JP7010796B2 - A method for manufacturing a photosensitive resin composition, a cured film, a laminate, a transfer film, and a touch panel. - Google Patents

Description

The present disclosure relates to a method for manufacturing a photosensitive resin composition, a cured film, a laminate, a transfer film, and a touch panel.

In electronic devices such as mobile phones, car navigation systems, personal computers, ticket vending machines, and bank terminals, tablet-type input devices are arranged on the surface of liquid crystal devices and the like in recent years. There is a device that can input information corresponding to an instruction image by touching a place where the instruction image is displayed with a finger or a stylus while referring to the instruction image displayed in the image display area of the liquid crystal device.

The input device as described above (hereinafter, may be referred to as a touch panel) includes a resistance film type and a capacitance type. The capacitance type input device has an advantage that a translucent conductive film may simply be formed on a single substrate. In such a capacitance type input device, for example, electrode patterns are extended in directions intersecting each other, and when a finger or the like comes into contact, the change in capacitance between the electrodes is detected to detect the input position. There is a type of device.
A transparent resin layer on the opposite side of the surface to be input with a finger, etc., for the purpose of protecting the electrode pattern of the capacitance type input device and the routing wiring (for example, metal wiring such as copper wire) gathered in the frame part. Is provided.

When using these capacitive input devices, for example, when the surface of the touch panel is visually observed at a position slightly away from the vicinity of the specular reflection of the incident light from the light source, the transparent electrode pattern existing inside is visually observed, and the appearance is apparent. It may cause problems. Therefore, it is required to improve the concealing property of the transparent electrode pattern on the surface of a touch panel or the like.

Examples of the method for forming a pattern of a cured resin film using a photosensitive resin composition include those described in Patent Document 1.
Patent Document 1 describes a first step of providing a photosensitive layer made of a photosensitive resin composition containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a thiol compound on a substrate. A second step of curing the predetermined portion of the photosensitive layer by irradiation with active light, and a third step of removing other than the predetermined portion of the photosensitive layer to form a cured film pattern of the predetermined portion of the photosensitive layer. Describes a method for forming a resin cured film pattern, wherein the photosensitive resin composition contains an oxime ester compound and / or a phosphine oxide compound as the photopolymerization initiator.

Further, examples of the photosensitive resin composition include those described in Patent Document 2 or 3.
Patent Document 2 describes [A] a polymer having a polymerization unit derived from an ethylenically unsaturated carboxylic acid and / or a polymerization unit derived from an ethylenically unsaturated carboxylic acid anhydride, and [B] an ethylenically unsaturated bond. Polymerizable compound having, [C] photopolymerization initiator and [D] the following formula (1) or (2):

（式（１）において、Ｒ_１は、メチレン基または炭素数２～２０のアルキレン基であり、Ｒ_２はメチレン基または炭素数２～６の直鎖もしくは分岐アルキレン基でありそしてｍは１～２０の整数を表わす）

(In formula (1), R ₁ is a methylene group or an alkylene group having 2 to 20 carbon atoms, R ₂ is a methylene group or a linear or branched alkylene group having 2 to 6 carbon atoms, and m is 1 to 1 to. Represents an integer of 20)

（式（２）において、Ｒは、同一もしくは異なり、－Ｈ、－ＯＨまたは下記式（２’）

(In the formula (2), R is the same or different, -H, -OH or the following formula (2').

₃ is a methylene group or a linear or branched alkylene group having 2 to 6 carbon atoms, wherein at least one of the four Rs is a group represented by the above formula (2'). ,)
Described is a photosensitive resin composition used for forming a spacer for a liquid crystal display element, which comprises a thiol compound represented by.

Patent Document 3 contains a polymerizable compound having an ethylenically unsaturated bond as the component A, a polymerization initiator as the component B, a thiol compound as the component S, and an organic solvent as the component D. A contains a 6-functional or higher functional urethane (meth) acrylate, the proportion of the above 6-functional or higher urethane (meth) acrylate in the component A is 70 to 100% by mass, and the content of the component S is curable. Described are curable compositions characterized in that they are 1-20% by mass based on the total solid content of the composition.

International Publication No. 2013/084872 Japanese Unexamined Patent Publication No. 2008-77067 International Publication No. 2015/072533

The problem to be solved by one embodiment of the present invention is to provide a photosensitive resin composition having excellent development residue inhibitory properties, low moisture permeability of the obtained cured film, and excellent bending resistance of the obtained cured film. be.
Another object to be solved by another embodiment of the present invention is to provide a method for manufacturing a cured film, a laminate, a transfer film, and a touch panel using the photosensitive resin composition.

The means for solving the above problems include the following aspects.
<1> A photosensitive compound containing a binder polymer, an ethylenically unsaturated compound, and a photopolymerization initiator, wherein the ethylenically unsaturated compound contains a bifunctional or higher functional ethylenically unsaturated compound A having a thioether bond. Resin composition.
<2> The number of atoms of the shortest connecting chain connecting between at least two ethylenically unsaturated bonds in the bifunctional or higher functional ethylenically unsaturated compound A is 10 to 30. Photosensitive resin composition.
<3> The photosensitive resin composition according to <1> or <2>, wherein the linking chain in the bifunctional or higher functional ethylenically unsaturated compound A is a chain composed of a carbon atom, an oxygen atom and a sulfur atom.
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the bifunctional or higher functional ethylenically unsaturated compound A has 1 or more and 4 or less sulfur atoms. ..
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the bifunctional or higher functional ethylenically unsaturated compound A is a bifunctional ethylenically unsaturated compound.
<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the bifunctional or higher functional ethylenically unsaturated compound A is a compound represented by the following formula A-1.

In formula (A-1), ^RA1 and ^RA2 independently represent a hydrogen atom or a methyl group, and ^LA1 and ^LA3 independently represent an alkylene group or ^−LA6 (SL ^A7 ) _nA −. , ^LA2 , ^LA6 and ^LA7 each independently represent an alkylene group and nA represents an integer of 1-8.

<7> The photosensitive resin composition according to any one of <1> to <6>, wherein the ethylenically unsaturated compound contains an ethylenically unsaturated compound B having an alicyclic structure.
<8> The mass ratio _MA / MB of the content _MA of the ethylenically unsaturated compound _A having two or more functionalities and the content MB of the ethylenically unsaturated compound _B is 0.2 to 1. The photosensitive resin composition according to <7>, which is 5.
<9> The photosensitive resin composition according to any one of <1> to <8> for forming a touch panel protective film.
<10> A transfer film having a temporary support and a photosensitive layer made of the photosensitive resin composition according to any one of <1> to <9>.
<11> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <9>.
<12> A laminate having a substrate and a cured film obtained by curing the photosensitive resin composition according to any one of <1> to <9>.
<13> A touch panel substrate having a structure in which at least one of a touch panel electrode and a touch panel wiring is arranged on the substrate is prepared, and at least one of the touch panel electrode and the touch panel wiring of the touch panel substrate is arranged. A photosensitive layer containing the photosensitive resin composition according to any one of <1> to <9> is formed on the surface on the side of the surface, and the touch panel substrate is formed. By pattern-exposing the photosensitive layer and developing the pattern-exposed photosensitive layer, a touch panel protective film that protects at least a part of at least one of the touch panel electrode and the touch panel wiring can be obtained. And, including how to manufacture a touch panel.
<14> The method for manufacturing a touch panel according to <13>, wherein the protective film for the touch panel is provided in the bent region of the touch panel.

According to one embodiment of the present invention, it is possible to provide a photosensitive resin composition having excellent development residue inhibitory properties, low moisture permeability of the obtained cured film, and excellent bending resistance of the obtained cured film.
Further, according to another embodiment of the present invention, it is possible to provide a method for manufacturing a cured film, a laminate, a transfer film, and a touch panel using the photosensitive resin composition.

It is a schematic sectional drawing which shows an example of the transfer film which concerns on this disclosure. It is a schematic sectional drawing which shows the 1st specific example of the touch panel which concerns on this disclosure. It is a schematic sectional drawing which shows the 2nd specific example of the touch panel which concerns on this disclosure. It is sectional drawing which shows the state of the sample for bending resistance evaluation in bending resistance evaluation.

The contents of the present disclosure will be described in detail below. The description of the constituents described below may be based on the representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.
In the present disclosure, "-" indicating a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.
In the numerical range described stepwise in the present specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. good. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
Further, in the notation of a group (atomic group) in the present disclosure, the notation that does not describe substitution or non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "total solid content" refers to the total mass of the components excluding the solvent from the total composition of the composition. Further, the "solid content" is a component excluding the solvent as described above, and may be, for example, a solid or a liquid at 25 ° C.
Further, in the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Further, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
In the present disclosure, the amount of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. do.
In the present disclosure, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
In the present disclosure, "(meth) acrylic acid" is a concept that includes both acrylic acid and methacrylic acid, and "(meth) acrylate" is a concept that includes both acrylate and methacrylate, and "(meth) acrylate" is a concept. ) Acryloyl group ”is a concept that includes both acryloyl group and methacrylic acid group.
Further, for the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure, unless otherwise specified, columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.) are used. The molecular weight is detected by the solvent THF (tetrahydrofuran) and the differential refractometer by the gel permeation chromatography (GPC) analyzer and converted using polystyrene as a standard substance.
In the present disclosure, the ratio of the constituent units in the resin represents the molar ratio unless otherwise specified.
In the present disclosure, the molecular weight when there is a molecular weight distribution represents a weight average molecular weight (Mw) unless otherwise specified.
Hereinafter, the present disclosure will be described in detail.

(Photosensitive resin composition)
The photosensitive resin composition according to the present disclosure contains a binder polymer, an ethylenically unsaturated compound, and a photopolymerization initiator, and the ethylenically unsaturated compound has a bifunctional or higher functionality having a thioether bond. Contains unsaturated compound A.
Further, the photosensitive resin composition according to the present disclosure can be suitably used as a photosensitive resin composition for forming a touch panel protective film, and more preferably used as a photosensitive resin composition for forming an electrode of a touch panel or a wiring protective film. be able to.

As a result of diligent studies by the present inventor, a photosensitive resin composition having excellent development residue inhibitory properties, low moisture permeability of the obtained cured film, and excellent bending resistance of the obtained cured film is provided. I found that I could do it.
The mechanism of action of this excellent effect is not clear, but it is estimated as follows.
By containing a bifunctional or higher functional unsaturated compound A having a thioether bond, a carbon-sulfur bond having a longer bond length than a carbon-carbon bond and a wide bond angle tolerance is introduced in the cured film. By forming the crosslinked structure, the bending resistance is improved and the crosslinked network can be made dense, so that the permeation rate of water vapor can be reduced and low moisture permeability can be ensured.
Further, by introducing a sulfur atom into a part of the crosslinked structure by the bifunctional or higher functional ethylenically unsaturated compound A having a thioether bond, the solubility in the developing solution is increased due to the polarity of the sulfur atom, and the development residue is developed. Is suppressed.

Hereinafter, the photosensitive resin composition according to the present disclosure will be described in detail.

<Ethylene unsaturated compound>
The photosensitive resin composition according to the present disclosure contains an ethylenically unsaturated compound, and the above-mentioned ethylenically unsaturated compound contains a bifunctional or higher functional ethylenically unsaturated compound A having a thioether bond.

<< Bifunctional or higher functional ethylenically unsaturated compound A >>
The photosensitive resin composition according to the present disclosure contains a bifunctional or higher functional ethylenically unsaturated compound A having a thioether bond as the ethylenically unsaturated compound.
The bifunctional or higher functional ethylenically unsaturated compound A is a compound having two or more ethylenically unsaturated bonds and one or more thioether bonds.
The number of ethylenically unsaturated bonds possessed by the bifunctional or higher ethylenically unsaturated compound A is preferably bifunctional or higher and 15 functional or less, more preferably bifunctional or higher and 6 functional or lower, and bifunctional. It is more preferably tetrafunctional or less, and particularly preferably bifunctional.
The ethylenically unsaturated group contained in the bifunctional or higher functional ethylenically unsaturated compound A is not particularly limited, and is, for example, a (meth) acryloxy group, a (meth) acrylamide group, a vinyl group, an allyl group, a vinyl ether group, or vinyl. Examples thereof include an ester group and a styryl group.
Above all, a (meth) acryloxy group is preferable from the viewpoint of reactivity and the strength of the obtained cured film.
Further, the two or more ethylenically unsaturated groups of the bifunctional or higher functional ethylenically unsaturated compound A may be the same group or different groups from each other, but the same group is preferable. ..

The number of atoms of the shortest connecting chain connecting between at least two ethylenically unsaturated bonds in the bifunctional or higher functional ethylenically unsaturated compound A is the development residue inhibitory property, and the moisture permeability and bending of the obtained cured film. From the viewpoint of resistance, the number is preferably 10 to 30, more preferably 12 to 26, further preferably 16 to 24, and particularly preferably 18 to 22. preferable.
In the present disclosure, "the number of atoms in the shortest connecting chain connecting between at least two ethylenically unsaturated bonds" means at least one other ethylenically unsaturated bond from an atom connected to at least one ethylenically unsaturated bond. It is the shortest number of atoms that connects up to the atom that connects to the bond.
When having three or more ethylenically unsaturated groups, the two ethylenically unsaturated bonds having the smallest number of atoms among the number of atoms in the shortest connecting chain between the two ethylenically unsaturated bonds. Let it be the number of atoms in the shortest connecting chain between.
Specifically, in the following compounds, the number of atoms of the shortest linking chain between wavy lines is 12, and the number of atoms of the shortest linking group is 12.

Further, in the following compound, the number of atoms of the shortest linking chain between wavy lines is 6, and the number of atoms of the shortest linking group is 6.

The linking chain in the bifunctional or higher functional ethylenically unsaturated compound A is a chain composed of carbon atoms, oxygen atoms and sulfur atoms from the viewpoint of suppressing development residue, moisture permeability and bending resistance of the obtained cured film. It is preferable to have.
In addition, the atom constituting the above-mentioned connecting chain is an atom constituting the shortest connecting chain connecting between two ethylenically unsaturated bonds, and has a hydrogen atom in a carbon atom like the above-mentioned compound. Even so, there are three types of atoms constituting the shortest connecting chain: carbon atom, oxygen atom, and sulfur atom.

The number of sulfur atoms contained in the bifunctional or higher functional ethylenically unsaturated compound A is preferably 1 or more and 8 or less, preferably 1 or more, from the viewpoint of suppressing development residue and moisture permeability of the obtained cured film. It is more preferably 4 or less, further preferably 2 or more and 4 or less, and particularly preferably 2 or 3.

The bifunctional or higher functional ethylenically unsaturated compound A may be linear, branched, or has a ring structure, but from the viewpoint of bending resistance of the obtained cured film. , Is preferably a linear compound.
The molecular weight of the bifunctional or higher ethylenically unsaturated compound A is preferably 260 or more and 600 or less, preferably 280 or more, from the viewpoint of suppressing development residue, moisture permeability and bending resistance of the obtained cured film. It is more preferably 500 or less, and particularly preferably 340 or more and 420 or less.

The bifunctional or higher functional ethylenically unsaturated compound A preferably has no ether bond, and more preferably has no oxygen atom other than an ester bond, from the viewpoint of moisture permeability and bending resistance of the obtained cured film.
Further, the bifunctional or higher functional ethylenically unsaturated compound A is preferably a compound consisting only of a carbon atom, a hydrogen atom, an oxygen atom and a sulfur atom from the viewpoint of moisture permeability and bending resistance of the obtained cured film.
Further, the bifunctional or higher functional ethylenically unsaturated compound A preferably has a linear alkylene group having 4 to 16 carbon atoms from the viewpoint of suppressing development residue, moisture permeability of the obtained cured film and bending resistance. It is more preferable to have a linear alkylene group having 6 to 14 carbon atoms, and particularly preferably to have a linear alkylene group having 8 to 12 carbon atoms.

The bifunctional or higher functional ethylenically unsaturated compound A is represented by the following formula (A-1) or formula (A-2) from the viewpoint of suppressing development residue, moisture permeability of the obtained cured film, and bending resistance. It is preferably a compound, and more preferably a compound represented by the following formula (A-1).

In formulas (A-1) and (A-2), ^{RA1 to RA4 independently} represent a hydrogen atom or a methyl group, and ^{LA1 and LA3 independently} represent an alkylene group or ^-LA6 (respectively). SL ^A7 ) represents ^nA- , LA2 and ^LA4 to ^LA7 independently represent an alkylene group, and _nA represents an integer of 1 to 8.

