TWI758668B - Substrate for forming transparent conductive layer, transparent conductive film, touch panel, and method for producing a substrate for forming transparent conductive layer - Google Patents

Abstract

An object of the present invention is to provide a substrate for forming a transparent conductive layer which is excellent in adhesion and scratch resistance of the laminated transparent conductive layer, a method for producing the same, a transparent conductive film and a touch panel using the same. The solution of the present invention is that the base material 10 for forming a transparent conductive layer has a base film 12 and a first resin layer 14 formed on the surface of the base film 12, and the first resin layer 14 is made of a material containing silsesquioxane. It consists of the cured product of the curable composition of the ultraviolet curable resin of the skeleton. The transparent conductive film 80 has the transparent conductive layer 26 on the surface of the first resin layer 14 of the base material 10 for forming a transparent conductive layer. In the 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.

A capacitive touch panel is known as an input device capable of operating a device by touching a display on a screen, such as a smartphone or a tablet terminator. 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. Then, 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 the plastic substrate on which the primer layer has been laminated. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 07-068690 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-007065

[Summary of Invention] [Problems to be solved by the invention]

The primer layer of Patent Document 2 is obtained by thermally curing a thiol group-containing silsesquioxane, a hydroxyl group-containing polyester resin, and a polyisocyanate-containing composition. When handling the transparent conductive layer made of metal oxide, there is a possibility that a scratch may be formed on the surface of the primer layer. When scratches are formed on the surface of the primer layer, the appearance defect of the transparent conductive film will occur.

The problem to be solved by the present invention is to provide a substrate for forming a transparent conductive layer, which is excellent in adhesion of the laminated transparent conductive layer and excellent in scratch resistance at the same time, a method for producing the same, a transparent conductive film and a touch panel using the same . [Means for solving problems]

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 that is a substrate for forming a transparent conductive layer, and the gist is that it has a substrate film and a substrate formed on the substrate film. The first resin layer on the surface is formed 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 mass % or more based on the total solid content of the curable composition. It is preferable to have 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 that does not have a silsesquioxane skeleton . It is possible to have a first resin layer only on one side of the base film, and a third resin layer on the other side of the base film. It consists of the cured product of the curable composition of the ultraviolet curable resin of the skeleton. 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 sides of a base film.

Furthermore, the gist 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 substrate 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 gist 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 an electrode.

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, which is a substrate for forming a transparent conductive layer, and the gist is to form a first substrate film on the surface of the substrate film. A resin layer, wherein 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 manufacturing method of the base material for forming a transparent conductive layer of the present invention, after forming the second resin layer on the surface of the base film, the first resin layer may be formed on the surface of the second resin layer, and the second resin layer may be It consists of a cured product of a curable composition containing an ultraviolet curable resin that does not have a silsesquioxane skeleton. [Inventive effect]

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

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 that does not have a silsesquioxane skeleton With this configuration, the optical adjustment function and the blocking prevention function can be easily designed.

In addition, if the first resin layer is provided only on one side of the base film, the third resin layer is provided on the other side of the base film, and the third resin layer is composed of If it consists of the hardened|cured material of the curable composition of the ultraviolet curable resin of a hemioxane skeleton, the other surface side of a base film is excellent also in abrasion resistance.

In addition, if the first resin layer is provided only on 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 therebetween, the base film can be prevented from forming on the base during processing. The other side of the film is scratched.

[Forms for Carrying Out 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 base material 10 for forming a transparent conductive layer according to the first embodiment of the present invention includes a base film 12 and a first resin layer 14 formed on the surface of the base 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 side 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. 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 said total transmittance can be measured according to JISK7361-1 (1997). The thickness of the base film 12 is not particularly limited, but is preferably within a range of 2 to 500 μm from the viewpoint of excellent handling properties. More preferably, it exists in the range of 2-200 micrometers. In addition, the term "film" generally refers to a film with a thickness of less than 0.25 mm, but as long as it can be rolled into a roll shape even if the thickness is 0.25 mm or more, even a film with a thickness of 0.25 mm or more is included in the "film" "middle.

Examples of the polymer material of the base film 12 include polyester resins such as polyethylene terephthalate resins and polyethylene naphthalate resins, polycarbonate resins, and poly(meth)acrylic acid. Polyolefin resins such as ester resin, polystyrene resin, polyamide resin, polyimide resin, polyacrylonitrile resin, polypropylene resin, polyethylene resin, polycycloolefin resin, cycloolefin copolymer resin, polyphenylene sulfide resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, etc. The polymer material of the base film 12 may be constituted by only one of these materials, or may be constituted by a combination of two or more. Among these, from the viewpoints of optical properties, durability, etc., 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 single layer may be composed of one or two or more layers containing the above-mentioned polymer materials, or may be composed of two or more layers, and the two or more layers may be composed of the above-mentioned layers. One or two or more layers of polymer materials, and one or two 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 adhesion of the laminated transparent conductive layer is excellent. Furthermore, since the compound having a silsesquioxane skeleton is an ultraviolet curable resin, the first resin layer 14 is excellent in 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, an integer of 2-200 is preferable, an integer of 2-150 is more preferable, and an integer of 2-100 is still more preferable. In formula (1), R is an organic group, and at least a part of the plural Rs is an ultraviolet reactive reactive group. Examples of the UV-reactive reactive group include radically polymerizable reactive groups having ethylenically unsaturated bonds, such as acryl, methacryloyl, allyl, and vinyl groups, or oxetanyl groups. ) and other cationic polymerizable reactive groups, etc. Among these, acryl group, methacryloyl group, and oxetanyl group are preferable, and acryl group and methacryloyl group are particularly preferable because they are excellent in weather resistance and optical transparency. That is, (meth)acrylate which has a silsesquioxane skeleton is especially preferable. In addition, in this specification, "(meth)acrylate" means "at least one of acrylate and methacrylate". The "(meth)acryloyl group" means "at least one of an acryl group and a methacryloyl group". "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid".

