WO2016052390A1

WO2016052390A1 - Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic electroluminescent display device, and touch panel

Info

Publication number: WO2016052390A1
Application number: PCT/JP2015/077288
Authority: WO
Inventors: 豪安藤; 大助柏木
Original assignee: 富士フイルム株式会社
Priority date: 2014-09-29
Filing date: 2015-09-28
Publication date: 2016-04-07
Also published as: TW201612250A

Abstract

Provided is a photosensitive resin composition exhibiting favorable sensitivity and unlikely to cause metal discoloration. Further provided are a method for producing a cured film using the photosensitive resin composition, a cured film, a liquid crystal display device, an organic electroluminescent display device, and a touch panel. This photosensitive resin composition contains a polysiloxane component, a photoacid generator for generating an acid having a pKa of 3 or less, a solvent, and a block isocyanate compound. It is preferable for the content of the block isocyanate compound to be 0.1-15 mass% of the total solid content of the photosensitive resin composition.

Description

Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic electroluminescence display device, and touch panel

The present invention relates to a photosensitive resin composition. More specifically, a photosensitive resin composition suitable for forming a flattening film, a protective film, an interlayer insulating film, and the like of electronic components such as a liquid crystal display device, an organic electroluminescence display device, a touch panel, an integrated circuit element, and a solid-state imaging element About. The present invention also relates to a method for producing a cured film, a cured film obtained by curing a photosensitive resin composition, a liquid crystal display device using the cured film, an image display device such as an organic electroluminescence display device, and an input device such as a touch panel.

An image display device such as an organic electroluminescence display device and a liquid crystal display device, and an input device such as a touch panel are provided with a patterned interlayer insulating film. In forming an interlayer insulating film, a photosensitive resin composition is widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained. As a characteristic of the photosensitive resin composition, good sensitivity is required.

Recently, heat treatment and film formation at higher temperatures (for example, about 300 ° C.) have been performed in the device manufacturing process after manufacturing the interlayer insulating film in order to improve manufacturing efficiency and display device performance. The interlayer insulating film is also required to have higher temperature resistance than before. The use of polysiloxane as such a high heat resistant interlayer insulating film has been studied.

Patent Document 1 discloses a photosensitive resin composition containing an alkali-soluble siloxane polymer and a photosensitive compound having a 1,2-naphthoquinone diad group.
In Patent Document 2, polysiloxane containing a structural unit having a carboxylic acid protected with an acid-decomposable group as component (A), a photoacid generator as component (B), an organic solvent as component (C), A photosensitive resin composition containing an epoxy group-containing siloxane compound as component (D) is disclosed.
Patent Document 3 discloses a photosensitive resin composition containing polysiloxane containing a structural unit having a protected silanol group and a structural unit having an epoxy group.

On the other hand, Patent Documents 4 to 6 disclose photosensitive resin compositions containing an acrylic resin, a photoacid generator, and a blocked isocyanate compound.

JP 2003-255546 A JP 2013-92633 A JP 2009-263522 A JP 2013-2425111 A International publication 2013/161861 pamphlet International Publication 2013/161862 Pamphlet

However, when the present inventors examined the photosensitive resin composition disclosed in Patent Document 1, it was found that the sensitivity was not sufficient.
Moreover, although the photosensitive resin composition disclosed by

patent document

2, 3 was excellent in the sensitivity, it turned out that it is easy to discolor a metal.
In addition, since polysiloxane generates water during polycondensation during polysiloxane synthesis, when a film is formed using a photosensitive resin composition using polysiloxane, the resulting film has a high moisture content, and metal is formed. It turned out that it tends to discolor easily.

On the other hand, Patent Documents 4 to 6 describe that a photosensitive resin composition using an acrylic resin improves heat resistance, chemical resistance, substrate adhesion, and the like by containing a blocked isocyanate compound. However, there is no description regarding suppression of discoloration of metals. In addition, since acrylic resin does not generate water during polycondensation during resin synthesis, forming a film using a photosensitive resin composition using an acrylic resin makes it difficult for water to be taken into the film, resulting in discoloration of the metal. It was not a problem in the first place.

Therefore, an object of the present invention is to provide a photosensitive resin composition which has good sensitivity and hardly discolors a metal even when polysiloxane is used. Moreover, it is providing the manufacturing method of a cured film using the photosensitive resin composition, a cured film, a liquid crystal display device, an organic electroluminescent display device, and a touch panel.

Under such circumstances, as a result of investigations by the present inventors, a photosensitive resin composition comprising a polysiloxane component, a photoacid generator that generates an acid having a pKa of 3 or less, a solvent, and a blocked isocyanate compound. It has been found that a photosensitive resin composition having good sensitivity and heat resistance and hardly discoloring a metal can be obtained, and the present invention has been completed. The present invention provides the following.

<1> Polysiloxane component satisfying at least one of the following 1 and 2 as component A,
1: The structural unit a1 is selected from a group in which a carboxy group is protected by an acid-decomposable group, a group in which a phenolic hydroxyl group is protected by an acid-decomposable group, and a group in which a silanol group is protected by an acid-decomposable group A polysiloxane component comprising a polysiloxane having a structural unit having at least one kind of group and a structural unit having a crosslinkable group as the structural unit a2.
2: The structural unit a1 is selected from a group in which a carboxy group is protected with an acid-decomposable group, a group in which a phenolic hydroxyl group is protected with an acid-decomposable group, and a group in which a silanol group is protected with an acid-decomposable group A polysiloxane component comprising a polysiloxane having a structural unit having at least one kind of group and a polysiloxane having a structural unit having a crosslinkable group as the structural unit a2.
As a component B, a photoacid generator that generates an acid having a pKa of 3 or less,
As component C, a solvent, and
A photosensitive resin composition containing a blocked isocyanate compound as component S.
<2> The photosensitive resin composition according to <1>, containing 0.1 to 15% by mass of a blocked isocyanate compound based on the total solid content of the photosensitive resin composition.
<3> The blocked isocyanate compound is a compound obtained by protecting the isocyanate group of at least one compound selected from an isocyanate compound selected from tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate, and a multimer of isocyanate compounds. The photosensitive resin composition according to <1> or <2>.
<4> A blocked isocyanate compound is a compound in which an isocyanate group is protected and a block structure is formed by a compound selected from an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound. The photosensitive resin composition according to any one of <1> to <3>.
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the block isocyanate compound has a molecular weight of 100 to 2,000.
<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the acid-decomposable group included in the polysiloxane component is an acetal group.
<7> The structural unit a1 is at least one selected from the structural unit represented by the following general formula a1-1 and the structural unit represented by the following general formula a1-2, <1> to <6 > The photosensitive resin composition in any one of>

In general formula a1-1 and general formula a1-2, a represents 0 or 1,
R ¹ and R ² each independently represents a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² represents an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group. R ¹ or R ² and R ³ may be linked to form a cyclic ether,
R ⁴ represents an alkyl group, an aryl group, or an aralkyl group,
L ¹ represents a single bond or a divalent linking group,
L ² represents a single bond or a divalent linking group,
R ^x represents an alkyl group or a halogen atom,
m1 represents an integer of 0 to 4.
<8> The photosensitive property according to any one of <1> to <7>, wherein the crosslinkable group of the polysiloxane component is at least one selected from a cyclic ether and a group having an ethylenically unsaturated bond. Resin composition.
<9> The photosensitive resin composition according to any one of <1> to <8>, wherein the polysiloxane further includes a structural unit having at least one group selected from a carboxy group and a phenolic hydroxyl group.
<10> The photosensitive resin composition according to any one of <1> to <9>, wherein the photoacid generator is at least one selected from an onium salt compound, an oxime sulfonate compound, and an imide sulfonate compound.
<11> A step of applying the photosensitive resin composition according to any one of <1> to <10> on a substrate, a step of removing a solvent from the photosensitive resin composition applied to the substrate, and the solvent is removed. A method for producing a cured film, comprising: exposing the exposed photosensitive resin composition; developing the exposed photosensitive resin composition; and thermally curing the developed photosensitive resin composition.
<12> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <10>.
<13> The cured film according to <12>, which is an interlayer insulating film.
<14> A liquid crystal display device having the cured film according to <12> or <13>.
<15> An organic electroluminescence display device having the cured film according to <12> or <13>.
<16> A touch panel having the cured film according to <12> or <13>.

It is now possible to provide a photosensitive resin composition that has good sensitivity and hardly discolors metal even when polysiloxane is used. Moreover, the manufacturing method of the cured film using the photosensitive resin composition, a cured film, a liquid crystal display device, an organic electroluminescent display device, and a touch panel can be provided now.

It is a composition conceptual diagram of an example of a liquid crystal display. It is a composition conceptual diagram of other examples of a liquid crystal display. 1 shows a conceptual diagram of a configuration of an example of an organic EL display device. It is sectional drawing which shows the structural example of a capacitive touch panel. It is explanatory drawing which shows an example of a front plate. It is explanatory drawing which shows an example of a 1st transparent electrode pattern and a 2nd transparent electrode pattern.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, “˜” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has 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).
The solid content concentration in this specification refers to the solid content concentration at 25 ° C.
The viscosity in this specification refers to a viscosity at 25 ° C.
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by a gel permeation chromatography (GPC) measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, using HLC-8120 (manufactured by Tosoh Corporation) and using TSK gel Multipore HXL-M (manufactured by Tosoh Corporation) as a column. 7.8 mm ID × 30.0 cm can be determined by using THF (tetrahydrofuran) as the eluent.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention contains a polysiloxane component described later, a photoacid generator that generates an acid having a pKa of 3 or less, a solvent, and a blocked isocyanate compound.
Since the photosensitive resin composition of this invention contains the polysiloxane component mentioned later and a photo-acid generator, a sensitivity is favorable. Moreover, the cured film excellent in heat resistance can also be formed by including a polysiloxane component. And discoloration of a metal can be suppressed by including a block isocyanate compound. The mechanism by which the discoloration of the metal can be suppressed by containing the blocked isocyanate compound is presumed to be as follows. That is, it is considered that the water generated during the polycondensation of polysiloxane was captured by the blocked isocyanate compound and the water content in the film was reduced, so that the discoloration of the metal could be suppressed.
The photosensitive resin composition of the present invention can be preferably used as a chemically amplified positive photosensitive resin composition.
Hereinafter, each component of the photosensitive resin composition of the present invention will be described in more detail.

<< (A) Polysiloxane Component (Component A) >>
In the photosensitive resin composition of the present invention, the polysiloxane component satisfies at least one of the following (1) and (2).
(1) (a1) selected from a group in which a carboxy group is protected with an acid-decomposable group, a group in which a phenolic hydroxyl group is protected with an acid-decomposable group, and a group in which a silanol group is protected with an acid-decomposable group A polysiloxane component comprising polysiloxane (A1) having a structural unit having at least one group and (a2) a structural unit having a crosslinkable group.
(2) (a1) selected from a group in which a carboxy group is protected by an acid-decomposable group, a group in which a phenolic hydroxyl group is protected by an acid-decomposable group, and a group in which a silanol group is protected by an acid-decomposable group A polysiloxane component comprising polysiloxane (A2) having a structural unit having at least one group and (a2) polysiloxane (A3) having a structural unit having a crosslinkable group.
(A) Unless otherwise stated, a polysiloxane component means what included other polysiloxane added as needed in addition to the said polysiloxane.
(A) The molar ratio between the structural unit (a1) and the structural unit (a2) contained in the polysiloxane component is preferably structural unit (a1): structural unit (a2) = 10: 90 to 90:10, 80: 20 to 20:80 is more preferable, and 60:40 to 30:70 is still more preferable.

In the aspect (1), at least one polysiloxane (A1) is contained, and the polysiloxane (A1) has the structural unit (a1) and the structural unit (a2). Each of the structural unit (a1) and the structural unit (a2) may contain two or more types. Moreover, the structural unit (a3) which has an acid group mentioned later, and the structural unit (a4) may be included.

The proportion of the structural unit (a1) of the polysiloxane (A1) is preferably 10 to 90 mol% with respect to the total structural units of the polysiloxane (A1) from the viewpoint of sensitivity. The lower limit is preferably 15 mol% or more, and more preferably 20 mol% or more. The upper limit is preferably 80 mol% or less, and more preferably 60 mol% or less.
The proportion of the structural unit (a2) is preferably 10 to 90 mol% with respect to all the structural units of the polysiloxane (A1) from the viewpoint of cured film characteristics. The lower limit is preferably 20 mol% or more, and more preferably 30 mol% or more. The upper limit is preferably 80 mol% or less, and more preferably 70 mol% or less.
In addition, the proportion of the structural unit (a3) is preferably 0 to 50 mol% with respect to all the structural units of the polysiloxane (A1) from the viewpoint of sensitivity. The lower limit is preferably 1 mol% or more, more preferably 5 mol% or more. The upper limit is preferably 30 mol% or less, and more preferably 20 mol% or less.
The proportion of the structural unit (a4) is preferably 0 to 40 mol% with respect to all the structural units of the polysiloxane (A1) from the viewpoints of developability and cured film characteristics. The lower limit is preferably 1 mol% or more, more preferably 5 mol% or more. The upper limit is preferably 30 mol% or less, and more preferably 20 mol% or less.

In the aspect (2), the polysiloxane (A2) having the structural unit (a1) and the polysiloxane (A3) having the structural unit (a2) are included. The polysiloxane (A2) containing the structural unit (a1) may further contain the structural unit (a2). Similarly, the polysiloxane (A3) containing the structural unit (a2) may contain the structural unit (a1). In such a case, the aspect satisfies both (1) and (2). Moreover, polysiloxane (A2) and polysiloxane (A3) may contain the structural unit (a3) which has the acid group mentioned later, and another structural unit (a4).
The proportion of the structural unit (a1) of the polysiloxane (A2) is preferably 10 to 90 mol% with respect to all the structural units of the polysiloxane (A2). The lower limit is preferably 30 mol% or more, and more preferably 40 mol% or more. The upper limit is preferably 90 mol% or less, and more preferably 80 mol% or less. The proportion of the structural unit (a3) is preferably 0 to 50 mol% with respect to all the structural units of the polysiloxane (A2). The lower limit is preferably 1 mol% or more, more preferably 5 mol% or more. The upper limit is preferably 30 mol% or less, and more preferably 20 mol% or less. The proportion of the structural unit (a4) is preferably 0 to 40 mol% with respect to all the structural units of the polysiloxane (A2). The lower limit is preferably 1 mol% or more, more preferably 5 mol% or more. The upper limit is preferably 30 mol% or less, and more preferably 20 mol% or less.
The proportion of the structural unit (a2) of the polysiloxane (A3) is preferably 10 to 90 mol% with respect to all the structural units of the polysiloxane (A3). The lower limit is preferably 30 mol% or more, and more preferably 50 mol% or more. The upper limit is preferably 90 mol% or less, and more preferably 80 mol% or less. The proportion of the structural unit (a4) is preferably 0 to 40 mol% with respect to all the structural units of the polysiloxane (A3). The lower limit is preferably 1 mol% or more, more preferably 5 mol% or more. The upper limit is preferably 30 mol% or less, and more preferably 20 mol% or less.
In the case of the above aspect (2), the mass ratio of the polysiloxane (A2) having the structural unit (a1) and the polysiloxane (A3) having the structural unit (a2) is 95: 5 to 5:95. Is preferable, 80:20 to 20:80 is more preferable, and 70:30 to 30:70 is more preferable.

