JPWO2020122114A1 - Method for manufacturing transparent conductive layer forming base material, transparent conductive film, touch panel and transparent conductive layer forming base material - Google Patents

Abstract

Provided are a base material for forming a transparent conductive layer having excellent adhesion and scratch resistance of the transparent conductive layer to be laminated, a method for producing the same, and a transparent conductive film and a touch panel using the same. The transparent conductive layer forming base material 10 has a base material film 12 and a first resin layer 14 formed on the surface of the base material film 12, and the first resin layer 14 is a silsesquioxane skeleton. It comprises a cured product of a curable composition containing an ultraviolet curable resin having. The transparent conductive film 80 has a transparent conductive layer 26 on the surface of the first resin layer 14 of the base material 10 for forming the transparent conductive layer. In the touch panel, the transparent conductive layer 26 of the transparent conductive film 80 is used for the electrode.

Description

The present invention relates to a base material for forming a transparent conductive layer, a transparent conductive film, a touch panel, and a method for manufacturing a base material for forming a transparent conductive layer.

A capacitive touch panel is known as an input device such as a smart phone or a tablet terminal that can operate a device by touching a display on the screen. A transparent conductive film is used for this type of touch panel. The transparent conductive film is made of, for example, a transparent conductive layer made of a metal oxide such as indium tin oxide (ITO) formed on the surface of a plastic base material (resin base material) (Patent Document 1).

When a transparent conductive layer made of a metal oxide is formed directly on the surface of the plastic base material, the adhesion between the plastic base material 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 the plastic base material on which the primer layers are laminated.

Japanese Unexamined Patent Publication No. 07-08690 Japanese Unexamined Patent Publication No. 2012-007065

The primer layer of Patent Document 2 is obtained by thermosetting a composition containing a thiol group-containing silsesquioxane, a hydroxyl group-containing polyester resin, and polyisocyanates, and has low scratch resistance and a metal oxide. There is a risk that the surface of the primer layer will be scratched during handling when forming the transparent conductive layer made of. If the surface of the primer layer is scratched, the appearance of the transparent conductive film will be poor.

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

In order to solve the above problems, the base material for forming a transparent conductive layer according to the present invention is a base material for forming a transparent conductive layer which is a base material for forming a transparent conductive layer, and is a base film and the base material. The gist is that the first resin layer having a first resin layer formed on the surface of the film, and the first resin layer is made of a cured product of a curable composition containing an ultraviolet curable resin having a silsesquioxane skeleton. Is to be.

The ultraviolet curable resin having a silsesquioxane skeleton is preferably a (meth) accrete 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. It is preferable to have a second resin layer made of a cured product of a curable composition containing an ultraviolet curable resin having no silsesquioxane skeleton between the base film and the first resin layer. The first resin layer has a curable composition on only one surface of the base film and contains an ultraviolet curable resin having no silsesquioxane skeleton on the other surface of the base film. It may have a third resin layer made of a cured product of the material. 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 the pressure-sensitive adhesive layer. The first resin layer may be provided on both surfaces of the base film.

The transparent conductive film according to the present invention is intended to have a transparent conductive layer on the surface of the first resin layer of the base material for forming the transparent conductive layer according to the present invention.

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

The gist of the transparent conductive film according to the present invention is that the transparent conductive layer of the transparent conductive film according to the present invention is used for the electrode.

The method for manufacturing a base material for forming a transparent conductive layer according to the present invention is a method for manufacturing a base material for forming a transparent conductive layer, which is a base material for forming a transparent conductive layer, and is on the surface of the base film. The main purpose is to form a first resin layer made of a cured product of a curable composition containing an ultraviolet curable resin having a silsesquioxane skeleton.

The method for producing a base material for forming a transparent conductive layer according to the present invention comprises a cured product of a curable composition containing an ultraviolet curable resin having no silsesquioxane skeleton on the surface of the base film. After forming the second resin layer, the first resin layer may be formed on the surface of the second resin layer.

According to the substrate for forming a transparent conductive layer according to the present invention, a cured product of a curable composition containing an ultraviolet curable resin in which the first resin layer formed on the surface of the substrate film has a silsesquioxane skeleton. Therefore, the transparent conductive layer to be laminated is excellent in adhesion and scratch resistance.

When a second resin layer made of a cured product of a curable composition containing an ultraviolet curable resin having no silsesquioxane skeleton is provided between the base film and the first resin layer, an optical adjustment function is provided. And the design of blocking prevention function becomes easy.

The first resin layer is cured only on one surface of the base film and contains an ultraviolet curable resin having no silsesquioxane skeleton on the other surface of the base film. When the third resin layer made of a cured product of the sex composition is provided, the other surface side of the base film is also excellent in scratch resistance.

When the first resin layer is provided only on one surface of the base film and the protective film is provided on the other surface of the base film via the adhesive layer, it is necessary to handle the first resin layer. In, it is possible to prevent the other surface of the base film from being scratched.

It is sectional drawing of the base material for forming a transparent conductive layer which concerns on 1st Embodiment of this invention. It is sectional drawing of the base material for forming a transparent conductive layer which concerns on 2nd Embodiment of this invention. It is sectional drawing of the base material for forming a transparent conductive layer which concerns on 3rd Embodiment of this invention. It is sectional drawing of the base material for forming a transparent conductive layer which concerns on 4th Embodiment of this invention. It is sectional drawing of the base material for forming a transparent conductive layer which concerns on 5th Embodiment of this invention. It is sectional drawing of the base material for forming a transparent conductive layer which concerns on 6th Embodiment of this invention. It is sectional drawing of the base material for forming a transparent conductive layer which concerns on 7th Embodiment of this invention. It is sectional drawing of the transparent conductive film which concerns on one Embodiment of this invention.

Hereinafter, the present invention will be described in detail.

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

As shown in FIG. 1, the transparent conductive layer forming base material 10 according to the first embodiment of the present invention includes a base film 12, a first resin layer 14 formed on the surface of the base film 12, and the like. Have. 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. Examples of the base film 12 include a transparent polymer film and a glass film. 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 total light transmittance can be measured according to JIS K7361-1 (1997). The thickness of the base film 12 is not particularly limited, but is preferably in the range of 2 to 500 μm from the viewpoint of excellent handleability and the like. More preferably, it is in the range of 2 to 200 μm. The term "film" generally means a film having a thickness of less than 0.25 mm, but even if the film has a thickness of 0.25 mm or more, if it can be rolled into a roll, the thickness is 0. Even if it is .25 mm or more, it shall be included in the "film".

