WO2018179096A1 - Transfer-type photosensitive film, method for forming cured film pattern, and touch panel - Google Patents

Abstract

This transfer-type photosensitive film is provided with a support film and a first resin layer that is arranged on the support film. The first resin layer contains a binder polymer, a photopolymerizable compound and a photopolymerization initiator; and the binder polymer contains a group that has a branched and/or alicyclic structure in a side chain, a group that has an acidic group in a side chain, and a group that has an ethylenically unsaturated group in a side chain, while having an ethylenically unsaturated group equivalent of 0.50-3.00 mmol/g.

Description

Transfer type photosensitive film, method for forming cured film pattern, and touch panel

The present invention relates to a transfer type photosensitive film, a method for forming a cured film pattern, 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 have a two-layer structure in order to express two-dimensional coordinates based on the X and Y axes. Forming. 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. In the touch panel, a corrosive component such as moisture or salt may enter the sensing region from the inside when touching the fingertip. 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 between the electrode and the driving circuit, or disconnection.

In order to prevent corrosion of metal wiring, a photosensitive resin composition layer containing a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure is provided on a touch panel substrate, and this photosensitive resin composition A method for forming a cured film of a photosensitive resin assembly, in which a predetermined part of a physical layer is cured by irradiation with actinic rays and then the part other than the predetermined part is removed to cover a part or all of the substrate, has been proposed. (Patent Document 1).

Japanese Patent Laying-Open No. 2015-121929

In order to further improve the reliability of the touch panel, improvement of the rust prevention effect by the protective film is required, and formation of a cured film pattern having a lower moisture permeability is important for its realization.

On the other hand, displays that can be bent or bent are becoming widespread, and for liquid crystal display elements and touch panels, touch panels in which electrodes are provided on a flexible substrate may be used. This touch panel is subjected to processing such as punching or cutting with a flat plate punching machine or a rotary cutter in order to improve productivity. In this case, the cured film pattern provided on the touch panel is required to have crack resistance that does not easily cause cracks even after the above-described steps.

An object of the present invention is to provide a transfer type photosensitive film capable of forming a cured film pattern having both low moisture permeability and crack resistance, a cured film pattern forming method using the same, and a touch panel. .

In order to solve the above problems, the present inventors have intensively studied, and in the photosensitive resin layer containing a binder polymer, a photopolymerizable compound, and a photopolymerization initiator, as a copolymerization component, branched and / or alicyclic rings. It has been found that a cured film pattern having low moisture permeability can be formed by using a binder polymer containing a monomer having a structure and a monomer having an acidic group. On the other hand, the present inventors have also obtained the knowledge that the above-mentioned cured film pattern tends to decrease the crack resistance. As a result of further investigation by the present inventors based on these findings, the compound having the functional group capable of reacting with the acidic group and the ethylenically unsaturated group is converted into an ethylenically unsaturated group equivalent of the binder polymer. It has been found that a cured film pattern that achieves both low moisture permeability and crack resistance can be formed by further reacting in such a way as to satisfy a specific range, and the present invention has been completed.

The present invention comprises a support film and a first resin layer provided on the support film, and the first resin layer contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator. The binder polymer contains a group having a branched and / or 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; Provided is a transfer type photosensitive film having an ethylenically unsaturated group equivalent of 50 to 3.00 (mmol / g).

According to the transfer type photosensitive film of the present invention, a cured film pattern having both low moisture permeability and crack resistance can be formed by having the above configuration. The cured film pattern formed on the metal wiring can function as a protective film for rust prevention of the metal wiring.

The reason why the above effect is obtained is that by adding a group having a branched and / or alicyclic structure in the side chain of the binder polymer, a bulky structure is added to reduce the moisture permeability of the cured film. It is considered that forming such a low moisture-permeable cured film pattern on the metal wiring makes it difficult for the moisture that causes corrosion to come into contact with the metal wiring. In addition, by containing a group having an ethylenically unsaturated group in the side chain of the binder polymer and adjusting the ethylenically unsaturated group equivalent of the binder polymer to a specific range, the distance between cross-linking points in the cured film becomes longer. It is considered that flexibility was improved and crack resistance was compatible.

The binder polymer may further contain a group having a phenyl group in the side chain.

The first resin layer may further contain a phosphoric ester having an ethylenically unsaturated group. In this case, the adhesion of the cured film pattern to be formed can be further improved, and a protective film capable of highly suppressing corrosion of metal wiring (for example, rust of copper wiring) due to a synergistic effect with low moisture permeability. be able to.

The photopolymerization initiator may contain an oxime ester compound. In this case, the transfer type photosensitive film has high sensitivity, and the moisture permeability of the formed cured film pattern can be further reduced.

The transfer type photosensitive film according to the present invention can further include a second resin layer containing metal oxide particles provided on the first resin layer.

According to the above transfer type photosensitive film, it is possible to form a cured film pattern having both low moisture permeability and crack resistance and having a function of adjusting the refractive index.