^{RA1 to RA4 in} the formulas (A-1) and (A-2) are preferably hydrogen atoms from the viewpoint of reactivity and bending resistance of the obtained cured film.
LA1 and ^LA3 in the formula ( ^A -1) are independently each of an alkylene group having 2 to 8 carbon atoms or ^-LA6 (SL) from the viewpoint of suppressing development residue, moisture permeability and bending resistance of the obtained cured film. ^A7 ) It is preferably _nA −, more preferably an alkylene group having 2 to 8 carbon atoms, further preferably an alkylene group having 2 to 4 carbon atoms, and particularly preferably an ethylene group.
^LA6 and ^LA7 are each independently preferably an alkylene group having 2 to 8 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms, from the viewpoint of suppressing development residue, moisture permeability of the obtained cured film, and bending resistance. It is more preferably a group, further preferably an alkylene group having 2 or 3 carbon atoms, and particularly preferably an ethylene group.
nA is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and 1 or 2 from the viewpoint of suppressing development residue, moisture permeability of the obtained cured film, and bending resistance. Is particularly preferred.
LA2 in the formula ( ^A -1) is preferably an alkylene group having 2 to 18 carbon atoms, preferably having 3 to 18 carbon atoms, from the viewpoint of suppressing development residue, moisture permeability of the obtained cured film, and bending resistance. It is more preferably an alkylene group, further preferably an alkylene group having 4 to 16 carbon atoms, particularly preferably an alkylene group having 6 to 14 carbon atoms, and particularly preferably an alkylene group having 8 to 12 carbon atoms. Is the most preferable.
LA4 and ^LA5 in the formula ( ^A -2) are preferably alkylene groups having 2 to 8 carbon atoms independently from the viewpoint of suppressing development residue, moisture permeability of the obtained cured film, and bending resistance. It is more preferably an alkylene group having 2 to 4 carbon atoms, further preferably an alkylene group having 2 or 3 carbon atoms, and particularly preferably an ethylene group.
The alkylene groups in ^{LA1 to LA7 may} be linear, have branches, or have a ring structure, but are linear from the viewpoint of bending resistance of the obtained cured film. It is preferably an alkylene group.

Preferred specific examples of the bifunctional or higher functional ethylenically unsaturated compound A are shown below, but it goes without saying that the compound A is not limited thereto.

The photosensitive resin composition may contain the bifunctional or higher functional ethylenically unsaturated compound A alone or may contain two or more.
The content of the above bifunctional or higher functional ethylenically unsaturated compound A is 1% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of suppressing development residue, moisture permeability of the obtained cured film and bending resistance. It is preferably ~ 40% by mass, more preferably 2% by mass to 30% by mass, and particularly preferably 5% by mass to 25% by mass.

<< Ethylene unsaturated compound B >>
The photosensitive resin composition according to the present disclosure preferably contains an ethylenically unsaturated compound B having an alicyclic structure as the ethylenically unsaturated compound.
The ethylenically unsaturated compound B may be a monofunctional ethylenically unsaturated compound or a polyfunctional ethylenically unsaturated compound, but from the viewpoint of moisture permeability of the obtained cured film, it is polyfunctional ethylenically. It is preferably an unsaturated compound, more preferably a 2-4 functional ethylenically unsaturated compound, even more preferably a bifunctional ethylenically unsaturated compound, and preferably a bifunctional (meth) acrylate compound. Especially preferred.
The ethylenically unsaturated compound B is preferably a compound different from the bifunctional ethylenically unsaturated compound A.
The ethylenically unsaturated group contained in the ethylenically unsaturated compound B is not particularly limited, and is, for example, a (meth) acryloxy group, a (meth) acrylamide group, a vinyl group, an allyl group, a vinyl ether group, a vinyl ester group, or a styryl. The group etc. can be mentioned.
Above all, a (meth) acryloxy group is preferable from the viewpoint of reactivity and the strength of the obtained cured film.

The alicyclic structure of the ethylenically unsaturated compound B may be an aliphatic hydrocarbon ring structure or an aliphatic heterocyclic structure, but from the viewpoint of moisture permeability and bending resistance of the obtained cured film. Therefore, it is preferable to have an aliphatic hydrocarbon ring structure.
Examples of the alicyclic structure of the ethylenically unsaturated compound B include a cycloalkane ring structure, a bicycloalkane ring structure, a tricycloalkane ring structure, and a tetracycloalkane ring structure.
Specifically, a cyclopentane ring structure, a cyclohexane ring structure, an adamantane ring structure, a norbornane ring structure, a norbornene ring structure, an isobornane ring structure, a tricyclodecane ring structure, a tetracyclododecane ring structure and the like are preferably mentioned.
Among them, as the alicyclic structure of the ethylenically unsaturated compound B, a condensed alicyclic structure having two or more rings is preferable, a condensed alicyclic structure having three or more rings is more preferable, and a tricyclodecane ring structure is particularly preferable.

Specific examples of the ethylenically unsaturated compound B include tricyclodecanedimethanol di (meth) acrylate, dicyclopentenyldi (meth) acrylate, dicyclopentanyldi (meth) acrylate, and decahydrodiacrylate. , Isobornyldi (meth) acrylate, tricyclodecantry (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) Examples thereof include acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl (meth) acrylate.

The photosensitive resin composition may contain the ethylenically unsaturated compound B alone or in combination of two or more.
The content of the ethylenically unsaturated compound B is 1% by mass to 50% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of suppressing development residue, moisture permeability of the obtained cured film and bending resistance. Is preferable, 5% by mass to 45% by mass is more preferable, and 10% by mass to 40% by mass is particularly preferable.

The mass ratio _MA / MB of the content _MA of the bifunctional or higher ethylenically unsaturated compound _A and the content MB of the ethylenically unsaturated compound _B in the photosensitive resin composition is developed. From the viewpoint of residue suppression, moisture permeability and bending resistance of the obtained cured film, it is preferably 0.05 to 5.0, more preferably 0.1 to 2.0, and 0.2 to 1. It is particularly preferable that it is 5.5.

<< Other ethylenically unsaturated compounds >>
The photosensitive resin composition according to the present disclosure is an ethylenically unsaturated compound (other ethylenically unsaturated compounds) other than the above bifunctional or higher ethylenically unsaturated compound A and the above ethylenically unsaturated compound B as ethylenically unsaturated compounds. It may contain a saturated compound).
The other ethylenically unsaturated compound is not particularly limited, and known ethylenically unsaturated compounds can be used.
The ethylenically unsaturated group contained in the other ethylenically unsaturated compound is not particularly limited, and may be any known ethylenically unsaturated group. Specific examples thereof include (meth) acryloxy group, (meth) acrylamide group, vinyl group, allyl group, vinyl ether group, vinyl ester group, styryl group and the like.
Above all, a (meth) acryloxy group is preferable from the viewpoint of reactivity and the strength of the obtained cured film.

The other ethylenically unsaturated compound may be a monofunctional ethylenically unsaturated compound or a polyfunctional ethylenically unsaturated compound, but a polyfunctional ethylenically unsaturated compound is preferable.
The content of the monofunctional ethylenically unsaturated compound in the photosensitive resin composition does not contain the monofunctional ethylenically unsaturated compound from the viewpoint of suppressing development residue, moisture permeability of the obtained cured film and bending resistance. Alternatively, the content is preferably more than 0% by mass and 5% by mass or less with respect to the total solid content of the photosensitive resin composition, and does not contain a monofunctional ethylenically unsaturated compound, or all of the photosensitive resin composition. It is more preferably more than 0% by mass and 1% by mass or less with respect to the solid content, and it does not contain a monofunctional ethylenically unsaturated compound, or 0% by mass with respect to the total solid content of the photosensitive resin composition. It is more preferably more than 0.5% by mass or less, and it is particularly preferable that it does not contain a monofunctional ethylenically unsaturated compound.

Further, the photosensitive resin composition according to the present disclosure contains an ethylenically unsaturated compound having an acid group as an ethylenically unsaturated compound from the viewpoint of suppressing development residue and moisture permeability of the obtained cured film. Is preferable.
Examples of the acid group include a phosphoric acid group, a sulfonic acid group, and a carboxy group, and a carboxy group is preferable.
Examples of the ethylenically unsaturated compound having an acid group include a 3- to 4-functional ethylenically unsaturated compound having an acid group (pentaerythritol tri and tetraacrylate (PETA)) having a carboxy group introduced into the skeleton (acid value =). 80 mgKOH / g to 120 mgKOH / g)), a 5- to 6-functional ethylenically unsaturated compound having an acid group (dipentaerythritol penta and hexaacrylate (DPHA)) with a carboxy group introduced into the skeleton (acid value = 25 mgKOH / g) ~ 70 mgKOH / g))) and the like.
These trifunctional or higher functional ethylenically unsaturated compounds having an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group, if necessary.

As the ethylenically unsaturated compound having an acid group, at least one selected from the group consisting of a bifunctional or higher functional ethylenically unsaturated compound containing a carboxy group and a carboxylic acid anhydride thereof is preferable, and the compound containing a carboxy group 2 A functional or higher ethylenically unsaturated compound is more preferable, and a bifunctional or higher functional (meth) acrylate compound containing a carboxy group is particularly preferable. In the above aspect, the developability and the strength of the cured film are enhanced.
The bifunctional or higher functional unsaturated compound containing a carboxy group is not particularly limited and can be appropriately selected from known compounds.
Examples of the bifunctional or higher functional unsaturated compound containing a carboxy group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix M-520 (manufactured by Toagosei Co., Ltd.), or , Aronix M-510 (manufactured by Toagosei Co., Ltd.) can be preferably used.

The ethylenically unsaturated compound having an acid group is also preferably a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942. The contents of this publication are incorporated herein.

The other ethylenically unsaturated compound preferably contains a urethane (meth) acrylate compound. When the urethane (meth) acrylate compound is contained, the content is preferably 10 parts by mass or more, preferably 20 parts by mass or more, based on 100 parts by mass of all the ethylenically unsaturated compounds contained in the photosensitive resin composition. It is more preferable to have. The upper limit is preferably 50 parts by mass or less. In the urethane (meth) acrylate compound, the number of functional groups of the ethylenically unsaturated group, that is, the number of (meth) acryloyl groups is preferably trifunctional or higher, and more preferably tetrafunctional or higher.

The photosensitive resin composition may contain one kind of ethylenically unsaturated compound having an acid group alone or two or more kinds thereof.
The content of the ethylenically unsaturated compound having an acid group is 1% by mass to 50% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of suppressing the development residue and the moisture permeability of the obtained cured film. It is preferably mass%, more preferably 1% by mass to 20% by mass, still more preferably 1% by mass to 10% by mass.

The photosensitive resin composition may contain the above-mentioned other ethylenically unsaturated compound alone or may contain two or more kinds.
The total content of the other ethylenic compounds including the ethylenically unsaturated compound having an acid group is a photosensitive resin from the viewpoint of suppressing development residue, moisture permeability and bending resistance of the obtained cured film. With respect to the total solid content of the composition, 1% by mass to 50% by mass is preferable, 1% by mass to 30% by mass is more preferable, 1% by mass to 20% by mass is further preferable, and 1% by mass to 10% by mass is particularly preferable. preferable.

The total content of the ethylenically unsaturated compound is 1% by mass to 70% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of suppressing the development residue and the moisture permeability and bending resistance of the obtained cured film. It is preferably mass%, more preferably 10% by mass to 70% by mass, further preferably 20% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass.

<Binder polymer>
The photosensitive resin composition according to the present disclosure contains a binder polymer.
The binder polymer is preferably an alkali-soluble resin.
The acid value of the binder polymer is not particularly limited, but from the viewpoint of developability, it is preferably a binder polymer having an acid value of 60 mgKOH / g or more, and more preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more. A carboxyl group-containing acrylic resin having an acid value of 60 mgKOH / g or more is preferable, and a carboxyl group-containing acrylic resin is particularly preferable.
It is presumed that the binder polymer having an acid value can be thermally crosslinked with a compound capable of reacting with an acid by heating to increase the three-dimensional crosslink density. Further, it is presumed that the carboxy group of the carboxy group-containing acrylic resin is anhydrousized and made hydrophobic, which contributes to the improvement of wet heat resistance.

The carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more (hereinafter, may be referred to as Specified Polymer A) is not particularly limited as long as the above acid value conditions are satisfied, and is appropriately selected from known resins. Can be used.
For example, a binder polymer which is a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs 0025 of JP-A-2011-95716, described in paragraphs 0033 to 0052 of JP-A-2010-237589. Among the polymers of the above, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be preferably used as the specific polymer A in the present embodiment.
Here, the (meth) acrylic resin refers to a resin containing at least one of a structural unit derived from (meth) acrylic acid and a structural unit derived from (meth) acrylic acid ester.
The total ratio of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester in the (meth) acrylic resin is preferably 30 mol% or more, more preferably 50 mol% or more.

The preferable range of the copolymerization ratio of the monomer having a carboxy group in the specific polymer A is 5% by mass to 50% by mass, and more preferably 5% by mass to 40% by mass with respect to 100% by mass of the specific polymer A. More preferably, it is in the range of 20% by mass to 30% by mass.
The specific polymer A may have a reactive group, and as means for introducing the reactive group into the specific polymer A, a hydroxyl group, a carboxy group, a primary amino group, a secondary amino group, and an aceto are used. Examples thereof include a method of reacting an acetyl group, a sulfonic acid or the like with an epoxy compound, a blocked isocyanate, an isocyanate, a vinyl sulfone compound, an aldehyde compound, a methylol compound, a carboxylic acid anhydride or the like.
Among these, the reactive group is preferably a radically polymerizable group, more preferably an ethylenically unsaturated group, and particularly preferably a (meth) acryloxy group.

Further, the binder polymer, particularly the specific polymer A, preferably has a structural unit having an aromatic ring from the viewpoint of moisture permeability and strength after curing.
Examples of the monomer forming a structural unit having an aromatic ring include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, benzyl (meth) acrylate and the like.
As the structural unit having an aromatic ring, it is preferable to contain at least one structural unit represented by the formula P-2 described later. Further, the structural unit having an aromatic ring is preferably a structural unit derived from a styrene compound.

When the binder polymer contains a structural unit having an aromatic ring, the content of the structural unit having an aromatic ring is preferably 5% by mass to 90% by mass, preferably 10% by mass or more, based on the total mass of the binder polymer. It is more preferably 70% by mass, and even more preferably 20% by mass to 50% by mass.

Further, the binder polymer, particularly the specific polymer A, preferably has a structural unit having an aliphatic cyclic skeleton from the viewpoint of tackiness and strength after curing.
Specific examples of the monomer forming a structural unit having an aliphatic cyclic skeleton include dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
Preferred examples of the aliphatic ring contained in the constituent unit having an aliphatic cyclic skeleton include a dicyclopentane ring, a cyclohexane ring, an isovoron ring, and a tricyclodecane ring. Among them, the tricyclodecane ring is particularly preferable.

When the binder polymer contains a structural unit having an alicyclic skeleton, the content of the structural unit having an alicyclic skeleton may be 5% by mass to 90% by mass with respect to the total mass of the binder polymer. It is preferably 10% by mass to 80% by mass, more preferably 20% by mass to 70% by mass.

Further, the binder polymer, particularly the specific polymer A, preferably has a structural unit having an ethylenically unsaturated group from the viewpoint of tackiness and strength after curing, and has an ethylenically unsaturated group in the side chain. It is more preferable to have a structural unit.
In the present disclosure, the "main chain" represents a relatively longest bound chain among the molecules of the polymer compound constituting the resin, and the "side chain" represents an atomic group branched from the main chain. ..
As the ethylenically unsaturated group, a (meth) acrylic group is preferable, and a (meth) acryloyl group is more preferable.
When the binder polymer contains a structural unit having an ethylenically unsaturated group, the content of the structural unit having an ethylenically unsaturated group may be 5% by mass to 70% by mass with respect to the total mass of the binder polymer. It is preferably 10% by mass to 50% by mass, more preferably 20% by mass to 40% by mass.

As the specific polymer A, the compound A shown below is preferable. The content ratio of each structural unit shown below can be appropriately changed according to the purpose.