Examples of the polymer material of the base film 12 include polyester resins such as polyethylene terephthalate resin and polyethylene naphthalate resin, polycarbonate resins, poly (meth) acrylate resins, polystyrene resins, polyamide resins, polyimide resins, polyacrylonitrile resins, and polypropylene resins. Examples thereof include polyolefin resins such as polyethylene resins, polycycloolefin resins and cycloolefin copolymer resins, polyphenylene sulfide resins, polyvinyl chloride resins, polyvinylidene chloride resins, and polyvinyl alcohol resins. The polymer material of the base film 12 may be composed of only one of these, or may be composed of a combination of two or more. Of these, polyethylene terephthalate resin, polyimide resin, polycarbonate resin, poly (meth) acrylate resin, polycycloolefin resin, and cycloolefin copolymer resin are more preferable from the viewpoint of optical properties and durability.

The base film 12 may be composed of a single layer composed of a layer containing one or more of the above-mentioned polymer materials, or a layer containing one or more of the above-mentioned polymer materials and the layer. It may be composed of two or more layers, such as a layer containing one kind or two or more kinds of polymer materials different from the layer.

The first resin layer 14 is made 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 transparent conductive layer to be laminated is excellent in adhesion. Further, 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 equation (1), n is an integer of 2 or more. As n, an integer of 2 to 200 is preferable, an integer of 2 to 150 is more preferable, and an integer of 2 to 100 is further preferable. In the formula (1), R is an organic group, and at least a part of the plurality of Rs is an ultraviolet-reactive reactive group. Examples of the UV-reactive reactive group include a radically polymerized reactive group having an ethylenically unsaturated bond such as an acryloyl group, a methacryloyl group, an allyl group and a vinyl group, and a cationically polymerizable reactive group such as an oxetanyl group. Can be mentioned. Of these, an acryloyl group, a methacryloyl group, and an oxetanyl group are more preferable, and an acryloyl group and a methacryloyl group are particularly preferable because they are excellent in weather resistance and optical transparency. That is, a (meth) acrylate having a silsesquioxane skeleton is particularly preferable. In addition, in this specification, "(meth) acrylate" means "at least one of acrylate and methacrylate". "(Meta) acryloyl" means "at least one of acryloyl and methacryloyl". "(Meta) acrylic" means "at least one of acrylic and methacryl".

The functional group equivalent of the ultraviolet curable resin having a silsesquioxane skeleton is preferably in the range of 80 to 10000 g / eq. It is more preferably in the range of 100 to 1000 g / eq, and even more preferably in the range of 150 to 300 g / eq. When the functional group equivalent is in this range, the ultraviolet curability is excellent. In the present invention, the functional group equivalent represents the mass (g) per functional group equivalent. Further, the functional group refers to a reactive group that is 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 and an alkoxy group, the adhesion of the transparent conductive layer to be laminated is improved. Sylsesquioxane includes a complete cage structure, a ladder structure, a random structure, and an incomplete cage structure. The complete cage type structure and the hashigo type structure do not contain hydroxyl groups and alkoxy groups, but the random structure and incomplete cage type structures contain hydroxyl groups and alkoxy groups. Therefore, it is preferable that a part or all of the silsesquioxane skeleton has a random structure or an incomplete cage structure.

Examples of the ultraviolet curable resin 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 manufactured by Toagosei. , OX-SQ TX-100, OX-SQ SI-20, OX-SQ HDX and the like.

The curable composition forming the first resin layer 14 may contain an ultraviolet curable resin having a silsesquioxane skeleton and an ultraviolet curable resin not having a silsesquioxane skeleton. However, it does not have to be included. Further, the non-ultraviolet curable resin may or may not be contained. Further, the curable composition forming the first resin layer 14 may contain a photopolymerization initiator. Further, if necessary, an additive or the like to be added to the curable composition may be contained. Examples of such an additive include a dispersant, a leveling agent, a defoaming agent, a stiffening agent, an antifouling agent, an antibacterial agent, a flame retardant, a slip agent, an inorganic particle, and a resin particle. Further, if necessary, a solvent may be contained.

In the curable composition forming the first resin layer 14, the content of the ultraviolet curable resin having a silsesquioxane skeleton shall be 0.5% by mass or more based on the total solid content of the curable composition. Is preferable. It is more preferably 2% by mass or more, still more preferably 4% by mass or more. The solid content of the curable composition is a component excluding the solvent. When the content is 1% by mass or more, the adhesiveness of the transparent conductive layers to be laminated is excellent. Further, 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. It is preferably 98% by mass or less. By setting the content in the above range, it is possible to make the transparent conductive layer excellent in adhesion and scratch resistance.

Examples of the ultraviolet curable resin having no silsesquioxane skeleton include monomers, oligomers, prepolymers and the like having an ultraviolet reactive reactive group and having no silsesquioxane skeleton. Examples of the UV-reactive reactive group include a radically polymerized reactive group having an ethylenically unsaturated bond such as an acryloyl group, a methacryloyl group, an allyl group and a vinyl group, and a cationically polymerizable reactive group such as an oxetanyl group. Can be mentioned. Of these, an acryloyl group, a methacryloyl group, and an oxetanyl group are more preferable, and an acryloyl group and a methacryloyl group are particularly preferable. That is, a (meth) acrylate having no silsesquioxane skeleton is particularly preferable.

Examples of the (meth) acrylate having no silsesquioxane skeleton include urethane (meth) acrylate, silicone (meth) acrylate, alkyl (meth) acrylate, and aryl (meth) having no silsesquioxane skeleton. Examples include acrylate. Of these, urethane (meth) acrylate is particularly preferable from the viewpoint of excellent flexibility.

Examples of the non-ultraviolet curable resin include thermoplastic resins and thermosetting resins. Examples of the thermoplastic resin include polyester resin, polyether resin, polyolefin resin, and polyamide resin. Examples of the thermosetting resin include unsaturated polyester resin, epoxy resin, alkyd resin, and phenol resin.

Examples of the photopolymerization initiator include alkylphenone-based, acylphosphine oxide-based, and oxime ester-based photopolymerization initiators. Examples of the alkylphenone-based photopolymerization initiator include 2,2'-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-. Propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hirodoxy-1-{4- [4- (4-( 2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzylmethyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- (4-morpholino) Phenyl) -1-butanone, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone, N, N-dimethylaminoacetophenone and the like can be mentioned. Examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxybenzoyl) -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-benzoyloxime), and etanone-1- [9-ethyl-6- (2-). Methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime) and the like can be mentioned. 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 in the range of 1 to 5% by mass.

Inorganic particles are added, for example, for the purpose of forming surface irregularities on the first resin layer 14 or adjusting the first resin layer 14 to a high refractive index. Further, the resin particles are added for the purpose of forming surface irregularities on the first resin layer 14, for example. By forming surface irregularities on the first resin layer 14, it is easy to suppress blocking in which the front surface and the back surface adhere to each other when the transparent conductive layer forming base material is wound in a roll shape. By adjusting the first resin layer 14 to a high refractive index, it is possible to make it difficult to visually recognize the conductive pattern of the transparent conductive layers to be laminated. 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 the inorganic particles whose first resin layer 14 can be optically adjusted 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. Examples thereof include metal oxide particles composed of. These may be used alone as the optically adjustable inorganic particles, or may be used in combination of two or more. Of these, titanium oxide and zirconium oxide are particularly preferable from the viewpoint of excellent compatibility between high refractive index and transparency.

