JP2017049327A - Photosensitive composition, method for manufacturing cured film, method for manufacturing liquid crystal display device, method for manufacturing organic electroluminescence display device, and method for manufacturing touch panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition having good application property, from which a cured film can be manufactured that has excellent adhesiveness to an overlay to be deposited on the cured film, and to provide methods for manufacturing a cured film, a liquid crystal display device, an organic electroluminescence display device and a touch panel.SOLUTION: The photosensitive composition comprises a polysiloxane component, a photoacid generator, a solvent, and a compound S having a structure represented by formula S1 and a structure represented by formula S2 below. In the formulae, a wavy line represents a bonding position to an atomic group constituting the compound S; Rrepresents an alkyl group; Rrepresents a hydrogen atom or an alkyl group; Lrepresents a single bond or a divalent connecting group; Rf represents a fluoroalkyl group having 3 or more fluorine atoms; Lrepresents an alkylene group having 1 to 12 carbon atoms or a carbonyl group; Rrepresents a hydrogen atom, a hydroxy group or an alkyl group having 1 to 12 carbon atoms; and n represents an integer of 0 to 30.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive composition. More specifically, it is suitable for forming a flattening film, a protective film, an interlayer insulating film, and the like of an electronic component such as an image display device such as a liquid crystal display device and an organic electroluminescence display device, a touch panel, an integrated circuit element, and a solid-state imaging device. The present invention relates to a photosensitive composition. Moreover, it is related with the manufacturing method of a cured film, the manufacturing method of a liquid crystal display device, the manufacturing method of an organic electroluminescent display device, and the manufacturing method of a touch panel.

  Image display devices such as liquid crystal display devices and organic electroluminescence display devices, and input devices such as touch panels are often provided with a patterned interlayer insulating film. In forming an interlayer insulating film, a photosensitive composition is widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.

  An attempt has been made to use an acrylic resin as a film forming component for the interlayer insulating film in the above-described apparatus.

  In recent years, attempts have been made to perform heat treatment or film formation at a higher temperature (eg, about 300 ° C.) than in the past in order to increase the production efficiency and the performance of the image display device. Therefore, 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 (see Patent Documents 1 to 3).

JP 2003-255546 A JP 2013-92633 A JP 2009-263522 A

  The photosensitive composition often uses a surfactant in order to improve the coating property. From the viewpoint of applicability, a fluorosurfactant is often used as the surfactant. However, the fluorosurfactant may be unevenly distributed on the surface of the coating film after coating. When a cured film produced using a photosensitive composition is used as a permanent film, various layers are often laminated on the cured film. At this time, if the fluorosurfactant is unevenly distributed on the film surface, the adhesion between the upper layer laminated on the cured film and the cured film may be lowered. For this reason, the surface layer of the cured film may be subjected to ashing or the like to remove the film surface layer in which the fluorosurfactant is unevenly distributed. Thus, conventionally, a process such as an ashing process may be required for the cured film, and the number of processes may be increased. In recent years, it has been desired to reduce the number of processes to simplify processes and reduce manufacturing costs.

  Moreover, when the present inventors examined the photosensitive composition disclosed by patent documents 1-3, it turned out that the applicability | paintability of a photosensitive composition and upper layer adhesiveness cannot be made compatible.

  Therefore, the objective of this invention is providing the photosensitive composition which can manufacture the cured film with favorable applicability | paintability and excellent adhesiveness with the upper layer laminated | stacked on a cured film. Moreover, it is providing the manufacturing method of a cured film, the manufacturing method of a liquid crystal display device, the manufacturing method of an organic electroluminescent display device, and the manufacturing method of a touch panel.

式中、波線は、化合物Ｓを構成する原子団との結合位置を表し、
Ｒ¹はアルキル基を表し、
Ｒ²は、水素原子またはアルキル基を表し、
Ｌ¹は、単結合または２価の連結基を表し、Ｌ¹が２価の連結基を表す場合、Ｒ¹はＬ¹と結合して環を形成してもよく、
Ｒｆは、フッ素原子を３以上有するフルオロアルキル基を表し、
Ｌ¹⁰⁰は、炭素数１〜１２のアルキレン基またはカルボニル基を表し、
Ｒ¹⁰⁰は、水素原子、ヒドロキシ基または炭素数１〜１２のアルキル基を表し、
ｎは、０〜３０の整数を表し、
ｎが０のとき、Ｒ¹⁰⁰は、ヒドロキシ基を表し、
ｎが１のとき、Ｌ¹⁰⁰は、炭素数１〜１２のアルキレン基またはカルボニル基を表し、Ｒ¹⁰⁰は水素原子または炭素数１〜６のアルキル基を表し、
ｎが２〜３０のとき、Ｌ¹⁰⁰は、炭素数１〜１２のアルキレン基を表し、Ｒ¹⁰⁰は水素原子または炭素数１〜１２のアルキル基を表し、複数のＬ¹⁰⁰は同一であってもよく、異なってもよい。
＜２＞ ポリシロキサン成分Ａの１００質量部に対して、化合物Ｓを０．００１〜２０質量部含有する、＜１＞に記載の感光性組成物。
＜３＞ 化合物Ｓが、式Ｓ１で表される構造を側鎖に有する構成単位Ｓ１−１と、式Ｓ２で表される構造を側鎖に有する構成単位Ｓ２−１とを有する重合体である、＜１＞または＜２＞に記載の感光性組成物。
＜４＞ 化合物Ｓが、下式Ｓ１−２で表される構成単位と、下式Ｓ２−２で表される構成単位とを有する重合体である、＜１＞〜＜３＞のいずれかに記載の感光性組成物；

式中、Ｒ¹¹は、水素原子または炭素数１〜３のアルキル基を表し、
Ｒ¹²はアルキル基を表し、
Ｒ¹³は、水素原子またはアルキル基を表し、
Ｌ¹⁰は、単結合または２価の連結基を表し、Ｌ¹⁰が２価の連結基を表す場合、Ｒ¹²はＬ¹⁰と結合して環を形成してもよく、
Ｒｆは、フッ素原子を３以上有するフルオロアルキル基を表し、
Ｌ¹⁰¹は、炭素数１〜１２のアルキレン基を表し、
Ｒ¹⁰¹は、水素原子または炭素数１〜１２のアルキル基を表し、
ｎ１は０〜３０の整数を表し、
ｎ１が０または１のとき、Ｒ¹⁰¹は、水素原子または炭素数１〜６のアルキル基を表し、
ｎ１が２〜３０のとき、複数のＬ¹⁰¹は同一であってもよく、異なってもよい。
＜５＞ 化合物Ｓが、下式Ｓ１−３で表される構成単位と、下式Ｓ２−３で表される構成単位とを有する重合体である、＜１＞〜＜４＞のいずれかに記載の感光性組成物；

式中、Ｒ²¹は、水素原子または炭素数１〜３のアルキル基を表し、
Ｒ²²は、炭素数１〜３のアルキル基を表し、
Ｒ²³は、水素原子を表し、
Ｌ²⁰は、炭素数１〜１２のアルキレン基を表し、
Ｒｆ¹は、炭素数３〜６のパーフルオロアルキル基を表し、
Ｒ²²は、Ｌ²⁰と結合して環を形成してもよく、
Ｌ²⁰¹は、炭素数１〜１２のアルキレン基を表し、
Ｒ²⁰¹は、水素原子または炭素数１〜６のアルキル基を表し、
ｎ２は１〜２０の整数を表し、ｎ２が２〜２０のとき、複数のＬ²⁰¹は同一であってもよく、異なってもよい。
＜６＞ 化合物Ｓは、構成単位Ｓ１−１と、構成単位Ｓ２−１とを、化合物Ｓの全構成単位の７０質量％以上含有する重合体であり、かつ、構成単位Ｓ１−１と、構成単位Ｓ２−１との質量比が、構成単位Ｓ１−１：構成単位Ｓ２−１＝５：９５〜９５：５である、＜３＞〜＜５＞のいずれかに記載の感光性組成物。
＜７＞ 化合物Ｓの重量平均分子量が１００〜１０００００である、＜１＞〜＜６＞のいずれかに記載の感光性組成物。
＜８＞ 構成単位ａ１が、下記一般式ａ１−１で表される構成単位、および、下記一般式ａ１−２で表される構成単位から選ばれる少なくとも１種である、＜１＞〜＜７＞のいずれかに記載の感光性組成物；

