measured by the following method [references: SUH, CLARKE, J. et al. P. S. A-1, 5, 1671-1681 (1967)].

Measurement temperature: 20 ° C
Sample: Weigh 0.5 g of resin in a 100 ml beaker, add 10 ml of good solvent using a whole pipette, and dissolve with a magnetic stirrer.
solvent:
Good solvent: Dioxane, acetone, etc. Poor solvent: n-hexane, ion-exchanged water, etc. Muddy point measurement: The poor solvent is added dropwise using a 50 ml burette, and the point at which turbidity occurs is defined as the amount added.

  The SP value δ of the resin is given by the following equation.

Vi: Molecular volume of the solvent (ml / mol)
φi: Volume fraction of each solvent at cloud point δi: SP value of solvent ml: Low SP poor solvent mixed system mh: High SP poor solvent mixed system

  The high refractive index anti-blocking layer forming composition of the present invention may further contain components such as various solvents, photopolymerization initiators and additives in addition to the first component and the second component.

  Preferred organic solvents when the first component and the second component are the above combinations include, for example, ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol An ether solvent such as anisole, phenetol propylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; One of these solvents may be used alone, or two or more organic solvents may be mixed and used. When using a solvent, for example, 1-9900 parts by mass, preferably 10-900 parts by mass is added to 100 parts by mass of the total amount of the first component and the second component (collectively referred to as “resin component”). Can do.

  The high refractive index antiblocking layer forming composition preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include 2-hydroxy-2methyl-1phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- [4- (methylthio) phenyl] -2. -Morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, etc. Can be mentioned. A preferable amount of the photopolymerization initiator is 0.01 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin component.

  The high refractive index antiblocking layer-forming composition may contain conventional additives such as an antistatic agent, a plasticizer, a surfactant, an antioxidant, and an ultraviolet absorber, if necessary. When using these additives, it is preferable that it is 0.01-20 mass parts with respect to 100 mass parts of resin components, and it is more preferable that it is 1-10 mass parts.

  The high refractive index anti-blocking layer forming composition can form a resin layer having irregularities without using resin particles or the like by using the first component and the second component as described above. There is. Therefore, it is preferable that the anti-blocking layer forming composition does not contain resin particles. However, the anti-blocking layer forming composition may contain at least one or more inorganic particles, organic particles, or a composite thereof, if necessary. These particles are not particularly added for the purpose of forming irregularities on the surface, but are added to form more uniform and fine irregularities by controlling phase separation and precipitation. These particles have an average particle size of 0.5 μm or less, preferably 0.01 to 0.3 μm. When it exceeds 0.5 μm, the transparency slightly decreases.

  Examples of the inorganic particles include at least one selected from the group consisting of silica, alumina, zeolite, mica, synthetic mica, calcium oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, indium oxide, and antimony oxide. .

  Examples of the organic particles include at least one selected from the group consisting of acrylic, olefin, polyether, polyester, urethane, polyester, silicone, polysilane, polyimide, and fluorine particles.

  The anti-blocking layer having fine irregularities on the surface can be formed by coating and then curing the high refractive index anti-blocking layer forming composition. Examples of the coating method of the anti-blocking layer forming composition include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and extrusion coating. Examples of the thickness of the anti-blocking layer include an embodiment having a thickness of 0.01 to 20 μm.

After coating the high refractive index antiblocking layer-forming composition, it can be phase separated and cured by irradiating light. As light to irradiate, for example, light having an exposure amount of 0.1 to 3.5 J / cm ² , preferably 0.5 to 1.5 J / cm ² can be used. Further, the wavelength of the irradiation light is not particularly limited, and for example, irradiation light having a wavelength of 360 nm or less can be used. Such light can be obtained using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like. By irradiating light in this way, phase separation and curing will occur.

  The anti-blocking layer formed by the high refractive index anti-blocking layer forming composition has fine irregularities. The arithmetic average roughness (Ra) of the surface roughness curve of the anti-blocking layer is preferably less than 0.1 μm, more preferably 0.001 to 0.09 μm, and 0.002 to 0.00. Particularly preferred is 08 μm. Here, the arithmetic mean roughness (Ra) of the roughness curve is a parameter defined in JIS B 0601-2001. When the arithmetic average roughness (Ra) of the surface roughness curve of the anti-blocking layer is 0.1 μm or more, problems such as generation of glare and whitening of the coating film may occur. If the value of Ra is less than the particularly preferable range, a blocking phenomenon occurs, which is not preferable. JIS B 0601-2001 is a Japanese industrial standard and is a standard based on ISO 4288.

  Arithmetic average roughness (Ra) of the roughness curve is a sample of only the reference length in the direction of the average line from the roughness curve, the X axis in the direction of the average line of this extracted portion, and Y in the direction of the vertical magnification. When the axis is taken and the roughness curve is expressed by y = f (x), the value obtained by the following formula is expressed in micrometers (μm).

  The anti-blocking layer formed from the high refractive index anti-blocking layer forming composition preferably has an Rz of 0.5 μm or less. Here, Rz is the ten-point average roughness of the roughness curve, and is a parameter specified in JIS B0601-2001. Rz is more preferably 0.3 μm or less, and further preferably 0.2 μm or less. The lower limit is preferably 0.01 μm.

  The arithmetic average roughness (Ra) and ten-point average roughness (Rz) of the surface roughness curve of the anti-blocking layer formed by the high refractive index anti-blocking layer forming composition are, for example, high values manufactured by Kosaka Laboratory. It can be measured according to JIS B 0601-2001 using an accurate fine shape measuring instrument or a color 3D laser microscope manufactured by Keyence Corporation.

  Since the anti-blocking layer formed by the high refractive index anti-blocking layer forming composition has an irregular, fine and dense concavo-convex shape, it exhibits excellent anti-blocking properties. The anti-blocking layer in the present invention is also advantageous in that the sharpness of an image displayed by a light source such as a liquid crystal module is not deteriorated. In particular, in recent high-definition liquid crystal display devices, the pitch of light rays emitted from the liquid crystal has become finer. Therefore, in order to maintain image clarity, a finer and denser uneven shape is required. The anti-blocking layer in the present invention has an advantage that it has a fine and dense concavo-convex shape and is not accompanied by a decrease in image sharpness such as a decrease in contrast and a decrease in luminance.

  The anti-blocking layer in the present invention is characterized in that a high refractive index of 1.565 to 1.620 of the anti-blocking layer is achieved without using a high refractive index agent. The refractive index of the anti-blocking layer can be measured according to JIS K7142 using, for example, an Abbe refractometer.

  Various additives can be added to the anti-blocking layer forming composition as necessary. Examples of such additives include conventional additives such as antistatic agents, plasticizers, surfactants, and antioxidants.

The anti-blocking layer forming composition does not need to include a high refractive index agent composed of a metal oxide such as ZnO, TiO ₂ , CeO ₂ , SnO ₂ , ZrO _2, or indium-tin oxide due to the above configuration. A high refractive index antiblocking layer having a high refractive index can be formed. Therefore, the high refractive index anti-blocking layer does not contain a high refractive index agent such as a metal oxide selected from the group consisting of ZnO, TiO ₂ , CeO ₂ , SnO ₂ , ZrO ₂ and indium-tin oxide. Is preferred. More specifically, the total content of ZnO, TiO ₂ , CeO ₂ , SnO ₂ , ZrO ₂ and indium-tin oxide contained in the high refractive index anti-blocking layer is 0.0001% by mass or less in the anti-blocking layer. Is preferred. This is because when a high refractive index agent such as a metal oxide is present in the high refractive index anti-blocking layer, the stretchability and the bending resistance are generally inferior as compared with the resin-only layer.

  The high refractive index anti-blocking layer formed using the anti-blocking layer forming composition has good hardness as a high refractive index anti-blocking layer and has a high refractive index of 1.565 to 1.620. It is characterized by. Since the high refractive index antiblocking layer has such a high refractive index, there is an advantage that the generation of interference fringes can be satisfactorily suppressed in the transparent conductive laminate.

