WO2014141921A1

WO2014141921A1 - Laminate for use in touch panel and manufacturing method of laminate for use in touch panel

Info

Publication number: WO2014141921A1
Application number: PCT/JP2014/055298
Authority: WO
Inventors: 伊藤　英明; 漢那　慎一; 後藤　英範; 直樹塚本; 健司勝田
Original assignee: 富士フイルム株式会社
Priority date: 2013-03-15
Filing date: 2014-03-03
Publication date: 2014-09-18
Also published as: JP6121204B2; JP2014178922A

Abstract

This laminate for use in a touch panel has, in order, a glass substrate, a transparent electrode layer, a protective layer covering the transparent electrode layer, and a polymer layer, wherein the glass substrate is formed by performing a chemical strengthening treatment involving substituting with potassium ions some or all of the ions in the glass having an ionic radius less than that of a potassium ion.

Description

Touch panel laminate and method for manufacturing touch panel laminate

The present invention relates to a laminate for a touch panel and a method for producing a laminate for a touch panel.

In recent years, electronic devices such as mobile phones, car navigation systems, personal computers, ticket vending machines, and bank terminals have been equipped with a tablet-type input device (touch panel) on the surface of a liquid crystal device, etc., and displayed in the image display area of the liquid crystal display device. The information corresponding to the instruction image can be input by touching a location where the instruction image is displayed with a finger or a touch pen while referring to the instruction image.

Since such a touch panel is provided on the surface layer of the electronic device and glass is affixed to the outermost surface, from a safety point of view, glass fragments used as a substrate even if damaged by external impact It is required to reduce scattering.

For example, in Patent Document 1, a light-transmitting hard coat layer having a value obtained by multiplying the film thickness and the internal haze is 4 or more and the 10-point average roughness of the surface is 2 μm or less is attached to the glass surface. It is described that scattering of glass can be prevented.
Patent Document 2 discloses an adhesive sheet in which a hard coat layer, a transparent substrate film having a thickness of 25 to 70 μm, an adhesive layer, a polyester film having a thickness of 5 to 25 μm, and an adhesive layer are laminated in this order. It is described that glass scattering can be prevented by sticking to the surface of a glass plate.

On the other hand, Patent Document 3 describes a glass reinforced by a float process and having a Young's modulus of 71 to 74 GPa and a Poisson's ratio of 0.22 to 0.24. However, it does not describe that when glass is chemically strengthened, the glass can be prevented from scattering when it is damaged by external impact.

JP 2008-216913 A JP 2012-35431 A JP 2007-11210 A

By sticking a hard coat layer or an adhesive sheet to the surface of a glass plate as in Patent Document 1 and Patent Document 2, it is possible to prevent glass fragments from being scattered when damaged by receiving a certain external impact. However, as a result of investigations by the present inventors, it was found that this is insufficient.

Therefore, the present inventors proceeded with studies in order to solve such problems of the prior art. The problem to be solved by the present invention is to provide a laminate for a touch panel that can prevent scattering of glass fragments when it is damaged by an external impact, and a method for manufacturing the same.

As a result of earnest studies to solve the above problems, the present inventors have laminated a glass substrate, a transparent electrode layer, a protective layer, and a polymer layer in this order, and the glass substrate has potassium ions in the glass. We found that even when glass with a chemical strengthening treatment that replaces some or all of the ions with smaller ionic radii with potassium ions is used, it is possible to prevent scattering of glass fragments when damaged by external impact. The present invention has been reached.
The present invention, which is a specific means for solving the above problems, has the following configuration.

[1] a glass substrate;
A transparent electrode layer;
A protective layer covering the transparent electrode layer;
A polymer layer;
In this order,
A laminate for a touch panel, wherein the glass substrate is subjected to a chemical strengthening treatment in which a part or all of ions having an ion radius smaller than that of potassium ions in the glass are replaced with potassium ions.
[2] The touch panel laminate according to [1], further comprising a hard coat layer on the surface of the polymer layer opposite to the surface on which the protective layer is formed.
[3] The laminate for a touch panel according to [2], having an easy adhesion layer between at least one of the protective layer and the polymer layer and between the polymer layer and the hard coat layer.
[4] The touch panel laminate according to any one of [1] to [3], wherein an antireflection layer is provided between the transparent electrode layer and the protective layer.
[5] The touch panel laminate according to any one of [2] to [4], wherein the hard coat layer includes a hydrolysis condensate of a curable resin or an alkoxysilane.
[6] The touch panel laminate according to any one of [1] to [5], wherein the protective layer includes an acrylic polymer.
[7] The touch panel laminate according to any one of [1] to [6], having a thickness of 0.3 to 1 mm.
[8] The touch panel laminate according to any one of [4] to [7], wherein the antireflection layer has a thickness of 500 nm or less.
[9] The touch panel laminate according to any one of [4] to [8], wherein the antireflective layer has a refractive index of 1.6 or more.
[10] The refractive index difference between the refractive index of the easy adhesion layer between the protective layer and the polymer layer and the refractive index of the protective layer and the polymer layer adjacent to the easy adhesion layer is 0. The touch panel laminate according to any one of [3] to [9], which is 02 or less.
[11] The laminate for a touch panel according to any one of [1] to [10], wherein the polymer layer has a thickness of 20 to 150 μm.
[12] The refractive index difference between the refractive index of the easy adhesion layer between the polymer layer and the hard coat layer and the refractive index of the polymer layer and the hard coat layer adjacent to the easy adhesion layer is as follows: The laminate for a touch panel according to any one of [3] to [11], which is 0.02 or less.
[13] The laminate for a touch panel according to any one of [1] to [12], wherein the polymer layer includes polyethylene terephthalate, polycarbonate, or a cycloolefin polymer.
[14] The laminate for a touch panel according to any one of [1] to [13], wherein the retardation of the polymer layer is 3000 to 12000 nm.
[15] The touch panel laminate according to any one of [1] to [14], wherein the retardation of the polymer layer is 100 to 200 nm.
[16] The touch panel laminate according to any one of [1] to [15], wherein the polymer layer has a refractive index of 1.60 to 1.75.
[17] The touch panel laminate according to any one of [1] to [16], having a surface modified layer having a thickness from the surface of the polymer layer to any depth within a range of 40 to 330 nm.
[18] The laminate for a touch panel according to [17], wherein the surface modification layer is formed by performing glow discharge treatment on a surface of the polymer layer.
[19] The touch panel laminate according to [17], wherein the surface modified layer is formed by performing glow discharge treatment on a surface of the polymer layer heated to Tg or more.
[20] The hydrolysis condensate of the alkoxysilane contained in the hard coat layer is any one of [5] to [19], which is a hydrolysis condensate of an epoxy group-containing alkoxysilane and an epoxy group-free alkoxysilane. Laminate for touch panel.
[21] The touch panel laminate according to any one of [5] to [20], wherein the hard coat layer is formed by hydrolyzing alkoxysilane and condensing the hydrolyzed alkoxysilane.
[22] The touch panel laminate according to any one of [4] to [21], wherein the hard coat layer has a refractive index of 1.64 or more and 2.10 or less.
[23] The touch panel laminate according to any one of [4] to [22], wherein the antireflection layer contains particles.
[24] The touch panel laminate according to any one of [4] to [23], wherein the antireflection layer contains particles having a refractive index of 1.60 to 3.00.
[25] The touch panel laminate according to any one of [4] to [24], wherein the antireflection layer contains metal oxide particles.
[26] The touch panel laminate according to any one of [4] to [26], wherein the antireflection layer includes particles of tin oxide or zirconium oxide.
[27] The touch panel laminate according to any one of [4] to [26], wherein the antireflection layer contains 40 to 80% by mass of particles with respect to the solid content contained in the antireflection layer.
[28] The touch panel laminate according to any one of [1] to [27], having the following elements (3) to (5) as the transparent electrode layer.
(3) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (4) electrically insulated from the first transparent electrode pattern, A plurality of second electrode patterns comprising a plurality of pad portions formed extending in a direction intersecting the first direction (5) electrically connecting the first transparent electrode pattern and the second electrode pattern Insulating layer [29] for electrically insulating (6) The first transparent electrode pattern and the second electrode pattern electrically connected to at least one of the first transparent electrode pattern and the second electrode pattern [28] The laminated body for touch panels which has another electroconductive element.
[30] The laminate for a touch panel according to [28], wherein the second electrode pattern is a transparent electrode pattern.
[31] (1) The touch panel laminate according to any one of [1] to [30], which has a decorative layer.
[32] The laminate for a touch panel according to any one of [1] to [31], having a decorating layer having a thickness of 1 to 40 μm.
[33] (2) The touch panel laminate according to any one of [1] to [32], having a mask layer.
[34] The touch panel laminate according to any one of [1] to [33], wherein the surface of the glass substrate is subjected to a surface treatment.
[35] The touch panel laminate according to any one of [1] to [34], wherein the surface of the glass substrate is subjected to a surface treatment using a silane compound.
[36] The touch panel laminate according to any one of [1] to [35], wherein the glass substrate has an opening at least in part.
[37] A laminated material having a protective layer and a polymer layer in this order on a front plate with a transparent electrode layer having a glass substrate and a transparent electrode layer, the surface on the transparent electrode layer side and the surface on the protective layer side Including a step of laminating to face each other,
Any one of [1] to [36], wherein the glass substrate is subjected to a chemical strengthening treatment in which part or all of ions having a smaller ion radius than potassium ions in the glass are replaced with potassium ions. Of manufacturing a laminate for a touch panel.
[38] The method for manufacturing a laminate for a touch panel according to [37], wherein the transparent electrode layer is formed by etching a transparent conductive material using an etching pattern formed of a curable resin composition.
[39] The method for producing a laminate for a touch panel according to [37], wherein the transparent electrode layer is formed using a conductive curable resin composition.

According to the present invention, it is possible to provide a laminated body for a touch panel that can prevent scattering of glass fragments when damaged by receiving an external impact, and a method for manufacturing the same.

It is a cross-sectional schematic diagram of the laminated body for touchscreens of this invention. It is sectional drawing which shows the structure of the electrostatic capacitance type input device of this invention. It is explanatory drawing which shows an example of the front plate in this invention. It is explanatory drawing which shows an example of the 1st transparent electrode pattern in this invention, and a 2nd transparent electrode pattern. It is a top view which shows an example of the tempered glass in which the opening part was formed. It is a top view which shows an example of the front board in which the mask layer was formed. It is a top view which shows an example of the front plate in which the 1st transparent electrode pattern was formed. It is a top view which shows an example of the front plate in which the 1st and 2nd transparent electrode pattern was formed. It is a top view which shows an example of the front plate in which the electroconductive element different from the 1st and 2nd transparent electrode pattern was formed. It is explanatory drawing which shows a metal nanowire cross section.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Laminate for touch panel]
The laminate for a touch panel of the present invention has a glass substrate, a transparent electrode layer, a protective layer covering the transparent electrode layer, and a polymer layer in this order, and the glass substrate is more than potassium ions in the glass. It is characterized in that it is subjected to a chemical strengthening treatment in which part or all of ions having a small ion radius are replaced with potassium ions.

In the present invention, scattering of glass fragments on the glass substrate can be prevented by adopting such a configuration, that is, a configuration having a polymer layer.
Moreover, by setting it as the more preferable structure of this invention mentioned later, light reflection reduces and it becomes difficult to see a transparent electrode pattern, and it is excellent in visibility, ie, a haze.
FIG. 1 is a schematic cross-sectional view showing an example of a laminate for a touch panel of the present invention. The laminate for a touch panel of the present invention comprises, from the outermost surface side (viewing side), the glass substrate 100, the transparent electrode layer 101, the protective layer 102 formed so as to cover the transparent electrode layer 101, and the polymer layer 103 in this order. Have in.
An easy adhesion layer 104 may be provided between the protective layer 102 and the polymer layer 103 as necessary. Moreover, the laminated body for touchscreens of this invention may have the hard-coat layer 105 in the surface on the opposite side to the surface by the side of the protective layer 102 of the polymer layer 103 as needed, An easy-adhesion layer 106 may be provided between the polymer layer 103. In addition, a decoration layer 107 may be provided at the end of the surface of the glass substrate 1 opposite to the surface on the viewing side.
Further, an antireflection layer (not shown) may be provided between the transparent electrode layer 101 and the protective layer 102, and on the opposite side of the surface of the glass substrate 100 where the transparent conductive layer 101 is formed. You may have a hard-coat layer (not shown).

The thickness of the laminate for a touch panel of the present invention is preferably 0.3 to 1 mm, more preferably 0.5 to 1 mm, and further preferably 0.7 to 1 mm.
Hereinafter, each member which comprises the laminated body for touchscreens of this invention is demonstrated.

<Glass substrate>
The glass substrate used in the laminate for a touch panel of the present invention is subjected to a chemical strengthening treatment in which part or all of ions having an ion radius smaller than that of potassium ions in the glass are replaced with potassium ions.
The glass used in the present invention is not particularly limited, but the strain point temperature obtained by a method according to JIS R3103-2 (2001) is preferably 500 ° C. to 520 ° C. Further, it is preferable that the temperature near the temperature at which glass is likely to be deformed, that is, the temperature of the molten salt is 490 to 530 ° C. The glass substrate used in the present invention is chemically strengthened on the surface of SiO ₂ —Na ₂ O—K ₂ O—CaO—MgO—Al ₂ O ₃ glass, for example, so-called soda lime glass produced by a float process. It is preferable that the compression layer is formed by performing the treatment.

The chemical strengthening treatment is performed, for example, by immersing glass in a molten salt. By this chemical strengthening treatment, sodium ions in the glass and potassium ions in the molten salt are exchanged to form a compressed layer. The compressed layer has a compressive stress value of 200 to 650 MPa. In the chemical strengthening treatment performed in the present invention, the temperature of the molten salt for immersion is 450 to 550 ° C. and the immersion time is 1 hour or more when chemically strengthening the glass so that the formed compressed layer has the value. 3 hours is preferable.

The thickness of the glass substrate is preferably 0.3 to 1.0 mm, and more preferably 0.4 to 0.8 mm. By setting the thickness of the glass substrate to 0.3 mm or more, insufficient strength can be solved.

<Transparent electrode layer>
It is preferable that the laminated body for touchscreens of this invention has a transparent electrode layer on a glass substrate, and is arrange | positioned at pattern shape.
The transparent electrode layer preferably has a refractive index of 1.75 to 2.1.
The material for the transparent electrode layer is not particularly limited, and a known material can be used. For example, it can be made of a light-transmitting conductive metal oxide film such as ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide). Examples of such metal films include ITO films; metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; metal oxide films such as SiO ₂ . At this time, the film thickness of each element can be set to 10 to 200 nm. Further, since the amorphous ITO film is made into a polycrystalline ITO film by firing, the electrical resistance can be reduced. In addition, when forming a conductive pattern or the like in the transparent electrode layer with ITO or the like, paragraphs [0014] to [0016] of Japanese Patent No. 4506785 can be referred to. Among them, the transparent electrode pattern is preferably an ITO film.
In the transparent laminate of the present invention, the transparent electrode pattern is preferably an ITO film having a refractive index of 1.75 to 2.1.

The thickness of the transparent electrode layer is preferably 10 to 200 nm, more preferably 20 to 150 nm, and even more preferably 30 to 100 nm.

<< Transparent electrode pattern >>
When the laminate of the present invention is used in a capacitance-type input device to be described later, the transparent electrode pattern is a first transparent electrode pattern and a second transparent electrode pattern in two directions substantially orthogonal to the row direction and the column direction, respectively. (See, for example, FIG. 4). For example, in the configuration of FIG. 4, the transparent electrode pattern in the laminate of the present invention may be the second transparent electrode pattern 4 or the pad portion 3 a of the first transparent electrode pattern 3. In other words, in the following description of the transparent laminate of the present invention, the reference numeral of the transparent electrode pattern may be represented by “4”. However, the transparent electrode pattern in the transparent laminate of the present invention is the static electrode of the present invention. It is not limited to the use for the second transparent electrode pattern 4 in the capacitive input device, but may be used as the pad portion 3a of the first transparent electrode pattern 3, for example.

The refractive index of the transparent electrode pattern is preferably 1.75 to 2.1.
The material for the transparent electrode pattern is not particularly limited, and a known material can be used. For example, ITO (Indium Tin Oxide) or IZO (Indium
It can be made of a light-transmitting conductive metal oxide film such as Zinc Oxide). Examples of such metal films include ITO films; metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; metal oxide films such as SiO ₂ . At this time, the film thickness of each element is 10-20.
It can be 0 nm. Further, since the amorphous ITO film is made into a polycrystalline ITO film by firing, the electrical resistance can be reduced. Moreover, said 1st transparent electrode pattern 3, the 2nd transparent electrode pattern 4, and the electroconductive element 6 mentioned later use the photosensitive film which has the photocurable resin layer using the said conductive fiber. It can also be manufactured. In addition, when the first conductive pattern or the like is formed of ITO or the like, paragraphs [0014] to [0016] of Japanese Patent No. 4506785 can be referred to. Among them, the transparent electrode pattern is preferably an ITO film.
The transparent electrode pattern is preferably an ITO film having a refractive index of 1.75 to 2.1.

<Protective layer>
The laminated body for touch panels of this invention has a protective layer which covers a transparent electrode layer, and it is preferable that a protective layer has a function which prevents the corrosion of a transparent electrode layer. The prevention of corrosion of the transparent electrode layer here is preferably carried out by removing the halogen-containing compound, in particular by dehalogenating the photopolymerization initiator.

The protective layer preferably contains metal oxide particles, a resin (preferably an alkali-soluble resin), a polymerizable compound, a polymerization initiator, or a polymerization initiation system. Furthermore, an additive etc. are used, but it is not restricted to this.

The protective layer may be a transparent resin film or an inorganic film.
As the inorganic film, inorganic films used in JP 2010-86684 A, JP 2010-152809 A, JP 2010-257492 A, and the like can be used, which are described in these documents. From the viewpoint of controlling the refractive index, it is preferable to use an inorganic film having a laminated structure of a low refractive index material and a high refractive index material, or an inorganic film having a mixed film of a low refractive index material and a high refractive index material. As the low refractive index material and the high refractive index material, the materials used in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used. The contents of these documents are incorporated herein.
The inorganic layer may be a mixed layer of SiO ₂ and Nb ₂ O _5, and more preferably that case is a mixed film of SiO ₂ and Nb ₂ O ₅ formed by sputtering.

In the present invention, the protective layer is preferably a transparent resin film.
A method for controlling the refractive index of the transparent resin film is not particularly limited, but a transparent resin film having a desired refractive index is used alone, or a transparent resin film to which fine particles such as metal fine particles and metal oxide fine particles are added is used. Can be used.

The resin composition used for the transparent resin film preferably contains metal oxide particles for the purpose of adjusting the refractive index and light transmittance. Since the metal oxide particles have high transparency and light transmittance, a composition having a high refractive index and excellent transparency can be obtained.
The metal oxide particles preferably have a refractive index higher than that of a resin composition made of a material excluding the particles. Specifically, the refractive index in light having a wavelength of 400 to 750 nm is used. Particles of 1.50 or more are more preferable, particles having a refractive index of 1.70 or more are further preferable, and particles of 1.90 or more are particularly preferable.
Here, the refractive index of light having a wavelength of 400 to 750 nm being 1.50 or more means that the average refractive index of light having a wavelength in the above range is 1.50 or more. It is not necessary that the refractive index of all light having a wavelength is 1.50 or more. The average refractive index is a value obtained by dividing the sum of the measured values of the refractive index for each light having a wavelength in the above range by the number of measurement points.

In addition, the metal of the metal oxide particles includes semimetals such as B, Si, Ge, As, Sb, and Te.
The light-transmitting and high refractive index metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, and Nb. Oxide particles containing atoms such as Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, and Te are preferable. Titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / Tin oxide and antimony / tin oxide are more preferable, titanium oxide, titanium composite oxide and zirconium oxide are more preferable, titanium oxide and zirconium oxide are particularly preferable, and titanium dioxide is most preferable. Titanium dioxide is particularly preferably a rutile type having a high refractive index. The surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability.

From the viewpoint of the transparency of the resin composition, the average primary particle diameter of the metal oxide particles is preferably 1 to 200 nm, particularly preferably 3 to 80 nm. Here, the average primary particle diameter of the particles refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the longest side is the diameter.

Moreover, the said metal oxide particle may be used individually by 1 type, and can also use 2 or more types together.
The content of the metal oxide particles in the resin composition may be appropriately determined in consideration of the refractive index required for the optical member obtained from the resin composition, light transmittance, and the like. The total solid content is preferably 5 to 80% by mass, more preferably 10 to 70% by mass.
The transparent resin film preferably has at least one of ZrO ₂ particles and TiO ₂ particles from the viewpoint of controlling the refractive index within the range of the refractive index of the antireflection layer, and more preferably ZrO ₂ particles.