It is preferable that the functional group equivalent of the ultraviolet curable resin which has a silsesquioxane skeleton exists in the range of 80-10000 g/eq. It is more preferable to exist in the range of 100-1000 g/eq, and it is still more preferable to exist in the range of 150-300 g/eq. When 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 above-mentioned functional group refers to an ultraviolet reactive reactive group.

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 complete cage-like structures, ladder structures, random structures, and incomplete cage-like structures. Although a hydroxyl group or an alkoxy group is not contained in a complete cage structure and a ladder structure, a hydroxyl group or an alkoxy group is contained in a random structure and an incomplete cage structure. Therefore, part or all of the silsesquioxane skeleton is preferably 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, and MAC- SQ HDM, OX-SQ TX-100, OX-SQ SI-20, OX-SQ HDX, etc.

The curable composition for forming the first resin layer 14 may contain, in addition to the ultraviolet curable resin having a silsesquioxane skeleton, an ultraviolet curable resin that does not have a silsesquioxane skeleton, or may not include an ultraviolet curable resin that does not have a silsesquioxane skeleton. UV curable resin with silsesquioxane skeleton. Moreover, a non-ultraviolet curable resin may be contained, and a non-ultraviolet curable resin may not be contained. Moreover, a photopolymerization initiator may be contained in the curable composition which forms the 1st resin layer 14. Moreover, additives etc. added to a curable composition may be contained as needed. Examples of such additives include dispersing agents, leveling agents, antifoaming agents, thixotropic agents, antifouling agents, antimicrobial agents, flame retardants, slipping agents, inorganic particles, resin particles, and the like. Moreover, a solvent may be contained 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 mass % or more based on the total solid content of the curable composition. More preferably, it is 2 mass % or more, and still more preferably 4 mass % or more. The solid content of the curable composition is a component from which the solvent is removed. When the said content is 1 mass % or more, the adhesiveness of the transparent conductive layer laminated|stacked is more excellent. Moreover, content of the ultraviolet curable resin which has a silsesquioxane skeleton may be 100 mass % based on the total solid content of a curable composition. Preferably it is 98 mass % or less. By making content into the said range, the adhesiveness of a transparent conductive layer can be made into what is excellent in abrasion resistance at the same time.

Examples of the ultraviolet curable resin not having a silsesquioxane skeleton include monomers, oligomers, prepolymers, and the like that do not have a silsesquioxane skeleton, which have a reactive group that is reactive to ultraviolet rays. Examples of the UV-reactive reactive group include radical polymerizable reactive groups having ethylenically unsaturated bonds such as acryl, methacryloyl, allyl, and vinyl groups, and cations such as oxetanyl groups. Polymeric reactive groups, etc. Among these, an acryl group, a methacryl group, and an oxetanyl group are more preferred, and an acryl group and a methacryl group are particularly preferred. That is, (meth)acrylate which does not have a silsesquioxane skeleton is especially preferable.

Examples of (meth)acrylates not having a silsesquioxane skeleton include urethane (meth)acrylates that do not have a silsesquioxane skeleton, polysiloxane (meth)acrylates, alkane base (meth)acrylate, aryl (meth)acrylate, etc. Among these, urethane (meth)acrylate is particularly preferable from the viewpoint of being excellent in flexibility.

As non-ultraviolet curable resin, thermoplastic resin, thermosetting resin, etc. are mentioned. As thermoplastic resin, polyester resin, polyether resin, polyolefin resin, polyamide resin, etc. are mentioned. As a thermosetting resin, an unsaturated polyester resin, an epoxy resin, an alkyd resin, a phenol resin, etc. are mentioned.

Examples of the photopolymerization initiator include photopolymerization initiators such as alkyl ketone-based, acylphosphine oxide-based, and oxime ester-based initiators. Examples of the alkyl ketone-based photopolymerization initiator include 2,2'-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2 -Hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane- 1-ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2 -Methyl-1-[4-(methylthio)phenyl]-2-N-𠰌olinylpropan-1-one, 2-benzylmethyl-2-(dimethylamino)-1 -(4-N-𠰌olinylphenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-N- 𠰌olinylphenyl)-1-butanone, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-N-𠰌olinylphenyl)-1-butanone Ketones, N,N-dimethylaminoacetophenone, etc. Examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyldiphenylphosphine) )-phenylphosphine oxide, bis(2,6-dimethoxybenzyl)-2,4,4-trimethyl-pentylphosphine oxide, and the like. Examples of the oxime ester-based photopolymerization initiator include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzyl oxime), and ethyl ketone. -1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) and the like. The photopolymerization initiator may be used alone or in combination of two or more.

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 1-5 mass %.

The inorganic particles are added for the purpose of, for example, forming surface irregularities in the first resin layer 14 or adjusting the first resin layer 14 to have a high refractive index. In addition, the resin particles are added for the purpose of, for example, forming surface irregularities in the first resin layer 14 . By forming the surface unevenness in the first resin layer 14, when the base material for forming a transparent conductive layer is rolled into a roll shape, it becomes easy to suppress clogging of the front and back surfaces. By adjusting the first resin layer 14 to have a high refractive index, it becomes difficult to visually recognize the conductive pattern of the laminated transparent conductive layer. The high refractive index means that the refractive index at the 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.