  The high-refractive index anti-blocking layer provided using the anti-blocking layer-forming composition also has high extensibility in addition to the performance required for the high-refractive index anti-blocking layer such as high visibility and good hardness. And And this high extensibility has the advantage that the visibility of the transparent conductive laminate is dramatically improved. In the production of a transparent conductive laminate, a partial load tends to be generated on a base film having a high refractive index antiblocking layer during processing for providing a transparent conductive layer. For example, in a base film having a high refractive index anti-blocking layer, a partial load is applied to the film based on the difference in thermal shrinkage / expansion coefficient between the high refractive index anti-blocking layer and the base film. Swelling and twisting may occur. The waviness / twisting of these films brings about a decrease in visibility in which a portion where a transparent conductive layer such as ITO is present and a portion where it is not present are visually distinguished. This greatly reduces visibility in a touch panel or the like.

  The high refractive index antiblocking layer provided by using the antiblocking layer forming composition used in the present invention has high extensibility in addition to the performance required in the high refractive index antiblocking layer such as high visibility and good hardness. It is characterized by having. Since the high refractive index anti-blocking layer in the present invention has high extensibility, even when the base film is locally thermally expanded by heating in the stage of providing the transparent conductive layer, the high refractive index anti-blocking layer The layer follows well, and as a result, there is an advantage that the problem of reduced visibility in which a portion where a transparent conductive layer such as ITO is present is visually distinguished from a portion where the transparent conductive layer is not present is eliminated.

Color difference adjusting layer The transparent conductive laminate of the present invention has a color difference adjusting layer on the high refractive index anti-blocking layer. That is, the color difference adjusting layer is a layer existing between the high refractive index anti-blocking layer and the transparent conductive layer. This color difference adjusting layer may be a single layer or a layer composed of two layers or more. The color difference adjusting layer is a layer that improves adhesion between layers and optical properties (such as transmittance and color tone) of the transparent conductive laminate.
In the present invention, this color difference adjusting layer is
Cured resin component (i) and metal oxide particles (ii) having an average primary particle size of 100 nm or less and / or metal fluoride particles (iii) having an average primary particle size of 100 nm or less
It is a layer containing. Here, the total mass of the particles (ii) and (iii) in the color difference adjusting layer is conditional on being in the range of 0 to 200 parts by mass with respect to 100 parts by mass of the cured resin component (i).

As the curable resin component (i), an ultraviolet curable resin or a thermosetting resin can be used. In the color difference adjusting layer of the present invention, it is more preferable to use an ultraviolet curable resin as the cured resin component (i).
The ultraviolet curable resin can be obtained by a composition containing a monomer having ultraviolet curing performance. Examples of the monomer having ultraviolet curing performance include monofunctional and polyfunctional acrylates such as polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, modified styrene acrylate, melamine acrylate, and silicon-containing acrylate.
Specific monomers include, for example, trimethylolpropane trimethacrylate, trimethylolpropane ethylene oxide modified acrylate, trimethylolpropane propylene oxide modified acrylate, isocyanuric acid alkylene oxide modified acrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, diester Multifunctional monomers such as methylol tricyclodecane diacrylate, tripropylene glycol triacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, epoxy-modified acrylate, urethane-modified acrylate such as urethane (meth) acrylate, and epoxy-modified acrylate Can be mentioned. These monomers may be used independently and may use 2 or more types together.
Among these monomers having ultraviolet curing performance, urethane-modified acrylate is preferable. A commercially available product can be used as the urethane-modified acrylate. For example, a purple light series manufactured by Nippon Synthetic Chemical Industry Co., Ltd., for example, UV1700B, UV6300B, UV765B, UV7640B, UV7600B, etc .; Art Resin Series manufactured by Negami Industrial Co., Ltd. Art Resin HDP, Art Resin UN 9000H, Art Resin UN 3320HA, Art Resin UN 3320HB, Art Resin UN 3320HC, Art Resin UN 3320HS, Art Resin UN 901M, Art Resin UN 902MS, Art Resin UN 903, UA manufactured by Shin-Nakamura Chemical Co., Ltd. H , U4H, U6H, U15HA, UA32P, U6LPA, U324A, U9HAMI, etc .; Ebecryl series made by Daicel UCB Co., Ltd., For example, 1290, 5129, 254, 264, 265, 1259, 1264, 4866, 9260, 8210, 204, 205, 6602, 220, 4450, etc .; Beam set series manufactured by Arakawa Chemical Industries, Ltd., for example, 371, 371MLV 371S, 577, 577BV, 577AK, etc .; RQ series manufactured by Mitsubishi Rayon Co., Ltd .; Unidic series manufactured by DIC Corporation, etc .; DPHA40H (manufactured by Nippon Kayaku Co., Ltd.), CN9006, CN968 (manufactured by SARTOMER) ) Etc. can be used.

When the curable resin component (i) is an ultraviolet curable resin, the composition forming the color difference adjusting layer preferably contains a photopolymerization initiator. As the photopolymerization initiator, commonly used photopolymerization initiators such as acetophenone, benzophenone, benzoin, benzoylbenzoate, and thioxanthone can be used.
The composition forming the color difference adjusting layer may further contain a photosensitizer. As the photosensitizer, for example, commonly used photosensitizers such as triethylamine and tri-n-butylphosphine can be used.
The composition forming the color difference adjusting layer may further contain hydrolysates of various alkoxysilanes.

  When the curable resin component (i) is a thermosetting resin, the composition for forming the color difference adjusting layer is an organosilane thermosetting monomer having a silane compound such as methyltriethoxysilane or phenyltriethoxysilane as a monomer. A thermosetting monomer such as a melamine thermosetting monomer, an isocyanate thermosetting monomer, a phenol thermosetting monomer, or an epoxy thermosetting monomer using a monomer or etherified methylol melamine as a monomer may be included. These thermosetting monomers may be used alone or in combination of two or more. In addition to the said thermosetting monomer, you may contain the thermoplastic resin component as needed.

  When the cured resin component (i) is a thermosetting resin, the composition forming the color difference adjusting layer preferably contains a reaction accelerator or a curing agent. Examples of the reaction accelerator include triethylenediamine, dibutyltin dilaurate, benzylmethylamine, pyridine and the like. Examples of the curing agent include methylhexahydrophthalic anhydride, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, diaminodiphenylsulfone, and the like.

In the present invention, in addition to the cured resin component (i), the color difference adjusting layer includes metal oxide particles (ii) having an average primary particle size of 100 nm or less and / or metal fluoride particles having an average primary particle size of 100 nm or less. (Iii) is included. And the total mass of these particle | grains (ii) and (iii) is on condition that it exists in the range of 0-200 mass parts with respect to 100 mass parts of hardening resin component (i). The total mass of the particles (ii) and (iii) can be adjusted as appropriate according to the refractive index of each of (i), (ii) and (iii) in order to obtain the desired optical properties. Is preferably in the range of 0 to 150 parts by mass, more preferably in the range of 0 to 100 parts by mass with respect to 100 parts by mass of the cured resin component (i).
When the total mass of the particles (ii) and (iii) in the color difference adjusting layer exceeds 200 parts by mass, there is a problem that interlayer adhesion is poor.

Specific examples of the metal oxide particles (ii) include ZnO, TiO ₂ , CeO ₂ , SnO ₂ , ZrO ₂ and indium-tin oxide. All of these metal oxide particles (ii) are characterized by having a high refractive index. Therefore, the color difference adjusting layer containing the metal oxide particles (ii) is basically a high refractive index layer. As the metal oxide particles (ii), ZnO, TiO ₂ and ZrO ₂ are more preferably used. As the metal oxide particles (ii), one type may be used alone, or two or more types may be used in combination.

  In addition, as above-mentioned, all of these metal oxide particles (ii) are on condition that an average primary particle diameter is 100 nm or less. When the average primary particle diameter exceeds 100 nm, the size is easily visible due to aggregation of particles during the formation of the color difference adjusting layer, so that there are problems such as an increase in haze value or a foreign appearance defect. In this specification, the average primary particle diameter represents a 50% volume particle diameter when a liquid in which particles are dispersed in a solvent such as n-BuOH is measured with a particle size distribution meter.

Specific examples of the metal constituting the metal fluoride particles (iii) include calcium, barium, magnesium, strontium and the like. Among these metals, magnesium is more preferable. These metal fluoride particles (iii) may be used alone or in combination of two or more. If necessary, the metal fluoride particles (iii) and SiO ₂ may be used in combination.

