TW202031476A - Substrate for forming transparent conductive layer, transparent conductive film, touch panel, and method for manufacturing substrate for forming transparent conductive layer - Google Patents

Abstract

Provided are a substrate for forming a transparent conductive layer which exhibits excellent adhesion to a transparent conductive layer to be stacked and has excellent scratch resistance, a method for manufacturing the same, and a transparent conductive film and a touch panel using the same. A substrate 10 for forming a transparent conductive layer includes a substrate film 12 and a first resin layer 14 which is formed on a surface of the substrate film 12, wherein the first resin layer 14 comprises a cured product of a curable composition that includes an ultraviolet-curable resin composition having a silsesquioxane skeleton. A transparent conductive film 80 has a transparent conductive layer 26 on a surface of the first resin layer 14 of the substrate 10 for forming a transparent conductive layer. In this touch panel, the transparent conductive layer 26 of the transparent conductive film 80 is used as an electrode.

Description

Substrate for forming transparent conductive layer, transparent conductive film, touch panel, and manufacturing method of substrate for forming transparent conductive layer

The present invention relates to a method for producing a substrate for forming a transparent conductive layer, a transparent conductive film, a touch panel, and a substrate for forming a transparent conductive layer.

As input devices such as smartphones and tablet terminators, which can operate devices by touching the display on the screen, electrostatic capacitive touch panels are known. In such a touch panel, a transparent conductive film can be used. The transparent conductive film is composed of, for example, a transparent conductive layer formed of a metal oxide such as indium tin oxide (ITO) on the surface of a plastic substrate (resin substrate) (Patent Document 1).

If the transparent conductive layer made of metal oxide is directly formed on the surface of the plastic substrate, the adhesion between the plastic substrate and the transparent conductive layer is low. Therefore, for example, in Patent Document 2, a transparent conductive layer made of a metal oxide is formed on the surface of the primer layer of a plastic substrate on which a primer layer has been laminated. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 07-068690 [Patent Document 2] JP 2012-007065 A

[Summary of the invention] [The problem to be solved by the invention]

The primer layer of Patent Document 2 is obtained by thermosetting a thiol group-containing silsesquioxane, a hydroxyl group-containing polyester resin, and a polyisocyanate-containing composition. The primer layer has low scratch resistance and is formed by During the treatment of the transparent conductive layer made of metal oxide, there is a risk of causing scratches on the surface of the primer layer. If scratches are caused on the surface of the primer layer, the appearance of the transparent conductive film will be defective.

The problem to be solved by the present invention is to provide a substrate for forming a transparent conductive layer having excellent adhesion of the laminated transparent conductive layer and excellent scratch resistance, a method of manufacturing the same, and a transparent conductive film and touch panel using the same . [Means used to solve the problem]

In order to solve the above-mentioned problems, the substrate for forming a transparent conductive layer of the present invention is a substrate for forming a transparent conductive layer as a substrate for forming a transparent conductive layer. It is intended to have a substrate film and a substrate formed on the substrate film. The first resin layer on the surface, the first resin layer is composed of a cured product of a curable composition containing an ultraviolet curable resin having a silsesquioxane skeleton.

The ultraviolet curable resin having a silsesquioxane skeleton is preferably a (meth)acrylate having a silsesquioxane skeleton. The content of the ultraviolet curable resin having a silsesquioxane skeleton is preferably 1% by mass or more based on the total solid content of the curable composition. There is preferably a second resin layer between the base film and the first resin layer, and the second resin layer is composed of a cured product of a curable composition containing an ultraviolet curable resin without a silsesquioxane skeleton . The first resin layer may be provided on only one side of the base film, and the third resin layer may be provided on the other side of the base film. The foregoing third resin layer may be composed of no silsesquioxane The skeleton is composed of a cured product of a curable composition of ultraviolet curable resin. The first resin layer may be provided only on one surface of the base film, and the protective film may be provided on the other surface of the base film via an adhesive layer. You may have a 1st resin layer on both surfaces of a base film.

Furthermore, the essential point of the transparent conductive film of the present invention is to have a transparent conductive layer on the surface of the first resin of the base material for forming a transparent conductive layer of the present invention.

The transparent conductive layer can be used for the electrodes of the touch panel.

Furthermore, the purpose of the transparent conductive film of the present invention is that the transparent conductive layer of the transparent conductive film of the present invention can be used for electrodes.

Furthermore, the method for producing a substrate for forming a transparent conductive layer of the present invention is a method for producing a substrate for forming a transparent conductive layer as a substrate for forming a transparent conductive layer, and it is intended to form a substrate on the surface of the substrate film. A resin layer. The first resin layer is composed of a cured product of a curable composition containing an ultraviolet curable resin having a silsesquioxane skeleton.

In the method for producing a substrate for forming a transparent conductive layer of the present invention, after the second resin layer is formed on the surface of the substrate film, the first resin layer may be formed on the surface of the second resin layer. It is composed of a cured product of a curable composition containing an ultraviolet curable resin without a silsesquioxane skeleton. [Invention Effect]

According to the substrate for forming a transparent conductive layer of the present invention, the first resin layer formed on the surface of the substrate film is made of a cured product of a curable composition containing an ultraviolet curable resin having a silsesquioxane skeleton. Due to the structure, the laminated transparent conductive layer has excellent adhesion and at the same time, excellent scratch resistance.

Furthermore, if there is a second resin layer between the base film and the first resin layer, and the second resin layer is a cured product of a curable composition containing an ultraviolet curable resin without a silsesquioxane skeleton With the structure, the design of the optical adjustment function and blocking prevention function becomes easy.

Furthermore, if the first resin layer is provided on only one side of the base film, and the third resin layer is provided on the other side of the base film, and the aforementioned third resin layer is composed of non-silicone It is composed of a cured product of a curable composition of an ultraviolet curable resin with a semioxane skeleton, and the other surface side of the base film is also excellent in scratch resistance.

In addition, if the first resin layer is provided on only one side of the base film and the protective film is provided on the other side of the base film with an adhesive layer interposed, it is possible to suppress The other side of the material film caused scars.

[Form for implementing the invention]

Hereinafter, the present invention will be described in detail.

Fig. 1 is a cross-sectional view of a substrate for forming a transparent conductive layer according to a first embodiment of the present invention.

As shown in FIG. 1, the transparent conductive layer forming substrate 10 of the first embodiment of the present invention has a substrate film 12 and a first resin layer 14 formed on the surface of the substrate film 12. The first resin layer 14 is in contact with the base film 12. The first resin layer 14 is provided only on one surface of the base film 12.

The base film 12 is not particularly limited as long as it has transparency. As the base film 12, a transparent polymer film, a glass film, etc. are mentioned. The so-called transparency means that the total light transmittance in the visible light wavelength region is 50% or more, and the total light transmittance is more preferably 85% or more. The above-mentioned total light transmittance can be measured in accordance with JIS K7361-1 (1997). The thickness of the base film 12 is not particularly limited, but from the viewpoint of excellent handling properties, etc., it is preferably in the range of 2 to 500 μm. It is more preferably in the range of 2 to 200 μm. In addition, the so-called "film" generally refers to those with a thickness of less than 0.25mm, but as long as they can be rolled into a roll even if the thickness is 0.25mm or more, even those with a thickness of 0.25mm or more are included in the "film" "in.

Examples of the polymer material of the base film 12 include polyester resins such as polyethylene terephthalate resin and polyethylene naphthalate resin, polycarbonate resin, and poly(meth)acrylic acid. Polyolefin resins such as ester resins, polystyrene resins, polyamide resins, polyimide resins, polyacrylonitrile resins, polypropylene resins, polyethylene resins, polycycloolefin resins, and cycloolefin copolymer resins, polyphenylene sulfide Resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, etc. The polymer material of the base film 12 may be composed of only one type of these, or may be composed of a combination of two or more types. Among these, from the viewpoints of optical properties and durability, polyethylene terephthalate resin, polyimide resin, polycarbonate resin, poly(meth)acrylate resin, Polycyclic olefin resin, cyclic olefin copolymer resin.

The base film 12 may be composed of a single layer, and the aforementioned single layer is composed of one or two or more layers including the above-mentioned polymer materials, or may be composed of two or more layers, and the aforementioned two or more layers include the above One or more layers of polymer materials, and one or more layers of polymer materials other than this layer.