一般式ａ１−１、および、一般式ａ１−２中、ａは０または１を表し、Ｒ^1AおよびＲ^2Aは、それぞれ独立に、水素原子、アルキル基またはアリール基を表し、Ｒ^1AおよびＲ^2Aの少なくとも一方は、アルキル基またはアリール基を表し、Ｒ^3Aは、アルキル基またはアリール基を表し、Ｒ^1AまたはＲ^2Aと、Ｒ^3Aとが連結して環状エーテルを形成してもよく、Ｒ^4Aは、アルキル基、アリール基、または、アラルキル基を表し、Ｌ^1Aは、単結合または２価の連結基を表し、Ｌ^2Aは、単結合または２価の連結基を表し、Ｒ^xは、アルキル基またはハロゲン原子を表し、ｍ１は、０〜４の整数を表す。
＜９＞ ポリシロキサン成分が有する架橋性基が、環状エーテル、および、エチレン性不飽和結合を有する基から選ばれる少なくとも１種である、＜１＞〜＜８＞のいずれかに記載の感光性組成物。
＜１０＞ ポリシロキサンは、カルボキシ基およびフェノール性水酸基から選ばれる少なくとも１種の基を有する構成単位をさらに含む、＜１＞〜＜９＞のいずれかに記載の感光性組成物。
＜１１＞ ＜１＞〜＜１０＞のいずれかに記載の感光性組成物を基板上に塗布する工程、塗布された感光性組成物から溶剤を除去する工程、溶剤が除去された感光性組成物を活性光線により露光する工程、露光された感光性組成物を現像液により現像する工程、および、現像された感光性組成物を熱硬化する工程、を含む硬化膜の製造方法。
＜１２＞ ＜１１＞に記載の硬化膜の製造方法を含む、液晶表示装置の製造方法。
＜１３＞ ＜１１＞に記載の硬化膜の製造方法を含む、有機エレクトロルミネッセンス表示装置の製造方法。
＜１４＞ ＜１１＞に記載の硬化膜の製造方法を含む、タッチパネルの製造方法。 Under such circumstances, as a result of investigations by the present inventors, the photosensitive composition contains a compound S having a structure represented by the following formula S1 and a structure represented by the following formula S2, thereby allowing coating. The present inventors have found that a cured film having good adhesion and excellent adhesion to an upper layer laminated on the cured film can be produced without passing through a process such as ashing, and the present invention has been completed. That is, the present invention provides the following.
<1> Polysiloxane component A satisfying at least one of the following 1 and 2;
1: at least one 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 containing a polysiloxane having a structural unit a1 having a group and a structural unit a2 having a crosslinkable group;
2: At least one 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 a1 having a group and a polysiloxane having a structural unit a2 having a crosslinkable group;
a photoacid generator B that generates an acid having a pKa of 3 or less,
Solvent C, and
Compound S having a structure represented by the following formula S1 and a structure represented by the following formula S2,
A photosensitive composition comprising:

In the formula, the wavy line represents the bonding position with the atomic group constituting the compound S,
R ¹ represents an alkyl group,
R ² represents a hydrogen atom or an alkyl group,
L ¹ represents a single bond or a divalent linking group, and when L ¹ represents a divalent linking group, R ¹ may combine with L ¹ to form a ring,
Rf represents a fluoroalkyl group having 3 or more fluorine atoms,
L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group,
R ¹⁰⁰ represents a hydrogen atom, a hydroxy group or an alkyl group having 1 to 12 carbon atoms,
n represents an integer of 0 to 30,
when n is 0, R ¹⁰⁰ represents a hydroxy group;
When n is 1, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group, R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When n is 2 to 30, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms, R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and a plurality of L ¹⁰⁰ may be the same. Well, it can be different.
<2> The photosensitive composition according to <1>, containing 0.001 to 20 parts by mass of the compound S with respect to 100 parts by mass of the polysiloxane component A.
<3> The compound S is a polymer having a structural unit S1-1 having a structure represented by the formula S1 in the side chain and a structural unit S2-1 having a structure represented by the formula S2 in the side chain. <1,> The photosensitive composition as described in <2>.
<4> The compound S is a polymer having a structural unit represented by the following formula S1-2 and a structural unit represented by the following formula S2-2. Any one of <1> to <3> The photosensitive composition as described;

In the formula, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R ¹² represents an alkyl group,
R ¹³ represents a hydrogen atom or an alkyl group,
L ¹⁰ represents a single bond or a divalent linking group, and when L ¹⁰ represents a divalent linking group, R ¹² may combine with L ¹⁰ to form a ring,
Rf represents a fluoroalkyl group having 3 or more fluorine atoms,
L ¹⁰¹ represents an alkylene group having 1 to 12 carbon atoms,
R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
n1 represents an integer of 0 to 30,
when n1 is 0 or 1, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
When n1 is 2 to 30, the plurality of L ¹⁰¹ may be the same or different.
<5> The compound S is a polymer having a structural unit represented by the following formula S1-3 and a structural unit represented by the following formula S2-3, to any one of <1> to <4> The photosensitive composition as described;

In the formula, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R ²² represents an alkyl group having 1 to 3 carbon atoms,
R ²³ represents a hydrogen atom,
L ²⁰ represents an alkylene group having 1 to 12 carbon atoms,
Rf ¹ represents a C 3-6 perfluoroalkyl group,
R ²² may combine with L ²⁰ to form a ring,
L ²⁰¹ represents an alkylene group having 1 to 12 carbon atoms,
R ²⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
n2 represents an integer of 1 to 20, and when n2 is 2 to 20, the plurality of L ²⁰¹ may be the same or different.
<6> The compound S is a polymer containing the structural unit S1-1 and the structural unit S2-1 in an amount of 70% by mass or more of the total structural units of the compound S, and the structural unit S1-1 and the structural unit The photosensitive composition in any one of <3>-<5> whose mass ratio with unit S2-1 is structural unit S1-1: structural unit S2-1 = 5: 95-95: 5.
<7> The photosensitive composition according to any one of <1> to <6>, wherein the compound S has a weight average molecular weight of 100 to 100,000.
<8> 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 <7 > The photosensitive composition in any one of>

In general formula a1-1 and general formula a1-2, a represents 0 or 1, R ^1A and R ^2A each independently represents a hydrogen atom, an alkyl group or an aryl group, and R ^1A and R ^2A At least one of, an alkyl group or an aryl group, R ^3A represents an alkyl group or an aryl group, and R ^1A or R ^2A, it may be linked and the R ^3A forms a cyclic ether, R ^4A Represents an alkyl group, an aryl group, or an aralkyl group, L ^1A represents a single bond or a divalent linking group, L ^2A represents a single bond or a divalent linking group, and R ^x represents an alkyl Represents a group or a halogen atom, and m1 represents an integer of 0 to 4.
<9> The photosensitivity according to any one of <1> to <8>, wherein the crosslinkable group of the polysiloxane component is at least one selected from cyclic ether and a group having an ethylenically unsaturated bond. Composition.
<10> The photosensitive composition according to any one of <1> to <9>, wherein the polysiloxane further includes a structural unit having at least one group selected from a carboxy group and a phenolic hydroxyl group.
<11> The process of apply | coating the photosensitive composition in any one of <1>-<10> on a board | substrate, the process of removing a solvent from the apply | coated photosensitive composition, The photosensitive composition from which the solvent was removed A method for producing a cured film comprising a step of exposing a product with actinic rays, a step of developing the exposed photosensitive composition with a developer, and a step of thermally curing the developed photosensitive composition.
<12> A method for producing a liquid crystal display device, comprising the method for producing a cured film according to <11>.
<13> A method for producing an organic electroluminescence display device, comprising the method for producing a cured film according to <11>.
<14> The manufacturing method of a touch panel including the manufacturing method of the cured film as described in <11>.