The structure of the polysiloxane used in the present invention is not particularly limited. Any of a straight chain shape, a ring shape, a ladder shape, and a mesh shape may be used, and a structure in which these are connected to each other may be used. It is preferable in terms of hardness of the cured film that a ladder-like or network-like structure is included.
The weight average molecular weight of the polysiloxane contained in the polysiloxane component is preferably 1,000 to 200,000, and more preferably 2,000 to 50,000. Various characteristics are favorable in the said range. The ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.

<< (a1) selected from a group in which a carboxy group is protected by an acid-decomposable group, a group in which a phenolic hydroxyl group is protected by an acid-decomposable group, and a group in which a silanol group is protected by an acid-decomposable group Constituent unit having at least one group >>
The polysiloxane used in the present invention includes a group in which a carboxy group is protected with an acid-decomposable group, a group in which a phenolic hydroxyl group is protected with an acid-decomposable group, and a group in which a silanol group is protected with an acid-decomposable group. It has a structural unit (a1) having at least one selected group. Hereinafter, the carboxy group, the phenolic hydroxyl group, and the silanol group are collectively referred to as an acid group.
In the present invention, “a group in which a carboxy group is protected with an acid-decomposable group”, “a group in which a phenolic hydroxyl group is protected with an acid-decomposable group”, and “a group in which a silanol group is protected with an acid-decomposable group” Means a group that causes a deprotection reaction using an acid as a catalyst (or an initiator), and generates the above-described acid group, a regenerated acid, and a decomposed structure.
The acid group is preferably a carboxy group or a phenolic hydroxyl group, and more preferably a carboxy group.
An acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal functional group such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group described later) or a group that is relatively difficult to decompose by an acid ( For example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group) can be used. Among these groups, an acetal group is preferable.
That is, the structural unit (a1) preferably has a protected carboxy group in which a carboxy group is protected with an acetal group, or a protected phenol group in which a phenolic hydroxyl group is protected with an acetal group, and the carboxy group is protected with an acetal group. It is more preferable to have a protected carboxy group. According to this aspect, it is preferable from the viewpoints of basic physical properties of the photosensitive resin composition, particularly sensitivity, pattern shape, contact hole formability, and storage stability of the photosensitive resin composition. The content of the group in which the silanol group is protected with an acid-decomposable group is preferably 30 mol% or less, more preferably 10 mol% or less, based on all the structural units of the polysiloxane including the structural unit (a1). More preferably, it is more preferably not more than mol%, and substantially not contained. “Substantially not contained” means, for example, preferably 1 mol% or less, more preferably 0.5 mol% or less, and even more preferably not to all polysiloxane structural units including the structural unit (a1). .

The structural unit (a1) is preferably a structural unit represented by the following general formula (a1-1) and / or a structural unit represented by the following general formula (a1-2).

In general formulas (a1-1) and (a1-2), a represents 0 or 1;
R ¹ and R ² each independently represents a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² represents an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group. R ¹ or R ² and R ³ may be linked to form a cyclic ether,
R ⁴ represents an alkyl group, an aryl group, or an aralkyl group,
L ¹ represents a single bond or a divalent linking group,
L ² represents a single bond or a divalent linking group,
R ^x represents an alkyl group or a halogen atom,
m1 represents an integer of 0 to 4.

R ¹ and R ² each independently represents a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² is an alkyl group or an aryl group.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. The alkyl group may be unsubstituted or may have a substituent. The alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, and a cyclohexyl group. Examples of the substituent that the alkyl group may have include an alkoxy group having 1 to 10 carbon atoms, a thioalkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a cyano group, and a halogen atom (fluorine atom, chlorine atom, bromine atom). , Iodine atom) and the like. These substituents may further have a substituent.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable. The aryl group may be unsubstituted or may have a substituent. Specific examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group. Examples of the substituent include those described above. In addition, an alkyl group having 1 to 10 carbon atoms can be used as a substituent.
R ¹ and R ² are each independently preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and ^one of R ¹ and R ² is a methyl group. The other is particularly preferably a hydrogen atom.

R ³ represents an alkyl group or an aryl group. The alkyl group and aryl group represented by R ³ have the same meanings as the alkyl group and aryl group in R ¹ and R ² . R ³ is preferably a methyl group, an ethyl group, or a propyl group, and more preferably an ethyl group or a propyl group.
R ³ may be linked to R ¹ or R ² to form a cyclic ether. The cyclic ether formed by linking with R ¹ or R ² is preferably a 3- to 6-membered cyclic ether, more preferably a 5- to 6-membered cyclic ether.

R ⁴ represents an alkyl group, an aryl group, or an aralkyl group.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. The alkyl group may have a substituent. The alkyl group may be linear, branched or cyclic.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable. The aryl group may have a substituent. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.
As the aralkyl group, a group in which a part of hydrogen atoms of an alkyl group having 1 to 10 carbon atoms is substituted with an aryl group having 6 to 20 carbon atoms is preferable. The aralkyl group may have a substituent. The alkyl group constituting the aralkyl group may be linear, branched or cyclic.
The substituents that the alkyl group, aryl group, and aralkyl group may have are the same as the substituents described for R ¹ and R ² .
R ⁴ is preferably a methyl group, a phenyl group, a propyl group, a butyl group, or a hexyl group from the viewpoint of solvent resistance or heat resistance, and more preferably a methyl group or a phenyl group.

R ^x represents an alkyl group or a halogen atom. As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable.

L ¹ and L ² represent a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 12 carbon atoms, an alkylene oxide group having 1 to 12 carbon atoms, and an arylene group having 6 to 12 carbon atoms. The alkylene oxide group and the alkylene oxide group may be linear, branched or cyclic. In addition, the alkylene group, alkylene oxide group, and arylene group may have a substituent. Examples of the substituent are the same as those described for R ¹ and R ² . Moreover, you may have acid groups, such as a carboxy group, a phenol group, a sulfonamide group, a phosphonyl group, a sulfonyl group, a sulfonamide group, a sulfonylimide group, as a substituent.
m1 represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and most preferably 0.

The structural unit represented by the general formula (a1-2) is preferably a structural unit represented by the following general formula (a1-2-1).

In general formula (a1-2-1), a represents 0 or 1, R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, or an aryl group, and at least one of R ¹ and R ² is Represents an alkyl group or an aryl group, R ³ represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, and R ⁴ represents an alkyl group, An aryl group or an aralkyl group is represented, L ² represents a single bond or a divalent linking group, R ^x represents an alkyl group or a halogen atom, and m1 represents an integer of 0 to 4.

Specific examples of the silane compound that can be used for obtaining the structural unit (a1) include the following silane compounds.

<<< Structural Unit (a2) Having Crosslinkable Group >>>
The structural unit (a2) has a crosslinkable group. In the present invention, the crosslinkable group means a group capable of causing a crosslinking reaction by heat.
The crosslinkable group is not particularly limited as long as it is a group having a crosslinking reaction starting temperature of 100 ° C. or higher during heat treatment at 1 atm. The initiation temperature of the cross-linking reaction can be analyzed using a known method, for example, by a method using DSC measurement (Differential scanning calorimetry).
Examples of the crosslinkable group include a cyclic ether, a group having an ethylenically unsaturated bond, an alkoxymethyl group, a methylol group, and an amino group. The crosslinkable group may be bonded via a linking group or the like.
Examples of the cyclic ether include an epoxy group and an oxetanyl group.
Examples of the group having an ethylenically unsaturated bond include vinyl group, allyl group, methallyl group, methacryloyl group, acryloyl group, allyloxycarbonyl group, and methallyloxycarbonyl group.
Examples of the alkoxymethyl group include a group represented by “—CH ₂ OR”. R represents an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. The alkyl group may be linear, branched or cyclic, but is preferably linear.
The amino group may be an amino group having a substituent or an unsubstituted amino group.
The crosslinkable group is preferably a cyclic ether or a group having an ethylenically unsaturated bond, more preferably a cyclic ether, still more preferably an epoxy group or an oxetanyl group, and particularly preferably an epoxy group. Cyclic ethers can consume unreacted acid groups to form a strong cured film. For this reason, since unreacted acid groups can hardly remain in the cured film, a cured film excellent in heat resistance, solvent resistance, substrate adhesion, and the like can be formed.
Specific examples of the crosslinkable group include the following, but are not limited thereto. In the formula, * represents a connecting portion with another group.

The structural unit (a2) may have at least one crosslinkable group in one structural unit, preferably 1 to 3 and more preferably 1. When the structural unit (a2) has a plurality of crosslinkable groups, they may all be of the same type or different types. When a plurality of crosslinkable groups are included, the same kind is preferable.

Examples of the structural unit (a2) include structural units represented by the following general formula (a2 ′).

In general formula (a2 ′), a represents 0 or 1, R ⁵ represents an alkyl group, an aryl group or an aralkyl group, L ³ represents a single bond or a divalent linking group, and X represents Represents a crosslinkable group.

The structural unit (a2) is a structural unit represented by the following general formula (a2-1) and / or a structural unit represented by the following general formula (a2-2) from the viewpoint of cured film properties. Is preferred.

In general formulas (a2-1) and (a2-2), a represents 0 or 1, R ⁵ represents an alkyl group, an aryl group or an aralkyl group, R ^y represents an alkyl group or a halogen atom, L ³ represents a single bond or a divalent linking group, n represents 0 or 1, m 2 represents an integer of 0 to 2 when n is 0, and 0 when n is 1. Represents an integer from 3 to 3, and m3 represents an integer from 0 to 6.

R ⁵ represents an alkyl group, an aryl group, or an aralkyl group. The alkyl group, aryl group and aralkyl group are the same as the ranges described for R ⁴ in the above (a1-1) and (a1-2), and the preferred ranges are also the same.
L ³ represents a single bond or a divalent linking group. The divalent linking group is the same as the range described for L ^{1 of} (a1-1) and L ² of (a1-2), and the preferred range is also the same.
R ^y represents an alkyl group or a halogen atom. The alkyl group and the halogen atom are the same as the range described for R ^x in (a1-2) described above, and the preferred range is also the same.
n represents 0 or 1, and 0 is preferable.
m2 represents an integer of 0 to 2 when n is 0, and represents an integer of 0 to 3 when n is 1. m2 is preferably 0.
m3 represents an integer of 0 to 6, and 0 is preferable.

Specific examples of silanes that can be used to obtain the structural unit (a2) include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxy. Mention may be made of propyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. . Moreover, the silane compound shown below can also be used.

<<< Structural Unit (a3) Having Acid Group >>>
(A) The polysiloxane component may contain the structural unit (a3) having an acid group. The structural unit (a3) may contain a polysiloxane having at least one structural unit selected from the structural unit (a1) and the structural unit (a2). Moreover, the polysiloxane which does not contain a structural unit (a1) and a structural unit (a2) substantially may be contained.
Specific examples of the acid group include a carboxy group, a sulfonamide group, a phosphonyl group, a sulfonyl group, a phenolic hydroxyl group, a sulfonamide group, and a sulfonylimide group. Preferred acid groups include a carboxy group and a phenolic hydroxyl group. Can be mentioned.
As the structural unit (a3) having an acid group, for example, a structure represented by the following general formula (a3-1) and / or a structure represented by the general formula (a3-2) are preferable specific examples. Can be mentioned.

(In the general formulas (a3-1) and (a3-2), a represents 0 or 1, R ⁶ represents an alkyl group, an aryl group, or an aralkyl group, and L ⁴ represents a single bond or a divalent group. L ⁵ represents a single bond or a divalent linking group, R ^z represents an alkyl group or a halogen atom, and m4 represents an integer of 0 to 4.)

R ⁶ represents an alkyl group, an aryl group, or an aralkyl group. The alkyl group, aryl group and aralkyl group are the same as the ranges described for R ⁴ in the above (a1-1) and (a1-2), and the preferred ranges are also the same.
L ⁴ represents a single bond or a divalent linking group. The divalent linking group is the same as the range described for L ¹ in (a1-1), and the preferred range is also the same.
L ⁵ represents a single bond or a divalent linking group. The divalent linking group is the same as the range described for L ² in (a1-2), and the preferred range is also the same.
R ^z represents an alkyl group or a halogen atom. The alkyl group and the halogen atom are the same as the range described for R ^x in (a1-2) described above, and the preferred range is also the same.
m4 represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and most preferably 0.

The structural unit represented by the general formula (a3-2) is preferably a structural unit represented by the following general formula (a3-2-1).

In general formula (a3-2-1), a represents 0 or 1, R ⁶ represents an alkyl group, an aryl group, or an aralkyl group, and L ⁵ represents a single bond or a divalent linking group. , R ^z represents an alkyl group or a halogen atom, and m4 represents an integer of 0-4.

As the silane compound that can be used to obtain the structural unit (a3), the same silane compound that can be used to obtain the structural unit (a1) can be used.

<<< Structural Unit (a4) Other than (a1) to (a3) >>>
The polysiloxane component can contain a structural unit (a4) other than the structural units (a1) to (a3) described above.
As the structural unit (a4), for example, a structure represented by general formula (a4-1) shown below is preferred.

In general formula (a4-1), a represents an integer of 0 to 3, and b represents an integer of 0 to 3. However, 0 ≦ a + b ≦ 3. R ⁷ and R ⁸ each independently represents an alkyl group, an aryl group, or an aralkyl group.
The alkyl group, aryl group and aralkyl group represented by R ⁷ and R ⁸ are the same as the ranges described for R ⁴ in (a1-1) and (a1-2) described above, and the preferred ranges are also the same.

Examples of silane compounds that can be used to obtain the structural unit (a4) include alkoxysilane compounds and chlorosilane compounds. Specific examples include methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, and trifluoropropyltrimethoxysilane. Moreover, the silane compound shown below can also be used.

(A) The polysiloxane component is the total number of moles of the structural unit (a1) and the moles of the structural unit (a3) and the number of moles of the structural unit (a2) in the total amount of polysiloxane contained in the photosensitive resin composition. The ratio is preferably 10:90 to 90:10, more preferably 30:70 to 70:30, and still more preferably 40:60 to 60:40. If the ratio between the total number of moles of the structural unit (a1) and the moles of the structural unit (a3) and the mole number of the structural unit (a2) is in the above range, a cured film having excellent solvent resistance can be formed.

(A) The polysiloxane contained in the polysiloxane component may contain silanol groups remaining during polymerization of the polysiloxane. The number of silanol groups in the total amount of polysiloxane is preferably 0 to 0.5 times, more preferably 0 to 0.2 times, and most preferably 0 to 0.05 times the number of Si atoms in the polysiloxane. When the number of silanol groups is in the above range, the storage stability of the photosensitive resin composition is good. The number of silanol groups in the total amount of polysiloxane here means the total number of silanol groups of the polysiloxane contained in the polysiloxane component. The same applies to the number of Si atoms.

