WO2018179102A1 - Transfer-type photosensitive refractive index adjustment film, method for forming refractive index adjustment pattern, cured film, and touch panel - Google Patents

Abstract

The present invention provides a transfer-type photosensitive refractive index adjustment film having a support film, a first resin layer disposed on the support film, and a second resin layer disposed on the first resin layer and containing metal oxide particles, wherein the first resin layer includes: a binder polymer, which contains a group having a branched structure and/or an alicyclic structure in a side chain, a group having an acidic group in a side chain, and a group having an ethylenically unsaturated group in a side chain; a photopolymerizable compound; a photopolymerization initiator; and a phosphate ester having an ethylenically unsaturated bond, and the content in the first resin layer, of the phosphate ester having an ethylenically unsaturated bond is 1.5-3.0 parts by mass with respect to 100 parts by mass total of the binder polymer and the photopolymerizable compound.

Description

Transfer type photosensitive refractive index adjusting film, forming method of refractive index adjusting pattern, cured film, and touch panel

The present invention relates to a transfer type photosensitive refractive index adjusting film, a method for forming a refractive index adjusting pattern, a cured film, and a touch panel.

For large electronic devices such as personal computers and televisions, small electronic devices such as car navigation, mobile phones, smartphones, electronic dictionaries, and display devices such as OA (Office Automation, Office Automation) and FA (Factory Automation, Factory Automation) devices Liquid crystal display elements and touch panels (touch sensors) are used.

Various types of touch panels have been put to practical use, but in recent years, the use of projected capacitive touch panels has progressed. In general, in a projected capacitive touch panel, a plurality of X electrodes and a plurality of Y electrodes orthogonal to the X electrodes are formed in order to express two-dimensional coordinates by the X axis and the Y axis. As a material for these electrodes, ITO (Indium-Tin-Oxide) is the mainstream.

By the way, since the frame area of the touch panel is an area where the touch position cannot be detected, reducing the area of the frame area is an important factor for improving the product value. In general, a metal wiring such as copper is formed in the frame region in order to transmit a touch position detection signal.

However, when the touch panel is contacted with a fingertip or the like, corrosive components such as moisture and salt may enter the inside from the sensing area. When a corrosive component enters the inside of the touch panel, the metal wiring corrodes, and there is a risk of an increase in electrical resistance or disconnection between the electrode and the driving circuit.

In order to prevent corrosion of metal wiring, a method of forming a protective film on a base material for a touch panel using a photosensitive resin composition is known. For example, as a method of providing a protective film (for example, a resist film) at a required location, a method of providing a photosensitive layer containing a photosensitive resin composition on a predetermined substrate, and exposing and developing the photosensitive layer is known. (For example, refer to Patent Document 1 below).

By the way, as described above, the projected capacitive touch panel has a large color difference due to a difference in optical reflection characteristics between a portion where the transparent electrode pattern is formed and a portion where the transparent electrode pattern is not formed. In addition, there is a problem of so-called “bone appearance phenomenon” in which the transparent electrode pattern is reflected on the screen. In addition, reflection between the transparent electrode pattern and the visibility improving film (OCA: Optical Clear Adhesive) that adheres the cover glass and the transparent electrode pattern used for modularization between the base material and the transparent electrode. There is also a problem that the light intensity increases and the transmittance of the screen decreases.

On the other hand, for example, in the following Patent Document 2, by providing an index matching layer (optical adjustment layer) between the base material and the transparent electrode pattern, a portion where the transparent electrode pattern is formed and a portion where the transparent electrode pattern is not formed A transparent conductive resin substrate that reduces the color difference and prevents the bone-visible phenomenon and the decrease in the transmittance of the screen is disclosed.

Also, for example, in Patent Document 3 below, as a technique for preventing the transparent electrode pattern from being visually recognized, a low refractive index first curable transparent resin layer adjusted to a specific refractive index range and a high refractive index A transfer film having a second curable transparent resin layer adjacent thereto is disclosed.

International Publication No. 2013/084873 JP-A-8-240800 International Publication No. 2014/084112

A protective film in a display device such as a touch panel is required to have good adhesion to a base material in order to prevent corrosion of metal wiring. Even when an index matching layer is provided between the transparent electrode pattern and the transparent electrode pattern, it is required to have good adhesion to the index matching layer. The index matching layer is composed of a resin composition containing metal particles such as ZrO ₂ , TiO ₂ , and SiO ₂ , but the index matching layer surface layer has active groups such as hydroxyl groups that contribute to adhesion to the protective film. Since there are few, there exists a subject that the adhesive force of an index matching layer and a protective film is low.

The protective film is required to have good developability on metal wiring such as copper wiring. Furthermore, the transfer film for forming the protective film is required to have good laminating properties on a substrate having a transparent electrode pattern.

However, in the conventional transfer film for forming a protective film, all of the good adhesion of the protective film to the substrate, the good developability on the metal wiring, and the good laminating property to the substrate are at a high level. It was difficult to achieve.

The present invention has been made in view of the above-described problems of the prior art, and is a cured film (protective film) that has achieved good adhesion to a substrate and good developability on a metal wiring at a high level. ) And a transfer type photosensitive refractive index adjusting film having good laminating property to a substrate, and a method for forming a refractive index adjusting pattern using the same, a cured film, and a touch panel are provided. Objective.

In order to achieve the above object, the present invention provides a support film, a first resin layer provided on the support film, and metal oxide particles provided on the first resin layer. Two resin layers, wherein the first resin layer is a group having a branched structure and / or an alicyclic structure in the side chain, a group having an acidic group in the side chain, and an ethylenically unsaturated group in the side chain. A binder polymer containing a group having a group, a photopolymerizable compound, a photopolymerization initiator, and a phosphoric acid ester having an ethylenically unsaturated bond, and the ethylenically unsaturated group in the first resin layer. A transfer type photosensitive refractive index adjusting film, wherein the content of a phosphate having a saturated bond is 1.5 to 3.0 parts by mass with respect to 100 parts by mass in total of the binder polymer and the photopolymerizable compound. provide.

According to the transfer type photosensitive refractive index adjusting film, the first resin layer contains the specific binder polymer, photopolymerizable compound, photopolymerization initiator, and phosphate ester having an ethylenically unsaturated bond. By setting the content of the phosphate ester within the above specific range, a cured film (protective film) that achieves good adhesion to the substrate and good developability on the metal wiring at a high level. ) And can have a good laminating property to the substrate. In particular, according to the transfer type photosensitive refractive index adjusting film, a cured film having good adhesion can be formed even on a substrate having an index matching layer and a substrate having a transparent electrode pattern.

The photopolymerizable compound may contain a compound having a tricyclodecane skeleton or a tricyclodecene skeleton. When a compound having a tricyclodecane skeleton or a tricyclodecene skeleton is used, the adhesion between the obtained cured film and the substrate can be further improved.

The photopolymerization initiator may contain an oxime ester compound and / or a phosphine oxide compound. When these photopolymerization initiators are used, a refractive index adjustment pattern can be formed with sufficient resolution even with a thin film having a thickness of 10 μm or less.

The binder polymer may have a carboxyl group. Here, the binder polymer includes (meth) acrylic acid, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, styrene, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meta It may be a binder polymer having a structural unit derived from at least one compound selected from the group consisting of acrylate butyl ester, (meth) acrylic acid 2-ethylhexyl ester and (meth) acrylic acid cyclohexyl ester. The binder polymer may be a binder polymer having a structural unit derived from (meth) acrylic acid cyclohexyl ester. When the binder polymer is used, the alkali developability, patterning property and transparency of the first resin layer can be improved. Moreover, when the binder polymer which has a structural unit derived from (meth) acrylic-acid cyclohexyl ester is used, the adhesiveness of the cured film obtained and a base material can be improved more.

The second resin layer includes at least one metal oxide particle selected from the group consisting of zirconium oxide, titanium oxide, tin oxide, zinc oxide, indium tin oxide, indium oxide, aluminum oxide, and yttrium oxide. May be. In this case, it is easy to adjust the refractive index of the second resin layer at a wavelength of 633 nm to an appropriate range.

The thickness of the second resin layer may be 0.01 to 1 μm. When the thickness of the second resin layer is within the above range, the reflected light intensity of the entire touch screen on the touch panel can be further reduced.