By the way, the projected capacitive touch panel has a two-layer structure on a substrate by a plurality of X electrodes using a transparent electrode material and a plurality of Y electrodes using a transparent electrode material orthogonal to the X electrodes. It has a structure in which a transparent electrode pattern is formed. In the projected capacitive touch panel having such a structure, a color difference becomes large 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.

According to the transfer type photosensitive film having the second resin layer according to the present invention, the above problem can be suppressed.

In the present invention, the first resin layer of the transfer type photosensitive film according to the present invention is adhered to the substrate having electrodes, and the side on which the electrodes of the substrate are provided and the first resin layer are in close contact with each other. And a step of laminating the first resin layer on the substrate so as to remove a portion other than the predetermined portion and forming a cured film covering a part or all of the electrode. A first method for forming a cured film pattern is provided.

In the present invention, the second resin layer and the first resin layer of the transfer type photosensitive film according to the present invention having the second resin layer are provided on the substrate having the electrode. Laminating the second side and the second resin layer in close contact with each other, and exposing the second resin layer and the predetermined portion of the first resin layer on the base material, then removing other than the predetermined portion, Forming a cured film pattern that covers a part or all of the electrode, and a second method for forming a cured film pattern.

According to the first and second methods for forming a cured film pattern according to the present invention, it is possible to form a cured film pattern having both low moisture permeability and crack resistance on the electrode. In addition, according to the second method of forming a cured film pattern according to the present invention, the cured film pattern can have a function of adjusting the refractive index, and suppress the above-described problems of bone appearance phenomenon and screen transmittance decrease. be able to.

The present invention also provides a cured film obtained by curing the first resin layer in the transfer type photosensitive film according to the present invention.

The present invention is also obtained by curing only the first resin layer or both the first resin layer and the second resin layer of the transfer type photosensitive film according to the present invention having the second resin layer. Provide a cured film.

The present invention also provides a cured product of the first resin layer in the transfer type photosensitive film according to the present invention or a second resin layer of the transfer type photosensitive film according to the present invention having a second resin layer. A touch panel provided with a cured film pattern comprising a cured product of the above and a cured product of a first resin layer is provided.

ADVANTAGE OF THE INVENTION According to this invention, the transfer type photosensitive film which can form the cured film pattern which makes low moisture permeability and crack tolerance compatible, the formation method of a cured film pattern using the same, and a touch panel can be provided. .

It is a schematic cross section which shows the transfer type photosensitive 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 pattern formed using the transfer type photosensitive 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 film>
The transfer type photosensitive film of the present embodiment comprises a support film and a first resin layer provided on the support film. The transfer type photosensitive film of the present embodiment may further include a second resin layer containing metal oxide particles provided on the first resin layer. These transfer type photosensitive films may further include a protective film provided on the first resin layer or the second resin layer.

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

By using the transfer-type photosensitive film, for example, a cured film satisfying both functions of protecting the metal wiring on the frame of the touch panel or the transparent electrode of the touch panel, and making the transparent electrode pattern invisible or improving the visibility of the touch screen. Patterns can be formed in a batch.

(Support film)
As the support film 10, a polymer film can be used. Examples of the material for 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). It is preferably formed from a photosensitive resin composition containing

<Binder polymer>
In this embodiment, the component (A) includes a group having a branched structure and / or an alicyclic structure in the side chain (hereinafter also referred to as (i) group), and a group having an acidic group in the side chain (hereinafter referred to as (ii) And a binder polymer (hereinafter also referred to as component (A-1)) containing a group having an ethylenically unsaturated group in the side chain (hereinafter also referred to as (iii) group). (I) The group can be introduced by a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain. (Ii) The group can be introduced by a monomer containing a group having an acidic group in the side chain.

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.

Specific examples of the monomer containing a group having an alicyclic structure in the side chain include (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 Tricyclodecane, (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, phenethyl (meth) acrylate, 2,2,5-trimethylcyclohexyl (meth) acrylate, ( And methacrylic acid cyclohexyl. 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, and tricyclodecane (meth) acrylate are preferred, cyclohexyl (meth) acrylate, (nor) bornyl (meth) acrylate, (meth) ) Isobornyl acrylate, 2-adamantyl (meth) acrylate, and tricyclodecane (meth) acrylate are particularly preferred.

When the component (A-1) contains a group having a branched structure and / or an alicyclic structure in the side chain, the moisture permeability of the formed cured film pattern can be sufficiently reduced.

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.

When the component (A-1) contains a group having an acidic group in the side chain, patterning by alkali development can be performed. Further, introduction of a group having an ethylenically unsaturated group in the side chain and adjustment of the ethylenically unsaturated group equivalent in the binder polymer are facilitated.