There are no particular restrictions on the resin (referred to as binder or polymer) and other additives used for the transparent resin film unless they are contrary to the spirit of the present invention.

As the resin (referred to as a binder or a polymer) used in the protective layer, an alkali-soluble resin is preferable. Examples of the alkali-soluble resin include paragraph [0025] of JP 2011-95716 A and paragraph of JP 2010-237589 A. The polymers described in [0033] to [0052] can be used.

As the polymerizable compound, the polymerizable compounds described in paragraphs [0023] to [0024] of Japanese Patent No. 4098550 can be used.
As the polymerization initiator or polymerization initiation system, the polymerizable compounds described in [0031] to [0042] described in JP2011-95716A can be used.

Furthermore, an additive may be used for the protective layer. Examples of the additive include surfactants described in paragraph [0017] of Japanese Patent No. 4502784, paragraphs [0060] to [0071] of JP-A-2009-237362, and paragraph [ And the other additives described in paragraphs [0058] to [0071] of JP-A No. 2000-310706.

The thickness of the protective layer is preferably 1 to 50 nm, more preferably 2 to 30 nm.
Further, the refractive index of the protective layer is preferably 1.5 to 1.53, more preferably 1.5 to 1.52, and particularly preferably 1.51 to 1.52.

<Polymer layer>
The laminated body for touchscreens of this invention has a polymer layer. In the present invention, the effect of the present invention is achieved by having a polymer layer and adopting a predetermined stacking order.

It is preferable to use a polymer film for the polymer layer.
The material of the polymer film used for the polymer layer is not particularly limited and is arbitrary. Examples thereof include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate, polystyrene, polyether ether ketone, polyphenylene sulfide, and cycloolefin polymer. Of these, polycarbonate, polyester (particularly, polyethylene terephthalate), or cycloolefin polymer is exemplified as a particularly preferable material. These resins are excellent in transparency and excellent in thermal and mechanical properties, and the retardation can be easily controlled by stretching. In particular, polyesters typified by polyethylene terephthalate are the most suitable materials because they have a large intrinsic birefringence and relatively large retardation can be obtained relatively easily even when the film thickness is thin.
The polyester film in the present invention refers to a film whose main component is polyester, and usually refers to a film in which 98% by mass or more of the resin component is polyester, and preferably 90% by mass of the component constituting the polyester film is polyester. Is a film. The kind in particular of polyester is not restrict | limited, A well-known thing can be used as polyester. Specific examples include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polybutylene naphthalate. Among them, it is particularly preferable to use polyethylene terephthalate (PET) from the viewpoint of cost and mechanical strength.

Since the polymer film has a specific birefringence, it is desirable to use an oriented film. However, the production method is not particularly limited as long as the film characteristics defined in the present invention are satisfied.

In the case of a polycarbonate film, a non-oriented sheet obtained by melting polycarbonate and extruding it into a sheet is stretched in one direction (or two directions if necessary) at a temperature equal to or higher than the glass transition temperature to obtain an orientation having a specific retardation. A polycarbonate film can be obtained. As the non-oriented polycarbonate sheet, a commercially available product or a solution prepared by solution film formation can be suitably used.
Moreover, when using a cycloolefin polymer, a well-known cycloolefin polymer can be used and it is preferable to use the cycloolefin polymer which has specific retardation. In the case of a cycloolefin film, a non-oriented sheet obtained by melting a cycloolefin polymer and extruding it into a sheet is stretched in one direction (or two directions if necessary) at a temperature equal to or higher than the glass transition temperature, and a specific retardation is obtained. An oriented cycloolefin polymer film having the following can be obtained.
As the oriented cycloolefin polymer having a specific retardation, commercially available ones may be used, and examples thereof include ZEON A FILM ZD14 manufactured by ZEON Corporation.
As the non-oriented cycloolefin polymer, a commercially available product or a solution prepared by solution casting can be suitably used.

Further, in the case of a polyester film, there is a method in which a non-oriented polyester obtained by melting polyester and extruding into a sheet is subjected to heat treatment after transverse stretching with a tenter at a temperature equal to or higher than the glass transition temperature.

Specifically, the transverse stretching temperature is preferably 80 to 130 ° C., particularly preferably 90 to 120 ° C. The transverse draw ratio is preferably 2.5 to 6.0 times, and particularly preferably 3.0 to 5.5 times. When the draw ratio is too high, the transparency of the resulting film tends to be lowered. On the other hand, if the draw ratio is too low, the draw tension is also small, so the birefringence of the resulting film is small, and the retardation is small, such being undesirable. In the subsequent heat treatment, the treatment temperature is preferably from 100 to 250 ° C., particularly preferably from 180 to 245 ° C.

In order to control the retardation of the polymer layer within a specific range, the stretching ratio, stretching temperature, and film thickness can be appropriately set. For example, the higher the stretching ratio, the lower the stretching temperature, and the thicker the film, the higher the retardation. Conversely, the lower the stretching ratio, the higher the stretching temperature, and the thinner the film, the lower the retardation.

The polymer layer preferably has a surface modification layer. The surface modified layer is a layer formed on the surface layer of the polymer layer, and means a layer having an amorphous degree (non-crystalline degree / crystalline degree) of 5% or more. The surface modification layer has a thickness from the surface of the polymer layer to any depth within the range of 40 to 330 nm. The surface modification layer preferably has a thickness up to any depth within the range of 330 nm, more preferably within the range of 50 to 220 nm, and within the range of 50 to 200 nm. Further preferred.

The non-crystallinity indicates the ratio of the non-crystalline part to the total of the non-crystalline part and the crystal part (content ratio of the non-crystalline part). The non-crystal part contains many Gauche crystal molecules, and the crystal part contains many trans-type crystal molecules. For this reason, the content rate of the non-crystal part and the crystal part can be calculated by the content rate of the crystal molecules. Specifically, the content ratio of the amorphous part and the crystalline part can be calculated by obtaining the spectrum of the surface modified layer by the ATR-IR method. A value obtained by dividing the amorphous degree (1175 cm ⁻¹ ) by the spectrum of the crystallinity spectrum (1341 cm ⁻¹ ) was defined as the amorphous degree (non-crystalline degree / crystalline degree).

The amorphousness (noncrystallinity / crystallinity) of the surface modification layer of the polymer layer is preferably 5% or more, more preferably 5 to 8.3%, and more preferably 5 to 8%. Further preferred. By setting the amorphous degree of the surface modified layer within the above range, it is possible to improve the oligomer block property and adhesion while preventing yellowing of the polymer layer.

The thickness of the surface modification layer can be obtained by osmium staining the polymer layer surface and observing a cross-section TEM. It is said that the portion where the chromaticity is L = 30 or less is dyed black, and this is a modified portion. In the untreated case, almost nothing can be seen, but when the glow discharge treatment is performed, the surface is dyed black.

By subjecting the polymer layer to glow discharge treatment, it is preferable to form the surface modified layer as described above on the surface of the polyester film. By heating to Tg or higher and glow discharge treatment, the surface of the polyester film is subjected to the above-described treatment. It is more preferable to form such a surface modified layer.

As the polymer layer, a glow discharge treatment may be applied to the surface of the polymer layer in order to impart adhesion to the protective layer or the easy-adhesion layer and the hard coat layer.
The glow discharge treatment is a method called vacuum plasma treatment or glow discharge treatment, in which plasma is generated by discharge in a gas (plasma gas) in a low-pressure atmosphere to treat the substrate surface. The low-pressure plasma used in the process of the present invention is a non-equilibrium plasma generated under conditions where the plasma gas pressure is low. The treatment of the present invention is performed by placing a film to be treated in this low-pressure plasma atmosphere.
In the glow discharge treatment of the present invention, as a method for generating plasma, methods such as direct current glow discharge, high frequency discharge, and microwave discharge can be used. The power source used for discharging may be direct current or alternating current. When alternating current is used, a range of about 30 Hz to 20 MHz is preferable. When alternating current is used, a commercial frequency of 50 or 60 Hz may be used, or a high frequency of about 10 to 50 kHz may be used. A method using a high frequency of 13.56 MHz is also preferable.

As the plasma gas used in the glow discharge treatment of the present invention, an inorganic gas such as oxygen gas, nitrogen gas, water vapor gas, argon gas, helium gas can be used, and in particular, oxygen gas or oxygen gas and argon gas The mixed gas is preferable. Specifically, it is desirable to use a mixed gas of oxygen gas and argon gas. When oxygen gas and argon gas are used, the ratio between the two is preferably oxygen gas: argon gas = 100: 0 to 30:70, more preferably 90:10 to 70:30, as a partial pressure ratio. In addition, a method is also preferable in which a gas such as the air entering the processing container due to a leak or water vapor coming out of the object to be processed is used as the plasma gas without introducing the gas into the processing container.

As the pressure of the plasma gas, a low pressure at which non-equilibrium plasma conditions are achieved is necessary. The specific plasma gas pressure is preferably in the range of about 0.005 to 10 Torr, more preferably about 0.008 to 3 Torr. When the pressure of the plasma gas is less than 0.005 Torr, the effect of improving the adhesiveness may be insufficient. Conversely, when the pressure exceeds 10 Torr, the current may increase and the discharge may become unstable.
The plasma output cannot be generally specified depending on the shape and size of the processing container, the shape of the electrode, and the like, but is preferably about 100 to 10,000 W, more preferably about 2000 to 10,000 W.

The treatment time of the glow discharge treatment of the present invention is preferably 0.05 to 100 seconds, more preferably about 0.5 to 30 seconds. If the treatment time is less than 0.05, the adhesion improving effect may be insufficient. Conversely, if the treatment time exceeds 100 seconds, problems such as deformation and coloring of the film to be treated may occur.

Discharge treatment intensity of the glow discharge treatment of the present invention will depend on the plasma power and treatment time, preferably in the range of 0.01 ~ 10kV · A · min ^{/ m 2, 0.1 ~ 7kV ·} A · min / m ² Gayori preferable.
Discharge treatment intensity that is sufficient adhesion improving effect of the 0.01 kV · A · min / m ² or more is obtained, and such deformation and coloration of the processed film by a 10 kV · A · min / m ² or less You can avoid problems.

In the glow discharge treatment of the present invention, it is preferable to heat a polymer layer that is a film to be treated in advance. The surface of the polyester film is preferably subjected to glow discharge treatment at a temperature equal to or higher than Tg and then subjected to glow discharge treatment. That is, during the glow discharge treatment, the surface of the polymer layer is preferably heated to Tg (69 ° C.) or higher. The surface of the polymer layer is more preferably heated within a temperature range of Tg to 200 ° C., and further preferably heated within a temperature range of Tg to 150 ° C. By performing the glow discharge treatment after heating within the above temperature range, it is possible to prevent the oligomer from being deposited on the polymer layer and to prevent the polymer layer from being whitened. Furthermore, it can suppress that a polymer layer yellows by performing a glow discharge process after heating within the said temperature range. Thereby, interference nonuniformity is eliminated and the laminated body for touchscreens with a small b ^* value and a haze value can be obtained.

Specific examples of the method for raising the temperature of the film to be processed in a vacuum include heating with an infrared heater and a heating method by contacting with a hot roll.

The b ^* value of the laminate for a touch panel of the present invention is preferably −2.0 to 2.0,
It is more preferably −1.5 to 1.5, and further preferably −1.2 to 1.2. In the present invention, the degree of yellowish coloring is represented by a b ^* value in the CIE 1976 L ^* a ^* b ^* color system.
The b ^* value of the polymer layer is preferably b ^* = 0.006t + 0.55 or less. The b ^* value is preferably b ^* = 0.006t + 0.38 or less, and b ^* = 0.006.
More preferably, it is t + 0.25 or less. In the above formula, t represents the thickness (μm) of the polymer layer. By making b ^* value below the said formula, the yellowing of the said polymer layer can be prevented and the transparency of a polyester film can be improved.

In the present invention, the b ^* value of the polymer layer is preferably 1.75 or less, more preferably 1.6 or less, and even more preferably 1.45 or less. The thickness of the polymer layer used in the present invention is not particularly limited, but when the thickness of the polymer layer is 10 to 100 μm, the b ^* value is preferably 1.2 or less. It is more preferably 0 or less, and further preferably 0.9 or less. Further, when the film thickness of the polymer layer is 100 to 150 μm, the b ^* value is preferably 1.45 or less, more preferably 1.3 or less, and further preferably 1.15 or less. . Further, when the film thickness of the polymer layer is 150 to 200 μm, the b ^* value is preferably 1.75 or less, more preferably 1.6 or less, and further preferably 1.45 or less. .

Further, it is preferable that the amount of change in b ^* value after the b ^* value and a glow discharge treatment before the glow discharge treatment is performed is performed ([Delta] b) is 0.3 or less, is 0.2 or less More preferably, it is more preferably 0.1 or less. A small change in the b ^* value before and after the glow discharge treatment indicates that no yellowing has occurred in the glow discharge treatment. In the present invention, the polymer layer in which yellowing is suppressed can be obtained by setting the change amount of the b ^* value before and after the glow discharge treatment to be equal to or less than the above upper limit value.

Moreover, it is preferable that the haze value of the laminated body for touchscreens of this invention is 2% or less, It is more preferable that it is 1.5% or less, It is further more preferable that it is 1% or less.
By setting the b ^* value and haze value of the laminated film within the above ranges, when the laminated body for a touch panel of the present invention is incorporated in a display device such as a touch panel, image coloring can be reduced and visibility is improved. Can be made good.

The polymer film used in the polymer layer preferably has a retardation of 3000 to 12000 nm (in-plane retardation, hereinafter also referred to as Re), more preferably has a retardation of 4500 to 10000 nm, and preferably 6000 to 8000 nm. More preferably, the phase difference is as follows. When the polymer layer retardation is less than 3000 nm, when the screen is observed through a polarizing plate such as sunglasses, a strong interference color is exhibited. Therefore, the envelope shape is different from the emission spectrum of the light source, and good visibility cannot be ensured. On the other hand, when the polymer layer retardation exceeds 12000 nm, even if a polymer film having a polymer layer retardation of more than that is used, a further improvement in visibility is not substantially obtained, and the thickness of the film is considerably increased. This is not preferable because it becomes thick and the handling property as an industrial material is lowered.

The Re of the polymer film used for the polymer layer is preferably in a range that allows it to function as a λ / 4 plate, from the viewpoint of the visibility of the display image when a polarizing plate such as polarized sunglasses is used.
In this case, Re of the polymer film used for the polymer layer is preferably 100 to 200 nm, more preferably 120 to 180 nm, and further preferably 130 to 160 nm.
If the Re of the polymer film used for the polymer layer falls outside this range, the polarization state of the display image of the liquid crystal display device cannot be made circularly polarized, and the display image when passing through a polarizing plate such as polarized sunglasses is displayed. The visibility is significantly deteriorated depending on the angle of the polarized sunglasses.

Further, the ratio of the retardation in the in-plane direction to the thickness direction retardation (Re / Rth) of the polymer layer is preferably 0.200 or more, more preferably 0.500 or more, and further preferably 0.600 or more. As the ratio of the retardation in the in-plane direction to the retardation in the thickness direction (Re / Rth) is larger, rainbow unevenness when viewed with polarized sunglasses can be eliminated.
On the other hand, the ratio (Re / Rth) of retardation in the in-plane direction and thickness direction retardation of the polymer layer is preferably 1.2 or less, more preferably 1.0 or less. If it is larger than 1.2, the polymer film needs to be stretched more and the strength may be inferior.

Retardation (Re (λ) and Rth (λ)) represents retardation in the in-plane direction (nm) and retardation in the thickness direction (nm), respectively, at the wavelength λ. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or WR (manufactured by Oji Scientific Instruments).

When the film to be measured is represented by a uniaxial or biaxial refractive index ellipsoid, Rth (λ) is calculated by the following method.
Rth (λ) is Re (λ), with the in-plane slow axis (determined by KOBRA 21ADH or WR) as the tilt axis (rotation axis) (if there is no slow axis, any in-plane film The light is incident at a wavelength of λ nm from the inclined direction in steps of 10 degrees from the normal direction to 50 degrees on one side with respect to the film normal direction of the rotation axis of KOBRA 21ADH or WR is calculated based on the measured retardation value, the assumed value of the average refractive index, and the input film thickness value.
In the above case, in the case of a film having a direction in which the retardation value is zero at a certain tilt angle with the in-plane slow axis from the normal direction as the rotation axis, retardation at a tilt angle larger than the tilt angle. The value is calculated by KOBRA 21ADH or WR after changing its sign to negative.
In addition, the retardation value is measured from the two inclined directions, with the slow axis as the tilt axis (rotation axis) (in the absence of the slow axis, the arbitrary direction in the film plane is the rotation axis), Based on the value, the assumed value of the average refractive index, and the input film thickness value, Rth can also be calculated from the following equations (11) and (12).

Note:
In the formula, Re (θ) represents a retardation value in a direction inclined by an angle θ from the normal direction.
nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction perpendicular to nx in the plane, and nz represents the refractive index in the direction perpendicular to nx and ny. d represents a film thickness.

In the case where the film to be measured cannot be expressed by a uniaxial or biaxial refractive index ellipsoid, that is, a film having no so-called optical axis, Rth (λ) is calculated by the following method.
Rth (λ) is from −50 degrees to +50 degrees with respect to the normal direction of the film, with Re (λ) as the slow axis (indicated by KOBRA 21ADH or WR) in the plane and the tilt axis (rotation axis). In each of the 10 degree steps, light of wavelength λ nm is incident from the inclined direction and measured at 11 points. Based on the measured retardation value, the assumed average refractive index, and the input film thickness value, KOBRA 21ADH or WR is calculated.

Here, as the assumed value of the average refractive index, values in the polymer handbook (John Wiley & Sons, Inc.) and catalogs of various optical films can be used. Those whose average refractive index is not known can be measured with an Abbe refractometer. Examples of the average refractive index of the main optical film are as follows: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Examples include polystyrene (1.59).
By inputting the assumed value of the average refractive index and the film thickness, nx, ny, and nz can be calculated by KOBRA 21ADH. The measurement wavelength is 550 nm unless otherwise specified.

By setting the retardation of the polymer film within the above range, it becomes possible to approximate the envelope shape of the spectrum of transmitted light to the emission spectrum of the light source with only a relatively simple configuration. That is, since the conventional technique uses a light source having a discontinuous emission spectrum, the visibility cannot be improved unless a birefringent body having an extremely high retardation (over 100,000 nm) is used. Using the property of a white LED light source having a spectrum, a unique effect of improving the visibility with a relatively simple configuration as described above is achieved.

The thickness of the polymer layer is preferably 20 to 150 μm, more preferably 30 to 125 μm, and even more preferably 50 to 100 μm. When the thickness is less than 20 μm, the anisotropy of the mechanical properties of the polymer film becomes remarkable, and tearing, tearing and the like are likely to occur, and the practicality as an industrial material is remarkably reduced. On the other hand, when it exceeds 150 μm, the polymer film is very rigid, and the flexibility specific to the polymer film is lowered, and the practicality as an industrial material may also be lowered.

The refractive index of the polymer layer varies depending on the material used, but is preferably 1.60 to 1.75, more preferably 1.62 to 1.68, and 1.64 to 1.67. It is particularly preferred that When the refractive index is within the above range, it is possible to obtain a laminate for a touch panel having excellent rigidity as a support for the laminate for a touch panel and having excellent transparency. In the present invention, the refractive index represents a measured value at a wavelength of 660 nm.

The polymer layer may contain other additives as long as they do not depart from the spirit of the present invention, and examples thereof include antioxidants and ultraviolet inhibitors.

<Hard coat layer>
It is preferable that the laminated body for touchscreens of this invention has a hard-coat layer in the surface on the opposite side to the surface in which the protective layer of a polymer layer is formed. By having a hard coat layer, not only the scattering property of glass but also haze, transparency, pencil hardness and the like can be improved.
In addition, you may have a hard-coat layer also on the opposite side of the surface in which the transparent conductive layer of a glass substrate is formed.