The types of the inorganic particles and the resin particles that form surface irregularities on the first resin layer 14 are not particularly limited. Examples of such inorganic particles include metal oxide particles made of metal oxides such as titanium, zirconium, silicon, aluminum, and calcium. Examples of such resin particles include (meth) acrylic resin, styrene resin, styrene- (meth) acrylic resin, urethane resin, polyamide resin, silicone resin, epoxy resin, phenol resin, polyethylene resin, cellulose and the like. Examples thereof include resin particles made of resin.

In order to form surface irregularities on the first resin layer 14, it is preferable that the average particle size of the inorganic particles and the resin particles is equal to or larger than the thickness of the first resin layer 14. More preferably 1.1 times or more and 20 times or less the thickness of the first resin layer 14, more preferably 1.5 times or more and 10 times or less the thickness of the first resin layer 14, and particularly preferably the thickness of the first resin layer 14. It is 1.5 times or more and 5 times or less. The average particle size is a volume-based average arithmetic value obtained by a laser diffraction / scattering method according to 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 and the like. It is more preferably 0.010 μm or more, 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 that curl due to the difference in heat shrinkage with the base film 12 can be easily suppressed. It is more preferably 5 μm or less, still more preferably 1 μm or less. The thickness of the first resin layer 14 is the thickness of a relatively smooth portion in the portion where the inorganic particles and the resin particles do not exist in the thickness direction.

The arithmetic average roughness Ra of the surface on which the surface irregularities of the first resin layer 14 are formed is 0.1 to 130 nm from the viewpoint of easily suppressing blocking in which the front surface and the back surface of the transparent conductive layer forming substrate adhere to each other. It is preferably within the range of. It is more preferably in the range of 0.5 to 50 nm, still more preferably in the range of 2 to 20 nm.

Then, from the viewpoint of suppressing the increase in haze while suppressing blocking and being superior in transparency, the distribution density of the inorganic particles and the resin particles is within the range of the average particle size and the range of the average arithmetic roughness. It 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 the solvent used in the curable composition include alcohol 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) and cyclohexanone. , Ketone solvents such as acetone, aromatic solvents such as toluene and xylene, and amide solvents such as N-methylpyrrolidone, acetamide and dimethylformamide. These may be used alone as a solvent, or may be used 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, it may be 1 to 90% by mass, 1.5 to 80% by mass, 2 to 70% by mass, and the like.

The transparent conductive layer forming base material 10 is manufactured by applying a curable composition forming the first resin layer 14 on the surface of the base material film 12, drying as necessary, and then curing by ultraviolet irradiation. can do. 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 surface-treated before coating. Examples of the surface treatment include corona treatment, plasma treatment, hot air treatment, ozone treatment, and ultraviolet treatment.

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, spin coating method, dip coating method, spray coating method, knife coating method, kiss coating. It can be performed by using various coating methods such as a method, and various printing methods such as an inkjet method, offset printing, screen printing, and flexographic printing.

The drying step is not particularly limited as long as the solvent 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 ultraviolet irradiation, a high-pressure mercury lamp, an electrodeless (microwave method) lamp, a xenon lamp, a metal halide lamp, or any other ultraviolet irradiation device can be used. Irradiation with ultraviolet rays may be carried out in an atmosphere of an inert gas such as nitrogen, if necessary. UV irradiation dose, but are not limited to, preferably ^{50~800mJ / cm 2, 100~300mJ / cm} 2 is more preferable.

According to the transparent conductive layer forming base material 10 having the above structure, the curable composition contains an ultraviolet curable resin in which the first resin layer 14 formed on the surface of the base material film 12 has a silsesquioxane skeleton. Since it is made of a cured product of the above, it is excellent in the adhesion of the transparent conductive layer to be laminated and also in the scratch resistance.

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

FIG. 2 shows the transparent conductive layer forming base material 20 according to the second embodiment. The transparent conductive layer forming base material 20 according to the second embodiment is formed on the base film 12, the second resin layer 16 formed on the surface of the base film 12, and the surface of the second resin layer 16. It has a first resin layer 14 and the like. 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 transparent conductive layer forming base material 20 has a base material 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 base material 20 according to the second embodiment is second between the base film 12 and the first resin layer 14 as compared with the transparent conductive layer forming base material 10 according to the first embodiment. The difference is that it has the resin layer 16, and other than that, it is the same as the transparent conductive layer forming base material 10 according to the first embodiment, and the description thereof will be omitted for the same configuration.

The second resin layer 16 is arranged 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 include 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 an ultraviolet reactive reactive group and having no silsesquioxane skeleton. Examples of the UV-reactive reactive group include a radically polymerized reactive group having an ethylenically unsaturated bond such as an acryloyl group, a methacryloyl group, an allyl group and a vinyl group, and a cationically polymerizable reactive group such as an oxetanyl group. Can be mentioned. Of these, an acryloyl group, a methacryloyl group, and an oxetanyl group are more preferable, and an acryloyl group and a methacryloyl group are particularly preferable. That is, a (meth) acrylate having no silsesquioxane skeleton is particularly preferable.

Examples of the (meth) acrylate having no silsesquioxane skeleton include urethane (meth) acrylate, silicone (meth) acrylate, alkyl (meth) acrylate, and aryl (meth) having no silsesquioxane skeleton. Examples include acrylate. Of these, urethane (meth) acrylate is particularly preferable from the viewpoint of excellent flexibility. When the curable composition for forming the second resin layer 16 contains urethane (meth) acrylate as the ultraviolet curable resin, for example, the base film 12 is formed from a polycycloolefin, a cycloolefin copolymer, or the like, and is compared. Even if it is easily cracked, it is easy to suppress the cracking of the base film 12.

The second resin layer 16 is preferably a hard coat layer. From this point of view, the pencil hardness is preferably in the range of 2B to 6H. 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, the pencil hardness is easily satisfied.

The curable composition forming the second resin layer 16 may or may not contain a non-ultraviolet curable resin in addition to the ultraviolet curable resin having no silsesquioxane skeleton. You may. Further, the curable composition forming the second resin layer 16 may contain a photopolymerization initiator. Further, if necessary, an additive or the like to be added to the curable composition may be contained. Examples of such an additive include a dispersant, a leveling agent, a defoaming agent, a stiffening agent, an antifouling agent, an antibacterial agent, a flame retardant, a slip agent, an inorganic particle, and a resin particle. Further, if necessary, a solvent may be contained. The non-ultraviolet curable resin, the photopolymerization initiator, and the solvent can be appropriately selected from those described in the curable composition forming the first resin layer 14.