  All of these metal fluoride particles (iii) are characterized by having a low refractive index. Therefore, the color difference adjusting layer containing the metal fluoride particles (iii) is basically a low refractive index layer. In addition, as above-mentioned, all of these metal fluoride particles (iii) are on condition that an average primary particle diameter is 100 nm or less. When the average primary particle diameter exceeds 100 nm, the size is easily visible due to aggregation of particles during the formation of the color difference adjusting layer, so that there are problems such as an increase in haze value or a foreign appearance defect.

  The color difference adjusting layer in the present invention may be composed of one layer or may be composed of two or more layers. For example, when the color difference adjusting layer is a single layer, it is preferably a high refractive index layer containing the metal oxide particles (ii). As another aspect, the aspect containing both the said metal oxide particle (ii) and metal fluoride particle (iii) is mentioned, for example. When the color difference adjusting layer is one layer, the thickness of the color difference adjusting layer is preferably 30 to 300 nm, and more preferably 50 nm to 200 nm.

  For example, when the color difference adjusting layer is two layers, it has a two-layer structure including a high refractive index layer containing the metal oxide particles (ii) and a low refractive index layer containing the metal fluoride particles (iii). Is preferred. In this case, it is more preferable that the high refractive index anti-blocking layer and the high refractive index layer are in contact with each other. When the color difference adjusting layer is composed of two layers consisting of one high refractive index layer and one low refractive index layer, the total thickness of the color difference adjusting layer is preferably 30 to 300 nm, preferably 50 nm to 200 nm. More preferably.

The color difference adjusting layer can be formed, for example, by using a composition containing a monomer having an ultraviolet curing property and the metal oxide particles (ii) and / or metal fluoride particles (iii) with a high refractive index antiblocking layer. It can be formed by coating on a high-refractive index antiblocking layer of a polymer substrate and then irradiating and curing with an active energy ray such as ultraviolet rays. Alternatively, the composition containing the thermosetting monomer and the metal oxide particles (ii) and / or the metal fluoride particles (iii) is made into a high refractive index anti-reflective layer of a transparent polymer substrate having a high refractive index antiblocking layer. It can be formed by painting on a blocking layer and then heat curing.
As an example of the case where the color difference adjusting layer has two layers, first, a composition containing metal oxide particles (ii) is coated on a high refractive index antiblocking layer and cured, and then metal fluoride particles (iii) By coating and curing a composition containing, a two-layer color difference adjusting layer can be formed.
As another example of the case where the color difference adjusting layer has two layers, first, a composition containing metal fluoride particles (iii) is coated and cured, and then a composition containing metal oxide particles (ii) is made high. By coating and curing on the refractive index antiblocking layer, a two-layer color difference adjusting layer can be formed.

  As a method for coating the above composition, a coating method using a coating machine usually used by those skilled in the art such as a doctor knife, bar coater, gravure roll coater, curtain coater, knife coater, spin coater, a coating method using a spray, Examples of the coating method include immersion.

  Moreover, the said composition may also contain the organic solvent as needed. Examples of the organic solvent include alcohol solvents such as ethanol, isopropyl alcohol, butanol and 1-methoxy-2-propanol, hydrocarbon solvents such as hexane, cyclohexane, ligroin and cyclohexanone, and ketone solvents such as methyl isobutyl ketone and isobutyl acetate. Examples thereof include aromatic solvents such as solvents, xylene and toluene. These organic solvents may be used individually by 1 type, and may use 2 or more types together.

In the case of curing a composition containing a monomer having ultraviolet curing performance, this curing can be performed by irradiating with a light source that emits an active energy ray having a wavelength as required. As the active energy ray to be irradiated, for example, light having an exposure amount of 0.1 to 1.5 J / cm ² , preferably 0.3 to 1.5 J / cm ² can be used. The wavelength of the irradiation light is not particularly limited, and for example, irradiation light having a wavelength of 360 nm or less can be used. Such light can be obtained using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like.

  Moreover, when hardening the composition containing a thermosetting monomer, it can be hardened by heating at 60-140 degreeC for 1 to 60 minutes, for example. Here, the heating temperature and the heating time can be selected according to the type of the thermosetting monomer contained in the composition.

Metal Oxide Layer In the transparent conductive laminate of the present invention, a metal oxide layer may be formed between the color difference adjusting layer and the transparent conductive layer as necessary. Examples of the component constituting the metal oxide layer include metal oxides such as silicon oxide, aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, indium oxide, and tin oxide. Examples of the metal oxide layer include a layer having a thickness of 0.5 to 5.0 nm.

  By providing a metal oxide layer between the color difference adjusting layer and the transparent conductive layer, the adhesion between the layers can be improved. In addition, the presence of the metal oxide layer has an advantage that the performance such as durability of the laminate is improved.

  The metal oxide layer can be formed by a known method. As a method for forming a metal oxide layer, for example, a physical formation method such as a DC magnetron sputtering method, an RF magnetron sputtering method, an ion plating method, a vacuum deposition method, or a pulse laser deposition method (hereinafter referred to as “PVD method”). Can be used. Among these methods, the DC magnetron sputtering method, which can form a metal oxide layer with a uniform thickness and is excellent in industrial production, is particularly preferable. In addition to the above physical formation method (PVD method), chemical formation methods such as Chemical Vapor Deposition (hereinafter referred to as “CVD method”) and sol-gel method can also be used.

  The target used in the sputtering method is preferably a metal target. As the sputtering method, a reactive sputtering method is widely used. This is because it is difficult to use the DC magnetron sputtering method in the case of a metal oxide target because an oxide of an element used as a metal oxide layer is often an insulator. A pseudo RF magnetron sputtering method in which formation of an insulator on the target is suppressed by discharging the two cathodes simultaneously can also be used.

Transparent conductive layer and transparent conductive laminate In the transparent conductive laminate of the present invention, a transparent conductive layer is formed on a color difference adjusting layer or a metal oxide layer. Although there is no restriction | limiting in particular as a constituent material of a transparent conductive layer, For example, a metal layer or a metal compound layer can be mentioned. Examples of the component constituting the transparent conductive layer include metal oxide layers such as silicon oxide, aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, indium oxide, and tin oxide. Of these, a crystalline layer mainly composed of indium oxide is preferable, and a layer made of crystalline ITO (Indium Tin Oxide) is particularly preferably used.
In the case where the transparent conductive layer is crystalline ITO, the crystal grain size need not be particularly limited, but is preferably 500 nm or less. If the crystal grain size exceeds 500 nm, the bending durability deteriorates, which is not preferable. Here, the crystal grain size is defined as the largest diagonal line or diameter in each polygonal or oval region observed under a transmission electron microscope (TEM). When the transparent conductive layer is amorphous ITO, environmental reliability may be lowered.

  The transparent conductive layer can be formed by a known method, for example, a physical forming method such as a DC magnetron sputtering method, an RF magnetron sputtering method, an ion plating method, a vacuum deposition method, a pulse laser deposition method, etc. Can be used. Focusing on industrial productivity of forming a metal compound layer having a uniform film thickness over a large area, the DC magnetron sputtering method is desirable. In addition to the physical formation method (PVD), a chemical formation method such as a chemical vapor deposition method or a sol-gel method can be used, but the sputtering method is desirable from the viewpoint of film thickness control.

  The film thickness of the transparent conductive layer is preferably 5 to 50 nm from the viewpoints of transparency and conductivity. More preferably, it is 5-30 nm. If the film thickness of the transparent conductive layer is less than 5 nm, the resistance value tends to be inferior in stability over time, and if it exceeds 50 nm, the bending durability is lowered and the color caused by the transparent conductive layer becomes strong, which is not preferable as a touch panel.

  When the transparent conductive laminate of the present invention is used for a touch panel, the surface resistance value of the transparent conductive layer is 10 to 2000Ω / □ at a film thickness of 10 to 40 nm due to reduction of power consumption of the touch panel and circuit processing. It is preferable to use a transparent conductive layer exhibiting a range of 30 to 1000Ω / □.

  As the transparent conductive layer, a wet dispersion method (for example, spin coating method, gravure, slot die, printing, etc.) on a polymer substrate with a dispersion liquid in which metal nanowires, carbon nanotubes, conductive oxide fine particles and the like are dispersed. A layer formed by the above can also be used.