The acid value of the binder polymer used in the present disclosure is preferably 60 mgKOH / g or more, more preferably 60 mgKOH / g to 200 mgKOH / g, still more preferably 60 mgKOH / g to 150 mgKOH / g. It is particularly preferably 60 mgKOH / g to 110 mgKOH / g.
In the present specification, the acid value means a value measured according to the method described in JIS K0070 (1992).

When the binder polymer contains a binder polymer having an acid value of 60 mgKOH / g or more, in addition to the above-mentioned advantages, the second resin layer described later contains an acrylic resin having an acid group to form a photosensitive layer. It is possible to improve the interlayer adhesion with the second resin layer.
The weight average molecular weight of the specific polymer A is preferably 10,000 or more, more preferably 20,000 to 100,000.

In addition to the specific polymer, any film-forming resin can be appropriately selected and used as the binder polymer according to the purpose. From the viewpoint of using the transfer film as an electrode protective film for a capacitance type input device, a film having good surface hardness and heat resistance is preferable, an alkali-soluble resin is more preferable, and among the alkali-soluble resins, a known photosensitive siloxane resin material. Etc. can be preferably mentioned.

The binder polymer used in the present disclosure preferably contains a polymer containing a structural unit having a carboxylic acid anhydride structure (hereinafter, also referred to as a specific polymer B). By containing the specific polymer B, it is more excellent in developability and strength after curing.
The carboxylic acid anhydride structure may be either a chain carboxylic acid anhydride structure or a cyclic carboxylic acid anhydride structure, but a cyclic carboxylic acid anhydride structure is preferable.
As the ring having a cyclic carboxylic acid anhydride structure, a 5- to 7-membered ring is preferable, a 5-membered ring or a 6-membered ring is more preferable, and a 5-membered ring is further preferable.
Further, the cyclic carboxylic acid anhydride structure may be condensed or bonded to another ring structure to form a polycyclic structure, but it is preferable that the cyclic carboxylic acid anhydride structure does not form a polycyclic structure.

When another ring structure is condensed or bonded to the cyclic carboxylic acid anhydride structure to form a polycyclic structure, the polycyclic structure is preferably a bicyclo structure or a spiro structure.
In the polycyclic structure, the number of other ring structures condensed or bonded to the cyclic carboxylic acid anhydride structure is preferably 1 to 5, and more preferably 1 to 3.
Examples of the other ring structure include a cyclic hydrocarbon group having 3 to 20 carbon atoms and a heterocyclic group having 3 to 20 carbon atoms.
The heterocyclic group is not particularly limited, and examples thereof include an aliphatic heterocyclic group and an aromatic heterocyclic group.
Further, as the heterocyclic group, a 5-membered ring or a 6-membered ring is preferable, and a 5-membered ring is particularly preferable.
Further, as the heterocyclic group, a heterocyclic group containing at least one oxygen atom (for example, an oxoran ring, an oxane ring, a dioxane ring, etc.) is preferable.

The structural unit having a carboxylic acid anhydride structure is a structural unit containing a divalent group obtained by removing two hydrogen atoms from the compound represented by the following formula P-1 in the main chain, or the following formula P. It is preferable that the monovalent group obtained by removing one hydrogen atom from the compound represented by -1 is a structural unit bonded directly to the main chain or via a divalent linking group.

In the formula P-1, ^RA1a represents a substituent, and ^{n1a RA1a} may be the same or different.
Z ^1a represents a divalent group forming a ring containing —C (= O) —OC (= O) —. n ^1a represents an integer of 0 or more.

Examples of the substituent represented by ^RA1a include the same substituents that the above-mentioned carboxylic acid anhydride structure may have, and the preferred range is also the same.

As Z ^1a , an alkylene group having 2 to 4 carbon atoms is preferable, an alkylene group having 2 or 3 carbon atoms is more preferable, and an alkylene group having 2 carbon atoms is particularly preferable.

The partial structure represented by the formula P-1 may be condensed or bonded to another ring structure to form a polycyclic structure, but it is preferable that the polycyclic structure is not formed.
Examples of the other ring structure referred to here include those similar to the above-mentioned other ring structures that may be condensed or bonded to the carboxylic acid anhydride structure, and the preferred range is also the same.

n ^1a represents an integer of 0 or more.
When Z ^1a represents an alkylene group having 2 to 4 carbon atoms, n ^1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.
When n ^1a represents an integer of 2 or more, a plurality of ^RA1a may be the same or different. Further, although a plurality of ^RA1a may be bonded to each other to form a ring, it is preferable that the RA1a are not bonded to each other to form a ring.

The structural unit having a carboxylic acid anhydride structure is preferably a structural unit derived from unsaturated carboxylic acid anhydride, more preferably a structural unit derived from unsaturated cyclic carboxylic acid anhydride, and unsaturated. It is more preferably a structural unit derived from an aliphatic ring-type carboxylic acid anhydride, further preferably a structural unit derived from maleic anhydride or itaconic anhydride, and a structural unit derived from maleic anhydride. Is particularly preferable.

Hereinafter, specific examples of the structural unit having a carboxylic acid anhydride structure will be given, but the structural unit having a carboxylic acid anhydride structure is not limited to these specific examples.
In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH ₂ OH group, or CF ₃ groups, and Me represents a methyl group.

The structural unit having a carboxylic acid anhydride structure is preferably at least one of the structural units represented by any of the above formulas a2-1 to a2-21, and is preferably the above formulas a2-1 to a2-1. It is more preferable that it is one of the structural units represented by any of a2-21.

The structural unit having a carboxylic acid anhydride structure is at least the structural unit represented by the formula a2-1 and the structural unit represented by the formula a2-2 from the viewpoint of developability and moisture permeability of the obtained cured film. It is preferable to include one, and it is more preferable to include a structural unit represented by the formula a2-1.

The content of the structural unit having a carboxylic acid anhydride structure in the specific polymer B (total content in the case of two or more kinds; the same applies hereinafter) is 0 mol% to 60 with respect to the total amount of the specific polymer B. It is preferably mol%, more preferably 5 mol% to 40 mol%, still more preferably 10 mol% to 35 mol%.
In the present disclosure, when the content of the "constituent unit" is specified by the molar ratio, the "constituent unit" shall be synonymous with the "monomer unit". Further, in the present disclosure, the above-mentioned "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

The specific polymer B preferably contains at least one structural unit represented by the following formula P-2. As a result, the moisture permeability of the obtained cured film becomes lower, and the strength is further improved.

In formula ^P -2, RP1 represents a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, a carboxy group, or a halogen atom, ^RP2 represents a hydrogen atom, an alkyl group or an aryl group, and nP represents 0 to 5. Represents an integer of. When nP is an integer of 2 or more, the ^RP1s existing in 2 or more may be the same or different.

The ^RP1 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a carboxy group, an F atom, a Cl atom, a Br atom, or an I atom. Is preferable, and it is more preferably an alkyl group having 1 to 4 carbon atoms, a phenyl group, an alkoxy group having 1 to 4 carbon atoms, a Cl atom, or a Br atom.
The ^RP2 is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is more preferably a hydrogen atom, a methyl group, or an ethyl group, and particularly preferably a hydrogen atom.

nP is preferably an integer of 0 to 3, more preferably 0 or 1, and even more preferably 0.

The structural unit represented by the formula P-2 is preferably a structural unit derived from a styrene compound.
Examples of the styrene compound include styrene, p-methylstyrene, α-methylstyrene, α, p-dimethylstyrene, p-ethylstyrene, pt-butylstyrene, 1,1-diphenylethylene and the like, and styrene or α. -Methylstyrene is preferred, and styrene is particularly preferred.
The styrene compound for forming the structural unit represented by the formula P-2 may be only one kind or two or more kinds.

When the specific polymer B contains a structural unit represented by the formula P-2, the content of the structural unit represented by the formula P-2 in the specific polymer B (in the case of two or more kinds, the total content). The same applies hereinafter.) Is preferably 5 mol% to 90 mol%, more preferably 30 mol% to 90 mol%, and 40 mol% to 90 mol% with respect to the total amount of the specific polymer B. Is more preferable.

The specific polymer B may contain at least one structural unit having a carboxylic acid anhydride structure and other structural units other than the structural unit represented by the formula P-2.
The other structural units preferably do not contain an acid group.
The other structural units are not particularly limited, and examples thereof include structural units derived from monofunctional ethylenically unsaturated compounds.
As the monofunctional ethylenically unsaturated compound, known compounds can be used without particular limitation, and for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) can be used. ) (Meta) acrylic acid derivatives such as acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, epoxy (meth) acrylate; N-vinyl such as N-vinylpyrrolidone and N-vinylcaprolactam. Compounds; derivatives of allyl compounds such as allyl glycidyl ether; and the like.

The content of the other structural units in the specific polymer B (total content in the case of two or more kinds) is preferably 10% by mass to 100% by mass, preferably 50% by mass, based on the total amount of the specific polymer B. More preferably, it is from% by mass to 100% by mass.

The weight average molecular weight of the binder polymer is not particularly limited, but is preferably more than 3,000, more preferably more than 3,000 and not more than 60,000, and preferably 5,000 to 50,000. More preferred.

The binder polymer may be used alone or may contain two or more kinds.
The content of the binder polymer is preferably 10% by mass to 90% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of the strength of the obtained cured film and the handleability in the transfer film. It is more preferably 20% by mass or more and 80% by mass or less, and further preferably 30% by mass or more and 70% by mass or less.

<Photopolymerization initiator>
The photosensitive resin composition according to the present disclosure contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited, and a known photopolymerization initiator can be used.
Examples of the photopolymerization initiator include a photopolymerization initiator having an oxime ester structure (hereinafter, also referred to as “oxym-based photopolymerization initiator”) and a photopolymerization initiator having an α-aminoalkylphenone structure (hereinafter, “α-”. Aminoalkylphenone-based photopolymerization initiator "), photopolymerization initiator having an α-hydroxyalkylphenone structure (hereinafter, also referred to as" α-hydroxyalkylphenone-based polymerization initiator "), acylphosphine oxide structure. Photopolymerization initiator (hereinafter, also referred to as “acylphosphine oxide-based photopolymerization initiator”), photopolymerization initiator having an N-phenylglycine structure (hereinafter, “N-phenylglycine-based photopolymerization initiator””. Also known as)) and the like.

The photopolymerization initiator is at least selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, an α-hydroxyalkylphenone-based polymerization initiator and an N-phenylglycine-based photopolymerization initiator. It is preferable to include at least one selected from the group consisting of an oxime-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator and an N-phenylglycine-based photopolymerization initiator. ..

Further, as the photopolymerization initiator, for example, the polymerization initiator described in paragraphs 0031 to 0042 of JP-A-2011-95716 and paragraphs 0064-0081 of JP-A-2015-014783 may be used.

Commercially available photopolymerization initiators include 1- [4- (phenylthio)] -1,2-octanedione-2- (O-benzoyloxime) (trade name: IRGACURE® OXE-01, BASF). (Manufactured by), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, manufactured by BASF) , 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE 379EG, manufactured by BASF), 2- Methyl-1- (4-Methylthiophenyl) -2-morpholinopropane-1-one (trade name: IRGACURE 907, manufactured by BASF), 2-hydroxy-1- {4- [4- (2-hydroxy-2) -Methyl-propionyl) benzyl] phenyl} -2-methylpropan-1-one (trade name: IRGACURE 127, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1 (trade name: IRGACURE 369, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propane-1-one (trade name: IRGACURE 1173, manufactured by BASF), 1-hydroxycyclohexylphenylketone (trade name: IRGACURE 1173, manufactured by BASF) Product name: IRGACURE 184, manufactured by BASF), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: IRGACURE 651, manufactured by BASF), oxime ester-based (trade name: Lunar 6, DKSH Japan Co., Ltd.) and the like.

The photopolymerization initiator may be used alone or in combination of two or more.
The content of the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass, based on the total solid content of the photosensitive resin composition. % Or more is more preferable.
The content of the photopolymerization initiator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total solid content of the photosensitive resin composition.

<Thermal crosslinkable compound>
The photosensitive resin composition according to the present disclosure preferably contains a heat-crosslinkable compound, and more preferably a blocked isocyanate compound, from the viewpoint of hardness after curing.
The heat-crosslinkable compound means "a compound having at least one functional group (heat-crosslinkable group) capable of causing a cross-linking reaction by heating" in one molecule.
Examples of the heat-crosslinkable compound include blocked isocyanate compounds, bisphenol A type, cresol novolak type, biphenyl type, epoxy compounds of alicyclic epoxy compounds, melamine compounds and the like.
Of these, a blocked isocyanate compound is preferable from the viewpoint of suppressing development residue, moisture permeability and bending resistance of the obtained cured film.
The blocked isocyanate compound means "a compound having a structure in which the isocyanate group of isocyanate is protected (masked) with a blocking agent".

The dissociation temperature of the blocked isocyanate compound is preferably 100 ° C. to 160 ° C., more preferably 130 ° C. to 150 ° C.
The dissociation temperature of blocked isocyanate in the present specification refers to the deprotection reaction of blocked isocyanate when measured by DSC (Differential scanning calorimetry) analysis with a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Co., Ltd.). The temperature of the accompanying endothermic peak ".

Examples of the blocking agent having a dissociation temperature of 100 ° C to 160 ° C include pyrazole compounds (3,5-dimethylpyrazole, 3-methylpyrazole, 4-bromo-3,5-dimethylpyrazole, 4-nitro-3,5-dimethyl). Pyrazole, etc.), active methylene compounds (malonic acid diesters (dimethyl malonate, diethyl malonate, din-butyl malate, di2-ethylhexyl malonate, etc.), etc.), triazole compounds (1,2,4-triazole, etc.), Examples thereof include oxime compounds (compounds having a structure represented by -C (= N-OH)-in the molecule such as formaldehyde, acetaldoxime, acetoxime, methylethylketooxime, cyclohexanoneoxime) and the like. Among them, an oxime compound or a pyrazole compound is preferable, and an oxime compound is particularly preferable, from the viewpoint of storage stability.

Further, it is preferable that the blocked isocyanate compound has an isocyanurate structure from the viewpoint of improving the brittleness of the membrane and improving the adhesion to the transferred body. The blocked isocyanate compound having an isocyanurate structure can be prepared, for example, by converting hexamethylene diisocyanate into isocyanurate and protecting it.
Among the blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure using an oxime compound as a blocking agent is more likely to have a dissociation temperature in a preferable range than a compound having no oxime structure, and it is easy to reduce development residues. It is preferable from.

The blocked isocyanate compound used in the present disclosure preferably has a radically polymerizable group from the viewpoint of hardness after curing.
The radically polymerizable group is not particularly limited, and a known polymerizable group can be used. For example, an ethylenically unsaturated group such as a (meth) acryloxy group, a (meth) acrylamide group or a styryl group, a glycidyl group or the like can be used. Examples thereof include a group having an epoxy group of. Among them, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth) acryloxy group, from the viewpoint of the surface surface condition, development speed and reactivity of the obtained cured film.

Examples of the blocked isocyanate compound used in the present disclosure include commercially available blocked isocyanate compounds. For example, Karenz AOI-BM, Karenz MOI-BM, Karenz, Karenz MOI-BP (all manufactured by Showa Denko KK), block type Duranate series (manufactured by Asahi Kasei Chemicals Co., Ltd.) and the like can be mentioned.

The blocked isocyanate compound used in the present disclosure preferably has a molecular weight of 200 to 3,000, more preferably 250 to 2,600, and particularly preferably 280 to 2,200.

In the present disclosure, one type of blocked isocyanate compound may be used alone, or two or more types may be used in combination.
The content of the blocked isocyanate compound is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, based on the total solid content of the photosensitive resin composition.

<Heterocyclic compound>
The photosensitive resin composition according to the present disclosure preferably further contains a heterocyclic compound from the viewpoint of preventing discoloration of the metal wiring in contact with the photosensitive resin composition and the linearity of the obtained pattern.
Examples of the hetero atom contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, a sulfur atom and the like. Among them, at least one atom selected from the group consisting of a nitrogen atom, a sulfur atom, and an oxygen atom is a heteroatom from the viewpoint of discoloration prevention of the metal wiring in contact and the linearity of the obtained pattern. It is preferable to have a nitrogen atom as at least a hetero atom.
The heterocyclic compound preferably has a nitrogen atom from the viewpoint of preventing discoloration of the metal wiring in contact with the heterocyclic compound and the linearity of the obtained pattern, and the heterocycle in the heterocyclic compound may contain a nitrogen atom. More preferably, the heterocycle in the heterocyclic compound is a 5-membered ring containing a nitrogen atom, and the heterocycle in the heterocyclic compound is a 5-membered ring containing a nitrogen atom, a sulfur atom and an oxygen atom. Especially preferable.
The heterocyclic ring of the heterocyclic compound is preferably a 5-membered ring or a 6-membered ring from the viewpoint of preventing discoloration of the metal wiring in contact with the heterocyclic compound and the linearity of the obtained pattern. It is more preferably a ring.