The hard coat layer preferably contains a hydrolysis condensate of curable resin or alkoxysilane.
As one of the preferable embodiments of the hard coat layer, it is preferable that the hard coat layer is mainly composed of a curable resin having high chemical resistance and scratch resistance (50% by mass or more). The hard coat layer may be formed by curing a curable resin by irradiation with ultraviolet rays or an electron beam, or may be formed by condensing and curing a hydrolyzate of alkoxysilane.
When the curable resin is cured by irradiation with ultraviolet rays or an electron beam, the curable resin includes an ionizing radiation curable resin, a thermosetting resin, a thermoplastic resin, and preferably a film forming operation. It is an ionizing radiation curable resin that is easy to increase and pencil hardness can be easily increased to a desired value. Moreover, when forming by condensing the hydrolyzate of alkoxysilane, it can form by apply | coating and drying the aqueous composition containing the hydrolyzate of alkoxysilane. For this reason, a hard-coat layer can be formed without using an organic solvent etc., and the load to an environment can be reduced significantly.

<< Ionizing radiation curable resin >>
As the ionizing radiation curable resin used for forming the hard coat layer, those having an acrylate functional group are preferable, and polyester acrylate or urethane acrylate is particularly preferable. The polyester acrylate is composed of an oligomer (meth) acrylate of a polyester-based polyol. The urethane acrylate is composed of an acrylated oligomer composed of a polyol compound and a diisocyanate compound. In addition, as a monomer constituting the acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2 ethylhexyl (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate And phenyl (meth) acrylate.

¡To further increase the hardness of the hard coat layer, a polyfunctional monomer can be used in combination. Specific polyfunctional monomers include, for example, trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, 1,6 hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like.

Polyester oligomers used to form the hard coat layer include adipic acid and glycol (ethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, polybutylene glycol, etc.) and triol (glycerin, trimethylolpropane, etc.) sebacic acid and glycol Examples thereof include polyadipate triol which is a condensation product with triol and polysebacate polyol. Note that a part or all of the aliphatic dicarboxylic acid may be substituted with another organic acid. In this case, as the other organic acid, isophthalic acid, terephthalic acid, phthalic anhydride, or the like is preferable because high hardness is expressed in the hard coat layer.

The polyurethane oligomer used for forming the hard coat layer can be obtained from a condensation product of polyisocyanate and polyol. Specific polyisocyanates include adducts of methylene bis (p-phenylene diisocyanate), hexamethylene diisocyanate / hexane triol, hexamethylene diisocyanate, tolylene diisocyanate, tolylene diisocyanate trimethylolpropane, 1,5 Examples include naphthylene diisocyanate, thiopropyl diisocyanate, ethylbenzene-2,4-diisocyanate, 2,4-tolylene diisocyanate dimer, hydrogenated xylylene diisocyanate, tris (4-phenyl isocyanate) thiophosphate, Specific polyols include polyether polyols such as polyoxytate and methylene glycol, polyadipate polyols, and polycarbonate polyols. What polyester polyols, such as copolymers of acrylic acid esters and hydroxyethyl methacrylate can be exemplified.

In addition, when UV curable resins are used as the above ionizing radiation curable resins, photopolymerization of acetophenones, benzophenones, mifilabenzoylbenzoate, α-amyloxime esters, thioxanthones, etc. in these resins is started. It is preferable to use n-butylamine, triethylamine, tri-n-butylphosphine or the like as a photosensitizer mixed as a photosensitizer.

In addition, urethane acrylate is rich in elasticity and flexibility and excellent in workability (foldability), but has insufficient surface hardness, and it is difficult to obtain a pencil hardness of 2H or more. On the other hand, the polyester acrylate can form a hard coat layer with extremely high hardness by selecting the constituent components of the polyester. Therefore, a hard coat layer in which 40 to 10 parts by mass of polyester acrylate is blended with 60 to 90 parts by mass of urethane acrylate is preferable because both high hardness and flexibility are easily achieved.

<< Alkoxysilane >>
When the hard coat layer is formed by condensing an alkoxysilane hydrolyzate, the thickness of the hard coat layer can be controlled by adjusting the coating amount of the aqueous composition.

In another preferred embodiment of the hard coat layer used in the present invention, the hard coat layer is formed by condensing a hydrolyzate of alkoxysilane. Alkoxysilane has a hydrolyzable group, and when this hydrolyzable group is hydrolyzed in an acidic aqueous solution, silanol is generated, and silanols condense with each other, so that a hydrolyzed condensate of alkoxysilane ( Oligomer) is produced. That is, the hard coat layer contains a hydrolysis condensate of alkoxysilane.
The hard coat layer may contain a portion of alkoxysilane or a hydrolyzate thereof in addition to the alkoxysilane hydrolysis condensate.
The hard coat layer used in the present invention can be formed by applying an aqueous composition containing alkoxysilane and drying it. The use of an aqueous composition is also preferable from the viewpoint of reducing environmental pollution caused by VOC (volatile organic compounds).

Moreover, it is preferable to use an epoxy group-containing alkoxysilane and an epoxy group-free alkoxysilane as the alkoxysilane. Each of the epoxy group-containing alkoxysilane and the epoxy group-free alkoxysilane has a hydrolyzable group. Therefore, the hydrolyzable group is hydrolyzed in an acidic aqueous solution, and the resulting silanol is condensed to contain an epoxy group. A hydrolysis condensate of alkoxysilane and epoxy group-free alkoxysilane is produced. That is, the hard coat layer used in the present invention includes a hydrolysis condensate of an epoxy group-containing alkoxysilane and an epoxy group-free alkoxysilane.

In the aqueous composition for forming the hard coat layer, the ratio of the epoxy group-containing alkoxysilane to the total alkoxysilane is preferably 20 to 85% by mass. The proportion of the epoxy group-containing alkoxysilane may be 20% by mass or more, preferably 25% by mass or more, and more preferably 30% by mass or more. Moreover, the ratio for which an epoxy-group-containing alkoxysilane accounts may be 85 mass% or less, it is preferable that it is 80 mass% or less, and it is more preferable that it is 75 mass% or less. By setting the ratio of the epoxy group-containing alkoxysilane to the total alkoxysilane within the above range, the stability of the aqueous composition can be increased, and further, a hard coat layer having strong alkali resistance can be formed. .

The epoxy group-containing alkoxysilane is an alkoxysilane having an epoxy group. Any epoxy group-containing alkoxysilane may be used as long as it has one or more epoxy groups in one molecule, and the number of epoxy groups is not particularly limited. In addition to the epoxy group, the epoxy group-containing alkoxysilane may further have a group such as an alkyl group, an amide group, a urethane group, a urea group, an ester group, a hydroxy group, or a carboxyl group.

As the epoxy group-containing alkoxysilane used in the present invention, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxy) Cyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Examples thereof include glycidoxypropyltriethoxysilane. Examples of commercially available products include KBE-403 (manufactured by Shin-Etsu Chemical Co., Ltd.).

The epoxy group-free alkoxysilane is an alkoxysilane having no epoxy group. The epoxy group-free alkoxysilane may be an alkoxysilane having no epoxy group, and may have a group such as an alkyl group, an amide group, a urethane group, a urea group, an ester group, a hydroxy group, or a carboxyl group. good.

The epoxy group-free alkoxysilane is preferably tetraalkoxysilane, trialkoxysilane, or a mixture thereof. It is preferably a mixture of tetraalkoxysilane or trialkoxysilane, and contains a mixture of tetraalkoxysilane and trialkoxysilane, so that when a hard coat layer is formed, while having appropriate flexibility, Sufficient hardness can be obtained.

When the epoxy group-free alkoxysilane is a mixture of tetraalkoxysilane and trialkoxysilane, the molar ratio of tetraalkoxysilane and trialkoxysilane is preferably 25:75 to 85:15, and 30:70 to 80:20 is more preferable, and 30:70 to 65:35 is even more preferable. By setting the molar ratio within the above range, it becomes easy to control the degree of polymerization of the alkoxysilane within a desired range and to control the hydrolysis rate and the solubility of the aluminum chelate.

The tetraalkoxysilane is a tetrafunctional alkoxysilane, more preferably one having 1 to 4 carbon atoms in each alkoxy group. Of these, tetramethoxysilane and tetraethoxysilane are particularly preferably used. By setting the number of carbon atoms to 4 or less, the hydrolysis rate of tetraalkoxysilane when mixed with acidic water does not become too slow, and the time required for dissolution until a uniform aqueous solution is shortened. Thereby, the manufacturing efficiency at the time of manufacturing a hard-coat layer can be improved. Examples of commercially available products include KBE-04 (manufactured by Shin-Etsu Chemical Co., Ltd.).

The trialkoxysilane is a trifunctional alkoxysilane represented by the following general formula (1).
RSi (OR ¹ ) ₃ (1)
Here, R is an organic group having 1 to 15 carbon atoms that does not contain an amino group, and R ¹ is an alkyl group having 4 or less carbon atoms such as a methyl or ethyl group.

The trifunctional alkoxysilane represented by the general formula (1) does not contain an amino group as a functional group. That is, this trifunctional alkoxysilane has an organic group R having no amino group. When R has an amino group, if it is mixed with a tetrafunctional alkoxysilane and hydrolyzed, dehydration condensation is promoted between the produced silanols. For this reason, an aqueous composition becomes unstable and is not preferable.

R in the general formula (1) may be an organic group having a molecular chain length in the range of 1 to 15 carbon atoms. By setting the number of carbon atoms to 15 or less, the flexibility when the hard coat layer is formed is not excessively increased, and sufficient hardness can be obtained. By setting the carbon number of R within the above range, a hard coat layer with improved brittleness can be obtained. Moreover, the adhesiveness of other films, such as a support body, and a hard-coat layer can be improved.

Furthermore, the organic group represented by R may have a heteroatom such as oxygen, nitrogen, or sulfur. When the organic group has a hetero atom, adhesion with other films can be further improved.

Examples of trialkoxysilane include vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, propyltrimethoxysilane, Phenyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-ureidopropyltriethoxysilane, methyltriethoxysilane, methyl Trimethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, phenyltriethoxysilane, fluorine It can be exemplified sulfonyl trimethoxysilane. Of these, methyltriethoxysilane and methyltrimethoxysilane are particularly preferably used. Examples of commercially available products include KBE-13 (manufactured by Shin-Etsu Chemical Co., Ltd.).

(Metal complex)
The hard coat layer used in the present invention may contain a metal complex as a curing agent. As the metal complex, a metal complex composed of Al, Mg, Mn, Ti, Cu, Co, Zn, Hf and Zr is preferable, and these can be used in combination.

These metal complexes can be easily obtained by reacting a metal alkoxide with a chelating agent. Examples of chelating agents that can be used include β-diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane, and β-keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate.

Preferable specific examples of the metal complex include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris (acetyl) Magnesium chelate compounds such as ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethylacetoacetate), alkyl acetoacetate magnesium monoisopropylate, magnesium bis (acetylacetonate), zirconium tetraacetylacetate Narate, zirconium tributoxyacetylacetonate, zirconium Chill acetonate bis (ethyl acetoacetate), manganese acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, titanium acetylacetonate and titanium oxy acetylacetonate. Of these, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), magnesium bis (acetylacetonate), magnesium bis (ethylacetoacetate), and zirconium tetraacetylacetonate are preferred, and storage stability Considering availability, aluminum tris (acetylacetonate) and aluminum tris (ethylacetoacetate), which are aluminum chelate complexes, are particularly preferable. Examples of commercially available products include aluminum chelate A (W), aluminum chelate D, aluminum chelate M (manufactured by Kawaken Fine Chemical Co., Ltd.), and the like.

The proportion of the metal complex is preferably 17 to 70 mol% with respect to the epoxy group-containing alkoxysilane. The proportion occupied by the metal complex may be 17% or more, and more preferably 20% or more. Moreover, the content rate of a metal complex should just be 70% or less, it is preferable that it is 65% or less, and it is more preferable that it is 60% or less.
In the present invention, when the metal complex is contained in the above lower limit value or more, excellent alkali resistance can be obtained when the hard coat layer is formed. Moreover, by setting it as the said upper limit or less, the dispersibility in aqueous solution can be made favorable, and manufacturing cost can be suppressed.

(Inorganic fine particles)
The hard coat layer used in the present invention may contain inorganic fine particles. The inorganic fine particles are added for the purpose of adjusting the refractive index of the hard coat layer to a preferable range and for increasing the alkali resistance of the hard coat layer.
A preferable example of the inorganic fine particles is a transparent and insulating metal oxide. For example, it is preferable to use fine particles composed of silica, alumina, zirconia, and titanium. In particular, it is preferable to use fine silica particles from the viewpoint of crosslinking with alkoxysilane.

As the silica fine particles, dry powdery silica produced by combustion of silicon tetrachloride can be used, but colloidal silica in which silicon dioxide or a hydrate thereof is dispersed in water is more preferable. Specific examples include, but are not limited to, Snowtex series manufactured by Nissan Chemical Industries, Ltd. such as Snowtex O-33. The average particle size of colloidal silica is 3 nm to 50 nm, preferably 4 nm to 50 nm, more preferably 4 nm to 40 nm, and particularly preferably 5 nm to 35 nm.
Here, the average particle diameter can be determined from a photograph obtained by observing dispersed inorganic fine particles with a transmission electron microscope. The projected area of the particles is obtained, and the equivalent circle diameter is obtained therefrom, and the average particle size (average primary particle size) is obtained. The average particle diameter of the inorganic fine particles can be calculated by measuring the projected area of 300 or more particles and obtaining the equivalent circle diameter.

The colloidal silica is more preferably adjusted to have a pH of 2 to 7 when added to the aqueous composition. When the pH is 2 to 7, the stability of silanol, which is a hydrolyzate of alkoxysilane, is better than when the pH is less than 2 or greater than 7, and the dehydration condensation reaction of the silanol proceeds faster. It is possible to suppress an increase in the viscosity of the coating liquid due to this.

When inorganic fine particles are contained, 0 <x ≦ 80, where x is the ratio (unit: mass%) of the inorganic fine particles to the total solid content contained in the aqueous composition. x is preferably 1 or more, and more preferably 3 or more. Moreover, x should just be 80 or less, it is preferable that it is 70 or less, and it is more preferable that it is 65 or less. By setting the proportion of the inorganic fine particles in the aqueous composition within the above range, higher alkali resistance can be obtained when the hard coat layer is formed.

The ratio (unit: mass%) of the epoxy group-containing alkoxysilane to the total alkoxysilane is x, where x is the ratio (unit: mass%) of the inorganic fine particles to the total solid content in the aqueous composition. When y, y ≧ x−5 is preferable. Furthermore, it is more preferable that y ≧ x. By setting the relationship between y and x in the above range, higher alkali resistance can be obtained, and a change in haze value when immersed in an alkaline solution can be suppressed. Furthermore, the stability of the aqueous composition can be increased.

The inorganic fine particles preferably have an average aspect ratio of 30 to 5000. The aspect ratio of the inorganic fine particles may be 30 or more, preferably 100 or more, more preferably 200 or more, and further preferably 300 or more. The aspect ratio of the inorganic fine particles may be 5000 or less, preferably 3000 or less, more preferably 1500 or less, and further preferably 800 or less.
In the present invention, a hard coat layer with higher hardness can be formed by setting the average aspect ratio of the inorganic fine particles within the above range.

Here, the average aspect ratio means that the average minor axis of the inorganic fine particles in the thickness direction perpendicular to the major axis direction of the inorganic fine particles is r (nm), and the average major axis of the inorganic fine particles in the major axis direction of the inorganic fine particles is L (nm). ) Means the L / r ratio. That is, the aspect ratio can be calculated by observing inorganic fine particles contained in the aqueous composition and dividing the long diameter of the inorganic fine particles by the short diameter.

In the present invention, the average minor axis r (nm) of the inorganic fine particles is preferably 1 to 20 nm. The average minor axis r (nm) is preferably 1 nm or more, and more preferably 2 nm or more. The average minor axis r (nm) is preferably 20 nm or less, more preferably 15 nm or less, and further preferably 10 nm or less. The average major axis L (nm) is preferably 100 to 10000 nm. The average major axis L (nm) is
The thickness is preferably 100 nm or more, more preferably 300 nm or more, and further preferably 700 nm or more. Further, the average major axis L (nm) is preferably 10000 nm or less, more preferably 8000 nm or less, and further preferably 5000 nm or less. By setting the minor axis and major axis of the inorganic fine particles within the above range, the average aspect ratio of the inorganic fine particles can be within a preferable range.

The length of the inorganic fine particles described above can be measured using an optical microscope or an electron microscope. For example, using a scanning electron microscope (SEM), select 100 arbitrary inorganic particles having a major axis of 100 nm or more present in a cross section perpendicular to the longitudinal direction of the hard coat layer and a cross section parallel to the longitudinal direction. The aspect ratio can be obtained by measuring the major axis and minor axis of the inorganic particles. The major axis and minor axis are measured for every 100 inorganic particles, and the average aspect ratio can be calculated from these aspect ratios.

(UV absorber)
The hard coat layer may contain an ultraviolet absorber. As a result, UV degradation of the laminated film and the colorant (particularly dye-based) can be prevented, and visibility and explosion-proof properties can be maintained for a long time. The kind of ultraviolet absorber is not specified. The addition amount is preferably 0.1 to 10% by mass with respect to the resin forming the hard coat layer. By setting the content to 0.1% by mass or more, the effect of preventing UV deterioration is sufficiently exhibited, and by setting the content to 10% by mass or less, it is possible to more effectively suppress a decrease in wear resistance and scratch resistance.
The addition method is preferably used by dispersing in a solvent.

(Other additives)
Furthermore, a surfactant, a slipping agent, and a matting agent may be added to the hard coat layer for the purpose of reducing friction on the coating film surface or improving the coating property.
Further, the hard coat layer may be colored by dispersing pigments, dyes, and other fine particles. Furthermore, for the purpose of improving the weather resistance, an ultraviolet absorber, an antioxidant or the like may be added.

As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.

Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, manufactured by BASF) 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 90
1,904,150R1, Pionein D-6512, D-6414, D-6112, D-6115, D-6120, D-6131, D-6108-W, D-6112-W, D-6115-W, D -6115-X, D-6120-X (manufactured by Takemoto Yushi Co., Ltd.), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NAROACTY CL-95, HN-100 (manufactured by Sanyo Chemical Industries, Ltd.), etc. Is mentioned.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and sanded BL (manufactured by Sanyo Chemical Industries, Ltd.).

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by BYK Chemie.
Only one type of surfactant may be used, or two or more types may be combined.
The addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the hard coat layer.

As the slipping agent, an aliphatic wax can be contained. Specific examples of the aliphatic wax include plant-based waxes such as carnauba wax, candelilla wax, rice wax, wood wax, jojoba oil, palm wax, rosin modified wax, cucumber wax, sugar cane wax, esparto wax, and bark wax. Animal waxes such as beeswax, lanolin, whale wax, ibota wax, shellac wax, mineral waxes such as montan wax, ozokerite, ceresin wax, petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam, and fishertro push wax And synthetic hydrocarbon waxes such as polyethylene wax, oxidized polyethylene wax, polypropylene wax, and oxidized polypropylene wax. Among these, carbana wax, paraffin wax, and polyethylene wax are particularly preferable because of easy adhesion to a hard coat layer and a pressure-sensitive adhesive and good lubricity. These are also preferably used as aqueous dispersions because they can reduce the environmental burden and are easy to handle. Examples of commercially available products include Cellosol 524 (manufactured by Chukyo Yushi Co., Ltd.).

As the matting agent, either organic or inorganic fine particles can be used. For example, polymer fine particles such as polystyrene, polymethyl methacrylate, silicone resin, and benzoguanamine resin, and inorganic fine particles such as silica, calcium carbonate, magnesium oxide, and magnesium carbonate can be used. Among these, polystyrene, polymethylmethacrylate, and silica are preferably used from the viewpoints of a slip improvement effect and cost.
These particles may be used alone or as a colloid dispersed in a dispersion medium such as water, such as colloidal silica. Examples of commercially available products include Snowtex XL (manufactured by Nissan Chemical Industries, Ltd.), Seahoster KE-P250 (manufactured by Nippon Shokubai Co., Ltd.), and the like. Two or more kinds of matting agents may be included.

The thickness of the hard coat layer is not particularly limited, but is preferably in the range of 1 to 15 μm.
The refractive index of the hard coat layer is preferably 1.50 to 2.10, more preferably 1.60 to 2.00, and further preferably 1.62 to 1.95.

<Easily adhesive layer>
The laminated body for touchscreens of this invention may have an easily bonding layer between at least one between a protective layer and a polymer layer, and between a polymer layer and a hard-coat layer.