The first resin layer 14 is composed of a cured product of a curable composition containing an ultraviolet curable resin having a silsesquioxane skeleton. Since the first resin layer 14 contains a compound having a silsesquioxane skeleton, the laminated transparent conductive layer has excellent adhesion. In addition, since the compound having a silsesquioxane skeleton is an ultraviolet curable resin, the first resin layer 14 has excellent scratch resistance. The ultraviolet curable resin having a silsesquioxane skeleton has a structure represented by the following formula (1). (Chemical 1) (R-SiO _1.5 ) n (1)

In formula (1), n is an integer of 2 or more. As n, the integer of 2-200 is preferable, the integer of 2-150 is more preferable, and the integer of 2-100 is still more preferable. In the formula (1), R is an organic group, and at least a part of the plurality of Rs is a reactive group reactive with ultraviolet rays. Examples of reactive groups reactive with ultraviolet rays include radical polymerization-type reactive groups having ethylenic unsaturated bonds such as acrylic, methacrylic, allyl, and vinyl groups, or oxetanyl groups. ) And other cationic polymerization reactive groups. Among these, acryloyl group, methacryloyl group, and oxetane group are preferable, and acryloyl group and methacryloyl group are excellent in weather resistance and optical transparency. That is, particularly preferred is a (meth)acrylate having a silsesquioxane skeleton. In addition, in this specification, "(meth)acrylate" means "at least one of acrylate and methacrylate". "(Meth)acryloyl group" means "at least one of an acryloyl group and a methacryloyl group". "(Meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid".

The functional group equivalent of the ultraviolet curable resin having a silsesquioxane skeleton is preferably in the range of 80 to 10,000 g/eq. It is more preferably in the range of 100 to 1000 g/eq, and still more preferably in the range of 150 to 300 g/eq. If the functional group equivalent is within this range, the ultraviolet curability is excellent. In the present invention, the functional group equivalent means the mass (g) per equivalent of the functional group. In addition, the aforementioned functional group means a reactive group reactive with ultraviolet rays.

The ultraviolet curable resin having a silsesquioxane skeleton preferably contains a hydroxyl group or an alkoxy group in the silsesquioxane skeleton before or after curing. By including a hydroxyl group or an alkoxy group, the adhesion of the laminated transparent conductive layer is improved. Among silsesquioxanes, there are cage-like structures, ladder-like structures, random structures, and incomplete cage-like structures. Although the complete cage structure and the ladder structure do not contain a hydroxyl group or an alkoxy group, the random structure and an incomplete cage structure contain a hydroxyl group or an alkoxy group. Therefore, it is preferable that part or all of the silsesquioxane skeleton has a random structure or an incomplete cage structure.

Examples of ultraviolet curable resins having a silsesquioxane skeleton include AC-SQ TA-100, MAC-SQ TM-100, AC-SQ SI-20, MAC-SQ SI-20, MAC- SQ HDM, OX-SQ TX-100, OX-SQ SI-20, OX-SQ HDX, etc.

In the curable composition forming the first resin layer 14, in addition to the ultraviolet curable resin having a silsesquioxane skeleton, it may further include an ultraviolet curable resin having no silsesquioxane skeleton, or may not include A UV curable resin with a silsesquioxane skeleton. In addition, a non-ultraviolet curable resin may be included, or may not include a non-ultraviolet curable resin. In addition, the curable composition forming the first resin layer 14 may contain a photopolymerization initiator. Furthermore, if necessary, additives etc. added to the curable composition may be included. Examples of such additives include dispersants, leveling agents, defoamers, thixotropic agents, antifouling agents, antibacterial agents, flame retardants, slipping agents, inorganic particles, and resin particles. Moreover, a solvent may be included as needed.

In the curable composition forming the first resin layer 14, the content of the ultraviolet curable resin having a silsesquioxane skeleton is preferably 0.5% by mass or more based on the total solid content of the curable composition. It is more preferably 2% by mass or more, and still more preferably 4% by mass or more. The solid content of the curable composition is a component from which the solvent is removed. If the content is 1% by mass or more, the adhesion of the laminated transparent conductive layer is more excellent. In addition, the content of the ultraviolet curable resin having a silsesquioxane skeleton may be 100% by mass based on the total solid content of the curable composition. Preferably it is 98 mass% or less. By setting the content in the aforementioned range, it is possible to obtain a transparent conductive layer having excellent adhesion and scratch resistance.

Examples of the ultraviolet curable resin having no silsesquioxane skeleton include monomers, oligomers, prepolymers, and the like having no silsesquioxane skeleton and having an ultraviolet-reactive reactive group. Examples of reactive groups reactive with ultraviolet rays include radical polymerization reactive groups having ethylenic unsaturated bonds such as acrylic, methacrylic, allyl, and vinyl, or cations such as oxycyclobutanyl. Polymeric reactive groups, etc. Among these, acryloyl, methacryloyl, and oxetane are more preferred, and acryloyl and methacryloyl are particularly preferred. That is, particularly preferred is a (meth)acrylate that does not have a silsesquioxane skeleton.

Examples of (meth)acrylates that do not have a silsesquioxane skeleton include urethane (meth)acrylates, polysiloxane (meth)acrylates, and alkylene esters that do not have silsesquioxane skeletons. Group (meth)acrylate, aryl (meth)acrylate, etc. Among these, urethane (meth)acrylate is particularly preferred from the viewpoint of excellent flexibility.

Examples of non-ultraviolet curable resins include thermoplastic resins and thermosetting resins. As a thermoplastic resin, polyester resin, polyether resin, polyolefin resin, polyamide resin, etc. are mentioned. Examples of thermosetting resins include unsaturated polyester resins, epoxy resins, alkyd resins, and phenol resins.

Examples of the photopolymerization initiator include photopolymerization initiators such as alkyl ketones, acylphosphine oxides, and oxime esters. Examples of the alkyl ketone-based photopolymerization initiator include 2,2'-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2 -Hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane- 1-ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanyl)-benzyl]phenyl}-2-methyl-propane-1-ketone, 2 －Methyl-1-[4-(methylthio)phenyl]-2-N-𠰌olinylpropane-1-one, 2-benzylmethyl-2-(dimethylamino)-1 －(4-N-𠰌linylphenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-N- 𠰌linylphenyl)-1-butanone, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-N-(4-N-𠰌linylphenyl)-1-butanone) Ketones, N,N-dimethylaminoacetophenone, etc. As the phosphine oxide-based photopolymerization initiator, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl ) -Phenylphosphine oxide, bis(2,6-dimethoxybenzyl)-2,4,4-trimethyl-pentylphosphine oxide, etc. Examples of the oxime ester-based photopolymerization initiator include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzyloxime), ethyl ketone -1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), etc. One kind of these photopolymerization initiators may be used alone, or two or more kinds may be used in combination.

The content of the photopolymerization initiator is preferably in the range of 0.1 to 10% by mass based on the total solid content of the curable composition. More preferably, it is the range of 1 to 5 mass %.

The inorganic particles are added for the purpose of forming surface irregularities on the first resin layer 14 or adjusting the first resin layer 14 to have a high refractive index, for example. In addition, the resin particles are added for the purpose of forming surface irregularities in the first resin layer 14, for example. By forming the surface irregularities on the first resin layer 14, when the transparent conductive layer forming base material is rolled into a roll shape, it is easy to suppress the blocking of the adhesion between the surface and the back surface. By adjusting the first resin layer 14 to have a high refractive index, it is difficult to visually recognize the conductive pattern of the laminated transparent conductive layer. The high refractive index means that the refractive index at a measurement wavelength of 589.3 nm is 1.50 or more, preferably in the range of 1.55 to 1.80, and more preferably in the range of 1.60 to 1.70.

As inorganic particles capable of optically adjusting the first resin layer 14 to a high refractive index, there can be mentioned oxides of metals such as titanium, zirconium, tin, zinc, silicon, niobium, aluminum, chromium, magnesium, germanium, gallium, antimony, and platinum. Metal oxide particles composed of objects. These may be used alone as the inorganic particles capable of optical adjustment, or may be used in combination of two or more kinds. Among these, titanium oxide and zirconium oxide are particularly preferred from the viewpoint of excellent high refractive index and transparency.

The types of inorganic particles and resin particles that form surface irregularities in the first resin layer 14 are not particularly limited. Examples of such inorganic particles include metal oxide particles composed of metal oxides such as titanium, zirconium, silicon, aluminum, and calcium. In addition, examples of such resin particles include (meth)acrylic resins, styrene resins, styrene-(meth)acrylic resins, urethane resins, polyamide resins, silicone resins, and epoxy resins. Resin particles composed of resin, phenol resin, polyethylene resin, cellulose, etc.