Examples of inorganic particles capable of optically adjusting the first resin layer 14 to have a high refractive index include oxides of metals such as titanium, zirconium, tin, zinc, silicon, niobium, aluminum, chromium, magnesium, germanium, gallium, antimony, and platinum. composed of metal oxide particles. These may be used individually as an optically adjustable inorganic particle, and may be used in combination of 2 or more types. Among these, titanium oxide and zirconium oxide are particularly preferred from the viewpoint of being excellent in both 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 oxides of metals such as titanium, zirconium, silicon, aluminum, and calcium. Moreover, as such resin particles, for example, (meth)acrylic resin, styrene resin, styrene-(meth)acrylic resin, urethane resin, polyamide resin, silicone resin, epoxy resin can be mentioned. Resin particles composed of resins such as resins, phenol resins, polyethylene resins, and cellulose.

In order to form surface irregularities in the first resin layer 14 , the average particle diameter of the inorganic particles and the resin particles is preferably equal to or larger than the thickness of the first resin layer 14 . More preferably, it is 1.1 times or more and 20 times or less of the thickness of the first resin layer 14 , more preferably 1.5 times or more and 10 times or less of the thickness of the first resin layer 14 , and particularly preferably 1.5 times the thickness of the first resin layer 14 . more than 5 times and less than 5 times. The average particle diameter is an average arithmetic value on a volume basis 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 is preferably 0.005 μm or more from the viewpoint of excellent film continuity. More preferably, it is 0.010 μm or more, and even 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 due to the difference in thermal shrinkage with the base film 12 . More preferably, it is 5 μm or less, and even more preferably 1 μm or less. The thickness of the first resin layer 14 is the thickness of the smoother portion in the thickness direction of the portion where the inorganic particles and resin particles do not exist.

The arithmetic mean roughness Ra of the surface on which surface irregularities of the first resin layer 14 are formed is preferably within a range of 0.1 to 130 nm from the viewpoint of easily suppressing clogging of the front and back surfaces of the substrate for forming a transparent conductive layer. More preferably, it exists in the range of 0.5-50 nm, More preferably, it exists in the range of 2-20 nm.

Furthermore, from the viewpoints of suppressing clogging, suppressing an increase in haze, and being more excellent in transparency, the distribution of inorganic particles and resin particles within the range of the above-mentioned average particle diameter and the range of the above-mentioned average arithmetic roughness The density is preferably in the range of 100 to 2000 pieces/mm ² . More preferably, it exists in the range of 100-1000 pieces/mm< ² >.

Examples of solvents that can be used in the curable composition include alcohol-based solvents such as ethylene glycol monomethyl ether (EGM), propylene glycol monomethyl ether (PGM), and diethylene glycol monobutyl ether, methyl ethyl ketone ( MEK), methyl isobutyl ketone (MIBK), cyclohexanone, acetone and other ketone solvents, toluene, xylene and other aromatic solvents, N-methylpyrrolidone, acetamide, dimethylformamide amide-based solvents such as amines, etc. These may be used individually by 1 type as a solvent, and may be used in combination of 2 or more types.

The solid content concentration (the 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 set it as 1-90 mass %, 1.5-80 mass %, 2-70 mass %, etc..

The base material 10 for forming a transparent conductive layer can be produced by applying the curable composition for forming the first resin layer 14 on the surface of the base film 12, drying it as necessary, and then curing it by irradiation with ultraviolet rays. 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. As surface treatment, corona treatment, plasma treatment, hot air treatment, ozone treatment, ultraviolet treatment, etc. are mentioned.

In coating, for example, a reverse gravure coating method, a direct gravure coating method, a die coating method, a bar coating method, a wire-bar coating method, a roll coating method can be used , spin coating, dip coating, spray coating, blade coating, kiss coating and other coating methods, or inkjet, lithographic, screen printing, flexographic printing and other printing methods. conduct.

The drying step is not particularly limited as long as the solvent and the like used in 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 the ultraviolet irradiation, a high-pressure mercury lamp, an electrodeless (microwave type) lamp, a xenon lamp, a metal halide lamp, or any other ultraviolet irradiation device can be used. The ultraviolet irradiation can also be carried out in an inert gas environment such as nitrogen as required. The ultraviolet irradiation amount is not particularly limited, but is preferably 50 to 800 mJ/cm ² , more preferably 100 to 300 mJ/cm ² .

According to the substrate 10 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. Since it is composed of a cured product, the laminated transparent conductive layer is excellent in adhesion and scratch resistance at the same time.

The base material for forming a transparent conductive layer of the present invention is not limited to the structure of the base material 10 for forming a transparent conductive layer according to the first embodiment. Hereinafter, another embodiment of the substrate for forming a transparent conductive layer of the present invention will be described.

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

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

The 2nd resin layer 16 is arrange|positioned between the base film 12 and the 1st resin layer 14, and is comprised by the hardened|cured material of the curable composition containing the ultraviolet curable resin which does not have a 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 not having a silsesquioxane skeleton include monomers, oligomers, prepolymers, and the like that do not have a silsesquioxane skeleton, which have a reactive group that is reactive to ultraviolet rays. Examples of the UV-reactive reactive group include radical polymerizable reactive groups having ethylenically unsaturated bonds such as acryl, methacryloyl, allyl, and vinyl groups, and cations such as oxetanyl groups. Polymeric reactive groups, etc. Among these, an acryl group, a methacryl group, and an oxetanyl group are more preferred, and an acryl group and a methacryl group are particularly preferred. That is, (meth)acrylate which does not have a silsesquioxane skeleton is especially preferable.

Examples of (meth)acrylates not having a silsesquioxane skeleton include urethane (meth)acrylates that do not have a silsesquioxane skeleton, polysiloxane (meth)acrylates, alkane base (meth)acrylate, aryl (meth)acrylate, etc. Among these, urethane (meth)acrylate is particularly preferable from the viewpoint of being excellent in 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 It is also easy to suppress the cracking of the base film 12 because it is formed by, etc., and is relatively easy to crack.