The heterocyclic compound is preferably a heterocyclic compound having a mercapto group (thiol group) from the viewpoint of preventing discoloration of the metal wiring in contact and the linearity of the obtained pattern, and the mercapto group on the heterocycle is preferable. Is more preferably a heterocyclic compound directly bonded to.
When the heterocyclic compound has a mercapto group, the number of mercapto groups in the heterocyclic compound is not particularly limited, but from the viewpoint of anti-discoloration of the metal wiring in contact and the linearity of the obtained pattern. It is preferably 1 to 6, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.

As the heterocyclic compound, for example, a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazol compound, a triazine compound, a rhonin compound, a thiazole compound, a benzothiazole compound, a benzoimidazole compound, a benzoxazole compound, or a pyrimidine compound is preferably mentioned. Be done.
Among them, triazole compound, benzotriazole compound, tetrazole compound, thiadiazol compound, triazine compound, rodonine compound, thiazole compound, benzoimidazole compound or benzoxazole compound are preferable, and triazole compound, benzotriazole compound, tetrazole compound, thiadiazol compound and thiazole compound are preferable. A compound, a benzothiazole compound, a benzoimidazole compound, or a benzoxazole compound is more preferable, and a thiadiazol compound, a thiazole compound, a benzothiazole compound, or a benzoxazole compound is particularly preferable.

The heterocyclic compound is not particularly limited, but is represented by any of the following formulas H1 to H13 from the viewpoints of adhesion, discoloration prevention of the metal wiring in contact, and linearity of the obtained pattern. Is preferable.

In formulas H1 to H13, R ^1h , R ^5h , R ^7h , R ^9h , R ^20h and R ^25h independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or an amino group, respectively, and R ^2h to R ^4h , R ^8h , R ^10h to R ^13h , R ^15h to R ^18h , R ^22h , R ^24h , R ^26h to R ^28h and R ^30h are independent hydrogen atoms, alkyl groups, aryl groups, heteroaryl groups, respectively. Represents an amino group, an alkylamino group, an arylamino group, a mercapto group, an alkylthio group or an arylthio group, and R ^6h , R ^14h , R ^21h , R ^23h and R ^29h are independently halogen atoms, alkyl groups and aryl groups, respectively. Heteroaryl group, amino group, alkylamino group, arylamino group, mercapto group, alkylthio group, arylthio group, carboxy group, hydroxy group, alkoxy group or aryloxy group, R ^19h represents hydrogen atom, alkyl group, aryl. Represents a group or a heteroaryl group, where n1 to n5 independently represent an integer of 0 to 4.

The compound represented by the above formula H1 or the above formula H2 is a triazole compound, the compound represented by the above formula H3 is a benzotriazole compound, and the compound represented by the above formula H4 is a tetrazole compound. The compounds represented by the formulas H5 to H7 are thiadiazol compounds, the compound represented by the above formula H8 is a triazine compound, and the compound represented by the above formula H9 is a loadonin compound, which is represented by the above formula H10. The compound is a benzothiazole compound, the compound represented by the above formula H11 is a benzoimidazole compound, the compound represented by the above formula H12 is a thiazole compound, and the compound represented by the above H13 is a benzoxazole compound. be.

R ^1h , R ^7h , R ^9h , R ^20h and R ^25h are each independently preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a hydrogen atom or an alkyl group, and hydrogen. It is particularly preferred to be an atom.
^R5 is preferably a hydrogen atom, an alkyl group or an amino group, and more preferably a hydrogen atom or an amino group.
R ^2h to R ^4h , R ^8h , R ^10h to R ^13h , R ^15h to R ^18h , R ^22h , R ^24h , R ^26h to R ^28h and R ^30h are independent hydrogen atoms, alkyl groups, aryl groups, and hetero. It is preferably an aryl group, an amino group, a mercapto group or an alkylthio group, and more preferably a hydrogen atom, an amino group, a mercapto group or an alkylthio group.
Each of R ^15h to R ^17h is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an amino group, a mercapto group or an alkylthio group, and more preferably an amino group or a heteroaryl group. It is particularly preferably an amino group or a pyridyl group.
Further, from the viewpoint of synthesis, it is preferable that R ¹⁵ to R ¹⁷ have the same group.
R ^18h is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an amino group, a mercapto group or an alkylthio group, more preferably a hydrogen atom, an amino group, a mercapto group or an alkylthio group, and hydrogen. It is more preferably an atom.
R ^6h , R ^14h , R ^21h , R ^23h and R ^29h are independent, alkyl group, aryl group, heteroaryl group, amino group, alkylamino group, arylamino group, mercapto group, alkylthio group, arylthio group, carboxy. It is preferably a group, a hydroxy group, an alkoxy group or an aryloxy group, and more preferably an alkyl group, an aryl group, a heteroaryl group, an amino group, a mercapto group, an alkylthio group, an arylthio group or a carboxy group.
Further, R ^6h , R ^14h , R ^21h , R ^23h and R ^29h can be bonded by substituting a hydrogen atom at an arbitrary position on the benzene ring in each of the above formulas.
R ^19h is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
n1 to n5 are each independently preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

From the viewpoint of adhesion, the heterocyclic compound is preferably a compound represented by any of the above formulas H1, H2 and formulas H4 to H13, and is represented by any of the above formulas H4 to H13. It is more preferably a compound represented by any of the above formulas H5 to H7, a formula H10 and a formula H13, and further preferably a compound represented by any of the above formulas H5 to H7 and formula H13. It is particularly preferable that it is a compound to be used.
Further, the heterocyclic compound may be a compound represented by any of the above formulas H5 to H7 and the above formula H13 from the viewpoint of the discoloration prevention property of the metal wiring in contact and the linearity of the obtained pattern. It is more preferable that the compound is represented by any of the above formulas H5, H6 and H13, and further preferably the compound represented by the above formula H6 or the compound represented by the above formula H13. It is particularly preferable that the compound is represented by the above formula H13.

Specifically, as the above heterocyclic compound, the compounds shown below can be preferably exemplified.
Examples of the triazole compound and the benzotriazole compound include the following compounds.

Examples of the tetrazole compound include the following compounds.

Examples of the thiadiazole compound include the following compounds.

Examples of the triazine compound include the following compounds.

Examples of the loadonine compound include the following compounds.

Examples of the thiazole compound include the following compounds.

Examples of the benzothiazole compound include the following compounds.

Examples of the benzimidazole compound include the following compounds.

Examples of the benzoxazole compound include the following compounds.

The photosensitive resin composition may contain the heterocyclic compound alone or in combination of two or more.
The content of the heterocyclic compound is not particularly limited, but is 0 with respect to the total solid content of the photosensitive resin composition from the viewpoint of preventing discoloration of the metal wiring in contact and the linearity of the obtained pattern. It is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass, further preferably 0.5% by mass to 8% by mass, and 1% by mass to 1% by mass. It is particularly preferably 5% by mass. Within the above range, the hardness of the obtained cured product and the corrosion prevention property to the metal wiring are excellent, and the transparency of the obtained cured product is excellent.

<Thiol compound>
The photosensitive resin composition according to the present disclosure may further contain a thiol compound.
As the thiol compound, a monofunctional thiol compound or a polyfunctional thiol compound is preferably used. Above all, from the viewpoint of hardness after curing, it is preferable to contain a bifunctional or higher functional thiol compound (polyfunctional thiol compound), and more preferably a polyfunctional thiol compound.
In the present disclosure, the polyfunctional thiol compound means a compound having two or more mercapto groups (thiol groups) in the molecule. As the polyfunctional thiol compound, a low molecular weight compound having a molecular weight of 100 or more is preferable, specifically, a molecular weight of 100 to 1,500 is more preferable, and 150 to 1,000 is further preferable.
The number of functional groups of the polyfunctional thiol compound is preferably bifunctional to 10 functional, more preferably bifunctional to 8 functional, and even more preferably bifunctional to 6 functional, from the viewpoint of hardness after curing.
The polyfunctional thiol compound is preferably an aliphatic polyfunctional thiol compound from the viewpoint of tackiness, bending resistance after curing and hardness.
Further, as the thiol compound, a secondary thiol compound is more preferable from the viewpoint of bending resistance and hardness after curing.

Specifically, as the polyfunctional thiol compound, trimethylolpropanetris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutylyloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1, 3,5-Tris (3-mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolethanetris (3-mercaptobutyrate), Tris [(3-mercaptopropionyloxy) ethyl] isocyanurate, trimethylolpropanetris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethyleneglycolbis (3-mercaptopropionate) ), Dipentaerythritol hexakis (3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis (3-mercaptobutylyloxy) butane, 1,2-benzenedithiol, 1,3- Benzenedithiol, 1,2-ethanedithiol, 1,3-propanedithiol, 1,6-hexamethylenedithiol, 2,2'-(ethylenedithio) dietanethiol, meso-2,3-dimercaptosuccinic acid, p. Examples thereof include -xylenedithiol, m-xylenedithiol, and di (mercaptoethyl) ether.

Among these, trimethylolethane propanthris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutylyloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyrate) 3-Mercaptobutylyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trion, trimethylolethaneethanol (3-mercaptobutyrate), tris [(3-mercapto) Propionyloxy) ethyl] isocyanurate, trimethylolethane propanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and dipenta. Elythritol hexakis (3-mercaptopropionate) is preferred.

As the monofunctional thiol compound, both an aliphatic thiol compound and an aromatic thiol compound can be used.
Specific examples of the monofunctional aliphatic thiol compound include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, and the like. Examples thereof include n-octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.
Examples of the monofunctional aromatic thiol compound include benzenethiol, toluenethiol, xylenethiol and the like.

The thiol compound is preferably a thiol compound having an ester bond from the viewpoint of tackiness, bending resistance after curing, and hardness, and more preferably contains a compound represented by the following formula 1.

In formula 1, n represents an integer of 1 to 6, A represents an n-valent organic group having 1 to 15 carbon atoms, or a group represented by the following formula 2, and R ¹ independently represents the number of carbon atoms. Represents 1 to 15 divalent organic groups.

In the formula 2, R ² to R ⁴ independently represent a divalent organic group having 1 to 15 carbon atoms, and the wavy line portion represents the bond position with the oxygen atom in the above formula 1.

N in the formula 1 is preferably an integer of 2 to 6 from the viewpoint of hardness after curing.
From the viewpoint of tackiness, bending resistance and hardness after curing, A in the formula 1 is preferably an n-valent aliphatic group having 1 to 15 carbon atoms or a group represented by the above formula 2. , An n-valent aliphatic group having 4 to 15 carbon atoms or a group represented by the above formula 2 is more preferable, and an n-valent aliphatic group having 5 to 10 carbon atoms or the above formula 2 is used. The group represented by the above formula 2 is more preferable, and the group represented by the above formula 2 is particularly preferable.
Further, A in the formula 1 is an n-valent group composed of a hydrogen atom and a carbon atom, or an n-valent group composed of a hydrogen atom, a carbon atom and an oxygen atom from the viewpoint of tackiness, bending resistance and hardness after curing. It is preferably a group of n-valent, more preferably an n-valent group consisting of a hydrogen atom and a carbon atom, and particularly preferably an n-valent aliphatic hydrocarbon group.
Independently, R ¹ in the formula 1 is preferably an alkylene group having 1 to 15 carbon atoms, and is an alkylene group having 2 to 4 carbon atoms, from the viewpoint of tackiness, bending resistance after curing, and hardness. It is more preferably an alkylene group having 3 carbon atoms, and particularly preferably a 1,2-propylene group. The alkylene group may be linear or may have a branch.

Independently, R ² to R ⁴ in the formula 2 are preferably aliphatic groups having 2 to 15 carbon atoms, preferably having 2 to 15 carbon atoms, from the viewpoint of tackiness, bending resistance after curing, and hardness. It is more preferably an alkylene group or a polyalkyleneoxyalkyl group having 3 to 15 carbon atoms, further preferably an alkylene group having 2 to 15 carbon atoms, and particularly preferably an ethylene group.

Further, as the polyfunctional thiol compound, a compound having two or more groups represented by the following formula S-1 is preferable.

In the formula S-1, R ^1S represents a hydrogen atom or an alkyl group, A ^1S represents -CO- or -CH _2- , and the wavy line portion represents a bonding position with another structure.

As the polyfunctional thiol compound, a compound having 2 or more and 6 or less groups represented by the formula S-1 is preferable.
The alkyl group in R ^1S in the formula S-1 is a linear, branched or cyclic alkyl group, and the carbon number range is preferably 1 to 16 and more preferably 1 to 10. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, 2-ethylhexyl group and the like. A methyl group, an ethyl group, a propyl group or an isopropyl group is preferable.
As R ^1S , a hydrogen atom, a methyl group, an ethyl group, a propyl group, or an isopropyl group is particularly preferable, and a methyl group or an ethyl group is most preferable.

Further, the polyfunctional thiol compound is particularly preferably a compound represented by the following formula S-2 having a plurality of groups represented by the above formula S-1.

In formula S-2, R ^1S independently represents a hydrogen atom or an alkyl group, A ^1S independently represents -CO- or -CH _2- , and L ^1S represents an nS-valent linking group. nS represents an integer of 2 to 8. From a synthetic point of view, it is preferable that all R ^1S are the same group, and it is preferable that all A ^1S are the same group.

R 1S in the formula S-2 has the same meaning as R ^1S in the above formula S- ¹ , and the preferred range is also the same. nS is preferably an integer of 2 to 6.
Examples of L ^1S which is a linking group of nS valence in the formula S-2 include a divalent linking group such as-(CH ₂ ) _mS- (mS represents an integer of 2 to 6), and a trimethylolpropane residue. A trivalent linking group such as an isocyanul ring having three groups,-(CH ₂ ) _pS- (pS represents an integer of 2 to 6), a tetravalent linking group such as a pentaerythritol residue, and dipentaerythritol. Examples include pentavalent or hexavalent linking groups such as residues.

Specific examples of the thiol compound include the following compounds, but it goes without saying that the thiol compound is not limited thereto.

The thiol compound may be used alone or in combination of two or more.
The content of the thiol compound is preferably 0.1% by mass to 40% by mass, more preferably 0.5% by mass to 30% by mass, and 1% by mass to 25% by mass with respect to the total solid content of the photosensitive resin composition. % Is particularly preferable.

<Surfactant>
The photosensitive resin composition according to the present disclosure may contain a surfactant.
As the surfactant, for example, the surfactants described in paragraphs 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP2009-237362A, known fluorosurfactants and the like can be used.
As the surfactant, a fluorine-based surfactant is preferable.
Examples of commercially available fluorosurfactants include Megafuck (registered trademark) F551 (manufactured by DIC Corporation).

When the photosensitive resin composition contains a surfactant, the content of the surfactant is preferably 0.01% by mass to 3% by mass, based on the total solid content of the photosensitive resin composition. It is more preferably 05% by mass to 1% by mass, and even more preferably 0.1% by mass to 0.8% by mass.

<Polymerization inhibitor>
The photosensitive resin composition according to the present disclosure may contain at least one polymerization inhibitor.
As the polymerization inhibitor, for example, the thermal polymerization inhibitor (also referred to as a polymerization inhibitor) described in paragraph 0018 of Japanese Patent No. 4502784 can be used.
Among them, phenothiazine, phenoxazine or 4-methoxyphenol can be preferably used.

When the photosensitive resin composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 3% by mass, based on the total solid content of the photosensitive resin composition. 01% by mass to 1% by mass is more preferable, and 0.01% by mass to 0.8% by mass is further preferable.