Inorganic particles are added, for example, for the purpose of forming surface irregularities on the first resin layer 14 and adjusting the second resin layer 16 to a high refractive index. Further, the resin particles are added for the purpose of forming surface irregularities on the first resin layer 14, for example. By forming surface irregularities on the first resin layer 14, it is easy to suppress blocking in which the front surface and the back surface adhere to each other when the transparent conductive layer forming base material is wound in a roll shape. By adjusting the second resin layer 16 to a high refractive index and adjusting the first resin layer 14 to a low refractive index, it is possible to make it difficult to visually recognize the conductive pattern of the transparent conductive layers to be laminated. 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 more preferably in the range of 1.41 to 1.50. ..

Examples of the inorganic particles whose second resin layer 16 can be optically adjusted 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. Examples thereof include metal oxide particles composed of. These may be used alone as the optically adjustable inorganic particles, or may be used in combination of two or more. Of these, titanium oxide and zirconium oxide are particularly preferable from the viewpoint of excellent compatibility between high refractive index and transparency.

On the other hand, examples of the inorganic particles whose first resin layer 14 can be optically adjusted to have a low refractive index include particles such as magnesium fluoride, silica, silsesquioxane, and calcium fluoride. It is more preferable that these particles have a hollow structure from the viewpoint that they can easily have a low refractive index.

The types of inorganic particles and resin particles that are particles added to the curable composition that forms the second resin layer 16 and that form surface irregularities on the first resin layer 14 are curable particles that form the first resin layer 14. It can be appropriately selected from those described in the composition. Further, the solid content concentration of the curable composition can be adjusted in the same manner as in 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 the resin particles is preferably equal to or larger than the total thickness of the first resin layer 14 and the second resin layer 16. More preferably, the total thickness of the first resin layer 14 and the second resin layer 16 is 1.1 times or more and 20 times or less, and more preferably 1.5 times the total thickness of the first resin layer 14 and the second resin layer 16. It is 5 times or more and 10 times or less, and particularly preferably 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 is preferably 0.005 μm or more from the viewpoint of excellent film continuity and the like. It is more preferably 0.010 μm or more, 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 that curl due to the difference in heat shrinkage with the base film 12 can be easily suppressed. It is more preferably 5 μm or less, still more preferably 1 μm or less. Further, the total thickness of the first resin layer 14 and the second resin layer 16 is preferably 10 μm or less from the viewpoint that curl due to the difference in heat shrinkage with the base film 12 can be easily suppressed. The thickness of the second resin layer 16 is the thickness of a relatively smooth portion in the portion where the inorganic particles and the resin particles do not exist in the thickness direction.

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 from the viewpoint of blocking and the like. It is more preferably in the range of 0.5 to 50 nm, still more preferably in the range of 2 to 20 nm.

Then, from the viewpoint of suppressing the increase in haze and improving the transparency while maintaining the blocking property, the distribution density of the inorganic particles and the resin particles is within the range of the average particle size and the range of the average arithmetic roughness. 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 transparent conductive layer forming base material 20 is formed by applying a curable composition for forming a second resin layer 16 on the surface of the base material film 12, drying as necessary, and then curing by ultraviolet irradiation. After forming the second resin layer 16 on the surface of the material film 12, a curable composition for forming the first resin layer 14 is applied on the surface of the second resin layer 16, and after drying as necessary. It can be produced by forming the first resin layer 14 on the surface of the second resin layer 16 by curing it by irradiation with ultraviolet rays. 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 the surface treatment include corona treatment, plasma treatment, hot air treatment, ozone treatment, and ultraviolet treatment.

According to the transparent conductive layer forming base material 20 having the above structure, the curable composition contains an ultraviolet curable resin in which the first resin layer 14 formed on the surface of the base material film 12 has a silsesquioxane skeleton. Since it is made of a cured product of the above, it is excellent in the adhesion of the transparent conductive layer to be laminated and also in the scratch resistance. Further, since the base film 12 and the first resin layer 14 have a second resin layer 16 made of a cured product of a curable composition containing an ultraviolet curable resin having no silsesquioxane skeleton. , It becomes easy to design the optical adjustment function and the blocking prevention function.

FIG. 3 shows the transparent conductive layer forming base material 30 according to the third embodiment. The transparent conductive layer forming base material 30 according to the third embodiment is the base film 12, the second resin layer 16 formed on one surface of the base film 12, and the surface of the second resin layer 16. It has a first resin layer 14 formed on the base film 12 and a third resin layer 18 formed on the other surface 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. Further, 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 transparent conductive layer forming base material 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 base material 30 according to the third embodiment has a third resin layer 18 on the other surface of the base material film 12 as compared with the transparent conductive layer forming base material 20 according to the second embodiment. The same as the transparent conductive layer forming base material 20 according to the second embodiment except for the above, and the description thereof will be omitted for the same configuration.

The third resin layer 18 is made 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 can 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 point of view, the pencil hardness is preferably in the range of 2B to 6H. Pencil hardness can be measured according to JIS K5600-5-4. The third resin layer 18 is formed from a composition containing an ultraviolet curable resin, so that the pencil hardness is easily satisfied.

The thickness of the third resin layer 18 is not particularly limited, and may be the same as the thickness of the second resin layer 16. Then, the thickness of the third resin layer 18 is set to be close to the thickness of the second resin layer 16 or the total thickness of the second resin layer 16 and the first resin layer 14 (for example, within ± 10%), so that at the time of curing. It is easy to suppress the curl that accompanies the shrinkage of the plastic.

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

According to the transparent conductive layer forming base material 30 having the above structure, the first resin layer 14 formed on one surface of the base material film 12 is curable including an ultraviolet curable resin having a silsesquioxane skeleton. Since it is made of a cured product of the composition, it has excellent adhesion to the transparent conductive layer to be laminated and also has excellent scratch resistance. Further, since the base film 12 and the first resin layer 14 have a second resin layer 16 made of a cured product of a curable composition containing an ultraviolet curable resin having no silsesquioxane skeleton. , It becomes easy to design the optical adjustment function and the blocking prevention function. Further, since the third resin layer 18 made of a cured product of the curable composition containing the ultraviolet curable resin having no silsesquioxane skeleton is formed on the other surface of the base film 12, the third resin layer 18 is formed. The other surface side of the base film 12 also has excellent scratch resistance.