The second resin layer 16 is preferably a hard coat layer. From this viewpoint, the pencil hardness is preferably within the range of 2B to 6H. The pencil hardness can be measured according to JIS K5600-5-4. Since the second resin layer 16 is formed of a composition containing an ultraviolet curable resin, it is easy to satisfy the aforementioned pencil hardness.

The curable composition for forming the second resin layer 16 may contain a non-ultraviolet curable resin, or may not contain a non-ultraviolet curable resin, in addition to the ultraviolet curable resin having no silsesquioxane skeleton. In addition, a photopolymerization initiator may be contained in the curable composition for forming the second resin layer 16 . Moreover, additives etc. added to a curable composition may be contained as needed. As such an additive, a dispersing agent, a leveling agent, an antifoaming agent, a thixotropic agent, an antifouling agent, an antibacterial agent, a flame retardant, a slip agent, an inorganic particle, a resin particle, etc. are mentioned. Moreover, a solvent may be contained as needed. The non-ultraviolet curable resin, photopolymerization initiator, and solvent can be appropriately selected from those described in the curable composition for forming the first resin layer 14 .

The inorganic particles are added for the purpose of, for example, forming surface irregularities in the first resin layer 14 or adjusting the second resin layer 16 to have a high refractive index. In addition, the resin particles are added for the purpose of, for example, forming surface irregularities in the first resin layer 14 . By forming the surface unevenness in the first resin layer 14, when the base material for forming a transparent conductive layer is rolled into a roll shape, it becomes easy to suppress clogging of the front and back surfaces. 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 becomes difficult to visually recognize the conductive pattern of the laminated transparent conductive layer. The high refractive index means that the refractive index at the 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 the measurement wavelength of 589.3 nm is less than 1.50, preferably in the range of 1.30 to 1.50, and further preferably in the range of 1.40 to 1.50.

Examples of inorganic particles capable of optically adjusting the second resin layer 16 to have a high refractive index include oxides of metals such as titanium, zirconium, tin, zinc, silicon, niobium, aluminum, chromium, magnesium, germanium, gallium, antimony, and platinum. composed of metal oxide particles. These may be used individually by 1 type as an inorganic particle which can be adjusted optically, and may be used in combination of 2 or more types. Among these, titanium oxide and zirconium oxide are particularly preferred from the viewpoint of being excellent in both high refractive index and transparency.

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

The particles added to the curable composition for forming the second resin layer 16 , that is, the types of inorganic particles and resin particles that form surface irregularities in the first resin layer 14 can be appropriately selected from the curable combination for forming the first resin layer 14 recorded in the thing. Moreover, the solid content concentration of a curable composition can be adjusted similarly to the curable composition which forms the 1st resin layer 14.

In order to form surface irregularities in the first resin layer 14 , the average particle diameter of the inorganic particles and the resin particles is preferably equal to or 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 the total thickness of the first resin layer 14 and the second resin layer 16 , and even 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, the total thickness of the first resin layer 14 and the second resin layer 16 is particularly preferably 1.5 times or more and 5 times or less.

The thickness of the second resin layer 16 is not particularly limited, but is preferably 0.005 μm or more from the viewpoint of excellent film continuity. More preferably, it is 0.010 μm or more, and even 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 with the base film 12 . More preferably, it is 5 μm or less, and even more preferably 1 μm or less. Moreover, the total thickness of the 1st resin layer 14 and the 2nd resin layer 16 is preferably 10 μm or less from the viewpoint of easily suppressing curling due to the difference in thermal shrinkage with the base film 12 . The thickness of the second resin layer 16 is the thickness of the smoother portion in the thickness direction of the portion where the inorganic particles and resin particles are not present.

From the viewpoint of clogging, etc., the arithmetic mean roughness Ra of the surface on which the surface irregularities of the first resin layer 14 are formed is preferably within a range of 0.1 to 130 nm. More preferably, it exists in the range of 0.5-50 nm, More preferably, it exists in the range of 2-20 nm.

Furthermore, in the range of the above-mentioned average particle diameter and the range of the above-mentioned average arithmetic roughness, from the viewpoints of maintaining the blocking property, suppressing the increase in haze, and being more excellent in transparency, the difference between the inorganic particles and the resin particles is The distribution density is preferably in the range of 100 to 2000 pieces/mm ² . More preferably, it exists in the range of 100-1000 pieces/mm< ² >.

The base material 20 for forming a transparent conductive layer can be coated with the curable composition for forming the second resin layer 16 on the surface of the base film 12, dried as necessary, and then cured by irradiation with ultraviolet rays. 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 applied on the surface of the second resin layer 16, dried as necessary, and then cured by irradiation with ultraviolet rays. The first resin layer 14 is formed on the surfaces of the two resin layers 16 and 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 subjected to surface treatment before coating. As surface treatment, corona treatment, plasma treatment, hot air treatment, ozone treatment, ultraviolet treatment, etc. are mentioned.

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. Since it is composed of a cured product, the laminated transparent conductive layer is excellent in adhesion and scratch resistance at the same time. In addition, the second resin layer 16 is provided between the base film 12 and the first resin layer 14, and the second resin layer 16 is made of a curable combination containing an ultraviolet curable resin that does not have a silsesquioxane skeleton. It is composed of a hardened material, so the design of the optical adjustment function and the blocking prevention function is easy.

FIG. 3 shows the substrate 30 for forming a transparent conductive layer according to the third embodiment. The substrate 30 for forming a transparent conductive layer according to the third 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 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 . Moreover, 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 side of the base film 12 . The base material for forming a transparent conductive layer has the third resin layer 18 , the base film 12 , the second resin layer 16 , and the first resin layer 14 in this order from the third resin layer 18 side.