In the present invention, the second resin layer and the first resin layer of the transfer type photosensitive refractive index adjusting film of the present invention are also formed on the base material. A step of laminating to adhere, and a step of forming a refractive index adjustment pattern by exposing the second resin layer and the predetermined portion of the first resin layer on the base material after exposure and removing other than the predetermined portion. And a method of forming a refractive index adjustment pattern.

The present invention is also a cured product obtained by curing only the first resin layer or both the first resin layer and the second resin layer of the transfer type photosensitive refractive index adjusting film of the present invention. Providing a membrane.

The present invention further provides a touch panel comprising a refractive index adjustment pattern comprising a cured product of the second resin layer and a cured product of the first resin layer in the transfer type photosensitive refractive index adjusting film of the present invention. In the touch panel, the refractive index adjustment pattern may be provided on a base material having an index matching layer.

ADVANTAGE OF THE INVENTION According to this invention, while being able to form the cured film (protective film) in which the favorable adhesiveness with respect to a base material and the favorable developability on a metal wiring were achieved at the high level, it can laminate to a base material A transfer type photosensitive refractive index adjusting film having good properties, a method for forming a refractive index adjusting pattern using the same, a cured film, and a touch panel can be provided. The cured film formed using the transfer type photosensitive refractive index adjusting film of the present invention can obtain good adhesion even to a substrate having an index matching layer and a substrate having a transparent electrode pattern. it can.

It is a schematic cross section which shows the transfer type photosensitive refractive index adjustment film which concerns on one Embodiment of this invention. It is a schematic cross section which shows the laminated body which equips the base material with a transparent electrode pattern with the cured film formed using the transfer type photosensitive refractive index adjustment film which concerns on one Embodiment of this invention. It is a model top view which shows the touchscreen which concerns on one Embodiment of this invention.

Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings as the case may be. However, the present invention is not limited to the following embodiments. In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid, and “(meth) acrylate” means acrylate or a corresponding methacrylate. “A or B” only needs to include one of A and B, or may include both.

In addition, in this specification, the term “layer” includes a structure formed in a part in addition to a structure formed in the entire surface when observed as a plan view. In addition, in this specification, the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended action of the process is achieved. included. The numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.

Furthermore, in the present specification, the content of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity. In addition, the exemplary materials may be used alone or in combination of two or more unless otherwise specified.

Also, in the numerical ranges described stepwise in this specification, the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.

<Transfer type photosensitive refractive index adjusting film>
The transfer type photosensitive refractive index adjusting film of the present embodiment includes a support film, a first resin layer provided on the support film, and metal oxide particles provided on the first resin layer. And a second resin layer. The transfer type photosensitive refractive index adjusting film may further include a protective film provided on the second resin layer.

FIG. 1 is a schematic cross-sectional view showing a transfer type photosensitive refractive index adjusting film according to an embodiment of the present invention. A transfer type photosensitive refractive index adjusting film 1 shown in FIG. 1 includes a support film 10, a first resin layer 20 provided on the support film 10, and a first resin layer 20 provided on the first resin layer. A second resin layer 30 and a protective film 40 provided on the second resin layer 30 are provided.

By using the transfer type photosensitive refractive index adjustment film, for example, the metal wiring on the frame of the touch panel or the transparent electrode protection function of the touch panel and the transparent electrode pattern invisibility or the touch screen visibility improvement function are satisfied. A cured film can be formed in a lump.

(Support film)
As the support film 10, a polymer film can be used. Examples of the material of the polymer film include polyethylene terephthalate, polycarbonate, polyethylene, polypropylene, polyethersulfone, and cycloolefin polymer.

The thickness of the support film 10 is preferably 5 to 100 μm, preferably 10 to 70 μm, from the viewpoint of ensuring coverage and suppressing the reduction in resolution when irradiated with actinic rays through the support film 10. Is more preferably 15 to 40 μm, and particularly preferably 15 to 35 μm.

(First resin layer)
The first resin layer 20 includes a binder polymer (hereinafter also referred to as (A) component), a photopolymerizable compound (hereinafter also referred to as (B) component), and a photopolymerization initiator (hereinafter referred to as (C) component). And a phosphoric acid ester having an ethylenically unsaturated bond (hereinafter also referred to as “component (E)”).

As the component (A), a binder polymer containing a group having a branched structure and / or an alicyclic structure in the side chain, a group having an acidic group in the side chain, and a group having an ethylenically unsaturated group in the side chain. Used. The binder polymer includes, for example, a monomer containing a group having a branched structure and / or an alicyclic structure in the side chain, a monomer containing a group having an acidic group in the side chain, and, if necessary, a copolymer with these monomers. It can be obtained by introducing a group having an ethylenically unsaturated group in the side chain into a copolymer obtained by copolymerizing a polymerizable monomer.

Specific examples of the monomer containing a group having a branched structure in the side chain include, for example, i-propyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, and (meth) acrylic. T-butyl acid, i-amyl (meth) acrylate, t-amyl (meth) acrylate, sec-iso-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3- (meth) acrylic acid 3- Examples include octyl and (meth) acrylic acid t-octyl. Among these, i-propyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl methacrylate are preferable, and i-propyl methacrylate and t-butyl methacrylate are more preferable.

Next, specific examples of the monomer containing a group having an alicyclic structure in the side chain include, for example, (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. More specific examples include, for example, (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, ) -3-methyl-1-adamantyl acrylate, 3,5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyladamantyl (meth) acrylate, 3-methyl-5 (meth) acrylate -Ethyl-1-adamantyl, (meth) acrylic acid-3,5,8-triethyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth) acrylic acid 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, (meth) actyl Octahydro-4,7-mentanoinden-5-yl sulfate, octahydro-4,7-mentanoinden-1-ylmethyl (meth) acrylate, (meth) acrylic acid-1-menthyl, (meth) acrylic acid Dicyclopentanyl, (meth) acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo [3.1.1] heptyl, (meth) acrylic acid-3,7,7-trimethyl-4-hydroxy -Bicyclo [4.1.0] heptyl, (nor) bornyl (meth) acrylate, isobornyl (meth) acrylate, fentil (meth) acrylate, -2,2,5-trimethylcyclohexyl (meth) acrylate, Examples include cyclohexyl (meth) acrylate. Among these (meth) acrylic acid esters, cyclohexyl (meth) acrylic acid, (nor) bornyl (meth) acrylic acid, isobornyl (meth) acrylic acid, (meth) acrylic acid-1-adamantyl, (meth) acrylic acid- 2-adamantyl, phentyl (meth) acrylate, 1-menthyl (meth) acrylate, dicyclopentanyl (meth) acrylate are preferred, cyclohexyl (meth) acrylate, (nor) bornyl (meth) acrylate, ( Particularly preferred are isobornyl (meth) acrylate and 2-adamantyl (meth) acrylate.

When the component (A) contains a group having a branched structure and / or an alicyclic structure in the side chain, good adhesion to the substrate, in particular, good adhesion to the substrate having an index matching layer can be obtained. it can. Moreover, the moisture permeability of a protective film can be reduced by having group which has alicyclic structure in a side chain.

Specific examples of the monomer containing a group having an acidic group in the side chain can be appropriately selected from known ones. For example, (meth) acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl ester , Fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer, addition reaction product of hydroxyl group-containing monomer and cyclic acid anhydride, ω-carboxy-polycaprolactone mono (meta ) Acrylate and the like. As these, those produced as appropriate may be used, or commercially available products may be used.

When the component (A) contains a group having an acidic group in the side chain, patterning by alkali development can be performed.

As the component (A), it is preferable to use a polymer having a carboxyl group as the acidic group from the viewpoint of improving the patterning property by alkali development.

The (A) component is preferably a copolymer containing structural units derived from (meth) acrylic acid and (meth) acrylic acid alkyl ester. The copolymer may contain in the structural unit other monomers that can be copolymerized with the (meth) acrylic acid and the (meth) acrylic acid alkyl ester. Specific examples of the other monomer include (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, and styrene.

Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid Examples thereof include hydroxyl ethyl ester.