The group having an ethylenically unsaturated group in the side chain is not particularly limited, and a (meth) acryloyl group is preferable. 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 It can be introduced into the component (A-1) by a method of adding a (meth) acrylate having an isocyanate group to a group having a group, a method of adding a (meth) acrylate having a hydroxy group to a group having an isocyanate group, or the like. Among them, the method of adding a (meth) acrylate having an epoxy group to a repeating unit having an acidic group is preferred because it is the easiest to produce and is low in cost.

When the component (A-1) contains a group having an ethylenically unsaturated group in the side chain, the crack resistance of the formed cured film pattern can be sufficiently improved.

Based on the total amount of monomers constituting the component (A-1), the ratio of the monomers constituting the group having a branched structure and / or alicyclic structure in the side chain is preferably 10 to 70 mol%, It is more preferably 65 mol%, particularly preferably 20 to 60 mol%. 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-1) is preferably 5 to 70 mol%, and 10 to 60 mol%. More preferred is 20 to 50 mol%. 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-1) is preferably 5 to 70 mol%. It is more preferably mol%, more preferably 20 to 50 mol%. By satisfying the above monomer ratio, the patterning property by alkali development, the laminate property to the base material, the good adhesion to the base material which may have an index matching layer, the low moisture permeability and the crack resistance are balanced. Can be improved.

In this embodiment, the ethylenically unsaturated group equivalent of the component (A-1) is 0.50 to 3.00 mmol / g from the viewpoint of achieving both low moisture permeability and crack resistance of the cured film pattern. Preferably, it is 1.00 to 3.00 mmol / g, more preferably 1.50 to 3.00 mmol / g. For example, the ethylenically unsaturated group equivalent of the component (A-1) reacted with glycidyl methacrylate is: ethylenically unsaturated group equivalent (mmol / g) = glycosyl methacrylate addition amount (mol) / total monomer addition amount ( g). Moreover, it can measure with the following method.

[Measurement method of ethylenically unsaturated group equivalent]
The ethylenically unsaturated group equivalent can be measured by a titration method using the addition reaction (Michael addition) of an amine to the ethylenically unsaturated group of the (meth) acryloyl group of the binder polymer. The specific measurement method is as follows.

(1) First, the binder polymer solution is heated at 130 ° C. for 1 hour to remove volatile components to obtain a solid content.
(2) About 1 g of a sample is precisely weighed and placed in an Erlenmeyer flask, and then about 10 ml of acetone is added and dissolved.
(3) Add 10 ml of morpholine standard solution [mixed morpholine and methanol at 1: 4 (volume ratio)] and then add 50% acetic acid standard solution [acetic acid and ion-exchanged water at 1: 1 (volume ratio)]. After adding 1.5 ml and stirring for 5 minutes, leave it at room temperature for 15 minutes.
(4) Add 15 ml of acetonitrile and 10 ml of acetic anhydride to the above Erlenmeyer flask and stir for 5 minutes.
(5) Titrate with a 0.5 mol / L acetic acid / methanol titration solution using a recording type automatic titrator.
(6) A blank test is performed at the same time, and the following formula is used.
Ethylenically unsaturated group equivalent (mmol / g) = f × (AB) / 2S
In the formula, A is a titration (ml) of a 0.5 mol / L acetic acid / methanol titration solution required for titration of the sample, and B is a 0.5 mol / L acetic acid / methanol titration solution required for a blank test. Titration volume (ml), f is a factor (concentration conversion factor) of 0.5 mol / L acetic acid / methanol titration solution, S is sampled amount (g) [if sample contains solvent, amount excluding solvent ( g)].

Component (A-1) is a group other than the group having a branched structure and / or 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. Structural units derived from other groups can be contained. The component (A-1) is preferably a copolymer containing a structural unit derived from (meth) acrylic acid and (meth) acrylic acid alkyl ester. In this case, the copolymer is the above (meth) The structural unit may contain other monomers that can be copolymerized with acrylic acid and (meth) acrylic acid alkyl ester.

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 And acid hydroxyl ethyl ester.

Other monomers are preferably compounds having a phenyl group. Examples of the compound having a phenyl group include phenylbenzyl (meth) acrylate, phenoxybenzyl (meth) acrylate, nonylphenoxypolyethylene glycol acrylate, ethoxylated o-phenylphenol acrylate, and benzyl (meth) acrylate. From the viewpoint of reducing the moisture permeability of the cured film, it is preferable to use benzyl (meth) acrylate. When the binder polymer contains a group having a phenyl group in the side chain, a bulky structure is added, so that the moisture permeability of the cured film is reduced.

Other monomers also include (meth) acrylic acid glycidyl ester, styrene and the like.