The base material 30 for forming a transparent conductive layer according to the third embodiment is different from the base material 20 for forming a transparent conductive layer according to the second embodiment in that it has a third resin layer on the other surface of the base film 12 18. Other than this, it is the same as the base material 20 for forming a transparent conductive layer according to the second embodiment, and the description of the same configuration 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 for forming the third resin layer 18 may be the same composition as the curable composition for 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 within the range of 2B to 6H. The pencil hardness can be measured according to JIS K5600-5-4. Since the third resin layer 18 is formed of a composition containing an ultraviolet curable resin, it is easy to satisfy the aforementioned pencil hardness.

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 . Furthermore, 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 base material 30 for forming a transparent conductive layer can be cured by ultraviolet irradiation after coating the curable composition for forming the second resin layer 16 on one side of the base film 12, drying as necessary, and curing the base material. After the second resin layer 16 is formed on one side 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, dried as necessary, and then irradiated with ultraviolet rays to make it 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 as necessary. , which is cured by ultraviolet irradiation, and the third resin layer 18 is formed on the other surface of the base film 12 to manufacture. 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 coated before coating. deal with. As surface treatment, corona treatment, plasma treatment, hot air treatment, ozone treatment, ultraviolet treatment, etc. are mentioned.

According to the base material 30 for forming a transparent conductive layer having the above-mentioned structure, the first resin layer 14 formed on one surface of the base film 12 is made of a curable resin containing an ultraviolet curable resin having a silsesquioxane skeleton. Since it is composed of a cured product of the composition, the laminated transparent conductive layer is excellent in adhesion and scratch resistance at the same time. In addition, the second resin layer 16 is provided 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 that does not have a silsesquioxane skeleton. It is composed of hardened material, so the design of the optical adjustment function and the blocking prevention function is easy. In addition, the third resin layer 18 is formed on the other surface of the base film 12, and the third resin layer 18 is made of a curable composition containing an ultraviolet curable resin that does not have a silsesquioxane skeleton. Since it consists of the hardened|cured material of the base film 12, the other surface side of the base film 12 is also excellent in scratch resistance.

In FIG. 4, the base material 40 for transparent conductive layer formation which concerns on 4th Embodiment is shown. The base material 40 for forming a transparent conductive layer according to the fourth embodiment has a base film 12 , a second resin layer 16 formed on one surface of the base 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 disposed on the other surface of the base film 12 with the adhesive layer 22 interposed therebetween. 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 . Moreover, the protective film 24 is in contact with the other surface of the base film 12 via the adhesive layer 22 . The first resin layer 14 is provided only on one side of the base film 12 . The base material 40 for forming a transparent conductive layer has the protective film 24 , the adhesive layer 22 , the base film 12 , the second resin layer 16 , and the 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 is different from the substrate 20 for forming a transparent conductive layer of the second embodiment in that an adhesive layer is provided on the other side of the substrate film 12 22 and has a protective film 24, except that, it is the same as the base material 20 for transparent conductive layer formation of 2nd Embodiment, and the description about the same structure is abbreviate|omitted.

The protective film 24 is one that can suppress the formation of scratches on the surface of the other side of the base film 12 during processing such as continuous processing by, for example, a roll process. 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 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 adhesive force between the base film 12 and the adhesive is stronger. The adhesive force between the layers 22 is adjusted to enable interfacial peeling.

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

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

The adhesive for forming the adhesive layer 22 is not particularly limited, and an acrylic adhesive, a polysiloxane-based adhesive, a urethane-based adhesive, or the like can be preferably used. In particular, acrylic adhesives are preferable because they are excellent in transparency and heat resistance. The acrylic adhesive is preferably formed from an adhesive composition comprising a (meth)acrylic polymer and a crosslinking agent.

(Meth)acrylic polymers are individual polymers or copolymers 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.

Examples of the alkyl group-containing (meth)acrylic monomer include (meth)acrylic monomers having an alkyl group having 2 to 30 carbon atoms. The alkyl group having 2 to 30 carbon atoms may be linear, branched, or cyclic. More specific examples of the alkyl group-containing (meth)acrylic monomer include isostearyl (meth)acrylate, octadecyl (meth)acrylate, lauryl (meth)acrylate, and (meth)acrylate. base) dodecyl acrylate, decyl (meth)acrylate, isononyl (meth)acrylate, nonyl (meth)acrylate, isooctyl (meth)acrylate, octyl (meth)acrylate, ( Isobutyl meth)acrylate, n-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, etc.

Examples of the carboxyl group-containing (meth)acrylic monomer 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 the hydroxyl group-containing (meth)acrylic monomer 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 of the above-mentioned monomers, or may be 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 oxazoline based crosslinking agents. Cross-linking agent, acridine-based cross-linking agent, melamine-based cross-linking agent, etc. The crosslinking agent may be used alone or in combination of two or more.

The adhesive composition may contain other additives in addition to the (meth)acrylic polymer and the crosslinking agent. As other additives, crosslinking accelerators, crosslinking retarders, tackifying resins (tackifiers), antistatic agents, silane coupling agents, plasticizers, release 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 application and purpose of the adhesive.

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

FIG. 5 discloses a substrate 50 for forming a transparent conductive layer according to a fifth embodiment. In the base material 50 for forming a transparent conductive layer according to the fifth embodiment, the second resin layers 16 are formed on both sides of the base film 12, and the first resin layers are respectively formed on the surfaces of both the second resin layers 16. 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 the first resin layer 14 , the second resin layer 16 , the base film 12 , the second resin layer 16 , and the first resin layer 14 in this order from the first resin layer 14 side.