  It has become possible to provide a photosensitive composition that can produce a cured film having good coating properties and excellent adhesion to the upper layer laminated on the cured film without passing through a process such as ashing. . Moreover, it has become possible to provide a method for producing a cured film, a cured film, and an apparatus.

It is a composition conceptual diagram of an example of a liquid crystal display. It is the schematic which shows an example of the liquid crystal display device which has a function of a touch panel. It is the schematic which shows an example of the liquid crystal display device which has a function of a touch panel.

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, “to” 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).
In the present specification, “(meth) acrylate” represents “acrylate” and “methacrylate”, “(meth) acryl” represents “acryl” and “methacryl”, and “(meth) acryloyl”. Represents “acryloyl” and “methacryloyl”.
In this specification, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are defined as a polystyrene conversion value by gel permeation chromatography (GPC) measurement.

  The photosensitive composition of the present invention is represented by a polysiloxane component A described later, a photoacid generator B that generates an acid having a pKa of 3 or less, a solvent C, a structure represented by the formula S1 described later, and a formula S2. And a compound S having the structure:

According to the present invention, by using the photosensitive composition having the above-described configuration, the coating property is good, and the adhesiveness with the upper layer laminated on the cured film is excellent without going through a process such as ashing. A cured film can be produced. The mechanism of the effect expression of the present invention is presumed as follows.
That is, the structure represented by the formula S1, which will be described later, has a fluoroalkyl group and thus has excellent hydrophobicity, and the structure represented by the formula S2 has a hydrophilic group and thus has excellent hydrophilicity. It is presumed that Compound S having both structures functions as a surfactant and can obtain excellent coating properties. Further, in the structure represented by the formula S1 of the compound S, since the fluoroalkyl group is bonded through an acetal bond, the acetal bond is broken during heating or the like, and the fluoroalkyl group part is eliminated and volatilized. It is considered that fluorine is not unevenly distributed on the surface layer of the cured film. For this reason, it is estimated that it became possible to manufacture the cured film excellent in adhesiveness with the upper layer laminated | stacked on a cured film, without passing through processes, such as ashing.
Further, in the structure represented by the formula S1 of the compound S, the fluoroalkyl group is bonded through an acetal bond, so that the acetal bond is broken by the action of an acid such as sulfonic acid, and the fluoroalkyl group moiety is Detach. Accordingly, the liquid repellency is lowered at the portion exposed to the acid. For this reason, the photosensitive composition of this invention has the outstanding characteristic that there is no image development residue by alkali image development and the roughness of the edge of a development pattern is small in addition to being excellent in applicability | paintability and upper layer contact | adherence.
The photosensitive composition of the present invention can be preferably used as a chemically amplified positive photosensitive composition.
The present invention will be described in detail below.

<Polysiloxane component A>
In the photosensitive composition of the present invention, the polysiloxane component A satisfies at least one of the following (1) and (2).
(1): at least one 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 The polysiloxane component containing polysiloxane A1 which has the structural unit a1 which has a seed group, and the structural unit a2 which has a crosslinkable group.
(2): at least one 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 The polysiloxane component containing polysiloxane A2 which has structural unit a1 which has a seed group, and polysiloxane A3 which has structural unit a2 which has a crosslinkable group.
Unless otherwise stated, the polysiloxane component A means one including other polysiloxane added in addition to the above polysiloxane.
The molar ratio of the structural unit a1 and the structural unit a2 contained in the polysiloxane component A is preferably structural unit a1: structural unit a2 = 10: 90 to 90:10, more preferably 80:20 to 20:80, 60 : 40-30: 70 is more preferable.

  In the aspect (1), at least one kind of polysiloxane A1 is included, 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 include two or more types. Moreover, the structural unit a3 which has the 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 all the 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.
In addition, 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.
In addition, 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.

  The aspect (2) is an aspect including polysiloxane A2 having the structural unit a1 and polysiloxane A3 having the structural unit a2. The polysiloxane A2 containing the structural unit a1 may further contain a 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 the other structural unit a4.

As for the ratio of the structural unit a1 of polysiloxane A2, 10-90 mol% is preferable with respect to all the structural units of 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.
As for the ratio of the structural unit a2 of polysiloxane A3, 10-90 mol% is preferable with respect to all the structural units of 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 preferably 95: 5 to 5:95, and 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 A 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, and more preferably 1.5 to 3.5.

<< Structural Unit a1 >>
The polysiloxane component A 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 having a structural unit a1 having at least one 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. More preferably, it has a protected carboxy group. According to this aspect, it is preferable from the viewpoints of basic physical properties of the photosensitive composition, particularly sensitivity, pattern shape, contact hole formation, and storage stability of the photosensitive 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, more preferably 5 mol%, based on all the structural units of the polysiloxane including the structural unit a1. The following is more preferable, and it is more preferable that the following is not substantially 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.

一般式ａ１−１、および、一般式ａ１−２中、ａは０または１を表し、
Ｒ^1AおよびＲ^2Aは、それぞれ独立に、水素原子、アルキル基またはアリール基を表し、Ｒ^1AおよびＲ^2Aの少なくとも一方は、アルキル基またはアリール基を表し、Ｒ^3Aは、アルキル基またはアリール基を表し、Ｒ^1AまたはＲ^2Aと、Ｒ^3Aとが連結して環状エーテルを形成してもよく、
Ｒ^4Aは、アルキル基、アリール基、または、アラルキル基を表し、
Ｌ^1Aは、単結合または２価の連結基を表し、
Ｌ^2Aは、単結合または２価の連結基を表し、
Ｒ^xは、アルキル基またはハロゲン原子を表し、
ｍ１は、０〜４の整数を表す。

In general formula a1-1 and general formula a1-2, a represents 0 or 1,
R ^1A and R ^2A each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ^1A and R ^2A represents an alkyl group or an aryl group, and R ^3A represents an alkyl group or an aryl group. R ^1A or R ^2A and R ^3A may be linked to form a cyclic ether,
R ^4A represents an alkyl group, an aryl group, or an aralkyl group,
L ^1A represents a single bond or a divalent linking group,
L ^2A 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 ^1A and R ^2A each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ^1A and R ^2A is an alkyl group or an aryl group.
1-10 are preferable, as for carbon number of an alkyl group, 1-8 are more preferable, and 1-6 are 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. 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.
6-20 are preferable, as for carbon number of an aryl group, 6-14 are more preferable, and 6-10 are more preferable. The aryl group may be unsubstituted or may have a substituent. Examples of the substituent include those described above. Moreover, a C1-C10 alkyl group can also be used as a substituent.
R ^1A and R ^2A are each independently preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and one of R ^1A and R ^2A is a methyl group. The other is particularly preferably a hydrogen atom.

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

R ^4A represents an alkyl group, an aryl group, or an aralkyl group.
1-10 are preferable, as for carbon number of an alkyl group, 1-8 are more preferable, and 1-6 are more preferable. The alkyl group may have a substituent. The alkyl group may be linear, branched or cyclic.
6-20 are preferable, as for carbon number of an aryl group, 6-14 are more preferable, and 6-10 are more preferable. The aryl group may have a substituent.
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.
Examples of the substituent that the alkyl group, aryl group, and aralkyl group may have are the same as those described for R ^1A and R ^2A .
R ^4A 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 an alkyl group, a C1-C4 alkyl group is preferable. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable.

L ^1A and L ^2A represent a single bond or a divalent linking group. As a bivalent coupling group, a C1-C12 alkylene group, a C1-C12 alkylene oxide group, a C6-C12 arylene group, etc. are mentioned. 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 ^1A and R ^2A . Moreover, you may have acid groups, such as a carboxy group, a phenol group, a phosphonyl group, a sulfo group, a sulfonamide group, and 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.

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

<< Structural Unit a2 >>
The polysiloxane component A contains polysiloxane containing the structural unit a2 having 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, and a methylol 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 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 only needs to 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 ^5A represents an alkyl group, an aryl group or an aralkyl group, L ^3A represents a single bond or a divalent linking group, and X represents a crosslinkable group Represents a group.