In order to form surface irregularities on the first resin layer 14, the average particle diameter of the inorganic particles and resin particles is preferably equal to or greater than the thickness of the first resin layer 14. More preferably, it is 1.1 times or more and 20 times or less the thickness of the first resin layer 14, still more preferably 1.5 times or more and 10 times the thickness of the first resin layer 14, particularly preferably 1.5 times the thickness of the first resin layer 14. Times more than 5 times. The average particle size is a volume-based average arithmetic value obtained by the laser diffraction/scattering method in accordance with JIS Z8825.

The thickness of the first resin layer 14 is not particularly limited, but from the viewpoint of excellent film continuity, etc., it is preferably 0.005 μm or more. It is more preferably 0.010 μm or more, and still more preferably 0.020 μm or more. On the other hand, the thickness of the first resin layer 14 is preferably 10 μm or less from the viewpoint of easily suppressing curling caused by the difference in thermal shrinkage from the base film 12. It is more preferably 5 μm or less, and still more preferably 1 μm or less. The thickness of the first resin layer 14 is the thickness of the smoother portion in the portion where the inorganic particles and resin particles are not present in the thickness direction.

From the viewpoint of easily suppressing the blocking of adhesion between the surface and the back surface of the substrate for forming a transparent conductive layer, the arithmetic average roughness Ra of the surface on which the surface irregularities of the first resin layer 14 are formed is preferably in the range of 0.1 to 130 nm. It is more preferably in the range of 0.5 to 50 nm, and still more preferably in the range of 2 to 20 nm.

Moreover, from the viewpoints of suppressing clogging, suppressing haze (haze) rise, and being more excellent in transparency, the distribution of inorganic particles and resin particles in the range of the above average particle diameter and the above average arithmetic roughness The density is preferably in the range of 100 to 2000 pieces/mm ² . More preferably, it is in the range of 100 to 1000 pieces/mm ² .

Examples of solvents that can be used in the curable composition include alcoholic solvents such as ethylene glycol monomethyl ether (EGM), propylene glycol monomethyl ether (PGM), and diethylene glycol monobutyl ether, and methyl ethyl ketone ( MEK), methyl isobutyl ketone (MIBK), ketone solvents such as cyclohexanone and acetone, aromatic solvents such as toluene and xylene, N-methylpyrrolidone, acetamide, dimethylformamide Amine-based solvents such as amines. These can be used alone as a solvent or in combination of two or more.

The solid content concentration (concentration of components other than the solvent) of the curable composition may be appropriately determined in consideration of coatability, film thickness, and the like. For example, what is necessary is just to be 1 to 90 mass %, 1.5 to 80 mass %, 2 to 70 mass %, etc.

The substrate 10 for forming a transparent conductive layer can be manufactured by applying a curable composition for forming the first resin layer 14 on the surface of the substrate film 12, drying if necessary, and curing it by ultraviolet irradiation. At this time, in order to improve the adhesion between the base film 12 and the first resin layer 14, the surface of the base film 12 may be subjected to surface treatment before coating. Examples of surface treatments include corona treatment, plasma treatment, hot air treatment, ozone treatment, ultraviolet treatment, and the like.

For coating, for example, reverse gravure coating method, direct gravure coating method, die coating method, bar coating method, wire-bar coating method, roll coating method can be used , Spin coating method, dip coating method, spray coating method, knife coating method, kiss coat method and other coating methods, or inkjet method, offset printing, screen printing, flexographic printing and other printing methods get on.

The drying step is not particularly limited as long as the solvent or the like used for the coating liquid can be removed, but it is preferably performed at a temperature of 50 to 150°C for about 10 seconds to 180 seconds. In particular, the drying temperature is preferably 50 to 120°C.

For ultraviolet irradiation, high-pressure mercury lamps, electrodeless (microwave) lamps, xenon lamps, metal halide lamps, and other arbitrary ultraviolet irradiation devices can be used. Ultraviolet radiation can also be carried out in an inert gas environment such as nitrogen as needed. The amount of ultraviolet irradiation is not particularly limited, but is preferably 50 to 800 mJ/cm ² , and more preferably 100 to 300 mJ/cm ² .

According to the substrate 10 for forming a transparent conductive layer with the above structure, the first resin layer 14 formed on the surface of the substrate film 12 is made of a curable composition containing an ultraviolet curable resin having a silsesquioxane skeleton It is composed of a cured product, so the laminated transparent conductive layer has excellent adhesion and excellent scratch resistance.

The substrate for forming a transparent conductive layer of the present invention is not limited to the configuration of the substrate 10 for forming a transparent conductive layer of the first embodiment. Hereinafter, other embodiments of the substrate for forming a transparent conductive layer of the present invention will be described.

Fig. 2 shows a substrate 20 for forming a transparent conductive layer according to a second embodiment. The transparent conductive layer forming substrate 20 of the second embodiment has a substrate film 12, a second resin layer 16 formed on the surface of the substrate film 12, and a first resin formed on the surface of the second resin layer 16. Layer 14. The second resin layer 16 is in contact with the base film 12, and the first resin layer 14 is in contact with the second resin layer 16. The first resin layer 14 is provided only on one surface of the base film 12. The base material 20 for forming a transparent conductive layer has a base film 12, a second resin layer 16, and a first resin layer 14 in this order from the base film 12 side.

The transparent conductive layer forming substrate 20 of the second embodiment differs from the transparent conductive layer forming substrate 10 of the first embodiment in that there is a second resin between the substrate film 12 and the first resin layer 14 The layer 16 is the same as the base material 10 for forming a transparent conductive layer of the first embodiment except for the layer 16, and the description of the same configuration is omitted.

The second resin layer 16 is disposed between the base film 12 and the first resin layer 14 and is composed of a cured product of a curable composition containing an ultraviolet curable resin having no silsesquioxane skeleton. The curable composition for forming the second resin layer 16 does not contain an ultraviolet curable resin having a silsesquioxane skeleton.

Examples of the ultraviolet curable resin having no silsesquioxane skeleton include monomers, oligomers, prepolymers, and the like having no silsesquioxane skeleton and having an ultraviolet-reactive reactive group. Examples of reactive groups reactive with ultraviolet rays include radical polymerization reactive groups having ethylenic unsaturated bonds such as acrylic, methacrylic, allyl, and vinyl, or cations such as oxycyclobutanyl. Polymeric reactive groups, etc. Among these, acryloyl, methacryloyl, and oxetane are more preferred, and acryloyl and methacryloyl are particularly preferred. That is, particularly preferred is a (meth)acrylate that does not have a silsesquioxane skeleton.

Examples of (meth)acrylates that do not have a silsesquioxane skeleton include urethane (meth)acrylates, polysiloxane (meth)acrylates, and alkylene esters that do not have silsesquioxane skeletons. Group (meth)acrylate, aryl (meth)acrylate, etc. Among these, urethane (meth)acrylate is particularly preferred from the viewpoint of excellent flexibility. In the case where the curable composition for forming the second resin layer 16 contains urethane (meth)acrylate as the ultraviolet curable resin, for example, even if the base film 12 is made of polycycloolefin or cycloolefin copolymer If it is formed and is relatively easy to break, it is easy to suppress the break of the base film 12.

The second resin layer 16 is preferably a hard coat layer. From this viewpoint, the pencil hardness is preferably in the range of 2B to 6H. Pencil hardness can be measured in compliance with JIS K5600-5-4. The second resin layer 16 is formed of a composition containing an ultraviolet curable resin, so that the pencil hardness described above can be easily satisfied.

In the curable composition forming the second resin layer 16, in addition to the ultraviolet curable resin that does not have a silsesquioxane skeleton, a non-ultraviolet curable resin may be further included, or a non-ultraviolet curable resin may not be included. In addition, the curable composition for forming the second resin layer 16 may contain a photopolymerization initiator. Furthermore, if necessary, additives etc. added to the curable composition may be included. Examples of such additives include dispersants, leveling agents, defoamers, thixotropic agents, antifouling agents, antibacterial agents, flame retardants, slip aids, inorganic particles, and resin particles. Moreover, a solvent may be included as needed. The non-ultraviolet curable resin, photopolymerization initiator, and solvent can be appropriately selected from those described in the curable composition forming the first resin layer 14.

The inorganic particles are added for the purpose of forming surface irregularities on the first resin layer 14 or adjusting the second resin layer 16 to a high refractive index, for example. In addition, the resin particles are added for the purpose of forming surface irregularities in the first resin layer 14, for example. By forming the surface irregularities on the first resin layer 14, when the transparent conductive layer forming base material is rolled into a roll shape, it is easy to suppress the blocking of the adhesion between the surface and the back surface. By adjusting the second resin layer 16 to a high refractive index and simultaneously adjusting the first resin layer 14 to a low refractive index, it is difficult to visually recognize the conductive pattern of the laminated transparent conductive layer. The high refractive index means that the refractive index at a measurement wavelength of 589.3 nm is 1.50 or more, preferably in the range of 1.55 to 1.80, and more preferably in the range of 1.60 to 1.70. The low refractive index means that the refractive index at a measurement wavelength of 589.3 nm is less than 1.50, preferably in the range of 1.30 to 1.50, and more preferably in the range of 1.40 to 1.50.