FIG. 4 shows the transparent conductive layer forming base material 40 according to the fourth embodiment. The transparent conductive layer forming base material 40 according to the fourth embodiment is a base film 12, a second resin layer 16 formed on one surface of the base film 12, and a surface of the second resin layer 16. It has a first resin layer 14 formed in the base film 12 and a protective film 24 arranged on the other surface 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. Further, the protective film 24 is in contact with the other surface of the base film 12 via the pressure-sensitive adhesive layer 22. The first resin layer 14 is provided only on one surface of the base film 12. The transparent conductive layer forming base material 40 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 transparent conductive layer forming base material 40 according to the fourth embodiment has the pressure-sensitive adhesive layer 22 on the other surface of the base film 12 as compared with the transparent conductive layer forming base material 20 according to the second embodiment. The difference is that the protective film 24 is provided therethrough, and other than that, it is the same as the transparent conductive layer forming base material 20 according to the second embodiment, and the description thereof will be omitted for the same configuration.

The protective film 24 can prevent the other surface of the base film 12 from being scratched during handling such as continuous processing by a roll process or the like. The protective film 24 is attached to the other surface of the base film 12 via the pressure-sensitive adhesive layer 22. The protective film 24 is peeled off from the other surface of the base film 12 together with the pressure-sensitive adhesive layer 22 after processing or the like. Therefore, the pressure-sensitive adhesive layer 22 has a stronger adhesive force between the protective film 24 and the pressure-sensitive adhesive layer 22 than the adhesive force between the base film 12 and the pressure-sensitive adhesive layer 22, and the base film 12 and the pressure-sensitive adhesive layer 22 have a stronger adhesive force. The adhesive strength is adjusted so that the interface can be peeled off between 22.

As the material constituting the protective film 24, those exemplified as the material constituting the base film 12 can be appropriately selected. The material for forming the protective film 24 is not particularly limited, but a material having a coefficient of thermal expansion and a coefficient of linear expansion similar to that of the base film 12 is preferable from the viewpoint of excellent suppression of curl due to heat treatment. For example, it is preferable that the material is the same as or the same as that of the base film 12. The same type can be used, for example, polyesters, poly (meth) acrylates, polyamides, and the like.

The thickness of the protective film 24 is not particularly limited, but may be, for example, as long as the base film 12 so that the coefficient of thermal expansion and the coefficient of linear expansion are close to those of the base film 12. Specifically, it can be, for example, within the range of 2 to 500 μm and within the range of 2 to 200 μm.

The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer 22 is not particularly limited, and an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, or the like can be preferably used. In particular, an acrylic pressure-sensitive adhesive is suitable because it has excellent transparency and heat resistance. The acrylic pressure-sensitive adhesive is preferably formed from a pressure-sensitive adhesive composition containing a (meth) acrylic polymer and a cross-linking agent.

The (meth) acrylic polymer is a homopolymer or a copolymer of the (meth) acrylic monomer. 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 chain, or cyclic. More specifically, examples of the alkyl group-containing (meth) acrylic monomer include, for example, isostearyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, and (meth). ) Decyl acrylate, (meth) isononyl acrylate, (meth) nonyl acrylate, (meth) isooctyl acrylate, (meth) octyl acrylate, (meth) isobutyl acrylate, (meth) n-butyl acrylate, ( Pentyl acrylate, (meth) hexyl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, propyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, etc. Can be mentioned.

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

Examples of the hydroxyl group-containing (meth) acrylic monomer include (meth) hydroxylauryl acrylate, (meth) hydroxydecyl acrylate, (meth) hydroxyoctyl acrylate, (meth) hydroxyhexyl acrylate, and (meth) hydroxybutyl acrylate. Examples thereof include hydroxypropyl (meth) acrylate and hydroxyethyl (meth) acrylate. The hydroxyl group may be located at the end of the alkyl chain or may be located in the middle of the alkyl chain.

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

Examples of the cross-linking agent include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, metal chelate-based cross-linking agents, metal alkoxide-based cross-linking agents, carbodiimide-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, and melamine-based cross-linking agents. .. As the cross-linking agent, one of these may be used alone, or two or more thereof may be used in combination.

The pressure-sensitive adhesive composition may contain other additives in addition to the (meth) acrylic polymer and the cross-linking agent. Other additives include cross-linking accelerators, cross-linking retarders, tackifiers, antistatic agents, silane coupling agents, plasticizers, release aids, pigments, dyes, wetting agents, and thickeners. , UV absorbers, preservatives, antioxidants, metal deactivators, alkylating agents, flame retardants and the like. These are appropriately selected and used according to the use and purpose of use of the pressure-sensitive adhesive.

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

FIG. 5 shows the transparent conductive layer forming base material 50 according to the fifth embodiment. In the transparent conductive layer forming base material 50 according to the fifth embodiment, the second resin layer 16 is formed on both surfaces of the base film 12, and the first resin is formed on both surfaces of the second resin layer 16. The layer 14 is formed. 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 transparent conductive layer forming base material 50 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. ing.

In the transparent conductive layer forming base material 50 according to the fifth embodiment, the second resin layer 16 and the first resin layer 14 are base films as compared with the transparent conductive layer forming base material 20 according to the second embodiment. 12 is different in that it is formed on both sides, and other than that, it is the same as the transparent conductive layer forming base material 20 according to the second embodiment, and the description thereof will be omitted.

Since the base material 50 for forming the transparent conductive layer has the first resin layers 14 on both sides of the base film 12, the base material for forming the transparent conductive film having the transparent conductive layers on both sides of the base film 12. Is suitable as.

FIG. 6 shows the transparent conductive layer forming base material 60 according to the sixth embodiment. The transparent conductive layer forming base material 60 according to the sixth embodiment uses two transparent conductive layer forming base materials 10 shown in FIG. 1, and the base film 12 sides of each other are bonded to each other via the pressure-sensitive adhesive layer 28. It is composed of what has been done. The transparent conductive layer forming base material 60 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 transparent conductive layer forming base material 60 has the first resin layers 14 on both sides, the group forming the transparent conductive film having the transparent conductive layers on both sides like the transparent conductive layer forming base material 50. Suitable as a material. The transparent conductive layer forming base material 60 uses two transparent conductive layer forming base materials 10 shown in FIG. 1 and has two base material films 12, so that it is difficult to break in the transparent conductive layer forming step. , Excellent handling.

The pressure-sensitive adhesive layer 28 is for adhering the two base films 12 to each other with good adhesion. It differs from the pressure-sensitive adhesive layer 22 of the transparent conductive layer forming base material 40 shown in FIG. 4 in that it is difficult to peel off. As the pressure-sensitive adhesive (pressure-sensitive adhesive composition) for forming the pressure-sensitive adhesive layer 28, the pressure-sensitive adhesive (pressure-sensitive adhesive composition) in the transparent conductive layer-forming base material 70 according to the seventh embodiment described later can be preferably used.