The component (A-1) is a (meth) acrylic acid tricyclodecane ester or (meth) acrylic acid cyclohexyl ester as a group (i) from the viewpoint of forming a cured film pattern having both low moisture permeability and crack resistance. A structural unit derived from (ii) as a structural unit derived from (meth) acrylic acid, and (iii) as a group from (meth) acrylic acid glycidyl ester, (meth) acrylate 2-isocyanate ethyl ester And a structural unit derived from at least one compound selected from the group consisting of:

The weight average molecular weight of the component (A-1) 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. 000 is more preferable, 30,000 to 100,000 is particularly preferable, and 40,000 to 100,000 is very preferable. 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-1) is preferably 75 mgKOH / g or more from the viewpoint of easily forming a cured film (cured film pattern) 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-1) is preferably 75 to 200 mgKOH / g, and preferably 75 to 150 mgKOH / g. g is more preferable, and 75 to 120 mgKOH / g is further more preferable. In addition, an acid value can be measured by the method described in the Example of this specification.

The first resin layer 20 may further contain a binder polymer other than the component (A-1) described above.

In the present embodiment, the content ratio of the component (A-1) in the component (A) is preferably 60 to 100% by mass, more preferably 70 to 100% by mass based on the total amount of the component (A). Preferably, it is 80 to 100% by mass.

<Photopolymerizable compound>
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). .

［一般式（Ｂ－１）中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子又はメチル基を示し、Ｘは、トリシクロデカン骨格又はトリシクロデセン骨格を有する２価の基を示し、Ｒ^３及びＲ^４は、それぞれ独立に炭素数１～４のアルキレン基を示し、ｎ及びｍは、それぞれ独立に０～２の整数を示し、ｐ及びｑは、それぞれ独立に０以上の整数を示し、ｐ＋ｑ＝０～１０となるように選択される。］

[In General Formula (B-1), R ¹ and R ² 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 ³ and R ⁴ 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 ³ and R ⁴ 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, 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.

Among these, the polyfunctional vinyl monomer includes a (meth) acrylate compound having a skeleton derived from pentaerythritol, a (meth) acrylate compound having a skeleton derived from dipentaerythritol, and a (meth) acrylate having a skeleton derived from trimethylolpropane. It is more preferable to include a compound, a (meth) acrylate compound having a skeleton derived from ditrimethylolpropane, or a (meth) acrylate compound having a skeleton derived from cyanuric acid. Among these, it is preferable to use a (meth) acrylate compound having a skeleton derived from ditrimethylolpropane because the crack resistance of the cured film can be improved.

Here, the “(meth) acrylate compound having a skeleton derived from” will be described by taking a (meth) acrylate compound having a skeleton derived from ditrimethylolpropane as an example. (Meth) acrylate having a skeleton derived from ditrimethylolpropane means an esterified product of ditrimethylolpropane and (meth) acrylic acid, and the esterified product includes a compound modified with an alkyleneoxy group. The The esterified product preferably has a maximum number of 4 ester bonds in one molecule, but a compound having 1 to 3 ester bonds may be mixed.

In addition, from the viewpoint of forming a cured film pattern having both low moisture permeability and crack resistance, the component (B) is a compound having a tricyclodecane skeleton or a tricyclodecene skeleton, ditrimethylolpropane tetra (meth) acrylate, or the like. It is preferable to include one or more of (meth) acrylate compounds having a skeleton derived from ditrimethylolpropane.

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.

<Photopolymerization initiator>
As the component (C), a conventionally known photopolymerization initiator can be used without any particular limitation, but a highly transparent photopolymerization initiator is preferably used. 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 above general formula (1) is available as IRGACURE OXE 01 (product name, manufactured by BASF Corporation).

The compound represented by the 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 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 8 to 8 parts by mass, further preferably from 1 to 6 parts by mass, and particularly preferably from 1 to 4 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 benzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole, etc. , 3-mercaptotriazole, 5-mercaptotriazole, and other triazole compounds containing a mercapto group are substituted with amino groups.

Examples of the tetrazole compounds having an amino group include 5-amino-1H-tetrazole, 1-methyl-5-amino-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, and 1-carboxymethyl-5-amino-tetrazole. Etc. 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. 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 further contains a phosphate ester containing an ethylenically unsaturated group (hereinafter also referred to as component (E)). Is preferred.

As the component (E), Unichemical Corporation has a high level of compatibility between the adhesion to the base material and the ITO electrode and the developability on the metal wiring while ensuring sufficient rust prevention of the cured film to be formed. The company's Phosmer series (Phosmer-M, Phosmer-CL, Phosmer-PE, Phosmer-MH, Phosmer-PP, etc.) or KAYAMER series (PM-21, PM-2, etc.) manufactured by Nippon Kayaku Co., Ltd. are preferred. .

In the case where the photosensitive resin composition contains the component (E), the content is the component (A) from the viewpoint of achieving both high adhesion to the base material and the ITO electrode and developability on the metal wiring. And 0.1 to 4.0 parts by weight, more preferably 0.2 to 3.0 parts by weight, and further 0.2 to 2.5 parts by weight with respect to 100 parts by weight of the total amount of component (B). 0.2 to 2.0 parts by mass is preferable.