The polysiloxane can be obtained by mixing and reacting a silane compound corresponding to each structural unit or oligosiloxane. For example, it can be obtained by hydrolysis and condensation of the corresponding trimethoxysilane or dimethoxysilane. Hydrolysis and condensation can be appropriately performed by known methods and conditions. For example, Japanese Patent Application Laid-Open No. 10-324748 (especially 0085 paragraph to 0087 paragraph), Japanese Patent Application Laid-Open No. 2005-283939 (particularly 0052 paragraph to 054 paragraph), Japanese Patent Application Laid-Open No. 2006-276598 (particularly 0009 paragraph to 0030 paragraph), etc. The procedures and conditions described in can be referred to.
The acid-decomposable group of the structural unit (a1) described above may be introduced using a protected silane compound or may be introduced by a polymer reaction.
As described in JP-A-10-324748 (particularly paragraphs 0085 to 0087), when a structural unit containing a carboxy group is introduced into (A) polysiloxane, the corresponding alkyl ester of carboxylic acid is used. It is preferable to synthesize a polysiloxane using a silane having an alkyl group and hydrolyze the alkyl ester by a general method to obtain a structural unit having a carboxy group.
In order to introduce a structural unit having a carboxy group protected with an acid-decomposable group into polysiloxane, after synthesizing a polysiloxane having a structure having a carboxy group, an acid-decomposable group is formed by a so-called polymer reaction. It is preferable to introduce carboxy to protect the carboxy group.
In order to introduce a structural unit having a group in which a phenolic hydroxyl group is protected with an acid-decomposable group into polysiloxane, after synthesizing a polysiloxane having a phenolic hydroxyl group, a so-called polymer reaction is performed to produce an acid-decomposable group. It is preferable to protect the phenolic hydroxyl group by introducing.

Hereinafter, preferred embodiments of the (A) polysiloxane component will be described, but the present invention is not limited thereto.
(First embodiment)
In the aspect (1) described above, the polysiloxane (A1) having the structural unit (a1) and the structural unit (a2) further has the structural unit (a3) and / or the structural unit (a4).
(Second Embodiment)
In the aspect (2) described above, the polysiloxane (A2) having the structural unit (a1) further has the structural unit (a3) and / or the structural unit (a4).
(Third embodiment)
In the aspect (2) described above, the polysiloxane (A3) having the structural unit (a2) further has the structural unit (a3) and / or the structural unit (a4).
(Fourth embodiment)
The aspect including at least the structural unit (a3) in any one of the first to third embodiments.
(Fifth embodiment)
In the aspect of (1) and / or (2) described above, a poly having a structural unit (a3) and / or a structural unit (a4) substantially not including the structural unit (a1) and the structural unit (a2). Embodiment with siloxane.
(Sixth embodiment)
A form comprising a combination of two or more of the first to fifth embodiments.

In the embodiment having the polysiloxane having the structural unit (a3) and / or the structural unit (a4) substantially free of the structural unit (a1) and the structural unit (a2), the structural unit (a1) and / or The total amount of the polysiloxane having the structural unit (a2) and the polysiloxane having the structural unit (a3) and / or the structural unit (a4) substantially not including the structural unit (a1) and the structural unit (a2) The mass ratio with respect to the total amount is preferably 99: 1 to 5:95, more preferably 97: 3 to 30:70, and still more preferably 95: 5 to 50:50.
The total content of the polysiloxane having the structural unit (a1) and / or the structural unit (a2) is preferably 60% by mass or more, preferably 70% by mass or more, and 90% by mass with respect to the total content of the polysiloxane. % Or more is most preferable.
The content of the (A) polysiloxane component in the photosensitive resin composition of the present invention is preferably 60 to 99% by mass with respect to the total solid content of the photosensitive resin composition. The upper limit is more preferably 98% by mass or less, for example. The lower limit is more preferably 65% by mass or more, and still more preferably 70% by mass or more.

<< (B) Photoacid Generator (B Component) >>
The photosensitive resin composition of the present invention contains a photoacid generator that generates an acid having a pKa of 3 or less. The photoacid generator is preferably one that generates an acid having a pKa of 2 or less. In the present invention, pKa basically refers to pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured after changing to a solvent suitable for measurement. Specifically, the pKa described in the chemical handbook can be referred to. The acid having a pKa of 3 or less is preferably sulfonic acid or phosphonic acid, and more preferably sulfonic acid.

The photoacid generator is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is not limited to its chemical structure. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.

Examples of the photoacid generator include onium salt compounds, trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds, and imide sulfonate compounds. Among these, from a sensitivity and developability viewpoint, 1 or more types chosen from an onium salt compound, an oxime sulfonate compound, and an imide sulfonate compound are preferable, and 1 or more types chosen from an oxime sulfonate compound and an imide sulfonate compound are more. preferable. A photo-acid generator can be used individually by 1 type or in combination of 2 or more types.

Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraph numbers 0083 to 0088 of JP2011-212494A. It can be illustrated.

Examples of the onium salt compounds include diphenyliodonium salts, triarylsulfonium salts, sulfonium salts, benzothiazonium salts, tetrahydrothiophenium salts, and the like. Compounds represented by the following general formula (1) and / or general formula (2) are preferred.

(In the formula, R ⁵ , R ⁶ and R ⁷ each independently represents an alkyl group or an aryl group, and in the case of representing an alkyl group, they may be linked together to form a ring, R ⁸ and R ⁹ each independently represents an aryl group, and X ⁻ represents a conjugate base.)

R ⁵ , R ⁶ and R ⁷ each independently represents an alkyl group or an aryl group, and the alkyl group or aryl group may have a substituent. Examples of the substituent include an aryl group having 1 to 10 carbon atoms, a thioaryl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a thioalkoxy group having 1 to 10 carbon atoms. , Hydroxyl group, cyano group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) and the like. These substituents may further have a substituent.
In general formula (1), the alkyl groups represented by R ⁵ , R ⁶ and R ⁷ are each preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and 1 to More preferred is an alkyl group of 4. Examples of the alkyl group include a methyl group, an ethyl group, and a t-butyl group. In the general formula (1), when two or more of R ⁵ , R ⁶ and R ⁷ are alkyl groups, the two or more alkyl groups may be linked to each other to form a ring, and a hetero atom A ring may be formed via (for example, an oxygen atom, a sulfur atom, etc.). Such a ring form is preferably a 5-membered ring (thiacyclopentane) or a 6-membered ring (thiacyclohexane) containing a sulfur atom. The alkyl group may have a substituent.
In the general formula (1), the aryl group represented by R ⁵ , R ⁶ and R ⁷ is preferably an aryl group having 6 to 15 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. The aryl group may have a substituent. Aryl groups include phenyl, naphthyl, 4-methoxyphenyl, 4-chlorophenyl, 4-methylphenyl, 4-tertiarybutylphenyl, 4-phenylthiophenyl, 2,4,6-trimethyl. Examples thereof include a phenyl group and a 4-methoxy-1-naphthyl group. Of these, a phenyl group, a 4-methoxyphenyl group, and a 4-chlorophenyl group are preferable.
R ⁵ , R ⁶ and R ⁷ are preferably aryl groups, and preferably represent the same group.

In the general formula (1), X ⁻ represents a conjugate base. The conjugate base represents a conjugate base of an alkyl sulfonic acid, a conjugate base of an aryl sulfonic acid, or a conjugate base of a bisperfluorosulfonylamide, and a conjugate base of an alkyl sulfonic acid or an aryl sulfonic acid is particularly preferable. As such a conjugate base, a conjugate base of an alkyl sulfonic acid having 1 to 7 carbon atoms is preferable, and a conjugate base having 1 to 4 carbon atoms is more preferable. When expressed in the form of an acid, for example, methanesulfonic acid, trifluoromethane Particularly preferred are sulfonic acid, n-propanesulfonic acid and heptanesulfonic acid. As the conjugate base of the aryl sulfonic acid, for example, benzene sulfonic acid, chlorobenzene sulfonic acid, and paratoluene sulfonic acid are particularly preferable when expressed in an acid form.

In general formula (2), the aryl groups independently represented by R ⁸ and R ⁹ are the same as the aryl groups represented by R ⁵ , R ⁶ and R ⁷ in general formula (1), and the preferred ranges are also the same. is there.
Specifically, R ⁸ and R ⁹ are particularly preferably a phenyl group, a 4-methoxyphenyl group, and a 4-chlorophenyl group. R ⁸ and R ⁹ preferably represent the same group.
In general formula (1), the conjugate base represented by X ⁻ has the same meaning as X ⁻ in general formula (1), and the preferred range is also the same.

Specific examples of the onium salt compound include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate. Moreover, the following compounds and the compounds described in JP-A-2011-232648, paragraphs 0083 to 0085 can be exemplified.

Preferred examples of the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B1).

(In the general formula (B1), R ²¹ represents an alkyl group or an aryl group. A wavy line represents a bond with another group.)

Any group of the alkyl group and aryl group in R ²¹ may be substituted. The alkyl group in R ²¹ may be linear, branched or cyclic.
The alkyl group for R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ²¹ may be substituted with a halogen atom, an aryl group having 6 to 11 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
The aryl group for R ²¹ is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group of R ²¹ may be substituted with an alkyl group, an alkoxy group, or a halogen atom.

As an example of a preferred form of the oxime sulfonate compound, description of paragraph numbers 0108 to 0141 of JP2013-190507A is exemplified, and the contents thereof are incorporated in the present specification.

A preferred embodiment of the compound containing the oxime sulfonate structure represented by the general formula (B1) is an oxime sulfonate compound represented by the following general formula (B1-1).

General formula (B1-1)

(In Formula (B1-1), R ⁴² represents an optionally substituted alkyl group or aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, and m4 represents 0-3. Represents an integer, and when m4 is 2 or 3, a plurality of Xs may be the same or different.

Preferred ranges of R ^42, the same as the preferable range of the ^{R 21.}
The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X is preferably a chlorine atom or a fluorine atom.
m4 is preferably 0 or 1. In the above general formula (B1-1), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R ⁴² is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound which is a 7-dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.

Specific examples of the oxime sulfonate compound represented by the general formula (B1-1) include the following compounds.

Another preferred embodiment of the compound containing an oxime sulfonate structure represented by the above general formula (B1) is an oxime sulfonate compound represented by the following general formula (B1-2).

General formula (B1-2)

(In the formula (B1-2), R ⁴³ has the same meaning as R ⁴² in the formula (B1-1), and X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents an alkoxy group, a cyano group or a nitro group, and n4 represents an integer of 0 to 5.)

R ⁴³ in the above general formula (B1-2) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n- A propyl group, a perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.
X ¹ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
n4 is preferably from 0 to 2, particularly preferably from 0 to 1.

Specific examples of the compound represented by the general formula (B1-2) and specific examples of preferred oxime sulfonate compounds include the following compounds. In addition to the compounds exemplified below, paragraphs 0080 to 0082 of JP2012-163937A can be referred to, and the contents thereof are incorporated in the present specification.

Another preferred embodiment of the compound containing an oxime sulfonate structure represented by the above general formula (B1) is a compound represented by the following general formula (OS-1).

In the general formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group. R ¹⁰² represents an alkyl group or an aryl group.
X ¹⁰¹ represents —O—, —S—, —NH—, —NR ¹⁰⁵ —, —CH ² —, —CR ¹⁰⁶ H—, or —CR ¹⁰⁵ R ¹⁰⁷ —, wherein R ¹⁰⁵ to R ¹⁰⁷ are alkyl groups. Or an aryl group.
R ¹²¹ to R ¹²⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring.
R ¹²¹ to R ¹²⁴ are preferably a hydrogen atom, a halogen atom, and an alkyl group, and an embodiment in which at least two of R ¹²¹ to R ¹²⁴ are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which all of R ¹²¹ to R ¹²⁴ are hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the functional groups described above may further have a substituent.

Specific examples of the compound represented by the general formula (OS-1) include compounds described in paragraph numbers 0128 to 0132 of JP2011-212494A (exemplary compounds b-1 to b-34). However, the present invention is not limited to this.

As another preferred embodiment of the compound containing the oxime sulfonate structure represented by the general formula (B1), the following general formula (OS-3), the following general formula (OS-4) or the following general formula (OS-5) It is an oxime sulfonate compound represented by these.

In the general formulas (OS-3) to (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represents an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ are Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X ¹ to X ³ each independently represents an oxygen atom or a sulfur atom, n ¹ to n ³ each independently represents 1 or 2, and m ¹ to m ³ each independently represents an integer of 0 to 6 To express. )

Regarding the general formulas (OS-3) to (OS-5), for example, the description of paragraph numbers 0098 to 0115 of JP2012-163937A can be referred to, and the contents thereof are incorporated in the present specification. Examples of the compound represented by the general formula (OS-3) include the following.

In addition, the compound having an oxime sulfonate structure represented by the general formula (B1) is, for example, the general formulas (OS-6) to (OS-) described in paragraph No. 0117 of JP2012-163937A. It is particularly preferable that the compound is represented by any one of 11), the contents of which are incorporated herein.
Preferred ranges in the general formulas (OS-6) to (OS-11) are the preferred ranges of (OS-6) to (OS-11) described in paragraph numbers 0110 to 0112 of JP2011-221494A. It is the same.

Specific examples of the oxime sulfonate compounds represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. The present invention is not limited to these.

Another preferred embodiment of the compound containing an oxime sulfonate structure represented by the general formula (B1) is an oxime sulfonate compound represented by the following general formula (B1-3).

General formula (B1-3)

In General Formula (B1-3), R ¹ represents an alkyl group or an aryl group, and R ² represents an alkyl group, an aryl group, or a heteroaryl group. R ³ to R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. However, R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may be bonded to form an alicyclic ring or an aromatic ring. X represents —O— or —S—.

R ¹ represents an alkyl group or an aryl group. Examples of the alkyl group include linear, branched, and cyclic groups, and branched or cyclic groups are preferable.
The alkyl group preferably has 3 to 10 carbon atoms. In the case of a branched alkyl group, the number of carbon atoms is preferably 3-6. In the case of a cyclic alkyl group, the number of carbon atoms is preferably 5 to 7.
Specific examples of the alkyl group include, for example, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group. Hexyl group, 2-ethylhexyl group, cyclohexyl group, octyl group and the like, preferably isopropyl group, tert-butyl group, neopentyl group, and cyclohexyl group.
The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and still more preferably 6 to 7 carbon atoms. Specific examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
The alkyl group and aryl group represented by R ¹ may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chloro atom, bromine atom, iodine atom), linear, branched or cyclic alkyl group (eg, methyl group, ethyl group, propyl group), alkenyl group, alkynyl group. , Aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxy group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group , A nitro group, a hydrazino group, a heterocyclic group, and the like. Further, these groups may be further substituted. Preferably, they are a halogen atom and a methyl group.

In the photosensitive resin composition of the present invention, R ¹ is preferably an alkyl group from the viewpoint of transparency, and R ¹ is a branched alkyl group having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity. Group, a cyclic alkyl group having 5 to 7 carbon atoms, or a phenyl group is preferable, and a branched alkyl group having 3 to 6 carbon atoms or a cyclic alkyl group having 5 to 7 carbon atoms is more preferable. By adopting such a bulky group (particularly a bulky alkyl group) as R ¹ , the transparency can be further improved.
Among the bulky substituents, an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.

R ² represents an alkyl group, an aryl group, or a heteroaryl group. The alkyl group represented by R ² is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group, and preferably a methyl group It is.
As the aryl group, an aryl group having 6 to 10 carbon atoms is preferable. Examples of the aryl group include a phenyl group, a naphthyl group, and a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable.
Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
The alkyl group, aryl group, and heteroaryl group represented by R ² may have a substituent. Examples of the substituent include an alkyl group and an aryl group R ¹ represents is same as the substituents which may be possessed.
R ² is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group. As the substituent for the phenyl group, a methyl group is preferred.