Among these, (meth) acrylic acid, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, styrene, from the viewpoint of alkali developability (particularly developability with respect to an inorganic alkaline aqueous solution), patternability, and transparency. (Meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl maleimide, Binder polymers having a structural unit derived from at least one compound selected from the group consisting of hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate are preferred, (meth) acrylic acid, (meth) acrylate Consists of glycidyl rillate, benzyl (meth) acrylate, styrene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate A binder polymer having a structural unit derived from at least one compound selected from the group is more preferable, and is selected from the group consisting of (meth) acrylic acid, (meth) acrylic acid alkyl ester, and (meth) acrylic acid glycidyl ester. Particularly preferred are binder polymers having structural units derived from at least one compound. By using a binder polymer having a structural unit derived from these compounds, it is possible to form a cured film in which good adhesion to a substrate and good developability on a metal wiring are achieved at a high level. It becomes easier and the laminating property to the substrate becomes better.

The group having an ethylenically unsaturated group in the side chain is not particularly limited, and a (meth) acryloyl group is preferred as the ethylenically unsaturated group. The connection between the ethylenically unsaturated group and the monomer is not particularly limited as long as it is a divalent linking group such as an ester group, an amide group, or a carbamoyl group. The method of introducing an ethylenically unsaturated group into the side chain can be appropriately selected from known methods. For example, a method of adding a (meth) acrylate having an epoxy group to a group having an acidic group, a hydroxy group Examples thereof include a method of adding a (meth) acrylate having an isocyanate group to a group having the same, a method of adding a (meth) acrylate having a hydroxy group to a group having an isocyanate group, and the like. Among these, the method of adding (meth) acrylate having an epoxy group to a repeating unit having an acidic group is most preferable because it is the easiest to produce and is low in cost.

The (meth) acrylate having an ethylenically unsaturated group and an epoxy group is not particularly limited as long as it has these. For example, the compound represented by the following general formula (6) and the following general formula (7) Are preferred.

In General Formula (6), R ¹ represents a hydrogen atom or a methyl group, and L ¹ represents a divalent organic group.

In general formula (7), R ² represents a hydrogen atom or a methyl group, L ² represents a divalent organic group, and W represents a 4- to 7-membered aliphatic hydrocarbon group.

Of the compound represented by the general formula (6) and the compound represented by the general formula (7), the compound represented by the general formula (6) is more than the compound represented by the general formula (7). preferable. As the compounds represented by the general formulas (6) and (7), compounds in which L ¹ and L ² are each independently an alkylene group having 1 to 4 carbon atoms are more preferable.

The compound represented by the general formula (6) or the compound represented by the general formula (7) is not particularly limited, and examples thereof include compounds represented by the following formulas (8) to (17). It is done.

When component (A) contains a group having an ethylenically unsaturated group in the side chain, good adhesion to the substrate, particularly good adhesion to the substrate having an index matching layer can be obtained. Further, the moisture permeability of the protective film can be reduced.

Other monomers that can be copolymerized with the above-described monomers used as necessary are not particularly limited. For example, (meth) acrylic acid ester having no branched structure and / or alicyclic structure, styrene, vinyl ether, two monomers. And monomers having a basic acid anhydride group, a vinyl ester group, a hydrocarbon alkenyl group, and the like.

Based on the total amount of the monomer constituting the component (A), the ratio of the monomer constituting the group having a branched structure and / or alicyclic structure in the side chain is preferably 10 to 70 mol%, preferably 15 to 65 mol. % Is more preferable, and 20 to 60 mol% is particularly preferable. The ratio of the monomer constituting the group having an acidic group in the side chain based on the total amount of the monomer constituting the component (A) is preferably 5 to 70 mol%, and preferably 10 to 60 mol%. Is more preferable, and 20 to 50 mol% is more preferable. Further, the ratio of the monomer constituting the group having an ethylenically unsaturated group in the side chain based on the total amount of the monomer constituting the component (A) is preferably 5 to 70 mol%, and 10 to 60 mol%. Is more preferable, and 20 to 50 mol% is more preferable. By satisfy | filling the ratio of the said monomer, the favorable adhesiveness with respect to the base material which may have the patternability by alkali image development, the laminating property to a base material, and the index matching layer can be improved with sufficient balance.

The weight average molecular weight of the component (A) is preferably 10,000 to 200,000, more preferably 15,000 to 150,000, and more preferably 30,000 to 150,000 from the viewpoint of resolution. More preferably, it is particularly preferably 30,000 to 100,000, and most preferably 40,000 to 100,000. In addition, a weight average molecular weight can be measured by the gel permeation chromatography method described in the Example of this specification.

The acid value of the component (A) is preferably 75 mgKOH / g or more from the viewpoint of easily forming a cured film (protective film) having a desired shape by alkali development. From the viewpoint of achieving both controllability of the cured film shape and rust prevention of the cured film, the acid value of the component (A) is preferably 75 to 200 mgKOH / g, and preferably 75 to 150 mgKOH / g. More preferably, it is more preferably 75 to 120 mgKOH / g. In addition, an acid value can be measured by the method described in the Example of this specification.

The first resin layer 20 contains a group having a branched structure and / or an alicyclic structure in the side chain, a group having an acidic group in the side chain, and a group having an ethylenically unsaturated group in the side chain. (A) A binder polymer other than the binder polymer may be further contained.

As the component (B), a photopolymerizable compound having an ethylenically unsaturated group can be used. Examples of the photopolymerizable compound having an ethylenically unsaturated group include a monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group in the molecule and two polymerizable ethylenically unsaturated groups in the molecule. Bifunctional vinyl monomers or polyfunctional vinyl monomers having at least three polymerizable ethylenically unsaturated groups in the molecule can be mentioned.

Examples of the monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group in the molecule include those exemplified as monomers used for the synthesis of a copolymer which is a preferred example of the component (A). Can be mentioned.

The bifunctional vinyl monomer having two polymerizable ethylenically unsaturated groups in the molecule includes a compound having a tricyclodecane skeleton or a tricyclodecene skeleton from the viewpoint of reducing the moisture permeability of the cured film. preferable. From the viewpoint of inhibiting corrosion of the metal wiring and transparent electrode pattern, it is preferable that the compound having a tricyclodecane skeleton or a tricyclodecene skeleton includes a di (meth) acrylate compound represented by the following general formula (B-1). .

[In General Formula (B-1), R ³¹ and R ³² each independently represent a hydrogen atom or a methyl group, X represents a divalent group having a tricyclodecane skeleton or a tricyclodecene skeleton, and R ³³ and R ³⁴ each independently represents an alkylene group having 1 to 4 carbon atoms, n and m each independently represents an integer of 0 to 2, and p and q each independently represents an integer of 0 or more. , P + q = 0 to 10 is selected. ]

In the general formula (B-1), R ³³ and R ³⁴ are preferably an ethylene group or a propylene group, and more preferably an ethylene group. The propylene group may be either an n-isopropylene group or an isopropylene group.

According to the compound represented by the general formula (B-1), the divalent group having a tricyclodecane skeleton or a tricyclodecene skeleton contained in X has a bulky structure, so that the cured film has a low viscosity. Moisture permeability can be realized, and the corrosion resistance of the metal wiring and the transparent electrode can be improved. Here, “tricyclodecane skeleton” and “tricyclodecene skeleton” in the present specification refer to the following structures (where each bond is an arbitrary position).

As the compound having a tricyclodecane skeleton or a tricyclodecene skeleton, a compound having a tricyclodecane skeleton such as tricyclodecane dimethanol di (meth) acrylate is preferable from the viewpoint of low moisture permeability of the obtained cured film pattern. These are available as DCP and A-DCP (both manufactured by Shin-Nakamura Chemical Co., Ltd.).

In the component (B), the proportion of the compound having a tricyclodecane skeleton or a tricyclodecene skeleton is, among the total amount of 100 parts by mass of the photopolymerizable compound contained in the photosensitive resin composition, from the viewpoint of reducing moisture permeability. , 50 parts by mass or more, preferably 70 parts by mass or more, and more preferably 80 parts by mass or more.

A bifunctional vinyl monomer having two polymerizable ethylenically unsaturated groups in the molecule, other than a compound having a tricyclodecane skeleton or a tricyclodecene skeleton, includes polyethylene glycol di (meth) acrylate and trimethylolpropane. Examples include di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxypolypropoxyphenyl) propane, and bisphenol A diglycidyl ether di (meth) acrylate.