<Hydrogen donating compound>
The photosensitive resin composition according to the present disclosure preferably further contains a hydrogen donating compound.
In the present disclosure, the hydrogen donating compound has an action of further improving the sensitivity of the photopolymerization initiator to active light, or suppressing the polymerization inhibition of the polymerizable compound by oxygen.
Examples of such hydrogen donating compounds include amines such as M. et al. R. Sander et al., "Journal of Polymer Society", Vol. 10, pp. 3173 (1972), JP-A-44-20189, JP-A-51-82102, JP-A-52-134692, JP-A-59-138205. Examples thereof include the compounds described in JP-A No. 60-84305, JP-A-62-18537, JP-A-64-33104, and Research Disclosure 33825, and specific examples thereof include triethanolamine. , P-Dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

Further, as yet another example of the hydrogen donating compound, an amino acid compound (eg, N-phenylglycine, etc.), an organometallic compound described in JP-A-48-42965 (eg, tributyltin acetate, etc.), JP-B-55. Examples thereof include a hydrogen donor described in JP-A-344414, a sulfur compound described in JP-A-6-308727 (eg, Tritian, etc.) and the like.

The content of these hydrogen donating compounds is 0.1% by mass or more and 30% by mass or less with respect to the total solid content of the photosensitive resin composition from the viewpoint of improving the curing rate by balancing the polymerization growth rate and the chain transfer. The range is preferable, the range of 1% by mass or more and 25% by mass or less is more preferable, and the range of 0.5% by mass or more and 20% by mass or less is further preferable.

<Other ingredients>
The photosensitive resin composition according to the present disclosure may contain other components other than the above-mentioned components.
Examples of other components include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784, and other additives described in paragraphs 0058 to 0071 of Japanese Patent Application Laid-Open No. 2000-310706.

Further, the photosensitive resin composition may contain at least one kind of particles (for example, metal oxide particles) as other components for the purpose of adjusting the refractive index and light transmittance.
The metal of the metal oxide particles also includes metalloids such as B, Si, Ge, As, Sb, and Te. From the viewpoint of the transparency of the cured film, the average primary particle diameter of the particles (for example, metal oxide particles) is preferably 1 to 200 nm, more preferably 3 to 80 nm. The average primary particle size is calculated by measuring the particle size of 200 arbitrary particles using an electron microscope and arithmetically averaging the measurement results. If the shape of the particle is not spherical, the longest side is the particle diameter.
The content of the particles is preferably 0% by mass to 35% by mass, more preferably 0% by mass to 10% by mass, still more preferably 0% by mass to 5% by mass, based on the total solid content of the photosensitive resin composition. , 0% by mass to 1% by mass, and 0% by mass (that is, the photosensitive resin composition does not contain particles) is particularly preferable.

Further, the photosensitive resin composition may contain a trace amount of a colorant (pigment, dye, etc.) as another component, but from the viewpoint of transparency, it may contain substantially no colorant. preferable.
Specifically, the content of the colorant in the photosensitive resin composition is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total solid content of the photosensitive resin composition.

<Solvent>
The photosensitive resin composition according to the present disclosure preferably further contains a solvent from the viewpoint of layer formation by coating.

As the solvent, a commonly used solvent can be used without particular limitation.
As the solvent, an organic solvent is preferable.
Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (also known as 1-methoxy-2-propyl acetate), diethylene glycol ethyl methyl ether, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, and caprolactam. , N-propanol, 2-propanol and the like. Further, the solvent used may contain a mixed solvent which is a mixture of these compounds.
As the solvent, a mixed solvent of methyl ethyl ketone and propylene glycol monomethyl ether acetate or a mixed solvent of diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate is preferable.

When a solvent is used, the solid content of the photosensitive resin composition is preferably 5% by mass to 80% by mass, more preferably 5% by mass to 40% by mass, based on the total amount of the photosensitive resin composition. 5% by mass to 30% by mass is particularly preferable.

When a solvent is used, the viscosity (25 ° C.) of the photosensitive resin composition is preferably 1 mPa · s to 50 mPa · s, more preferably 2 mPa · s to 40 mPa · s, and 3 mPa · s from the viewpoint of coatability. s to 30 mPa · s is particularly preferable.
The viscosity is measured using, for example, VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.).
When the photosensitive resin composition contains a solvent, the surface tension (25 ° C.) of the photosensitive resin composition is preferably 5 mN / m to 100 mN / m, preferably 10 mN / m to 80 mN / m, from the viewpoint of coatability. More preferably, 15 mN / m to 40 mN / m is particularly preferable.
The surface tension is measured using, for example, Automatic Surface Tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).

As the solvent, the Solvent described in paragraphs 0054 and 0055 of US Patent Application Publication No. 2005/282073 can also be used, the contents of which are incorporated herein.
Further, as the solvent, an organic solvent (high boiling point solvent) having a boiling point of 180 ° C. to 250 ° C. can be used, if necessary.

(Hardened film)
The cured film according to the present disclosure is a cured film obtained by curing the photosensitive resin composition according to the present disclosure. When the photosensitive resin composition according to the present disclosure contains a solvent, the cured film according to the present disclosure is a cured film obtained by curing the solid content of the photosensitive resin composition according to the present disclosure.
When the photosensitive resin composition according to the present disclosure contains a solvent, a known method such as heat-drying, air-drying, and vacuum-drying after applying the photosensitive resin composition according to the present disclosure to a substrate in the form of a film is performed. It is preferable to remove at least a part of the solvent and then perform curing to form a cured film.
Further, the cured film may have a desired pattern shape.
The cured film according to the present disclosure can be suitably used as an interlayer insulating film (insulating film) or an overcoat film (protective film), and is more preferably used as a protective film for a touch panel.
The cured film obtained by curing the solid content of the photosensitive resin composition according to the present disclosure has excellent film physical characteristics, and is therefore useful for applications in organic EL display devices and liquid crystal display devices.
Above all, the cured film according to the present disclosure can be more preferably used as a protective film for a touch panel, and can be more preferably used as a protective film for touch panel wiring.
The thickness of the cured film is not particularly limited, but is preferably 1 μm or more and 20 μm or less, more preferably 2 μm or more and 15 μm or less, and particularly preferably 3 μm or more and 12 μm or less.

(Transfer film)
The transfer film according to the present disclosure includes a temporary support and a layer containing the photosensitive resin composition according to the present disclosure (hereinafter, also referred to as “photosensitive layer”).

<Temporary support>
The transfer film according to the present disclosure has a temporary support.
The temporary support is preferably a film, more preferably a resin film.
As the temporary support, a film having flexibility and not causing significant deformation, shrinkage or elongation under pressure, or under pressure and heating can be used.
Examples of such a film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polyimide film, and a polycarbonate film.
Of these, a biaxially stretched polyethylene terephthalate film is particularly preferable.
Further, it is preferable that the film used as the temporary support is not deformed such as wrinkles or scratched.

The thickness of the temporary support is not particularly limited, but is preferably 5 μm to 200 μm, and is particularly preferably 10 μm to 150 μm from the viewpoint of ease of handling and versatility.

<Photosensitive layer>
The transfer film according to the present disclosure includes a layer (photosensitive layer) containing the photosensitive resin composition according to the present disclosure.
The photosensitive layer may be a layer containing the photosensitive resin composition according to the present disclosure, but may be a layer composed of the photosensitive resin composition according to the present disclosure or a solid of the photosensitive resin composition according to the present disclosure. It is preferably a layer composed of components.
When the photosensitive resin composition contains a solvent, it is preferable to remove at least a part of the solvent by a known method to form the photosensitive layer. The solvent does not need to be completely removed, but the content of the solvent in the photosensitive layer is preferably 1% by mass or less, preferably 0.5% by mass, based on the total mass of the photosensitive layer. The following is more preferable.

The thickness of the photosensitive layer is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 12 μm or less.
When the thickness of the photosensitive layer is 20 μm or less, the entire transfer film is thinned, the transmittance of the photosensitive layer or the obtained cured film is improved, and the yellow coloring of the photosensitive layer or the obtained cured film is suppressed. It is advantageous in terms of.
From the viewpoint of manufacturing suitability, the thickness of the photosensitive layer is preferably 1 μm or more, more preferably 2 μm or more, and particularly preferably 3 μm or more.

The refractive index of the photosensitive layer is preferably 1.47 to 1.56, more preferably 1.50 to 1.53, further preferably 1.50 to 1.52, and 1.51 to 1.52. Especially preferable.
In the present disclosure, "refractive index" refers to the refractive index at a wavelength of 550 nm.
Unless otherwise specified, the "refractive index" in the present disclosure means a value measured by ellipsometry with visible light having a wavelength of 550 nm at a temperature of 23 ° C.

The method for forming the photosensitive layer is not particularly limited, and a known method can be used.
As an example of the method for forming the photosensitive layer, there is a method of applying a photosensitive resin composition containing a solvent on a temporary support and drying it if necessary.
As a coating method, a known method can be used, and for example, a printing method, a spray method, a roll coating method, a bar coating method, a curtain coating method, a spin coating method, a die coating method (that is, a slit coating method) and the like can be used. The die coat method is preferable.
As a drying method, known methods such as natural drying, heat drying, and vacuum drying can be applied alone or in combination of two or more.

<Second resin layer>
The transfer film according to the present disclosure may further be provided with a second resin layer on the side opposite to the side where the temporary support is present when viewed from the photosensitive layer (see, for example, specific examples of the transfer film described later). ..
As the second resin layer, a refractive index adjusting layer is preferably mentioned.
According to the transfer film provided with the refractive index adjusting layer, when the touch panel protective layer is formed by transferring the refractive index adjusting layer and the photosensitive layer of the transfer film to the touch panel substrate provided with the transparent electrode pattern. , The transparent electrode pattern becomes less visible (that is, the concealing property of the transparent electrode pattern is further improved). The phenomenon in which the transparent electrode pattern is visually recognized is generally referred to as "bone visibility".
Regarding the phenomenon in which the transparent electrode pattern is visually recognized and the concealing property of the transparent electrode pattern, JP-A-2014-10814 and JP-A-2014-108541 can be appropriately referred to.

The second resin layer is preferably arranged adjacent to the photosensitive layer.
The refractive index of the second resin layer is preferably higher than that of the photosensitive layer from the viewpoint of suppressing the appearance of bone.
The refractive index of the second resin layer is preferably 1.50 or more, more preferably 1.55 or more, and particularly preferably 1.60 or more.
The upper limit of the refractive index of the second resin layer is not particularly limited, but is preferably 2.10 or less, more preferably 1.85 or less, still more preferably 1.78 or less, and particularly preferably 1.74 or less.

The second resin layer may have photocurability (that is, photosensitive), may have thermosetting property, or may have both photocurability and thermosetting property. good.
From the viewpoint of forming a cured film having excellent strength by photocuring after transfer, the second resin layer is preferably photocurable.
Further, the second resin layer is preferably thermosetting from the viewpoint that the strength of the cured film can be further improved by thermosetting.
The second resin layer is preferably thermosetting and photocurable.
The second resin layer is preferably alkaline soluble (eg, soluble in a weak alkaline aqueous solution).

The aspect in which the second resin layer is photosensitive has an advantage that the photosensitive layer and the second resin layer transferred onto the substrate can be collectively patterned by a single photolithography after the transfer.

The film thickness of the second resin layer is preferably 500 nm or less, more preferably 110 nm or less, and particularly preferably 100 nm or less.
The film thickness of the second resin layer is preferably 20 nm or more, more preferably 50 nm or more, further preferably 55 nm or more, and particularly preferably 60 nm or more.

The refractive index of the second resin layer is preferably adjusted according to the refractive index of the transparent electrode pattern.
For example, when the refractive index of the transparent electrode pattern is in the range of 1.8 to 2.0, such as a transparent electrode pattern made of ITO (Indium Tin Oxide), the refractive index of the second resin layer is , 1.60 or more is preferable. In this case, the upper limit of the refractive index of the second resin layer is not particularly limited, but is preferably 2.1 or less, more preferably 1.85 or less, still more preferably 1.78 or less, and particularly preferably 1.74 or less.
Further, when the refractive index of the transparent electrode pattern exceeds 2.0, for example, as in the transparent electrode pattern made of IZO (Indium Zinc Oxide), the refractive index of the second resin layer is 1. It is preferably 70 or more and 1.85 or less.

The method for controlling the refractive index of the second resin layer is not particularly limited, and for example, a method using a resin having a predetermined refractive index alone, a method using a resin and metal oxide particles or metal particles, and a metal salt. Examples thereof include a method using a composite with a resin. The type of the metal oxide particles is not particularly limited, and known metal oxide particles can be used. Specifically, it preferably contains at least one of zirconium oxide particles (ZrO ₂ particles), Nb ₂ O ₅ particles, titanium oxide particles (TiO ₂ particles) and silicon dioxide particles (SiO ₂ particles). Among them, zirconium oxide particles or titanium oxide particles are more preferable because the refractive index of the second resin layer can be easily adjusted to 1.6 or more.

Examples of silicon dioxide particles include colloidal silica and fumed silica, and examples of commercially available products on the market include Snowtex ST-N (coloidal silica; non-volatile content 20%) manufactured by Nissan Chemical Industry Co., Ltd. ), Snowtex ST-C (colloidal silica; non-volatile content 20%) and the like.
Examples of zirconium oxide particles include Nanouse OZ-S30M (methanol dispersion, non-volatile content 30.5% by mass) manufactured by Nissan Chemical Industry Co., Ltd. and SZR-CW manufactured by Sakai Chemical Industry Co., Ltd.
(Water dispersion, non-volatile content 30% by mass), SZR-M (methanol dispersion, non-volatile content 30% by mass) and the like can be mentioned.
Examples of titanium oxide particles include TS-020 (water dispersion, non-volatile content 25.6% by mass) manufactured by TAYCA Corporation, and titaniasol R (methanol dispersion, non-volatile content 32.1) manufactured by Nissan Chemical Industry Co., Ltd. Mass%) and the like.

When zirconium oxide particles are used as the metal oxide particles, the hiding power of the concealed object such as an electrode pattern is improved, and the visibility of the concealed object can be effectively improved. The content is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, still more preferably 40% by mass to 85% by mass, based on the total mass of the second resin layer.
When titanium oxide is used as the metal oxide particles, the titanium oxide particles are contained from the viewpoint that the concealing property of the concealed object such as an electrode pattern is improved and the visibility of the concealed object can be effectively improved. The amount is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, still more preferably 40% by mass to 85% by mass, based on the total mass of the second resin layer.

Further, the second resin layer preferably contains a binder polymer and an ethylenically unsaturated compound.
Regarding the components of the second resin layer, paragraphs 0019 to 0040 and 0144 to 0150 of JP-A-2014-108541, paragraphs of JP-A-2014-10814, which are components of the curable second resin layer. The components of the transparent layer described in 0024 to 0035 and 0110 to 0112, the components of the composition having an ammonium salt described in paragraphs 0034 to 0056 of International Publication No. 2016/099980, and the like can be referred to. ..
Further, as the binder polymer and ethylenically unsaturated compound contained in the second resin layer, the same binder polymer and ethylenically unsaturated compound contained in the first resin layer can be used, which is preferable. The range is similar.

Further, the second resin layer preferably contains at least one metal oxidation inhibitor.
When the second resin layer contains a metal oxidation inhibitor, a member (for example, for example) that is in direct contact with the second resin layer when the second resin layer is transferred onto a substrate (that is, a transfer target). The conductive member) formed on the substrate can be surface-treated. This surface treatment imparts a metal oxidation suppressing function (protective property) to a member that is in direct contact with the second resin layer.
Examples of the metal oxidation inhibitor include those described above.

The second resin layer may contain other components other than the above-mentioned components.
Examples of other components that can be contained in the second resin layer include the same components as those contained in the above-mentioned photosensitive layer.
The second resin layer preferably contains a surfactant as another component.

The method for forming the second resin layer is not particularly limited.
As an example of the method for forming the second resin layer, the composition for forming the second resin layer in the embodiment containing an aqueous solvent is applied onto the above-mentioned photosensitive layer formed on the temporary support, and it is necessary. A method of forming by drying is mentioned.
Specific examples of the coating and drying methods are the same as the specific examples of coating and drying when forming the photosensitive layer, respectively.

The composition for forming the second resin layer may contain each component of the second resin layer described above.
The composition for forming the second resin layer contains, for example, a binder polymer, an ethylenically unsaturated compound, particles, and an aqueous solvent.
Further, as the second resin layer forming composition, the composition having an ammonium salt described in paragraphs 0034 to 0056 of International Publication No. 2016/099980 is also preferable.