The substrate 50 for forming a transparent conductive layer of the fifth embodiment is different from the substrate 20 for forming a transparent conductive layer of the second embodiment in that the second resin layer 16 and the first resin layer 14 are formed on the substrate film Both sides of 12 are the same as those of the base material 20 for forming a transparent conductive layer of the second embodiment, and the description thereof is omitted.

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

FIG. 6 discloses a substrate 60 for forming a transparent conductive layer according to a sixth embodiment. The base material 60 for forming a transparent conductive layer according to the sixth embodiment is formed by using two sheets of the base material 10 for forming a transparent conductive layer as shown in FIG. constitute. The base material 60 for forming a transparent conductive layer has the first resin layer 14 , the base film 12 , the adhesive layer 28 , the base film 12 , and the first resin layer 14 in this order.

Since the base material 60 for forming a transparent conductive layer has the first resin layers 14 on both sides, it is suitable as a base material for forming a transparent conductive film similarly to the base material 50 for forming a transparent conductive layer. 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 , and has two substrate films 12 , so it is difficult to break during the transparent conductive layer forming step, and has excellent handleability.

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

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

The adhesive layer 28 can be formed by the following methods: a method of directly coating the adhesive composition on the other side of the base film 12; after coating the adhesive composition on the surface of the release film and forming , 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, the second release film is attached, and any one of the release films is peeled off. A method of transferring the film to the other surface of the base film 12 or the like.

FIG. 7 discloses a substrate 70 for forming a transparent conductive layer according to a seventh embodiment. The substrate 70 for forming a transparent conductive layer according to 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 are provided. 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 side of the base film 12 . The base material 70 for forming a transparent conductive layer has the release film 34 , the adhesive layer 32 , the base film 12 , and the first resin layer 14 in this order from the release film 34 side.

The base material 70 for forming a transparent conductive layer according to the seventh embodiment is different from the base material 10 for forming a transparent conductive layer according to the first embodiment in that the base film 12 has an adhesive layer 32 on the other surface of the base film 12 The release film 34 is the same as that of the base material 10 for forming a transparent conductive layer 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 for forming the adhesive layer 32 may contain known adhesive resins such as acrylic adhesives, polysiloxane-based adhesives, and urethane-based adhesives. Among them, an acrylic adhesive is preferable from the viewpoint of optical transparency and heat resistance. In order to improve the cohesive force of the adhesive layer 32, the adhesive composition preferably contains a crosslinking agent. As a crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, acryl type crosslinking agent, a chelate type crosslinking agent, etc. are mentioned.

In the adhesive composition, additives may be included as required. Examples of the additives include known additives such as plasticizers, silane coupling agents, surfactants, antioxidants, fillers, curing accelerators, and curing retarders. In addition, from the viewpoint of productivity, etc., it can be diluted with an organic solvent.

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

The adhesive layer 32 can be formed by the following methods: a method of directly coating the adhesive composition on the other side surface of the base film 12; coating the adhesive composition on the surface of the release film 34 and forming 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, attaching the second release film, and peeling off any one of the release films. A method of transferring the mold film to the other surface of the base film 12 or the like.

From the viewpoint of good adhesion, the adhesive force of the adhesive layer 32 with respect to glass is preferably 4 N/25 mm or more. More preferably, it is 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 off from the adhesive layer 32 at the time of 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 in contact with the adhesive layer 32 may be subjected to release treatment. As the release agent used for the release treatment, for example, release agents such as polysiloxane-based, fluorine-based, alkyd-based, unsaturated polyester-based, polyolefin-based, wax-based, and the like can be exemplified.

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 which concerns on one Embodiment of this invention has the transparent conductive layer 26 on the surface of the 1st resin layer 14 of the base material 10 for transparent conductive layer formation. 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 includes 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, and examples thereof include 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, and the like Metal oxide. Among these, indium tin oxide and indium zinc oxide are particularly preferred from the viewpoint that transparency and conductivity can be highly compatible.

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

Examples of the transparent conductive layer 26 include sputtering, vacuum deposition, CVD, ion plating, and the like. Among them, the sputtering method is preferable 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, drum heating at the time of sputtering, a hot-air heating furnace, a far-infrared heating furnace, or the like. The heating temperature at the time of sintering may be appropriately selected according to the type of the conductive material. For example, 50-200 degreeC, 80-180 degreeC, 100-160 degreeC, etc. can be set. The heating time at the time of sintering is not particularly limited, but can be set to 3 to 180 minutes, 5 to 120 minutes, 10 to 90 minutes, or the like.

According to the transparent conductive film 80 having the above-mentioned configuration, since the transparent conductive layer 26 is provided on the surface of the first resin layer 14 of the base material 10 for forming a transparent conductive layer of the present invention, the first resin layer 14 and the transparent conductive layer 26 are separated from each other. Excellent adhesion. In addition, since the first resin layer 14 is excellent in scratch resistance, it is possible to suppress the occurrence of scratches on the surface of the first resin layer 14 during handling.

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 formed using 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 an electrostatic capacitance type, a resistive film type, or the like. As the touch panel of the present invention, those of the GFF method and the GF2 method are exemplified. The touch panel of the GFF method is composed of, for example, a transparent conductive film as shown in FIG. The transparent conductive layer 26 is formed on the surfaces of the respective first resin layers 12 of the transparent conductive layer forming substrates 60 that are laminated on the material film 12 side; or as shown in FIG. The transparent conductive films 80 having the first resin layer 14 and the transparent conductive layer 26 on one surface side of the base film 12 are bonded to each other on the base film 12 side with a transparent adhesive, and further use a transparent The adhesive of one side sticks the transparent conductive layer 26 on one side to a transparent substrate such as glass or resin film. In addition, the touch panel of the GF2 method is constituted, for example, by a transparent one having a first resin layer 14 and a transparent conductive layer 26 on both sides of the base film 12 as shown in FIG. 5 . The transparent conductive film formed from the base material 50 for forming a conductive layer is bonded to a transparent base material 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.