In the photosensitive resin composition forming the first resin layer according to the present embodiment, as other additives, if necessary, an adhesion imparting agent such as a silane coupling agent, a rust inhibitor, a leveling agent, A plasticizer, a filler, an antifoaming agent, a flame retardant, a stabilizer, an antioxidant, a fragrance, a thermal crosslinking agent, a polymerization inhibitor, etc. are each added to 100 parts by mass of the total amount of the component (A) and the component (B). About 0.01 to 20 parts by mass can be contained. These can be used alone or in combination of two or more.

The thickness of the first resin layer may be 1 to 15 μm, preferably 2 to 10 μm, more preferably 3 to 8 μm, still more preferably 4 to 6 μm, and 5 to 6 μm. It is particularly preferred that When the thickness is 1 to 15 μm, there are few defects at the time of coating, and film formation with excellent transparency is possible. The thickness of the first resin layer after curing (that is, the thickness of the cured film pattern) is also preferably within the above 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. Can further be contained. 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.

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 a transfer type photosensitive film is prepared, it becomes 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. These can be used alone or in combination of two or more.

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.

When the second resin layer is a single layer and the film thickness is uniform in the film thickness direction, the refractive index of the second resin layer 30 is as follows using ETA-TCM (product name, manufactured by AudioDev GmbH). Can be requested. 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, since it is difficult to measure the refractive index of the second resin layer single layer in the form of the transfer type photosensitive film, the value of the outermost surface layer on the protective film side of the second resin layer is used.

(Other layers)
The transfer type photosensitive film of this 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 another 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 transfer type photosensitive 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 from the viewpoint of storing the transfer type photosensitive film 1 in a roll shape, it is preferably 70 μm or less, more preferably 60 μm or less, and 50 μm or less. More preferably, it is particularly preferably 40 μm or less.

The entire 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 film 1 in the visible light region having a wavelength of 400 to 700 nm. The minimum value of the light transmittance (Tt) 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. The total light transmittance (Tt) in the visible light region can be measured by the method described in the examples of this specification.

The first resin layer 20 and the second resin layer 30 of the transfer type photosensitive film 1 are prepared, for example, by preparing a first resin layer forming coating solution and a second resin layer forming coating solution. It can form by apply | coating and drying on the support film 10 and the protective film 40, respectively. The transfer type photosensitive 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. It can form by pasting together in the state which opposed resin layer 30 of this. In addition, the transfer type photosensitive film 1 is formed by applying and drying a first resin layer forming coating solution on the support film 10, and then forming a second resin layer forming coating solution on the first resin layer 20. Can be formed by applying, drying, and attaching the protective film 40.

The coating liquid can be obtained by uniformly dissolving or dispersing each component constituting the photosensitive resin composition according to the present embodiment and the second resin layer 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 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 composed of the cured first resin layer 22 and the cured second resin layer 32, and is formed using the transfer type photosensitive 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 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. Lamination (transfer) is performed by pressure bonding from the 30 side. 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 film 1 is thermocompression bonded as described above, the pre-heat 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 in close contact with each other. From the point of further improving the property, 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. The pattern in this specification is not limited to the shape of the fine wiring that forms the circuit, but also includes the shape in which only the connection portion with the other base material is removed in a rectangular shape and the shape in which only the frame portion of the base material is removed. It is.

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.

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.

-Development process-
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 aqueous alkaline 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.

In this embodiment, the cured film pattern is formed using the transfer type photosensitive film having the second resin layer. However, the same method is used when using the transfer type photosensitive film not having the second resin layer. A cured film pattern can be formed.

(Cured film)
The cured film according to the present invention may be a cured film obtained by curing the first resin layer and the second resin layer of the transfer photosensitive film of the present embodiment. For example, when most of the second resin layer is covered with the first resin layer and is not exposed, the second resin layer does not necessarily need to be cured. The cured film according to the present invention includes such a case that the first resin layer is cured and the second resin layer is not cured. The cured film according to the present invention is preferably formed in a pattern.

The cured film according to the present invention may be a cured film obtained by curing the first resin layer when the transfer type photosensitive film does not have the second resin layer.

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

For example, the touch sensor can include the laminate 100 shown in FIG. When the touch sensor is a module such as a touch panel, OCA that adheres the cover glass and the laminate 100 can be used.

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, a cured film pattern is formed across the portion where the transparent electrode pattern is formed and the portion where the transparent electrode pattern is not formed, using the transfer type photosensitive film of the present embodiment. 123 is formed. The cured film pattern 123 includes a cured first resin layer and a cured second resin layer. In addition, when the transfer type photosensitive film which does not have a 2nd resin layer is used, the cured film pattern 123 consists of a hardened 1st resin layer. According to this cured film 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 bone of the sensing region (touch screen) 102 formed from the transparent electrode pattern A visual phenomenon prevention function can be performed at the same time. In addition, by using the transfer type photosensitive film of the present embodiment, the cured film pattern 123 can have a sufficiently small step on the surface.