The refractive index n of the easy-adhesion layer is preferably | n−np | ≦ 0.02 with respect to the refractive index np of the adjacent layer. That is, the refractive index difference between the refractive index of the protective layer and the easy adhesion layer, the refractive index difference between the refractive index of the polymer layer and the refractive index of the easy adhesion layer, the refraction of the refractive index of the polymer layer and the refractive index of the easy adhesion layer. Of the difference in refractive index, the refractive index difference between the refractive index of the hard coat layer and the refractive index of the easy adhesion layer, at least one is preferably 0.02 or less, more preferably 0.015 or less, and More preferably, it is 01 or less. By making the refractive index of the easy-adhesion layer used in the present invention in the above range, reflection between the respective layers can be prevented, and occurrence of interference unevenness can be reduced. The refractive index difference between the refractive index of the easy adhesion layer between the protective layer and the polymer layer and the refractive index of the protective layer and the polymer layer adjacent to the easy adhesion layer is 0.02 or less. It is preferable. The refractive index difference between the refractive index of the easy adhesion layer between the polymer layer and the hard coat layer and the refractive index of the polymer layer adjacent to the easy adhesion layer and the hard coat layer is 0. 02 or less is preferable.
Specifically, the refractive index n of the easy-adhesion layer used in the present invention is preferably 1.63 or more and 1.69 or less, and more preferably 1.63 or more and 1.66 or less. By setting it as the said range, it can be made easy to adjust a refractive index with respect to another layer.

The thickness of the easy adhesion layer used in the present invention is 200 nm or less. The thickness of the easy-adhesion layer used in the present invention is determined by required optical performance, easy adhesion, and the like. The thickness of the easy adhesion layer used in the present invention is preferably 50 nm or more, and more preferably 80 nm or more. By making the thickness of the easy-adhesion layer used in the present invention in the above range, the easy-adhesion can be enhanced when the easy-adhesion layer functions as the easy-adhesion layer. In addition, the thickness of the easy-adhesion layer used in the present invention is preferably 180 nm or less, and more preferably 150 nm or less. By setting the thickness of the easy-adhesion layer used in the present invention in the above range, the surface state of the easy-adhesion layer can be made to be in a better state, and interference unevenness can be suppressed.

<< Polyester having naphthalene skeleton >>
The easy-adhesion layer used in the present invention preferably contains a polyester having a naphthalene skeleton.
The polyester having a naphthalene skeleton represents that a monomer having a naphthalene skeleton is included as a monomer constituting the polyester. The monomer having a naphthalene skeleton is preferably contained as a dicarboxylic acid component, and examples thereof include 2,6-naphthalenedicarboxylic acid.

As a monomer constituting the polyester having a naphthalene skeleton, a monomer having no naphthalene skeleton can be included as necessary, such as adjustment of the refractive index. In the monomer having no naphthalene skeleton used in the present invention, examples of the dicarboxylic acid component include terephthalic acid and isophthalic acid, and examples of the diol component include ethylene glycol and diethylene glycol.
When the monomer having a naphthalene skeleton is a dicarboxylic acid component, the structural unit derived from the monomer having a naphthalene skeleton is preferably from 50 mol% to 100 mol%, more preferably from 60 mol% to 80 mol% in the dicarboxylic acid component. .

The number average molecular weight of the polyester having a naphthalene skeleton is preferably 15000 to 40000, more preferably 17000 to 30000, and further preferably 18000 to 25000. By adjusting the number average molecular weight of the polyester having a naphthalene skeleton used in the present invention within the above range, the adhesion between the polymer layer and the polyester film, particularly the adhesion after wet heat aging can be enhanced.
In the present invention, the number average molecular weight represents the number average molecular weight measured by GPC (Gel Permeation Chromatography) as a standard material as polystyrene.

The refractive index of the polyester having a naphthalene skeleton is preferably 1.60 or more and 1.75 or less, and more preferably 1.60 or more and 1.70 or less. By adjusting the refractive index of the easy-adhesion layer, the addition amount of particles described later can be reduced and the adhesion when the polymer layer functions as the easy-adhesion layer can be increased. .

The content of the polyester having a naphthalene skeleton in the polymer layer is preferably 5% by mass or more and 80% by mass or less, and more preferably 10% by mass or more and 60% by mass or less with respect to the total solid content in the polymer layer.

<< Particles >>
The easy-adhesion layer used in the present invention may contain particles. The particles used in the present invention can easily adjust the refractive index of the easy-adhesion layer. There may be only one type of particles used in the present invention, or two or more types.

The refractive index of the particles is preferably 1.60 or more and 3.00 or less, more preferably 1.80 or more and 2.80 or less, and further preferably 1.90 or more and 2.60 or less. By setting it as the said range, it can be made easy to adjust the refractive index of an easily bonding layer.

The average particle diameter of the particles is preferably 0.65 times or less with respect to the thickness of the easy adhesion layer. It is more preferably 0.50 times or less, and further preferably 0.40 times or less. By setting it as the said range, an unevenness | corrugation becomes difficult to be formed in the surface of an easily bonding layer, scattering of light can be reduced, and the color of a laminated | multilayer film can be made favorable. Although it does not specifically limit about a minimum, It is preferable that it is 0.05 times or more.
Specifically, the average particle diameter of the particles is preferably 5 nm or more and 130 nm or less. 5 nm or more and 100 nm or less are more preferable, and 5 nm or more and 80 nm or less are more preferable. By setting the thickness to 130 nm or less, the influence of light being scattered by the particles is reduced, and by setting the thickness to 5 nm or more, the particles are not aggregated and can hardly be made large.

The average particle size of the particles was measured using a laser diffraction / scattering particle size distribution analyzer LA910 (manufactured by Horiba, Ltd.) using an aqueous dispersion of particles, and expressed in median size.
Moreover, after manufacturing the laminated body of this invention, the average particle diameter of the particle | grains contained in the easily bonding layer of the laminated body of this invention is contained in an easily bonding layer after dissolving only an easily bonding layer in a solvent. After preparing an aqueous dispersion of particles, measurement can be performed using the above-described apparatus.

The particles are preferably contained in an amount of 40% by mass to 80% by mass with respect to the solid content of the easy adhesion layer. It is preferably 45 to 75% by mass, and more preferably 50 to 70% by mass. By setting it as the said range, while making it easy to adjust the refractive index of an easily bonding layer, particle | grains do not overflow from an easily bonding layer, but it can make it difficult to form the unevenness | corrugation on the surface of a polymer layer.

Examples of the particles include conductive metal particles and metal oxide particles, and metal oxide particles are preferable.

Examples of the conductive metal particles include particles of antimony, selenium, titanium, tungsten, tin, zinc, indium and the like.

Examples of the metal oxide particles include particles containing any one of tin oxide, zirconium oxide and titanium oxide as a main component. Here, the particle containing any one of tin oxide, zirconium oxide and titanium oxide as the main component in the present invention means that the compounding amount of any one of tin oxide, zirconium oxide and titanium oxide contained in the particle is 80% by mass or more. A certain particle.
Among these, it is preferable to use tin oxide or zirconium oxide.

As the tin oxide, tin (IV) oxide having a SnO ₂ composition is preferably used. In the case of using tin oxide, the use of tin oxide doped with antimony or the like has the effect of reducing the surface resistivity of the laminated film and preventing impurities such as dust from adhering because of its conductivity. Since it is obtained, it is preferable. As such antimony-doped tin oxide, commercially available products can also be used. FS-10D, SN-38F, SN-88F, SN-100F, TDL-S, TDL-1 (all of which are Ishihara Sangyo) Etc.).
On the other hand, in order to prevent malfunction of the touch panel, inorganic oxide fine particles having no conductivity may be preferably used. For example, tin oxide prepared so that tin oxide is not doped with antimony or the like and the surface resistance is not lowered can be suitably used.
Further, tin oxide doped with phosphorus (for example, EP SPDL-2 manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd., an aqueous dispersion of P-doped SnO _{2 having} a particle size of 130 nm) can be used.
Among these, in the present invention, it is particularly preferable to use tin oxide not doped with antimony as tin oxide.

Zirconium oxide has a composition of ZrO ₂ , for example, NZS-20A, NZS-30.
A, OZ-S30K (all manufactured by Nissan Chemical Industries, Ltd.) and SZR-CW (manufactured by Sakai Chemical Industry Co., Ltd.) can be mentioned, and these can also be suitably used in the present invention.

As titanium oxide, titanium oxide (IV) having a composition of TiO ₂ is preferably used. Titanium oxide has a rutile type (tetragonal high-temperature type), anatase type (tetragonal low-temperature type), etc. depending on the difference in crystal structure, but is not particularly limited. Further, titanium oxide subjected to surface treatment may be used. Examples of the titanium oxide used in the present invention include IT-S, IT-O, IT-W (all manufactured by Idemitsu Kosan Co., Ltd.), TTO-W-5 (manufactured by Ishihara Sangyo Co., Ltd.), and the like. And can also be suitably used in the present invention.

The shape of the particles used in the present invention may be acicular or spherical, but is preferably spherical. In addition, even when the shape of the particles used in the present invention is not perfectly spherical, the average particle diameter of the particles can be measured by the above-described method. However, when the shape of the particles is not perfectly spherical, When it is difficult to measure by the measuring method, the diameter of a circle circumscribing such shaped particles can be determined as the particle diameter in the present invention.

(Other parts)
The easily bonding layer used for this invention may contain members other than the member mentioned above as needed. An example will be described below.

((Second polyester))
The easy-adhesion layer used in the present invention may further contain a second polyester in addition to the above-described polyester having a naphthalene skeleton.

Further, when the easy adhesion layer contains the second polyester, the glass transition temperature Tg ₁ of the polyester having a naphthalene skeleton is set to 80 to 130 ° C., and the glass transition temperature Tg ₂ of the second polyester is set to 0 to 80 ° C. It is also preferable to do.
By setting Tg ₁ and Tg ₂ in the above range, adhesion between the polymer layer and other layers, particularly a hard coat layer described later, can be improved.
Tg ₁ is preferably 90 to 120 ° C., and more preferably 100 to 115 ° C. Tg ₂ is preferably 20 to 70 ° C., more preferably 30 to 60 ° C.

Tg ₁ -Tg ₂ is preferably 20 ° C. or higher, and more preferably 40 ° C. or higher. By setting Tg ₁ -Tg ₂ to be equal to or more than the above lower limit value, the adhesion can be more effectively improved.

In the present invention, the glass transition temperature represents a glass transition temperature measured by DSC (Differential Scanning Calibration) as follows.
Weigh 10 mg of polyester and set in an aluminum pan. At a rate of temperature increase of 10 ° C./min, the temperature is raised from room temperature to 300 ° C., rapidly cooled, and again heated at 10 ° C./min to obtain a DSC curve. The temperature at which the obtained DSC curve is bent is defined as the glass transition temperature.

The second polyester may contain one or more of terephthalic acid, isophthalic acid and sodium sulfoisophthalate as the acid component.

The second polyester resin may contain triethylene glycol as a diol component. Triethylene glycol can enhance the adhesiveness of the easy-adhesion layer formed using the second polyester.

The content of triethylene glycol is 10 to 50 mol% with respect to the total diol component of the second polyester resin. The content of triethylene glycol may be 10 to 50 mol%, preferably 15 to 45 mol%, and more preferably 20 to 40 mol%.

The number average molecular weight of the second polyester is preferably 15000 to 40000. The number average molecular weight of the second polyester is preferably 17000 to 30000, and more preferably 18000 to 25000. By setting the number average molecular weight of the second polyester within the above range, the adhesion between the polymer layer and the polyester film, particularly the adhesion after wet heat aging can be enhanced.

When the content of the polyester having a naphthalene skeleton contained in the easy-adhesion layer is P and the content of the second polyester is Q, it is preferable that P: Q = 20: 80 to 80:20, : 70 to 70:30 is more preferable, and 40:60 to 60:40 is even more preferable. By setting P: Q within the above range, good adhesiveness can be obtained.

((binder))
The easy-adhesion layer used in the present invention may contain polyolefin, acrylic, polyurethane, rubber-based resin or the like as a binder in order to further improve the adhesion to the polyester film.

As content in the easily bonding layer of the binder used for this invention, 0.5 to 40 mass% is preferable with respect to the total solid of an easily bonding layer, and 1.5 to 30 mass% is preferable. Is more preferable.

The polyolefin preferably has a polar group such as a carboxyl group as an ionomer of the polyolefin having a polar group. It may be used by dissolving in an organic solvent, or an aqueous dispersion may be used. However, since the environmental load is small, it is preferable to attach with an aqueous system using an aqueous dispersion. A commercially available product may be used as the aqueous dispersion and is not particularly limited. Examples of those that can be preferably used in the present invention include Chemipearl S75N (manufactured by Mitsui Chemicals), Arrow Base SE1200. Arrowbase SB1200 (above, manufactured by Unitika Ltd.), Hitech S3111, S3121 (above, produced by Toho Chemical Co., Ltd.), and the like. Only one type of polyolefin may be included, or two or more types may be included.

As the acrylic, acrylic containing methacrylate and ethyl acrylate and other copolymerization components is preferable, and those described in paragraphs [0145] to [0146] of JP2012-101449A can be used. Commercially available products may also be used, and specific examples include AS-563A manufactured by Daicel Finechem Co., Ltd. (product name) and the like.
Acrylic has a glass transition temperature of preferably −50 to 120 ° C., and more preferably −30 to 100 ° C. The weight average molecular weight of acrylic is preferably 3000 to 1000000.

The polyurethane is preferably composed of polyol, polyisocyanate, chain extender, cross-linking agent, etc., and those described in paragraph [0035] of JP2012-056220A can be used.

((Crosslinking agent))
The easy-adhesion layer used in the present invention may contain a crosslinking agent. Examples of the crosslinking agent include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents. Among these, a carbodiimide type crosslinking agent and an oxazoline type crosslinking agent are preferable.

As the carbodiimide-based crosslinking agent, a compound having a plurality of carbodiimide structures in the molecule is preferable. By including such a compound, the adhesion between the hard coat layer and the easy-adhesion layer tends to be improved when the hard coat layer is provided. A compound having a plurality of carbodiimide groups in the molecule can be used without particular limitation. Polycarbodiimide is usually synthesized by condensation reaction of organic diisocyanate, but the organic group of the organic diisocyanate used in this synthesis is not particularly limited, either aromatic or aliphatic, or a mixture thereof It can be used. From the viewpoint of reactivity, an aliphatic type is particularly preferable. As the synthetic raw material, organic isocyanate, organic diisocyanate, organic triisocyanate and the like are used. As examples of the organic isocyanate, those described in paragraph [0024] of JP2009-220316A can be used.
The carbodiimide-based crosslinking agent used in the present invention may be a commercially available product, and specific examples include Carbodilite V-02-L2 manufactured by Nisshinbo Co., Ltd.

As the oxazoline-based crosslinking agent, those described in paragraph [0078] of JP 2012-231029 A can be used. Commercial products may also be used, such as Epochros K2010E, K2020E, K2030E, WS500, WS500, and WS700 manufactured by Nippon Shokubai Chemical Industry Co., Ltd.

The cross-linking agent used in the present invention is preferably added in the range of 0.5 to 50% by mass, more preferably in the range of 1 to 30% by mass, with respect to the total solid content of the easy-adhesion layer. That is. By making the addition amount 1% by mass or more, the particles contained in the easy-adhesion layer can be effectively prevented from peeling off. On the other hand, when the addition amount is 50% by mass or less, the surface shape tends to be further improved. Two or more types of crosslinking agents may be included, and when two or more types are included, the total amount is preferably within the above range.

((Matting agent))
The easy-adhesion layer used in the present invention may contain a matting agent for improving the slipperiness of the laminated film.
As the matting agent, either organic or inorganic fine particles can be used. For example, polymer fine particles such as polystyrene, polymethyl methacrylate, silicone resin, and benzoguanamine resin, and inorganic fine particles such as silica, calcium carbonate, magnesium oxide, and magnesium carbonate can be used. Among these, polystyrene, polymethyl methacrylate, and silica are preferable from the viewpoint of the effect of improving the slipperiness and cost.
These particles may be used alone or as a colloid dispersed in a dispersion medium such as water, such as colloidal silica. Examples of commercially available products include Snowtex XL (manufactured by Nissan Chemical Industries, Ltd.).
Two or more kinds of matting agents may be included.

The average particle size of the matting agent is preferably 0.03 to 1 μm, more preferably 0.05 to 0.5 μm. When the average particle size of the matting agent is 0.03 μm or more, the effect of improving the slip property is effectively exhibited, and when the average particle size is 1 μm or less, the laminated film is incorporated into a display device such as a touch panel. There is a tendency to suppress the deterioration of display quality.

Also, the average particle size of the matting agent is preferably 0.65 times or less the thickness of the easy-adhesion layer, like the average particle size of the particles of the polymer layer. It is more preferably 0.50 times or less, and further preferably 0.40 times or less. By setting it as the said range, an unevenness | corrugation becomes difficult to be formed in the surface of an easily bonding layer, scattering of light can be reduced more, and the color tone of a laminated film can be made still more favorable.

In addition, the average particle diameter of the matting agent in the present invention is a value measured by the same method as the average particle diameter of the particles included in the polymer layer.

((Surfactant))
The easy-adhesion layer used in the present invention may have a surfactant to reduce repellency and the like when a functional layer such as a hard coat layer is applied to the surface of the easy-adhesion layer. As the surfactant, the above-described surfactants can be used.

((Antistatic agent))
The easy-adhesion layer used in the present invention may have an antistatic agent to prevent the easy-adhesion layer from being charged by static electricity or the like.
The type of the antistatic agent is not particularly limited. For example, an electron conductive polymer such as polyaniline and polypyrrole, an ion conductive polymer having a carboxyl group or a sulfonic acid group in the molecular chain, conductive fine particles, etc. Is mentioned. Of these, the conductive tin oxide fine particles described in JP-A-61-20033 can be preferably used from the viewpoints of conductivity and transparency.

The addition amount of the antistatic agent is preferably added so that the surface resistivity of the easy adhesion layer measured in an atmosphere of 25 ° C. and 30% relative humidity is 1 × 10 ⁵ Ω or more and 1 × 10 ¹³ Ω or less. The surface resistivity can be suppressed 1 × 10 and a ⁵ Omega or lower the amount of the antistatic agent tends to improve transparency of the laminate, by the following 1 × 10 ¹³ Omega, dust It tends to be less likely to adhere.

((Slip agent))
The easy-adhesion layer used in the present invention preferably contains an aliphatic wax as a slipping agent in order to obtain the lubricity of the layer surface.

Specific examples of the aliphatic wax include plant-based waxes such as carnauba wax, candelilla wax, rice wax, wood wax, jojoba oil, palm wax, rosin modified wax, cucumber wax, sugar cane wax, esparto wax, and bark wax. Animal waxes such as beeswax, lanolin, whale wax, ibota wax, shellac wax, mineral waxes such as montan wax, ozokerite, ceresin wax, petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam, and fishertro push wax And synthetic hydrocarbon waxes such as polyethylene wax, oxidized polyethylene wax, polypropylene wax, and oxidized polypropylene wax. Among these, carnauba wax, paraffin wax, and polyethylene wax are particularly preferable because they are easy to adhere to a hard coat layer and a pressure-sensitive adhesive and have good lubricity. These are also preferably used as aqueous dispersions because they can reduce the environmental burden and are easy to handle. Examples of commercially available products include Cellosol 524 (manufactured by Chukyo Yushi Co., Ltd.).

<Antireflection layer>
The laminate for a touch panel of the present invention may have an antireflection layer between the transparent electrode layer and the protective layer. By having the antireflection layer, the pattern visibility of the transparent electrode layer is improved.

The refractive index of the antireflection layer is preferably 1.6 or more, more preferably 1.65 or more. Although there is no restriction | limiting in particular about an upper limit, it is practically preferable that it is 1.78 or less, and 1.74 or less may be sufficient.

The antireflection layer preferably contains metal oxide particles, a resin (preferably an alkali-soluble resin), a polymerizable compound, a polymerization initiator, or a polymerization initiation system. Furthermore, an additive etc. are used, but it is not restricted to this.

The antireflection layer may be a transparent resin film or an inorganic film.
As the inorganic film, inorganic films used in JP 2010-86684 A, JP 2010-152809 A, JP 2010-257492 A, and the like can be used, which are described in these documents. From the viewpoint of controlling the refractive index, it is preferable to use an inorganic film having a laminated structure of a low refractive index material and a high refractive index material, or an inorganic film having a mixed film of a low refractive index material and a high refractive index material. As the low refractive index material and the high refractive index material, the materials used in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used. The contents of these documents are incorporated herein.
The inorganic layer may be a mixed layer of SiO ₂ and Nb ₂ O _5, and more preferably that case is a mixed film of SiO ₂ and Nb ₂ O ₅ formed by sputtering.

In the present invention, the antireflection layer is preferably a transparent resin film.