As inorganic particles capable of optically adjusting the second resin layer 16 to a high refractive index, there can be mentioned oxides of metals such as titanium, zirconium, tin, zinc, silicon, niobium, aluminum, chromium, magnesium, germanium, gallium, antimony, and platinum. Metal oxide particles composed of objects. These may be used alone as the inorganic particles capable of optical adjustment, or may be used in combination of two or more kinds. Among these, titanium oxide and zirconium oxide are particularly preferred from the viewpoint of excellent high refractive index and transparency.

On the other hand, as inorganic particles capable of optically adjusting the first resin layer 14 to a low refractive index, particles such as magnesium fluoride, silica, silsesquioxane, and calcium fluoride can be cited. From the viewpoint of being easy to have a low refractive index, these particles are more preferably a hollow structure.

The type of particles added to the curable composition forming the second resin layer 16, that is, the inorganic particles and resin particles that form surface irregularities on the first resin layer 14, can be appropriately selected from the curable composition used in forming the first resin layer 14. Those recorded in the material. In addition, the solid content concentration of the curable composition can be adjusted in the same manner as the curable composition forming the first resin layer 14.

In order to form surface irregularities on the first resin layer 14, the average particle size of the inorganic particles and resin particles is preferably greater than the total thickness of the first resin layer 14 and the second resin layer 16. More preferably, it is 1.1 times or more and 20 times or less of the total thickness of the first resin layer 14 and the second resin layer 16, and still more preferably 1.5 times or more and 10 times the total thickness of the first resin layer 14 and the second resin layer 16 Hereinafter, it is particularly preferable to be 1.5 times or more and 5 times or less the total thickness of the first resin layer 14 and the second resin layer 16.

The thickness of the second resin layer 16 is not particularly limited, but from the viewpoint of excellent film continuity, etc., it is preferably 0.005 μm or more. It is more preferably 0.010 μm or more, and still more preferably 0.10 μm or more. On the other hand, the thickness of the second resin layer 16 is preferably 10 μm or less from the viewpoint of easily suppressing curling due to the difference in thermal shrinkage from the base film 12. It is more preferably 5 μm or less, and still more preferably 1 μm or less. In addition, from the viewpoint of easily suppressing curling caused by the difference in thermal shrinkage from the base film 12, the total thickness of the first resin layer 14 and the second resin layer 16 is preferably 10 μm or less. The thickness of the second resin layer 16 is the thickness of the smoother part in the part where there are no inorganic particles and resin particles in the thickness direction.

From the viewpoint of clogging, etc., the arithmetic average roughness Ra of the surface on which the surface irregularities of the first resin layer 14 are formed is preferably in the range of 0.1 to 130 nm. It is more preferably in the range of 0.5 to 50 nm, and still more preferably in the range of 2 to 20 nm.

In addition, from the viewpoints of maintaining obstructive properties, suppressing haze (haze) rise, and being more excellent in transparency, within the range of the above average particle diameter and the above average arithmetic roughness, the inorganic particles and resin particles The distribution density is preferably in the range of 100 to 2000 pieces/mm ² . More preferably, it is in the range of 100 to 1000 pieces/mm ² .

The substrate 20 for forming a transparent conductive layer can be formed by coating a curable composition for forming the second resin layer 16 on the surface of the substrate film 12, drying it as needed, and curing it by ultraviolet radiation to form the substrate film. After the second resin layer 16 is formed on the surface of the second resin layer 16, the curable composition for forming the first resin layer 14 is coated on the surface of the second resin layer 16, dried as necessary, and then cured by ultraviolet radiation. The first resin layer 14 is formed on the surface of the second resin layer 16 to be manufactured. At this time, in order to improve the adhesion between the base film 12 and the second resin layer 16, the surface of the base film 12 may be surface-treated before coating. Examples of surface treatments include corona treatment, plasma treatment, hot air treatment, ozone treatment, ultraviolet treatment, and the like.

According to the substrate 20 for forming a transparent conductive layer having the above configuration, the first resin layer 14 formed on the surface of the substrate film 12 is made of a curable composition containing an ultraviolet curable resin having a silsesquioxane skeleton. It is composed of a cured product, so the laminated transparent conductive layer has excellent adhesion and excellent scratch resistance. In addition, because there is a second resin layer 16 between the base film 12 and the first resin layer 14, and the second resin layer 16 is composed of a curable combination containing an ultraviolet curable resin that does not have a silsesquioxane skeleton It is composed of hardened material, so the design of optical adjustment function and blocking prevention function becomes easy.

Fig. 3 shows a base material 30 for forming a transparent conductive layer of the third embodiment. The transparent conductive layer forming substrate 30 of the third embodiment has a substrate film 12, a second resin layer 16 formed on one surface of the substrate film 12, and a first resin layer 16 formed on the surface of the second resin layer 16. A resin layer 14 and a third resin layer 18 formed on the other side of the base film 12. The second resin layer 16 is in contact with one surface of the base film 12, and the first resin layer 14 is in contact with the second resin layer 16. In addition, the third resin layer 18 is in contact with the other surface of the base film 12. The first resin layer 14 is provided only on one surface of the base film 12. The base material for forming a transparent conductive layer has a third resin layer 18, a base film 12, a second resin layer 16, and a first resin layer 14 in this order from the third resin layer 18 side.

The transparent conductive layer forming substrate 30 of the third embodiment differs from the transparent conductive layer forming substrate 20 of the second embodiment in that it has a third resin layer on the other side of the substrate film 12 18. Other than that, it is the same as the transparent conductive layer forming substrate 20 of the second embodiment, and the description of the same structure is omitted.

The third resin layer 18 is composed of a cured product of a curable composition containing an ultraviolet curable resin having no silsesquioxane skeleton. The curable composition forming the third resin layer 18 may be the same composition as the curable composition forming the second resin layer 16.

The third resin layer 18 is preferably a hard coat layer. From this viewpoint, the pencil hardness is preferably in the range of 2B to 6H. Pencil hardness can be measured in compliance with JIS K5600-5-4. The third resin layer 18 is formed of a composition containing an ultraviolet curable resin, so that the pencil hardness described above can be easily satisfied.

The thickness of the third resin layer 18 is not particularly limited, and may be the same thickness as the thickness of the second resin layer 16. Moreover, by setting the thickness of the third resin layer 18 to be close to the thickness of the second resin layer 16 or close to the total thickness of the second resin layer 16 and the first resin layer 14 (for example, within ±10%), it is easy to suppress Curl with shrinkage during hardening.

The substrate 30 for forming a transparent conductive layer can be formed by coating a curable composition for forming the second resin layer 16 on one surface of the substrate film 12, drying as necessary, and curing it by ultraviolet radiation to form the substrate. After the second resin layer 16 is formed on one surface of the material film 12, the curable composition for forming the first resin layer 14 is coated on the surface of the second resin layer 16, and dried if necessary, and then irradiated with ultraviolet rays. After curing, the first resin layer 14 is formed on the surface of the second resin layer 16, and the curable composition for forming the third resin layer 18 is coated on the other surface of the base film 12, and dried if necessary. , The third resin layer 18 is formed on the other surface of the base film 12 to be manufactured by curing by ultraviolet irradiation. At this time, in order to improve the adhesion between the base film 12 and the second resin layer 16 or the adhesion between the base film 12 and the third resin layer 18, the surface of the base film 12 may also be applied before coating. deal with. Examples of surface treatments include corona treatment, plasma treatment, hot air treatment, ozone treatment, ultraviolet treatment, and the like.

According to the substrate 30 for forming a transparent conductive layer with the above configuration, the first resin layer 14 formed on one side of the substrate film 12 is made of curable resin containing ultraviolet curable resin having a silsesquioxane skeleton. The composition is composed of a cured product, so the laminated transparent conductive layer has excellent adhesion and at the same time excellent scratch resistance. In addition, because there is a second resin layer 16 between the base film 12 and the first resin layer 14, and the second resin layer 16 is made of a curable composition containing an ultraviolet curable resin without a silsesquioxane skeleton The design of optical adjustment function and blocking prevention function becomes easy. In addition, since the third resin layer 18 is formed on the other side of the base film 12, and the third resin layer 18 is made of a curable composition containing an ultraviolet curable resin having no silsesquioxane skeleton The surface side of the other side of the base film 12 is also excellent in scratch resistance.