R ³ to R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom). The alkyl group represented by R ³ to R ⁶ has the same meaning as the alkyl group represented by R ² , and the preferred range is also the same. The aryl group represented by R ³ to R ⁶ has the same meaning as the aryl group represented by R ¹ , and the preferred range is also the same.
Among R ³ to R ⁶ , R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may combine to form a ring, and the ring forms an alicyclic ring or an aromatic ring. It is preferable that a benzene ring is more preferable.
R ³ to R ⁶ are a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chloro atom, bromine atom), or R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ It preferably constitutes a benzene ring, and a hydrogen atom, a methyl group, a fluorine atom, a chloro atom, a bromine atom, or R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ are bonded to form a benzene ring Is more preferable.
Preferred embodiments of R ³ to R ⁶ are as follows.
(Aspect 1) At least two are hydrogen atoms.
(Aspect 2) The number of alkyl groups, aryl groups, or halogen atoms is one or less.
(Aspect 3) R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ are combined to form a benzene ring.
(Aspect 4) An aspect satisfying the

above aspects

1 and 2 and / or an aspect satisfying the

above aspects

1 and 3.

Specific examples of the general formula (B1-3) include the following compounds, but the present invention is not particularly limited thereto. In the exemplified compounds, Ts represents a tosyl group (p-toluenesulfonyl group), Me represents a methyl group, Bu represents an n-butyl group, and Ph represents a phenyl group.

As the imide sulfonate compound, an imide sulfonate compound having a structure represented by the following general formula (B2) can be preferably used.

(In the general formula (B2), R ²⁰⁰ represents a monovalent organic group having 16 or less carbon atoms. The wavy line represents a bond with another group.)

R ²⁰⁰ represents a monovalent organic group having 16 or less carbon atoms. R ²⁰⁰ preferably does not contain other than C, H, O, and F. Examples of R ²⁰⁰ include a methyl group, a trifluoromethyl group, a propyl group, a phenyl group, and a tosyl group.
A preferred embodiment of the compound containing the structure represented by the general formula (B2) is an imide sulfonate compound represented by the following general formula (I).

In the formula, R ¹ and R ² each represent a group represented by the following general formula (A) or a hydrogen atom. R ³ represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with any one or more of a halogen atom, an alkylthio group and an alicyclic hydrocarbon group, a halogen atom, an alkylthio group, an alkyl group and an acyl An aryl group having 6 to 20 carbon atoms which may be substituted with any one or more of the groups, an arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom and / or an alkylthio group, 10-camphoryl group Or represents the group represented by the following general formula (B).

In general formula (A), X ¹ represents an oxygen atom or a sulfur atom, Y ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrocarbon group having 1 to 12 carbon atoms. R ⁵ represents an alkylene group having 1 to 4 carbon atoms, R ⁶ represents a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms, or an alicyclic carbon atom having 3 to 10 carbon atoms. Represents a hydrogen group, a heterocyclic group, or a hydroxyl group. n represents an integer of 0 to 5. When n is 2 to 5, a plurality of R ⁵ may be the same or different.

In the formula, X ¹ represents an oxygen atom or a sulfur atom, Y ¹ represents a single bond or an alkanediyl group having 1 to 4 carbon atoms, R ¹¹ represents a hydrocarbon group having 1 to 12 carbon atoms, R ¹² represents an alkanediyl group having 1 to 4 carbon atoms, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a branch or an alicyclic hydrocarbon having 3 to 10 carbon atoms. Represents a group or a heterocyclic group, m represents 0 to 5, and when m is 2 to 5, a plurality of R ¹² may be the same or different.

In general formula (B), Y ² represents a single bond or an alkylene group having 1 to 4 carbon atoms, R ⁷ represents an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, carbon Represents an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms, and R ⁸ represents a single bond, an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, carbon Represents an arylene group having 6 to 20 carbon atoms or a halogenated arylene group having 6 to 20 carbon atoms, and R ⁹ represents an alkyl group having 1 to 18 carbon atoms which may be branched, or 1 to 1 carbon atoms which may be branched. 18 halogenated alkyl groups, aryl groups having 6 to 20 carbon atoms, halogenated aryl groups having 6 to 20 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, or halogenated arylalkyl groups having 7 to 20 carbon atoms. To express. a and b each independently represents 0 or 1, and at least one of a and b is 1.

Regarding the general formula (I), for example, the description of paragraph numbers 0019 to 0063 of International Publication No. WO11 / 087011 can be referred to, and the contents thereof are incorporated in the present specification. Examples of the compound represented by the general formula (I) include the following. In addition to the compounds exemplified below, the description of paragraphs 0065 to 0075 of International Publication No. WO11 / 087011 and the description of paragraph 0084 of Japanese Patent No. 5510347 can be taken into account, the contents of which are incorporated herein. .

The content of the (B) photoacid generator in the photosensitive resin composition of the present invention is preferably 0.1 to 10% by mass, and preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive resin composition. Is more preferable, and 1 to 5% by mass is even more preferable.
The (B) photoacid generator is preferably contained in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the (A) polysiloxane component. Part by mass is more preferable.
(B) Only 1 type may be sufficient as a photo-acid generator, and it can also use 2 or more types together. When using 2 or more types together, it is preferable that the total amount becomes the said range.

<< (C) Solvent (Component C) >>
The photosensitive resin composition of the present invention contains a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in a solvent. As the solvent, a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
In the present invention, a known solvent can be used as the solvent. For example, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol Examples thereof include monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones. Further, the solvent described in paragraph Nos. 0174 to 0178 of JP2011-221494A and the solvent described in paragraph numbers 0167 to 0168 of JP2012-194290A are also included, and the contents thereof are incorporated in the present specification. . For example, specific examples of the solvent include propylene glycol 1-monomethyl ether 2-acetate, methyl ethyl diglycol and the like.

In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added. These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. And diethylene glycol dialkyl ethers or esters and butylene glycol alkyl ether acetates are more preferably used in combination.

The solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.

The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass with respect to 100 parts by mass of all components in the photosensitive resin composition. 55 mass% or more is more preferable, and 60 mass parts or more is further more preferable. The upper limit is more preferably 90 parts by mass or less. Only one type of solvent may be used, or two or more types may be used. When using 2 or more types, it is preferable that the total amount becomes the said range.

<< (S) Blocked isocyanate compound (S component) >>
The photosensitive resin composition of the present invention contains a blocked isocyanate. By containing the blocked isocyanate compound, it is considered that water generated during polycondensation of polysiloxane can be captured, and the water content in the film can be reduced, thereby suppressing discoloration of the metal.
The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule. The upper limit of the number of blocked isocyanate groups is preferably 6 or less.
In addition, in this invention, a blocked isocyanate compound points out the compound different from the polysiloxane demonstrated by the (A) polysiloxane component mentioned above.
The “block isocyanate group” in the present invention means a group capable of generating an isocyanate group by heat, and a group obtained by reacting a blocking agent with an isocyanate group to protect the isocyanate group can be preferably exemplified. The blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 to 250 ° C., for example.

In the present invention, the molecular weight of the blocked isocyanate compound is preferably 100 to 2000. The lower limit is more preferably 150 or more, and even more preferably 200 or more. The upper limit is more preferably 1000 or less, and still more preferably below. When the molecular weight of the blocked isocyanate compound is in the above range, the discoloration of the metal can be effectively suppressed.
In the present invention, the molecular weight of the blocked isocyanate compound is a theoretical value calculated from the structural formula, and when the molecular weight cannot be calculated from the structural formula, it is a weight average molecular weight based on polystyrene conversion by GPC measurement.

The isocyanate compound serving as the skeleton of the blocked isocyanate compound is not particularly limited, and any compound may be used as long as it has two isocyanate groups in one molecule. Any of aliphatic, alicyclic or aromatic polyisocyanate compounds may be used. Specific examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'- Diethyl ether diisocyanate, diphenylmethane-4,4′-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexane Isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methylene ditolylene-4,4'- Isocyanate compounds such as diisocyanate, 4,4′-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate, and multimers thereof, and Prepolymer type skeleton compounds derived from these compounds can be preferably used.
Among these, blocked isocyanate compounds in which the isocyanate group of at least one compound selected from tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate, and a multimer of these isocyanate compounds is protected. Is more preferable.
The isocyanate compound multimer is not particularly limited as long as it is a dimer or higher multimer (preferably a dimer or trimer), and examples thereof include a biuret structure, an adduct structure, and an isocyanurate structure. A biuret structure is preferred.

The biuret structure is a structure represented by the following formula (bi), preferably a structure represented by the following formula (bi-1), and a structure represented by the following formula (bi-2). It is more preferable. In the following formula, the wavy line portion is a portion connected to another structure.

In formula (bi-1) and formula (bi-2), R ¹ , R ² and R ³ each independently represent a group other than an isocyanate group of the isocyanate compound, and R ⁴ and R ⁵ each independently Represents a hydrogen atom, an alkyl group or an aryl group.

The method for forming the biuret structure is not particularly limited and may be formed by a known method. For example, the biuret structure can be easily formed by trimerization of an isocyanate compound.

The adduct structure refers to an adduct of a polyhydric alcohol and an isocyanate compound.
As an isocyanate compound used for formation of an adduct structure, the isocyanate compound mentioned above is mentioned, A diisocyanate compound is preferable. The molecular weight of the diisocyanate compound is preferably 100 to 1000.
As the polyhydric alcohol used for forming the adduct structure, the lower limit of the valence is preferably 3 or more, and the upper limit of the valence is preferably 6 or less. As the molecular weight, those having a molecular weight of 50 to 700 are preferred, and those having a molecular weight of 50 to 500 are more preferred. Moreover, it is preferable that it is an aliphatic polyhydric alcohol, and it is preferable that it is an aliphatic polyhydric alcohol which does not have a cyclic structure. The polyhydric alcohol used in the present invention is preferably a group in which three or more OH groups are bonded to a branched aliphatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 4 to 20 carbon atoms. The number of OH groups is preferably 3-6.
Specifically, glycerol, trimethylolethane, trimethylolpropane (TMP), trimethyloloctane, 1,2,6-hexanetriol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,1,1-tris Trivalent alcohols such as (bishydroxymethyl) propane and 2,2-bis (hydroxymethyl) butanol; tetrahydric alcohols such as pentaerythritol and diglycerol; pentavalent alcohols such as arabit, ribitol and xylitol (pentit); Examples thereof include hexavalent alcohols (hexit) such as mannit, galactitol, and allozulcit. Of these, trimethylolpropane and pentaerythritol are particularly preferable.
Examples of commercially available isocyanate compounds having an adduct structure include Takenate D-140N and D-212L (manufactured by Mitsui Chemicals, Inc.).

The blocked isocyanate compound having an adduct structure is preferably a compound represented by the following general formula (ad).
Ra- {O (C = O) -NH-Rb-NCO-B} _n (ad)
In general formula (ad), Ra is an n-valent hydrocarbon group, Rb is a divalent hydrocarbon group, and B represents a group that blocks isocyanate. n is an integer of 3-6. n Rb and B may be the same or different.
Ra is a hydrocarbon group, preferably an aliphatic hydrocarbon group, and preferably a branched aliphatic hydrocarbon group. The carbon number of Ra is preferably 3 to 30, more preferably 4 to 20, and still more preferably 4 to 15.
Rb is a hydrocarbon group, and may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Further, it may be a linear, branched or cyclic hydrocarbon group. Rb preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and still more preferably 2 to 15 carbon atoms.
B is more preferably a group derived from a blocking agent described later, and more preferably a group derived from an oxime compound.
n is an integer of 3 to 6, and 3 or 4 is more preferable.

The isocyanurate structure is a structure represented by the following formula (cy). In the following formula, the wavy line portion is a portion connected to another structure.

In formula (cy), R ¹ , R ² and R ³ each independently represent a group other than the isocyanate group of the isocyanate compound.

Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, and an imide compound. Can do. Among these, oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, or pyrazole compounds are preferable, oxime compounds and lactam compounds are more preferable, oxime compounds are more preferable, and methyl ethyl ketone oxime is more preferable. Particularly preferred.
Examples of the oxime compound include oxime and ketoxime. Specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, and benzophenone oxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.

The blocked isocyanate compound is available as a commercial product. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (above, manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate B -830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (manufactured by Mitsui Chemicals, Inc.), Duranate 17B-60P, 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above, manufactured by Asahi Kasei Chemicals Corporation) ), Death Module BL1100, BL12 5 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumijour BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.) and the like are preferably used. Can do.

The content of the (S) blocked isocyanate compound in the photosensitive resin composition of the present invention is preferably 0.1 to 15% by mass with respect to the total solid content of the photosensitive resin composition. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 10% by mass or less, and still more preferably 5% by mass or less.
The (S) blocked isocyanate compound is preferably contained in an amount of 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the (A) polysiloxane component. Part is more preferred.
(S) A block isocyanate compound may be only 1 type and can also use 2 or more types together. When using 2 or more types together, it is preferable that a total amount is the said range.

<< Sensitizer >>
The photosensitive resin composition of the present invention can contain a sensitizer in order to promote the decomposition of the photoacid generator in combination with the photoacid generator. The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. Examples of preferable sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges of 350 to 450 nm.

Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine oleoresin) Di, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squaliums (eg, squalium), styryls, base styryls ( For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7 -Tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-non).
Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.

The content of the sensitizer is preferably 0 to 1000 parts by weight, more preferably 10 to 500 parts by weight, and more preferably 50 to 200 parts by weight with respect to 100 parts by weight of the photoacid generator. Further preferred. Only one type of sensitizer may be used, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount is the said range.

<< Crosslinking agent >>
The photosensitive resin composition of this invention can contain crosslinking agents other than the block isocyanate compound mentioned above as needed. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
The crosslinking agent is a compound containing at least two crosslinking groups in the molecule. The cross-linking group means a group that reacts with one or more kinds selected from a cross-linkable group, a benzene ring, a hydroxy group, and a carboxy group of polysiloxane by heat. As the crosslinking group, a methylol group, an epoxy group, an oxetanyl group, an alkoxymethyl group, a methacryloyl group and an acryloyl group are preferable, and a methylol group, an epoxy group, an alkoxymethyl group, a methacryloyl group and an acryloyl group are more preferable.
The number of crosslinking groups in one molecule of the crosslinking agent is preferably 3 or more, and more preferably 4 or more.
The cross-linking group may have two or more of the same type of cross-linking group in the molecule, or may have two or more different types of cross-linking groups in the molecule.
The molecular weight of the crosslinking agent is preferably from 150 to 30,000, more preferably from 200 to 10,000. By setting it as such a range, the effect of this invention is exhibited more effectively.

When the photosensitive resin composition of the present invention contains a crosslinking agent, the content of the crosslinking agent is 0.01 to 50 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. Preferably, the amount is 0.1 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass. If it is the said range, the cured film excellent in mechanical strength and solvent tolerance will be obtained. Only one type of crosslinking agent may be used, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount is the said range.
Moreover, the photosensitive resin composition of this invention can also be set as the structure which does not contain a crosslinking agent substantially. The configuration that is not practically used means that the crosslinking agent is, for example, 1% by mass or less of the solid content of the photosensitive resin composition.

<<< Compound having two or more epoxy groups in the molecule >>>
In the present invention, a compound having two or more epoxy groups in the molecule can be used as the crosslinking agent. Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and epoxy group containing An acrylic resin having a structural unit can be given.
These are available as commercial products. For example, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.) and the like are commercially available products described in paragraph No. 0189 of JP2011-212494, etc. EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX- 321L, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, X-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (manufactured by Nagase Chemtech), YH-300 YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by Nippon Steel Chemical Co., Ltd.), Celoxide 2021P, Celoxide 2081, EHPE3150, EHPE3150CE (above, Daicel Corporation), and the like. These can be used alone or in combination of two or more.
Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.