The method for controlling the refractive index of the antireflection layer that is the transparent resin film is not particularly limited, but a transparent resin film having a desired refractive index is used alone, or fine particles such as metal fine particles and metal oxide fine particles are added. A transparent resin film that has been used can be used. In the present invention, the antireflection layer preferably contains particles, and more preferably contains metal oxide particles.

The resin composition used for the antireflection layer which is the transparent resin film preferably contains metal oxide particles for the purpose of adjusting the refractive index and light transmittance. Since the metal oxide particles have high transparency and light transmittance, a composition having a high refractive index and excellent transparency can be obtained.
The metal oxide particles preferably have a refractive index higher than the refractive index of the resin composition made of a material excluding the particles. Specifically, the antireflection layer has a wavelength of 400 to 750 nm. It is preferable to include particles having a refractive index of 1.60 to 3.00 in the light having, preferably including particles having a refractive index of 1.70 or more, and more preferably including particles of 1.90 or more.
Here, the refractive index of light having a wavelength of 400 to 750 nm being 1.60 or more means that the average refractive index of light having a wavelength in the above range is 1.60 or more. It is not necessary that the refractive index of all light having a wavelength is 1.60 or more. The average refractive index is a value obtained by dividing the sum of the measured values of the refractive index for each light having a wavelength in the above range by the number of measurement points.

In addition, the metal of the metal oxide particles includes semimetals such as B, Si, Ge, As, Sb, and Te.
The light-transmitting and high refractive index metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, and Nb. Oxide particles containing atoms such as Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, Te, etc. are preferable, titanium oxide, titanium composite oxide, zinc oxide, tin oxide, oxidation Zirconium, indium / tin oxide and antimony / tin oxide particles are more preferred, titanium oxide, titanium composite oxide, tin oxide and zirconium oxide particles are more preferred, and zirconium oxide particles are most preferred. The surface of these metal oxide particles can be treated with an organic material in order to impart dispersion stability.

From the viewpoint of the transparency of the antireflection layer which is a transparent resin film, the average primary particle diameter of the metal oxide particles is preferably 1 to 200 nm, particularly preferably 3 to 80 nm. Here, the average primary particle diameter of the particles refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the longest side is the diameter.

Moreover, the said metal oxide particle may be used individually by 1 type, and can also use 2 or more types together.
The content of the metal oxide particles in the antireflection layer that is the transparent resin film may be appropriately determined in consideration of the refractive index required for the optical member obtained from the resin composition, light transmittance, and the like. The content of the antireflection layer, which is the transparent resin film, can be 5 to 95% by mass, preferably 5 to 80% by mass, and more preferably 40 to 80% by mass. preferable.
The antireflection layer that is the transparent resin film preferably has at least one of ZrO ₂ particles and TiO ₂ particles from the viewpoint of controlling the refractive index within the range of the refractive index of the antireflection layer, and the ZrO ₂ particles are more preferable.

The resin (referred to as binder and polymer) used for the antireflection layer which is a transparent resin film and other additives are not particularly limited as long as they are not contrary to the gist of the present invention. When the antireflection layer is a transparent resin film, components other than the particles of the antireflection layer can be the same as those of the protective layer.

As the resin (referred to as binder or polymer) used in the antireflection layer, an alkali-soluble resin is preferable. Examples of the alkali-soluble resin include paragraphs [0025] of JP2011-95716A and JP2010-237589A. The polymers described in paragraphs [0033] to [0052] can be used.

Furthermore, an additive may be used in the antireflection layer. Examples of the additive include surfactants described in paragraph [0017] of Japanese Patent No. 4502784, paragraphs [0060] to [0071] of JP-A-2009-237362, and paragraph [ And the other additives described in paragraphs [0058] to [0071] of JP-A No. 2000-310706.

The thickness of the antireflection layer is preferably 500 nm or less, and more preferably 100 nm or less. The thickness of the antireflection layer is particularly preferably from 55 to 100 nm, more preferably from 60 to 90 nm, even more preferably from 70 to 90 nm.

[Method for producing laminate for touch panel]
The manufacturing method of the laminated body for touchscreens of this invention is a laminated body for touchscreens of this invention, Comprising: A front layer board with a transparent electrode layer which has a glass substrate and a transparent electrode layer has a protective layer and a polymer layer in this order. Including a step of laminating a laminated material such that the surface on the transparent electrode layer side and the surface on the protective layer side face each other, wherein the glass substrate is a part of ions having an ion radius smaller than potassium ions in glass or It is characterized by being subjected to a chemical strengthening treatment that replaces all with potassium ions.
The manufacturing method of the laminated body for touchscreens of this invention can be manufactured by laminating | stacking the laminated material which has a protective layer and a polymer layer at least on the transparent conductive layer side of the glass substrate in which the transparent conductive layer was formed.

<Lamination process>
The said transfer process is a process of laminating | stacking the laminated material which has a protective layer and a polymer layer in this order on the transparent electrode pattern mentioned later.
At this time, it is not necessary to remove the polymer layer after laminating the laminated material having the protective layer and the polymer layer in this order on the transparent electrode pattern.
Lamination (bonding) of the protective layer and the polymer layer to the surface of the glass substrate is performed by stacking the protective layer and the polymer layer on the surface of the transparent electrode pattern, and applying pressure and heating. For laminating, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.

<Surface treatment of glass substrate>
In order to improve the adhesion of each layer by lamination in the subsequent transfer step, a surface treatment can be applied to the non-contact surface of the glass substrate (front plate) in advance. As the surface treatment, it is preferable to perform a surface treatment (silane coupling treatment) using a silane compound. As the silane coupling agent, those having a functional group that interacts with the photosensitive resin are preferable. For example, a silane coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3% by mass aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) is sprayed for 20 seconds by a shower, and pure water shower washing is performed. To do. Thereafter, the reaction is carried out by heating. A heating tank may be used, and the reaction can be promoted by preheating the substrate of the laminator.

<Filming of transparent electrode pattern>
The transparent electrode pattern is formed by using the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 forming method in the description of the capacitive input device of the present invention described later. A method using a photosensitive film that can be formed on a glass substrate is preferred.

-Transfer process-
The transfer step includes the first photocurable resin layer for etching and the second photocurable resin layer for etching (hereinafter collectively referred to as photocurable resin layer) of the transfer film from which the protective film has been removed, which will be described later. Is also transferred onto the transparent electrode layer.
At this time, a method including a step of removing the temporary support after laminating the photocurable resin layer of the transfer film on the transparent electrode pattern is preferable.
Transfer (bonding) of the photocurable resin layer to the surface of the base material is performed by overlaying the photocurable resin layer on the surface of the transparent electrode pattern, and applying pressure and heating. For laminating, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.

<Transfer film>
The transfer film has a temporary support and the first photocurable resin layer for etching or the second photocurable resin layer for etching.
As the temporary support, a material that is flexible and does not cause significant deformation, shrinkage, or elongation under pressure or under pressure and heating can be used. Examples of such a support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film, and among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

The thickness of the temporary support is not particularly limited and is generally in the range of 5 to 200 μm, and in the range of easy handling and versatility, the range of 10 to 150 μm is particularly preferable.
Further, the temporary support may be transparent or may contain dyed silicon, alumina sol, chromium salt, zirconium salt or the like.
Further, the temporary support can be imparted with conductivity by the method described in JP-A-2005-221726.
<< Thermoplastic resin layer >>
The transfer film is preferably provided with a thermoplastic resin layer between the temporary support and the first photocurable resin layer for etching or the second photocurable resin layer for etching. If a transparent laminate is formed by transferring a photocurable resin layer using a transfer film having the thermoplastic resin layer, bubbles are less likely to be generated in each element formed by transfer, and image unevenness is caused in the image display device. Etc. are less likely to occur and excellent display characteristics can be obtained.
The thermoplastic resin layer is preferably alkali-soluble. The thermoplastic resin layer plays a role as a cushioning material so as to be able to absorb unevenness of the base surface (including unevenness due to already formed images, etc.), and according to the unevenness of the target surface. It is preferable to have a property that can be deformed.

The thermoplastic resin layer preferably includes an organic polymer substance described in JP-A-5-72724 as a component. The Vicat method [specifically, a polymer obtained by American Material Testing Method ASTM D1235] An embodiment containing at least one selected from organic polymer substances having a softening point of about 80 ° C. or less according to the softening point measurement method] is particularly preferable.

Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers with ethylene and vinyl acetate or saponified products thereof, copolymers of ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride and vinyl chloride, Vinyl chloride copolymer with vinyl acetate or saponified product thereof, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer with styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, Vinyl toluene copolymer of vinyl toluene and (meth) acrylic acid ester or saponified product thereof, poly (meth) acrylic acid ester, (meth) acrylic acid ester copolymer weight of butyl (meth) acrylate and vinyl acetate, etc. Copolymer, vinyl acetate copolymer nylon, copolymer nylon N- alkoxymethyl nylon, and organic polymers such as polyamide resins such as N- dimethylamino nylon.

The layer thickness of the thermoplastic resin layer is preferably 3 to 30 μm. When the thickness of the thermoplastic resin layer is less than 3 μm, followability at the time of lamination may be insufficient, and unevenness on the base surface may not be completely absorbed. In addition, when the layer thickness exceeds 30 μm, a load is applied to drying (solvent removal) at the time of forming the thermoplastic resin layer on the temporary support, or it takes time to develop the thermoplastic resin layer, May deteriorate process suitability. The thickness of the thermoplastic resin layer is more preferably 4 to 25 μm, and particularly preferably 5 to 20 μm.

The thermoplastic resin layer can be formed by applying a preparation liquid containing a thermoplastic organic polymer, and the preparation liquid used for the application can be prepared using a solvent. The solvent is not particularly limited as long as it can dissolve the polymer component constituting the layer, and examples thereof include methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, 2-propanol and the like.

(Viscosity of thermoplastic resin layer and photocurable resin layer)
The viscosity of the thermoplastic resin layer measured at 100 ° C. is in the region of 1000 to 10,000 Pa · sec, the viscosity of the photocurable resin layer measured at 100 ° C. is in the region of 2000 to 50000 Pa · sec, and the following formula ( It is preferable to satisfy A).
Formula (A): Viscosity of thermoplastic resin layer <viscosity of photocurable resin layer

Here, the viscosity of each layer can be measured as follows. The solvent is removed from the coating solution for the thermoplastic resin layer or the photocurable resin layer by drying under atmospheric pressure and reduced pressure to obtain a measurement sample. For example, as a measuring instrument, Vibron (DD-III type: manufactured by Toyo Baldwin Co., Ltd.) Can be used under the conditions of a measurement start temperature of 50 ° C., a measurement end temperature of 150 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz / deg, and a measurement value of 100 ° C. can be used.

<Intermediate layer>
The transfer film further includes an intermediate layer between the photo-curable resin layer and the thermoplastic resin, from the viewpoint of preventing mixing of components when applying a plurality of layers and during storage after application. ,preferable. As the intermediate layer, an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A No. 5-72724, is preferable. And productivity is improved.

The transfer film is preferably further provided with a protective film (protective release layer) or the like on the surface of the photocurable resin layer.

As the intermediate layer and the protective film, those described in paragraphs [0083] to [0087] and [0093] of JP-A-2006-259138 can be appropriately used.

[Transfer Film Manufacturing Method]
The transfer film can be produced according to the method for producing a photosensitive transfer material described in paragraphs [0094] to [0098] of JP-A-2006-259138.

-Exposure process, development process, and other processes-
As examples of the exposure step, the development step, and other steps, the methods described in paragraph numbers [0035] to [0051] of JP-A-2006-23696 can be preferably used in the present invention.

The exposure step is a step of exposing the photocurable resin layer transferred onto the transparent electrode layer.
Specifically, a predetermined mask is disposed above the photocurable resin layer formed on the transparent electrode layer, and then the light is applied from above the mask through the mask, the thermoplastic resin layer, and the intermediate layer. Examples thereof include a method of exposing the curable resin layer, and a method of exposing the entire surface of the photocurable resin layer through a thermoplastic resin layer and an intermediate layer without using a mask.
Here, the light source for the exposure can be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photocurable resin layer (for example, 365 nm, 405 nm, etc.). Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. The exposure amount is usually about 5 to 200 mJ / cm ² , preferably 10 to 100 m.
It is about J / cm ² .

The developing step is a step of developing the exposed photocurable resin layer for etching.
In the present invention, the developing step is not a developing step in a narrow sense in which the pattern-exposed photocurable resin layer is pattern-developed with a developer, but only the thermoplastic resin layer and the intermediate layer are removed after the entire surface exposure. The photo-curable resin layer itself is a developing step that includes a case where a pattern is not formed.
The development can be performed using a developer. The developer is not particularly limited, and known developers such as those described in JP-A-5-72724 can be used. The developer is preferably one in which the photocurable resin layer exhibits a dissolution type development behavior, for example, one containing a compound having a pKa = 7 to 13 at a concentration of 0.05 to 5 mol / L. On the other hand, the developer in the case where the photo-curable resin layer itself does not form a pattern preferably has a development behavior that does not dissolve the non-alkali development type colored composition layer. For example, a compound having pKa = 7 to 13 Is preferably contained at a concentration of 0.05 to 5 mol / L. A small amount of an organic solvent miscible with water may be added to the developer. Examples of organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol And acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass. Further, a known surfactant can be added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.

The development method may be any of paddle development, shower development, shower & spin development, dip development, and the like. Here, the shower development will be described. An uncured portion can be removed by spraying a developer onto the photocurable resin layer after exposure. When a thermoplastic resin layer or an intermediate layer is provided, an alkaline solution having a low solubility of the photocurable resin layer is sprayed by a shower or the like before development to remove the thermoplastic resin layer or the intermediate layer. It is preferable to keep it. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like. The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

The manufacturing method of the capacitance-type input device may have other processes such as a post-exposure process and a post-bake process. When the first photocurable resin layer for etching and the second photocurable resin layer for etching are thermosetting transparent resin layers, it is preferable to perform a post-bake process.

In addition, patterning exposure and whole surface exposure may be performed after peeling the temporary support, or may be performed before peeling the temporary support, and then the temporary support may be peeled off. Exposure through a mask or digital exposure using a laser or the like may be used.

[Capacitance type input device]
The capacitance-type input device of the present invention has the laminate of the present invention.
The capacitive input device of the present invention has a transparent electrode pattern, an antireflection layer disposed adjacent to the transparent electrode pattern, and a protective layer disposed adjacent to the antireflection layer, The refractive index of the antireflection layer is preferably higher than the refractive index of the protective layer, and the refractive index of the antireflection layer is preferably 1.6 or more.
Hereinafter, the detail of the preferable aspect of the electrostatic capacitance type input device of this invention is demonstrated.

The capacitance-type input device of the present invention includes at least the following (3) to (5), (7) on the front plate (corresponding to the glass substrate in the laminate of the present invention) and the non-contact side of the front plate. And it is preferable to have the laminated body of this invention.
(3) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (4) electrically insulated from the first transparent electrode pattern, A plurality of second electrode patterns comprising a plurality of pad portions formed extending in a direction intersecting the first direction (5) electrically connecting the first transparent electrode pattern and the second electrode pattern Insulating layer (7) for electrically insulating Antireflection layer (8) formed so as to cover all or part of the elements (3) to (5) Adjacent to cover the element (7) Formed Protective Layer Here, (7) the antireflection layer corresponds to the antireflection layer in the laminate of the invention. The (8) protective layer corresponds to the protective layer in the laminate of the present invention. The protective layer is preferably a so-called transparent protective layer in a generally known capacitance type input device.

In the capacitance-type input device of the present invention, the (4) second electrode pattern may be a transparent electrode pattern or a transparent electrode pattern, but is preferably a transparent electrode pattern.
The capacitive input device of the present invention may further have the following element (6).
(6) A conductive element that is electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern and is different from the first transparent electrode pattern and the second transparent electrode pattern Here, when (7) the second electrode pattern is not a transparent electrode pattern and (8) does not have another conductive element, (7) the first transparent electrode pattern is It corresponds to the transparent electrode pattern in the laminate.
When the (7) second electrode pattern is a transparent electrode pattern and (6) does not have another conductive element, the (3) first transparent electrode pattern and the (7) second electrode pattern At least one of the electrode patterns corresponds to the transparent electrode pattern in the laminate of the present invention.
(7) When the second electrode pattern is not a transparent electrode pattern but has (6) another conductive element, (3) the first transparent electrode pattern and (6) another conductive element At least one of them corresponds to the transparent electrode pattern in the laminate of the present invention.
When (7) the second electrode pattern is a transparent electrode pattern and (6) has another conductive element, (3) the first transparent electrode pattern, (7) the second electrode pattern At least one of the other conductive elements (6) corresponds to the transparent electrode pattern in the transparent laminate of the present invention.

The capacitance-type input device of the present invention preferably further has (1) a mask layer and / or a decoration layer as necessary. The mask layer is provided as a black frame around the area touched by a finger or a touch pen so that the transparent wiring of the transparent electrode pattern cannot be seen from the contact side or is decorated. The decoration layer is provided for decoration, for example, it is preferable to provide a white decoration layer.
The (1) mask layer and / or the decorative layer may comprise (2) the transparent film and the front plate, (3) the first transparent electrode pattern and the front plate, and (4) the second transparent electrode pattern. And the front plate or (6) another conductive element and the front plate. The (1) mask layer and / or decorative layer is more preferably provided adjacent to the front plate.

Even if the capacitance-type input device of the present invention includes such various members, the antireflection layer disposed adjacent to the transparent electrode pattern and the antireflection layer disposed adjacent to the transparent electrode pattern. By including the protective layer, the transparent electrode pattern can be made inconspicuous, and the visibility problem of the transparent electrode pattern can be improved. Furthermore, as described above, the transparent electrode pattern is sandwiched between the transparent film having the refractive index of 1.6 to 1.78 and the film thickness of 55 to 110 nm and the antireflection layer, thereby further transparent. The problem of the visibility of the electrode pattern can be improved.

<Configuration of capacitance type input device>
First, the configuration of a capacitive input device formed by the manufacturing method of the present invention will be described. FIG. 2 is a cross-sectional view showing a preferred configuration of the capacitive input device of the present invention. In FIG. 2, the capacitive input device has the laminate of the present invention. Specifically, the front plate 1, the decorative layer 2a, the mask layer 2b, the first transparent electrode pattern 3, The second transparent electrode pattern 4, the insulating layer 5, the conductive element 6, and the transparent protective layer 7 are included. A transparent protective plate 7 has a polymer layer (not shown) on the opposite side of the front plate 1 side.

A mask layer 2 b is provided on the non-contact surface of the front plate 1. The mask layer 2b is a frame-like pattern around the display area formed on the non-contact side of the front panel of the touch panel, and is formed so as not to show the lead wiring or the like.
As shown in FIG. 1, the capacitance type input device of the present invention is provided with a mask layer 2 so as to cover a part of the front plate 1 (a region other than the input surface in FIG. 1). . Further, the front plate 1 can be provided with an opening 8 in part as shown in FIG. A mechanical switch by pressing can be installed in the opening 8.

On the contact surface of the front plate 1, a plurality of first transparent electrode patterns 3 formed by extending a plurality of pad portions in the first direction via connection portions; A plurality of second transparent electrode patterns 4 made of a plurality of pad portions that are electrically insulated and extend in a direction intersecting the first direction, the first transparent electrode pattern 3 and the second An insulating layer 5 that electrically insulates the transparent electrode pattern 4 is formed. As the first transparent electrode pattern 3, the second transparent electrode pattern 4, and the conductive element 6 to be described later, those mentioned as the material for the transparent electrode pattern in the laminate of the present invention can be used. A membrane is preferred.

In addition, at least one of the first transparent electrode pattern 3 and the second transparent electrode pattern 4 extends over both the non-contact surface of the front plate 1 and the region of the mask layer 2 opposite to the front plate 1. Can be installed. In FIG. 2, a diagram is shown in which the second transparent electrode pattern is disposed across both the non-contact surface of the front plate 1 and the area of the mask layer 2 opposite to the front plate 1. Yes. Thus, even when a photosensitive film is laminated across the mask layer and the back surface of the front plate that require a certain thickness, an expensive film such as a vacuum laminator can be used by using a photosensitive film having a specific layer structure to be described later. Even without the use of equipment, it is possible to perform lamination without generating bubbles at the boundary of the mask portion with a simple process.