In FIG. 4, a base material 40 for forming a transparent conductive layer of the fourth embodiment is disclosed. The substrate 40 for forming a transparent conductive layer of the fourth embodiment includes a substrate film 12, a second resin layer 16 formed on one surface of the substrate film 12, and a first resin layer 16 formed on the surface of the second resin layer 16. A resin layer 14 and a protective film 24 arranged on the other side of the base film 12 via an adhesive layer 22. The second resin layer 16 is in contact with one surface of the base film 12, and the first resin layer 14 is in contact with the second resin layer 16. In addition, the protective film 24 is in contact with the other side surface of the base film 12 via the adhesive layer 22. The first resin layer 14 is provided only on one surface of the base film 12. The base material 40 for forming a transparent conductive layer has a protective film 24, an adhesive layer 22, a base film 12, a second resin layer 16, and a first resin layer 14 in this order from the protective film 24 side.

The substrate 40 for forming a transparent conductive layer of the fourth embodiment differs from the substrate 20 for forming a transparent conductive layer of the second embodiment in that an adhesive layer is interposed on the other side of the substrate film 12 22 and having a protective film 24, except that it is the same as the transparent conductive layer forming substrate 20 of the second embodiment, and the description of the same configuration is omitted.

The protective film 24 is capable of suppressing scratches on the other side of the base film 12 when performing continuous processing or the like by a roll process or the like. The protective film 24 is attached to the other surface of the base film 12 via the adhesive layer 22. After processing or the like, the protective film 24 is peeled off from the other side surface of the base film 12 together with the adhesive layer 22. Therefore, regarding the adhesive layer 22, the adhesive force between the protective film 24 and the adhesive layer 22 is stronger than the adhesive force between the base film 12 and the adhesive layer 22, and the base film 12 and the adhesive The layers 22 are adjusted to have an adhesive force capable of interfacial peeling.

The material constituting the protective film 24 can be appropriately selected from those exemplified as the material constituting the base film 12. The material for forming the protective film 24 is not particularly limited, but from the viewpoint of excellent suppression of curling due to heat treatment, etc., a material whose heat shrinkage rate and linear expansion coefficient are similar to those of the base film 12 is preferable. For example, it is preferably the same or the same kind of material as the base film 12. The same type can mean, for example, polyesters, poly(meth)acrylates, and polyamides.

The thickness of the protective film 24 is not particularly limited, but for example, it may be the same thickness as the base film 12 so that the heat shrinkage rate and linear expansion coefficient are close to the base film 12. Specifically, it can be set in the range of 2-500 micrometers, and the range of 2-200 micrometers, for example.

The adhesive that forms the adhesive layer 22 is not particularly limited, and acrylic adhesives, silicone adhesives, urethane adhesives, and the like can be preferably used. In particular, acrylic adhesives are preferred because they are excellent in transparency and heat resistance. The acrylic adhesive is preferably formed of an adhesive composition containing a (meth)acrylic polymer and a crosslinking agent.

The (meth)acrylic polymer is a single polymer or copolymer of (meth)acrylic monomers. Examples of the (meth)acrylic monomer include an alkyl group-containing (meth)acrylic monomer, a carboxyl group-containing (meth)acrylic monomer, and a hydroxyl group-containing (meth)acrylic monomer.

As an alkyl group-containing (meth)acrylic monomer, the (meth)acrylic monomer which has a C2-C30 alkyl group is mentioned. The alkyl group having 2 to 30 carbon atoms may be linear, branched, or cyclic. As an alkyl group-containing (meth)acrylic monomer, more specifically, for example, isostearyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, (meth)acrylate Base) lauryl acrylate, decyl (meth)acrylate, isononyl (meth)acrylate, nonyl (meth)acrylate, isooctyl (meth)acrylate, octyl (meth)acrylate, ( Isobutyl meth)acrylate, n-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethyl (meth)acrylate Base hexyl ester, propyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, etc.

Examples of the (meth)acrylic monomer containing a carboxyl group include (meth)acrylic acid, carboxyethyl (meth)acrylate, and carboxypentyl (meth)acrylate. The carboxyl group can be located at the end of the alkyl chain or in the middle of the alkyl chain.

Examples of (meth)acrylic monomers containing hydroxyl groups include hydroxylauryl (meth)acrylate, hydroxydecyl (meth)acrylate, hydroxyoctyl (meth)acrylate, hydroxyhexyl (meth)acrylate, Hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, etc. The hydroxyl group can be located at the end of the alkyl chain or in the middle of the alkyl chain.

The (meth)acrylic monomer that forms the (meth)acrylic polymer may be any one of the above, or a combination of two or more.

Examples of the crosslinking agent include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, metal chelate-based crosslinking agents, metal alkoxide-based crosslinking agents, carbodiimide-based crosslinking agents, and azoline-based crosslinking agents. Cross-linking agent, acridine-based cross-linking agent, melamine-based cross-linking agent, etc. One of these crosslinking agents may be used alone, or two or more of them may be used in combination.

In addition to the (meth)acrylic polymer and the crosslinking agent, the adhesive composition may also contain other additives. Examples of other additives include crosslinking accelerators, crosslinking retarders, adhesiveness imparting resins (tackifiers), antistatic agents, silane coupling agents, plasticizers, peeling aids, pigments, dyes, wetting agents, Tackifiers, UV absorbers, preservatives, antioxidants, metal deactivators, alkylating agents, flame retardants, etc. These are appropriately selected and used according to the purpose and purpose of the adhesive.

The thickness of the adhesive layer 22 is not particularly limited, but it is preferably in the range of 1 to 10 μm. More preferably, it is in the range of 2-7 micrometers.

Fig. 5 shows a substrate 50 for forming a transparent conductive layer according to a fifth embodiment. In the transparent conductive layer forming substrate 50 of the fifth embodiment, the second resin layer 16 is formed on both sides of the substrate film 12, and the first resin layer is formed on the surfaces of the second resin layer 16 of both sides. 14. The second resin layer 16 is in contact with the base film 12, and the first resin layer 14 is in contact with the second resin layer 16. The base material 50 for forming a transparent conductive layer has a first resin layer 14, a second resin layer 16, a base film 12, a second resin layer 16, and a first resin layer 14 in this order from the first resin layer 14 side.

The transparent conductive layer forming substrate 50 of the fifth embodiment differs from the transparent conductive layer forming substrate 20 of the second embodiment in that the second resin layer 16 and the first resin layer 14 are formed on the substrate film Except for both sides of 12, it is the same as the base material 20 for transparent conductive layer formation of 2nd Embodiment, and the description is abbreviate|omitted.

Since the base material 50 for forming a transparent conductive layer has the first resin layer 14 on both sides of the base film 12, it is suitable as a base material for forming a transparent conductive film whose constitution is in the base film 12 There are transparent conductive layers on both sides.

Fig. 6 shows a substrate 60 for forming a transparent conductive layer of the sixth embodiment. The transparent conductive layer forming substrate 60 of the sixth embodiment is formed by using two transparent conductive layer forming substrates 10 as shown in FIG. 1 with an adhesive layer 28 interposed on the substrate film 12 sides. constitute. The base 60 for forming a transparent conductive layer has a first resin layer 14, a base film 12, an adhesive layer 28, a base film 12, and a first resin layer 14 in this order.

Since the base material 60 for forming a transparent conductive layer has the first resin layer 14 on both sides, it is suitable as a base material for forming a transparent conductive film like the base material 50 for forming a transparent conductive layer. The structure of the transparent conductive film is There are transparent conductive layers on both sides. The transparent conductive layer forming substrate 60 uses two transparent conductive layer forming substrates 10 as shown in FIG. 1. Since the two substrate films 12 are provided, it is difficult to break in the transparent conductive layer forming step, and has excellent handling properties.

The adhesive layer 28 is for attaching two base films 12 to each other with good adhesion. The difference from the adhesive layer 22 of the transparent conductive layer forming substrate 40 shown in FIG. 4 is that it is difficult to peel off. The adhesive (adhesive composition) forming the adhesive layer 28 can be preferably used for the adhesive (adhesive composition) in the transparent conductive layer forming substrate 70 of the seventh embodiment described later.

The thickness of the adhesive layer 28 is not particularly limited, but it is preferably in the range of 5 to 100 μm. More preferably, it is in the range of 10-50 micrometers.

The adhesive layer 28 can be formed by the following method: a method of directly coating the adhesive composition on the other side of the base film 12; and forming the adhesive composition on the surface of the release film , The method of transferring to the other side of the base film 12; after coating the adhesive composition on the surface of the first release film and forming it, attach the second release film to peel off any one of the release The method of transferring the film to the other surface of the base film 12, etc.