<<< Crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule >>>
In the present invention, a crosslinking agent containing an alkoxymethyl group or a methylol group can be used as the crosslinking agent. The crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule is a crosslinking agent having two or more structures represented by the following general formula (1) or general formula (2) in the molecule. , One or both of an alkoxymethyl group and a methylol group are contained in the molecule in a total of two or more.
—CH ₂ OR ¹ (1)
(Wherein R ¹ represents an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.)
—CH ₂ OH (2)

The alkoxymethyl group or methylol group is preferably bonded to a nitrogen atom or a carbon atom forming an aromatic ring.

Examples of the crosslinking agent in which an alkoxymethyl group or a methylol group is bonded to a nitrogen atom include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril, alkoxy Methylated urea and methylolated urea are preferred. Alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, and alkoxymethylated urea convert methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylol group of methylolated urea to alkoxymethyl group, respectively. Can be obtained. Examples of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group, and the methoxymethyl group is particularly preferable from the viewpoint of outgas generation amount.
Of these compounds, alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril are preferred, and from the viewpoint of transparency, alkoxymethylated glycoluril and methylol Glycoluril is particularly preferred.
In addition, an alkoxymethyl group-containing crosslinking agent described in paragraph No. 0107 of JP2012-8223A can be used, and the contents thereof are incorporated herein.

Preferred structures of the crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule include compounds represented by the following formulas (8-1) to (8-4).

In the above formulas (8-1) to (8-4), R ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁸ to R ¹¹ each independently represents a hydrogen atom, A hydroxyl group, an alkyl group or an alkoxyl group is represented, and X ² represents a single bond, a methylene group or an oxygen atom.

The alkyl group represented by R ⁷ has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
The alkyl group represented by R ⁸ to R ¹¹ preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
The alkoxyl group represented by R ⁸ to R ¹¹ preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a propoxy group. X ² is preferably a single bond or a methylene group.
R ⁷ to R ¹¹ and X ² may be substituted with an alkyl group such as a methyl group or an ethyl group, or a halogen atom. The plurality of R ⁷ and R ⁸ to R ¹¹ may be the same or different.

Crosslinkers containing two or more alkoxymethyl groups or methylol groups in the molecule are also available as commercial products, for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalac MX-750, -032, -706, -708, -40,- 31, -270, -280, -290, -750LM, Nicarak MS-11, Nicarak MW-30HM, -100LM, -390, (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used. These can be used alone or in combination of two or more.

<<< Compound containing two or more methacryloyl groups or acryloyl groups in the molecule >>>
In the present invention, a compound containing a methacryloyl group or an acryloyl group may be used as a crosslinking agent. The compound containing a methacryloyl group or an acryloyl group is a compound selected from the group consisting of acrylic acid esters and methacrylic acid esters. It is preferable that the acryloyl group and the methacryloyl group are compounds having two or more, more preferably trifunctional or more in one molecule.

Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate.
Examples of the tri- or more functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
Preferable commercially available products are KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., NK ester series manufactured by Shin-Nakamura Chemical Co., Ltd., bifunctional A-200, A-400, A-600, A-1000, ABE-300, A- BPE-4, A-BPE-10, A-BPE-20, A-BPE-30, A-BPP-3, A-DOD, A-DCP, A-IBD-2E, A-NPG, 701A, A- B1206PE, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, APG-700, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, BD, HD- N, NOD, IND, BPE-100, BPE-200, BPE-300, BPE-500, BPE-900, BPE-1300N, NPG, DCP, 1206PE, 701, 3 G, 9PG, trifunctional A-9300, AT-30E, A-TMPT-3EO, A-TMPT-9EO, A-TMPT-3PO, A-TMM-3, A-TMM-3L, A-TMM-3LM -N, TMPT, TMPT-9EO, tetra- or higher functional ATM-35E, ATM-4E, AD-TMP, AD-TMP-L, ATM-4P, A-TMMT, A-DPH and the like can be mentioned.

<<< Compound containing two or more oxetanyl groups in the molecule >>>
In the present invention, a compound containing an oxetanyl group may be used as a crosslinking agent. It is preferable that there are two or more oxetanyl groups in the molecule. Examples of the compound having two or more oxetanyl groups in the molecule include the compounds described in paragraphs 0134 to 0145 of JP-A-2008-224970, the contents of which are incorporated herein. As specific examples, Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX (above, manufactured by Toagosei Co., Ltd.) can be used.

<< basic compound >>
The photosensitive resin composition of the present invention can contain a basic compound. The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in JP-A 2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
Specifically, as the aliphatic amine, for example, trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tributylamine, di-n-pentylamine, tri-n-pentylamine, Examples include diethanolamine, triethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0 ] -5-Nonene, 1,8-di And azabicyclo [5.3.0] -7-undecene.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.

The content of the basic compound is preferably 0.001 to 3 parts by mass and more preferably 0.005 to 1 part by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. preferable. A basic compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount is the said range.

<< Surfactant >>
The photosensitive resin composition of the present invention can contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant. Examples of the surfactant used in the composition of the present invention include those described in paragraph Nos. 0201 to 0205 in JP2012-88459A, and paragraphs 0185 to 0188 in JP2011-215580A. Can be used and these descriptions are incorporated herein.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . The following trade names are FA-630, KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), Ftop (manufactured by Mitsubishi Materials Kasei), MegaFuck F-430, F-444, F-477, F-553, F-554, F-556, F-557, F-559, F-562, F-565, F-567, F-569, R-40 (manufactured by DIC Corporation), Florard Novec FC-4430 (manufactured by Sumitomo 3M Corporation), Surflon S- 242 (manufactured by AGC Seimi Chemical Co., Ltd.), PolyFox PF-6320 (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), and Fategent FTX-218G (manufactured by Neos).
Further, the surfactant is measured by gel permeation chromatography using the structural unit A and the structural unit B represented by the following general formula (I-1-1) and using tetrahydrofuran (THF) as a solvent. A preferred example is a copolymer having a polystyrene-reduced weight average molecular weight (Mw) of 1,000 or more and 10,000 or less.

Formula (I-1-1)

(In formula (I-1-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents hydrogen. Represents an atom or an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is 10 mass% to 80 mass%. The following numerical values are represented, q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.

L is preferably a branched alkylene group represented by the following general formula (I-1-2). R ⁴⁰⁵ in formula (I-1-2) represents an alkyl group having 1 to 4 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. And an alkyl group having 2 or 3 carbon atoms is more preferred. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.

Formula (I-1-2)

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

The content of the surfactant is preferably 10 parts by mass or less, more preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. More preferably, the content is 0.01 to 3 parts by mass. Surfactant may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount is the said range.

<< Antioxidant >>
The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
Examples of antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites. Examples thereof include salts, thiosulfates, and hydroxylamine derivatives. Among these, phenolic antioxidants, hindered amine antioxidants, phosphorus antioxidants, amide antioxidants, hydrazide antioxidants, sulfur antioxidants from the viewpoint of coloring the cured film and reducing film thickness Agents are preferred, and phenolic antioxidants are most preferred. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include compounds described in paragraph numbers 0026 to 0031 of JP-A-2005-29515, and compounds described in paragraph numbers 0106 to 0116 of JP-A-2011-227106. It is incorporated herein.
Preferred commercially available products are ADK STAB AO-20, ADK STAB AO-60, ADK STAB AO-80, ADK STAB LA-52, ADK STAB LA-81, ADK STAB AO-412S, ADK STAB PEP-36, IRGANOX 1035, IRGANOX 1098, and Tinuvin 144. Can be mentioned.
The content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% by mass. By setting it within this range, it is easy to form a film having excellent transparency. Furthermore, the sensitivity at the time of pattern formation is also good.

<< Acid Proliferator >>
In the photosensitive resin composition of the present invention, an acid proliferating agent can be used for the purpose of improving sensitivity.
The acid proliferating agent is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid.
Specific examples of the acid proliferating agent include acid proliferating agents described in paragraph numbers 0226 to 0228 of JP2011-212494A, the contents of which are incorporated herein.

<< Development accelerator >>
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, those described in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated herein.
The content of the development accelerator in the photosensitive resin composition of the present invention is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition from the viewpoint of sensitivity and residual film ratio. More preferably, it is 1 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass. A development accelerator may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount is the said range.

<< alkoxysilane compound >>
The photosensitive resin composition of the present invention can contain an alkoxysilane compound.
As the alkoxysilane compound, a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable. The alkoxy group contained in the alkoxysilane compound preferably has 1 to 5 carbon atoms.
The alkoxysilane compound is a compound that improves the adhesion between an insulating material and an inorganic material serving as a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum. It is preferable. Specifically, a known silane coupling agent or the like is also effective.

<< Other ingredients >>
The photosensitive resin composition of the present invention is a known additive such as a plasticizer, a thermal radical generator, a thermal acid generator, a thermal radical generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. An agent can be added. As these compounds, for example, the description of paragraph numbers 0201 to 0224 of JP2012-88459A can be referred to, and the contents thereof are incorporated in the present specification.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition of the present invention can be prepared by mixing each component at a predetermined ratio and by any method, stirring and dissolving. For example, the photosensitive resin composition of the present invention can also be prepared by mixing each component with a predetermined ratio after preparing each solution in advance in a solvent. The composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore diameter of 0.2 μm.

The solid content concentration of the photosensitive resin composition of the present invention at 25 ° C. is preferably 1 to 60% by mass, more preferably 3 to 40% by mass, further preferably 5 to 30% by mass, and particularly preferably 5 to 17% by mass. preferable. The viscosity is preferably 1 to 100 mPa · s, more preferably 2 to 60 mPa · s, and most preferably 3 to 40 mPa · s. By setting the solid content concentration and viscosity of the photosensitive resin composition within the above ranges, high-quality coating can be achieved. Viscosity can be measured, for example, using a viscometer RE85L (rotor: 1 ° 34 ′ × R24 measurement range 0.6 to 1200 mPa · s) manufactured by Toki Sangyo Co., Ltd., with the temperature adjusted to 25 ° C. .

The photosensitive resin composition of this invention can also be preserve | saved at the temperature of 10 to 30 degreeC, for example. Further, it can be stored at a temperature of 0 ° C. or higher and lower than 10 ° C., preferably 0 ° C. or higher and lower than 5 ° C. Further, it can be stored at a temperature of less than 0 ° C., preferably −5 ° C. or less, more preferably −20 ° C. or less, more preferably −20 to −40 ° C.
In order to ensure long-term storage stability, so-called frozen storage (preferably −5 ° C. or lower, more preferably −20 ° C. or lower, more preferably −20 to −40 ° C.) is preferable.

<Method for producing cured film>
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) The process of apply | coating the photosensitive resin composition of this invention on a board | substrate (application | coating process)
(2) Step of removing the solvent from the applied photosensitive resin composition (solvent removal step)
(3) Step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays (exposure step)
(4) Step of developing the exposed photosensitive resin composition with a developer (exposure step)
(5) Step of thermosetting the developed photosensitive resin composition (post-baking step)
Each step will be described below in order.

In the step (1), it is preferable to apply the photosensitive resin composition of the present invention on a substrate to form a wet film containing a solvent.
In the step (1), before the photosensitive resin composition is applied to the substrate, the substrate may be subjected to cleaning such as alkali cleaning or plasma cleaning. Further, the substrate surface may be treated with hexamethyldisilazane or the like with respect to the cleaned substrate. The method of treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method of exposing the substrate to hexamethyldisilazane vapor.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
The resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound And the like.
These substrates are rarely used in the above-described form, and a multilayer laminated structure such as a thin film transistor (TFT) may be formed depending on the form of the final product.
The method for applying the photosensitive resin composition to the substrate is not particularly limited. For example, an inkjet method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, etc. Can be used.
In the case of the slit coating method, the relative movement speed between the substrate and the slit die is preferably 50 to 120 mm / sec.
The wet film thickness when the photosensitive resin composition is applied is not particularly limited, and can be applied with a film thickness according to the application. For example, 0.5 to 10 μm is preferable.
Before applying the photosensitive resin composition of the present invention to the substrate, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.

In the step (2), the solvent is removed from the wet film formed by applying the photosensitive resin composition by vacuum (vacuum) and / or heating to form a dry film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced.

In the step (3), the substrate provided with the dry film is irradiated with actinic rays having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to generate a carboxy group, a phenolic hydroxyl group, a silanol group, and the like.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used, i-line (365 nm), h-line (405 nm), g-line ( Actinic rays having a wavelength of 300 nm to 450 nm, such as 436 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed. The exposure amount is preferably 1 to 500 mJ / cm ² .
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, and a laser exposure can be used. Further, exposure using so-called super-resolution technology can also be performed. Examples of the super-resolution technique include multiple exposure in which exposure is performed a plurality of times, a method using a phase shift mask, a deformation proof method represented by an annular illumination method, and the like. By using these super-resolution techniques, it is possible to form a higher definition pattern, which is preferable.
In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as “PEB”) can be performed. By PEB, the production | generation of the carboxy group, phenolic hydroxyl group, and silanol group from an acid-decomposable group can be accelerated | stimulated. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.

In the step (4), a copolymer having a free carboxy group, a phenolic hydroxyl group, and a silanol group is developed using a developer to form a positive image.
The developer used in the development step preferably contains an aqueous solution of a basic compound. Examples of basic compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; sodium bicarbonate, potassium bicarbonate Alkali metal bicarbonates such as: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide, and other tetraalkylammonium hydroxides: Alkyl) trialkylammonium hydroxides; silicates such as sodium silicate and sodium metasilicate; ethylamine, propylamine, diethylamine, triethylammonium Alkylamines such as diamine; Alcoholamines such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0 ] Cycloaliphatic amines such as 5-nonene can be used.
Of these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable.
An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dipping method, and the like.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.

In the step (5), by heating the obtained positive image, the acid-decomposable group is thermally decomposed to generate a carboxy group, a phenolic hydroxyl group, and a silanol group, and crosslinked with a crosslinkable group, a crosslinking agent, and the like. Thus, a cured film can be formed.
This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 400 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. It is preferable to By proceeding the crosslinking reaction in this way, a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like can be formed. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process). When performing middle baking, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 180 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film. The preferred exposure amount in the case of including a post-exposure step, preferably 100 ~ 3,000mJ / cm ^2, particularly preferably 100 ~ 500mJ / cm ^2.

The cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist. In the case where a cured film obtained by thermal curing in a post-baking process is used as a dry etching resist, dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.

<Curing film>
The cured film of the present invention is a cured film obtained by curing the above-described photosensitive resin composition of the present invention. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention mentioned above.
The cured film of the present invention can be suitably used as an interlayer insulating film. It is preferable to use at least a part of the cured film in contact with the metal part, and it can be particularly preferably used as an insulating substrate for metal wiring.
The photosensitive resin composition of the present invention can provide an interlayer insulating film having high transparency even when baked at a high temperature. The interlayer insulation film formed using the photosensitive resin composition of the present invention has high transparency and is useful for applications such as a liquid crystal display device, an organic electroluminescence display device, and a touch panel.