As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment at all, Various changes are possible in the range which does not deviate from the summary of this invention.

For example, in the above-described 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 described that the surface of the base film 12 may be subjected to surface treatment However, it may be a configuration in which an easily bonding layer is provided on the surface of the base film 12 instead of the surface treatment.

In addition, in the above-described 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 for forming irregularities is not limited to this. For example, the surface unevenness may be formed on a layer where surface unevenness is formed, 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 may be reduced by subjecting the particles to surface treatment or using a surfactant in combination, and the particles may be unevenly distributed on the surface of the layer to which the particles are added. A method of forming surface irregularities 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. More preferably, it exists in the range of 80-400 nm, More preferably, it exists in the range of 120-400 nm. Moreover, the average particle diameter is preferably 1/2 or less of the thickness of the layer to which the particles are added.

In addition, as shown in FIG. 4 , the above-mentioned protective film 24 is shown in the form added to the base material 20 for forming a transparent conductive layer of the second embodiment shown in FIG. The form of the substrate 10 for forming a transparent conductive layer according to one embodiment. Moreover, the form added to the transparent conductive film, such as the transparent conductive film 80 shown in FIG. 8, may be sufficient.

In addition, as shown in FIG. 7 , the above-mentioned adhesive layer 32 is shown in the form of being added to the base material 10 for forming a transparent conductive layer according to the first embodiment shown in FIG. The form of the substrates 20 to 30 for forming a transparent conductive layer is shown. Moreover, the form added to the transparent conductive film, such as the transparent conductive film 80 shown in FIG. 8, may be sufficient.

Further, the sixth transparent conductive layer forming substrate 60 shown in FIG. 6 is in the form of bonding two transparent conductive layer forming substrates 10 to each other on the substrate film 12 side with the adhesive layer 28 interposed therebetween. However, one or both of the two transparent conductive layer forming substrates 10 may be the transparent conductive layer forming substrates 20 to 30 shown in FIGS. 2 to 3 . Moreover, a transparent conductive film, such as the transparent conductive film 80 shown in FIG. 8, may be sufficient.

In addition, as shown in FIG. 8, the transparent conductive film 80 shows an example in which the substrate for forming a transparent conductive layer 10 of the first embodiment shown in FIG. 1 is used as the substrate for forming a transparent conductive layer. The substrates 20 to 70 for forming a transparent conductive layer shown in FIGS. 2 to 7 are used as the substrates for forming a transparent conductive layer.

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

Hereinafter, the present invention will be described in detail using Examples and Comparative Examples.

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

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

(Preparation of a base material for forming a transparent conductive layer) (Examples 1 to 3) A wire rod of #5 was used on one side of the base film (PET film "Lumirror UH1H" manufactured by TORAY, thickness 50 μm). bar) apply the curable composition for forming the second resin layer and dry it at 80°C for 1 minute, then use a high-pressure mercury lamp to irradiate the coating film with ultraviolet rays at a light intensity of 200 mJ/cm ² to cure the coating film with ultraviolet rays, thereby forming the first Two resin layers. Next, on the surface of the second resin layer, the curable composition for forming the first resin layer was applied using a wire bar of #4, dried at 80° C. for 1 minute, and then a high pressure mercury lamp was used under a nitrogen gas atmosphere with a light intensity of 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. Then, the curable composition for forming the third resin layer was applied on the other side of the base film using a wire bar of #4, dried at 80° C. for 1 minute, and then a high pressure mercury lamp was used with a light intensity of 200 mJ/cm. ^2. The coating film is irradiated with ultraviolet rays to cure the coating film with ultraviolet rays, thereby forming a third resin layer. By the above, the base material for transparent conductive layer formation of Examples 1-3 was produced.

(Example 4) The base film was changed to "Zeonor Film ZF16-55" (thickness 55μm), a COP film manufactured by Zeonor, and a corona treatment was applied to one side of the film. The second resin layer was not formed, and the wire of #5 was used. Except having formed the 1st resin layer with the rod, it carried out similarly to Example 1, and produced the base material for transparent conductive layer formation of Example 4. The third resin layer is not formed on the other surface of the base film.

(Examples 5 to 8) The base film was changed to COP film "Zeonor Film ZF16-55" (thickness 55 μm) manufactured by Japan Zeonor, and after corona treatment was applied to one side of the film, a second resin layer was formed. Except having used the wire bar of #5 to form the first resin layer on the surface, it carried out similarly to Example 1, and produced the base material for transparent conductive layer formation of Examples 5-8. The third resin layer is not formed on the other surface of the base film.

(Comparative Example 1) Except that the curable composition for 1st resin layer formation was different, it carried out similarly to Example 1, and produced the base material for transparent conductive layer formation of the comparative example 1. In the curable composition for 1st resin layer formation of the comparative example 1, the ultraviolet curable resin which has a silsesquioxane skeleton is not contained.

(Comparative Example 2) Except that the curable composition for 1st resin layer formation was different, it carried out similarly to Example 3, and produced the base material for transparent conductive layer formation of the comparative example 2. The curable composition for 1st resin layer formation of the comparative example 2 does not contain the ultraviolet curable resin which has a silsesquioxane skeleton.

(Comparative Example 3) Except that the curable composition for 1st resin layer formation was different, it carried out similarly to Example 3, and produced the base material for transparent conductive layer formation of the comparative example 3. The curable composition for forming the first resin layer of Comparative Example 3 did not contain an ultraviolet curable resin having a silsesquioxane skeleton, but contained a thermosetting epoxy resin having a silsesquioxane skeleton.