Fig. 7 shows a substrate 70 for forming a transparent conductive layer of the seventh embodiment. The substrate 70 for forming a transparent conductive layer of the seventh embodiment has a substrate film 12, a first resin layer 14 formed on one side of the substrate film 12, and a surface formed on the other side of the substrate film 12 The upper adhesive layer 32 and the release film 34 formed on the surface of the adhesive layer 32. The first resin layer 14 is in contact with one surface of the base film 12, and the adhesive layer 32 is in contact with the other surface of the base film 12. The first resin layer 14 is provided only on one surface of the base film 12. The base material 70 for forming a transparent conductive layer has a release film 34, an adhesive layer 32, a base film 12, and a first resin layer 14 in this order from the release film 34 side.

The substrate 70 for forming a transparent conductive layer of the seventh embodiment differs from the substrate 10 for forming a transparent conductive layer of the first embodiment in that it has an adhesive layer 32 on the other side of the substrate film 12 Except for the release film 34, it is the same as the transparent conductive layer forming substrate 10 of the first embodiment, and the description of the same configuration is omitted.

The adhesive layer 32 is used for attaching the base material 70 for forming a transparent conductive layer to a substrate such as a polymer film or glass with good adhesion.

The adhesive composition forming the adhesive layer 32 may contain known adhesive resins such as acrylic adhesives, silicone adhesives, and urethane adhesives. Among them, from the viewpoint of optical transparency and heat resistance, an acrylic adhesive is preferred. In order to increase the cohesive force of the adhesive layer 32, the adhesive composition preferably contains a crosslinking agent. Examples of the crosslinking agent include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, acridine-based crosslinking agents, chelate-based crosslinking agents, and the like.

The adhesive composition may contain additives as needed. Examples of additives include well-known additives such as plasticizers, silane coupling agents, surfactants, antioxidants, fillers, hardening accelerators, and hardening retarders. In addition, from the viewpoint of productivity and the like, an organic solvent may be used for dilution.

The thickness of the adhesive layer 32 is not particularly limited, but it is preferably in the range of 5 to 100 μm. More preferably, it is in the range of 10-50 micrometers.

The adhesive layer 32 can be formed by the following method: a method of directly applying an adhesive composition on the other side of the base film 12; and a method of applying an adhesive composition on the surface of the release film 34 to form Then, the method of transferring to the other side of the base film 12; after coating the adhesive composition on the surface of the first release film to form, attach the second release film, and peel off any one of the release films. The method of transferring to the other surface of the base film 12 and the like.

From the viewpoint of good adhesion, the adhesive force of the adhesive layer 32 to glass is preferably 4 N/25 mm or more. It is more preferably 6N/25mm or more, and still more preferably 10N/25mm or more.

The release film 34 functions as a protective layer of the adhesive layer 32 before use, and is peeled from the adhesive layer 32 during use. The release film 34 is not particularly limited, and the same material as that used for the base film 12 can be used.

The surface of the release film 34 that is in contact with the adhesive layer 32 may be subjected to a release treatment. Examples of the release agent used in the release treatment include silicone-based, fluorine-based, alkyd-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents.

Next, the transparent conductive film of the present invention will be described.

Fig. 8 shows a transparent conductive film 80 according to an embodiment of the present invention. As shown in FIG. 8, the transparent conductive film 80 according to one embodiment of the present invention has a transparent conductive layer 26 on the surface of the first resin layer 14 of the base 10 for forming a transparent conductive layer. The substrate 10 for forming a transparent conductive layer is the substrate for forming a transparent conductive layer of the present invention. The transparent conductive film 80 has the base film 12, the first resin layer 14, and the transparent conductive layer 26 in this order from the base film 12 side.

The transparent conductive layer 26 contains a conductive substance. The conductive substance is not particularly limited, but ZnO (zinc oxide), barium oxide, indium tin oxide, indium zinc oxide, zirconium oxide, ytterbium oxide, yttrium oxide, tantalum oxide, aluminum oxide, cerium oxide, titanium oxide, etc. can be mentioned Metal oxide. Among these, in view of achieving a high degree of compatibility between transparency and conductivity, indium tin oxide and indium zinc oxide are particularly preferred.

The thickness of the transparent conductive layer 26 is not particularly limited, but it is preferably in the range of 10-40 nm. More preferably, it is in the range of 15-30 nm.

Examples of the transparent conductive layer 26 include sputtering, vacuum evaporation, CVD, and ion plating. Among these, the sputtering method is preferred from the viewpoint of stably producing a low-resistance and uniform film.

In order to promote the crystallization of the conductive material, the transparent conductive layer 26 preferably has a step of sintering the conductive material after film formation. The sintering method is not particularly limited, but can be performed using, for example, roller heating during sputtering, or using a hot-air heating furnace, a far-infrared heating furnace, or the like. The heating temperature during sintering may be appropriately selected according to the type of conductive material. For example, it can be set to 50 to 200°C, 80 to 180°C, 100 to 160°C, or the like. The heating time during sintering is not particularly limited, but can be 3 to 180 minutes, 5 to 120 minutes, 10 to 90 minutes, or the like.

According to the transparent conductive film 80 configured as above, since the transparent conductive layer 26 is provided on the surface of the first resin layer 14 of the transparent conductive layer forming substrate 10 of the present invention, the first resin layer 14 and the transparent conductive layer 26 are Excellent adhesion. In addition, since the first resin layer 14 has excellent scratch resistance, it is possible to suppress scratches on the surface of the first resin layer 14 during processing.

The transparent conductive film 80 of the present invention can use the transparent conductive layer 26 as an electrode of a touch panel. The electrodes of the touch panel are formed by forming the transparent conductive layer 26 into a desired electrode pattern. The electrode pattern can be formed by etching treatment of the transparent conductive layer 26 or the like.

Next, the touch panel of the present invention will be described.

The touch panel of the present invention is composed of the transparent conductive film 80 of the present invention, and the transparent conductive layer 26 of the transparent conductive film 80 can be used as an electrode of the touch panel. The touch panel is a touch panel of electrostatic capacitance type or resistive film type. As the touch panel of the present invention, GFF method and GF2 method can be cited. The touch panel of the GFF system is composed of, for example, the following: a transparent conductive film as shown in FIG. 6 in which two transparent conductive layer forming substrates 10 are interposed on the basis of the adhesive layer 28 The transparent conductive layer 26 is formed on the surface of each first resin layer 12 of the transparent conductive layer forming substrate 60 which is laminated on the side of the material film 12; or as shown in FIG. The base film 12 has a transparent conductive film 80 composed of a first resin layer 14 and a transparent conductive layer 26 on the side of the base film 12, and the base film 12 side is bonded with a transparent adhesive, and a transparent adhesive is further used. Adhesive for bonding one side of the transparent conductive layer 26 to a transparent substrate such as glass or resin film. In addition, the touch panel of the GF2 method is composed of, for example, the following: as shown in FIG. 5, it will be a transparent structure having a first resin layer 14 and a transparent conductive layer 26 on both sides of the base film 12 The transparent conductive film formed by the substrate 50 for forming a conductive layer is bonded to a transparent substrate such as glass or a resin film with a transparent adhesive.

The image display method of the touch panel of the present invention is not particularly limited, and can be used for any display device such as a liquid crystal display device and an organic EL display device.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above-mentioned embodiments at all, and various changes can be made without departing from the gist of the present invention.

For example, in the above embodiment, in order to improve the adhesion between the base film 12 and the first resin layer 14, the second resin layer 16, or the third resin layer 18, it is stated that the surface of the base film 12 may be surface-treated However, it may be a configuration in which an easy-adhesive layer is provided on the surface of the base film 12 instead of surface treatment.

In addition, in the above embodiment, the surface irregularities of the first resin layer 14 are set to add particles having an average particle diameter larger than the thickness of the layer to which the particles are added, but the method of forming irregularities is not limited to this. For example, it may be a layer forming surface irregularities such as the first resin layer 14 by mold transfer. In addition, when particles are added to form surface irregularities, the surface free energy of the particles can be reduced by applying surface treatment to the particles or combined with a surfactant, and the particles can be unevenly distributed on the surface of the layer where the particles are added. A method of forming irregularities on the surface caused by particles. In this case, the average particle diameter of the particles may be smaller than the thickness of the layer to which the particles are added. For example, when such particles are added to the first resin layer 14, the average particle diameter of the particles is preferably in the range of 50 to 500 nm. It is more preferably in the range of 80 to 400 nm, and still more preferably in the range of 120 to 400 nm. In addition, the average particle diameter is preferably 1/2 or less of the thickness of the layer to which the particles are added.