  The transparent conductive layer thus formed is subjected to pattern formation by etching. This etching process is generally performed by covering the transparent conductive layer with a pattern formation mask and then etching the transparent conductive layer using an etching solution such as an acidic aqueous solution. Examples of the etchant include inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitric acid, and phosphoric acid, organic acids such as acetic acid, and mixtures thereof, and aqueous solutions thereof. As a more specific etching solution, a strong acid aqueous solution obtained by mixing 12N hydrochloric acid, 16N nitric acid and water in a mass ratio of 12N hydrochloric acid: 16N nitric acid: water = 3.3: 1.0: 7.6 can be mentioned.

  In addition, you may heat-process as needed before or after patterning a transparent conductive layer. In the case of ITO in which the transparent conductive layer is crystallized by heat treatment, there is an advantage that transparency and conductivity can be improved by performing the heat treatment. The heat treatment can be performed, for example, by heating at 100 to 150 ° C. for 15 to 180 minutes.

In the transparent conductive laminate of the present invention, the reflectance (R1) when the transparent conductive laminate is irradiated with a light source having a wavelength of 500 to 750 nm, and the transparent conductive laminate are 12N hydrochloric acid, 16N. After being dipped in a strong acid aqueous solution obtained by mixing nitric acid and water at a mass ratio of 12N hydrochloric acid: 16N nitric acid: water = 3.3: 1.0: 7.6 at 40 ° C. for 3 minutes and then dried. The difference ΔR between R1 and R2 is 1 or less in the reflectance (R2) when the transparent conductive laminate is irradiated with a light source having a wavelength of 500 to 750 nm.
The strong acid aqueous solution is a so-called aqua regia strong acid aqueous solution that is generally used in an etching process. By performing the etching process using the strong acid aqueous solution, the transparent conductive layer is etched. FIG. 1 is a schematic explanatory view showing an etched transparent conductive laminate. The transparent conductive laminate (10) has a high refractive index anti-blocking layer (3), a color difference adjusting layer (5), and a transparent conductive layer (7) sequentially on one surface of the transparent polymer substrate (1). It has a laminated structure. Here, the portion indicated by (11) is a portion where the transparent conductive layer (7) has been removed by patterning by the etching treatment, and the portion indicated by (13) is a portion masked by the etching treatment. The transparent conductive layer is left as it is. Here, the reflectance R1 means the reflectance at the portion (13) in FIG. 1, and the reflectance R2 means the reflectance at the portion (11) in FIG. And in the transparent conductive laminated body of this invention, the difference (DELTA) R of R1 and R2 is 1 or less in the reflectance at the time of irradiating the light source of the wavelength range of 500-750 nm, It is characterized by the above-mentioned. That is, in the transparent conductive laminate of the present invention, there is almost no difference in reflectance between the portion where the transparent conductive layer (7) is present and the portion where it is not present. Thereby, extremely high visibility was achieved.

  The reflectance of the transparent conductive laminate can be measured by using a spectrophotometer such as Hitachi U-3000, for example, and measuring the spectral reflectance at an incident angle of 10 degrees according to JIS K5600-4-5. it can.

  In the transparent conductive laminate of the present invention, the haze value (H1) of the transparent conductive laminate, the transparent conductive laminate, 12N hydrochloric acid, 16N nitric acid and water, 12N hydrochloric acid: 16N nitric acid: water = 3. The difference in haze value (H2) of the transparent conductive laminate after being dipped in a strong acid aqueous solution obtained by mixing at a mass ratio of 3: 1.0: 7.6 at 40 ° C. for 3 minutes and then dried. ΔH is preferably 0.3% or less. Here, the haze value H1 means a haze value at a portion (13) in FIG. 1, and the haze value H2 means a haze value at a portion (11) in FIG. And in the transparent conductive laminated body of this invention, it is preferable that the difference (DELTA) H of haze value H1 and H2 is 0.3% or less. In this case, in the transparent conductive laminate of the present invention, there is almost no difference in haze value between the portion where the transparent conductive layer (7) is present and the portion where it is not present. Thereby, extremely high visibility was achieved.

Ｈ：ヘイズ（曇価）（％）
Ｔ_ｄ：拡散透光率（％）
Ｔ_ｔ：全光線透過率（％） In addition, the haze value of the transparent conductive laminate is calculated from the following formula in accordance with JIS K7105.

H: Haze (cloudiness value) (%)
T _d : Diffuse transmittance (%)
T _t : Total light transmittance (%)

The total light transmittance (T _t (%)) is calculated by the following equation by measuring the incident light intensity (T ₀ ) with respect to the laminate and the total transmitted light intensity (T ₁ ) transmitted through the laminate. .

  The haze value can be measured using, for example, a haze meter (manufactured by Suga Test Instruments Co., Ltd.).

Anti-blocking layer The transparent conductive laminate of the present invention has a structure in which a high refractive index anti-blocking layer, a color difference adjusting layer, and a transparent conductive layer are sequentially laminated on one surface of a transparent polymer substrate. In the transparent conductive laminate, an anti-blocking layer may be formed on the other surface of the transparent polymer substrate as necessary. By forming the anti-blocking layer on the other surface, the occurrence of the blocking phenomenon in the production process of the transparent conductive laminate can be suppressed, and there is an advantage that the storage stability during production is improved.

  The “anti-blocking layer” herein may be the above-described high-refractive index anti-blocking layer, or may be an anti-blocking layer that does not correspond to the high-refractive index anti-blocking layer in the present invention.

  As a composition which forms the anti blocking layer which does not correspond to the high refractive index anti blocking layer in this invention, the anti blocking layer forming composition containing a 1st component and a 2nd component is mentioned, for example. The difference ΔSP between the SP value (SP1) of the first component and the SP value (SP2) of the second component is in the range of 1 to 2, and after coating the anti-blocking layer forming composition, the first component and the second component More preferably, the composition is an anti-blocking layer-forming composition in which the component causes phase separation and an anti-blocking layer having fine irregularities on the surface is formed.

  As the first component, an unsaturated double bond-containing acrylic copolymer is used. An unsaturated double bond-containing acrylic copolymer is, for example, a resin obtained by copolymerizing a (meth) acrylic monomer and another monomer having an ethylenically unsaturated double bond, a (meth) acrylic monomer and another ethylenically unsaturated Acrylic acid or glycidyl acrylate for resins reacted with monomers having double bonds and epoxy groups, resins made by reacting (meth) acrylic monomers with other monomers having ethylenically unsaturated double bonds and isocyanate groups, etc. And those having an unsaturated double bond and other functional groups added thereto. One of these unsaturated double bond-containing acrylic copolymers may be used alone, or two or more thereof may be mixed and used. The unsaturated double bond-containing acrylic copolymer preferably has a weight average molecular weight of 2,000 to 100,000, more preferably 5,000 to 50,000.

  The monomer or oligomer of the second component is more preferably a polyfunctional unsaturated double bond-containing monomer or an oligomer thereof. The “oligomer” in the present specification refers to a polymer having a repeating unit and having 3 to 10 repeating units. As the polyfunctional unsaturated double bond-containing monomer, for example, a polyfunctional acrylate which is a dealcoholization reaction product of a polyhydric alcohol and (meth) acrylate, specifically, dipentaerythritol hexa (meth) acrylate, dipenta Erythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like can be used. In addition, an acrylate monomer having a polyethylene glycol skeleton such as polyethylene glycol # 200 diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used. One of these polyfunctional unsaturated double bond-containing monomers may be used alone, or two or more thereof may be mixed and used. The second component is more preferably a polyfunctional acrylate.

  Preferred organic solvents when the first component and the second component are the above combinations include, for example, ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol An ether solvent such as anisole, phenetol propylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; One of these solvents may be used alone, or two or more organic solvents may be mixed and used.

  The anti-blocking layer forming composition preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include 2-hydroxy-2methyl-1phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- [4- (methylthio) phenyl] -2. -Morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, etc. Can be mentioned.

  In the anti-blocking layer forming composition, phase separation is caused by the difference in SP value between the first component and the second component. By this phase separation, an anti-blocking layer having fine irregularities on the surface is formed. The difference between the SP value of the first component and the SP value of the second component is preferably 1 or more, and more preferably in the range of 1 to 2. When the difference between the SP value of the first component and the SP value of the second component is 1 or more, the compatibility of the resins with each other is low, whereby the first component and the second component are applied after application of the anti-blocking layer forming composition. It is thought that phase separation is brought about.