As the polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups in the molecule, conventionally known ones can be used without particular limitation. From the viewpoint of corrosion prevention and developability of metal wiring or transparent electrode, the polyfunctional vinyl monomer includes a (meth) acrylate compound having a skeleton derived from trimethylolpropane such as trimethylolpropane tri (meth) acrylate; tetramethylolmethane (Meth) acrylate compounds having a skeleton derived from tetramethylolmethane such as tri (meth) acrylate and tetramethylolmethanetetra (meth) acrylate; derived from pentaerythritol such as pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate (Meth) acrylate compounds having the following skeleton: bones derived from dipentaerythritol such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate A (meth) acrylate compound having a skeleton derived from ditrimethylolpropane such as ditrimethylolpropane tetra (meth) acrylate; or a (meth) acrylate compound having a skeleton derived from diglycerin; derived from cyanuric acid It is preferable to use a (meth) acrylate compound having a skeleton.

A monomer having at least three polymerizable ethylenically unsaturated groups in the molecule and a bifunctional vinyl monomer having one polymerizable ethylenically unsaturated group in the molecule or two polymerizable ethylenically unsaturated groups in the molecule; When a bifunctional vinyl monomer having a saturated group is used in combination, the ratio to be used is not particularly limited, but from the viewpoint of preventing photocuring and electrode corrosion, at least three polymerizable ethylenically unsaturated groups in the molecule. The proportion of the monomer having a ratio of 100 parts by mass of the total amount of the photopolymerizable compound contained in the photosensitive resin composition is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and 75 More preferably, it is at least part by mass.

The content of the component (A) and the component (B) is preferably 35 to 85 parts by mass of the component (A) with respect to 100 parts by mass of the total amount of the components (A) and (B). The amount is more preferably 80 parts by mass, further preferably 50 to 70 parts by mass, and particularly preferably 55 to 65 parts by mass. In particular, the component (A) is preferably 35 parts by mass or more with respect to 100 parts by mass of the total amount of the component (A) and the component (B) in terms of maintaining the pattern formability and transparency of the cured film. 40 parts by mass or more, more preferably 50 parts by mass or more, and particularly preferably 55 parts by mass or more.

As the component (C), conventionally known photopolymerization initiators can be used without particular limitation, but it is preferable to use a photopolymerization initiator having high transparency. The component (C) preferably contains an oxime ester compound and / or a phosphine oxide compound in that a cured resin film pattern can be formed with sufficient resolution even on a substrate with a thickness of 10 μm or less. Examples of the phosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

The oxime ester compound is preferably a compound represented by the following general formula (1), a compound represented by the following general formula (2), or a compound represented by the following general formula (3).

In the formula (1), R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group, and having 1 to 8 carbon atoms An alkyl group, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group is preferable, and an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group or a tolyl group is preferable. More preferred is a methyl group, a cyclopentyl group, a phenyl group or a tolyl group. R ¹³ represents —H, —OH, —COOH, —O (CH ₂ ) OH, —O (CH ₂ ) ₂ OH, —COO (CH ₂ ) OH or —COO (CH ₂ ) ₂ OH; It is preferably H, —O (CH ₂ ) OH, —O (CH ₂ ) ₂ OH, —COO (CH ₂ ) OH, or —COO (CH ₂ ) ₂ OH, and —H, —O (CH ₂ ) ₂ OH or —COO (CH ₂ ) ₂ OH is more preferable.

In the formula (2), two R ¹⁴ each independently represents an alkyl group having 1 to 6 carbon atoms, and is preferably a propyl group. R ¹⁵ represents NO ₂ or ArCO (wherein Ar represents an aryl group), and Ar is preferably a tolyl group. R ¹⁶ and R ¹⁷ each independently represent an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group, preferably a methyl group, a phenyl group, or a tolyl group.

In the formula (3), R ¹⁸ represents an alkyl group having 1 to 6 carbon atoms, and is preferably an ethyl group. R ¹⁹ is an organic group having an acetal bond, and is preferably a substituent corresponding to R ¹⁹ in a compound represented by the formula (3-1) described later. R ²⁰ and R ²¹ each independently represents an alkyl group having 1 to 12 carbon atoms, a phenyl group or a tolyl group, preferably a methyl group, a phenyl group or a tolyl group, and more preferably a methyl group. . R ²² represents a hydrogen atom or an alkyl group.

The compound represented by the general formula (1) is available as IRGACURE OXE 01 (manufactured by BASF Corporation, product name).

The compound represented by the above general formula (2) is available as DFI-091 (product name, manufactured by Daito Chemix Co., Ltd.).

The compound represented by the general formula (3) is available as, for example, Adekaoptomer N-1919 (product name, manufactured by ADEKA Corporation).

The content of the component (C) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B) in terms of excellent photosensitivity and resolution. It is more preferably from 5 to 5 parts by mass, further preferably from 1 to 3 parts by mass, and particularly preferably from 1 to 2 parts by mass.

The photosensitive resin composition according to this embodiment has a triazole compound having a mercapto group, a tetrazole compound having a mercapto group, a thiadiazole compound having a mercapto group, and an amino group from the viewpoint of further improving the rust prevention property of the cured film. It is preferable to further contain at least one compound selected from the group consisting of a triazole compound and a tetrazole compound having an amino group (hereinafter also referred to as component (D)). Examples of the triazole compound having a mercapto group include 3-mercapto-triazole (manufactured by Wako Pure Chemical Industries, Ltd., product name: 3MT). Examples of the thiadiazole compound having a mercapto group include 2-amino-5-mercapto-1,3,4-thiadiazole (product name: ATT, manufactured by Wako Pure Chemical Industries, Ltd.).

Examples of the triazole compound having an amino group include, for example, benzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole, and the like substituted with an amino group. Examples thereof include compounds in which an amino group is substituted for a triazole compound containing a mercapto group such as 3-mercaptotriazole and 5-mercaptotriazole.

Examples of the tetrazole compound having an amino group include 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 1-carboxymethyl-5-amino- Examples include tetrazole. These tetrazole compounds may be water-soluble salts thereof. Specific examples include alkali metal salts of 1-methyl-5-amino-tetrazole such as sodium, potassium and lithium.

When the photosensitive resin composition contains the component (D), the content thereof is preferably 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). 0.1 to 2.0 parts by mass is more preferable, 0.2 to 1.0 part by mass is further preferable, and 0.3 to 0.8 part by mass is particularly preferable.

The photosensitive resin composition according to the present embodiment has adhesiveness to a transparent electrode such as a substrate and an ITO electrode that may have an index matching layer, and good developability on a metal wiring such as a copper wiring. However, from the viewpoint of forming a cured film that has been achieved at a high level, and from the viewpoint of preventing the occurrence of development residue, it contains a phosphoric ester containing an ethylenically unsaturated bond (hereinafter also referred to as component (E)). In addition, in this specification, the phosphate ester containing an ethylenically unsaturated bond shall be handled as (E) component instead of (B) component.

(E) As a phosphoric acid ester containing an ethylenically unsaturated bond as the component, while ensuring sufficient rust prevention of the cured film to be formed, adhesion to the substrate and ITO electrode and developability on the metal wiring From the viewpoint of achieving a high level of compatibility, the Phosmer series (Phosmer-M, Phosmer-CL, Phosmer-PE, Phosmer-MH, Phosmer-PP, etc.) manufactured by Unichemical Co., Ltd., or the KAYAMER series manufactured by Nippon Kayaku Co., Ltd. (PM-21, PM-2, etc.) are preferred.

The content of the component (E) is 100 parts by mass of the total amount of the component (A) and the component (B) in order to achieve both high adhesion to the substrate and the ITO electrode and developability on the metal wiring. Is required to be 1.5 to 3.0 parts by mass, preferably 1.75 to 3.0 parts by mass, and more preferably 2.0 to 2.5 parts by mass. . Even if the content of the component (E) is less than 1.5 parts by mass or more than 3.0 parts by mass, the resulting cured film has good adhesion to the substrate and the ITO electrode, or development on a metal wiring. The performance will be reduced. The present inventors have found that the adhesiveness decreases when the content of the component (E) exceeds 3.0 parts by mass. About this cause, when the content of the component (E) is more than 3.0 parts by mass, the cured film is easily peeled off from the base material because the elastic modulus of the formed cured film decreases and becomes brittle. I think it will be. Specifically, when the content of the component (E) is within the range of 1.5 to 3.0 parts by mass, compared to the case where the content is out of the range, the obtained cured film with respect to the substrate and ITO electrode Adhesiveness and developability on metal wiring can be achieved at a high level. In addition, the content range includes a group having a branched structure and / or an alicyclic structure in the side chain, a group having an acidic group in the side chain, and a group having an ethylenically unsaturated group in the side chain ( It is found as a suitable range when A) a binder polymer and (E) a phosphate ester containing an ethylenically unsaturated bond are used in combination. By using the specific component (A) and the specific component (E) in combination and setting the content of the component (E) within the specific range, the effects of the present invention can be sufficiently obtained. .