Furthermore, the protective film 24 is shown in the form of being added to the transparent conductive layer forming substrate 20 of the second embodiment shown in FIG. 2 as shown in FIG. 4, but may be added to the first embodiment shown in FIG. The form of the substrate 10 for forming a transparent conductive layer of one embodiment. In addition, it may be a form added to a transparent conductive film such as the transparent conductive film 80 shown in FIG. 8.

Furthermore, the above-mentioned adhesive layer 32 is shown in the form of being added to the transparent conductive layer forming substrate 10 of the first embodiment shown in FIG. 1, as shown in FIG. 7, but may be added to the form shown in FIGS. 2 to 3 The form of the base material 20-30 for forming a transparent conductive layer is shown. In addition, it may be a form added to a transparent conductive film such as the transparent conductive film 80 shown in FIG. 8.

In addition, the sixth transparent conductive layer forming substrate 60 shown in FIG. 6 is in a form in which two transparent conductive layer forming substrates 10 are bonded to each other on the substrate film 12 side via an adhesive layer 28 However, one or both of the two substrates 10 for forming a transparent conductive layer may be the substrates 20 to 30 for forming a transparent conductive layer shown in FIGS. 2 to 3. In addition, it may be a transparent conductive film such as the transparent conductive film 80 shown in FIG. 8.

Furthermore, the transparent conductive film 80, as shown in FIG. 8, discloses an example in which the transparent conductive layer forming substrate 10 of the first embodiment shown in FIG. 1 is used as a transparent conductive layer forming substrate, but it may be The base materials 20 to 70 for forming a transparent conductive layer shown in FIGS. 2 to 7 are used as the base materials for forming a transparent conductive layer.

Furthermore, various functional layers such as a gas barrier property improvement layer, an antistatic layer, and an oligomer block layer may be provided on the surface of the base film 12 before forming each layer. [Example]

Hereinafter, the present invention will be explained in detail using examples and comparative examples.

(Preparation of curable composition for forming the first resin layer) Each component was blended with the blending composition (mass%) described in Table 1 to prepare a curable composition for forming the first resin layer.

(Preparation of curable composition for forming the second resin layer) Each component was blended with the blending composition (mass%) described in Table 1 to prepare a curable composition for forming the second resin layer.

(Preparation of curable composition for forming third resin layer) Each component was blended with the blending composition (mass%) described in Table 1 to prepare a curable composition for forming the third resin layer.

(Preparation of base material for forming transparent conductive layer) (Examples 1 to 3) On one side of the base film (PET film "Lumirror UH1H" made by TORAY, thickness 50μm), a #5 wire rod was used. bar) Apply the curable composition for forming the second resin layer, dry it at 80°C for 1 minute, and then use a high-pressure mercury lamp to irradiate the coating film with ultraviolet rays at a light intensity of 200mJ/cm ² to cure the coating film with ultraviolet rays to form the second resin layer. Two resin layer. Next, on the surface of the second resin layer, use the #4 wire rod to coat the curable composition for forming the first resin layer, dry it at 80°C for 1 minute, and then use a high-pressure mercury lamp in a nitrogen atmosphere with light intensity The coating film was irradiated with ultraviolet rays at 200 mJ/cm ² to cure the coating film with ultraviolet rays, thereby forming the first resin layer. Furthermore, on the other side of the base film, the curable composition for forming the third resin layer was coated with a #4 wire rod, dried at 80°C for 1 minute, and then a high-pressure mercury lamp was used at a light intensity of 200mJ/cm ^{2 The} coating film is irradiated with ultraviolet rays to cure the coating film with ultraviolet rays, thereby forming a third resin layer. Through the above, the transparent conductive layer forming substrates of Examples 1 to 3 were produced.

(Example 4) Change the base film to Zeonon's COP film "Zeonor Film ZF16-55" (thickness 55μm). After corona treatment is applied to one side, the second resin layer is not formed, and #5 thread is used. Except for forming the first resin layer with the rod, the same procedure as in Example 1 was carried out to prepare a base material for forming a transparent conductive layer of Example 4. The third resin layer was not formed on the other surface of the base film.

(Examples 5-8) The base film was changed to Zeonon's COP film "Zeonor Film ZF16-55" (thickness 55μm), and corona treatment was applied to one side of the film to form a second resin layer. The first resin layer was formed on the surface using the #5 wire rod, and except that the first resin layer was formed in the same manner as in Example 1, the transparent conductive layer forming substrates of Examples 5 to 8 were produced. The third resin layer was not formed on the other surface of the base film.

(Comparative example 1) Except for the difference in the curable composition for forming the first resin layer, the same procedure as in Example 1 was carried out to prepare a substrate for forming a transparent conductive layer of Comparative Example 1. The curable composition for forming the first resin layer of Comparative Example 1 does not include an ultraviolet curable resin having a silsesquioxane skeleton.

(Comparative example 2) Except for the difference in the curable composition for forming the first resin layer, the same procedure as in Example 3 was carried out to prepare a substrate for forming a transparent conductive layer of Comparative Example 2. The curable composition for forming the first resin layer of Comparative Example 2 does not include an ultraviolet curable resin having a silsesquioxane skeleton.

(Comparative example 3) Except for the difference in the curable composition for forming the first resin layer, the same procedure as in Example 3 was carried out to prepare a substrate for forming a transparent conductive layer of Comparative Example 3. The curable composition for forming the first resin layer of Comparative Example 3 does not include an ultraviolet curable resin having a silsesquioxane skeleton, but includes a thermosetting epoxy resin having a silsesquioxane skeleton.

The material systems used as the materials of the first resin layer, the second resin layer, and the third resin layer are as follows. ‧UV resin containing SQ <1>: UV curable resin with a silsesquioxane skeleton ("MAC-SQ HDM" manufactured by Toagosei, methacrylic resin, solvent (PGB) solid content concentration 50% by mass, functional Group: methacrylic acid group, functional group equivalent 239g/eq) ‧UV resin containing SQ<2>: UV curable resin with a silsesquioxane skeleton ("MAC-SQ SI-20" manufactured by Toagosei, methacrylic resin, solid content 100% by mass, functional group: Methacrylic group, functional group equivalent 224g/eq) ‧UV resin <1>: UV curable resin without silsesquioxane skeleton ("Lioduras TYZ59-10-S" made by TOYOCHEM, (meth)acrylic resin containing zirconium particles, solvent (PGM, MIBK, fat) Group solvent and cyclohexanone), solid content concentration 40% by mass, high refractive index hard coating agent) ‧UV resin <2>: UV curable resin without silsesquioxane skeleton ("OPSTAR Z7527" manufactured by Arakawa Chemical Industry, (meth)acrylic resin containing silica particles, solvent (MEK), solid content concentration 50% by mass) ‧UV resin <3>: UV curable resin without silsesquioxane skeleton ("Lioduras TYZ65-01" made by TOYOCHEM, (meth)acrylic resin containing zirconium particles, solvent (PGM, MIBK, aliphatic series) Solvent and cyclohexanone), solid content concentration 40% by mass, high refractive index hard coat agent) ‧UV resin <4>: UV curable resin without silsesquioxane skeleton (AICAAITRON Z-735-35L manufactured by AICA Industries, (meth)acrylic resin, solvent (ethyl acetate, butyl acetate and MEK), solid content concentration 50% by mass) ‧UV resin <5>: UV curable resin without silsesquioxane skeleton ("GRANDIC PC16-2291" made by DIC, (meth)acrylic resin, solvent (MEK, BuAc and MIBK), solid content concentration 40 quality%) ‧Resin particles: Polymethyl methacrylate particles (1% by mass MEK dispersion of "Chemisnow MX-80H3wT" manufactured by Soken Chemical, with an average particle size of 800nm) ‧Photopolymerization initiator: "IRGACURE127" made by BASF JAPAN ‧EP resin containing SQ: thermosetting epoxy resin with a silsesquioxane skeleton ("COMPOCERAN SQ506" manufactured by Arakawa Chemical Industry) ‧EP hardener: 1-benzyl-2-methimidazole ‧Solvent <1>: Methyl ethyl ketone (MEK) ‧Solvent <2>: butyl acetate (BuAc) ‧Solvent <3>: Propylene glycol n-butyl ether (PGB) ‧Solvent <4>: Propylene glycol monomethyl ether (PGM) ‧Solvent <5>: Methyl isobutyl ketone (MIBK)

The thicknesses of the first resin layer, the second resin layer, and the third resin layer of the prepared transparent conductive layer forming substrate were measured by the spectral interference method using "Filmetrics F20 Film Thickness Measurement System" manufactured by FILMETRICS. In addition, the thickness of the layer containing resin particles is the thickness of a portion where no resin particles are present in the thickness direction.