  From the viewpoint of cured film properties, the structural unit a2 is preferably a structural unit represented by the following general formula a2-1 and / or a structural unit represented by the following general formula a2-2.

In the general formulas a2-1 and a2-2, a represents 0 or 1, R ^5A represents an alkyl group, an aryl group or an aralkyl group, R ^y represents an alkyl group or a halogen atom, and L ^3A represents A single bond or a divalent linking group is represented, n represents 0 or 1, m2 represents an integer of 0 to 2 when n is 0, and an integer of 0 to 3 when n is 1 M3 represents an integer of 0-6.

R ^5A represents an alkyl group, an aryl group, or an aralkyl group. Alkyl group, an aryl group, the aralkyl group is the same and ranges described for the R ^4A of a1-1 and a1-2 described above, and preferred ranges are also the same.
L ^3A represents a single bond or a divalent linking group. Examples of the divalent linking groups include the same range as described in L ^2A of L ^1A and a1-2 of a1-1, preferred ranges are also the same.
^Ry represents an alkyl group or a halogen atom. Alkyl groups and, as the halogen atom is the same as the range described in a1-2 of R ^x may described above, and preferred ranges are 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 the silane compound that can be used to obtain the structural unit a2 include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyl. Examples include triethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. Moreover, the silane compound shown below can also be used.

<< Structural Unit (a3) >>
The polysiloxane contained in the polysiloxane component A may contain a 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 the structural unit a1 and the structural unit a2 substantially may be contained.
Specific examples of the acid group include a carboxy group, a phosphonyl group, a sulfo group, a phenolic hydroxyl group, a sulfonamide group, and a sulfonylimide group. Preferred acid groups include a carboxy group and a phenolic hydroxyl group.
Specific examples of the structural unit a3 having an acid group include a structure represented by the following general formula a3-1 and / or a structure represented by the general formula a3-2.

In General Formulas a3-1 and a3-2, a represents 0 or 1, R ^6A represents an alkyl group, an aryl group, or an aralkyl group, and L ^4A represents a single bond or a divalent linking group. , L ^5A 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.

The alkyl group, aryl group, and aralkyl group represented by R ^6A are the same as those described above for R ^4A of a1-1 and a1-2, and the preferred ranges are also the same.
The divalent linking group represented by L ⁴ is the same as the range described for L ^1A in a1-1, and the preferred range is also the same.
The divalent linking group represented by L ^5A is the same as the range described for L ^2A in a1-2, and the preferred range is also the same.
Alkyl group R ^z represents and, as the halogen atom is the same as the range described in a1-2 of R ^x may described above, and preferred ranges are also the same.
m4 represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and most preferably 0.

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

<< Structural Unit a4 >>
The polysiloxane component A can include a structural unit a4 other than the structural units a1 to a3 described above.
Examples of the structural unit a4 include structures represented by the following general formula a4-1.

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 ^7A and R ^8A each independently represents an alkyl group, an aryl group, or an aralkyl group.
The alkyl group, aryl group and aralkyl group represented by R ^7A and R ^8A are the same as the ranges described for R ^4A of 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.

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

  The polysiloxane contained in the polysiloxane component A 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 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 to 0087), Japanese Patent Application Laid-Open No. 2005-283939 (particularly 0052 to 054), Japanese Patent Application Laid-Open No. 2006-276598 (particularly 0009 to 0030), 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.
In addition, 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 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 polysiloxane component A will be described, but the present invention is not limited thereto.
(First embodiment)
In the above-described aspect (1), 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 above-described aspect (2), the polysiloxane A2 having the structural unit a1 further has the structural unit a3 and / or the structural unit a4.
(Third embodiment)
In the above-described aspect (2), the polysiloxane A3 having the structural unit a2 further has the structural unit a3 and / or the structural unit a4.
(Fourth embodiment)
A mode including at least the structural unit a3 in any one of the first to third embodiments.
(Fifth embodiment)
The aspect which has polysiloxane which has the structural unit a3 and / or the structural unit a4 in the aspect of (1) and / or (2) mentioned above substantially not including the structural unit a1 and the structural unit a2.
(Sixth embodiment)
The form which consists of 2 or more combinations of the said 1st-5th embodiment.

In an embodiment having a 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 total amount of the polysiloxane having the structural unit a1 and / or the structural unit a2 The mass ratio of 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 is preferably 99: 1 to 5:95, 97 : 3-30: 70 is more preferable, and 95: 5-50: 50 is further more preferable.
Further, 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 most preferably 90% by mass or more with respect to the total content of the polysiloxane. preferable.

  The content of the polysiloxane component A in the photosensitive composition of the present invention is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and 70 parts by mass with respect to 100 parts by mass of the total solid components of the photosensitive composition. The above is more preferable. The upper limit is more preferably 99 parts by mass or less, for example.

<Photoacid generator B>
The photosensitive composition of the present invention contains a photoacid generator B that generates an acid having a pKa of 3 or less. The photoacid generator B is preferably a compound that reacts with an actinic ray 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. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 3 or less, and more preferably a photoacid generator 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.

  Examples of photoacid generators include onium salt compounds, trichloromethyl-s-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. . Among these, onium salt compounds, imide sulfonate compounds, and oxime sulfonate compounds are preferable, and onium salt compounds and oxime sulfonate compounds are particularly 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 compounds include compounds described in paragraphs 0083 to 0088 of JP2011-221494A; Examples of the compounds described in JP-A 2011-105645, paragraphs 0013 to 0049, and the contents thereof are incorporated in the present specification.
Specific examples of the imidosulfonate compound include compounds described in paragraph numbers 0065 to 0075 of WO2011 / 087011, and the contents thereof are incorporated herein.

Preferred examples of the onium salt include diaryliodonium salts and triarylsulfonium salts.
Diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl, 4- (2′-hydroxy- 1'-tetradecaoxy) phenyliodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecoxy) phenyliodonium hexafluoroantimonate, phenyl, 4- (2'-hydroxy-1'-tetra Decaoxy) phenyliodonium-p-toluenesulfonate is preferred.
Examples of triarylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium. Trifluoromethanesulfonate or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate is preferred.

  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 (B1-1).

一般式（Ｂ１−１）中、Ｒ²¹は、アルキル基またはアリール基を表す。波線は他の基との結合を表す。 General formula (B1-1)

In General Formula (B1-1), R ²¹ represents an alkyl group or an aryl group. Wavy lines represent bonds with other groups.

In general formula (B1-1), any group may be substituted, and the alkyl group in R ²¹ may be linear, branched or cyclic. Acceptable substituents are described below.
As the alkyl group for R ²¹ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R ²¹ is a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cyclic alkyl group (such as a 7,7-dimethyl-2-oxonorbornyl group). It may be substituted with a bridged alicyclic group, preferably a bicycloalkyl group or the like.
As the aryl group for R ^21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.

  It is also preferable that the compound containing the oxime sulfonate structure represented by the general formula (B1-1) is an oxime sulfonate compound described in paragraphs 0108 to 0133 of JP 2014-238438 A.

  As an imide sulfonate type compound, a naphthalene imide type compound is preferable, the description of international publication WO11 / 087011 pamphlet can be referred and these content is integrated in this specification. In the present invention, in particular, trifluoromethylsulfonyloxybicyclo [2.2.1] hept-5-enedicarboximide, succinimide trifluoromethyl sulfonate, phthalimide trifluoromethyl sulfonate, N-hydroxynaphthalimide methanesulfonate, N-hydroxy- 5-norbornene-2,3-dicarboximidopropanesulfonate is preferred.

  In the photosensitive composition of the present invention, the content of the photoacid generator B is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total solid components of the photosensitive composition. For example, the lower limit is more preferably 0.2 parts by mass or more, and further preferably 0.5 parts by mass or more. For example, the upper limit is more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.

<Solvent C>
The photosensitive composition of the present invention contains a solvent C. The photosensitive composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and any of the components described below are dissolved in a solvent. The solvent C is preferably one that dissolves essential components and optional components and does not react with each component.
In the present invention, a known solvent can be used as the solvent C. 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 (for example, Diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, etc.), diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides And lactones Kill. 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. . Specific examples of preferable solvents include propylene glycol monomethyl ether acetate, diethylene glycol ethyl methyl ether, γ-butyrolactone, N-methylpyrrolidone, and 1,3-butylene glycol diacetate.