The first transparent electrode pattern 3 and the second transparent electrode pattern 4 will be described with reference to FIG. FIG. 4 is an explanatory diagram showing an example of the first transparent electrode pattern and the second transparent electrode pattern in the present invention. As shown in FIG. 4, the first transparent electrode pattern 3 is formed such that the pad portion 3a extends in the first direction via the connection portion 3b. The second transparent electrode pattern 4 is electrically insulated by the first transparent electrode pattern 3 and the insulating layer 5 and extends in a direction intersecting the first direction (second direction in FIG. 4). It is constituted by a plurality of pad portions that are formed. Here, when the first transparent electrode pattern 3 is formed, the pad portion 3a and the connection portion 3b may be manufactured as one body, or only the connection portion 3b is manufactured and the pad portion 3a and the second portion 3b are formed. The transparent electrode pattern 4 may be integrally formed (patterned). When the pad portion 3a and the second transparent electrode pattern 4 are manufactured (patterned) as a single body (patterning), a part of the connection part 3b and a part of the pad part 3a are connected as shown in FIG. Each layer is formed so that the first transparent electrode pattern 3 and the second transparent electrode pattern 4 are electrically insulated by 5.

In FIG. 2, a conductive element 6 is provided on the side of the mask layer 2 opposite to the front plate 1. The conductive element 6 is electrically connected to at least one of the first transparent electrode pattern 3 and the second transparent electrode pattern 4, and is different from the first transparent electrode pattern 3 and the second transparent electrode pattern 4. Is another element. FIG. 2 shows a diagram in which the conductive element 6 is connected to the second transparent electrode pattern 4.

Moreover, in FIG. 2, the protective layer 7 is installed so that all of each component may be covered. The protective layer 7 may be configured to cover only a part of each component. The insulating layer 5 and the protective layer 7 may be made of the same material or different materials. As the material constituting the insulating layer 5, those mentioned as the material for the antireflection layer or protective layer in the laminate of the present invention can be preferably used.

<Method for Manufacturing Capacitive Input Device>
Examples of the embodiment formed in the process of manufacturing the capacitive input device of the present invention include the embodiments shown in FIGS. FIG. 5 is a top view showing an example of the tempered glass 11 in which the opening 8 is formed. FIG. 6 is a top view showing an example of the front plate on which the mask layer 2 is formed. FIG. 7 is a top view showing an example of the front plate on which the first transparent electrode pattern 3 is formed. FIG. 8 is a top view showing an example of a front plate on which the first transparent electrode pattern 3 and the second transparent electrode pattern 4 are formed. FIG. 9 is a top view showing an example of a front plate on which conductive elements 6 different from the first and second transparent electrode patterns are formed. These show examples embodying the following explanation, and the scope of the present invention is not limitedly interpreted by these drawings.

In the method of manufacturing a capacitance-type input device, when the antireflection layer 12, the protective layer 7, and the polymer layer are formed, a laminate material is used to form a surface on the front plate 1 on which each element is arbitrarily formed. It can be formed by laminating the antireflection layer.

In the method for manufacturing the capacitance type input device, at least one element of the mask layer 2, the first transparent electrode pattern 3, the second transparent electrode pattern 4, the insulating layer 5, and the conductive element 6 is: It is preferable to form using the said photosensitive film which has a temporary support body and a photocurable resin layer in this order.
When each element is formed using a transfer film or the photosensitive film, even a substrate (front plate) having an opening has no resist component leakage from the opening, and a light shielding pattern is formed from the opening to the boundary of the front plate. Since there is no protrusion of the resist component from the glass edge in the necessary mask layer, it is possible to manufacture a touch panel having a merit of thin layer / light weight by a simple process without contaminating the back side of the substrate.

Using the photosensitive film, permanent materials such as the first transparent electrode pattern, the second transparent electrode pattern, and the conductive element when the mask layer, the insulating layer, and the conductive photocurable resin layer are used are formed. In this case, the photosensitive film is laminated on the substrate and then exposed in a pattern as necessary. In the case of negative type material, the non-exposed part is exposed, and in the case of positive type material, the exposed part is developed and removed. By doing so, a pattern can be obtained. In the development, the thermoplastic resin layer and the photocurable layer may be developed and removed with separate liquids, or may be removed with the same liquid. You may combine well-known image development facilities, such as a brush and a high pressure jet, as needed. After the development, post-exposure and post-bake may be performed as necessary.

(Photosensitive film)
The photosensitive film other than the transfer film, which is preferably used when manufacturing the capacitive input device of the present invention, will be described. The photosensitive film preferably has a temporary support and a photocurable resin layer, and preferably has a thermoplastic resin layer between the temporary support and the photocurable resin layer. If a mask layer or the like is formed using the photosensitive film having the thermoplastic resin layer, bubbles are not easily generated in the element formed by transferring the photocurable resin layer, and image unevenness occurs in the image display device. Therefore, excellent display characteristics can be obtained.
The photosensitive film may be a negative type material or a positive type material.

-Layers other than the photo-curable resin layer, production method-
As the temporary support and the thermoplastic resin layer in the photosensitive film, the same materials as those used in the transfer film of the present invention can be used. Also, as the method for producing the photosensitive film, the same method as the method for producing the transfer film can be used.

-Photocurable resin layer-
The said photosensitive film adds an additive to a photocurable resin layer according to the use. That is, when using the said photosensitive film for formation of a mask layer, a coloring agent is contained in a photocurable resin layer. Moreover, when the said photosensitive film has an electroconductive photocurable resin layer, an electroconductive fiber etc. contain in the said photocurable resin layer.

When the photosensitive film is a negative material, the photocurable resin layer preferably contains an alkali-soluble resin, a polymerizable compound, a polymerization initiator, or a polymerization initiation system. Furthermore, conductive fibers, colorants, other additives, and the like are used, but are not limited thereto.

--Alkali-soluble resin, polymerizable compound, polymerization initiator or polymerization initiation system--
As the alkali-soluble resin, the polymerizable compound, the polymerization initiator, or the polymerization initiation system contained in the photosensitive film, those similar to those used for the transfer film of the present invention can be used.

--Conductive fiber (when used as conductive photo-curing resin layer)-
When the photosensitive film on which the conductive photocurable resin layer is laminated is used for forming a transparent electrode pattern or another conductive element, the following conductive fibers may be used for the photocurable resin layer. it can.

There is no restriction | limiting in particular as a structure of an electroconductive fiber, Although it can select suitably according to the objective, A solid structure or a hollow structure is preferable.
Here, the fiber having a solid structure may be referred to as “wire”, and the fiber having a hollow structure may be referred to as “tube”. A conductive fiber having an average minor axis length of 5 nm to 1,000 nm and an average major axis length of 1 μm to 100 μm may be referred to as “nanowire”.
In addition, a conductive fiber having an average minor axis length of 1 nm to 1,000 nm, an average major axis length of 0.1 μm to 1,000 μm, and having a hollow structure may be referred to as “nanotube”.
The material of the conductive fiber is not particularly limited as long as it has conductivity, and can be appropriately selected according to the purpose. However, at least one of metal and carbon is preferable, and among these, The conductive fiber is particularly preferably at least one of metal nanowires, metal nanotubes, and carbon nanotubes.

The material of the metal nanowire is not particularly limited. For example, at least one metal selected from the group consisting of the fourth period, the fifth period, and the sixth period of the long periodic table (IUPAC 1991) is preferable. More preferably, at least one metal selected from Group 2 to Group 14 is selected from Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13, and Group 14. At least one metal selected from the group is more preferable, and it is particularly preferable to include it as a main component.

Examples of the metal include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantel, titanium, bismuth, antimony, and lead. And alloys thereof. Among these, in view of excellent conductivity, those mainly containing silver or those containing an alloy of silver and a metal other than silver are preferable.
Containing mainly silver means that the metal nanowire contains 50% by mass or more, preferably 90% by mass or more.
Examples of the metal used in the alloy with silver include platinum, osmium, palladium and iridium. These may be used alone or in combination of two or more.

The shape of the metal nanowire is not particularly limited and can be appropriately selected depending on the purpose. In applications where high transparency is required, a cylindrical shape and a cross-sectional shape with rounded polygonal corners are preferred.
The cross-sectional shape of the metal nanowire can be examined by applying a metal nanowire aqueous dispersion on a substrate and observing the cross-section with a transmission electron microscope (TEM).
The corner of the cross section of the metal nanowire means a peripheral portion of a point that extends each side of the cross section and intersects with a perpendicular drawn from an adjacent side. Further, “each side of the cross section” is a straight line connecting these adjacent corners. In this case, the ratio of the “outer peripheral length of the cross section” to the total length of the “each side of the cross section” was defined as the sharpness. For example, in the metal nanowire cross section as shown in FIG. 10, the sharpness can be represented by the ratio of the outer peripheral length of the cross section indicated by the solid line and the outer peripheral length of the pentagon indicated by the dotted line. A cross-sectional shape having a sharpness of 75% or less is defined as a cross-sectional shape having rounded corners. The sharpness is preferably 60% or less, and more preferably 50% or less. If the sharpness exceeds 75%, the electrons may be localized at the corners, and plasmon absorption may increase, or the transparency may deteriorate due to yellowing or the like. Moreover, the linearity of the edge part of a pattern may fall and a shakiness may arise. The lower limit of the sharpness is preferably 30%, more preferably 40%.

The average minor axis length of the metal nanowire (sometimes referred to as “average minor axis diameter” or “average diameter”) is preferably 150 nm or less, more preferably 1 nm to 40 nm, and more preferably 10 n
m to 40 nm is more preferable, and 15 nm to 35 nm is particularly preferable.
When the average minor axis length is less than 1 nm, the oxidation resistance may be deteriorated and the durability may be deteriorated. When the average minor axis length is more than 150 nm, scattering due to metal nanowires occurs and sufficient transparency is obtained. There are times when you can't.
The average minor axis length of the metal nanowires was determined by observing 300 metal nanowires using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX). The average minor axis length of was determined. In addition, the shortest axis length when the short axis of the metal nanowire is not circular is the shortest axis.

The average major axis length (sometimes referred to as “average length”) of the metal nanowire is preferably 1 μm to 40 μm, more preferably 3 μm to 35 μm, and even more preferably 5 μm to 30 μm.
If the average major axis length is less than 1 μm, it may be difficult to form a dense network and sufficient conductivity may not be obtained. If it exceeds 40 μm, the metal nanowires are too long and manufactured. Sometimes entangled and agglomerates may occur during the manufacturing process.
The average major axis length of the metal nanowires is, for example, observed with 300 metal nanowires using a transmission electron microscope (TEM; manufactured by JEOL Ltd., JEM-2000FX). The average major axis length of the wire was determined. In addition, when the said metal nanowire was bent, the circle | round | yen which makes it an arc was considered and the value calculated from the radius and curvature was made into the major axis length.

The thickness of the conductive photocurable resin layer is preferably from 0.1 to 20 μm, and preferably from 0.5 to 18 μm, from the viewpoint of process suitability such as coating solution stability, drying during coating, and development time during patterning. Further preferred is 1 to 15 μm. The content of the conductive fiber based on the total solid content of the conductive photocurable resin layer is preferably 0.01 to 50% by mass, and 0.05 to 30% by mass from the viewpoints of conductivity and coating solution stability. % Is more preferable, and 0.1 to 20% by mass is particularly preferable.

--Colorant (when used as a mask layer)-
Moreover, when using the said photosensitive film as a mask layer, a coloring agent can be used for a photocurable resin layer. As the colorant used in the present invention, known colorants (organic pigments, inorganic pigments, dyes, etc.) can be suitably used. In the present invention, in addition to the black colorant, a mixture of pigments such as red, blue, and green can be used.

When the photocurable resin layer is used as a black mask layer, it is preferable to include a black colorant from the viewpoint of optical density. Examples of the black colorant include carbon black, titanium carbon, iron oxide, titanium oxide, and graphite. Among these, carbon black is preferable.

When the photocurable resin layer is used as a white mask layer, white pigments described in paragraphs [0015] and [0114] of JP-A-2005-7765 can be used. For use as a mask layer of other colors, pigments or dyes described in paragraphs [0183] to [0185] of Japanese Patent No. 4546276 may be mixed and used. Specifically, pigments and dyes described in paragraph numbers [0038] to [0054] of JP-A-2005-17716, and pigments described in paragraph numbers [0068] to [0072] of JP-A-2004-361447. The colorants described in paragraph numbers [0080] to [0088] of JP-A-2005-17521 can be suitably used.

The colorant (preferably a pigment, more preferably carbon black) is desirably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the colorant and the pigment dispersant in an organic solvent (or vehicle) described later. The vehicle is a portion of a medium in which a pigment is dispersed when the paint is in a liquid state, and is a liquid component that binds to the pigment to form a coating film (binder) and dissolves and dilutes it. Component (organic solvent).
The disperser used for dispersing the pigment is not particularly limited. For example, the kneader described in Kazuzo Asakura, “Encyclopedia of Pigments”, first edition, Asakura Shoten, 2000, 438, Known dispersing machines such as a roll mill, an atrider, a super mill, a dissolver, a homomixer, and a sand mill can be used. Further, fine grinding may be performed using frictional force by mechanical grinding described on page 310 of the document.

The colorant preferably has a number average particle size of 0.001 μm to 0.1 μm, more preferably 0.01 μm to 0.08 μm, from the viewpoint of dispersion stability. The “particle diameter” as used herein refers to the diameter when the electron micrograph image of the particle is a circle of the same area, and the “number average particle diameter” is the above-mentioned particle diameter for a large number of particles, This 100 average value is said.

The layer thickness of the photocurable resin layer containing the colorant is preferably 0.5 to 10 μm, more preferably 0.8 to 5 μm, and particularly preferably 1 to 3 μm, from the viewpoint of thickness difference from other layers. The content of the colorant in the solid content of the colored photosensitive resin composition is not particularly limited, but is preferably 15 to 70% by mass from the viewpoint of sufficiently shortening the development time, and preferably 20 to 60%. More preferably, it is more preferably 25 to 50% by mass.
The total solid content as used in this specification means the total mass of the non-volatile component remove | excluding the solvent etc. from the coloring photosensitive resin composition.

When forming the insulating layer using the photosensitive film, the layer thickness of the photocurable resin layer is preferably from 0.1 to 5 μm, more preferably from 0.3 to 3 μm from the viewpoint of maintaining insulation. 0.5 to 2 μm is particularly preferable.

-Other additives-
Furthermore, you may use another additive for the said photocurable resin layer. As said additive, the thing similar to what is used for the transfer film of this invention can be used.
Moreover, as a solvent at the time of manufacturing the said photosensitive film by application | coating, the thing similar to what is used for the transfer film of this invention can be used.

As described above, the case where the photosensitive film is a negative type material has been mainly described, but the photosensitive film may be a positive type material. When the photosensitive film is a positive type material, for example, a material described in JP-A-2005-221726 is used for the photocurable resin layer, but the material is not limited thereto.

-Viscosity of thermoplastic resin layer and photocurable resin layer-
The viscosity of the thermoplastic resin layer measured at 100 ° C. is in the region of 1000 to 10,000 Pa · sec, the viscosity of the photocurable resin layer measured at 100 ° C. is in the region of 2000 to 50000 Pa · sec, and the following formula ( It is preferable to satisfy A).
Formula (A): Viscosity of thermoplastic resin layer <viscosity of photocurable resin layer

Here, the viscosity of each layer can be measured as follows. The solvent is removed from the coating solution for the thermoplastic resin layer or the photocurable resin layer by drying under atmospheric pressure and reduced pressure to obtain a measurement sample. For example, as a measuring instrument, Vibron (DD-III type: manufactured by Toyo Baldwin Co., Ltd.) Can be used under the conditions of a measurement start temperature of 50 ° C., a measurement end temperature of 150 ° C., a heating rate of 5 ° C./min, and a frequency of 1 Hz / deg.

(Formation of mask layer and insulating layer with photosensitive film)
The mask layer 2 and the insulating layer 5 can be formed by transferring a photocurable resin layer to the front plate 1 or the like using the photosensitive film. For example, when the black mask layer 2 is formed, the black photocurable resin is formed on the surface of the front plate 1 using the photosensitive film having a black photocurable resin layer as the photocurable resin layer. It can be formed by transferring the layer. When forming the insulating layer 5, the front plate 1 on which the first transparent electrode pattern is formed using the photosensitive film having an insulating photocurable resin layer as the photocurable resin layer. It can be formed by transferring the photocurable resin layer to the surface.
Furthermore, in the formation of the mask layer 2 that needs light shielding properties, the photosensitive film having the specific layer structure including the thermoplastic resin layer between the photocurable resin layer and the temporary support is used. Generation of bubbles during lamination can be prevented, and a high-quality mask layer 2 and the like having no light leakage can be formed.

(Formation of first and second transparent electrode patterns and other conductive elements by a photosensitive film)
The first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 may be formed by using the photosensitive film having an etching treatment or a conductive photocurable resin layer, or using a photosensitive film. It can be formed using as a lift-off material.

-Etching treatment-
When the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 are formed by etching, first, on the non-contact surface of the front plate 1 on which the mask layer 2 and the like are formed. A transparent electrode layer such as ITO is formed by sputtering. Next, an etching pattern is formed by exposure and development using the photosensitive film having an etching photocurable resin layer as the photocurable resin layer on the transparent electrode layer. Thereafter, the transparent electrode layer is etched to pattern the transparent electrode, and the etching pattern is removed, whereby the first transparent electrode pattern 3 and the like can be formed.

Also when the photosensitive film is used as an etching resist (etching pattern), a resist pattern can be obtained in the same manner as in the above method. For the etching, etching or resist stripping can be applied by a known method described in paragraphs [0048] to [0054] of JP 2010-152155 A.

For example, as an etching method, there is a commonly performed wet etching method of dipping in an etching solution. As an etching solution used for wet etching, an acid type or an alkaline type may be appropriately selected according to an object to be etched. Examples of acidic etching solutions include aqueous solutions of acidic components such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid, and mixed aqueous solutions of acidic components and salts of ferric chloride, ammonium fluoride, potassium permanganate, and the like. Is done. As the acidic component, a combination of a plurality of acidic components may be used. In addition, alkaline type etching solutions include sodium hydroxide, potassium hydroxide, ammonia, organic amines, aqueous solutions of alkali components such as organic amine salts such as tetramethylammonium hydroxide, alkaline components and potassium permanganate. A mixed aqueous solution of a salt such as A combination of a plurality of alkali components may be used as the alkali component.

The temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower. The resin pattern used as an etching mask (etching pattern) in the present invention is formed by using the above-described photocurable resin layer, so that it is particularly suitable for acidic and alkaline etching solutions in such a temperature range. Excellent resistance. Therefore, the resin pattern is prevented from peeling off during the etching process, and the portion where the resin pattern does not exist is selectively etched.
After the etching, a cleaning process and a drying process may be performed as necessary to prevent line contamination. The cleaning process is performed by cleaning the substrate with pure water for 10 to 300 seconds at room temperature, for example, and the air blowing pressure (about 0.1 to 5 kg / cm ² ) is appropriately adjusted using an air blow for the drying process. Just do it.

Next, the method of peeling the resin pattern is not particularly limited, and examples thereof include a method of immersing the substrate in a peeling solution being stirred at 30 to 80 ° C., preferably 50 to 80 ° C. for 5 to 30 minutes. The resin pattern used as an etching mask in the present invention exhibits excellent chemical resistance at 45 ° C. or lower as described above, but exhibits a property of swelling by an alkaline stripping solution when the chemical temperature is 50 ° C. or higher. . Due to such properties, when the peeling process is performed using a peeling solution of 50 to 80 ° C., there are advantages that the process time is shortened and the resin pattern peeling residue is reduced. That is, by providing a difference in chemical temperature between the etching process and the peeling process, the resin pattern used as an etching mask in the present invention exhibits good chemical resistance in the etching process, while in the peeling process. Good peelability will be exhibited, and both conflicting properties of chemical resistance and peelability can be satisfied.

Examples of the stripping solution include inorganic alkali components such as sodium hydroxide and potassium hydroxide, organic alkali components such as tertiary amine and quaternary ammonium salt, water, dimethyl sulfoxide, N-methylpyrrolidone, or these. What was melt | dissolved in this mixed solution is mentioned. You may peel by the spray method, the shower method, the paddle method etc. using the said peeling liquid.

-Photosensitive film with conductive photocurable resin layer-
When forming the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 using the photosensitive film having a conductive photocurable resin layer, the front plate 1 It can be formed by transferring the conductive photocurable resin layer to the surface.
When the first transparent electrode pattern 3 or the like is formed using a photosensitive film having the conductive photocurable resin layer, there is no leakage of resist components from the opening portion even on a substrate (front plate) having an opening portion. Without contaminating the back side of the substrate, it is possible to manufacture a touch panel having a merit of thin layer / light weight by a simple process.
Furthermore, the first transparent electrode pattern 3 or the like is formed by using the photosensitive film having a specific layer structure including a thermoplastic resin layer between the conductive photocurable resin layer and the temporary support. It is possible to prevent the generation of bubbles when laminating the conductive film, and to form the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 with excellent conductivity and low resistance.