  The anti-blocking layer forming composition may contain conventional additives such as an antistatic agent, a plasticizer, a surfactant, an antioxidant, and an ultraviolet absorber, if necessary.

  In addition to the first component and the second component, the anti-blocking layer forming composition may contain a resin that is usually used. The anti-blocking layer forming composition is characterized in that, by using the first component and the second component as described above, a resin layer having irregularities can be formed without including resin particles or the like. . Therefore, it is preferable that the anti-blocking layer forming composition does not contain resin particles. However, the anti-blocking layer forming composition may contain at least one or more inorganic particles, organic particles, or a composite thereof, if necessary. These particles are not particularly added for the purpose of forming irregularities on the surface, but are added to form more uniform and fine irregularities by controlling phase separation and precipitation. These particles have an average particle size of 0.5 μm or less, preferably 0.01 to 0.3 μm. When it exceeds 0.5 μm, the transparency slightly decreases.

  Examples of inorganic particles include silica, alumina, titania, zeolite, mica, synthetic mica, calcium oxide, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide / tin oxide), ATO There may be mentioned at least one selected from the group consisting of (antimony oxide / tin oxide), tin oxide, indium oxide and antimony oxide.

  Examples of the organic particles include at least one selected from the group consisting of acrylic, olefin, polyether, polyester, urethane, polyester, silicone, polysilane, polyimide, and fluorine particles.

  The anti-blocking layer forming composition is prepared by mixing the first component and the second component, and additives such as a solvent, a photopolymerization initiator, a catalyst, and a photosensitizer as necessary. The ratio of the first component and the second component in the anti-blocking layer forming composition is preferably 0.1: 99.9 to 50:50, more preferably 0.3: 99.7 to 20:80, and 0 5: 99.5-10: 90 is more preferable. When a polymerization initiator, a catalyst, and a photosensitizer are used, the first component, the second component, and other resin as necessary (referred to collectively as “resin component”) are 100 parts by mass. 0.01 to 20 parts by mass, preferably 1 to 10 parts by mass can be added. When using a solvent, it is 1-9900 mass parts with respect to 100 mass parts of said resin components, Preferably 10-900 mass parts can be added.

  By coating the anti-blocking layer forming composition and then curing, an anti-blocking layer having fine irregularities on the surface can be formed. Examples of the coating method of the anti-blocking layer forming composition include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and extrusion coating. Examples of the thickness of the anti-blocking layer include an embodiment having a thickness of 0.01 to 20 μm.

After coating the anti-blocking layer forming composition, it can be phase-separated and cured by irradiating light. As light to irradiate, for example, light having an exposure amount of 0.1 to 3.5 J / cm ² , preferably 0.5 to 1.5 J / cm ² can be used. Further, the wavelength of the irradiation light is not particularly limited, and for example, irradiation light having a wavelength of 360 nm or less can be used. Such light can be obtained using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like. By irradiating light in this way, phase separation and curing will occur.

Touch panel The touch panel of the present invention has the transparent conductive laminate. Examples of the touch panel of the present invention include a capacitive touch panel. Moreover, you may use the transparent conductive laminated body of this invention for a resistive film type touch panel.

Specific examples of the layer structure in the case where the transparent conductive laminate of the present invention is used as a touch panel substrate include the following structures:
Transparent conductive layer / color difference adjusting layer / high refractive index anti-blocking layer / transparent polymer substrate,
Transparent conductive layer / metal oxide layer / color difference adjusting layer / high refractive index anti-blocking layer / transparent polymer substrate,
Transparent conductive layer / color difference adjusting layer / high refractive index anti-blocking layer / transparent polymer substrate / anti-blocking layer,
Transparent conductive layer / metal oxide layer / color difference adjusting layer / high refractive index anti-blocking layer / transparent polymer substrate / anti-blocking layer,
Transparent conductive layer / color difference adjusting layer / high refractive index antiblocking layer / transparent polymer substrate / high refractive index antiblocking layer / color difference adjusting layer / transparent conductive layer,
Transparent conductive layer / metal oxide layer / color difference adjusting layer / high refractive index antiblocking layer / transparent polymer substrate / high refractive index antiblocking layer / color difference adjusting layer / metal oxide layer / transparent conductive layer,
Auxiliary electrode layer / transparent conductive layer / color difference adjusting layer / high refractive index anti-blocking layer / transparent polymer substrate,
Auxiliary electrode layer / transparent conductive layer / metal oxide layer / color difference adjusting layer / high refractive index anti-blocking layer / transparent polymer substrate,
Auxiliary electrode layer / transparent conductive layer / color difference adjusting layer / high refractive index antiblocking layer / transparent polymer substrate / antiblocking layer, auxiliary electrode layer / transparent conductive layer / metal oxide layer / color difference adjusting layer / high refractive index anti Blocking layer / transparent polymer substrate / anti-blocking layer,
Auxiliary electrode layer / transparent conductive layer / color difference adjusting layer / high refractive index antiblocking layer / transparent polymer substrate / high refractive index antiblocking layer / color difference adjusting layer / transparent conductive layer / auxiliary electrode layer,
Auxiliary electrode layer / transparent conductive layer / metal oxide layer / color difference adjusting layer / high refractive index antiblocking layer / transparent polymer substrate / high refractive index antiblocking layer / color difference adjusting layer / metal oxide layer / transparent conductive layer / Auxiliary electrode layer.

The auxiliary electrode layer mentioned here means a layer that can be used as an electrode material for wiring. As a material for the auxiliary electrode layer, a material having a specific resistance of 1 × 10 ⁻⁶ Ωcm or more and 1 × 10 ⁻⁴ Ωcm or less is desirable. When a metal material having a specific resistance of less than 1 × 10 ⁻⁶ Ωcm is used, it is unstable in terms of application functions, and it becomes difficult to form a thin film. On the other hand, when a metal material having a specific resistance larger than 1 × 10 ⁻⁴ Ωcm is used, the resistance value is too high, and thus the resistance value is increased when thin wire processing is performed. For the above reasons, a metal suitable for practical use is recommended to be a single metal selected from the group consisting of Cu, Ag, Al, Au, Ni, Ni / Cr, and Ti, or an alloy composed of a plurality of types. In particular, it is a metal with high electrical conductivity and excellent workability such as pattern etching and electroplating, and has good electrical and mechanical connectivity (solder, anisotropic conductive connector, etc.) between the electrode and the lead portion of the circuit, Cu, Al, and the like are preferable in terms of bending resistance, high thermal conductivity, and low cost, and Cu is particularly preferable.

  The thickness of the auxiliary electrode layer is not particularly limited, but a normal design specification of 0.001 to 100 μm, preferably 0.01 to 25 μm is recommended. A known treatment method can be used for forming the auxiliary electrode, but it is preferable to form the auxiliary electrode by a sputtering method. Further, if necessary, the electroconductivity may be increased by further increasing the film thickness by electrolysis / electroless wet metal plating.

  In addition, for the purpose of protecting the auxiliary electrode layer (mainly antioxidation), a refractory metal layer made of Ni, Ni / Cr, Cr, Ti, Mo, or the like is formed on the upper and lower layers of the auxiliary electrode layer as necessary. An oxide layer may be provided.

  The following examples further illustrate the present invention, but the present invention is not limited thereto. In the examples, “parts” and “%” are based on mass unless otherwise specified.

Production Example 1 Production of Unsaturated Double Bond-Containing Acrylic Copolymer (I) A mixture consisting of 187.2 g of isobornyl methacrylate, 2.8 g of methyl methacrylate, and 10.0 g of methacrylic acid was mixed. This mixture was added to 360 g of propylene glycol monomethyl ether heated to 110 ° C. under a nitrogen atmosphere in a 1000 ml reaction vessel equipped with a stirring blade, a nitrogen introducing tube, a cooling tube and a dropping funnel. At the same time as an 80.0 g solution of propylene glycol monomethyl ether containing 2.0 g of ate, the solution was dropped at a constant rate over 3 hours, and then reacted at 110 ° C. for 1 hour.

  Thereafter, a 17 g solution of propylene glycol monomethyl ether containing 0.2 g of tertiary butyl peroxy-2-ethyl hexaate was added dropwise and reacted at 110 ° C. for 30 minutes.