<Protective film>
The transfer film according to the present disclosure may further include a protective film on the side opposite to the temporary support when viewed from the photosensitive layer.
When the transfer film according to the present disclosure includes a second resin layer on the side opposite to the temporary support when viewed from the photosensitive layer, the protective film is preferably a temporary support when viewed from the second resin layer. Is placed on the opposite side.
Examples of the protective film include polyethylene terephthalate film, polypropylene film, polystyrene film, and polycarbonate film.
As the protective film, for example, those described in paragraphs 0083 to 0087 and 093 of JP-A-2006-259138 may be used.

<Thermoplastic resin layer>
The transfer film according to the present disclosure may further include a thermoplastic resin layer between the temporary support and the photosensitive layer.
When the transfer film includes a thermoplastic resin layer, when the transfer film is transferred to a substrate to form a laminate, bubbles are less likely to be generated in each element of the laminate. When this laminated body is used in an image display device, image unevenness and the like are less likely to occur, and excellent display characteristics can be obtained.
The thermoplastic resin layer preferably has alkali solubility.
The thermoplastic resin layer functions as a cushioning material that absorbs irregularities on the surface of the substrate during transfer.
The irregularities on the surface of the substrate include images, electrodes, wiring, etc. that have already been formed. It is preferable that the thermoplastic resin layer has a property of being deformable according to the unevenness.

The thermoplastic resin layer preferably contains the organic polymer substance described in JP-A-5-72724, and the polymer softening point according to the Vicat method (specifically, the American material test method ASTMD1235). It is more preferable to contain an organic polymer substance having a softening point of about 80 ° C. or lower according to the measurement method).

The thickness of the thermoplastic resin layer is preferably 3 μm to 30 μm, more preferably 4 μm to 25 μm, still more preferably 5 μm to 20 μm.
When the thickness of the thermoplastic resin layer is 3 μm or more, the followability to the unevenness of the substrate surface is improved, so that the unevenness of the substrate surface can be absorbed more effectively.
When the thickness of the thermoplastic resin layer is 30 μm or less, the process suitability is further improved. For example, the load of drying (solvent removal) when the thermoplastic resin layer is applied and formed on the temporary support is further reduced, and the development time of the thermoplastic resin layer after transfer is shortened.

The thermoplastic resin layer can be formed by applying a composition for forming a thermoplastic resin layer containing a solvent and a thermoplastic organic polymer to a temporary support and drying it if necessary.
Specific examples of the coating and drying methods are the same as the specific examples of coating and drying when forming the photosensitive layer, respectively.
The solvent is not particularly limited as long as it dissolves the polymer component forming the thermoplastic resin layer, and is an organic solvent (for example, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, and 2-propanol. ).

The thermoplastic resin layer preferably has a viscosity measured at 100 ° C. of 1,000 to 10,000 Pa · s. Further, it is preferable that the viscosity of the thermoplastic resin layer measured at 100 ° C. is lower than the viscosity of the photosensitive layer measured at 100 ° C.

<Middle layer>
The transfer film according to the present disclosure may further include an intermediate layer between the temporary support and the photosensitive layer.
When the transfer film according to the present disclosure includes a thermoplastic resin layer, the intermediate layer is preferably arranged between the thermoplastic resin layer and the photosensitive layer.
Examples of the components of the intermediate layer include polyvinyl alcohol, polyvinylpyrrolidone, cellulose, or a resin which is a mixture containing at least two of them.
Further, as the intermediate layer, a layer described as a "separation layer" in JP-A-5-72724 can also be used.

In the case of producing a transfer film in which a thermoplastic resin layer, an intermediate layer, and a photosensitive layer are provided in this order on a temporary support, the intermediate layer is, for example, a solvent that does not dissolve the thermoplastic resin layer and an intermediate layer. It can be formed by applying a composition for forming an intermediate layer containing the above resin as a component and drying it if necessary. Specific examples of the coating and drying methods are the same as the specific examples of coating and drying when forming the photosensitive layer, respectively.
In the above case, for example, first, the composition for forming a thermoplastic resin layer is first applied on the temporary support and dried to form the thermoplastic resin layer. Next, the composition for forming an intermediate layer is applied onto the thermoplastic resin layer and dried to form an intermediate layer. Then, a photosensitive resin composition containing an organic solvent is applied onto the intermediate layer and dried to form a photosensitive layer. The organic solvent in this case is preferably an organic solvent that does not dissolve the intermediate layer.

<Specific example of transfer film>
FIG. 1 is a schematic cross-sectional view of a transfer film 10 which is a specific example of the transfer film according to the present disclosure.
As shown in FIG. 1, the transfer film 10 has a laminated structure of a protective film 16 / a second resin layer 20A / a photosensitive layer 18A / a temporary support 12 (that is, a temporary support 12 and a photosensitive layer 18A. , The second resin layer 20A and the protective film 16 are arranged in this order).
However, the transfer film according to the present disclosure is not limited to the transfer film 10, and for example, the second resin layer 20A and the protective film 16 may be omitted. Further, at least one of the above-mentioned thermoplastic resin layer and intermediate layer may be provided between the temporary support 12 and the photosensitive layer 18A.

The second resin layer 20A is a layer arranged on the side opposite to the side where the temporary support 12 exists when viewed from the photosensitive layer 18A, and has a refractive index of 1.50 or more at a wavelength of 550 nm.
The transfer film 10 is a negative type material (negative type film).

The method for producing the transfer film 10 is not particularly limited.
The method for producing the transfer film 10 includes, for example, a step of forming a photosensitive layer 18A on the temporary support 12, a step of forming a second resin layer 20A on the photosensitive layer 18A, and a second resin layer 20A. The steps of forming the protective film 16 on the top are included in this order.
The method for producing the transfer film 10 is described in paragraph 0056 of International Publication No. 2016/099980, which volatilizes ammonia between the step of forming the second resin layer 20A and the step of forming the protective film 16. It may include a step of causing.

(Laminated body and capacitance type input device)
The laminate according to the present disclosure described below may have a cured film according to the present disclosure, but is a laminate formed by laminating a substrate, electrodes, and a cured film according to the present disclosure in this order. Is preferable.
Further, the photosensitive layer may have a desired pattern shape.
Further, it is preferable that the laminate according to the present disclosure has a photosensitive layer on the substrate after removing the temporary support from the transfer film according to the present disclosure.
The capacitance type input device according to the present disclosure has a cured film according to the present disclosure or a laminate according to the present disclosure.
The substrate is preferably a substrate including an electrode of a capacitance type input device.
Further, the electrode is preferably an electrode of a capacitance type input device.

The electrode of the capacitance type input device may be a transparent electrode pattern or a routing wiring. In the laminated body, the electrodes of the capacitance type input device are preferably an electrode pattern, and more preferably a transparent electrode pattern.

In the laminate according to the present disclosure, the substrate, the transparent electrode pattern, the second resin layer arranged adjacent to the transparent electrode pattern, and the photosensitive layer arranged adjacent to the second resin layer are used. , And the refractive index of the second resin layer is preferably higher than that of the photosensitive layer. The refractive index of the second resin layer is preferably 1.6 or more.
By adopting the above-mentioned laminated body configuration, the concealing property of the transparent electrode pattern is improved.

As the substrate, a glass substrate or a resin substrate is preferable.
Further, the substrate is preferably a transparent substrate, and more preferably a transparent resin substrate. Transparency in the present disclosure is intended to have a transmittance of 85% or more for all visible light, and is preferably 90% or more, more preferably 95% or more.
The refractive index of the substrate is preferably 1.50 to 1.52.
As the glass substrate, for example, tempered glass such as Corning's gorilla glass (registered trademark) can be used.
As the resin substrate, it is preferable to use at least one of which is optically free and has high transparency. For example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), and triacetyl cellulose (TAC) are used. ), Polyimide (PI), polybenzoxazole (PBO), cycloolefin polymer (COP) and other resins.
As the material of the transparent substrate, the materials described in JP-A-2010-86684, JP-A-2010-152809, and JP-A-2010-257492 are preferably used.

A touch panel is preferably mentioned as the capacitance type input device.
Examples of the touch panel electrode include a transparent electrode pattern arranged in at least an image display area of the touch panel. The touch panel electrode may extend from the image display area to the frame portion of the touch panel.
Examples of the wiring for the touch panel include wiring wiring (take-out wiring) arranged in the frame portion of the touch panel.
A preferred embodiment of the touch panel substrate and the touch panel is that the transparent electrode pattern and the routing wiring are electrically connected by laminating a part of the routing wiring on the portion extending to the frame portion of the touch panel of the transparent electrode pattern. Is preferable.

As the material of the transparent electrode pattern, a metal oxide film such as ITO (indium tin oxide) or IZO (zinc oxide) is preferable.
Metal is preferable as the material of the routing wiring. Examples of the metal that is the material of the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc and manganese, and alloys composed of two or more of these metal elements. As the material of the routing wiring, copper, molybdenum, aluminum or titanium is preferable, and copper is particularly preferable.

The touch panel electrode protective film formed by using the transfer film according to the present disclosure has an electrode or the like directly or another layer for the purpose of protecting the electrode or the like (that is, at least one of the touch panel electrode and the touch panel wiring). It is provided so as to cover through.
The preferred range of the thickness of the electrode protective film for the touch panel is the same as the preferred range of the thickness of the photosensitive layer described above.

Further, it is preferable that the protective film for the touch panel is provided in the bent region of the touch panel. According to the above aspect, the effect of the cured film formed from the photosensitive resin composition according to the present disclosure, which is excellent in bending resistance, can be further exerted.
In the present disclosure, the bent region means a region bent with a predetermined radius of curvature or a region that can be bent with a predetermined radius of curvature. The predetermined radius of curvature is preferably 40 mm or less, more preferably 10 mm or less, and particularly preferably 5 mm or less.
In another embodiment, the touch panel may be folded in the bent region. Further, in another embodiment, the touch panel may have a bent region in the vicinity of the central portion thereof.

The electrode protective film according to the present disclosure, preferably the electrode protective film for a touch panel, may have an opening.
The opening can be formed by dissolving the non-exposed portion of the photosensitive layer with a developer.
In this case, even when the touch panel electrode protective film is formed by using a transfer film under high temperature laminating conditions, the development residue at the opening of the touch panel electrode protective film is suppressed.

The touch panel may further include a first refractive index adjusting layer between the electrodes and the like and the electrode protective layer for the touch panel (see, for example, the first specific example of the touch panel described later).
The preferred embodiment of the first refractive index adjusting layer is the same as the preferred embodiment of the second resin layer that can be provided on the transfer film. The first refractive index adjusting layer may be formed by applying and drying the composition for forming the first refractive index adjusting layer, or by separately transferring the refractive index adjusting layer of the transfer film provided with the refractive index adjusting layer. It may be formed.
The touch panel in the embodiment including the first refractive index adjusting layer preferably uses the transfer film according to the present disclosure in the embodiment including the second resin layer to transfer the photosensitive layer and the second resin layer in the transfer film. It is preferable to form by. In this case, the touch panel electrode protective layer is formed from the photosensitive layer of the transfer film, and the first refractive index adjusting layer is formed from the second resin layer of the transfer film.

Further, the touch panel or the touch panel substrate may be provided with a second refractive index adjusting layer between the substrate and the electrodes (see, for example, the first specific example of the touch panel described later).
The preferred embodiment of the second refractive index adjusting layer is the same as the preferred embodiment of the second resin layer that can be provided on the transfer film.

In the embodiment in which the touch panel includes the first refractive index adjusting layer (more preferably, the first refractive index adjusting layer and the second refractive index adjusting layer are provided), the electrodes and the like are less likely to be visually recognized (that is, so-called bone visibility is suppressed). It has the advantage of.

For the structure of the touch panel, the structure of the capacitance type input device described in JP-A-2014-10814 or JP-A-2014-108541 may be referred to.

<First specific example of touch panel>
FIG. 2 is a schematic cross-sectional view of a touch panel 30 which is a first specific example of the touch panel according to the present disclosure. More specifically, FIG. 2 is a schematic cross-sectional view of an image display area of the touch panel 30.
As shown in FIG. 2, the touch panel 30 includes a substrate 32, a second refractive index adjusting layer 36, a transparent electrode pattern 34 as a touch panel electrode, a first refractive index adjusting layer 20, and a touch panel electrode protective film. 18 and have a structure arranged in this order.
In the touch panel 30, the touch panel electrode protective film 18 and the first refractive index adjusting layer 20 cover the entire transparent electrode pattern 34. However, the touch panel according to the present disclosure is not limited to this aspect. The electrode protective film 18 for the touch panel and the first refractive index adjusting layer 20 may cover at least a part of the transparent electrode pattern 34.

Further, the second refractive index adjusting layer 36 and the first refractive index adjusting layer 20 directly or other the first region 40 in which the transparent electrode pattern 34 exists and the second region 42 in which the transparent electrode pattern 34 does not exist, respectively. It is preferable to continuously cover the layers. This makes the transparent electrode pattern 34 less visible.
It is preferable that the second refractive index adjusting layer 36 and the first refractive index adjusting layer 20 directly cover both the first region 40 and the second region 42 rather than covering them through other layers. Examples of the "other layer" include an insulating layer, an electrode pattern other than the transparent electrode pattern 34, and the like.

The first refractive index adjusting layer 20 is laminated over both the first region 40 and the second region 42. The first refractive index adjusting layer 20 is adjacent to the second refractive index adjusting layer 36, and is also adjacent to the transparent electrode pattern 34.
When the shape of the end portion of the transparent electrode pattern 34 at the point of contact with the second refractive index adjusting layer 36 is a tapered shape as shown in FIG. 2, the shape is along the tapered shape (that is, at the same inclination as the taper angle). ), It is preferable that the first refractive index adjusting layer 20 is laminated.

As the transparent electrode pattern 34, the ITO transparent electrode pattern is suitable.
The transparent electrode pattern 34 can be formed, for example, by the following method.
A thin film for electrodes (for example, an ITO film) is formed by sputtering on the substrate 32 on which the second refractive index adjusting layer 36 is formed. An etching protective layer is formed by applying a photosensitive resist for etching on the thin film for electrodes or by transferring a photosensitive film for etching. Next, the etching protective layer is patterned into a desired pattern shape by exposure and development. Then, the portion of the electrode thin film that is not covered by the patterned etching protective layer is removed by etching. As a result, the thin film for electrodes is formed into a pattern having a desired shape (that is, a transparent electrode pattern 34). Subsequently, the etching protective layer patterned by the stripping liquid is removed.

The first refractive index adjusting layer 20 and the touch panel electrode protective film 18 are, for example, the substrate 32 (that is, the touch panel substrate) in which the second refractive index adjusting layer 36 and the transparent electrode pattern 34 are sequentially provided as follows. Formed on top.
First, the transfer film 10 shown in FIG. 1 (that is, the transfer film 10 having a laminated structure of the protective film 16 / the second resin layer 20A / the photosensitive layer 18A / the temporary support 12) is prepared.
Next, the protective film 16 is removed from the transfer film 10.
Next, the transfer film 10 from which the protective film 16 has been removed is laminated on a substrate 32 (that is, a touch panel substrate) in which the second refractive index adjusting layer 36 and the transparent electrode pattern 34 are sequentially provided. Lamination is performed in the direction in which the second resin layer 20A of the transfer film 10 from which the protective film 16 has been removed and the transparent electrode pattern 34 are in contact with each other. By this laminating, a laminated body having a laminated structure of a temporary support 12 / a photosensitive layer 18A / a second resin layer 20A / a transparent electrode pattern 34 / a second refractive index adjusting layer 36 / a substrate 32 can be obtained.
Next, the temporary support 12 is removed from the laminated body.
Next, the photosensitive layer 18A and the second resin layer 20A are cured in a pattern by pattern-exposing the laminate from which the temporary support 12 has been removed. The photosensitive layer 18A and the second resin layer 20A may be cured separately in a pattern by separate pattern exposures, but it is preferably performed simultaneously by one pattern exposure.
Next, by removing the non-exposed portion (that is, the non-curing portion) of the photosensitive layer 18A and the second resin layer 20A by development, the electrode protective film for a touch panel which is a patterned cured product of the photosensitive layer 18A. 18 (not shown for the pattern shape) and the first refractive index adjusting layer 20 (not shown for the pattern shape), which is a cured product of the pattern of the second resin layer 20A, are obtained, respectively. The development of the photosensitive layer 18A and the second resin layer 20A after the pattern exposure may be performed separately by separate development, but it is preferable that the development is performed simultaneously by one development.