The refractive index of the first resin layer at a wavelength of 633 nm is usually 1.40 to 1.49.

The thickness of the first resin layer 20 is sufficiently effective as a protective film and is preferably 15 μm or less in terms of thickness after drying in order to sufficiently embed a step on the surface of the substrate with a transparent electrode pattern. It is more preferably 2 to 10 μm, and further preferably 3 to 8 μm. Moreover, it is preferable that the thickness of the 1st resin layer after hardening is also in the said range.

(Second resin layer)
The second resin layer 30 is a layer containing metal oxide particles. The second resin layer 30 can have a refractive index relatively higher than that of the first resin layer 20 by containing metal oxide particles. The second resin layer 30 preferably has a refractive index in the range of 1.40 to 1.90 at 633 nm, more preferably 1.50 to 1.90, and 1.53 to 1.85. More preferably, it is particularly preferably 1.55 to 1.75. Moreover, when the 2nd resin layer contains a sclerosing | hardenable component, it is preferable that the refractive index in 633 nm of the 2nd resin layer after hardening is also in the said range.

When the refractive index at 633 nm of the second resin layer 30 is within the above range, various members (for example, modules) used on the cured film pattern when the cured film pattern is provided on a transparent electrode pattern such as ITO. It becomes an intermediate value of the refractive index of the cover glass and the OCA that bonds the transparent electrode pattern to the transparent electrode pattern, and is optical in the portion where the transparent electrode pattern such as ITO is formed and the portion where it is not formed. It is possible to reduce the color difference due to reflection and prevent the appearance of bone. Moreover, it becomes possible to reduce the reflected light intensity of the whole screen, and to suppress the transmittance | permeability fall on a screen.

The refractive index of a transparent electrode such as ITO is preferably 1.80 to 2.10, more preferably 1.85 to 2.05, and even more preferably 1.90 to 2.00. . Further, the refractive index of a member such as OCA is preferably 1.45 to 1.55, more preferably 1.47 to 1.53, and further preferably 1.48 to 1.51. .

The second resin layer 30 preferably has a minimum light transmittance of 80% or more in a wavelength region of 450 to 650 nm, more preferably 85% or more, and further preferably 90% or more. When the second resin layer contains a curable component, it is preferable that the minimum light transmittance in the wavelength region of 450 to 650 nm of the second resin layer after curing is also within the above range.

The 2nd resin layer 30 can contain said (A) component, (B) component, and (C) component, and said (D) component and / or said (E) component as needed. Furthermore, it can contain. The second resin layer 30 does not necessarily contain a photopolymerization component such as the component (B) or the component (C), and the second resin layer is formed by utilizing a photopolymerization component that migrates from an adjacent resin layer due to layer formation. The layer can also be photocured. Further, the second resin layer 30 has, as a binder polymer, a group having a branched structure and / or an alicyclic structure in the side chain, a group having an acidic group in the side chain, and an ethylenically unsaturated group in the side chain. It is also possible to contain a binder polymer other than the (A) binder polymer containing a group.

The second resin layer 30 contains metal oxide particles (hereinafter also referred to as “component (F)”). The metal oxide particles preferably contain metal oxide particles having a refractive index of 1.50 or more at a wavelength of 633 nm. Thereby, when the transfer type photosensitive refractive index adjusting film is prepared, it is possible to improve the transparency of the second resin layer and the refractive index at a wavelength of 633 nm. Moreover, developability can be improved, suppressing adsorption | suction to a base material.

Examples of the metal oxide particles include particles made of metal oxides such as zirconium oxide, titanium oxide, tin oxide, zinc oxide, indium tin oxide, indium oxide, aluminum oxide, and yttrium oxide. Among these, particles of zirconium oxide or titanium oxide are preferable from the viewpoint of suppressing the bone appearance phenomenon.

As the zirconium oxide particles, when the material of the transparent electrode is ITO, it is preferable to use zirconium oxide nanoparticles from the viewpoint of improving the refractive index and adhesion between the ITO and the transparent substrate. Among the zirconium oxide nanoparticles, the particle size distribution Dmax is preferably 40 nm or less.

Zirconium oxide nanoparticles are OZ-S30K (product name, manufactured by Nissan Chemical Industries, Ltd.), OZ-S40K-AC (product name, manufactured by Nissan Chemical Industries, Ltd.), SZR-K (dispersion of zirconium oxide methyl ethyl ketone, Sakai Chemical). Kogyo Co., Ltd., product name) and SZR-M (zirconium oxide methanol dispersion, Sakai Chemical Industry Co., Ltd., product name) are commercially available.

It is also possible for the second resin layer 30 to contain titanium oxide nanoparticles as the component (F). Of the titanium oxide nanoparticles, the particle size distribution Dmax is preferably 50 nm or less, more preferably 10 to 50 nm.

As the component (F), in addition to the metal oxide particles, oxide particles or sulfide particles containing atoms such as Mg, Al, Si, Ca, Cr, Cu, Zn, and Ba can be used.

In addition to the metal oxide particles, organic compounds such as a compound having a triazine ring, a compound having an isocyanuric acid skeleton, and a compound having a fluorene skeleton can also be used. Thereby, the refractive index in wavelength 633nm can be improved.

The thickness of the second resin layer 30 may be 0.01 to 1 μm, preferably 0.03 to 0.5 μm, more preferably 0.04 to 0.3 μm, The thickness is more preferably from 0.07 to 0.25 μm, particularly preferably from 0.05 to 0.2 μm. When the thickness is 0.01 to 1 μm, the reflected light intensity of the entire screen can be further reduced. Moreover, it is preferable that the thickness of the 2nd resin layer after hardening is also in the said range.

The transfer type photosensitive refractive index adjusting film of the present embodiment is laminated on the base material so that the second resin layer 30 is in contact with the base material, that is, between the first resin layer 20 and the base material. Even when the second resin layer 30 is interposed between the second resin layer 30 and the second resin layer 30, the physical properties such as adhesion and resolution are affected by the composition of the first resin layer 20 because the thickness of the second resin layer 30 is sufficiently thin. Receive greatly. In addition, component movement may occur between the first resin layer 20 and the second resin layer 30, and the composition of the first resin layer 20 may also be in close contact with the substrate. Affect. Therefore, the transfer type photosensitive refractive index adjusting film of the present embodiment has the second resin between the base material and the first resin layer 20 because the first resin layer 20 has the specific composition described above. Even in the case where the layer 30 is interposed, it is possible to realize good adhesion to the substrate and good developability (particularly good resolution) on the metal wiring.

When the second resin layer is a single layer and the thickness is uniform in the thickness direction, the refractive index of the second resin layer 30 is obtained as follows using ETA-TCM (product name, manufactured by AudioDev GmbH). be able to. The following measurement is performed under the condition of 25 ° C.
(1) A coating solution for forming the second resin layer is uniformly applied on a glass substrate having a thickness of 0.7 mm, a length of 10 cm and a width of 10 cm by a spin coater, and a hot air residence type dryer at 100 ° C. Dry for 3 minutes to remove the solvent and form a second resin layer.
(2) Next, the sample is allowed to stand for 30 minutes in a box dryer (model number: NV50-CA, manufactured by Mitsubishi Electric Corporation) heated to 140 ° C. to obtain a refractive index measurement sample having a second resin layer.
(3) Next, the refractive index at a wavelength of 633 nm is measured for the obtained sample for refractive index measurement using ETA-TCM (product name, manufactured by AudioDev GmbH).

The refractive index in the single first resin layer can also be measured by the same method. In addition, in the form of the transfer type photosensitive refractive index adjusting film, it is difficult to measure the refractive index of the second resin layer single layer, and therefore the value of the outermost surface layer on the protective film side of the second resin layer is used.