  It is preferable that content of the solvent C in the photosensitive composition of this invention is 50-95 mass parts with respect to 100 mass parts of all the components in a photosensitive composition. The lower limit is more preferably 60 parts by mass or more. 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.

式中、波線は、化合物Ｓを構成する原子団との結合位置を表し、
Ｒ¹はアルキル基を表し、
Ｒ²は、水素原子またはアルキル基を表し、
Ｌ¹は、単結合または２価の連結基を表し、Ｌ¹が２価の連結基を表す場合、Ｒ¹はＬ¹と結合して環を形成してもよく、
Ｒｆは、フッ素原子を３以上有するフルオロアルキル基を表し、
Ｌ¹⁰⁰は、炭素数１〜１２のアルキレン基またはカルボニル基を表し、
Ｒ¹⁰⁰は、水素原子、ヒドロキシ基または炭素数１〜１２のアルキル基を表し、
ｎは、０〜３０の整数を表し、
ｎが０のとき、Ｒ¹⁰⁰は、ヒドロキシ基を表し、
ｎが１のとき、Ｌ¹⁰⁰は、炭素数１〜１２のアルキレン基またはカルボニル基を表し、Ｒ¹⁰⁰は水素原子または炭素数１〜６のアルキル基を表し、
ｎが２〜３０のとき、Ｌ¹⁰⁰は、炭素数１〜１２のアルキレン基を表し、Ｒ¹⁰⁰は水素原子または炭素数１〜１２のアルキル基を表し、複数のＬ¹⁰⁰は同一であってもよく、異なってもよい。 <Compound S>
The photosensitive composition of the present invention includes a compound S having a structure represented by the following formula S1 and a structure represented by the following formula S2. Hereinafter, the structure represented by S1 is also referred to as structure S1. Moreover, the structure represented by Formula S2 is also called structure S2.

In the formula, the wavy line represents the bonding position with the atomic group constituting the compound S,
R ¹ represents an alkyl group,
R ² represents a hydrogen atom or an alkyl group,
L ¹ represents a single bond or a divalent linking group, and when L ¹ represents a divalent linking group, R ¹ may combine with L ¹ to form a ring,
Rf represents a fluoroalkyl group having 3 or more fluorine atoms,
L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group,
R ¹⁰⁰ represents a hydrogen atom, a hydroxy group or an alkyl group having 1 to 12 carbon atoms,
n represents an integer of 0 to 30,
when n is 0, R ¹⁰⁰ represents a hydroxy group;
When n is 1, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group, R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When n is 2 to 30, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms, R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and a plurality of L ¹⁰⁰ may be the same. Well, it can be different.

First, the structure S1 will be described.
In the formula S1, R ¹ represents an alkyl group. 1-10 are preferable, as for carbon number of an alkyl group, 1-6 are more preferable, 1-3 are still more preferable, 1 or 2 is especially preferable, and 1 is the most preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched, more preferably linear.
When L ¹ represents a divalent linking group, R ¹ may combine with L ¹ to form a ring. Examples of the ring formed by combining R ¹ and L ¹ include a tetrahydrofuranyl group and a tetrahydropyranyl group.

In formula S1, R ² represents a hydrogen atom or an alkyl group. Examples of the alkyl group include the alkyl groups described for R ¹ , and the preferred range is also the same. R ² is preferably a hydrogen atom.

In Formula S1, L ¹ represents a single bond or a divalent linking group.
Examples of the divalent linking group include an alkylene group, an arylene group, and a group formed by combining these.
1-12 are preferable, as for carbon number of an alkylene group, 1-10 are more preferable, 1-6 are more preferable, and 1-4 are especially preferable. The alkylene group is preferably linear or cyclic, and more preferably linear. The alkylene group may be linked through one or more bonds selected from an ether bond, an ester bond, and an amide bond, or may not have these bonds. The alkylene group preferably does not have the aforementioned bond. The alkylene group may be unsubstituted or may have a substituent, but is preferably unsubstituted. An example of the substituent is a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
6-20 are preferable and, as for carbon number of an arylene group, 6-12 are more preferable. The arylene group may be unsubstituted or may have a substituent. Unsubstituted is preferred. An example of the substituent is a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
L ¹ is preferably a single bond or an alkylene group, and more preferably an alkylene group.

In Formula S1, Rf represents a fluoroalkyl group having 3 or more fluorine atoms. As for carbon number of a fluoroalkyl group, 1-12 are preferable. The lower limit is preferably 3 or more, and more preferably 4 or more. The upper limit is preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less.
The fluoroalkyl group represented by Rf may be linear, branched or cyclic, preferably linear or cyclic, and more preferably linear. According to this aspect, applicability can be improved. Furthermore, adhesiveness with the upper layer laminated | stacked on a cured film can be improved more.
In the present invention, Rf is preferably a perfluoroalkyl group. 3-6 are preferable and, as for carbon number of a perfluoroalkyl group, 4-6 are still more preferable. According to this aspect, applicability can be improved. Furthermore, adhesiveness with the upper layer laminated | stacked on a cured film can be improved more.
In the present invention, the fluoroalkyl group means an alkyl group in which at least a part of hydrogen atoms of the alkyl group is substituted with a fluorine atom. That is, the fluoroalkyl group is an alkyl group having a fluorine atom as a substituent. The perfluoroalkyl group is a kind of fluoroalkyl group, and means an alkyl group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.

In Formula S1, the following is mentioned as a preferable specific example of the combination of L ¹ and Rf. CF ₃ CH ₂ CH ₂ —, CF ₃ CF ₂ CH ₂ CH ₂ —, CF ₃ (CF ₂ ) ₂ CH ₂ CH ₂ —, CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ —, CF ₃ (CF ₂ ) ₄ CH ₂ CH ₂ —, CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ —, CF ₃ (CF ₂ ) ₆ CH ₂ CH ₂ —, CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ —, (CF ₃ ) ₃ CCH ₂ CH ₂ — and the like. Among _{this, CF 3 (CF 2) 3} CH 2 CH 2 -, CF 3 (CF 2) 4 CH 2 CH 2 -, CF 3 (CF 2) 5 CH 2 CH 2 -, (CF 3) 3 CCH 2 CH ₂ — is preferable, and CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ — is particularly preferable.

Next, the structure S2 will be described.
In Formula S2, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group,
R ¹⁰⁰ represents a hydrogen atom, a hydroxy group or an alkyl group having 1 to 12 carbon atoms,
n represents an integer of 0 to 30.

In formula S2, the number of carbon atoms of the alkylene radical L ¹⁰⁰ represents preferably 1 to 12, more preferably 1 to 6, 2 to 4 is more preferable. The alkylene group represented by L ¹⁰⁰ is preferably linear or branched and more preferably branched. Number of branches of the alkylene group L ¹⁰⁰ represents the 1-2 is preferred, and more preferably 1. The alkylene group represented by L ¹⁰⁰ may have a substituent, but is preferably unsubstituted.
In formula S2, the number of carbon atoms in the alkyl group R ¹⁰⁰ represents preferably 1 to 12, more preferably 1 to 6, 1 to 3 is more preferable. The alkyl group represented by R ¹⁰⁰ is preferably linear or branched, and more preferably linear. The alkyl group represented by R ¹⁰⁰ may have a substituent, but is preferably unsubstituted.

In formula S2, n represents an integer of 0 to 30. The lower limit is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. The upper limit is preferably 20 or less, and more preferably 15 or less.
In addition, although n represents the integer of 0-30, the photosensitive composition of this invention may contain multiple things in which n in the compound S differs. Therefore, the average value of n of the compound S contained in the photosensitive composition of the present invention may not be an integer. In the present invention, n in one compound S preferably represents an integer of 0-30.