Preferred embodiments of laminating, pattern exposure and development will be described later.

For the structure of the touch panel, the structure of the capacitance type input device described in JP-A-2014-10814 or JP-A-2014-108541 may be referred to.

<Second specific example of touch panel>
FIG. 3 is a schematic cross-sectional view of a touch panel 90, which is a second specific example of the touch panel according to the present disclosure.
As shown in FIG. 3, the touch panel 90 has an image display area 74 and an image non-display area 75 (that is, a frame portion).
As shown in FIG. 3, the touch panel 90 includes touch panel electrodes on both sides of the substrate 32. Specifically, the touch panel 90 is provided with a first transparent electrode pattern 70 on one surface of the substrate 32 and a second transparent electrode pattern 72 on the other surface.
In the touch panel 90, the routing wiring 56 is connected to each of the first transparent electrode pattern 70 and the second transparent electrode pattern 72. The routing wiring 56 is, for example, a copper wiring.
In the touch panel 90, a touch panel electrode protective film 18 is formed on one surface of the substrate 32 so as to cover the first transparent electrode pattern 70 and the routing wiring 56, and the second transparent electrode is formed on the other surface of the substrate 32. A touch panel electrode protective film 18 is formed so as to cover the pattern 72 and the routing wiring 56.
The first refractive index adjusting layer and the second refractive index adjusting layer in the first specific example may be provided on one surface and the other surface of the substrate 32, respectively.

(Manufacturing method of touch panel)
The method for manufacturing the touch panel according to the present disclosure is not particularly limited, but the following manufacturing method is preferable.
A preferred method for manufacturing a touch panel according to the present disclosure is
Preparing a touch panel substrate having a structure in which electrodes and the like (that is, at least one of the touch panel electrodes and the touch panel wiring) are arranged on the substrate (hereinafter, also referred to as “preparation step”).
Forming a photosensitive layer using the transfer film according to the present disclosure on the surface of the touch panel substrate on the side where the electrodes and the like are arranged (hereinafter, also referred to as “photosensitive layer forming step”).
Pattern exposure of the photosensitive layer formed on the above-mentioned surface of the touch panel substrate (hereinafter, also referred to as "pattern exposure step") is performed.
By developing the photosensitive layer exposed to the pattern, an electrode protective film for a touch panel that protects at least a part of an electrode or the like is obtained (hereinafter, also referred to as "development process").
including.

According to the above-mentioned preferable manufacturing method, a touch panel provided with an electrode protective film for a touch panel having excellent bending resistance can be manufactured.
Further, it is preferable that the protective film for the touch panel is provided in the bent region of the touch panel. According to the above aspect, the effect of the electrode protective film for a touch panel having excellent bending resistance can be further exhibited.
Further, in the above preferred production method, even when the photosensitive layer is formed under high temperature laminating conditions using the transfer film according to the present disclosure, the generation of development residue is suppressed in the non-exposed portion of the photosensitive layer after development. To.

Hereinafter, each step of the above preferable manufacturing method will be described.

<Preparation process>
The preparation step is a step for convenience, and is a step of preparing a touch panel substrate having a structure in which electrodes and the like (that is, at least one of a touch panel electrode and a touch panel wiring) are arranged on the substrate.
The preparation step may be a step of simply preparing a touch panel substrate manufactured in advance, or a step of manufacturing a touch panel substrate.
The preferred embodiment of the touch panel substrate is as described above.

<Photosensitive layer forming process>
The photosensitive layer forming step is a step of forming a photosensitive layer on the surface of the touch panel substrate on the side where the electrodes and the like are arranged by using the transfer film according to the present disclosure.

Hereinafter, an embodiment in which the transfer film according to the present disclosure is used in the photosensitive layer forming step will be described.
In this aspect, the transfer film according to the present disclosure is laminated on the surface on the side where the electrodes and the like of the touch panel substrate are arranged, and the photosensitive layer of the transfer film according to the present disclosure is transferred onto the surface. , A photosensitive layer is formed on the above surface.
Lamination (transfer of the photosensitive layer) can be performed using a known laminator such as a vacuum laminator or an auto-cut laminator.

As the laminating condition, general conditions can be applied.
The laminating temperature is preferably 80 ° C. to 150 ° C., more preferably 90 ° C. to 150 ° C., and particularly preferably 100 ° C. to 150 ° C.
As described above, in the embodiment using the transfer film according to the present disclosure, the generation of development residue due to heat fog is suppressed even when the laminating temperature is high (for example, 120 ° C. to 150 ° C.).
When using a laminator equipped with a rubber roller, the laminating temperature refers to the rubber roller temperature.
There is no particular limitation on the substrate temperature during laminating. Examples of the substrate temperature at the time of laminating include 10 ° C. to 150 ° C., preferably 20 ° C. to 150 ° C., and more preferably 30 ° C. to 150 ° C. When a resin substrate is used as the substrate, the substrate temperature at the time of laminating is preferably 10 ° C to 80 ° C, more preferably 20 ° C to 60 ° C, and particularly preferably 30 ° C to 50 ° C.
The linear pressure at the time of laminating is preferably 0.5 N / cm to 20 N / cm, more preferably 1 N / cm to 10 N / cm, and particularly preferably 1 N / cm to 5 N / cm.
The transport speed (lamination speed) at the time of laminating is preferably 0.5 m / min to 5 m / min, more preferably 1.5 m / min to 3 m / min.

When using a transfer film having a laminated structure of a protective film / photosensitive layer / intermediate layer / thermoplastic resin layer / temporary support, first, the protective film is peeled off from the transfer film to expose the photosensitive layer, and then the photosensitive layer is exposed. The transfer film and the touch panel substrate are bonded to each other so that the exposed photosensitive layer and the surface on the side where the electrodes of the touch panel substrate are arranged are in contact with each other, and then heating and pressurization are applied. As a result, the photosensitive layer of the transfer film is transferred onto the surface of the touch panel substrate on the side where the electrodes and the like are arranged, and the temporary support / thermoplastic resin layer / intermediate layer / photosensitive layer / electrodes and the like / substrate. A laminated body having a laminated structure is formed. In this laminated structure, the portion of "electrodes and the like / substrate" is a touch panel substrate.
Then, if necessary, the temporary support is peeled off from the laminated body. However, it is also possible to perform the pattern exposure described later while leaving the temporary support.

As an example of a method of transferring the photosensitive layer of the transfer film onto the touch panel substrate, subjecting it to a pattern, and developing it, the description in paragraphs 0035 to 0051 of JP-A-2006-23696 can also be referred to.

<Pattern exposure process>
The pattern exposure step is a step of pattern exposure of the photosensitive layer formed on the touch panel substrate.
Here, the pattern exposure refers to an aspect of exposing in a pattern, that is, an aspect in which an exposed portion and a non-exposed portion are present.
Of the photosensitive layers on the touch panel substrate, the exposed portion in pattern exposure is cured and finally becomes a cured film.
On the other hand, of the photosensitive layer on the touch panel substrate, the non-exposed portion in the pattern exposure is not cured and is removed (dissolved) by the developing solution in the next developing step. The unexposed portion may form an opening in the cured film after the developing step.
The pattern exposure may be an exposure through a mask or a digital exposure using a laser or the like.

As the light source for pattern exposure, any light source in a wavelength range capable of curing the photosensitive layer (for example, 365 nm or 405 nm) can be appropriately selected and used. Examples of the light source include various lasers, light emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, and metal halide lamps. The exposure amount is preferably 5 mJ / cm ² to 200 mJ / cm ² , and more preferably 10 mJ / cm ² to 200 mJ / cm ² .

When the photosensitive layer is formed on the substrate by using the transfer film, the pattern exposure may be performed after the temporary support is peeled off, or the temporary support is exposed before the temporary support is peeled off, and then the temporary support is temporarily peeled off. The support may be peeled off.
Further, in the exposure step, the photosensitive layer may be heat-treated (so-called PEB (Post Exposure Bake)) after pattern exposure and before development.

<Development process>
In the developing step, an electrode protective film for a touch panel that protects at least a part of an electrode or the like is provided by developing a photosensitive layer exposed to a pattern (that is, by dissolving a non-exposed portion in a pattern exposure in a developing solution). This is the process of obtaining.

The developer used for development is not particularly limited, and a known developer such as the developer described in JP-A-5-72724 can be used.
It is preferable to use an alkaline aqueous solution as the developing solution.
Examples of the alkaline compound that can be contained in the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide. , Tetrabutylammonium hydroxide, choline (2-hydroxyethyltrimethylammonium hydroxide), and the like.
The pH of the alkaline aqueous solution at 25 ° C. is preferably 8 to 13, more preferably 9 to 12, and particularly preferably 10 to 12.
The content of the alkaline compound in the alkaline aqueous solution is preferably 0.1% by mass to 5% by mass, more preferably 0.1% by mass to 3% by mass, based on the total amount of the alkaline aqueous solution.

The developer may contain an organic solvent that is miscible with water.
Examples of the organic solvent include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol, acetone and methyl ethyl ketone. , Cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, and N-methylpyrrolidone.
The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.
The developer may contain a known surfactant. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.
The liquid temperature of the developing solution is preferably 20 ° C to 40 ° C.

Examples of the development method include paddle development, shower development, shower and spin development, dip development, and the like.
When shower development is performed, the non-exposed portion of the photosensitive layer is removed by spraying the developer on the photosensitive layer after pattern exposure in a shower shape. When a transfer film including a photosensitive layer and at least one of a thermoplastic resin layer and an intermediate layer is used, the photosensitive layer is photosensitive after transfer onto the substrate and before the development of the photosensitive layer. At least one of the thermoplastic resin layer and the intermediate layer (both if both are present) may be removed in advance by spraying an alkaline liquid having low solubility of the layer in a shower manner.
Further, after development, it is preferable to remove the development residue by rubbing with a brush or the like while spraying a cleaning agent or the like with a shower.
The liquid temperature of the developing solution is preferably 20 ° C to 40 ° C.

The developing step may include a step of performing the above-mentioned development and a step of heat-treating (hereinafter, also referred to as “post-baking”) the cured film obtained by the above-mentioned development.
When the substrate is a resin substrate, the post-baking temperature is preferably 100 ° C. to 160 ° C., more preferably 130 ° C. to 160 ° C.
By this post-baking, the resistance value of the transparent electrode pattern can also be adjusted.
When the photosensitive layer contains a carboxy group-containing (meth) acrylic resin, at least a part of the carboxy group-containing (meth) acrylic resin can be changed to a carboxylic acid anhydride by post-baking. As a result, the developability and the strength of the cured film are excellent.

Further, the developing step may include a step of performing the above-mentioned development and a step of exposing the cured film obtained by the above-mentioned development (hereinafter, also referred to as “post-exposure”).
When the developing step includes a post-exposure step and a post-baking step, it is preferably carried out in the order of post-exposure and post-baking.

For pattern exposure, development, and the like, for example, the description in paragraphs 0035 to 0051 of JP-A-2006-23696 can also be referred to.

The preferred manufacturing method of the touch panel according to the present disclosure may include other steps other than the above-mentioned steps. As other steps, a step (for example, a cleaning step) that may be provided in a normal photolithography step can be applied without particular limitation.

(Image display device)
The image display device according to the present disclosure includes a capacitance type input device according to the present disclosure, preferably a touch panel according to the present disclosure (for example, a touch panel according to the first and second specific examples).
As the image display device according to the present disclosure, a liquid crystal display device having a structure in which the touch panel according to the present disclosure is superimposed on a known liquid crystal display element is preferable.
The structure of the image display device equipped with a touch panel is, for example, "Latest Touch Panel Technology" (Published on July 6, 2009, Techno Times Co., Ltd.), supervised by Yuji Mitani, "Touch Panel Technology and Development", CMC Publishing (2004). , 12), FPD International 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292 can be applied.

The present disclosure will be described in more detail with reference to examples below. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples may be appropriately changed as long as they do not deviate from the gist of the present disclosure. Therefore, the scope of the present disclosure is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

(Example 1)
<Preparation of photosensitive transfer material (transfer film)>
<< Formation of photosensitive layer >>
Using a slit-shaped nozzle on a 16 μm-thick polyethylene terephthalate film (temporary support, 16QS62 (manufactured by Toray Industries, Inc.)), a coating liquid for a photosensitive layer consisting of the following formulation 101 is applied to a coating liquid for a photosensitive layer having a thickness of 9 after drying. The film was adjusted to 0.0 μm and applied, and dried with a hot air convection dryer having a temperature gradient of 75 ° C. to 120 ° C. to remove the solvent to form a photosensitive layer.

-Coating liquid for photosensitive layer: Formulation 101 (organic solvent-based resin composition)-
-Compound (1) (Ethylene unsaturated compound A, the following compound, synthetic product): 12.51 parts

<Method for synthesizing compound (1)>
60 g of 3,6-dithia-1,8-octanediol, 73.3 g of triethylamine and 500 mL of acetonitrile were mixed. A solution prepared by dissolving 65.5 g of acrylic acid chloride under ice-cooling in 100 mL of acetonitrile was added dropwise over 2 hours. The reaction solution was heated to room temperature and reacted for another 1 hour. After adding 10 mL of water to the reaction solution and stirring for 10 minutes, 900 ml of ethyl acetate was added. The organic layer was washed with water and dried, and then 0.6 g of p-methoxyphenol was added and concentrated to obtain a crude product. When this was purified by column chromatography, 65 g of compound (1) was obtained.

-Tricyclodecanedimethanol diacrylate (ethylenically unsaturated compound B, A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.): 18.30 parts-Multifunctional ethylenically unsaturated compound having a carboxylic acid group (Aronix TO2349) , Toa Synthetic Co., Ltd.): 3.05 parts ・ Polymer A (binder polymer, resin shown below, acid value 95 mgKOH / g, Mw = 27,000): 50.82 parts

The unit of the number in the lower right of the parentheses of each structural unit is mol%.

1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone-1- (O-acetyloxime) (photopolymerization initiator, Irgacure OXE-02, manufactured by BASF) : 0.39 part ・ 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (photopolymerization initiator, Irgacure 907, manufactured by BASF): 0.77 part ・ Acryloyl group Blocked isocyanate compound (thermally crosslinkable compound, Karenz AOI-BM, manufactured by Showa Denko Co., Ltd.): 12.50 parts, rust preventive agent (1,2,4-triazole, manufactured by Tokyo Kasei Kogyo Co., Ltd.): 0 .20 parts-hydrogen donating compound (N-phenylglycine, manufactured by Genuine Kagaku Co., Ltd.): 0.10 parts-styrene / maleic anhydride = 4: 1 (molar ratio) copolymer (SMA EF-40, Acid anhydride price 1.94 mmol / g, weight average polymer weight 10,500, manufactured by Cray Valley): 1.20 parts, surfactant (Megafuck F551, manufactured by DIC Co., Ltd.): 0.16 parts, 1-methoxy -2-propyl acetate: 122.41 parts, methyl ethyl ketone: 122.41 parts

<< Formation of second resin layer >>
Next, on the photosensitive layer, the coating liquid for the second resin layer consisting of the following formulation 201 was adjusted and applied so that the thickness after drying was 70 nm using a slit-shaped nozzle. The solvent was removed by drying with a hot air convection dryer having a temperature gradient of 40 ° C. to 95 ° C. to form a second resin layer arranged in direct contact with the photosensitive layer.
Here, Formulation 201 is prepared using a resin having an acid group and an aqueous ammonia solution, and the resin having an acid group is neutralized with the aqueous ammonia solution and contains an ammonium salt of the resin having an acid group. A coating liquid for the second resin layer, which is a product, was prepared.