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

The pressure-sensitive adhesive layer 28 is formed by directly applying the pressure-sensitive adhesive composition on the other surface of the base film 12, and after applying the pressure-sensitive adhesive composition on the surface of the release film, the base material is formed. A method of transferring onto the other surface of the film 12, after the pressure-sensitive adhesive composition is applied and formed on the surface of the first release film, the second release film is bonded, and one of the release films is released. It can be formed by a method of peeling the film and transferring it onto the other surface of the base film 12.

FIG. 7 shows the transparent conductive layer forming base material 70 according to the seventh embodiment. The transparent conductive layer forming base material 70 according to the seventh embodiment has a base film 12, a first resin layer 14 formed on one surface of the base film 12, and the other surface of the base film 12. It has a pressure-sensitive adhesive layer 32 formed on the top and a release film 34 formed on the surface of the pressure-sensitive adhesive layer 32. The first resin layer 14 is in contact with one surface of the base film 12, and the pressure-sensitive 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 transparent conductive layer forming base material 70 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 transparent conductive layer forming base material 70 according to the seventh embodiment has a pressure-sensitive adhesive layer 32 on the other surface of the base material film 12 as compared with the transparent conductive layer forming base material 10 according to the first embodiment. The difference is that it has the release film 34, and other than that, it is the same as the transparent conductive layer forming base material 10 according to the first embodiment, and the description thereof will be omitted for the same configuration.

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

The pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer 32 can contain a known pressure-sensitive adhesive resin such as an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, and a urethane-based pressure-sensitive adhesive. Among them, an acrylic pressure-sensitive adhesive is preferable from the viewpoint of optical transparency and heat resistance. The pressure-sensitive adhesive composition preferably contains a cross-linking agent in order to enhance the cohesive force of the pressure-sensitive adhesive layer 32. Examples of the cross-linking agent include an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, an aziridine-based cross-linking agent, and a chelate-based cross-linking agent.

The pressure-sensitive adhesive composition may contain additives, if necessary. Examples of the additive include known additives such as plasticizers, silane coupling agents, surfactants, antioxidants, fillers, curing accelerators, and curing retarders. Further, from the viewpoint of productivity and the like, it may be diluted with an organic solvent.

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

The pressure-sensitive adhesive layer 32 is formed by directly applying the pressure-sensitive adhesive composition on the other surface of the base film 12, and after applying the pressure-sensitive adhesive composition on the surface of the release film 34, the base film 32 is formed. A method of transferring onto the other surface of the material film 12, after the pressure-sensitive adhesive composition is applied and formed on the surface of the first release film, the second release film is bonded and one of the release films is released. It can be formed by a method of peeling off the mold film and transferring it onto the other surface of the base film 12.

From the viewpoint of good adhesion, the pressure-sensitive adhesive layer 32 preferably has an adhesive force with respect to glass of 4N / 25 mm or more. It is more preferably 6 N / 25 mm or more, still more preferably 10 N / 25 mm or more.

The release film 34 functions as a protective layer of the pressure-sensitive adhesive layer 32 before use, and is peeled off from the pressure-sensitive 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 pressure-sensitive adhesive layer 32 may be subjected to a release treatment. Examples of the mold release agent used for the mold release treatment include silicone-based, fluorine-based, alkyd-based, unsaturated polyester-based, polyolefin-based, and wax-based mold release agents.

Next, the transparent conductive film according to 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 the embodiment of the present invention has a transparent conductive layer 26 on the surface of the first resin layer 14 of the transparent conductive layer forming base material 10. The transparent conductive layer forming base material 10 is the transparent conductive layer forming base material according to the present invention. The transparent conductive film 80 has a base film 12, a first resin layer 14, and a 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 includes zinc oxide, barium oxide, indium tin oxide, indium zinc oxide, zinc oxide, ytterbium oxide, yttrium oxide, tantalum oxide, aluminum oxide, cerium oxide, titanium oxide and the like. Metal oxides can be mentioned. Of these, indium tin oxide and zinc oxide are particularly preferable from the viewpoint of achieving both transparency and conductivity at a high level.

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 is in the range of 15 to 30 nm.

Examples of the transparent conductive layer 26 include a sputtering method, a vacuum vapor deposition method, a CVD method, and an ion plating method. Of these, the sputtering method is preferable from the viewpoint of stably producing a uniform film with low resistance.

The transparent conductive layer 26 preferably has a step of firing the conductive substance after the film formation in order to promote the crystallization of the conductive substance. The firing method is not particularly limited, but for example, it may be performed by using drum heating for sputtering, a hot air heating furnace, a far infrared heating furnace, or the like. The heating temperature at the time of firing may be appropriately selected according to the type of the conductive substance. For example, the temperature may be 50 to 200 ° C, 80 to 180 ° C, 100 to 160 ° C, or the like. The heating time at the time of firing is not particularly limited, but may be 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 configuration, since the transparent conductive layer 26 is provided on the surface of the first resin layer 14 of the transparent conductive layer forming base material 10 according to the present invention, the transparent conductive layer 14 and the first resin layer 14 The transparent conductive layer 26 has excellent adhesion. Further, since the first resin layer 14 is excellent in scratch resistance, it is possible to prevent the surface of the first resin layer 14 from being scratched during handling.

In the transparent conductive film 80 according to the present invention, the transparent conductive layer 26 can be used as an electrode of a touch panel. The electrode of the touch panel is made of a transparent conductive layer 26 formed into a desired electrode pattern. The electrode pattern can be formed by etching the transparent conductive layer 26 or the like.

Next, the touch panel according to the present invention will be described.

The touch panel according to the present invention is configured by using the transparent conductive film 80 according to the present invention, and the transparent conductive layer 26 of the transparent conductive film 80 is used as an electrode of the touch panel. The touch panel is a touch panel such as a capacitance type or a resistance film type. Examples of the touch panel according to the present invention include a GF type and a GF2 type. In the GFF type touch panel, for example, as shown in FIG. 6, a transparent conductive layer in which two base film 12 sides of two transparent conductive layer forming base materials 10 are bonded to each other via an adhesive layer 28. The transparent conductive film in which the transparent conductive layer 26 is formed on the surface of each first resin layer 12 of the forming base material 60, or only on one surface side of the base film 12 as shown in FIG. A transparent conductive film 80 having a resin layer 14 and a transparent conductive layer 26, in which two base film 12 sides of each other are bonded together with a transparent adhesive, and further using a transparent adhesive. The surface of one of the transparent conductive layers 26 is bonded to a transparent base material such as glass or a resin film. Further, the GF2 type touch panel is transparent formed from a transparent conductive layer forming base material 50 having a first resin layer 14 and a transparent conductive layer 26 on both sides of the base film 12, for example, as shown in FIG. It consists of a conductive film bonded to a transparent base material such as glass or resin film with a transparent adhesive.

The image display method of the touch panel according to 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 embodiments, and various modifications can be made without departing from the spirit of the present invention.