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

[Preparation of binder polymer solution]
(Polymer solution 1)
85.7 parts by mass of 1-methoxy-2-propanol (manufactured by Daicel Chemical Industries) was added in advance to the reaction vessel, and the temperature was raised to 80 ° C. On the other hand, 48.5 parts by weight of methacrylic acid, 11.5 parts by weight of benzyl methacrylate, 40.0 parts by weight of tricyclodecane methacrylate, and 10 parts by weight of an azo polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) Parts were mixed to obtain a mixed solution. This mixed solution was dropped into the reaction vessel at 80 ° C. over 2 hours under a nitrogen gas atmosphere. Reaction was performed for 4 hours after the dropwise addition to obtain an acrylic 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 acrylic resin solution, and then 38.1 parts by mass of glycidyl methacrylate was added dropwise over 2 hours. After dripping, after reacting at 80 ° C. for 4 hours while blowing air, propylene glycol monomethyl ether acetate was added as a solvent so that the solid content concentration was 45% by mass, and a binder polymer solution 1 was obtained.

(Polymer solutions 2-5 and 8)
Binder polymer solutions 2 to 5 and 8 (all having a solid content of 45% by mass) were obtained in the same manner as in the binder polymer solution 1 except that the blending amount was changed as shown in Table 1.

(Polymer solutions 6, 7 and 9)
A flask equipped with a stirrer, reflux condenser, inert gas inlet and thermometer was charged with 62 parts by weight of propylene glycol monomethyl ether and 62 parts by weight of toluene as a solvent, and the temperature was raised to 80 ° C. in a nitrogen gas atmosphere. Then, while maintaining the reaction temperature at 80 ° C. ± 2 ° C., a solution in which the compound shown in Table 1 and 1.5 parts by mass of 2,2′-azobis (isobutyronitrile) were mixed was uniformly added dropwise over 4 hours. . After the dropping, stirring was continued at 80 ° C. ± 2 ° C. for 6 hours to obtain binder polymer solutions 6, 7 and 9 having a solid content of 45% by mass (all of which had a solid content of 45% by mass).

The ethylenically unsaturated group equivalent, the weight average molecular weight, and the acid value of the binder polymer described above were determined by the following methods. The results are shown in Table 1.

[Calculation method of ethylenically unsaturated group equivalent]
The double bond equivalent of the binder polymer was calculated from the charged amount according to the following formula.
Ethylenically unsaturated group equivalent (mmol / g) = Glycidyl methacrylate addition amount (mmol) / Total monomer addition amount (g)

[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 (concentration conversion factor) of 0.1 mol / L potassium hydroxide aqueous solution,
Wp represents the mass (g) of the measured resin solution, and I represents the proportion (mass%) of the non-volatile content in the measured resin solution.

(Polymer solution 10)
A flask equipped with a stirrer, reflux condenser, inert gas inlet and thermometer was charged with 62 parts by mass of propylene glycol monomethyl ether and 62 parts by mass of toluene, and the temperature was raised to 80 ° C. in a nitrogen gas atmosphere, and the reaction temperature was increased. Was maintained at 80 ° C. ± 2 ° C., and the compounds shown in Table 2 and 1.5 parts by mass of 2,2′-azobis (isobutyronitrile) were uniformly added dropwise over 4 hours. After dropping, stirring was continued at 80 ° C. ± 2 ° C. for 6 hours to obtain a binder polymer solution 10 (solid content: 45 mass%) having a weight average molecular weight of 30000 and an acid value of 156.6 mgKOH / g.

(Examples 1 to 7 and Comparative Examples 1 to 4)
[Preparation of first resin layer forming coating solution]
Methyl ethyl ketone is prepared as a solvent, the components shown in Table 3 or 4 are blended in the blending amounts (unit: parts by mass) shown in the same table, and mixed for 15 minutes using a stirrer to form a first resin layer forming coating solution Was made. In Tables 3 and 4, the amount of component (A) indicates the amount of solids.
[Preparation of second resin layer forming coating solution]

The components shown in Table 3 or 4 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 coating solution for forming a resin layer. In Tables 3 and 4, the blending amount of the binder polymer solution 10 indicates the blending amount of the solid content.

[Production of transfer-type photosensitive film]

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. 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 μm.

Using a polypropylene film having a thickness of 30 μm (product name: ES-201, manufactured by Oji F-Tex Co., Ltd.) as the protective film, the second coating solution for forming a resin layer prepared above was used on the protective film using a die coater. The solution was uniformly applied and dried for 3 minutes with a hot air retention drier at 110 ° C. to remove the solvent, thereby forming a second resin layer having a thickness of 60 nm and a refractive index of 1.4.

Next, the support film having the first resin layer and the protective film having the second resin layer are bonded at 23 ° C. using a laminator (manufactured by Hitachi Chemical Co., Ltd., product name: HLM-3000 type). Then, a transfer type photosensitive film in which the support film, the first resin layer, the second resin layer, and the protective film were laminated in this order was produced.