Using the prepared substrates for forming transparent conductive layers, indium tin oxide was sputtered with a thickness of 20 nm on the surface of the first resin layer to form an ITO layer. On the surface of the ITO layer, an ITO layer was formed with a thickness of 200 nm. After the copper is sputtered to form a copper layer, it is allowed to stand at 150° C.×1 hour in a thermostat to crystallize the ITO layer. With the above, a transparent conductive film is produced.

(ITO adhesion) From the copper surface side of the produced transparent conductive film to the interface between the ITO layer and the first resin layer, a lattice-shaped notch was cut, and an adhesion test based on JIS K5400-8.5 (JIS D0202) was performed. Among 100 masses, all those who did not see peeling were regarded as good "○", and those who saw one or more peeling were regarded as bad "╳". Among the good ones, those who did not see peeling at the outer cutting edge of 100 pieces were set as particularly good "◎".

(Scratch resistance) Using the produced substrates for forming transparent conductive layers, set them in the Gakushin rubbing fastness tester manufactured by TESTER Sangyo Co., Ltd., using "Steel Wool#0000" manufactured by NIHON STEEL WOOL, and the first resin layer under a load of 200g Rub the surface 20 times. After that, under a fluorescent lamp, the surface of the first resin layer was visually observed from directly above, and those who saw no scratches were set as good "○", and those who saw scratches were set as bad "╳".

[Table 1] Example Comparative example 1 2 3 4 5 6 7 8 1 2 3 The first resin layer UV resin containing SQ<1> 1.55 1.40 1.09 2.73 0.07 0.32 0.63 1.16 - - - UV resin containing SQ<2> - 0.08 0.23 - - - - - - - - UV resin <1> - - - 30.30 8.30 7.66 7.06 5.80 - 8.34 - UV resin<2> - - - - - - - - 1.40 - - Resin particles - - - 0.30 0.27 0.27 0.28 0.28 - 0.27 - Photopolymerization initiator 0.02 0.02 0.02 - - - - - - - - EP resin containing SQ - - - - - - - - - - 3.84 EP hardener - - - - - - - - - - 0.10 Solvent <1> 98.43 98.50 98.66 - - - - - 39.45 - - Solvent <2> - - - - - - - - 59.15 - - Solvent <3> - - - 66.67 91.36 91.75 92.03 92.76 - 91.39 96.06 SQ-containing UV resin content in total solid content (mass%) 97 97 97 10 1 5 10 20 0 0 0 Thickness (nm) 20 20 20 451 88 88 92 92 20 90 109 Second resin layer UV resin<3> 50 50 50 - - - - - 50 - - UV resin＜4＞ - - - 69 69 69 69 - 69 69 Solvent <4> - - - 31 31 31 31 - 31 31 Solvent <5> 50 50 50 - - - - 50 - - Thickness (μm) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Base film Material type PET PET PET COP COP COP COP COP PET COP COP Thickness (μm) 50 50 50 55 55 55 55 55 50 55 55 The third resin layer UV resin<5> 62.50 62.50 62.50 - - - - - 62.50 - - Solvent <1> 18.75 18.75 18.75 18.75 Solvent <2> 18.75 18.75 18.75 18.75 Thickness (μm) 1.0 1.0 1.0 1.0 Evaluation ITO adhesion ◎ ◎ ◎ ◎ ○ ◎ ◎ ◎ ╳ ╳ ◎ Scratch resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ╳

It can be seen from the examples and comparative examples that the first resin layer is composed of a cured product of a curable composition containing an ultraviolet curable resin having a silsesquioxane skeleton, and the transparent conductive layer has excellent adhesion and at the same time The first resin layer has excellent scratch resistance. In Comparative Examples 1 and 2, since the curable composition for forming the first resin layer does not contain the ultraviolet curable resin having a silsesquioxane skeleton, the adhesion of the transparent conductive layer is poor. In Comparative Example 3, the curable composition used to form the first resin layer does not contain the ultraviolet curable resin having a silsesquioxane skeleton but only contains a thermosetting epoxy resin having a silsesquioxane skeleton. The film thickness is thick, but the scratch resistance of the first resin layer is still poor. Moreover, it can be seen from the comparison of the examples that the adhesion to ITO is particularly excellent when the content of the SQ-containing UV resin in the first resin layer is 5% by mass or more.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above-mentioned embodiments at all, and various changes can be made without departing from the scope of the present invention.

10, 20, 30, 40, 50, 60, 70: base material for transparent conductive layer formation 12: Base film 14: The first resin layer 16: second resin layer 18: The third resin layer 22: Adhesive layer 24: Protective film 26: Transparent conductive layer 28: Adhesive layer 32: Adhesive layer 34: Release film 80: Transparent conductive layered film

[Fig. 1] A cross-sectional view of a substrate for forming a transparent conductive layer according to a first embodiment of the present invention. [Fig. 2] A cross-sectional view of a substrate for forming a transparent conductive layer according to a second embodiment of the present invention. [Fig. 3] A cross-sectional view of a substrate for forming a transparent conductive layer according to a third embodiment of the present invention. [Fig. 4] A cross-sectional view of a substrate for forming a transparent conductive layer according to a fourth embodiment of the present invention. [Fig. 5] A cross-sectional view of a substrate for forming a transparent conductive layer according to a fifth embodiment of the present invention. [Fig. 6] A cross-sectional view of a substrate for forming a transparent conductive layer according to a sixth embodiment of the present invention. [Fig. 7] A cross-sectional view of a substrate for forming a transparent conductive layer according to a seventh embodiment of the present invention. [Fig. 8] A cross-sectional view of a transparent conductive film according to an embodiment of the present invention.

10: Base material for forming transparent conductive layer

12: Base film

14: The first resin layer

Claims (12)

A substrate for forming a transparent conductive layer, which serves as a substrate for forming a transparent conductive layer, is a substrate for forming a transparent conductive layer, and is characterized in that: Having a base film and a first resin layer formed on the surface of the aforementioned base film, The first resin layer is composed of a cured product of a curable composition containing an ultraviolet curable resin having a silsesquioxane skeleton. The substrate for forming a transparent conductive layer according to claim 1, wherein the ultraviolet curable resin having a silsesquioxane skeleton is a (meth)acrylate having a silsesquioxane skeleton. The substrate for forming a transparent conductive layer according to claim 1 or 2, wherein the content of the ultraviolet curable resin having a silsesquioxane skeleton is 1% by mass or more based on the total solid content of the curable composition. The substrate for forming a transparent conductive layer according to any one of claims 1 to 3, wherein a second resin layer is provided between the substrate film and the first resin layer, and the second resin layer includes It is composed of a curable composition of a sesquioxane skeleton ultraviolet curable resin. The substrate for forming a transparent conductive layer according to any one of claims 1 to 4, wherein the first resin layer is provided only on one side of the substrate film, and the substrate film is on the other side of the substrate film. There is a third resin layer on the surface, and the third resin layer is composed of a cured product of a curable composition containing an ultraviolet curable resin having no silsesquioxane skeleton. The substrate for forming a transparent conductive layer according to any one of claims 1 to 5, wherein the first resin layer is provided on only one side of the substrate film, and the substrate film is provided on the other side of the substrate film. The surface has a protective film through the adhesive layer. The substrate for forming a transparent conductive layer according to any one of claims 1 to 4, wherein the first resin layer is provided on both sides of the substrate film. A transparent conductive film characterized by having a transparent conductive layer on the surface of the first resin layer of the substrate for forming a transparent conductive layer according to any one of claims 1 to 7. The transparent conductive film of claim 8, wherein the aforementioned transparent conductive layer is used for electrodes of a touch panel. A touch panel, characterized in that the transparent conductive layer as in claim 8 is used for electrodes. A method for manufacturing a substrate for forming a transparent conductive layer, which is a method for manufacturing a substrate for forming a transparent conductive layer to be a substrate for forming a transparent conductive layer, characterized in that: A first resin layer is formed on the surface of the base film, and the first resin layer is composed of a cured product of a curable composition containing an ultraviolet curable resin having a silsesquioxane skeleton. The method of manufacturing a substrate for forming a transparent conductive layer according to claim 11, wherein after forming the second resin layer on the surface of the substrate film, the first resin layer is formed on the surface of the second resin layer, and the first resin layer is formed on the surface of the second resin layer. The second resin layer is composed of a cured product of a curable composition containing an ultraviolet curable resin having no silsesquioxane skeleton.

Images