The materials 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 Base: methacryloyl group, functional group equivalent 239g/eq) ‧UV resin containing SQ <2>: UV curable resin with silsesquioxane skeleton ("MAC-SQ SI-20" manufactured by Toagosei, methacrylic resin, solid content concentration 100% by mass, functional group: Methacryloyl group, functional group equivalent 224g/eq) ‧UV resin <1>: UV curable resin without silsesquioxane skeleton (“Lioduras TYZ59-10-S” manufactured by TOYOCHEM, (meth)acrylic resin containing zirconium particles, solvent (PGM, MIBK, fat) family 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 Co., Ltd., (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” manufactured by TOYOCHEM, (meth)acrylic resin containing zirconium particles, solvent (PGM, MIBK, aliphatic type) Solvent and cyclohexanone), solid content concentration 40% by mass, high refractive index hard coating agent) ‧UV resin <4>: UV curable resin without silsesquioxane skeleton ("AICAAITRON Z-735-35L" manufactured by AICA Industry, (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” manufactured by DIC, (meth)acrylic resin, solvent (MEK, BuAc and MIBK), solid content concentration 40 quality%) ‧Resin particles: polymethyl methacrylate particles (1 mass % MEK dispersion of "Chemisnow MX-80H3wT" manufactured by Soken Chemical Co., Ltd., average particle size 800 nm) ‧Photopolymerization initiator: "IRGACURE127" manufactured by BASF JAPAN ‧EP resin containing SQ: Thermosetting epoxy resin with silsesquioxane skeleton (“COMPOCERAN SQ506” manufactured by Arakawa Chemical Industry Co., Ltd.) ‧EP hardener: 1-benzyl-2-methylimidazole ‧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 produced base material for forming a transparent conductive layer 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 particle is set as the thickness of the part which does not exist resin particle in the thickness direction.

Using each of the prepared substrates for forming a transparent conductive layer, on the surface of the first resin layer, indium tin oxide was sputtered to a thickness of 20 nm to form an ITO layer, and on the surface of the ITO layer, a thickness of 200 nm was applied. After copper was sputtered to form a copper layer, the ITO layer was crystallized by standing at 150° C. for 1 hour in a constant temperature bath. By the above, a transparent conductive film was 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 slit was cut out, and an adhesion test based on JIS K5400-8.5 (JIS D0202) was implemented. Among the 100 pieces (mass), all those with no peeling were seen as good "○", and those with one or more peelings were seen as bad "╳". Among the good ones, those in which peeling was not seen in the perimeter of the incision on the outer side of 100 pieces were regarded as particularly good "⊚".

(scratch resistance) Using each of the produced substrates for forming a transparent conductive layer, the first resin layer was placed in a Gakushin-type rubbing fastness tester manufactured by TESTER Sangyo, using "Steel Wool #0000" manufactured by NIHON STEEL WOOL, under a load of 200 g. rub the surface 20 times. Then, under a fluorescent lamp, the surface of the first resin layer was visually observed from directly above, and those with no scratches were rated as good "╳", and those where scratches were seen as poor "╳".

[Table 1] Example Comparative example 1 2 3 4 5 6 7 8 1 2 3 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 Content (mass %) of UV resin containing SQ in total solid content 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 substrate film type of material PET PET PET COP COP COP COP COP PET COP COP Thickness (μm) 50 50 50 55 55 55 55 55 50 55 55 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 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ╳

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

As mentioned above, although the Example of this invention was described, this invention is not limited to the said Example at all, Various changes can be made in the range which does not deviate from the meaning of this invention.

10, 20, 30, 40, 50, 60, 70: substrates for forming transparent conductive layers

12: substrate 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 film

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

10: Substrate for forming transparent conductive layer

12: substrate film

14: The first resin layer

Claims (12)

A substrate for forming a transparent conductive layer, which is a substrate for forming a transparent conductive layer, which is a substrate for forming a transparent conductive layer, characterized by comprising a substrate film and a first substrate formed 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, the thickness of the first resin layer is 10 μm or less, and the first resin layer is The resin layer is exposed on the outermost surface of the substrate for forming a transparent conductive layer. 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 mass % or more based on the total solid content of the curable composition, 100% by mass or less. The substrate for forming a transparent conductive layer according to claim 1 or 2, wherein a second resin layer is provided between the substrate film and the first resin layer, and the second resin layer is made of a material containing no silsesquioxane. It consists of a cured product of a curable composition of an ultraviolet curable resin having an alkane skeleton. The substrate for forming a transparent conductive layer according to claim 1 or 2, wherein the first resin layer is provided only on one side of the substrate film, and the substrate film has the first resin layer on the other side of the substrate film. 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 claim 1 or 2, wherein the first resin layer is provided only on one side of the substrate film, and the substrate film is separated from the other side of the substrate film. The adhesive layer has a protective film. The substrate for forming a transparent conductive layer according to claim 1 or 2, wherein the substrate is The above-mentioned first resin layer is provided on both sides of the material 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 transparent conductive layer is used for an electrode of a touch panel. A touch panel characterized in that the transparent conductive layer as claimed in claim 8 is used for electrodes. A method for producing a substrate for forming a transparent conductive layer, which is a method for producing a substrate for forming a transparent conductive layer that becomes a substrate for forming a transparent conductive layer, wherein a first substrate film is formed on the surface of the substrate film. In the 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. The method for producing a substrate for forming a transparent conductive layer according to claim 11, wherein after the second resin layer is formed 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 two resin layers are composed of a cured product of a curable composition containing an ultraviolet curable resin that does not have a silsesquioxane skeleton.

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