The symbols of the components in Tables 3 to 4 have the following meanings.
[Component (A)]
Polymer solutions 1 to 9: Binder polymer solution prepared by the method described above Polymer solution 10: Binder polymer solution prepared by the method described above

[(B) component]
A-DCP: Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)
T-1420: Ditrimethylolpropane tetraacrylate (Nippon Kayaku Co., Ltd., product name)

[Component (C)]
OXE01: 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (product name “IRGACURE OXE 01” manufactured by BASF Corporation)

[(Other) ingredients]
ADDITIVE 8032: Octamethylcyclotetrasiloxane (product name, manufactured by Toray Dow Corning Co., Ltd.)
AW500: 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (product name, manufactured by Kawaguchi Chemical Co., Ltd.)
B6030: 5-1H-aminotetrazole (product name, manufactured by Chiyoda Chemical Co., Ltd.)

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

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

[Measurement of moisture permeability]
While peeling off the protective film of the transfer type photosensitive film obtained in Examples and Comparative Examples, Lamination was performed under conditions of a roll temperature of 80 ° C., a substrate feed rate of 0.6 m / min, and a pressure of pressure (cylinder pressure) of 0.5 MPa so that the second resin layer was in contact with 5C filter paper (manufactured by Advantech). A laminate in which the second resin layer, the first resin layer, and the support film were laminated on 5C filter paper was produced.

After producing the laminated body obtained above, using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.), the exposure amount is 5 × 10 ² J / m ² (i-line) from vertically above the support film surface. (Measured value at a wavelength of 365 nm) and ultraviolet rays were irradiated imagewise. Subsequently, the support film laminated | stacked on the 1st resin layer is removed, and also with the exposure amount of 1 * 10 < ⁴ > J / m < ² > from the upper side of the 1st resin layer side (measurement value in i line (wavelength 365nm)) Ultraviolet rays were irradiated to obtain a moisture permeability measurement sample in which a cured film made of the cured product of the second resin layer and the cured product of the first resin layer was formed.

Next, with reference to JIS standard (Z0208), a cup method was performed as a moisture permeability measurement. About 20 g of dried calcium chloride is put in the measuring cup, and the lid is covered with a circular sample cut out with scissors to a size of about φ70 mm from the above test sample, and 60 ° C. and 90% RH in a constant temperature and humidity chamber. The condition was left for 24 hours. The moisture permeability [g / m ² · 24 h] was calculated from the weight change before and after being left standing. In addition, if the moisture permeability of a cured film is 250 or less, sufficient rust prevention effect will be acquired.

[Evaluation of crack resistance]
While peeling off the protective film of the transfer type photosensitive film obtained in the examples and comparative examples, a roll temperature of 100 ° C. and a substrate feed rate of 0.6 m are provided so that the second resin layer is in contact with the polyethylene terephthalate film having a thickness of 50 μm. / Min. And a pressure bonding pressure (cylinder pressure) of 0.5 MPa, and a laminate in which a second resin layer, a first resin layer, and a support film were laminated on a polyethylene terephthalate film was produced.

After producing the laminated body obtained above, a photomask is placed on the support film, and an exposure amount of 5 is applied from above the photomask surface vertically using a parallel light exposure machine (EXM1201 manufactured by Oak Manufacturing Co., Ltd.). At 10 ² J / m ² (measured value at i-line (wavelength 365 nm)), ultraviolet rays were imagewise irradiated. Subsequently, the support film laminated | stacked on the 1st resin layer is removed, and also with the exposure amount of 1 * 10 < ⁴ > J / m < ² > from the upper side of the 1st resin layer side (measurement value in i line (wavelength 365nm)) The sample for a mandrel test in which a cured film composed of the cured product of the second resin layer and the cured product of the first resin layer was formed by irradiation with ultraviolet rays was obtained.

Next, a mandrel test was performed with reference to the JIS standard (K5400). The test sample was cut with scissors to a size of 1.5 cm × 4.0 cm and set in a cylindrical mandrel bending tester (manufactured by BYK Gardner). One side of the sample is fixed, a weight of 100 g is attached to one side, the protective film side is bent to 180 degrees around the cylinder with the protective film side as the upper surface, and the cured film side is observed with a microscope. According to the following rating Crack resistance was evaluated.
φ0.5: Uses a cylinder of φ0.5mm, and there is no crack in the protective film.
φ1: A cylinder of φ1.0mm is used, and there is no crack in the protective film.
φ2: Uses a cylinder with a diameter of φ2.0mm, and there is no crack in the protective film.
φ3: Uses a cylinder with a diameter of φ3.0mm, and there is no crack in the protective film.