  6 g of propylene glycol monomethyl ether solution containing 1.5 g of tetrabutylammonium bromide and 0.1 g of hydroquinone was added to the reaction solution, and further, 24.4 g of 4-hydroxybutyl acrylate glycidyl ether and propylene glycol monomethyl ether 5 were added while air bubbling. 0.0 g of the solution was added dropwise over 1 hour, followed by further reaction over 5 hours.

  An unsaturated double bond-containing acrylic copolymer having a number average molecular weight of 5500 and a weight average molecular weight (Mw) of 18000 was obtained. This resin had SP value: 9.7 and Tg: 92 ° C.

Production Example 2 Production of Phenol Novolac Type Acrylate (1) In a reactor equipped with a stirrer, thermometer, dropping funnel and reflux device, 150 g of phenol novolac resin (weight average molecular weight 700-900, epoxy equivalent 150-200) and epichlorohydrin 550g was mixed and 110g of 48.5% sodium hydroxide aqueous solution was dripped over 2 hours under 100 degreeC and 100-200 mg pressure reduction conditions. After completion of the reaction, the temperature is cooled to room temperature, an excess aqueous sodium hydroxide solution is neutralized with an acid, heated under reduced pressure to remove excess epichlorohydrin, the product is dissolved in methyl isobutyl ketone, washed with water and filtered. By-product salts were removed to obtain a phenol novolac type epoxy resin solution.
Methoquinone 1000 ppm and triphenylphosphine 2000 ppm are added to 100 parts by mass of the solid content of the obtained phenol novolac type epoxy resin, and acrylic acid is added dropwise at 100 ° C. until the acid value becomes 1 mg KOH / g or less. A phenol novolac type epoxy acrylate (1) was obtained.
The obtained phenol novolac epoxy acrylate (1) had a weight average molecular weight of 950, a hydroxyl value of 140 mgKOH / g, a refractive index of 1.572, and an SP value of 12.7.

Production Example 3 Production of Phenol Novolac Type Acrylate (2) In a reactor equipped with a stirrer, a thermometer, a dropping funnel and a reflux device, 150 g of phenol novolac resin (weight average molecular weight 900-1100, epoxy equivalent 150-200) and epichlorohydrin 550g was mixed and 110g of 48.5% sodium hydroxide aqueous solution was dripped over 2 hours under 100 degreeC and 100-200 mg pressure reduction conditions. After completion of the reaction, the temperature is cooled to room temperature, an excess aqueous sodium hydroxide solution is neutralized with an acid, heated under reduced pressure to remove excess epichlorohydrin, the product is dissolved in methyl isobutyl ketone, washed with water and filtered. By-product salts were removed to obtain a phenol novolac type epoxy resin solution.
Methoquinone 1000 ppm and triphenylphosphine 2000 ppm are added to 100 parts by mass of the solid content of the obtained phenol novolac type epoxy resin, and acrylic acid is added dropwise at 100 ° C. until the acid value becomes 1 mg KOH / g or less. A phenol novolac epoxy acrylate (2) was obtained.
The obtained phenol novolac epoxy acrylate (2) had a weight average molecular weight of 1200, a hydroxyl value of 137 mgKOH / g, a refractive index of 1.571, and an SP value of 12.6.

Example 1
The unsaturated double bond-containing acrylic copolymer (I) obtained in Production Example 1 was used as the first component for forming the high refractive index antiblocking layer . As the component (A) of the second component, the phenol novolac type epoxy acrylate (1) obtained in Production Example 2 is used, and as the component (B), ethoxylated orthophenylphenol acrylate (acrylate having 1 mol of ethoxy structure in the molecule, An anti-blocking layer forming composition was prepared using a viscosity of 130 mPa · s at 25 ° C. and a refractive index of 1.577) in the amounts shown in Table 1. Here, the SP value of the second component was 12.2.
The raw materials shown in Table 1 were sequentially mixed at the solid content mass shown in Table 1 and stirred to obtain an anti-blocking layer forming composition. The SP value of the second component was calculated as a weight average with respect to the component (A), the component (B) SP value, and the content contained in the second component.

The obtained anti-blocking layer-forming composition was dropped onto a Teijin Chemicals 100 μm optical PC film (Pure Ace) and coated using a bar coater # 9.
After coating, it was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet light with an ultraviolet irradiator (manufactured by Fusion) to form a high refractive index antiblocking layer having a thickness of 3.0 μm on the polycarbonate film. .

The viscosity of the ethoxylated orthophenylphenol acrylate of component (B) was measured using a B-type viscometer (TVB-22L manufactured by Toki Sangyo Co., Ltd.). 100 ml of a test sample was collected in a glass container, adjusted to a temperature of 20 ° C., and then measured using a M1Rotor at a rotation speed of 60 rpm.
The refractive index of component (B) was measured according to JIS K0062.

Formation of color difference adjusting layer A 15% titanium oxide dispersion having an average particle diameter of 40 nm is diluted to 5% with isobutyl alcohol, and urethane acrylate (manufactured by Negami Kogyo Co., Ltd., UN-3320HS), which is a monomer having ultraviolet curing performance, is added to MIBK (methyl). Diluted to 5% with isobutyl ketone) was prepared. 40 parts by weight of the diluted titanium oxide dispersion and 0.25 parts by weight of a photopolymerization initiator (Irgacure 184 manufactured by BASF) are mixed with 100 parts by weight of the urethane acrylate diluted liquid, and further IBA (isobutyl). What was diluted to 2.5% by mass with alcohol was applied using a bar coater # 3.
After coating, the film was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet light using a UV irradiation machine (manufactured by Fusion) in a nitrogen atmosphere to form a color difference adjusting layer on the high refractive index antiblocking layer.

Formation of transparent conductive layer Amorphous ITO was formed on the obtained color difference adjusting layer by sputtering using an indium oxide-tin oxide target having a composition of indium oxide and tin oxide of 95: 5 and a filling density of 98%. A layer was formed. The film thickness of the formed ITO layer was about 20 nm, and the surface resistance value after film formation was about 210Ω / □. Subsequently, a heat treatment was performed at 130 ° C. for 90 minutes, and the transparent conductive layer (ITO layer) was crystallized to produce a transparent conductive laminate. The surface resistance value of the transparent conductive layer after the ITO layer was crystallized was about 150Ω / □. The properties of the produced transparent conductive laminate are shown in Table 1.

Examples 2-5
In the formation of the high-refractive index anti-blocking layer, the high-refractive index anti-blocking layer was formed in the same procedure as in Example 1 except that the composition of the anti-blocking layer forming composition was changed to that described in Table 1. did. Thereafter, in the formation of the color difference adjusting layer, the same procedure as in Example 1 was applied except that the diluted liquid filling amount of the titanium oxide dispersion was changed to the amount shown in Table 1 on the high refractive index antiblocking layer. A color difference adjusting layer was formed. Further, a transparent conductive layer was produced on the color difference adjusting layer in the same procedure as in Example 1.
In Example 3, a transparent conductive laminate was produced using a 70 μm optical PC film (Pure Ace) C110 manufactured by Teijin Chemicals.

Examples 6-10, 12, 14, 15
In the formation of the high refractive index antiblocking layer, the high refractive index antiblocking layer was formed in the same procedure as in Example 1. Thereafter, in the formation of the color difference adjusting layer, the same procedure as in Example 1 was applied except that the diluted liquid filling amount of the titanium oxide dispersion was changed to the amount shown in Table 1 on the high refractive index antiblocking layer. A color difference adjusting layer was formed. Further, a transparent conductive layer was produced on the color difference adjusting layer in the same procedure as in Example 1.
In Examples 7 and 8, a transparent conductive laminate was produced using a Teijin DuPont 188 μm optical PET film (Teijin Tetron KEFW).
In Example 9, a transparent conductive laminate was produced using a 125 μm optical PET film (Teijin Tetron KEFW) manufactured by Teijin DuPont.
In Example 10, a transparent conductive laminate was produced using a Teijin DuPont 50 μm optical PET film (Teijin Tetron KEL86W).
In Example 14, a transparent conductive laminate was produced using a 75 μm optical modified PC film (Pure Ace WR W-142) manufactured by Teijin Chemicals.
In Example 15, a transparent conductive laminate was prepared using a modified PC film (Pure Ace WR S-148) manufactured by Teijin Chemicals Limited for 50 μm optics.