For example, in the above embodiment, the surface of the base film 12 is surface-treated 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. Although it may be described, the structure may be such that an easy-adhesion layer is provided on the surface of the base film 12 instead of the surface treatment.

Further, in the above embodiment, the surface unevenness of the first resin layer 14 is determined to add particles having an average particle size larger than the thickness of the layer to which the particles are added, but the method for forming the unevenness is limited to this. It is not something that will be done. For example, the surface irregularities may be formed on a layer that forms surface irregularities such as the first resin layer 14 by mold transfer. Even when particles are added to form surface irregularities, the surface free energy of the particles can be reduced by subjecting the particles to surface treatment or by using a surfactant in combination, and the particles can be placed on the surface of the layer to which the particles are added. May be a method of forming surface irregularities due to particles by unevenly distributing the particles. In this case, the average particle size 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 size 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 even more preferably in the range of 120 to 400 nm. Further, the average particle size is preferably ½ or less of the thickness of the layer to which the particles are added.

And, as shown in FIG. 4, the protective film 24 is shown in the form of being added to the transparent conductive layer forming base material 20 of the second embodiment shown in FIG. 2, but the first embodiment shown in FIG. It may be added to the transparent conductive layer forming base material 10 of the above. Further, it may be added to the transparent conductive film such as the transparent conductive film 80 shown in FIG.

The pressure-sensitive adhesive layer 32 is shown in the form of being added to the transparent conductive layer forming base material 10 of the first embodiment shown in FIG. 1, as shown in FIG. 7, but is transparent as shown in FIGS. 2 to 3. It may be added to the conductive layer forming base material 20 to 30. Further, it may be added to the transparent conductive film such as the transparent conductive film 80 shown in FIG.

Further, the sixth transparent conductive layer forming base material 60 shown in FIG. 6 is formed by bonding the two base material films 12 sides of the two transparent conductive layer forming base materials 10 to each other via the pressure-sensitive adhesive layer 28. Although shown in the form, one or both of the two transparent conductive layer forming base materials 10 may be the transparent conductive layer forming base materials 20 to 30 shown in FIGS. 2 to 3. Further, it may be a transparent conductive film such as the transparent conductive film 80 shown in FIG.

As shown in FIG. 8, the transparent conductive film 80 shows an example in which the transparent conductive layer forming base material 10 of the first embodiment shown in FIG. 1 is used as the transparent conductive layer forming base material. The transparent conductive layer forming base materials 20 to 70 shown in FIGS. 2 to 7 may be used as the transparent conductive layer forming base material.

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

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.

(Preparation of curable composition for forming the first resin layer)
A curable composition for forming the first resin layer was prepared by blending each component with the blending composition (mass%) shown in Table 1.

(Preparation of curable composition for forming the second resin layer)
A curable composition for forming a second resin layer was prepared by blending each component with the blending composition (mass%) shown in Table 1.

(Preparation of Curable Composition for Forming Third Resin Layer)
A curable composition for forming a third resin layer was prepared by blending each component with the blending composition (mass%) shown in Table 1.

(Preparation of base material for forming transparent conductive layer)
(Examples 1 to 3)
A curable composition for forming a second resin layer is coated on one surface of a base film (Toray PET film "Lumilar UH1H", thickness 50 μm) using a # 5 wire bar, and 1 at 80 ° C. After drying for a minute, the second resin layer was formed by irradiating the coating film with ultraviolet rays at a light amount of 200 mJ / cm ^{2 and curing the coating film with ultraviolet rays using a high-pressure mercury lamp.}
Next, a curable composition for forming the first resin layer was applied onto the surface of the second resin layer using a # 4 wire bar, dried at 80 ° C. for 1 minute, and then used with a high-pressure mercury lamp. The first resin layer was formed by irradiating the coating film with ultraviolet rays at a light amount of 200 mJ / cm ^{2 under a nitrogen atmosphere and curing the coating film with ultraviolet rays.}
Then, a curable composition for forming a third resin layer was applied onto the other surface of the base film using a # 4 wire bar, dried at 80 ° C. for 1 minute, and then used with a high-pressure mercury lamp. The third resin layer was formed by irradiating the coating film with ultraviolet rays at a light amount of 200 mJ / cm ^{2 and curing the coating film with ultraviolet rays.}
As described above, the base material for forming the transparent conductive layer according to Examples 1 to 3 was produced.

(Example 4)
After changing the base film to ZEON Corporation COP film "Zeonor Film ZF16-55" (thickness 55 μm) and applying corona treatment on one surface, the wire bar of # 5 was not formed with the second resin layer. The transparent conductive layer forming base material according to Example 4 was produced in the same manner as in Example 1 except that the first resin layer was formed using the above. No third resin layer was formed on the other surface of the base film.

(Examples 5 to 8)
The base film was changed to ZEON Corporation COP film "Zeonor Film ZF16-55" (thickness 55 μm), and one surface of the base film was corona-treated to form a second resin layer, and the surface of the second resin layer was formed. The transparent conductive layer forming base material according to Examples 5 to 8 was produced in the same manner as in Example 1 except that the first resin layer was formed on the wire bar of # 5. No third resin layer was formed on the other surface of the base film.

(Comparative Example 1)
The transparent conductive layer forming base material according to Comparative Example 1 was produced in the same manner as in Example 1 except that the curable composition for forming the first resin layer was different. The curable composition for forming the first resin layer of Comparative Example 1 does not contain an ultraviolet curable resin having a silsesquioxane skeleton.

(Comparative Example 2)
The transparent conductive layer forming base material according to Comparative Example 2 was produced in the same manner as in Example 3 except that the curable composition for forming the first resin layer was different. The curable composition for forming the first resin layer of Comparative Example 2 does not contain an ultraviolet curable resin having a silsesquioxane skeleton.

(Comparative Example 3)
The transparent conductive layer forming base material according to Comparative Example 3 was produced in the same manner as in Example 3 except that the curable composition for forming the first resin layer was different. The curable composition for forming the first resin layer of Comparative Example 3 does not contain an ultraviolet curable resin having a silsesquioxane skeleton, but contains a thermosetting epoxy resin having a silsesquioxane skeleton. It has been.