In the formula S2, when n is 0, R ¹⁰⁰ represents a hydroxy group,
When n is 1, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group, R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When n is 2 to 30, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms, R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and a plurality of L ¹⁰⁰ may be the same. Well, it can be different.
According to this aspect, excellent hydrophilicity is easily obtained. In particular, from the viewpoint of improving hydrophilicity, Formula (S2) preferably has the following aspects (1) to (3), more preferably (2) or (3), and still more preferably (3).
(1) A structure in which n is 0 and R ¹⁰⁰ represents a hydroxy group.
(2) A structure in which n is 1, L ¹⁰⁰ represents an alkylene group or a carbonyl group having 1 to 12 carbon atoms, and R ¹⁰⁰ represents a hydrogen atom. (3) n is 2 to 30 and L ¹⁰⁰ is 1 to 1 carbon atoms. A structure of 12 alkylene groups, wherein R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

Compound S may have only one structure S1 or two or more. Moreover, when it has two or more structures S1, the same structure may be sufficient and a different structure may be sufficient.
Moreover, the compound S may have only one structure S2 and may have two or more. Moreover, when it has two or more structures S2, the same structure may be sufficient and a different structure may be sufficient.

  It is preferable that the photosensitive composition of this invention contains 0.001-20 mass parts of compounds S with respect to 100 mass parts of the polysiloxane component A. The lower limit is preferably 0.005 parts by mass or more, and more preferably 0.01 parts by mass or more. The upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, and particularly preferably 2 parts by mass or less.

  In the present invention, the compound S may be a low molecular compound or a polymer. From the viewpoint of applicability, the compound S is preferably a polymer.

Ｒ¹はアルキル基を表し、
Ｒ²は、水素原子またはアルキル基を表し、
Ｌ¹は、単結合または２価の連結基を表し、Ｌ¹が２価の連結基を表す場合、Ｒ¹はＬ¹と結合して環を形成してもよく、
Ｒｆは、フッ素原子を３以上有するフルオロアルキル基を表し、
Ｌ¹⁰⁰は、炭素数１〜１２のアルキレン基またはカルボニル基を表し、
Ｒ¹⁰⁰は、水素原子、ヒドロキシ基または炭素数１〜１２のアルキル基を表し、
ｎは、０〜３０の整数を表し、
ｎが０のとき、Ｒ¹⁰⁰は、ヒドロキシ基を表し、
ｎが１のとき、Ｌ¹⁰⁰は、炭素数１〜１２のアルキレン基またはカルボニル基を表し、Ｒ¹⁰⁰は水素原子または炭素数１〜６のアルキル基を表し、
ｎが２〜３０のとき、Ｌ¹⁰⁰は、炭素数１〜１２のアルキレン基を表し、Ｒ¹⁰⁰は水素原子または炭素数１〜１２のアルキル基を表し、複数のＬ¹⁰⁰は同一であってもよく、異なってもよく、
Ａは単結合または（ｐ＋ｑ）価の連結基を表し、
ｐおよびｑは、それぞれ独立に１以上の整数を表し、
Ａは単結合が単結合の場合、ｐおよびｑは、それぞれ１を表す。 (When compound S is a low molecular weight compound)
When the compound S is a low molecular compound, the compound S is preferably a compound represented by the following formula S-100.

R ¹ represents an alkyl group,
R ² represents a hydrogen atom or an alkyl group,
L ¹ represents a single bond or a divalent linking group, and when L ¹ represents a divalent linking group, R ¹ may combine with L ¹ to form a ring,
Rf represents a fluoroalkyl group having 3 or more fluorine atoms,
L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group,
R ¹⁰⁰ represents a hydrogen atom, a hydroxy group or an alkyl group having 1 to 12 carbon atoms,
n represents an integer of 0 to 30,
when n is 0, R ¹⁰⁰ represents a hydroxy group;
When n is 1, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group, R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When n is 2 to 30, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms, R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and a plurality of L ¹⁰⁰ may be the same. Well, it can be different,
A represents a single bond or a (p + q) -valent linking group,
p and q each independently represent an integer of 1 or more,
When A is a single bond, p and q each represent 1.

In the formula S-100, R ¹ , R ² , L ¹ , Rf, L ¹⁰⁰ , R ¹⁰⁰ and n are synonymous with the ranges described in the above-described formulas S1 and S2.

In formula S-100, A represents a single bond or a (p + q) -valent linking group.
(P + q) -valent linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and Groups consisting of 0 to 20 sulfur atoms are included.
Specific examples of the (n + k) -valent linking group include a group composed of a combination of two or more of the following structural units or the following structural units (which may form a ring structure). .

  In Formula S-100, p and q each independently represent an integer of 1 or more. The upper limit of the total number of p and q is not particularly limited, but can be 10 or less, and can be 6 or less. The lower limit is 2 or more.

  When the compound S is a low molecular compound, the molecular weight of the compound S is preferably 100 to 1000. The lower limit is preferably 120 or more, and more preferably 150 or more. The upper limit is preferably 500 or less, and more preferably 400 or less. When the molecular weight of the low molecular weight compound can be calculated from the structural formula, the molecular weight is a theoretical value obtained from the structural formula. When the molecular weight cannot be calculated from the structural formula, polystyrene by GPC measurement based on the method described in Examples described later is used. It is a weight average molecular weight according to a converted value.

Specific examples of the low molecular compound include the following compounds. In the following, Rf ^a represents a linear or branched perfluoroalkyl group having 3 to 8 carbon atoms. Rf ^a is preferably perfluoroalkyl group linear 4 to 6 carbon atoms.

(When compound S is a polymer)
When the compound S is a polymer, the compound S is preferably a polymer having a structural unit S1-1 having the structure S1 in the side chain and a structural unit S2-1 having the structure S1 in the side chain.

Examples of the main chain structure of the structural unit S1-1 and the structural unit S2-1 include acrylic, styrene, and cycloolefin, and acrylic is preferable. Examples of the acrylic main chain structure include a structure represented by P1 below. Examples of the styrenic main chain structure include a structure represented by P2 below. Examples of the cycloolefin-based main chain structure include structures represented by the following P3. In the formula, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and * represents a bonding position with a side chain.

式Ｓ１−１、Ｓ１−１００およびＳ１−２００において、
Ｒ¹¹は、水素原子または炭素数１〜３のアルキル基を表し、Ｒ¹²はアルキル基を表し、
Ｒ¹³は、水素原子またはアルキル基を表し、
Ｌ¹⁰は、単結合または２価の連結基を表し、Ｌ¹⁰が２価の連結基を表す場合、Ｒ¹²はＬ¹⁰と結合して環を形成してもよく、
Ｒｆは、フッ素原子を３以上有するフルオロアルキル基を表す。
式Ｓ２−２において、
Ｌ¹⁰¹は、炭素数１〜１２のアルキレン基を表し、
Ｒ¹⁰¹は、水素原子または炭素数１〜１２のアルキル基を表し、
ｎ１は０〜３０の整数を表し、
ｎ１が０または１のとき、Ｒ¹⁰¹は、水素原子または炭素数１〜６のアルキル基を表し、
ｎ１が２〜３０のとき、複数のＬ¹⁰¹は同一であってもよく、異なってもよい。
式Ｓ２−１００およびＳ２−２００において、
Ｌ¹¹⁰は、炭素数１〜１２のアルキレン基またはカルボニル基を表し、
Ｒ¹¹⁰は、水素原子、ヒドロキシ基または炭素数１〜１２のアルキル基を表し、
ｎ１０は、０〜３０の整数を表し、
ｎ１０が０のとき、Ｒ¹¹⁰は、ヒドロキシ基を表し、
ｎ１０が１のとき、Ｌ¹¹⁰は、炭素数１〜１２のアルキレン基またはカルボニル基を表し、Ｒ¹¹⁰は水素原子または炭素数１〜６のアルキル基を表し、
ｎ１０が２〜３０のとき、Ｌ¹¹⁰は、炭素数１〜１２のアルキレン基を表し、Ｒ¹¹⁰は水素原子または炭素数１〜１２のアルキル基を表し、複数のＬ¹¹⁰は同一であってもよく、異なってもよい。 Specific examples of the structural unit S1-1 having an acrylic main chain structure include, for example, the structure represented by the following S1-2. Specific examples of the structural unit S1-1 having a styrenic main chain structure include, for example, the structure represented by the following S1-100. Specific examples of the structural unit S1-1 having a cycloolefin-based main chain structure include, for example, a structure represented by the following S1-200.
Moreover, as a specific example in which the structural unit S2-1 has an acrylic main chain structure, for example, a structure represented by the following S2-2 can be given. Specific examples of the structural unit S2-1 having a styrenic main chain structure include, for example, the structure represented by the following S2-100. Specific examples of the structural unit S2-1 having a cycloolefin-based main chain structure include, for example, the structure represented by the following S2-200.