Example 11
In the formation of the high refractive index antiblocking layer, the high refractive index antiblocking layer was formed in the same procedure as in Example 1. Thereafter, in the formation of the color difference adjusting layer, a 15% titanium oxide dispersion having an average particle size of 40 nm is diluted with isobutyl alcohol to 5%, and a urethane acrylate which is a monomer having UV curing performance (Negami Kogyo Co., Ltd., UN-3320HS). Was diluted to 5% with MIBK. 40 parts by weight of the diluted titanium oxide dispersion and 0.25 parts by weight of the photopolymerization initiator (Irgacure 184 manufactured by BASF) are mixed with 100 parts by weight of the urethane acrylate diluted liquid, and further 2 by IBA. The solution diluted to 5% was applied using a bar coater # 3.
After coating, the coating was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet light with a UV irradiation machine (manufactured by Fusion) in a nitrogen atmosphere, thereby forming the color difference adjusting layer 1 on the high refractive index antiblocking layer. .
Next, 40 parts by mass of a 5% magnesium fluoride dispersion and 0.25 parts by mass of a photopolymerization initiator (Irgacure 184 manufactured by BASF) are mixed with 100 parts by mass of the urethane acrylate diluent, A solution diluted to 2.5% with isobutyl alcohol was applied using a bar coater # 3.
After coating, the coating was dried at 70 ° C. for 1 minute, and irradiated with 350 mJ of ultraviolet light with a UV irradiation machine (manufactured by Fusion) in a nitrogen atmosphere, whereby the color difference adjusting layer 2 was formed on the color difference adjusting layer 1. Furthermore, a transparent conductive layer was formed by forming a transparent conductive layer on the color difference adjusting layer 2 in the same procedure as in Example 1.

Example 13
In the formation of the color difference adjusting layer 2, 5 parts by mass of a photopolymerization initiator (Irgacure 184: manufactured by BASF) is mixed with 100 parts by mass of silicon acrylate (EB-1360: manufactured by Daicel Cytec), and methyl isobutyl ketone is used. A high refractive index anti-blocking layer, a color difference adjustment layer 1, a color difference adjustment layer 2, and a transparent layer are sequentially formed in the same procedure as in Example 11 except that the adjustment liquid diluted to 2.5% is used. A conductive layer was formed.

Comparative Examples 1-2
A transparent conductive laminate was prepared in the same manner as in Example 1 except that a high refractive index antiblocking layer was prepared using the antiblocking layer forming composition obtained by the formulation shown in Table 2.

Comparative Examples 3-9
A transparent conductive laminate was prepared in the same manner as in Example 9 except that a high refractive index antiblocking layer was prepared using the antiblocking layer forming composition obtained by the formulation shown in Table 2.

Comparative Example 10
A transparent conductive laminate was produced in the same manner as in Example 9 except that the amount of diluted solution of the titanium oxide dispersion was changed to the amount shown in Table 2 in the formation of the color difference adjusting layer.

  The following evaluation was performed about the transparent conductive laminated body obtained in the said Example and comparative example. The evaluation results are shown in Tables 1 and 2.

Evaluation of anti-blocking (AB) performance The anti-blocking films obtained in Examples and Comparative Examples were cut into a size of 2 × 5 cm, and the coated surface was superposed on the surface of the PET film (no adhesive layer applied), and a glass plate And left at room temperature for 24 hours under the condition of 200 gf / cm ² . Thereafter, the blocking phenomenon (AB property) was visually evaluated according to the following criteria.
○: With anti-blocking property ×: Without anti-blocking property

Measurement of Reflectance Difference ΔR Using the spectrophotometer (Hitachi U-3000), the reflectance of the transparent conductive laminates obtained in the Examples and Comparative Examples was JIS K5600-4 at an incident angle of 10 degrees. Based on -5, the reflectance R1 was measured. The wavelength of the light source used in the reflectance measurement was 500 to 750 nm.
Next, the obtained transparent conductive laminate was mixed with 12N hydrochloric acid, 16N nitric acid and water in a mass ratio of 12N hydrochloric acid: 16N nitric acid: water = 3.3: 1.0: 7.6. It was immersed in an aqueous solution at 40 ° C. for 3 minutes and dried. The transparent conductive laminate was irradiated with light having a wavelength of 500 to 750 nm, and the reflectance R2 was measured. The reflectance R1 means the reflectance of the portion where the transparent conductive layer is present as shown in the portion (13) in FIG. 1, and the reflectance R2 is the portion (11) in FIG. The reflectance of the part where a transparent conductive layer does not exist as shown in FIG.
The difference between R1 and R2 thus obtained was taken as ΔR. Tables 1 and 2 show the values of ΔR at which ΔR became the maximum between wavelengths of 500 to 750 nm.

Measurement of haze value difference ΔH The haze values of the transparent conductive laminates obtained in Examples and Comparative Examples were measured using a haze meter (manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K7105. The value H1 was obtained.
Next, the obtained transparent conductive laminate was mixed with 12N hydrochloric acid, 16N nitric acid and water in a mass ratio of 12N hydrochloric acid: 16N nitric acid: water = 3.3: 1.0: 7.6. It was immersed in an aqueous solution at 40 ° C. for 3 minutes and dried. The haze value of this transparent conductive laminate was measured in the same manner as described above to obtain a haze value H2. The haze value H1 means the haze value of the portion where the transparent conductive layer is present as shown in the portion (13) in FIG. 1, and the haze value H2 is shown in the portion (11) in FIG. This means the haze value of the portion where the transparent conductive layer does not exist. The difference between H1 and H2 obtained in this way was taken as ΔH.

The interference fringe evaluation test piece was bonded to a 100 × 100 mm black acrylic plate using an optical film adhesive so that the coated surface was on the surface. A sample is placed at a distance of 10 cm vertically from the fluorescent tube of a stand-type three-wavelength fluorescent lamp (SLH-399, manufactured by TWINBARD) and visually observed. Visual observation was performed and judged based on the following evaluation criteria.

◎: Interference fringes (interference patterns) are not visually recognized under a three-wavelength fluorescent lamp or sunlight ○: Interference fringes (interference patterns) are not visually recognized under a three-wavelength fluorescent lamp, but slightly visible under sunlight Δ: Interference fringes (interference patterns) are slightly visible ×: Interference fringes (interference patterns) are clearly visible

Etching mark evaluation Hydrochloric acid (12 N): Nitric acid (16 N): Pure water mixed at a mass ratio of 3.3: 1.0: 7.6 is immersed in a strong acid at 40 ° C. for 3 minutes to perform etching treatment Then, using the patterned sample, the sample was placed at a distance of 10 cm vertically from the fluorescent tube of a stand-type three-wavelength fluorescent lamp (SLH-399 manufactured by TWINBARD) and visually observed. The above samples were further visually observed under sunlight, and the appearance was evaluated according to the following criteria.

◎: Difficult to distinguish between pattern part and non-pattern part under sunlight and under 3-wavelength fluorescent lamp ○: Pattern part and non-pattern part are slightly distinguishable under sunlight, but pattern part under 3-wavelength fluorescent lamp Difficult to distinguish between non-patterned part and Δ: Slightly distinguishable between pattern part and non-patterned part under three-wavelength fluorescent lamp x: Easy to distinguish between pattern part and non-patterned part under three-wavelength fluorescent lamp

Adhesion evaluation An adhesion test was performed in accordance with JIS K5400. The transparent conductive laminates obtained in Examples and Comparative Examples were cross-cut using a cutter knife so that 100 1 mm ² cuts (cross cuts) could be made. Next, the cellophane adhesive tape was completely adhered on the created grid, and one end of the tape was lifted and peeled upward. This peeling operation was performed three times at the same location. Thereafter, the number of peeled grids was determined according to the criteria described below.