<Liquid crystal display device>
The liquid crystal display device of the present invention has the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a planarizing film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal display devices having various structures. Can be mentioned.
For example, specific examples of the TFT included in the liquid crystal display device of the present invention include an amorphous silicon-TFT, a low-temperature polysilicon-TFT, an oxide semiconductor (for example, indium gallium zinc oxide) TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
Further, the liquid crystal driving methods that can be adopted by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Virtual Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, OCB (Optical). Compensated Bend) method and the like.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) of Japanese Patent Application Laid-Open No. 2005-284291, or Japanese Patent Application Laid-Open No. 2005-346054. It can be used as an organic insulating film (212). Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.
FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10. The liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel is disposed on all pixels disposed between two

glass substrates

14 and 15 having a polarizing film attached thereto. Corresponding TFT 16 elements are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, white light emitting diodes (LEDs), multicolor LEDs such as blue, red, and green, fluorescent lamps (cold cathode tubes), organic electroluminescence (organic EL), and the like can be given.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, a flexible type can also be used. The second interlayer insulating film (48) described in JP2011-145686A, the interlayer insulating film (520) described in JP2009-258758A, JP It can be used as an organic insulating film (PAS) described in FIG. 1 of 2007-328210.
Further, even in a static drive type liquid crystal display device, a pattern with high designability can be displayed by applying the present invention. As an example, the present invention can be applied as an insulating film of a polymer network type liquid crystal as described in JP-A-2001-125086.

The liquid crystal display device shown in FIG. 1 of Japanese Patent Application Laid-Open No. 2007-328210 will be described with reference to FIG.
In FIG. 2, reference numeral SUB1 denotes a glass substrate, which has a plurality of scanning signal lines and a plurality of video signal lines intersecting with the plurality of scanning signal lines. A TFT is provided in the vicinity of each intersection.
On the glass substrate SUB1, a base film UC, a semiconductor film PS such as silicon, a gate insulating film GI, a TFT gate electrode GT, and a first interlayer insulating film IN1 are formed in this order from the bottom. A drain electrode SD1 of the TFT and a source electrode SD2 of the TFT are formed on the first interlayer insulating film IN1.
The drain electrode SD1 is connected to the drain region of the TFT through a contact hole formed in the gate insulating film GI and the first interlayer insulating film IN1. The source electrode SD2 is connected to the source region of the TFT through a contact hole formed in the gate insulating film GI and the first interlayer insulating film IN1.
A second interlayer insulating film IN2 is formed on the drain electrode SD1 and the source electrode SD2. An organic insulating film PAS is formed on the second interlayer insulating film IN2. The organic insulating film PAS can be formed using the photosensitive resin composition of the present invention.
On the organic insulating film PAS, a counter electrode CT and a reflective film RAL are formed.
A third interlayer insulating film IN3 is formed on the counter electrode CT and the reflective film RAL. A pixel electrode PX is formed on the third interlayer insulating film IN3. The pixel electrode PX is connected to the source electrode SD2 of the TFT through a contact hole formed in the second interlayer insulating film IN2 and the third interlayer insulating film IN3.
In the case where the organic insulating film PAS is formed using the photosensitive resin composition of the present invention, since the heat resistance of the organic insulating film PAS is excellent, the film forming temperature of the third interlayer insulating film IN3 is increased. And a denser film can be formed.
Note that the first interlayer insulating film IN1, the second interlayer insulating film IN2, and the third interlayer insulating film IN3 can also be formed using the photosensitive resin composition of the present invention.
The details of the liquid crystal display device shown in FIG. 2 can be referred to the description in Japanese Patent Application Laid-Open No. 2007-328210, and the contents thereof are incorporated in this specification.

<Organic electroluminescence display device>
The organic electroluminescence (organic EL) display device of the present invention has the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known organic materials having various structures. An EL display device and a liquid crystal display device can be given.
For example, specific examples of TFTs included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 3 is a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening film 4 is formed on the insulating film 3 with the unevenness due to the wiring 2 being embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. be able to.
Further, although not shown in FIG. 3, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.

Since the photosensitive resin composition of the present invention has good sensitivity and excellent pattern adhesion during development, it is formed using the photosensitive resin composition of the present invention as a structural member of a MEMS (Micro Electro Mechanical Systems) device. The resist pattern thus formed is used as a partition wall or incorporated as a part of a mechanical drive component. Examples of MEMS devices include parts such as SAW (Surface Acoustic Wave) filters, BAW (Bulk Acoustic Wave) filters, gyro sensors, micro shutters for displays, image sensors, electronic paper, inkjet heads, biochips, and sealants. It is done. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010- The partition wall (12) and the planarization film (102) described in FIG. 4 (a) of Japanese Patent No. 9793, the bank layer (221) and the third interlayer insulating film (216b) described in FIG. 10 of Japanese Patent Application Laid-Open No. 2010-27591. ), The second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4A of JP-A-2009-128577, and the flatness described in FIG. 3 of JP-A-2010-182638. It can also be used to form a chemical film (12) and a pixel isolation insulating film (14). In addition, spacers for maintaining the thickness of the liquid crystal layer in liquid crystal display devices, imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and micro lenses for optical fiber connectors are also used. It can be used suitably.

<Touch panel and touch panel display device>
The touch panel of the present invention is a touch panel in which all or part of the insulating layer and / or protective layer is made of a cured product of the photosensitive resin composition of the present invention. Moreover, it is preferable that the touch panel of this invention has a transparent substrate, an electrode, an insulating layer, and / or a protective layer at least.
The touch panel display device of the present invention is preferably a touch panel display device having the touch panel of the present invention. As the touch panel of the present invention, any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, and an electromagnetic induction method may be used. Among these, the electrostatic capacity method is preferable.
Examples of the capacitive touch panel include those disclosed in JP 2010-28115 A and those disclosed in International Publication No. 2012/057165.
As a touch panel display device, a so-called in-cell type (for example, FIG. 5, FIG. 6, FIG. 7 and FIG. 8 of JP-A-2012-517051), a so-called on-cell type (for example, FIG. 19 of JP2013-168125A). , OGS type, TOL type, and other configurations (for example, FIG. 6 of Japanese Patent Application Laid-Open No. 2013-164877). The capacitive touch panel has at least a front plate and a non-contact side of the front plate. The following (1) to (5) elements are preferable, and the insulating layer (4) is preferably a cured film using the photosensitive resin composition of the present invention.
(1) Frame layer (2) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (3) First transparent electrode pattern and electrical And a plurality of second transparent electrode patterns comprising a plurality of pad portions formed extending in a direction crossing the first direction. (4) First transparent electrode pattern and second transparent electrode pattern (5) The first transparent electrode pattern and the second transparent electrode pattern are electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern. Another conductive element In the capacitive input device of the present invention, it is preferable that a transparent protective layer is further provided so as to cover all or a part of the elements (1) to (5). The cured film of the present invention is more preferable. There.

First, the configuration of the capacitive touch panel will be described. FIG. 4 is a cross-sectional view illustrating a configuration example of a capacitive touch panel. In FIG. 4, the capacitive touch panel 30 includes a front plate 31, a frame layer 32, a first transparent electrode pattern 33, a second transparent electrode pattern 34, an insulating layer 35, and a conductive element 36. And a transparent protective layer 37.

The front plate 31 is made of a transparent substrate such as a glass substrate, and tempered glass represented by gorilla glass manufactured by Corning Inc. can be used. In addition, as a transparent substrate, a glass substrate, a quartz substrate, a transparent resin substrate, etc. are mentioned preferably. Moreover, in FIG. 4, the side in which each element of the front plate 31 is provided is called a non-contact surface. In the capacitive touch panel 30, input is performed by bringing a finger or the like into contact with the contact surface of the front plate 31 (the surface opposite to the non-contact surface). Hereinafter, the front plate may be referred to as a “base material”.

A frame layer 32 is provided on the non-contact surface of the front plate 31. The frame layer 32 is a frame-like pattern around the display area formed on the non-contact side of the front panel of the touch panel, and is formed so as not to show the lead wiring and the like.
As shown in FIG. 5, the capacitive touch panel may be provided with a frame layer 32 so as to cover a part of the front plate 31 (a region other than the input surface in FIG. 5). Further, the front plate 31 can be provided with an opening 38 in part as shown in FIG. A mechanical switch by pressing can be installed in the opening 38.

As shown in FIG. 6, on the non-contact surface of the front plate 31, a plurality of first transparent electrode patterns 33 formed with a plurality of pad portions extending in the first direction via the connection portions, A plurality of second transparent electrode patterns consisting of a plurality of pad portions that are electrically insulated from the first transparent electrode pattern 33 and extend in a direction crossing the first direction; An insulating layer 35 that electrically insulates the transparent electrode pattern 33 and the second transparent electrode pattern 34 is formed. The 1st transparent electrode pattern 33, the 2nd transparent electrode pattern 34, and the electroconductive element 36 mentioned later can be produced with a metal film, for example. As such a metal film, an ITO (Indium Tin Oxide) film; an IZO (Indium Zinc Oxide) film; a metal film such as Al, Cu, Ag, Ti, Mo, and alloys thereof; a metal oxide film such as SiO ₂ ; Is mentioned. At this time, the film thickness of each element can be 10 to 200 nm. Further, the amorphous ITO film can be crystallized into a polycrystalline ITO film by firing, and the electrical resistance can be reduced. Moreover, the 1st transparent electrode pattern 33, the 2nd transparent electrode pattern 34, and the electroconductive element 36 mentioned later are manufactured using the photosensitive transfer material which has the photosensitive resin composition using a conductive fiber. You can also In addition, when the first conductive pattern or the like is formed of ITO or the like, paragraphs 0014 to 0016 of Japanese Patent No. 4506785 can be referred to, and the contents thereof are incorporated in this specification.

Further, at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 extends over both the non-contact surface of the front plate 31 and the region of the frame layer 32 opposite to the front plate 31. Can be installed. In FIG. 4, a diagram is shown in which the second transparent electrode pattern is installed across both areas of the non-contact surface of the front plate 31 and the surface opposite to the front plate 31 of the frame layer 32. Yes.

The first transparent electrode pattern 33 and the second transparent electrode pattern 34 will be described with reference to FIG. FIG. 6 is an explanatory diagram showing an example of the first transparent electrode pattern and the second transparent electrode pattern. As shown in FIG. 6, the first transparent electrode pattern 33 is formed such that the pad portion 33a extends in the first direction via the connection portion 33b. The second transparent electrode pattern 34 is electrically insulated by the first transparent electrode pattern 33 and the insulating layer 35, and extends in a direction intersecting the first direction (second direction in FIG. 6). It is constituted by a plurality of pad portions that are formed. Here, when the first transparent electrode pattern 33 is formed, the pad portion 33a and the connection portion 33b may be manufactured integrally, or only the connection portion 33b is manufactured, and the pad portion 33a and the second transparent electrode pattern 33 are formed. The electrode pattern 34 may be integrally formed (patterned). When the pad portion 33a and the second transparent electrode pattern 34 are integrally formed (patterned), as shown in FIG. 6, a part of the connection part 33b and a part of the pad part 33a are connected and an insulating layer is formed. Each layer is formed so that the first transparent electrode pattern 33 and the second transparent electrode pattern 34 are electrically insulated by 35.

In FIG. 4, a conductive element 36 is installed on the surface side of the frame layer 32 opposite to the front plate 31. The conductive element 36 is electrically connected to at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34, and is different from the first transparent electrode pattern 33 and the second transparent electrode pattern 34. Is another element. In FIG. 4, a view in which the conductive element 36 is connected to the second transparent electrode pattern 34 is shown.

Moreover, in FIG. 4, the transparent protective layer 37 is installed so that all of each component may be covered. The transparent protective layer 37 may be configured to cover only a part of each component. The insulating layer 35 and the transparent protective layer 37 may be made of the same material or different materials.

The touch panel display device including the capacitive touch panel and the capacitive touch panel as a constituent element is “Latest Touch Panel Technology” (Techno Times, issued July 6, 2009), supervised by Yuji Mitani, “Touch Panel The configurations disclosed in “Technology and Development” CMC Publishing (2004, 12), “FPD International 2009 Forum T-11 Lecture Textbook”, “Cypress Semiconductor Corporation Application Note AN2292” and the like can be applied.

The touch panel of the present invention can be manufactured, for example, as follows.
That is, the photosensitive resin composition of the present invention is applied by various methods such as an inkjet coating method so as to be in contact with the ITO electrode, and an opening pattern having a predetermined shape is formed on the photosensitive resin composition applied to the ITO electrode. It can be manufactured through Step 2 in which a mask is placed and exposed by irradiation with active energy rays, Step 3 in which the exposed photosensitive resin composition is developed, and Step 4 in which the photosensitive resin composition after development is heated. .

In Step 1, when the photosensitive resin composition is applied so as to be in contact with the ITO electrode, it is sufficient that at least a part of the applied photosensitive resin composition of the present invention is in contact with the ITO electrode.
Step 2 can be performed in the same manner as the exposure step described above, and the preferred embodiment is also the same.
Step 3 can be performed in the same manner as the development step described above, and the preferred embodiment is also the same.
Step 4 can be performed in the same manner as the post-baking step described above, and the preferred embodiment is also the same.
Moreover, as an example of the ITO electrode pattern in the touch panel of this invention, the pattern shown in FIG. 6 mentioned above is mentioned preferably.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the following.
NMR is an abbreviation for nuclear magnetic resonance.

<Synthesis example of polysiloxane>
(Synthesis of A1-1) Synthesis of polysiloxane having a carboxyl group protected with an acid-decomposable group and an epoxy group 12.4 g (0.045 mol) of 3-trichlorosilyl-1-cyclohexylcarboxylic acid methyl ester, 11.2 g (0.045 mol) of Sidoxypropyltrichlorosilane, 0.745 g (0.005 mol) of methyltrichlorosilane and 1.06 g (0.005 mol) of phenyltrichlorosilane were dissolved in 150 g of toluene and dissolved in 300 g of water at room temperature. Added dropwise with stirring. After completion of the dropwise addition, the acidic aqueous layer was separated from the reaction mixture, then the organic layer was washed with 1 L of water, and further washed twice with water after the aqueous layer became neutral. The organic layer was evaporated using an evaporator. The concentrate was heated at 60 ° C. for 5 hours to polymerize.
A polymer dissolved in 800 g of tetrahydrofuran was dropped into 1,000 g of a 10% sodium hydroxide solution and heated at 40 ° C. for 3 hours to hydrolyze the methyl ester group. The polymer was crystallized with hydrochloric acid, crystallized, filtered and dried to obtain A1-1 precursor (polymer in which the carboxyl group of A1-1 was not protected with tetrahydrofuranyl).
100 g of the resulting A1-1 precursor was dissolved in 400 mL of tetrahydrofuran, and after adding a catalytic amount of p-toluenesulfonic acid, a solution in which 30 g of dihydrofuran was dissolved in 30 g of tetrahydrofuran was added dropwise with stirring at 20 ° C. .
After reacting for 30 minutes, the reaction solution was neutralized with concentrated aqueous ammonia and neutralized with 5 L of water, and a white solid was obtained. This was filtered, dissolved in 300 ml of acetone, dropped into 5 L of water, filtered and dried to obtain A1-1. A1-1 was a polysiloxane having a carboxy group, a carboxy group, an epoxy group, a methyl group, and a phenyl group protected by a tetrahydrofuranyl group in the side chain.
Analysis by 1H-NMR revealed that 78 mol% of the carboxy group was tetrahydrofuranylated in A1-1.
The types and molar ratios of the silane compounds used for the synthesis of A1-1 are shown below.