-Coating liquid for the second resin layer: Formulation 201 (water-based resin composition)-
Acrylic resin (ZB-015M, manufactured by Fujifilm Fine Chemicals Co., Ltd., methacrylic acid / allyl methacrylate copolymer resin, weight average molecular weight 25,000, composition ratio (molar ratio) = 20/80, solid content 5. 00%, aqueous ammonia solution): 4.92 parts, polyfunctional ethylenically unsaturated compound having a carboxylic acid group (Aronix TO-2349, manufactured by Toa Synthetic Co., Ltd.): 0.04 parts, ZrO ₂ particles (nano-use OZ-) S30M, solid content 30.5%, methanol 69.5%, refractive acid 2.2, average particle size: about 12 nm, manufactured by Nissan Chemical Industry Co., Ltd.): 4.34 parts, rust preventive (benzotriazole derivative) , BT-LX, manufactured by Johoku Chemical Industry Co., Ltd.): 0.03 parts ・ Surfactant (Megafuck F444, manufactured by DIC Co., Ltd.): 0.01 parts ・ Distilled water: 24.83 parts ・ Methanol: 65 .83 copies

<< Formation of protective film >>
The second of the laminated bodies obtained as described above in which the photosensitive layer and the second resin layer arranged in direct contact with the photosensitive layer are provided on the temporary support in this order. A polyethylene terephthalate film (protective film, 16QS62 (manufactured by Toray Industries, Inc.)) having a thickness of 16 μm was pressure-bonded onto the resin layer of Example 1 to prepare a photosensitive transfer material of Example 1.

(Examples 2 to 10 and Comparative Examples 1 to 5)
Photosensitivity of Examples 2 to 19 and Comparative Examples 1 to 5 in the same manner as in Example 1 except that the solid content ratio was changed to the coating liquid for a photosensitive layer having the composition shown in Table 1 or Table 2 below. Sex transfer materials (transfer films) were prepared respectively.

The obtained photosensitive transfer material was used and evaluated as follows. The evaluation results are shown in Table 1 or Table 2.

<Evaluation method>
<< Evaluation of bending resistance >>
-Preparation of sample for bending resistance evaluation-
The obtained photosensitive transfer material was laminated on both surfaces of Cosmoshine A4300 (thickness 50 μm) of a polyethylene terephthalate film manufactured by Toyobo Co., Ltd., which had been heat-treated at 145 ° C. for 30 minutes after peeling off the protective film. , A laminated body A having a layered structure of temporary support / photosensitive layer / second resin layer / Cosmoshine A4300 (thickness 50 μm) / second resin layer / photosensitive layer / temporary support was formed. The laminating conditions were a lamirol temperature of 100 ° C., a linear pressure of 3 N / cm, and a transport speed of 4 m / min.
Then, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp, both sides were exposed on the entire surface with an exposure amount of 120 mJ / cm ² (i-line) via a temporary support. After peeling off the temporary supports on both sides, double-sided exposure is performed with an exposure amount of 375 mJ / cm ² (i-line), and then post-baking is performed at 145 ° C. for 30 minutes to cure the photosensitive layer and cure the film. Was formed.
In this way, a bending resistance evaluation sample composed of a cured film having a thickness of 8 μm / Cosmoshine A4300 (thickness 50 μm) / a cured film having a thickness of 8 μm was obtained.

-Evaluation of bending resistance-
Bending resistance was evaluated as follows using a sample for bending resistance evaluation.
FIG. 4 is a schematic cross-sectional view showing a state of a sample for bending resistance evaluation in bending resistance evaluation.
The bending resistance evaluation sample obtained above was cut into a rectangle of 5 cm × 12 cm. As shown in FIG. 4, of the cut bending resistance evaluation sample 102, a weight 104 of 100 g is attached to one of the short sides and weighted so as to be in contact with the metal rod 106 having a diameter of d mm at an angle of 90 °. Hold (state of sample 102 for bending resistance evaluation in FIG. 4). Then, the bending resistance evaluation sample is bent to a state in which the bending resistance evaluation sample 102 is bent 180 ° so as to be wound around the metal rod 106 (the state of the bending resistance evaluation sample 102A after bending in FIG. 4). Then, the motion of returning to the original position (reciprocating direction D) was reciprocated 10 times, and the presence or absence of cracks on the surface of the sample was visually confirmed.
The above operation was performed while changing the diameter d of the metal rod 106, and the smallest d at which cracks did not occur was obtained. In the following evaluation criteria, A has the best bending resistance and E has the worst bending resistance. It is preferably any of A, B and C, and A is most preferable.
A: The smallest d that does not generate cracks is 2 mm or less B: The smallest d that does not generate cracks is larger than 2 mm and 3 mm or less C: The smallest d that does not generate cracks is larger than 3 mm and 4 mm or less D: The smallest that does not generate cracks d is greater than 4 mm and 5 mm or less E: The smallest d that does not generate cracks is greater than 5 mm

<< Evaluation of Moisture Vapor Transmission (WVTR) >>
-Preparation of sample for moisture permeability measurement-
The photosensitive transfer material of each example or comparative example is temporarily supported by peeling off the protective film and then laminating it on a PTFE (tetrafluoroethylene resin) membrane filter FP-100-100 manufactured by Sumitomo Electric Industries, Ltd. A laminated body A having a layer structure of a body / photosensitive layer / second resin layer / membrane filter was formed. The laminating conditions were a membrane filter temperature of 40 ° C., a lamirol temperature of 100 ° C., a linear pressure of 3 N / cm, and a transport speed of 4 m / min.
Further, the temporary support is peeled off from the laminated body A, and the transfer film from which the protective film is peeled off is laminated on the photosensitive layer four more times in the same manner as described above, and the temporary support / (photosensitive layer / second resin layer) is laminated. ) X 4 layers / laminated body B having a laminated structure of a membrane filter was formed.
The photosensitive layer of the obtained laminate B was exposed to an exposure amount of 120 mJ / cm ² (i) via a temporary support using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp. It was exposed with a line). After peeling off the temporary support, the photosensitive layer was further exposed to an exposure amount of 375 mJ / cm ² (i-line) and then post-baked at 145 ° C. for 30 minutes to cure the photosensitive layer and form a cured film. ..
From the above, a sample for moisture permeability measurement having a laminated structure of a cured film / membrane filter having a total film thickness of 40 μm was obtained.

-Measurement of water vapor transmission rate (WVTR)-
Using a sample for measuring moisture permeability, the moisture permeability was measured by the cup method with reference to JIS-Z-0208 (1976). The details will be described below.
First, a circular sample having a diameter of 70 mm was cut out from the sample for measuring moisture permeability. Next, a measuring cup with a lid was prepared by putting 20 g of dried calcium chloride in the measuring cup and then covering with the above circular sample.
This measuring cup with a lid was left in a constant temperature and humidity chamber at 65 ° C. and 90% RH for 24 hours. The water vapor transmission rate (WVTR) (unit: g / (m ² · day)) of the circular sample was calculated from the mass change of the measuring cup with a lid before and after the standing.
The above measurement was carried out three times, and the average value of WVTR in the three measurements was calculated. The water vapor transmission rate (WVTR) was evaluated according to the following evaluation criteria based on the average value of WVTR. In the following evaluation criteria, any of A, B, and C is preferable, A or B is more preferable, and A is most preferable.
The results are shown in Table 1 or Table 2.
In the above measurement, as described above, the WVTR of a circular sample having a laminated structure of a cured film / membrane filter was measured. However, since the WVTR of the membrane filter is extremely high as compared with the WVTR of the cured film, in the above measurement, the WVTR of the cured film itself is substantially measured.

-Evaluation criteria for water vapor transmission rate (WVTR)-
A: The average value of WVTR is less than 220 g / ( ^m2・ day) B: The average value of WVTR is 220 g / ( ^m2・ day) or more and less than 240 g / ( ^m2・ day) C: The average value of WVTR is 240 g / (M ² · day) or more and less than 260 g / (m ² · day) D: Average value of WVTR is 260 g / (m ² · day) or more and less than 280 g / (m ² · day) E: Average value of WVTR is 280 g / ( ^M2・ day) or more

<< Evaluation of development residue >>
The obtained photosensitive transfer material was peeled off from the protective film and then laminated on one side of the copper plate. The laminating conditions were a lamirol temperature of 100 ° C., a linear pressure of 3 N / cm, and a transport speed of 4 m / min.
After that, an exposure mask (quartz exposure mask having an overcoat forming pattern) was used on the obtained unexposed laminate using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp. The distance between the 1 mm line and space: 5 lines) surface and the temporary support was set to 125 μm, and the pattern was exposed through the temporary support with an exposure amount of 100 mJ / cm ² (i-line).
After peeling off the temporary support, the laminate after pattern exposure was washed with a 1% aqueous solution of sodium carbonate at 33 ° C. for 45 seconds. Ultrapure water was sprayed onto the copper substrate after the cleaning treatment from an ultrahigh pressure cleaning nozzle. Subsequently, air was blown to remove the moisture on the copper substrate.
The residue in the space portion of this pattern was confirmed visually and with an optical microscope.
In the following evaluation criteria, A is the best and E is the worst. It is preferably any of A, B and C, and A is most preferable.
A: No residue at all when observed visually and under a microscope B: No residue is observed visually, but there is a slight residue only near the pattern when observed under a microscope C: No residue is observed visually but under a microscope When observed, there is a slight residue in the space part. D: No residue is observed visually, but when observed under a microscope, there is a remarkable residue in the space part. E: The residue is noticeably observed in the visual observation.

Details of the components shown in Tables 1 and 2 other than those described above are shown below.
-Compounds (2) to (8), (C1) and (C2): The following compounds

<Method for synthesizing compound (2)>
80 g of 1,6-hexanedithiol, 136.4 g of 2-bromoethanol and 1,200 mL of methanol were mixed, and 72.2 g of potassium hydroxide was slowly added thereto. After refluxing for 4 hours, the mixture was allowed to cool to room temperature, and this was poured into 2 L of water. The precipitated solid was collected by filtration and dried to obtain 88 g of 3,10-dithia-1,12-dodecanediol. The compound (1) was synthesized using the same method as that of the compound (1) except that the obtained 3,10-dithia-1,12-dodecanediol was used in place of the 3,6-dithia-1,8-octanediol. 2) was obtained.

<Method for synthesizing compound (3)>
Compound (3) was synthesized using the same method as compound (2) except that 1,10-dodecanedithiol was used instead of 1,6-hexanedithiol.

<Method for synthesizing compound (4)>
Compound (4) was synthesized using the same method as compound (2) except that 3,7-dithia-1,9-nonanedithiol was used instead of 1,6-hexanedithiol.

<Method for synthesizing compound (5)>
Compound (5) was synthesized using the same method as that for compound (2) using thiodiglycol and acrylate chloride.

<Method for synthesizing compound (6)>
Compound (6) was synthesized using the same method as that for compound (2).

<Method for synthesizing compound (7)>
Using 2,3-dimercapto-1-propanol as a raw material, compound (7) was obtained by reacting with acrylate chloride after introducing thioether linkage by the same method as the synthesis of compound (2).

<Method for synthesizing compound (8)>
Using dithioerythritol as a raw material, compound (8) was obtained by reacting with acrylate chloride after introducing thioether linkage by the same method as in the synthesis of compound (2).

<Method for synthesizing compound (C1)>
Compound (C1) was synthesized using the same method as compound (1) except that 1,8-octanediol was used instead of 3,6-dithia-1,8-octanediol.

<Method for synthesizing compound (C2)>
Compound (C2) was synthesized using the same method as compound (1) except that 1,16-hexadecanediol was used instead of 3,6-dithia-1,8-octanediol.

-Monofunctional thioether monomer (compound (C3))

<Method for synthesizing compound (C3)>
20 g of dodecanethiol, 13.7 g of 2-bromoethanol and 200 mL of methanol were mixed, and 7.2 g of potassium hydroxide was slowly added thereto. After refluxing for 4 hours, the mixture was allowed to cool to room temperature, and 500 mL of ethyl acetate was added thereto. The organic layer was washed with water, dried and concentrated to obtain 22 g of 3-thia-1-pentadecanol. 22 g of 3-thia-1-pentadecanol, 10.8 g of triethylamine, and 200 mL of tetrahydrofuran were mixed, and 8.9 g of acrylic acid chloride under ice-cooling was added dropwise over 30 minutes. After raising the temperature to room temperature and reacting for another 1 hour, 10 mL of water was added, and the mixture was stirred for 10 minutes, and then 500 mL of ethyl acetate was added. The organic layer was washed with water and dried, and then 0.6 g of p-methoxyphenol was added and concentrated to obtain a crude product. When this was purified by column chromatography, 20 g of the comparative compound (C3) was obtained.

Polymer B (resin shown below, acid value 103 mgKOH / g, Mw = 20,000)

The unit of the number in the lower right of the parentheses of each structural unit is mol%.

Duranate TPA-B80E (thermocrosslinkable compound, blocked isocyanate compound, manufactured by Asahi Kasei Chemicals Co., Ltd.)

From the results shown in Tables 1 and 2, the photosensitive resin compositions of Examples 1 to 19 are more excellent in developing residue inhibitory than the photosensitive resin compositions of Comparative Examples 1 to 5, and the obtained cured film is obtained. It can be seen that the moisture permeability is low and the obtained cured film has excellent bending resistance.

10: Transfer film 12: Temporary support 16: Protective film 18, 18A: Photosensitive layer 20, 20A: Second resin layer (first refractive index adjusting layer)
30: Touch panel 32: Substrate 34: Transparent electrode pattern 36: Second refractive index adjusting layer 40: First region 42 in which the transparent electrode pattern exists: Second region 56 in which the transparent electrode pattern does not exist 56: Routing wiring 70: First transparent Electrode pattern 72: Second transparent electrode pattern 74: Image display area 75: Image non-display area 90: Touch panel 102: Bending resistance evaluation sample 102A: Bending resistance evaluation sample 104 in a state of being bent at 180 °: Weight 106: Metal Rod D: Reciprocating direction d: Diameter of metal rod 106

Claims (14)

Binder polymer and
Ethylene unsaturated compounds and
Contains a photopolymerization initiator,
The ethylenically unsaturated compound contains a bifunctional or higher functional ethylenically unsaturated compound A having a thioether bond.
The bifunctional or higher functional ethylenically unsaturated compound A is a compound, compound (7) or compound (8) represented by the following formula (A-1) or formula (A-2).
Photosensitive resin composition.

In formulas (A-1) and (A-2), ^RA1 to ^RA4 independently represent a hydrogen atom or a methyl group, and ^LA1 and ^LA3 independently represent an alkylene group or -LA6 ⁽ respectively) . SL ^A7 ) represents ^nA- , LA2 and ^LA4 to ^LA7 independently represent an alkylene group, and _nA represents an integer of 1 to 8.

The photosensitive resin according to claim 1, wherein the shortest linking chain of the bifunctional or higher functional ethylenically unsaturated compound A having at least two ethylenically unsaturated bonds has 10 to 30 atoms. Composition. The photosensitive resin composition according to claim 1 or 2, wherein the linking chain in the bifunctional or higher functional ethylenically unsaturated compound A is a chain composed of a carbon atom, an oxygen atom and a sulfur atom. The photosensitive resin composition according to any one of claims 1 to 3, wherein the number of sulfur atoms contained in the bifunctional or higher functional ethylenically unsaturated compound A is 1 or more and 4 or less. The photosensitive resin composition according to any one of claims 1 to 4, wherein the bifunctional or higher functional ethylenically unsaturated compound A is a bifunctional ethylenically unsaturated compound. The photosensitive resin composition according to any one of claims 1 to 5, wherein the bifunctional or higher functional ethylenically unsaturated compound A is a compound represented by the above formula A-1. The photosensitive resin composition according to any one of claims 1 to 6, wherein the ethylenically unsaturated compound contains an ethylenically unsaturated compound B having an alicyclic structure. The mass ratio _MA / MB of the content _MA of the bifunctional or higher functional ethylenically unsaturated compound _A and the content MB of the ethylenically unsaturated compound _B is 0.2 to 1.5. The photosensitive resin composition according to claim 7. The photosensitive resin composition according to any one of claims 1 to 8, which is used for forming a touch panel protective film. Temporary support and
A transfer film having a photosensitive layer made of the photosensitive resin composition according to any one of claims 1 to 9. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 9. Board and
A laminate having a cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 9. To prepare a touch panel board having a structure in which at least one of a touch panel electrode and a touch panel wiring is arranged on the board.
The photosensitive resin composition according to any one of claims 1 to 9 is contained on the surface of the touch panel substrate on the side where at least one of the touch panel electrode and the touch panel wiring is arranged. Forming a photosensitive layer and
Pattern exposure of the photosensitive layer formed on the touch panel substrate and
A method for manufacturing a touch panel, comprising developing a photosensitive layer exposed to a pattern to obtain a protective film for a touch panel that protects at least a part of the electrode for the touch panel and wiring for the touch panel. The method for manufacturing a touch panel according to claim 13, wherein the touch panel protective film is provided in a bent region of the touch panel.

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