-Use of photosensitive film as lift-off material-
Moreover, a 1st transparent electrode layer, a 2nd transparent electrode layer, and another electroconductive member can also be formed using the said photosensitive film as a lift-off material. In this case, after patterning using the photosensitive film, a transparent conductive layer is formed on the entire surface of the base material, and then the desired transparent conductive layer is formed by dissolving and removing the photocurable resin layer together with the deposited transparent conductive layer. A pattern can be obtained (lift-off method).

[Touch panel]
The touch panel of this invention contains the laminated body of this invention mentioned above.

The touch panel of the present invention can be used as an input device by being incorporated in a display device such as a liquid crystal display, a plasma display, an organic EL display, a CRT display, and electronic paper. By using the touch panel of the present invention, occurrence of interference unevenness can be suppressed and a touch panel with good color can be obtained.
There are two types of touch panel configurations, such as a resistance film type and a capacitance type. Capacitance type input devices have the advantage of simply forming a light-transmitting conductive film on a single substrate. A capacitance type is preferred. In such a capacitance-type input device, for example, when the electrode pattern is extended in a direction intersecting each other as the transparent electrode layer and a finger or the like comes into contact, it is detected that the capacitance between the electrodes changes. Thus, a type that detects the input position can be preferably used. Regarding the configuration of such a touch panel, for example, descriptions in JP 2010-86684 A, JP 2010-152809 A, JP 2010-257492 A, and the like can be referred to.
Regarding the configuration of an image display device equipped with a touch panel as a component, “Latest Touch Panel Technology” (published July 6, 2009, Techno Times), supervised by Yuji Mitani, “Technology and Development of Touch Panels”, CM Publishing (2004, 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292, and the like can be applied.
In addition, regarding the configuration of a liquid crystal display in which a touch panel can be incorporated, description in JP-A-2002-48913 can be referred to.

Hereinafter, the features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Example 1]
<Preparation of decorative film-forming photosensitive film K1>
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Furthermore, the coating liquid for black photocurable resin layers which consists of the following prescription K1 was apply | coated and dried. In this way, the thermoplastic film layer having a dry film thickness of 15.1 μm, the intermediate layer having a dry film thickness of 1.6 μm, and the dry film thickness so that the optical density is 4.0 are formed on the temporary support. A 2.2 μm black photocurable resin layer was provided, and finally a protective film (12 μm thick polypropylene film) was pressure-bonded. Thus, a transfer material in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the black photocurable resin layer were integrated was prepared, and the sample name was designated as a decorative pattern forming photosensitive film K1. .

(Coating solution for thermoplastic resin layer: Formulation H1)
Methanol: 11.1 parts by mass Propylene glycol monomethyl ether acetate: 6.36 parts by mass Methyl ethyl ketone: 52.4 parts by mass Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio) (Molar ratio) = 55 / 11.7 / 4.5 / 28.8, molecular weight = 100,000, Tg≈70 ° C.): 5.83 parts by mass. Styrene / acrylic acid copolymer (copolymerization composition ratio (mol) Ratio) = 63/37, weight average molecular weight = 10,000, Tg≈100 ° C.): 13.6 parts by mass Monomer 1 (trade name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.): 9.1 mass parts fluorine-based polymer: 0.54 parts by weight _{_{_{(C 6 F 13 CH 2 CH}}} 2 O OCH = CH ₂ 40 parts of _{H (OCH (CH 3) CH} 2) 7 OCOCH = copolymer of CH ₂ 55 parts of _{_{H (OCHCH 2) 7 OCOCH =}} CH 2 5 parts, weight average molecular weight of 30,000, methyl ethyl ketone 30% by weight solution, trade name: MegaFuck F780F, manufactured by Dainippon Ink & Chemicals, Inc.)
The viscosity at 120 ° C. after removing the solvent from the coating liquid H1 for the thermoplastic resin layer was 1500 Pa · s.

(Coating liquid for intermediate layer: prescription P1)
Polyvinyl alcohol: 32.2 parts by mass (trade name: PVA205, manufactured by Kuraray Co., Ltd., saponification degree = 88%, polymerization degree 550)
・ Polyvinylpyrrolidone: 14.9 parts by mass (trade name: K-30, manufactured by IS Japan Co., Ltd.)
-Distilled water: 524 parts by mass-Methanol: 429 parts by mass

(Coating liquid for black light curable resin layer: Formula K1)
-K pigment dispersion 1: 31.2 parts by mass (composition of K pigment dispersion 1)
Carbon black (trade name: Nipex 35, manufactured by Degussa): 13.1% by mass
・ The following dispersant 1: 0.65 mass%
Binder 1 (Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, weight average molecular weight 37,000): 6.72% by mass
Propylene glycol monomethyl ether acetate: 79.53 mass% R pigment dispersion 1 (the following composition): 3.3 parts by mass MMPGAc (manufactured by Daicel Chemical Industries): 6.2 parts by mass Methyl ethyl ketone (Tonen Chemical) (Manufactured by Co., Ltd.): 34.0 parts by mass / cyclohexanone (manufactured by Kanto Denka Kogyo Co., Ltd.): 8.5 parts by mass / binder 2 (random copolymer having a benzyl methacrylate / methacrylic acid = 78/22 molar ratio, weight (Average molecular weight 38,000): 10.8 parts by mass / phenothiazine (manufactured by Tokyo Chemical Industry Co., Ltd.): 0.01 parts by mass / propylene glycol monomethyl of DPHA (dipentaerythritol hexaacrylate, Nippon Kayaku Co., Ltd.) Ether acetate solution (76 mass%): 5.5 mass 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bis (ethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine: 0.4 parts by mass Surfactant (Product name: Megafuck F-780F, manufactured by Dainippon Ink Co., Ltd.)
: 0.1 mass part In addition, the viscosity of 100 degreeC after the solvent removal of the coating liquid K1 for black photocurable resin layers was 10000 Pa.s.

(Composition of R pigment dispersion 1)
Pigment (CI Pigment Red 177): 18% by mass
-Binder 1 (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, weight average molecular weight 37,000)
: 12% by mass
Propylene glycol monomethyl ether acetate: 70% by mass

<Decorative pattern formation on glass substrate>
For a glass substrate (thickness 0.7 mm, Gorilla glass, manufactured by Corning) that has been subjected to a chemical strengthening treatment in which part or all of ions having a smaller ion radius than potassium ions in the glass are replaced with potassium ions, Silane coupling treatment was performed.
A glass cleaner solution adjusted to 25 ° C. is sprayed with a rotating brush having nylon bristles while sprayed for 20 seconds in a shower. After pure water shower cleaning, a silane coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxy) is washed. Silane 0.3% by mass aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. This substrate was heated at 140 ° C. for 2 minutes with a substrate preheating device. The surface of the black photocurable resin layer exposed to the silane coupling-treated glass substrate obtained by removing the cover film from the decorative film-forming photosensitive film K1 obtained from the above and the silane coupling is removed. The surface of the treated glass substrate is overlapped with each other, and the substrate heated at 140 ° C. using a laminator (manufactured by Hitachi Industries (Lamic II type)), a rubber roller temperature of 130 ° C., a wire Lamination was performed at a pressure of 100 N / cm and a conveyance speed of 2.2 m / min. Subsequently, the polyethylene terephthalate temporary support was peeled off at the interface with the thermoplastic resin layer to remove the temporary support. After peeling off the temporary support, the substrate and the exposure mask (quartz exposure mask with a frame pattern) were set up vertically with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. In this state, the distance between the exposure mask surface and the black light curable resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² (i-line).

Next, a triethanolamine developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water) at 33 ° C. for 60 seconds, Shower development was performed at a flat nozzle pressure of 0.1 MPa to remove the thermoplastic resin layer and the intermediate layer. Subsequently, air was blown onto the upper surface of the glass base material to drain the liquid, and then pure water was sprayed for 10 seconds by a shower, pure water shower washing was performed, and air was blown to reduce the liquid pool on the base material.

Thereafter, the shower pressure was reduced to 0.1 MPa at 32 ° C. using a sodium carbonate / sodium hydrogen carbonate developer (trade name: T-CD1 (manufactured by FUJIFILM Corporation) diluted 5 times with pure water). It was set, developed for 45 seconds, and washed with pure water.

Subsequently, using a surfactant-containing cleaning solution (trade name: T-SD3 (manufactured by Fuji Film Co., Ltd.) diluted 10-fold with pure water) at 33 ° C. for 20 seconds, cone-type nozzle pressure of 0.1 MPa The residue was removed by rubbing the formed pattern image with a rotating brush having soft nylon hairs. Furthermore, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultra-high pressure cleaning nozzle to remove residues, followed by post-exposure at an exposure amount of 1300 mJ / cm ^{2 in the} atmosphere, and further at 240 ° C. for 80 minutes. A post-baking process was performed to form a decorative pattern having an optical density of 4.0 and a film thickness of 2.0 μm on the glass substrate subjected to the tempering process.

<Formation of transparent electrode pattern>
<< Formation of transparent electrode layer >>
The substrate on which the decorative pattern was formed was introduced into a vacuum chamber, and DC magnetron sputtering (conditions) was performed using an ITO target (indium: tin = 95: 5 (molar ratio)) with a SnO ₂ content of 10% by mass. : A base material temperature of 250 ° C., an argon pressure of 0.13 Pa, an oxygen pressure of 0.01 Pa) was used to form an ITO thin film having a thickness of 40 nm to obtain a substrate on which a transparent electrode layer was formed. The surface resistance of the ITO thin film was 80Ω / □.

(Preparation of photosensitive film E1)
In the preparation of the decorative film forming photosensitive film K1, the coating liquid for black photocurable resin layer was used for forming a decorative pattern except that the coating liquid for etching photocurable resin layer comprising the following formulation E1 was used. In the same manner as in the preparation of the photosensitive film K1, a photosensitive film E1 for etching was obtained (the film thickness of the photocurable resin layer for etching was 2.0 μm).

(Coating liquid for photocurable resin layer for etching: prescription E1)
Methyl methacrylate / styrene / methacrylic acid copolymer (copolymer composition (mass%): 31/40/29, mass average molecular weight: 60000, acid value 163 mg KOH / g)
: 16 parts by mass-Monomer 1 (Brand name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.): 5.6 parts by mass-Tetraethylene oxide monomethacrylate 0.5 mol adduct of hexamethylene diisocyanate: 7 parts by mass Cyclohexanedimethanol monoacrylate as a compound having one polymerizable group in the molecule: 2.8 parts by mass, 2-chloro-N-butylacridone: 0.42 parts by mass, 2,2-bis (o-chlorophenyl) ) -4,4 ', 5,5'-tetraphenylbiimidazole: 2.17 parts by mass Malachite green oxalate: 0.02 parts by mass Leucocrystal violet: 0.26 parts by mass Phenothiazine: 0.013 Part by mass / surfactant ( Product name: Megafac F-780F, Dainippon Ink Co., Ltd.)
: 0.03 parts by mass · Methyl ethyl ketone: 40 parts by mass · 1-methoxy-2-propanol: 20 parts by mass The viscosity of the coating solution E1 for photocurable resin layer for etching after removing the solvent is 2500 Pa · s. Met.

(Formation of first transparent electrode pattern)
Similarly to the formation of the decorative pattern, the substrate on which the transparent electrode layer was formed was washed, and the etching photosensitive film E1 from which the cover film was removed was laminated (base material temperature: 130 ° C., rubber roller temperature 120 ° C., wire Pressure 100 N / cm, conveyance speed 2.2 m / min). After peeling off the temporary support, the distance between the exposure mask (quartz exposure mask having a transparent electrode pattern) surface and the photocurable resin layer for etching is set to 200 μm, and the exposure amount is 50 mJ / cm ² (i-line). ) For pattern exposure.
Next, a triethanolamine developer (containing 30% by mass of triethanolamine, a trade name: T-PD2 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water) at 25 ° C. for 100 seconds, A surfactant-containing cleaning solution (trade name: T-SD3 (manufactured by FUJIFILM Corporation) diluted 10-fold with pure water) was treated at 33 ° C. for 20 seconds, using a rotating brush and an ultra-high pressure cleaning nozzle. The residue was removed, and a post-bake treatment at 130 ° C. for 30 minutes was further performed to obtain a substrate on which a transparent electrode layer and a photocurable resin layer pattern for etching were formed.

The substrate on which the transparent electrode layer and the photocurable resin layer pattern for etching are formed is immersed in an etching tank containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), treated for 100 seconds, and etched light. The transparent electrode layer in the exposed region not covered with the curable resin layer was dissolved and removed to obtain a substrate with a transparent electrode layer pattern having a photocurable resin layer pattern for etching.

Next, a substrate with a transparent electrode layer pattern with a photocurable resin layer pattern for etching is applied to a resist stripping solution (N-methyl-2-pyrrolidone, monoethanolamine, a surfactant (trade name: Surfynol 465, Nissin Chemical Industry Co., Ltd.) immersed in a resist stripping tank containing a liquid temperature of 45 ° C., treated for 200 seconds, removed the photo-curable resin layer for etching, and the mask layer and the first transparent electrode pattern A formed substrate was obtained.

<< Formation of insulating layer >>
(Preparation of photosensitive film W1 for insulating layer formation)
For the preparation of the decorative pattern-forming photosensitive film K1, the black-light-curable resin layer coating solution was replaced with an insulating-layer photocurable resin layer coating solution composed of the following formulation W1. In the same manner as in the preparation of the photosensitive film K1, a photosensitive film W1 for forming an insulating layer was obtained (the film thickness of the photocurable resin layer for the insulating layer was 1.4 μm).

(Insulating layer forming coating solution: Formula W1)
Binder 3 (cyclohexyl methacrylate (a) / methyl methacrylate (b) / methacrylic acid copolymer (c) glycidyl methacrylate adduct (d) (composition (% by mass): a / b / c / d = 46/1) / 10/43, mass average molecular weight: 36000, acid value 66 mgKOH / g) 1-methoxy-2-propanol, methyl ethyl ketone solution (solid content: 45%)): 12.5 parts by mass. DPHA (dipentaerythritol hexaacrylate) , Nippon Kayaku Co., Ltd.) propylene glycol monomethyl ether acetate solution (76% by mass)
: 1.4 parts by mass / urethane-based monomer (trade name: NK Oligo UA-32P, manufactured by Shin-Nakamura Chemical Co., Ltd .: non-volatile content 75%, propylene glycol monomethyl ether acetate: 25%)
: 0.68 parts by mass · Tripentaerythritol octaacrylate (trade name: V # 802, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 1.8 parts by mass · Diethylthioxanthone: 0.17 parts by mass · 2- (dimethylamino ) -2-[(4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: Irgacure 379, manufactured by BASF)
: 0.17 parts by mass-Dispersant (trade name: Solsperse 20000, manufactured by Avicia): 0.19 parts by mass-Surfactant (trade name: Megafac F-780F, manufactured by Dainippon Ink)
: 0.05 parts by mass-Methyl ethyl ketone: 23.3 parts by mass-MMPGAc (manufactured by Daicel Chemical Co., Ltd.): 59.8 parts by mass The viscosity at 100 ° C. after removing the solvent of the coating liquid W1 for forming the insulating layer is 4000 Pa.・ It was s.

In the same manner as the decoration pattern formation, the front plate with the first transparent electrode pattern was washed, treated with silane coupling, and laminated with the insulating film forming photosensitive film W1 from which the cover film was removed (base temperature). : 100 ° C., rubber roller temperature 120 ° C., linear pressure 100 N / cm, transport speed 2.3 m / min). After peeling off the temporary support, the distance between the exposure mask (quartz exposure mask having the insulating layer pattern) surface and the photocurable resin layer for etching is set to 100 μm, and the exposure dose is 30 mJ / cm ² (i Line).

Next, a triethanolamine developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water) at 33 ° C. for 60 seconds, Sodium carbonate / bicarbonate developer (trade name: T-CD1 (Fuji Film Co., Ltd.) diluted 5-fold with pure water) at 25 ° C. for 50 seconds, surfactant-containing cleaning solution (trade name) : T-SD3 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water for 20 seconds at 33 ° C, and the residue is removed with a rotating brush and ultra-high pressure washing nozzle. A post-baking treatment for 60 minutes was performed to obtain a substrate on which a decorative pattern, a first transparent electrode pattern, and an insulating layer pattern were formed.

<< Formation of Second Transparent Electrode Pattern >>
(Formation of transparent electrode layer)
In the same manner as the formation of the first transparent electrode pattern, the front plate on which the first transparent electrode pattern and the insulating layer pattern were formed was subjected to DC magnetron sputtering treatment (conditions: substrate temperature 50 ° C., argon pressure 0.13 Pa). An ITO thin film having an oxygen pressure of 0.01 Pa and a thickness of 80 nm was formed to obtain a substrate on which a transparent electrode layer was formed. The surface resistance of the ITO thin film was 110Ω / □.

In the same manner as the formation of the first transparent electrode pattern, the first transparent electrode pattern, the insulating layer pattern, the transparent electrode layer, and the photocurable resin layer pattern for etching are formed using the etching photosensitive film E1. The obtained front plate was obtained (post-baking treatment; 130 ° C. for 30 minutes).
Further, in the same manner as in the formation of the first transparent electrode pattern, the decorative pattern, the first are obtained by etching (30 ° C. for 50 seconds) and removing the photocurable resin layer for etching (45 ° C. for 200 seconds). A substrate on which a transparent electrode pattern, an insulating layer pattern, and a second transparent electrode pattern were formed was obtained.

(Formation of conductive elements different from the first and second transparent electrode patterns)
Similar to the formation of the first and second transparent electrode patterns, the front plate on which the first transparent electrode pattern, the insulating layer pattern, and the second transparent electrode pattern were formed was subjected to DC magnetron sputtering treatment to a thickness of 200 nm. A front plate on which an aluminum (Al) thin film was formed was obtained.

Similar to the formation of the first and second transparent electrode patterns, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the photocuring for etching are performed using the etching photosensitive film E1. A front plate on which a conductive resin layer pattern was formed was obtained. (Post-bake treatment; 130 ° C. for 30 minutes).
Further, in the same manner as in the formation of the first transparent electrode pattern, the decorative pattern, the first are obtained by etching (30 ° C. for 50 seconds) and removing the photocurable resin layer for etching (45 ° C. for 200 seconds). A substrate on which a conductive element different from the transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns was formed was obtained.

<Production of laminated material>
While discharging a PET film having a thickness of 75 μm and a refractive index of 1.66 at a transfer speed of 80 m / min, both surfaces were subjected to glow discharge treatment under vacuum conditions. The conditions for the glow discharge treatment were 4.0 KJ / m ² , and the surface temperature of the PET film before the glow discharge treatment was 150 ° C. P
The thickness of the surface modification layer obtained on the surface of the ET film was 60 nm, and the non-crystallinity (non-crystallinity / crystallinity) was 6%.

<Preparation of easy adhesion layer>
The following formulation was used for the polymer layer coating solution.
Tin oxide fine particle dispersion 8 parts by mass (average particle size 60 nm) as solid content
2.8 parts by mass of polyurethane (manufactured by Mitsui Chemicals, Takelac WS-5100)
Cross-linking agent 4.2 parts by mass (manufactured by Nisshinbo Chemical Co., Ltd., 10% diluted solution of Carbodilite V-02-L2)
Surfactant A 0.2 parts by mass (manufactured by Sanyo Chemical Industries, Ltd., 10% aqueous solution of sanded BL, anionic)
Surfactant B 0.2 parts by mass (Sanyo Chemical Industry Co., Ltd., 10% diluted solution of NAROACTY CL-95, nonionic)
84.6 parts by weight of water

The above formulation is adjusted so that the refractive index of the easy-adhesion layer after coating and drying is 1.58. An easy-adhesion layer coating solution was applied to the surface of the PET film subjected to the glow discharge treatment by a bar coating method. And this was dried at 150 degreeC for 2 minutes. A laminated film having an easy-adhesion layer applied on both sides of the PET film was obtained. In addition, the film thickness of the easy-adhesion layer was measured by observing the laminated film at a magnification of 200,000 using a transmission electron microscope (JEM2010 (manufactured by JEOL Ltd.)). The film thickness was 100 nm.

<Preparation of hard coat layer>
The easy-adhesion layer obtained as described above was subjected to corona treatment, and then an aqueous composition for forming a hard coat layer was applied. And this was dried at 150 degreeC for 2 minutes, and the hard-coat layer containing the hydrolysis-condensation product of an alkoxysilane was formed. The film thickness of the hard coat layer was 1 μm. The hard coat layer produced by this method is described as “sol gel” in the following table.