[Evaluation of adhesion]
An index matching layer (IM layer) and a substrate with ITO were prepared. While peeling the protective film of the transfer type photosensitive film obtained in Examples and Comparative Examples on the ITO of the base material, the second resin layer is opposed to the base material, and the roll temperature is 100 ° C., the substrate feed speed. Lamination was performed under the conditions of 0.4 m / min and pressure bonding pressure (cylinder pressure) of 4 × 10 ⁵ Pa. After laminating, the substrate was cooled, and when the temperature of the substrate reached 23 ° C., using an exposure machine having a high-pressure mercury lamp from the support film side (manufactured by Oak Manufacturing Co., Ltd., trade name: EXM-1201), Light irradiation was performed at an exposure amount of 80 mJ / cm ² . Next, a sample for cross-cut adhesion test composed 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 was obtained.

A cross-cut test was performed based on ASTM D3359 for the adhesion of the cured film to the index matching layer (IM layer) and the substrate with ITO, and the ratio of the peeled portion was measured. Based on this measurement result, a case where adhesion was the best (no peeling at all) was “5”, and a case where it was the worst (all peeling) was “0”. .

[Evaluation of reliability (85 ° C., 85% RH)]
While peeling the protective film of the transfer type photosensitive film obtained in Examples and Comparative Examples on a copper substrate (length 12 cm × width 5 cm), the second resin layer was opposed to the substrate, and the roll temperature 100 Lamination was performed at a temperature of 0 ° C., a substrate feed rate of 0.4 m / min, and a pressure bonding pressure (cylinder pressure) of 4 × 10 ⁵ Pa. After laminating, the substrate was cooled, and when the temperature of the substrate reached 23 ° C., using an exposure machine having a high-pressure mercury lamp from the support film side (manufactured by Oak Manufacturing Co., Ltd., trade name: EXM-1201), Light irradiation was performed at an exposure amount of 80 mJ / cm ² . Next, the support film was removed and irradiated with light at an exposure amount of 400 mJ / cm ² . Next, using a dryer, sintering was performed at 140 ° C. for 30 minutes to obtain a sample for reliability test including a cured film of the first resin layer having a thickness of 8.0 μm and a cured product of the second resin layer. The obtained sample was left in a high-temperature and high-humidity tank at 85 ° C. and 85% RH, and the time until the copper substrate was corroded with the naked eye was evaluated.

DESCRIPTION OF SYMBOLS 1 ... Transfer type photosensitive film, 10 ... Support film, 20 ... 1st resin layer, 22 ... Cured 1st resin layer, 30 ... 2nd resin layer, 32 ... 2nd cured resin layer, 40 DESCRIPTION OF SYMBOLS ... Protective film, 50 ... Base material with transparent electrode pattern, 50a ... Transparent electrode pattern, 60 ... Cured film, 100 ... Laminated body, 101 ... Transparent base material, 102 ... Sensing region, 103, 104 ... Transparent electrode, 105 ... Drawer Wiring, 106... Connection electrode, 107... Connection terminal, 123.

Claims (10)

A support film, and a first resin layer provided on the support film,
The first resin layer contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator,
The binder polymer contains a group having a branched and / or 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 0.50 A transfer type photosensitive film having an ethylenically unsaturated group equivalent of ˜3.00 mmol / g. The transfer type photosensitive film according to claim 1, wherein the binder polymer further contains a group having a phenyl group in a side chain. The transfer type photosensitive film according to claim 1 or 2, wherein the first resin layer further comprises a phosphate ester having an ethylenically unsaturated group. The transfer type photosensitive film according to any one of claims 1 to 3, wherein the photopolymerization initiator contains an oxime ester compound. 5. The transfer type photosensitive film according to claim 1, further comprising a second resin layer containing metal oxide particles provided on the first resin layer. The first resin layer of the transfer type photosensitive film according to any one of claims 1 to 4 is formed on a substrate having an electrode, the side of the substrate on which the electrode is provided, and the first resin layer. Laminating so that one resin layer is in close contact,
After exposing a predetermined portion of the first resin layer on the substrate, removing the portion other than the predetermined portion, forming a cured film pattern that covers a part or all of the electrode;
A method for forming a cured film pattern. The second resin layer and the first resin layer of the transfer type photosensitive film according to claim 5 on the substrate having an electrode, the side of the substrate on which the electrode is provided and the first resin layer. Laminating so that the two resin layers are in close contact with each other;
A step of forming a cured film pattern that covers a part or all of the electrode by removing a part other than the predetermined part after exposing the predetermined part of the second resin layer and the first resin layer on the substrate. When,
A method for forming a cured film pattern. A cured film obtained by curing the first resin layer in the transfer type photosensitive film according to any one of claims 1 to 4. 6. A cured film obtained by curing only the first resin layer of the transfer type photosensitive film according to claim 5, or both the first resin layer and the second resin layer. The cured product of the first resin layer in the transfer type photosensitive film according to any one of claims 1 to 4, or the second resin layer of the transfer type photosensitive film according to claim 5. A touch panel comprising a cured film pattern comprising a cured product and a cured product of the first resin layer.

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