(Other layers)
The photosensitive refractive index adjusting film of the present embodiment may be provided with other appropriately selected layers as long as the effects of the present invention are obtained. There is no restriction | limiting in particular as said other layer, According to the objective, it can select suitably, For example, a cushion layer, an oxygen shielding layer, a peeling layer, an adhesive layer etc. are mentioned. The said photosensitive refractive index adjustment film may have these layers individually by 1 type, and may have 2 or more types. Moreover, you may have 2 or more of the same kind of layers.

(Protective film)
Examples of the protective film 40 include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, a polyethylene-vinyl acetate copolymer, a polyethylene-vinyl acetate copolymer film, and a laminated film of these films and polyethylene.

The thickness of the protective film 40 is preferably 5 to 100 μm, but is preferably 70 μm or less and more preferably 60 μm or less from the viewpoint of storing the transfer type photosensitive refractive index adjusting film 1 in a roll shape. 50 μm or less is more preferable, and 40 μm or less is particularly preferable.

Visible light having a wavelength of 400 to 700 nm of a cured film portion (excluding the support film 10 and the protective film 40) obtained by curing the first resin layer 20 and the second resin layer 30 in the transfer type photosensitive refractive index adjusting film 1 The minimum value of the total light transmittance (Tt) in the region is preferably 90.00% or more, more preferably 90.50% or more, and further preferably 90.70% or more. If the total light transmittance in a general visible light wavelength range of 400 to 700 nm is 90.00% or more, when protecting the transparent electrode in the sensing area of the touch panel (touch sensor), image display in the sensing area It can suppress sufficiently that quality, a hue, and a brightness | luminance fall.

[Method for producing photosensitive refractive index adjusting film]
The first resin layer 20 and the second resin layer 30 of the transfer type photosensitive refractive index adjusting film 1 are, for example, a coating liquid containing a photosensitive resin composition and a coating liquid containing a high refractive index composition. It can form by preparing and apply | coating and drying this on the support film 10 and the protective film 40, respectively. The transfer type photosensitive refractive index adjusting film 1 includes a support film 10 on which the first resin layer 20 is formed and a protective film 40 on which the second resin layer 30 is formed. And the second resin layer 30 can be formed by being bonded together. In addition, the transfer type photosensitive refractive index adjusting film 1 is obtained by applying a coating liquid containing a photosensitive resin composition on the support film 10 and drying it, and then, on the first resin layer 20, the high refractive index composition. It can also form by apply | coating and drying the coating liquid containing this, and affixing the protective film 40. FIG.

The coating solution can be obtained by uniformly dissolving or dispersing each component constituting the photosensitive resin composition and the high refractive index composition according to the present embodiment described above in a solvent.

The solvent used as the coating solution is not particularly limited, and known ones can be used. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, methanol, ethanol, propanol, butanol, methylene glycol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether , Diethylene glycol diethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, chloroform, methylene chloride and the like.

Application methods include doctor blade coating method, Mayer bar coating method, roll coating method, screen coating method, spinner coating method, inkjet coating method, spray coating method, dip coating method, gravure coating method, curtain coating method, and die coating method. Etc.

The drying conditions are not particularly limited, but the drying temperature is preferably 60 to 130 ° C., and the drying time is preferably 0.5 to 30 minutes.

[Method of forming cured film pattern]
FIG. 2 is a schematic cross-sectional view showing a laminate comprising a cured film formed using a transfer type photosensitive refractive index adjusting film according to an embodiment of the present invention on a substrate with a transparent electrode pattern. The laminated body 100 shown by FIG. 2 is provided with the base material 50 with the transparent electrode pattern which has the transparent electrode pattern 50a, and the cured film 60 provided on the transparent electrode pattern 50a of the base material 50 with a transparent electrode pattern. The cured film 60 is a cured film including the cured first resin layer 22 and the cured second resin layer 32, and is formed using the transfer type photosensitive refractive index adjusting film 1 of the present embodiment. The cured film 60 satisfies both the protective function of the transparent electrode pattern 50a and the function of making the transparent electrode pattern 50a invisible or improving the visibility of the touch screen. Hereinafter, an embodiment of a method for producing a laminate in which a cured film is formed on a substrate with a transparent electrode pattern will be described.

-Lamination process-
First, after removing the protective film 40 of the transfer type photosensitive refractive index adjusting film 1, the second resin layer 30, the first resin layer 20, and the support film 10 are placed on the surface of the substrate 50 with a transparent electrode pattern. Is laminated (transferred) so that the resin layer 30 side is in close contact. Examples of the pressing means include a pressing roll. The pressure roll may be provided with a heating means so that it can be heat-pressure bonded.

In the case of thermocompression bonding, the heating temperature is such that the components of the first resin layer 20 or the second resin layer 30 are heated from the viewpoint of adhesion between the second resin layer 30 and the substrate 50 with the transparent electrode pattern. From the viewpoint of making it hard to be cured or thermally decomposed, it is preferably 10 to 160 ° C, more preferably 20 to 150 ° C, and further preferably 30 to 150 ° C.

In addition, the pressing pressure at the time of thermocompression bonding is a line from the viewpoint of suppressing the deformation of the substrate 50 with the transparent electrode pattern while ensuring sufficient adhesion between the second resin layer 30 and the substrate 50 with the transparent electrode pattern. The pressure is preferably 50 to 1 × 10 ⁵ N / m, more preferably 2.5 × 10 ² to 5 × 10 ⁴ N / m, and 5 × 10 ² to 4 × 10 ⁴ N / m. More preferably.

If the transfer type photosensitive refractive index adjusting film 1 is thermocompression bonded as described above, the preheat treatment of the substrate 50 with a transparent electrode pattern is not necessarily required, but the second resin layer 30 and the substrate 50 with a transparent electrode pattern are used. From the point of further improving the adhesion to the substrate 50, the substrate 50 with a transparent electrode pattern may be preheated. The treatment temperature at this time is preferably 30 to 150 ° C.

(Base material)
As a base material which comprises the base material 50 with a transparent electrode pattern, base materials, such as a glass plate used for a touch panel (touch sensor), a plastic plate, a ceramic board, are mentioned, for example.

(Transparent electrode and metal wiring)
The transparent electrode can be formed using a conductive metal oxide film such as ITO and IZO (Indium Zinc Oxide). The transparent electrode can also be formed using a photosensitive film having a photocurable resin layer using conductive fibers such as silver fibers and carbon nanotubes. The metal wiring can be formed by a method such as screen printing or vapor deposition using a conductive material such as Au, Ag, Cu, Al, Mo, and C, for example. In addition, an insulating layer or an index matching layer may be provided on the base material between the base material and the electrode. The index matching layer may have the same composition as the second resin layer 30 described above.

-Exposure process-
Next, actinic rays are irradiated in a pattern form to a predetermined portion of the first resin layer and the second resin layer after transfer via a photomask. When the support film 10 on the first resin layer and the second resin layer is transparent when irradiating with actinic light, it can be irradiated with actinic light as it is. Irradiate light. A known active light source can be used as the active light source. In addition, in this specification, the pattern is not limited to the shape of the fine wiring forming the circuit, but the shape in which only the connection portion with the other base material is removed in a rectangle, the shape in which only the frame portion of the base material is removed, etc. Is also included.

The irradiation amount of actinic rays is 1 × 10 ² to 1 × 10 ⁴ J / m ² , and heating can be accompanied during irradiation. If the irradiation amount of this actinic ray is 1 × 10 ² J / m ² or more, it is possible to sufficiently proceed the photocuring of the first resin layer and the second resin layer, and 1 × 10 ⁴ J If it is / m ² or less, there is a tendency that the first resin layer and the second resin layer can be prevented from being discolored.

-Development process-
Subsequently, the unexposed portions of the first resin layer and the second resin layer after irradiation with actinic rays are removed with a developer, and a cured film (refractive index adjustment pattern) 60 covering a part or all of the transparent electrode is obtained. Form. In addition, after irradiation of actinic rays, when the support film 10 is laminated | stacked on the 1st resin layer and the 2nd resin layer, after developing it, the image development process is performed.

The development step can be performed by a known method such as spraying, showering, rocking dipping, brushing, or scrubbing using a known developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. Of these, spray development is preferably performed using an alkaline aqueous solution from the viewpoint of environment and safety. The development temperature and time can be adjusted within a conventionally known range.