In formulas S1-1, S1-100 and S1-200,
R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ¹² represents an alkyl group,
R ¹³ represents a hydrogen atom or an alkyl group,
L ¹⁰ represents a single bond or a divalent linking group, and when L ¹⁰ represents a divalent linking group, R ¹² may combine with L ¹⁰ to form a ring,
Rf represents a fluoroalkyl group having 3 or more fluorine atoms.
In formula S2-2,
L ¹⁰¹ represents an alkylene group having 1 to 12 carbon atoms,
R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
n1 represents an integer of 0 to 30,
when n1 is 0 or 1, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
When n1 is 2 to 30, the plurality of L ¹⁰¹ may be the same or different.
In formulas S2-100 and S2-200,
L ¹¹⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group,
R ¹¹⁰ represents a hydrogen atom, a hydroxy group or an alkyl group having 1 to 12 carbon atoms,
n10 represents an integer of 0 to 30,
when n10 is 0, R ¹¹⁰ represents a hydroxy group;
When n10 is 1, L ¹¹⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group, R ¹¹⁰ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When n10 is 2 to 30, L ¹¹⁰ represents an alkylene group having 1 to 12 carbon atoms, R ¹¹⁰ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and a plurality of L ¹¹⁰ may be the same. Well, it can be different.

In the present invention, the compound S may further have a structural unit (other structural unit) other than the structural unit S1-1 and the structural unit S2-1.
Examples of other structural units include structural units having a crosslinkable group. Examples of the structural unit having a crosslinkable group include an epoxy group, an oxetanyl group, —NH—CH ₂ —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and ethylenic groups. Examples thereof include structural units containing at least one selected from the group consisting of unsaturated groups. The crosslinkable group is preferably at least one selected from an epoxy group, an oxetanyl group, and a group represented by —NH—CH ₂ —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). An epoxy group and / or an oxetanyl group are more preferable.
The content of other structural units is preferably 30% by mass or less, and more preferably 20% by mass or less, based on all the structural units of the polymer. The lower limit can be set to 1% by mass, for example. Further, other structural units can be substantially not contained. The content of other structural units is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, with respect to all the structural units of the polymer. More preferably, no other structural unit is contained.

式中、Ｒ¹¹は、水素原子または炭素数１〜３のアルキル基を表し、
Ｒ¹²はアルキル基を表し、
Ｒ¹³は、水素原子またはアルキル基を表し、
Ｌ¹⁰は、単結合または２価の連結基を表し、Ｌ¹⁰が２価の連結基を表す場合、Ｒ¹²はＬ¹⁰と結合して環を形成してもよく、
Ｒｆは、フッ素原子を３以上有するフルオロアルキル基を表し、
Ｌ¹⁰¹は、炭素数１〜１２のアルキレン基を表し、
Ｒ¹⁰¹は、水素原子または炭素数１〜１２のアルキル基を表し、
ｎ１は０〜３０の整数を表し、
ｎ１が０または１のとき、Ｒ¹⁰¹は、水素原子または炭素数１〜６のアルキル基を表し、
ｎ１が２〜３０のとき、複数のＬ¹⁰¹は同一であってもよく、異なってもよい。 In the present invention, the compound S includes a structural unit represented by the following formula S1-2 (hereinafter also referred to as structural unit S1-2) and a structural unit represented by the following formula S2-2 (hereinafter referred to as structural unit S2-). 2) is preferable.

In the formula, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R ¹² represents an alkyl group,
R ¹³ represents a hydrogen atom or an alkyl group,
L ¹⁰ represents a single bond or a divalent linking group, and when L ¹⁰ represents a divalent linking group, R ¹² may combine with L ¹⁰ to form a ring,
Rf represents a fluoroalkyl group having 3 or more fluorine atoms,
L ¹⁰¹ represents an alkylene group having 1 to 12 carbon atoms,
R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
n1 represents an integer of 0 to 30,
when n1 is 0 or 1, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
When n1 is 2 to 30, the plurality of L ¹⁰¹ may be the same or different.

In Formula S1-2, R ¹² , R ¹³ , L ¹⁰ and Rf have the same meanings as R ¹ , R ² , L ¹ and Rf described in Formula S1 described above.

In Formula S1-2 and Formula S2-2, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and preferably a hydrogen atom or a methyl group.

In Formula S2-2, L ¹⁰¹ represents an alkylene group having 1 to 12 carbon atoms. 1-12 are preferable, as for carbon number of an alkylene group, 1-6 are more preferable, and 2-4 are still more preferable. The alkylene group is preferably linear or branched and more preferably branched. The number of branches of the alkylene group is preferably 1 to 2, and more preferably 1. The alkylene group may have a substituent but is preferably unsubstituted.

In Formula S2-2, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. Number of carbon atoms of the alkyl group R ¹⁰¹ represents preferably 1 to 12, more preferably 1 to 6, 1 to 3 is more preferable. The alkyl group represented by R ¹⁰¹ is preferably linear or branched, and more preferably linear. The alkyl group represented by R ¹⁰¹ may have a substituent, but is preferably unsubstituted. R ¹⁰¹ is preferably a hydrogen atom.

n1 represents the integer of 0-30. The lower limit is preferably 1 or more. The upper limit is preferably 20 or less, and more preferably 15 or less. When n1 is 0 or 1, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, when n1 is 2 to 30, a plurality of L ¹⁰¹ may be the same.
In addition, although n1 represents the integer of 0-30, the photosensitive composition of this invention may contain multiple things in which n1 in the compound S differs. Therefore, the average value of n1 of the compound S contained in the photosensitive composition of the present invention may not be an integer.

In the present invention, in the compound S, the total content of the structural unit S1-1 and the structural unit S2-1 is preferably 70% by mass or more, and 75% by mass or more of all the structural units of the compound S. It is more preferable, and it is still more preferable that it is 80 mass% or more. If it is the said range, applicability | paintability is favorable and it is easy to form the cured film excellent in adhesiveness with the upper layer laminated | stacked on a cured film. Moreover, it is preferable that mass ratio of structural unit S1-1 and structural unit S2-1 is structural unit S1-1: structural unit S2-1 = 5: 95-95: 5, 10: 90-90. : 10 is more preferable, and 15:85 to 85:15 is more preferable.
In the present invention, the compound S preferably contains the structural unit S1-1 and the structural unit S2-1 in an amount of 60 mol% or more, more preferably 70 mol% or more of all the structural units of the compound S. It is more preferable to contain 80 mol% or more. If it is the said range, applicability | paintability is favorable and it is easy to form the cured film excellent in adhesiveness with the upper layer laminated | stacked on a cured film. The molar ratio between the structural unit S1-1 and the structural unit S2-1 is preferably the structural unit S1-1: the structural unit S2-1 = 95: 5 to 5:95, and 80:20 to 10 : 90 is more preferable, and 70:30 to 10:90 is more preferable.