(Synthesis of A1-2) Synthesis of polysiloxane having phenolic hydroxyl group protected with acid-decomposable group and epoxy group 114.2 g (0.5 mol) of 4-hydroxybenzyltrimethoxysilane, 3-glycid 94.5 g (0.4 mol) of xylpropyltrimethoxysilane, 6.8 g (0.05 mol) of methyltrimethoxysilane, 9.9 g (0.05 mol) of phenyltrimethoxysilane, 250 g of DAA (diacetone alcohol) Was added to a three-necked flask, and an aqueous phosphoric acid solution in which 0.176 g of phosphoric acid (0.1 wt% with respect to the charged silane compound) was dissolved in 54 g of water was added over 30 minutes while stirring at room temperature. Thereafter, the three-necked flask was immersed in an oil bath at 40 ° C. and stirred for 30 minutes, and then reacted at 60 ° C. for 5 hours.
During the reaction, methanol as a by-product was distilled off. The obtained polysiloxane DAA solution was poured into a large amount of water to precipitate a polymer, filtered and dried to obtain an A1-2 precursor.
100 g of the obtained A1-2 precursor was dissolved in 400 mL of tetrahydrofuran, and after adding a catalytic amount of p-toluenesulfonic acid, a solution of 30 g of ethyl vinyl ether dissolved in 30 g of tetrahydrofuran was added dropwise with stirring at 20 ° C. .
After reacting for 30 minutes, the reaction solution was neutralized with concentrated aqueous ammonia and neutralized with 5 L of water, and a white solid was obtained. This was filtered, dissolved in 300 ml of acetone, dropped into 5 L of water, filtered and dried to obtain A1-2.
The weight average molecular weight in terms of polystyrene by GPC was 5000.
Analysis by ¹ H-NMR confirmed that 70 mol% of the hydrogen atoms of the phenolic hydroxyl group were ethoxyethylated in A1-2.
The types and molar ratios of the silane compounds used for the synthesis of A1-2 are shown below.

(Synthesis of A1-3) Synthesis of polysiloxane having silanol group protected with acid-decomposable group and epoxy group Phenyltrimethoxysilane 89.2 g (0.45 mol), 2- (3,4-epoxy Cyclohexyl) ethyltrimethoxysilane (110.9 g, 0.45 mol) and methanol (360 g) were charged into a three-necked flask and cooled with ice to 10 ° C. or lower with stirring. When 90 g of 0.1 M acetic acid aqueous solution was charged into the dropping funnel and dropped while cooling with ice, hydrolysis condensation reaction proceeded with heat generation. After raising the internal temperature to room temperature and aging for 2 hours, an ester adapter was installed, and methanol was distilled off under heating and normal pressure. Distillation was continued until the internal temperature exceeded the boiling point of methanol to obtain a cloudy viscous polysiloxane solution. At this time, the amount of captured methanol was 382 g. To this polysiloxane solution, 300 g of ethyl acetate was added, and the dissolved solution was washed twice with pure water. The polysiloxane solution was concentrated with a rotary evaporator to obtain 233 g of a colorless and transparent polysiloxane solution (solid content concentration: 62.2% by mass).
The resulting polysiloxane solution 80.4 g was solvent-substituted from an ethyl acetate solution to a tetrahydrofuran solution (solid content concentration 20% by mass), and then charged into a three-necked flask. Added.
Next, 19.4 g (0.23 mol) of ethyl-1-propenyl ether was added dropwise while keeping the internal temperature at 10 ° C. or less with a dropping funnel while cooling with ice at 10 ° C. or lower and stirring. After dropping, the mixture was reacted at room temperature for 2 hours, and then 1.0 g (0.01 mol) of triethylamine was added to complete the reaction. The reaction solution was transferred to a 1 L eggplant flask, tetrahydrofuran was distilled off with a rotary evaporator under reduced pressure at room temperature, 300 g of methyl isobutyl ketone and 250 ml of 0.01N acetic acid aqueous solution were added, and the reaction solution was washed with water. After repeating this washing operation three times in total, the organic layer was separated and concentrated by a rotary evaporator to obtain 49.0 g of polysiloxane A1-3 in which a colorless and transparent silanol group was acetal protected.
The acetal substitution rate of polysiloxane A1-3 was calculated to be 32.5 mol% from the NMR results.

(Synthesis of A1-4) Synthesis of polysiloxane having a carboxyl group protected with an acid-decomposable group and an epoxy group A silane compound was used in the following compounds and molar ratios, and the types and amounts of the protecting groups were changed. A1-4 was synthesized in the same manner as A1-1 except that the following silane compounds were mixed and reacted and a protecting group was introduced by a polymer reaction.
Analysis by ¹ H-NMR confirmed that 78 mol% of the carboxy group was tetrahydrofuranylated in A1-4.

(Synthesis of A1-5) Synthesis of polysiloxane having a carboxyl group protected with an acid-decomposable group and an epoxy group The silane compound is used in the following compounds and molar ratio, and the protective group is changed to an ethoxyethyl group The following silane compounds were mixed and reacted in the same manner as A1-1 except that the amount was adjusted, and a protective group was introduced by a polymer reaction to synthesize A1-5.
Analysis by ¹ H-NMR confirmed that 70 mol% of the carboxy group was ethoxyethylated in A1-5.

(Synthesis of A1-6) Synthesis of polysiloxane having a carboxyl group protected with an acid-decomposable group and an epoxy group The silane compound is used in the following compounds and molar ratios, and the kind and amount of the protecting group are adjusted. Except for the above, A1-5 was synthesized in the same manner as A1-1 by mixing and reacting the following silane compounds and introducing a protecting group by a polymer reaction.
^The analysis by ¹ H-NMR confirmed that 82 mol% of the carboxy group was tetrahydrofuranylated in A1-5.

(Synthesis of A2-1) Synthesis of polysiloxane having a carboxy group protected with an acid-decomposable group A1 except that the silane compound was used in the following compounds and molar ratios and the type and amount of the protecting group were adjusted. In the same manner as -1, the following silane compounds were mixed and reacted to obtain an A2-1 precursor (polysiloxane before the carboxy group was protected with tetrahydrofuran).
A2-1 was synthesized by introducing a protecting group into the A2-1 precursor by a polymer reaction.
In A2-1, it was confirmed by NMR that 90 mol% of the carboxy group was tetrahydrofuranylated. The weight average molecular weight in terms of polystyrene by GPC was 5000.

(Synthesis of A2-2) Synthesis of polysiloxane having a phenolic hydroxyl group protected with an acid-decomposable group The silane compound was used in the following compounds and molar ratios, and the type and amount of the protecting group were adjusted. In the same manner as A1-2, the following silane compounds were mixed and reacted, and a protective group was introduced by a polymer reaction to synthesize A2-2.
Analysis by ¹ H-NMR confirmed that 85 mol% of the hydrogen atoms of the phenolic hydroxyl group were ethoxyethylated in A2-2.
The weight average molecular weight in terms of polystyrene by GPC was 6000.

(Synthesis of A2-3) Synthesis of polysiloxane having silanol group protected with acid-decomposable group 99.1 g (0.5 mol) of phenyltrimethoxysilane, 60.1 g (0.5 mol) of dimethyldimethoxysilane, 277 g of methanol was charged into a three-necked flask and ice-cooled to 10 ° C. or lower with stirring. When 84 g of a 0.1 M aqueous methanesulfonic acid solution was added to the dropping funnel and dropped while cooling with ice, the hydrolysis condensation reaction proceeded with heat generation. After raising the internal temperature to room temperature and aging for 2 hours, an ester adapter was installed, and methanol was distilled off under heating and normal pressure. Distillation was continued until the internal temperature exceeded the boiling point of methanol to obtain a cloudy viscous polysiloxane solution. At this time, the amount of captured methanol was 280 g. 200 g of ethyl acetate was added to the polysiloxane solution, and the dissolved solution was washed twice with pure water. The polysiloxane solution was concentrated with a rotary evaporator to obtain 185 g of a colorless and transparent polysiloxane solution (solid content concentration: 60.5% by mass). The weight average molecular weight of this polysiloxane in terms of polystyrene by GPC was 3800.
The resulting polysiloxane (82.6 g) was solvent-substituted from an ethyl acetate solution to a tetrahydrofuran solution (siloxane concentration: 20% by mass), then charged into a three-necked flask, and 1.0 g (0.01 mol) of methanesulfonic acid was added. .
Next, 23.6 g (0.28 mol) of 3,4-dihydro-2H-pyran was added dropwise while keeping the internal temperature at 10 ° C. or less with a dropping funnel while cooling with ice at 10 ° C. or lower and stirring. After dropping, the mixture was reacted at room temperature for 2 hours, and then 1.0 g (0.01 mol) of triethylamine was added to complete the reaction. The reaction solution was transferred to an eggplant flask, tetrahydrofuran was distilled off with a rotary evaporator under reduced pressure at room temperature, 300 g of methyl isobutyl ketone and 250 ml of 0.01N acetic acid aqueous solution were added, and the reaction solution was washed with water. After repeating this washing operation three times in total, the organic layer was separated and concentrated by a rotary evaporator to obtain 48.4 g of colorless and transparent acetalized polysiloxane A2-3.
The acetal substitution rate of polysiloxane A2-3 was calculated to be 61.5 mol% from the NMR results.

(A2-4 synthesis) Synthesis of polysiloxane having carboxy group protected with acid-decomposable group Using silane compound in the following compounds and molar ratio, changing the protecting group to ethoxyethyl group to adjust the amount Except that, A2-4 was synthesized in the same manner as A1-1 by mixing and reacting the following silane compounds and introducing a protecting group by polymer reaction.
^In analysis by ¹ H-NMR, it was confirmed that A2-4 was ethoxyethylated in 85 mol% of the carboxy group.

(Synthesis of A3-1) Synthesis of polysiloxane having a carboxy group and an epoxy group A silane compound was used in the following compounds and molar ratios, and the same reaction as in A1-1 was conducted except that a protective reaction with dihydrofuran was not performed. The following silane compounds were mixed and reacted to synthesize polysiloxane A3-1 having a carboxy group and an epoxy group.
The weight average molecular weight in terms of polystyrene by GPC was 5000.

(Synthesis of A3-2) Synthesis of polysiloxane having phenolic hydroxyl group and epoxy group The same as A1-2 except that a silane compound is used in the following compounds and molar ratio and no protective group is introduced. Then, the following silane compounds were mixed and reacted to synthesize A3-2.
The weight average molecular weight in terms of polystyrene by GPC was 6000.

(Synthesis of A3-3) Synthesis of polysiloxane having a carboxy group and an oxetanyl group As in A1-1, except that a silane compound is used in the following compounds and molar ratio and no protective group is introduced. Then, the following silane compounds were mixed and reacted to synthesize A3-3.
The weight average molecular weight in terms of polystyrene by GPC was 6000.

<Preparation of photosensitive resin composition>
As shown in the following table, each component was blended and stirred to obtain a solvent solution, which was filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm to obtain photosensitive resin compositions of Examples and Comparative Examples. .

The details of the abbreviations indicating the compounds used in Examples and Comparative Examples are as follows.
<(A) Polysiloxane component>
A1-1 to A1-6, A2-1 to A2-4, A3-1 to A3-3, A1-1 precursor: polysiloxane synthesized according to the above synthesis example <(B) Photoacid generator>
B-1: PAG-103 (trade name, structure shown below, manufactured by BASF)
B-1 is a photoacid generator that generates an acid having a pKa of 3 or less.

B-2: PAI101 (trade name, structure shown below, manufactured by Midori Chemical Co., Ltd.)
B-2 is a photoacid generator that generates an acid having a pKa of 3 or less.

B-3: DTS-105 (trade name, triarylsulfonium salt, manufactured by Midori Chemical Co., Ltd.)
B-3 is a photoacid generator that generates an acid having a pKa of 3 or less.
B-4: Structure shown below (synthesized according to the method described in paragraph 249 of WO2011 / 087011 pamphlet)
B-4 is a photoacid generator that generates an acid having a pKa of 3 or less.

B-5: GSID-26-1 (trade name, triarylsulfonium salt, structure shown below, manufactured by BASF)
B-5 is a photoacid generator that generates an acid having a pKa of 3 or less.

B-6: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate B-6 is a photoacid generator that generates an acid having a pKa of 3 or less.
B-7: Structure shown below B-7 is a photoacid generator that generates an acid having a pKa of 3 or less.

B′-1: (Structure shown below. Quinonediazide compound)
B′-1 is a compound that generates an acid having a pKa of more than 3.

<(C) Solvent>
C-1: Propylene glycol 1-monomethyl ether 2-acetate C-2: Methyl ethyl diglycol C-3: Diethyl diglycol C-4: Butylene glycol diacetate C-5: Cyclohexanol acetate C-6: Ethylene glycol monomethyl Ether acetate <(S) blocked isocyanate compound>
S-1: Compound S-1 below (methyl ethyl ketone oxime protecting compound of isophorone diisocyanate, molecular weight 396)
S-2: Compound S-2 below (methyl ethyl ketone oxime protecting compound of hexamethylene diisocyanate trimer, molecular weight 739)
S-3: Compound S-3 below (methyl ethyl ketone oxime protecting compound of diphenylmethane diisocyanate, molecular weight 424)
S-4: Compound S-4 below (ε caprolactam protecting compound of hexamethylene diisocyanate trimer, molecular weight 817)
S-5: Blocked isocyanate with isophorone diisocyanate blocked with ε-caprolactam S-6: Blocked isocyanate with isophorone diisocyanate blocked with phenol S-7: Blocked isocyanate with isophorone diisocyanate blocked with butanol S-8: Isophorone diisocyanate with diphenylamine Blocked blocked isocyanate S-9: Blocked isocyanate obtained by blocking isophorone diisocyanate with ethyl acetoacetate S-10: Blocked isocyanate obtained by blocking isophorone diisocyanate with dimethylpyrazole S-11: Blocked isocyanate obtained by blocking isophorone diisocyanate with butyl mercaptan S-12 : The following compound S-12 (tolylene diisocyanate Methyl ethyl ketone oxime-protected compound of the over preparative molecular weight 348)
S-13: Polymer obtained by copolymerizing the following monomers (M-1, M-2, M-3) (methyl ethyl ketone oxime protecting compound)
M-1: Methacrylic acid 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl M-2: Methacrylic acid M-3: 3-Methacryloxypropyltrimethoxysilane (M-1: M-2) : M-3 = 50: 25: 25 (molar ratio), weight average molecular weight 1800)

<Basic compounds and other additives>
TBA: Tributylamine TPI: Triphenylimidazole DBA: 9,10-dibutoxyanthracene FA-630: Silicone surfactant (FA-630, trade name, manufactured by Shin-Etsu Chemical)
F-554: Perfluoroalkyl group-containing nonionic surfactant (Megafac F-554, trade name, manufactured by DIC)

<Evaluation of sensitivity>
A glass substrate having a size of 680 mm × 880 mm (EAGLE XG, 0.7 mm thickness (manufactured by Corning)) was exposed to hexamethyldisilazane vapor for 30 seconds, and each photosensitive resin composition was slit-coated, followed by 90 ° C./120 Pre-baked on a second hot plate to volatilize the solvent to form a photosensitive resin composition layer having a thickness of 3.0 μm.
Next, the obtained photosensitive resin composition layer was exposed with a mask pattern having a hole shape of 8 μm in diameter using MPA 5500CF manufactured by Canon Inc. The exposed photosensitive resin composition layer was developed with an alkali developer (0.6% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds. Through these operations, the optimum i-line exposure amount (Eopt) when resolving a hole having a diameter of 8 μm was determined and used as the sensitivity. Evaluation is based on the following criteria, and 1, 2 and 3 are practical levels.
1: 80mJ / cm ² less than ^2: 80mJ / cm 2 or more, 100 mJ / cm ² less than 3: 100mJ / cm ² or more and less than ^{150mJ / cm 2 4: 150mJ /} cm 2 or more, 190 mJ / cm ² less than 5: 190 mJ / cm ² or more

<Evaluation of metal discoloration (copper)>
After each photosensitive resin composition is slit-coated on a glass substrate with a copper film, the solvent is volatilized by pre-baking on a hot plate at 90 ° C./120 seconds to form a photosensitive resin composition layer having a thickness of 3.0 μm. did.
Next, the entire surface was exposed with an exposure amount of 100 mJ / cm ² using MPA 7800CF (high pressure mercury lamp) manufactured by Canon Inc., and heated in an oven at 280 ° C. for 30 minutes to form a cured film.
After performing a test in which this substrate is left in a chamber (“HAST CAHMBER EHS-221MD (trade name)” manufactured by ESPEC CORP.) For 24 hours at a temperature of 50 ° C., a humidity of 100%, and an atmospheric pressure of 212.8 kPa (2.1 atm). The degree of copper discoloration was evaluated. 1, 2 and 3 are practical levels.
1: Discoloration is not seen in the copper under the cured film before and after the test.
2: Less than 1% of the substrate area was discolored before and after the test.
3: 1% or more and less than 5% of the substrate area was discolored before and after the test.
4: Before and after the test, 5% or more and less than 10% of the substrate area was discolored.
5: 10% or more of the substrate area is discolored before and after the test.