10: No peeling 8: Peeling is within 5 eyes 6: Peeling is over 5 eyes and within 15 eyes 4: Peeling is over 15 eyes and within 35 eyes 2: Peeling is over 35 eyes It is within 65 eyes 0: Peeling exceeds 65 eyes and is within 100 eyes

In Table 1 and Table 2 above,
I-184: 1-hydroxycyclohexyl phenyl ketone, photopolymerization initiator bisphenol A EO-modified diacrylate: manufactured by Toagosei Co., Ltd., Aronix M-211B, bisphenol A EO (2 mol) -modified diacrylate, SP value 11.3
Acryloylmorpholine: SP value 11.9
Bifunctional urethane acrylate: NV100: CN-9893 (manufactured by Sartomer), SP value 11.1
High refractive index filler 1: Zirconia ZRMIBK30WT% (zirconium oxide, manufactured by CIK Nanotech)
High refractive index filler 2: Titania TiMIBK15WT% (titanium oxide, manufactured by CIK Nanotech)
Indicates.

  The high refractive index antiblocking layer included in the transparent conductive laminate of the example had good antiblocking performance. Furthermore, in any of the transparent conductive laminates of Examples, ΔR is 1 or less and ΔH is 0.3% or less. Thereby, even after performing the etching process, it can be confirmed that extremely excellent visibility is secured. The transparent conductive laminate of the present invention was further free from interference fringes, was excellent in etching mark performance, and was excellent in adhesion.

Comparative Examples 1 and 2 are examples in which the amounts of components (A) and (B) are outside the scope of the present invention. In these cases, ΔH exceeded 0.3%, and visibility was lowered.
Comparative Example 3 is an example in which diacrylate having a bisphenol A skeleton was used instead of component (A). In Comparative Example 3, ΔR exceeded 1 and the visibility was lowered. In addition, generation of interference fringes was confirmed.
Comparative Example 4 is an example using acryloylmorpholine instead of component (B). In Comparative Example 4, ΔR exceeded 1 and the visibility was lowered. In addition, generation of interference fringes was confirmed.
Comparative Examples 5 and 6 are examples in which zirconia oxide or titanium oxide, which is a high refractive index agent, was used instead of using components (A) and (B). In these comparative examples, ΔR greatly exceeded 1, and the visibility was greatly reduced. In addition, generation of interference fringes was confirmed.
Comparative Examples 7 to 9 are examples using a bifunctional urethane acrylate for the purpose of imparting extensibility to the high refractive index antiblocking layer. In these comparative examples, even if the extensibility is improved by using a bifunctional urethane acrylate in the formation of the high refractive index antiblocking layer, ΔR exceeds 1, and good visibility cannot be obtained. It was.
Comparative Example 10 is an example in which the total amount of particles contained in the color difference adjusting layer exceeds 200 parts by mass with respect to 100 parts by mass of the cured resin component. In this case, the adhesiveness was lowered.

  The transparent conductive laminate of the present invention is characterized by having extremely high visibility. This transparent conductive laminate can be suitably used in a touch panel, particularly a capacitive touch panel.

1: transparent conductive laminate,
3: High refractive index anti-blocking layer,
5: Color difference adjustment layer,
7: transparent conductive layer,
10: transparent conductive laminate,
11: A portion where the transparent conductive layer (7) has been removed by patterning by etching,
13: A portion masked in the etching process.

Claims (12)

A transparent conductive laminate in which a high refractive index antiblocking layer, a color difference adjusting layer and a transparent conductive layer are sequentially laminated on at least one surface of a transparent polymer substrate,
(1) The high refractive index antiblocking layer is a layer formed of an antiblocking layer forming composition containing a first component and a second component,
The first component is an unsaturated double bond-containing acrylic copolymer,
The second component is
(A) A phenol novolak acrylate having 2 or more acrylate groups, and (B) an aromatic group-containing mono- or poly (meth) having 1 to 2 mol of an alkylene oxide structure having 2 or 3 carbon atoms in the molecule. Acrylate,
Including
The phenol novolac acrylate (A) is included in an amount of 60 to 85 parts by mass and the (meth) acrylate (B) in an amount of 15 to 30 parts by mass with respect to 100 parts by mass of the second component.
The difference ΔSP between the SP value (SP1) of the first component and the SP value (SP2) of the second component is in the range of 1 to 4,
The mass ratio of the first component and the second component contained in the composition is: first component: second component = 0.5: 99.5 to 20:80,
After coating the anti-blocking layer forming composition, the first component and the second component cause layer separation, and an anti-blocking layer having fine irregularities on the surface is formed,
(2) The color difference adjustment layer
A cured resin component (i), and metal oxide particles (ii) having an average primary particle diameter of 100 nm or less and / or metal fluoride particles (iii) having an average primary particle diameter of 100 nm or less, and in the color difference adjusting layer The total mass of the particles (ii) and (iii) is 0 to 200 parts by mass with respect to 100 parts by mass of the cured resin component (i).
(3) Reflectivity (R1) when the transparent conductive laminate is irradiated with a light source having a wavelength in the range of 500 to 750 nm, and the transparent conductive laminate is 12N hydrochloric acid, 16N nitric acid, and water is 12N hydrochloric acid: 16N nitric acid: water = 3.3: 1.0: In a transparent conductive laminate after being dipped in a strong acid aqueous solution obtained by mixing at a mass ratio of 3: 1.0: 7.6 at 40 ° C. for 3 minutes and then dried. On the other hand, in the reflectance (R2) when the light source in the wavelength range of 500 to 750 nm is irradiated, the difference ΔR between R1 and R2 is 1 or less.
Transparent conductive laminate. The cured resin component (i) of the color difference adjusting layer is an ultraviolet curable resin, the haze value (H1) of the transparent conductive laminate, and the transparent conductive laminate is 12N hydrochloric acid, 16N nitric acid and water are 12N hydrochloric acid. : 16N nitric acid: water = 3.3: 1.0: 7.6 transparent conductive laminate after being dipped in a strong acid aqueous solution obtained at 40 ° C. for 3 minutes and then dried. The haze value (H2) difference ΔH is 0.3% or less,
The transparent conductive laminate according to claim 1. The phenol novolac acrylate (A) has the following formula (I)

(I)
[In Formula (I), R ¹ is H or CH ₂ OH, R ² is H or OH, n is 2 to 5, and m is 0 to 5. ]
The transparent conductive laminated body of Claim 1 or 2 shown by these.   The said (meth) acrylate (B) is an aromatic group containing (meth) acrylate whose refractive index exists in the range of 1.56-1.64, The transparent electroconductivity in any one of Claims 1-3. Laminated body. The total content of ZnO, TiO ₂ , CeO ₂ , SnO ₂ , ZrO ₂ and indium-tin oxide contained in the high refractive index anti-blocking layer is 0.0001% by mass or less in the anti-blocking layer, The transparent conductive laminated body in any one of Claims 1-4. The high refractive index antiblocking layer has a refractive index of 1.565 to 1.620, and the high refractive index antiblocking layer has an arithmetic average roughness (Ra) of 0.001 to 0.09 μm. The point average roughness (Rz) is 0.01 to 0.5 μm.
The transparent conductive laminated body in any one of Claims 1-5.   The transparent conductive laminate according to claim 1, wherein the high refractive index antiblocking layer has a thickness of 0.05 to 10 μm.   The transparent conductive laminate according to claim 1, wherein the transparent conductive layer is a crystalline layer containing indium oxide, and the thickness of the transparent conductive layer is 5 to 50 nm.   The transparent conductive property according to any one of claims 1 to 8, wherein a metal oxide layer is present between the color difference adjusting layer and the transparent conductive layer, and the thickness of the metal oxide layer is 0.5 to 5.0 nm. Laminated body. On one surface of the transparent polymer substrate, a high refractive index anti-blocking layer, a color difference adjusting layer and a transparent conductive layer are sequentially laminated, and
The transparent conductive laminate according to any one of claims 1 to 9, wherein an anti-blocking layer is formed on the other surface of the transparent polymer substrate. The anti-blocking layer is a layer formed by an anti-blocking layer forming composition containing a first component and a second component,
The first component includes an unsaturated double bond-containing acrylic copolymer, the second component includes a polyfunctional acrylate,
The difference ΔSP between the SP value (SP1) of the first component and the SP value (SP2) of the second component is in the range of 1 to 2,
After coating the anti-blocking layer forming composition, the first component and the second component undergo phase separation, and an anti-blocking layer having fine irregularities on the surface is formed.
The transparent conductive laminate according to claim 10.   A touch panel having the transparent conductive laminate according to claim 1.

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