(Cured film)
The cured film of the present embodiment cures only the first resin layer or both the first resin layer and the second resin layer of the transfer type photosensitive refractive index adjusting film of the present embodiment. It is the cured film obtained by the above.

For example, when the second resin layer is mostly covered with the first resin layer and is not exposed, the second resin layer does not necessarily need to be cured. The cured film of this embodiment includes the case where such a first resin layer is cured and the second resin layer is not cured. The cured film of this embodiment is preferably formed in a pattern.

The transfer type photosensitive refractive index adjusting film according to this embodiment can be applied to the formation of a protective film in various electronic components. The electronic component according to this embodiment includes a refractive index adjustment pattern formed using a transfer type photosensitive refractive index adjustment film. Examples of the electronic component include a touch panel, a liquid crystal display, an organic electroluminescence, a solar cell module, a printed wiring board, and electronic paper.

FIG. 3 is a schematic top view showing a touch panel according to an embodiment of the present invention. FIG. 3 shows an example of a capacitive touch panel. The touch panel shown in FIG. 3 has a touch screen 102 for detecting a touch position coordinate on one side of a transparent substrate 101, and the transparent electrode 103 and the transparent electrode 104 for detecting a change in capacitance in this region are transparent. It is provided on the base material 101.

The transparent electrode 103 and the transparent electrode 104 detect the X position coordinate and the Y position coordinate of the touch position, respectively.

On the transparent base material 101, a lead-out wiring 105 for transmitting a touch position detection signal from the transparent electrode 103 and the transparent electrode 104 to an external circuit is provided. The lead-out wiring 105 is connected to the transparent electrode 103 and the transparent electrode 104 by a connection electrode 106 provided on the transparent electrode 103 and the transparent electrode 104. A connection terminal 107 for connecting to an external circuit is provided at the end of the lead-out wiring 105 opposite to the connection portion between the transparent electrode 103 and the transparent electrode 104.

As shown in FIG. 3, in the touch panel according to the present embodiment, the transfer type photosensitive refractive index adjusting film of the present embodiment is used to span the portion where the transparent electrode pattern is formed and the portion where it is not formed. A refractive index adjustment pattern 123 is formed. The refractive index adjustment pattern 123 is a cured film including a cured first resin layer and a cured second resin layer. According to this refractive index adjustment pattern 123, the function of protecting the transparent electrode 103, the transparent electrode 104, the lead-out wiring 105, the connection electrode 106 and the connection terminal 107, and the sensing region (touch screen) 102 formed from the transparent electrode pattern The function of preventing the appearance of bone phenomenon can be performed at the same time.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

A binder polymer represented by a compound structure (A1) described later was synthesized according to Synthesis Example 1 below.

(Synthesis Example 1)
85.7 parts by mass of 1-methoxy-2-propanol (manufactured by Daicel Chemical Industries, Ltd.) was added in advance to the reaction vessel and the temperature was raised to 80 ° C., and 52 parts by mass of methacrylic acid, 2 parts by mass of methyl methacrylate, and cyclohexyl. A mixed solution consisting of 46 parts by mass of methacrylate and 10 parts by mass of an azo polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., V-601) was dropped into a reaction vessel at 80 ° C. over 2 hours in a nitrogen gas atmosphere. Reaction was performed for 4 hours after the dropwise addition to obtain a resin solution.

Next, 2.5 parts by mass of hydroquinone monomethyl ether and 8.4 parts by mass of tetoethylammonium bromide were added to the resin solution, and then 32 parts by mass of glycidyl methacrylate was added dropwise over 2 hours. After dropping, the mixture is reacted at 80 ° C. for 4 hours while blowing air, and then prepared by adding propylene glycol monomethyl ether acetate as a solvent so that the solid content concentration becomes 45% by mass, and has an alicyclic structure in the side chain. A solution containing a binder polymer represented by the compound structure (A1) containing a group, a group having an acidic group in the side chain, and a group having an ethylenically unsaturated group in the side chain was obtained.

The weight average molecular weight and acid value of the binder polymer described above were measured by the following method. The results are shown in Table 1.

[Method for measuring weight average molecular weight]
The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC), and was derived by conversion using a standard polystyrene calibration curve. The measurement conditions for GPC are shown below.
<GPC measurement conditions>
Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd., product name)
Column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (product name, manufactured by Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., product name)

[Measurement method of acid value]
The acid value was measured by a neutralization titration method based on JIS K0070 as shown below. First, the binder polymer solution was heated at 130 ° C. for 1 hour to remove volatile matter, thereby obtaining a solid content. Then, after accurately weighing 1 g of the solid binder polymer, 30 g of acetone was added to the binder polymer, and this was uniformly dissolved to obtain a resin solution. Next, an appropriate amount of an indicator, phenolphthalein, was added to the resin solution, and neutralization titration was performed using a 0.1 mol / L potassium hydroxide aqueous solution. And the acid value was computed by following Formula.
Acid value = 0.1 × V × f ₁ × 56.1 / (Wp × I / 100)
In the formula, V is a titration amount (mL) of 0.1 mol / L potassium hydroxide aqueous solution used for titration,
f ₁ is a factor of 0.1 mol / L potassium hydroxide aqueous solution (concentration conversion factor),
Wp is the mass (g) of the measured resin solution,
I shows the ratio (mass%) of the non volatile matter in the measured said resin solution.

(Examples 1 to 4 and Comparative Examples 1 to 6)
[Preparation of first resin layer forming coating solution]
The components shown in Table 2 were blended in the blending amounts (unit: parts by mass) shown in the same table and mixed for 15 minutes using a stirrer to prepare a first resin layer forming coating solution. In addition, the 1st coating liquid for resin layer formation added methyl ethyl ketone suitably, and prepared it so that solid content might be 35 mass%. Moreover, the compounding quantity of (A) component in Table 2 shows the compounding quantity of solid content.

[Preparation of second resin layer forming coating solution]
The components shown in Table 2 were blended in the blending amounts (unit: parts by mass) shown in the same table and mixed for 15 minutes using a stirrer to prepare a second resin layer forming coating solution. In Table 2, the amount of component (A) indicates the amount of solids.

The symbol of the component in Table 2 has the following meaning.
[Component (A)]
A1: Binder polymer solution prepared by the above-described method A2: monomer blending ratio (methacrylic acid / methyl methacrylate / butyl acrylate / butyl methacrylate = 24 / 43.5 / 15.2 / 17.3 (mass ratio)) A copolymer of propylene glycol monomethyl ether / toluene, weight average molecular weight 30,000, acid value 157 mg KOH / g, hydroxyl value 2 mg KOH / g, Tg 65 ° C.

[(B) component]
A-DCP: Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)

[Component (C)]
IRGACURE OXE-01: 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (product name “IRGACURE OXE 01” manufactured by BASF Corporation)

[Component (D)]
B-6030: 5-amino-1H-tetrazole (product name, manufactured by Chiyoda Chemical Co., Ltd.)

[(E) component]
PM-21: Phosphate ester containing ethylenically unsaturated bond (manufactured by Nippon Kayaku Co., Ltd.)

[(F) component]
OZ-S30K: Zirconia dispersion (manufactured by Nissan Chemical Industries, Ltd., product name: Nanouse OZ-S30K)

[Other ingredients]
ADDITIVE 8032: Octamethylcyclotetrasiloxane (manufactured by Dow Corning Toray)
AW500: 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (manufactured by Kawaguchi Chemical Co., Ltd.)
L-7001: Octamethylcyclotetrasiloxane (manufactured by Dow Corning Toray)

[Preparation of transfer type photosensitive refractive index adjusting film]
Using a polypropylene film (product name: E-201F, manufactured by Oji F-Tex Co., Ltd.) having a thickness of 30 μm as the protective film, the second coating solution for forming a resin layer prepared above was applied onto the protective film using a die coater. Apply uniformly, dry for 3 minutes with a 100 ° C. hot air drier, remove the solvent, and adjust the amount of coating solution so that the thickness after drying is 0.06 μm. Formed.

Using a polyethylene terephthalate film (product name: FB40, manufactured by Toray Industries, Inc.) having a thickness of 16 μm as a support film, the first resin layer-forming coating solution prepared above is uniformly applied on the support film using a comma coater. Then, the solvent was removed by drying with a hot air convection dryer at 100 ° C. for 3 minutes to form a first resin layer having a thickness of 8.0 μm.