<Evaluation of metal discoloration (aluminum)>
After each photosensitive resin composition is slit-coated on a glass substrate with an aluminum film, it is pre-baked on a hot plate at 90 ° C. for 120 seconds to evaporate the solvent, thereby forming a photosensitive resin composition layer having a thickness of 3.0 μm. did.
Next, the entire surface was exposed with an exposure amount of 100 mJ / cm ² using MPA 7800CF (high pressure mercury lamp) manufactured by Canon Inc., and heated in an oven at 280 ° C. for 30 minutes to form a cured film.
After performing a test in which this substrate was left in a chamber (Espec Corp., “HAST CAHMBER EHS-221MD (trade name)”) at 60 ° C., 90% humidity, and atmospheric pressure 162.1 kPa (1.6 atm) for 20 hours. ,
The degree of discoloration of copper was evaluated. 1, 2 and 3 are practical levels.
1: Discoloration is not seen in the aluminum under the cured film before and after the test.
2: Less than 1% of the substrate area was discolored before and after the test.
3: 1% or more and less than 5% of the substrate area was discolored before and after the test.
4: Before and after the test, 5% or more and less than 10% of the substrate area was discolored.
5: 10% or more of the substrate area is discolored before and after the test.

From the said result, the photosensitive resin composition of an Example was excellent in the sensitivity. Moreover, it was excellent in heat-and-moisture resistance, and the metal discoloration could be suppressed. Moreover, the cured film formed with the photosensitive resin composition of an Example had favorable heat resistance with respect to 300 degreeC.
On the other hand, the photosensitive resin composition of the comparative example was inferior in either sensitivity or wet heat resistance.

<Production of liquid crystal display device>
(Example 100)
In the active matrix liquid crystal display device described in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 100 was obtained. That is, using the photosensitive resin composition of Example 1, a cured film 17 was formed as an interlayer insulating film.
As a pretreatment for improving the wettability of the substrate and the interlayer insulating film 17 in paragraph 0058 of Japanese Patent No. 3321003, the substrate is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then the photosensitive resin of Example 1 is used. After spin-coating the composition, it was prebaked on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent, thereby forming a photosensitive resin composition layer having a thickness of 3 μm. Next, the obtained photosensitive resin composition layer is 40 mJ / cm ² (energy intensity: 20 mW / cm ² ) through a hole pattern mask of 10 μmφ using MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. , I-line). The exposed photosensitive resin composition layer was heat-treated on a hot plate at 90 ° C. for 2 minutes, and then paddled at 23 ° C./60 seconds with an alkali developer (0.4% tetramethylammonium hydroxide aqueous solution). After developing, it was rinsed with ultrapure water for 20 seconds. Subsequently, the entire surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), and then this substrate was heated in an oven at 280 ° C. for 30 minutes. Thus, a cured film was obtained.
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking.
When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.

(Example 101)
In the liquid crystal display device described in FIG. 1 of JP-A-2007-328210, the organic insulating film PAS was formed by the following method to obtain a liquid crystal display device.
First, according to Japanese Patent Application Laid-Open No. 2007-328210, an array substrate formed up to just before the organic insulating film PAS was produced.
Next, this substrate was exposed to hexamethyldisilazane vapor for 30 seconds, and then the photosensitive resin composition of Example 1 was slit-coated and then pre-baked on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent. A photosensitive resin composition layer was formed. Next, the obtained photosensitive resin composition layer was subjected to an optimum exposure dose mJ / cm ² (energy intensity: 20 mW / cm ²⁾ through a hole pattern mask of 8 μmφ using MPA 7800CF manufactured by Canon Inc. i-line) exposure. The exposed photosensitive resin composition layer was developed with an alkali developer (0.6% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds. Subsequently, the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm ² (energy intensity: 20 mW / cm ² , measured by i-line), and then the substrate was heated at 280 ° C. in an oven at 30 ° C. The organic insulating film PAS was obtained by heating for a few minutes.
In the subsequent steps, a liquid crystal display device was obtained according to Japanese Patent Application Laid-Open No. 2007-328210.
In this embodiment, since a material having high heat resistance is used for PAS, the interlayer insulating film IN3 is formed at the same temperature as the interlayer insulating film IN2. Thereby, IN3 could be made into a dense film.
When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed very good display characteristics and had high reliability.

<Production of organic EL display device>
(Example 201)
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 1 on a substrate, pre-baking (90 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiation with i-line (365 nm) at 45 mJ / cm ² (energy intensity 20 mW / cm ² ) using a mercury lamp, development is performed with an alkaline aqueous solution (0.4% TMAH aqueous solution) to form a pattern. Was used to expose the entire surface so that the integrated dose was 300 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), and a heat treatment was performed at 230 ° C./30 minutes.
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.

Next, a bottom emission type organic EL element was formed on the obtained flattening film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film 8, the photosensitive resin composition of Example 16 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.

Further, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.

As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving it was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.

<Production of touch panel>
(Example 301)
A touch panel was produced by the method described below.
<Formation of first transparent electrode pattern>
<< Formation of transparent electrode layer >>
A front plate of tempered glass (300 mm × 400 mm × 0.7 mm) with a frame layer formed in advance is introduced into a vacuum chamber, and an ITO target (indium: tin = 95: 5) with a SnO ₂ content of 10% by mass. (Molar ratio)) was used to form an ITO thin film having a thickness of 40 nm by DC magnetron sputtering (conditions: substrate temperature 250 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa), and a transparent electrode layer was formed. A formed front plate was obtained. The surface resistance of the ITO thin film was 80Ω / □.

Next, a commercially available etching resist was applied onto ITO and dried to form an etching resist layer. The distance between the exposure mask (quartz exposure mask having a transparent electrode pattern) surface and the etching resist layer is set to 100 μm, pattern exposure is performed at an exposure amount of 50 mJ / cm ² (i-line), and development is performed with a developer. Then, a post-baking treatment at 130 ° C. for 30 minutes was performed to obtain a front plate on which a transparent electrode layer and a photosensitive resin layer pattern for etching were formed.

The front plate on which the transparent electrode layer and the photo-sensitive resin layer pattern for etching are formed is immersed in an etching tank containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), treated for 100 seconds, and etched resist. The exposed transparent electrode layer not covered with the layer was dissolved and removed to obtain a front plate with a transparent electrode layer pattern with an etching resist layer pattern.
Next, the transparent electrode layer-patterned front plate with the etching resist layer pattern is immersed in a dedicated resist stripping solution, the etching photosensitive resin layer is removed, and the frame layer and the first transparent electrode pattern A front plate formed was obtained.

<< Formation of insulating layer >>
On the front plate on which the frame layer and the first transparent electrode pattern were formed, the photosensitive resin composition of Example 1 was applied and dried (film thickness: 1 μm, 90 ° C., 120 seconds) to form a photosensitive resin composition layer. Got. The distance between the surface of the exposure mask (quartz exposure mask having a pattern for insulating layer) and the photosensitive resin composition layer was set to 30 μm, and pattern exposure was performed with the optimum exposure amount obtained by sensitivity evaluation.
Next, the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 15 seconds and rinsed with ultrapure water for 10 seconds. Subsequently, a post-baking process at 220 ° C. for 45 minutes was performed to obtain a front plate on which a frame layer, a first transparent electrode pattern, and an insulating layer pattern were formed.

<Formation of second transparent electrode pattern>
<< Formation of transparent electrode layer >>
In the same manner as the formation of the first transparent electrode pattern, the front plate formed up to the insulating layer pattern was subjected to DC magnetron sputtering treatment (conditions: substrate temperature 50 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa). An ITO thin film having a thickness of 80 nm was formed to obtain a front plate on which a transparent electrode layer was formed. The surface resistance of the ITO thin film was 110Ω / □.
Furthermore, in the same manner as the formation of the first transparent electrode pattern, etching was performed and the etching resist layer was removed to form the frame layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1. A front plate on which an insulating layer pattern and a second transparent electrode pattern were formed was obtained.

<Formation of Conductive Element Different from First and Second Transparent Electrode Pattern>
Similar to the formation of the first and second transparent electrode patterns, the first transparent electrode pattern, the insulating layer pattern formed using the photosensitive resin composition of Example 1, and the second transparent electrode pattern The front plate on which was formed was subjected to DC magnetron sputtering to obtain a front plate on which an aluminum (Al) thin film having a thickness of 200 nm was formed.
Further, etching is performed in the same manner as the formation of the first transparent electrode pattern, and the etching resist layer is removed to form the frame layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1. A front plate on which conductive elements different from the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns were formed was obtained.

<Formation of transparent protective layer>
In the same manner as the formation of the insulating layer, the photosensitive resin composition of Example 1 was applied and dried (film thickness: 1 μm) on the front plate formed up to the conductive element different from the first and second transparent electrode patterns. , 90 ° C. for 120 seconds) to obtain a photosensitive resin composition film. Further, exposure, heat treatment, development, post-exposure (1,000 mJ / cm ² ), and post-bake treatment are performed to form the frame layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1. Insulating layer pattern, second transparent electrode pattern, insulating layer formed using the photosensitive resin composition of Example 1 so as to cover all the conductive elements different from the first and second transparent electrode patterns A front plate laminated with a (transparent protective layer) was obtained.

<Production of touch panel>
A liquid crystal display device manufactured by the method described in Japanese Patent Application Laid-Open No. 2009-47936 was bonded to the previously manufactured front plate, and a touch panel including a capacitive touch panel as a constituent element was manufactured by a known method.

<Evaluation of front plate and touch panel>
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and other conductive elements, while the first transparent electrode pattern and the second transparent electrode pattern Between the electrode patterns, there was insulation, and good display characteristics as a touch panel were obtained.

1: TFT, 2: wiring, 3: insulating film, 4: planarization film, 5: first electrode, 6: glass substrate, 7: contact hole, 8: insulating film, 10: liquid crystal display device, 12: backlight Units 14, 15: glass substrate, 16: TFT, 17: cured film, 18: contact hole, 19: ITO transparent electrode, 20: liquid crystal, 22: color filter, 30: capacitive touch panel, 31: front Face plate, 32: Frame layer, 33: First transparent electrode pattern, 33a: Pad portion, 33b: Connection portion, 34: Second transparent electrode pattern, 35: Insulating layer, 36: Conductive element, 37: Transparent protection Layer, 38: opening, CT: counter electrode, GI: gate insulating film, GT: gate electrode, IN1: first interlayer insulating film, IN2: second interlayer insulating film, IN3: third interlayer insulating film, PAS: Organic Film, PS: semiconductor film, PX: pixel electrode, RAL: reflective film, SD1: drain electrode, SD2: source electrode, SUB1: glass substrate, UC: base film

Claims

As component A, a polysiloxane component that satisfies at least one of the following 1 and 2,
1: The structural unit a1 is selected from a group in which a carboxy group is protected by an acid-decomposable group, a group in which a phenolic hydroxyl group is protected by an acid-decomposable group, and a group in which a silanol group is protected by an acid-decomposable group A polysiloxane component comprising a polysiloxane having a structural unit having at least one kind of group and a structural unit having a crosslinkable group as the structural unit a2.
2: The structural unit a1 is selected from a group in which a carboxy group is protected with an acid-decomposable group, a group in which a phenolic hydroxyl group is protected with an acid-decomposable group, and a group in which a silanol group is protected with an acid-decomposable group A polysiloxane component comprising a polysiloxane having a structural unit having at least one kind of group and a polysiloxane having a structural unit having a crosslinkable group as the structural unit a2.
As a component B, a photoacid generator that generates an acid having a pKa of 3 or less,
As component C, a solvent, and
A photosensitive resin composition containing a blocked isocyanate compound as component S.
The photosensitive resin composition according to claim 1, comprising 0.1 to 15% by mass of the blocked isocyanate compound based on the total solid content of the photosensitive resin composition.
The blocked isocyanate compound is obtained by protecting an isocyanate group of at least one compound selected from an isocyanate compound selected from tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate, and a multimer of the isocyanate compound. The photosensitive resin composition of Claim 1 or 2.
The blocked isocyanate compound is a compound in which a block structure is formed by protecting an isocyanate group with a compound selected from an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound. The photosensitive resin composition according to any one of claims 1 to 3.
The photosensitive resin composition according to claim 1, wherein the molecular weight of the blocked isocyanate compound is 100 to 2,000.
The photosensitive resin composition according to any one of claims 1 to 5, wherein the acid-decomposable group of the polysiloxane component is an acetal group.
The structural unit a1 is at least one selected from a structural unit represented by the following general formula a1-1 and a structural unit represented by the following general formula a1-2. The photosensitive resin composition according to item 1;

In general formula a1-1 and general formula a1-2, a represents 0 or 1,
R 1 and R 2 each independently represents a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 represents an alkyl group or an aryl group, and R 3 represents an alkyl group or an aryl group. R 1 or R 2 and R 3 may be linked to form a cyclic ether,
R 4 represents an alkyl group, an aryl group, or an aralkyl group,
L 1 represents a single bond or a divalent linking group,
L 2 represents a single bond or a divalent linking group,
R x represents an alkyl group or a halogen atom,
m1 represents an integer of 0 to 4.
The photosensitive resin composition according to any one of claims 1 to 7, wherein the crosslinkable group of the polysiloxane component is at least one selected from cyclic ether and a group having an ethylenically unsaturated bond. object.
The photosensitive resin composition according to any one of claims 1 to 8, wherein the polysiloxane further comprises a structural unit having at least one group selected from a carboxy group and a phenolic hydroxyl group.
The photosensitive resin composition according to any one of claims 1 to 9, wherein the photoacid generator is at least one selected from an onium salt compound, an oxime sulfonate compound, and an imide sulfonate compound.
Applying the photosensitive resin composition according to any one of claims 1 to 10 on a substrate;
Removing the solvent from the photosensitive resin composition applied to the substrate;
Exposing the photosensitive resin composition from which the solvent has been removed,
Developing the exposed photosensitive resin composition; and
A step of thermosetting the developed photosensitive resin composition;
The manufacturing method of the cured film containing this.
A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 10.
The cured film according to claim 12, which is an interlayer insulating film.
A liquid crystal display device having the cured film according to claim 12.
An organic electroluminescence display device having the cured film according to claim 12 or 13.
A touch panel having the cured film according to claim 12 or 13.