The following formulation was used for the aqueous composition.
Acetic acid aqueous solution 100 parts by mass (manufactured by Daicel Chemical Industries, Ltd., 1% aqueous solution of industrial acetic acid)
80 parts by mass of 3-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-403)
20 parts by mass of tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-04)
Aluminum chelate complex 22.1 parts by mass (made by Kawaken Fine Chemicals, aluminum chelate D)
200 parts by mass of inorganic fine particles (manufactured by Nissan Chemical Industries, Snowtex O-33)
Surfactant A 0.2 parts by mass (manufactured by Sanyo Chemical Industries, Ltd., 10% aqueous solution of sanded BL, anionic)
Surfactant B 0.2 parts by mass (Sanyo Chemical Industry Co., Ltd., 10% diluted solution of NAROACTY CL-95, nonionic)
Matting agent 0.02 parts by mass (Nippon Shokubai Co., Ltd., Seahoster KE-P250)

Preparation was performed according to the following procedure. 3-Glycidoxypropyltriethoxysilane (KBE-403) was added to 100 parts by mass of 1% acetic acid and sufficiently hydrolyzed, and then tetraalkoxysilane (KBE-04) was added. A necessary part by mass of the aluminum chelate complex with respect to the epoxy group-containing alkoxysilane was added, and inorganic fine particles (Snowtex O-33) were added thereto. Add 0.2 parts by mass of 10% dilution of Surfactant A (Sandet BL) and 10% dilution of Surfactant B (Naroacty CL-95), and add matting agent (Seahoster KE-P250) And water was added so that solid content concentration might be 15%, and it was set as the aqueous composition.

<Formation of protective layer>
On the surface where the hard coat layer is not formed, the protective layer coating solution prepared by the following composition is adjusted to a film thickness of 10 μm while changing the coating amount, and coated and dried to form a protective layer. Then, a cover film (12 μm thick polypropylene film) was pressure-bonded.

As described above, a laminated material with a function of preventing scattering consisting of a hard coat layer / easy adhesion layer / PET film / easy adhesion layer / protective layer / cover film was produced.

(Coating solution composition for protective layer)

Polymer solution 2

<Production of laminate>
A substrate on which a conductive element different from the decorative pattern, the first transparent electrode pattern, the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns is formed at 25 ° C. The adjusted glass cleaner solution was washed with a rotating brush having nylon bristles while spraying the glass cleaner solution for 20 seconds by showering, and after pure water shower washing, a silane coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxysilane. A 3% by weight aqueous solution, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower and washed with pure water. The substrate was heated at 140 ° C. for 2 minutes with a base material preheating device. The surface of the curable transparent resin layer exposed after the removal of the cover film from the above-mentioned laminated material with an anti-scattering function, which has been cut into a desired shape of the substrate in advance to the obtained silane coupling treatment substrate, and the silane cup The substrate was heated so as to be in contact with the surface of the ring-treated substrate, and the substrate heated at 140 ° C. using a laminator (manufactured by Hitachi Industries (Lamic II type)), rubber roller temperature 130 ° C., linear pressure Lamination was performed at 100 N / cm and a conveyance speed of 2.2 m / min, and a heat curing treatment was performed at 150 ° C. for 60 minutes.

[Example 2]
After the protective layer was formed, UV lamp irradiation (exposure amount 300 mJ / cm ² , methane halide lamp) was irradiated. Thereafter, an antireflection layer was formed on the protective layer with a coating solution (refractive index: 1.72) having the composition of the following material-8 so as to have a film thickness of 52 nm.
A laminated material was produced in the same manner as in Example 1 except for this.

[Example 3]
A laminate was produced in the same manner as in Example 1 except that the PET film of Example 1 was changed to a TAC film having a thickness of 80 μm (Fuji Film, Fujitac).

[Example 4]
A laminate was prepared in the same manner as in Example 1 except that the PET film of Example 1 was changed to a TAC film having a thickness of 40 μm (Fujifilm, Fujitac).

[Example 5]
The PET film of Example 1 was stretched, and a laminate was produced in the same manner as in Example 1 except that a film having a thickness of 50 μm and a retardation of 3000 nm (Re / Rth = 1.03) was used. The retardation was measured by KOBRA 21ADH.

[Example 6]
A laminate was produced in the same manner as in Example 1 except that the PET film of Example 1 was stretched and a film having a thickness of 100 μm and a retardation of 12000 nm (Re / Rth = 0.78) was used.

[Example 7]
A laminate was prepared in the same manner as in Example 1 except that the PET film of Example 1 was replaced with a 66 μm thick polycarbonate film (manufactured by Kaneka Corporation, Elmec).

[Example 8]
In Example 1, a laminate was produced in the same manner as in Example 1 except that a laminate material without a hard coat layer was used.

[Example 9]
A laminate was produced in the same manner as in Example 1 except that a laminate material having a hard coat layer containing an acrylic resin produced as follows was used. In the table below, “acrylic” was indicated.

<Synthesis of curable acrylic polymer>
In accordance with the description in Japanese Patent No. 2574201, a reactor equipped with a reflux cooler, a stirrer, a thermometer, a temperature control device, and a water separator is used as a multi-branched polymer (HB-1) as a BOLTORN manufactured by Belstruer Baer. 55.0 g of H20 (OH value: 510 mg KOH / g), 39.6 g (0.55 mol) of acrylic acid, 63.4 g of toluene as a reaction solvent, 0.143 g of hydroquinone as a polymerization inhibitor, 0 methanesulfonic acid as an acid catalyst .953 g was charged, and the reaction was performed while removing the produced water azeotropically with the solvent at a reaction temperature of 100 to 115 ° C., and the reaction was terminated when the produced water reached 1.35 ml. The reaction mixture was dissolved in 40 g of toluene, neutralized with 25% aqueous sodium hydroxide solution, and then washed 3 times with 20 g of 15% brine. The solvent was distilled off under reduced pressure to obtain a curable multi-branched polymer (RHB-1). The OH value of the curable multi-branched polymer (RHB-1) was 434 mgKOH / g, and the conversion rate from the reactive hydroxyl group to the curable reactive group was 15 mol%.

<Adjustment of coating solution>
40 parts by mass of the polymer (RHB-1) DPHA (dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.)
10 parts by mass Irgacure 907 (manufactured by BASF) 2.5 parts by mass Methyl ethyl ketone 20 parts by mass Methyl isobutyl ketone 30 parts by mass

In accordance with the above composition, each well-mixed solution was filtered and adjusted with a polypropylene filter having a pore size of 30 μm.
<Coating of hard coat layer>
It is applied by a bar coating method so as to have a film thickness of 1 μm, dried at 30 ° C. for 15 seconds and 90 ° C. for 20 seconds, and further irradiated with 160 W / cm ² of UV under a nitrogen purge to cure the coating film, A hard coat layer was formed on the polymer layer.

[Example 10]
A laminate was produced in the same manner as in Example 1 except that a laminate material without an easy-adhesion layer was used.

[Example 11]
Using a hard coat layer having a refractive index of 1.64 containing zirconium formed by the following method as a hard coat layer, and forming an easy adhesion layer having a refractive index of 1.65 prepared from a coating solution having the composition shown in the following table The difference between the refractive index difference with the hard coat layer is 0.02 or less, and the difference between the refractive index difference with the polymer layer is 0.02 or less and a laminated material having an easy-adhesion layer is used. A laminate was produced in the same manner.

<Formation of hard coat layer containing zirconium>
A hard coat layer coating solution having the following composition was applied by a bar coating method to a WET thickness of about 2 μm. After drying at 90 ° C. for 1 minute, the resin was cured by irradiating ultraviolet rays at a dose of 1600 mJ / cm ² using a high-pressure mercury lamp. This produced the hard-coat layer on the surface of the easily bonding layer described below. The hard coat layer had a thickness of 1 μm and a refractive index of 1.64.
UV curable resin (manufactured by JSR Corporation, Z7410B) 100 parts by mass Inorganic fine particles (zirconium oxide manufactured by Nissan Chemical Industries, Ltd. OZ-S30K 20 parts by mass

[Example 12]
A laminate was produced in the same manner as in Example 1 except that the PET film of Example 1 was changed to a cycloolefin polymer film (Zeon Corporation, Zeon film ZD14) having a thickness of 60 μm and a retardation of 140 nm. In addition, the transparent laminate is placed on a liquid crystal display device (a liquid crystal cell is sandwiched between two polarizing plates) with an absorption axis of the polarizing plate and a slow axis of the polymer film of 45 degrees. Visibility was good when the image was viewed through a polarizing plate such as sunglasses.

[Comparative Example 1]
Without forming a polymer layer, a protective layer having the same composition as that used in Example 1 was formed by coating, and an easy-adhesion layer was coated using a bar coater so as to have a film thickness described in the table. It was formed by partial drying, and the hard coat layer was applied by a bar coating method to a thickness of 1 μm and dried at 150 ° C. for 2 minutes to form a laminate.

[Evaluation]
<Spattering prevention performance>
The transparent laminates of Examples and Comparative Examples obtained by laminating on a glass substrate were subjected to impact resistance measurement according to JIS K 7211 drop impact test method and calculated as impact energy (E50). (However, the diameter of the tip of the heavy bell used is 4 mm.)
A: (Good): Impact energy (E50) ≧ 1.00 (J)
B: (usable): 1.00> impact energy (E50) ≧ 0.45 (J)
C: (Unusable): Impact energy (E50) <0.45 (J)

<Haze>
The amount of change of the haze before and after the heat treatment at 150 ° C. for 10 minutes was measured on the laminated material before being transferred to the glass substrate, and the measurement result was evaluated. Haze was measured according to JIS-K-7105 using a haze meter (NDH-2000, Nippon Denshoku Industries Co., Ltd.).
Regarding the amount of change in haze before and after heat treatment (unit:%), the haze before and after the heat treatment under a predetermined condition (that is, no heat treatment) was measured, and the haze before the heat treatment was determined as H1. When the haze after heat treatment is H2,
| H2-H1 | / H1 × 100.
The heat treatment in the haze measurement was performed by placing the sample in an oven whose internal temperature was set to 150 ° C. and holding it for 10 minutes. In addition, the haze measurement after heat processing was implemented after cooling the sample taken out from oven.
A: (Good): 0.5% or less B: (Preferably usable): Less than 0.5 to 1% C: (Useable): 1% or more

<Transparency (transmittance)>
The transmittance of 440 nm was evaluated for the laminated material before being transferred to the glass substrate. Measurement was performed using a spectrophotometer (UV2100, manufactured by Shimadzu Corporation).
A: (Good): 95% or more B: (Preferably usable): 90 to less than 95% C: (Useable): Less than 90%

<Pencil hardness>
As an index of scratch resistance, pencil hardness evaluation described in JIS K 5400 was performed. The transparent laminates of Examples and Comparative Examples obtained by transfer film formation on a glass substrate were conditioned for 1 hour at a temperature of 25 ° C. and a relative humidity of 60%, and then a 2H test pencil specified in JIS S 6006. Using,
Evaluation of n = 7 was performed with a load of 500 g.
A: There are less than 3 scratches.
B: There are 3 or more and less than 5 scratches.
C: There are 5 or more and less than 6 scratches.
D: There are 6 or more scratches.

<Transparent electrode pattern visibility>
The transparent laminated body of each Example and Comparative Example was bonded to the transparent laminated body and the black PET material via a transparent adhesive tape (trade name, OCA tape 8171CL, manufactured by 3M), and the entire substrate was shielded from light.
The visibility of the transparent electrode pattern was performed by making light incident on the fluorescent lamp (light source) and the prepared substrate from the glass surface side and visually observing reflected light from the glass surface obliquely in a dark room.
A: The transparent electrode pattern is not visible at all.
B: The transparent electrode pattern is slightly visible but hardly visible.
C: A transparent electrode pattern is visible (unclear).
D: Although a transparent electrode pattern can be seen, it is practically acceptable.
E: The transparent electrode pattern is clearly visible (easy to understand).

<Visibility with polarized sunglasses>
The transparent laminated body of each Example and Comparative Example is placed on a liquid crystal display device using a white LED light source (a liquid crystal cell has a configuration sandwiched between two polarizing plates) and passed through a polarizing plate such as sunglasses. I visually confirmed the image.
A: Visibility of display screen is good B: Interference color is recognized C: The whole surface becomes dark depending on the direction of polarized sunglasses

<Adhesion>
Using a single-blade razor on the surface of the transparent laminates of each Example and Comparative Example, 11 vertical and horizontal scratches were made to form 100 squares. Next, a cellophane tape (No. 405 manufactured by Nichiban Co., Ltd., 24 mm width) is applied on this, and then completely adhered by rubbing with poppy rubber from above, and then peeled off in the direction of 90 ° to peel off the peeled-off mesh By determining the number, the following ranking was performed to evaluate the adhesion. The width of the scratch was 1 mm both vertically and horizontally.
A: When there is no peeling B: When the number of peeled squares is less than 5 C: When the number of peeled squares is 5 or more and less than 10 D: When the number of peeled squares is 10 or more and less than 30 E: Number of peeled squares When is 30 or more

<Interference unevenness>
Irradiate the surface of the laminate opposite to the glass substrate with the diffused light of the three-wavelength fluorescent lamp through the milky white acrylic plate from the transparent laminated body of each Example and Comparative Example on a desk with a black doskin cloth laminated The generated reflected light was visually observed. And by visually observing the rainbow-colored interference unevenness observed at this time, ranking was performed according to the following evaluation criteria, and the interference unevenness of the laminate was evaluated. In addition, when visually observing, each laminate was subjected to a blackening treatment as a compulsory condition, and a 500 nm light transmittance adjusted to 1% or less was separately evaluated. As the blackening treatment, magic ink (artline oil marker supplementary ink KR-20 black, manufactured by shachihata Co., Ltd.) is applied to the surface (glass substrate surface) opposite to the surface to be observed, and then dried. It was.
A: Iridescent interference unevenness is not visually observed in both the sample after the blackening treatment and the untreated sample.
C: Iridescent interference unevenness is visually observed in both the blackened sample and the untreated sample.

From Table 5, it turned out that the laminated body for touchscreens of this invention can prevent glass scattering.
Moreover, in the preferable embodiment of the laminated body for touchscreens of this invention, it turns out that the property which is excellent also in haze, transparency, pencil hardness, and visibility was given.

DESCRIPTION OF SYMBOLS 1 Front plate 1a Non-contact side 2a of front plate Decorating layer 2b Mask layer 3 1st transparent electrode pattern

3a Pad part

3b Connection part 4 2nd transparent electrode pattern 5 Insulating layer 6 Conductive element 7 Transparent protective layer 8 Opening Part 10 Capacitive input device 11 Tempered glass C First direction D Second direction 100 Glass substrate 101 Transparent conductive layer 102 Protective layer 103 Polymer layer 104 Easy adhesion layer 105 Hard coat layer 106 Easy adhesion layer 107 Decoration layer

Claims

A glass substrate;
A transparent electrode layer;
A protective layer covering the transparent electrode layer;
A polymer layer;
In this order,
A laminate for a touch panel, wherein the glass substrate is subjected to a chemical strengthening treatment in which a part or all of ions having an ion radius smaller than that of potassium ions in the glass are replaced with potassium ions.
Furthermore, the laminated body for touchscreens of Claim 1 which has a hard-coat layer in the surface on the opposite side to the surface in which the said protective layer is formed of the said polymer layer.
The touch panel laminate according to claim 2, further comprising an easy-adhesion layer between at least one of the protective layer and the polymer layer, and between the polymer layer and the hard coat layer.
The touch panel laminate according to claim 1, further comprising an antireflection layer between the transparent electrode layer and the protective layer.
The laminate for a touch panel according to claim 2, wherein the hard coat layer contains a hydrolysis condensate of a curable resin or an alkoxysilane.
The laminate for a touch panel according to claim 1, wherein the protective layer contains an acrylic polymer.
The laminate for a touch panel according to any one of claims 1 to 6, wherein the thickness is 0.3 to 1 mm.
The laminate for a touch panel according to claim 4, wherein the antireflection layer has a thickness of 500 nm or less.
The laminate for a touch panel according to claim 4, wherein a refractive index of the antireflection layer is 1.6 or more.
The refractive index difference between the refractive index of the easy adhesion layer between the protective layer and the polymer layer and the refractive index of the protective layer and the polymer layer adjacent to the easy adhesion layer is 0.02 or less. The laminated body for touchscreens of Claim 3 which exists.
The laminate for a touch panel according to claim 1, wherein the polymer layer has a thickness of 20 to 150 µm.
The refractive index difference between the refractive index of the easy adhesion layer between the polymer layer and the hard coat layer and the refractive index of the polymer layer and the hard coat layer adjacent to the easy adhesion layer is 0.02. The laminated body for touchscreens of Claim 3 which is the following.
The laminate for a touch panel according to claim 1, wherein the polymer layer contains polyethylene terephthalate, polycarbonate, or cycloolefin polymer.
The laminate for a touch panel according to claim 1, wherein the retardation of the polymer layer is 3000 to 12000 nm.
The laminate for a touch panel according to claim 1, wherein the retardation of the polymer layer is 100 to 200 nm.
The laminate for a touch panel according to claim 1, wherein the polymer layer has a refractive index of 1.60 to 1.75.
2. The touch panel laminate according to claim 1, further comprising a surface modification layer having a thickness ranging from the surface of the polymer layer to any depth within a range of 40 to 330 nm.
The touch panel laminate according to claim 17, wherein the surface modification layer is formed by performing glow discharge treatment on a surface of the polymer layer.
The touch panel laminate according to claim 17, wherein the surface-modified layer is formed by performing glow discharge treatment on the surface of the polymer layer heated to Tg or more.
The laminate for a touch panel according to claim 5, wherein the hydrolysis condensate of the alkoxysilane contained in the hard coat layer is a hydrolysis condensate of an epoxy group-containing alkoxysilane and an epoxy group-free alkoxysilane.
The laminate for a touch panel according to claim 5, wherein the hard coat layer is formed by hydrolyzing alkoxysilane and condensing the hydrolyzed alkoxysilane.
The laminated body for touchscreens of Claim 4 whose refractive index of the said hard-coat layer is 1.64 or more and 2.10 or less.
The laminate for a touch panel according to claim 4, wherein the antireflection layer contains particles.
The touch panel laminate according to claim 4, wherein the antireflection layer comprises particles having a refractive index of 1.60 to 3.00.
The laminate for a touch panel according to claim 4, wherein the antireflection layer contains metal oxide particles.
The laminate for a touch panel according to claim 4, wherein the antireflection layer contains particles of tin oxide or zirconium oxide.
The laminate for a touch panel according to claim 4, wherein the antireflection layer contains 40 to 80% by mass of particles with respect to the solid content contained in the antireflection layer.
The touch panel laminate according to claim 1, wherein the transparent electrode layer includes the following elements (3) to (5).
(3) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (4) electrically insulated from the first transparent electrode pattern, A plurality of second electrode patterns comprising a plurality of pad portions formed extending in a direction intersecting the first direction (5) electrically connecting the first transparent electrode pattern and the second electrode pattern Insulating layer
(6) It is electrically connected to at least one of the first transparent electrode pattern and the second electrode pattern, and has a conductive element different from the first transparent electrode pattern and the second electrode pattern. The laminated body for touchscreens of Claim 28.
29. The touch panel laminate according to claim 28, wherein the second electrode pattern is a transparent electrode pattern.
(1) The laminated body for touchscreens of Claim 1 which has a decoration layer.
The laminate for a touch panel according to claim 1, wherein the laminate has (1) a decorative layer having a thickness of 1 to 40 µm.
(2) The laminate for a touch panel according to claim 1, comprising a mask layer.
The laminate for a touch panel according to claim 1, wherein the surface of the glass substrate is subjected to a surface treatment.
The touch panel laminate according to claim 1, wherein the surface of the glass substrate is subjected to a surface treatment using a silane compound.
The laminate for a touch panel according to claim 1, wherein the glass substrate has an opening at least in part.
A laminated material having a protective layer and a polymer layer in this order on a front plate with a transparent electrode layer having a glass substrate and a transparent electrode layer so that the surface on the transparent electrode layer side and the surface on the protective layer side face each other Including the step of laminating
37. The glass substrate according to claim 1, wherein the glass substrate is subjected to a chemical strengthening treatment in which a part or all of ions having an ion radius smaller than that of potassium ions in the glass are replaced with potassium ions. The manufacturing method of the laminated body for touchscreens of description.
The manufacturing method of the laminated body for touchscreens of Claim 37 which forms the said transparent electrode layer by etching a transparent conductive material using the etching pattern formed with the curable resin composition.
The manufacturing method of the laminated body for touchscreens of Claim 37 which forms the said transparent electrode layer using a conductive curable resin composition.