Next, the obtained protective film having the second resin layer and the support film having the first resin layer were placed at 23 ° C. using a laminator (manufactured by Hitachi Chemical Co., Ltd., product name: HLM-3000 type). And a transfer type photosensitive refractive index adjusting film in which a protective film, a second resin layer, a first resin layer, and a support film were laminated in this order.

[Evaluation of adhesion]
While peeling off the protective film of the transfer-type photosensitive refractive index adjusting film obtained in the examples and comparative examples on the index matching layer and the substrate with ITO, the second resin layer is placed on the surface of the index matching layer of the substrate. Using a laminator (manufactured by Hitachi Chemical Co., Ltd., product name: HLM-3000 type), the roll temperature is 100 ° C., the substrate feed rate is 0.4 m / min, and the pressure (cylinder pressure) is 4 × 10 ⁵ Pa. Laminated. After laminating, the substrate is cooled, and when the temperature of the substrate reaches 23 ° C., using an exposure machine having a high-pressure mercury lamp from the support film side (manufactured by Oak Manufacturing Co., Ltd., product name: EXM-1201), Light-irradiated with an exposure amount of 80 mJ / cm ² , peels off the support film, and consists of a cured film of the first resin layer having a thickness of 8.0 μm and a cured product of the second resin layer having a thickness of 0.06 μm. A sample for adhesion test was obtained.

Next, with reference to the JIS standard (K5400), a cross cut test of 100 squares was performed twice. Using a cutter knife on the test surface, cut a 1 × 1 mm square grid, and press the Mending Tape # 810 (manufactured by 3M Co., Ltd.) strongly onto the grid, and the end of the tape is approximately 180 °. I peeled off quickly at an angle. Thereafter, the cross-cut state was observed, and the cross-cut adhesion was evaluated according to the following scores.
5: Almost 100% of the total area is in close contact.
4: 95% or more and less than 100% of the total area remains adhered.
3: 85% or more and less than 95% of the total area remains adhered.
2: 65% or more and less than 85% of the total area remains adhered.
1: 35% or more and less than 65% of the total area remains adhered.
0: 0% or more and less than 35% of the total area remains adhered.

[Developability (resolution) evaluation test]
The protective film of the obtained transfer type photosensitive refractive index adjusting film is peeled off, and a laminator (manufactured by Hitachi Chemical Co., Ltd., product name: HLM-3000 type) is used on a copper base (12 cm long × 5 cm wide). Lamination is performed under the conditions of a roll temperature of 100 ° C., a base material feed rate of 0.6 m / min, and a pressure bonding pressure (cylinder pressure) of 0.4 MPa. The copper base material, the second resin layer, the first resin layer, and the support film are Laminated samples for developability evaluation test were prepared.

The uppermost support film of the sample for developability evaluation test obtained above was peeled off. Thereafter, spray development was performed at 30 ° C. for 40 seconds using a 1.0 mass% sodium carbonate aqueous solution. The surface state of the obtained substrate was observed with the naked eye, and the development residue was evaluated according to the following viewpoints, where “7” was the best developability and “1” was the worst. The results are shown in Table 2.
1: 100% development residue on substrate surface
2: Development residue on substrate surface is 81 to 99%
3: 61 to 80% of development residue on substrate surface
4: 41 to 60% of development residue on substrate surface
5: 21 to 40% of development residue on substrate surface
6: 1 to 20% of development residue on substrate surface
7: 0% development residue on substrate surface.

[Measurement of push-in amount]
The protective film of the obtained transfer-type photosensitive refractive index adjusting film was peeled off, and a laminator (manufactured by Hitachi Chemical Co., Ltd., product) Name: HLM-3000 type), laminating under conditions of a roll temperature of 23 ° C., a substrate feed rate of 0.6 m / min, and a pressure bonding pressure (cylinder pressure) of 0.4 MPa, a glass plate, a second resin layer, A sample for indentation amount evaluation test in which the first resin layer and the support film were laminated was prepared.

The indentation amount evaluation test sample obtained above was loaded up to 300 mN with a load time of 10 seconds and a load speed of 30 mN / second using FISCHERSCOPE H1000SMC (manufactured by Fischer Instruments, product name), and a load of 300 mN And then unloaded under the conditions of an unloading time of 5 seconds and an unloading speed of 0.08 mN / sec. The indentation amount (h _maxl , the indentation amount before creep) when the maximum load reached 300 mN was calculated. The results are shown in Table 2. The larger the indentation value, the better the laminating properties. If the pressing amount is 4 μm or more, it can be said that the laminate has sufficient laminating properties.

DESCRIPTION OF SYMBOLS 1 ... Transfer type photosensitive refractive index adjustment film, 10 ... Support film, 20 ... 1st resin layer, 22 ... Hardened 1st resin layer, 30 ... 2nd resin layer, 32 ... 2nd cured resin Layer, 40 ... protective film, 50 ... substrate with transparent electrode pattern, 50a ... transparent electrode pattern, 60 ... cured film, 100 ... laminate, 101 ... transparent substrate, 102 ... sensing region, 103, 104 ... transparent electrode, 105 ... Lead-out wiring, 106 ... Connection electrode, 107 ... Connection terminal, 123 ... Refractive index adjustment pattern (cured film).

Claims (12)

1. A support film, a first resin layer provided on the support film, and a second resin layer containing metal oxide particles provided on the first resin layer,
   A binder polymer in which the first resin layer contains a group having a branched structure and / or an alicyclic structure in the side chain, a group having an acidic group in the side chain, and a group having an ethylenically unsaturated group in the side chain. And a photopolymerizable compound, a photopolymerization initiator, and a phosphate ester having an ethylenically unsaturated bond,
   The content of the phosphate ester having an ethylenically unsaturated bond in the first resin layer is 1.5 to 3.0 parts by mass with respect to 100 parts by mass in total of the binder polymer and the photopolymerizable compound. A transfer type photosensitive refractive index adjusting film.
2. The transfer type photosensitive refractive index adjusting film according to claim 1, wherein the photopolymerizable compound includes a compound having a tricyclodecane skeleton or a tricyclodecene skeleton.
3. The transfer type photosensitive refractive index adjusting film according to claim 1 or 2, wherein the photopolymerization initiator contains an oxime ester compound and / or a phosphine oxide compound.
4. The transfer type photosensitive refractive index adjusting film according to any one of claims 1 to 3, wherein the binder polymer has a carboxyl group.
5. The binder polymer is (meth) acrylic acid, (meth) acrylic acid glycidyl ester, (meth) acrylic acid benzyl ester, styrene, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid 5. A binder polymer having a structural unit derived from at least one compound selected from the group consisting of butyl ester, (meth) acrylic acid 2-ethylhexyl ester, and (meth) acrylic acid cyclohexyl ester. The transfer type photosensitive refractive index adjusting film according to claim 1.
6. The transfer type photosensitive refractive index adjusting film according to any one of claims 1 to 5, wherein the binder polymer is a binder polymer having a structural unit derived from (meth) acrylic acid cyclohexyl ester.
7. The second resin layer includes at least one metal oxide particle selected from the group consisting of zirconium oxide, titanium oxide, tin oxide, zinc oxide, indium tin oxide, indium oxide, aluminum oxide, and yttrium oxide. The transfer type photosensitive refractive index adjusting film according to any one of claims 1 to 6.
8. The transfer type photosensitive refractive index adjusting film according to any one of claims 1 to 7, wherein the thickness of the second resin layer is 0.01 to 1 µm.
9. The second resin layer and the first resin layer of the transfer type photosensitive refractive index adjusting film according to any one of claims 1 to 8 are formed on the substrate, the substrate and the second resin layer. Laminating so that the resin layer is in close contact with the resin layer;
   After exposing a predetermined portion of the second resin layer and the first resin layer on the substrate, removing other than the predetermined portion, forming a refractive index adjustment pattern;
   A method for forming a refractive index adjustment pattern.
10. The transfer type photosensitive refractive index adjusting film according to any one of claims 1 to 8, wherein only the first resin layer or both the first resin layer and the second resin layer are cured. Cured film.
11. A touch panel comprising a refractive index adjustment pattern comprising a cured film of the first resin layer and the second resin layer in the transfer type photosensitive refractive index adjustment film according to any one of claims 1 to 8.
12. The touch panel according to claim 11, wherein the refractive index adjustment pattern is provided on a base material having an index matching layer.

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