The materials used as the materials for the first resin layer, the second resin layer, and the third resin layer are as follows.
-SQ-containing UV resin <1>: Ultraviolet curable resin having a silsesquioxane skeleton ("MAC-SQ HDM" manufactured by Toagosei, methacrylic resin, solvent (PGB) solid content concentration 50% by mass, functional group; methacryloyl group , Functional group equivalent 239 g / eq)
-UV resin containing SQ <2>: UV curable resin having a silsesquioxane skeleton ("MAC-SQ SI-20" manufactured by Toagosei, methacrylic resin, solid content concentration 100% by mass, functional group; methacryloyl group, functional Base equivalent 224 g / eq)
UV resin <1>: UV curable resin that does not have a silsesquioxane skeleton (“Riodurus TYZ59-10-S” manufactured by Toyochem, zirconium particle-containing (meth) acrylic resin, solvent (PGM, MIBK, aliphatic) System solvent and cyclohexanone), solid content concentration 40% by mass, high refractive index hard coat agent)
UV resin <2>: UV curable resin that does not have a silsesquioxane skeleton ("Opstar Z7527" manufactured by Arakawa Chemical Industries, silica particle-containing (meth) acrylic resin, solvent (MEK), solid content concentration 50 mass %)
UV resin <3>: UV curable resin that does not have a silsesquioxane skeleton (“Riodurus TYZ65-01” manufactured by Toyochem, zirconium particle-containing (meth) acrylic resin, solvent (PGM, MIBK, aliphatic solvent) , And cyclohexanone), solid content concentration 40% by mass, high refractive index hard coat agent)
UV resin <4>: UV curable resin that does not have a silsesquioxane skeleton (Aica Kogyo "Aika Aitron Z-735-35L", (meth) acrylic resin, solvent (ethyl acetate, butyl acetate, And MEK), solid content concentration 50% by mass)
UV resin <5>: UV curable resin having no silsesquioxane skeleton (DIC "GRANDIC PC16-2291", (meth) acrylic resin, solvent (MEK, BuAc, and MIBK), solid content concentration 40% by mass)
-Resin particles: Polymethyl methacrylate particles (1% by 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
-SQ-containing EP resin: Thermosetting epoxy resin having a silsesquioxane skeleton ("Composelan SQ506" manufactured by Arakawa Chemical Industries)
-EP curing agent: 1-benzyl-2-methylimidazole-solvent <1>: methyl ethyl ketone (MEK)
-Solvent <2>: Butyl acetate (BuAc)
-Solvent <3>: Propylene glycol normal 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 substrate for forming a transparent conductive layer were measured by a spectroscopic interference method using a "Filmetics F20 film thickness measuring system" manufactured by Filmometrics. The thickness of the layer containing the resin particles was defined as the thickness of the portion where the resin particles did not exist in the thickness direction.

Using each of the prepared base materials for forming a transparent conductive layer, indium tin oxide was sputtered on the surface of the first resin layer to a thickness of 20 nm to form an ITO layer, and copper was placed on the surface of the ITO layer at 200 nm. After sputtering to a thickness to form a copper layer, the copper layer was allowed to stand in a constant temperature bath at 150 ° C. for 1 hour to crystallize the ITO layer. From the above, a transparent conductive film was produced.

(ITO adhesion)
A grid-like cut was made from the copper surface side of the produced transparent conductive film to the interface between the ITO layer and the first resin layer, and an adhesion test based on JIS K5400-8.5 (JIS D0202) was carried out. Of the 100 squares, those in which no peeling was observed were rated as good "○", and those in which peeling was observed in even one square were rated as "x". Among the good ones, those in which no peeling was observed around the notch on the outside of 100 squares were marked as particularly good "◎".

(Scratch resistance)
Using each of the prepared base materials for forming a transparent conductive layer, set it in a Gakushin type friction fastness tester manufactured by Tester Sangyo, and use "Steel Wool # 0000" made by Nippon Steel Wool with a load of 200 g to form the first resin layer. The surface was rubbed 20 times. After that, the surface of the first resin layer was visually observed from directly above under a fluorescent lamp, and those without scratches were marked as good "○" and those with scratches were marked with "x".

From Examples and Comparative Examples, the first resin layer is made of a cured product of a curable composition containing an ultraviolet curable resin having a silsesquioxane skeleton, so that the transparent conductive layer has excellent adhesion and the first resin. It can be seen that the layer has excellent scratch resistance. In Comparative Examples 1 and 2, since the curable composition for forming the first resin layer does not contain an ultraviolet curable resin having a silsesquioxane skeleton, the adhesiveness of the transparent conductive layer is inferior. In Comparative Example 3, the curable composition for forming the first resin layer contains only a thermosetting epoxy resin instead of an ultraviolet curable resin although it has a silsesquioxane skeleton, so that the film thickness is thick. Nevertheless, the scratch resistance of the first resin layer is inferior. From the comparison between the examples, it can be seen that when the content of the SQ-containing UV resin in the first resin layer is 5% by mass or more, the adhesion to ITO is particularly excellent.

Although the examples of the present invention have been described above, the present invention is not limited to the above examples, and various modifications can be made without departing from the spirit of the present invention.

10, 20, 30, 40, 50, 60, 70 Base material for forming a transparent conductive layer 12 Base film 14 First resin layer 16 Second resin layer 18 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 layer film

Claims (12)

A base material for forming a transparent conductive layer, which is a base material for forming a transparent conductive layer.
It has a base film and a first resin layer formed on the surface of the base film.
A base material for forming a transparent conductive layer, wherein the first resin layer is made of a cured product of a curable composition containing an ultraviolet curable resin having a silsesquioxane skeleton. The base material for forming a transparent conductive layer according to claim 1, wherein the ultraviolet curable resin having a silsesquioxane skeleton is a (meth) accrete having a silsesquioxane skeleton. The 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. Substrate for formation. It is characterized by having a second resin layer made of a cured product of a curable composition containing an ultraviolet curable resin having no silsesquioxane skeleton between the base film and the first resin layer. The base material for forming a transparent conductive layer according to any one of claims 1 to 3. The first resin layer is provided only on one surface of the base film, and contains an ultraviolet curable resin having no silsesquioxane skeleton on the other surface of the base film. The base material for forming a transparent conductive layer according to any one of claims 1 to 4, which has a third resin layer made of a cured product of the curable composition. The first resin layer is provided only on one surface of the base film, and has a protective film on the other surface of the base film via an adhesive layer. Item 2. The substrate for forming a transparent conductive layer according to any one of Items 1 to 5. The base material for forming a transparent conductive layer according to any one of claims 1 to 4, wherein the first resin layer is provided on both surfaces of the base film. A transparent conductive film 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 according to claim 8, wherein the transparent conductive layer is used as an electrode of a touch panel. A touch panel according to claim 8, wherein the transparent conductive layer is used for an electrode. A method for manufacturing a base material for forming a transparent conductive layer, which is a base material for forming a transparent conductive layer.
A substrate for forming a transparent conductive layer, which comprises forming a first resin layer made of a cured product of a curable composition containing an ultraviolet curable resin having a silsesquioxane skeleton on the surface of the substrate film. Production method. A second resin layer made of a cured product of a curable composition containing an ultraviolet curable resin having no silsesquioxane skeleton is formed on the surface of the base film, and then on the surface of the second resin layer. The method for producing a base material for forming a transparent conductive layer according to claim 11, wherein the first resin layer is formed therein.

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