式中、Ｒ¹¹は、水素原子または炭素数１〜３のアルキル基を表し、
Ｌ¹⁰¹は、炭素数１〜１２のアルキレン基を表し、
Ｒ¹⁰²は、水素原子または炭素数１〜１２のアルキル基を表し、
Ｒ¹⁰³は、炭素数１〜６のアルキル基を表し、
ｎ１ａは１〜３０の整数を表し、
ｎ１ａが１のとき、Ｒ¹⁰²は、水素原子または炭素数１〜６のアルキル基を表し、
ｎ１ａが２〜３０のとき、複数のＬ¹⁰¹は同一であってもよく、異なってもよい。 In the present invention, as the structural unit S2-2, the compound S may have one or more types of structures in which n1 is represented by 0 and structures in which n1 is represented by 1 or more.
That is, the compound S is represented by the structural unit S1-2, the structural unit represented by the following formula S2-2-1 (also referred to as the structural unit S2-2-1), and the following formula S2-2-2. A structural unit (also referred to as a structural unit S2-2-2) and at least one structural unit selected from structural units represented by the following formula S2-2-3 (also referred to as a structural unit S2-2-3): It may be a polymer.
Especially, the polymer which has structural unit S1-2, structural unit S2-2-1, and / or structural unit S2-2-2 is preferable.
The total content of the structural unit S2-2-1 and the structural unit S2-2-2 in all the structural units of the polymer is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass or more. Is more preferable, and 40% by mass or more is particularly preferable. For example, the upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.
The content of the structural unit S2-2-1 in all the structural units of the polymer is preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and 40% by mass or more. Is particularly preferred. For example, the upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.
In addition, the content of the structural unit S2-2-2 in all the structural units of the polymer is preferably 1 to 20% by weight, more preferably 1 to 15% by weight, based on all the structural units of the polymer. 1-10 mass% is still more preferable, and 1-5 mass% is especially preferable.
Further, the content of the structural unit S2-2-3 in all the structural units of the polymer is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and 1% by mass or less. Is particularly preferred. It is also preferable that the structural unit S2-2-3 is not substantially contained. “Containing substantially no structural unit S2-2-3” means that the content of the structural unit S2-2-3 is preferably 0.5% by mass or less, and 0.1% by mass with respect to all the structural units of the polymer. % Or less is more preferable, and it is more preferable not to contain the structural unit S2-2-3. According to this aspect, it is easy to obtain excellent coating properties.

In the formula, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
L ¹⁰¹ represents an alkylene group having 1 to 12 carbon atoms,
R ¹⁰² represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
R ¹⁰³ represents an alkyl group having 1 to 6 carbon atoms,
n1a represents an integer of 1 to 30,
When n1a is 1, R ¹⁰² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When n1a is 2 to 30, the plurality of L ¹⁰¹ may be the same or different.

R ¹¹ , L ¹⁰¹ and R ¹⁰² have the same meanings as R ¹¹ , L ¹⁰¹ and R ¹⁰¹ in S2-2.
Number of carbon atoms of the alkyl group R ¹⁰³ represents is 1 to 6 preferably 1 to 3 is more preferable. The alkyl group is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent, but is preferably unsubstituted.

式中、Ｒ²¹は、水素原子または炭素数１〜３のアルキル基を表し、
Ｒ²²は、炭素数１〜３のアルキル基を表し、
Ｒ²³は、水素原子を表し、
Ｌ²⁰は、炭素数１〜１２のアルキレン基を表し、
Ｒｆ¹は、炭素数３〜６のパーフルオロアルキル基を表し、
Ｒ²²は、Ｌ²⁰と結合して環を形成してもよく、
Ｌ²⁰¹は、炭素数１〜１２のアルキレン基を表し、
Ｒ²⁰¹は、水素原子または炭素数１〜６のアルキル基を表し、
ｎ２は１〜２０の整数を表し、ｎ２が２〜２０のとき、複数のＬ²⁰¹は同一であってもよく、異なってもよい。 In the present invention, the compound S includes a structural unit represented by the following formula S1-3 (hereinafter also referred to as structural unit S1-3) and a structural unit represented by the following formula S2-3 (hereinafter referred to as structural unit S2-). 3) is preferable.

In the formula, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R ²² represents an alkyl group having 1 to 3 carbon atoms,
R ²³ represents a hydrogen atom,
L ²⁰ represents an alkylene group having 1 to 12 carbon atoms,
Rf ¹ represents a C 3-6 perfluoroalkyl group,
R ²² may combine with L ²⁰ to form a ring,
L ²⁰¹ represents an alkylene group having 1 to 12 carbon atoms,
R ²⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
n2 represents an integer of 1 to 20, and when n2 is 2 to 20, the plurality of L ²⁰¹ may be the same or different.

In Formula S1-3 and Formula S2-3, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and preferably a hydrogen atom or a methyl group.

In formula S1-3, R ²² represents an alkyl group having 1 to 3 carbon atoms, and R ²³ represents a hydrogen atom. The number of carbon atoms of the alkyl group represented by R ²² is preferably 1 or 2, and more preferably 1.
R ²² may combine with L ²⁰ to form a ring. Examples of the ring formed by combining R ²² and L ²⁰ include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyranyl group.

In Formula S1-3, L ²⁰ represents an alkylene group having 1 to 12 carbon atoms. 1-12 are preferable, as for carbon number of an alkylene group, 1-10 are more preferable, and 1-6 are more preferable. The alkylene group is preferably linear or cyclic, and more preferably linear. The alkylene group may have one or more bonds selected from an ether bond, an ester bond, and an amide bond, and may not have these bonds. The alkylene group preferably does not have the aforementioned bond. Moreover, the alkylene group may be unsubstituted or may have a substituent. Unsubstituted is preferred.

In Formula S1-3, Rf ¹ represents a C 3-6 perfluoroalkyl group. 3-6 are preferable and, as for carbon number of a perfluoroalkyl group, 4-6 are still more preferable. The perfluoroalkyl group may be linear, branched or cyclic, and is preferably linear or cyclic, more preferably linear.

In Formula S2-3, the number of carbon atoms of the alkylene radical L ²⁰¹ represents the 1 to 12 preferably 1 to 6 is more preferable. Alkylene group L ²⁰¹ represents a linear, branched is preferred, branching it is more preferable. Number of branches of the alkylene group L ²⁰¹ represents the 1-2 is preferred, and more preferably 1. Alkylene group L ²⁰¹ represents is may have a substituent, unsubstituted is preferred.
In formula S2-3, the alkyl group represented by ^R201 preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. The alkyl group represented by ^R201 is preferably linear or branched, and more preferably linear. The alkyl group represented by ^R201 may have a substituent, but is preferably unsubstituted. R ²⁰¹ is preferably a hydrogen atom.

  In Formula S2-3, n2 represents an integer of 1-20. The lower limit is preferably 2 or more, and more preferably 3 or more. The upper limit is preferably 15 or less. In addition, although n2 represents the integer of 1-20, the photosensitive composition of this invention may contain multiple things in which n2 in the compound S differs. Therefore, the average value of n2 of the compound S contained in the photosensitive composition of the present invention may not be an integer. In the present invention, n2 in one compound S preferably represents an integer of 1 to 20.

In the present invention, the compound S may further have the structure S2-2-2 and / or the structure S2-2-3 in addition to the structural unit S1-3 and the structural unit S2-3. The other structural unit is preferably the structural unit S2-2-2. According to this aspect, the coatability and the adhesion with the upper layer can be improved.
1-20 mass% is preferable with respect to all the structural units of a polymer, as for content of structural unit S2-2-2, 1-15 mass% is more preferable, 1-10 mass% is still more preferable, 5% by mass is particularly preferred.
The content of the structural unit S2-2-3 is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and more preferably 1% by mass or less with respect to all the structural units of the polymer. Particularly preferred. Moreover, it is also preferable that a polymer does not contain structural unit S2-2-3 substantially. “Containing substantially no structural unit S2-2-3” means that the content of the structural unit S2-2-3 is preferably 0.5% by mass or less, based on all the structural units of the polymer. % Or less is more preferable, and it is more preferable not to contain the structural unit S2-2-3. According to this aspect, it is easy to obtain excellent coating properties.

In the present invention, when the compound S is a polymer, the weight average molecular weight of the compound S is preferably 100 to 100,000. The lower limit is preferably 300 or more, and more preferably 1000 or more. The upper limit is preferably 30000 or less, more preferably 10,000 or less, and particularly preferably 5000 or less. When the molecular weight of the compound S is in the above range, the coating property is good.
The dispersity (Mw / Mn) of the compound S is preferably 1.0 to 5.0, and more preferably 1.2 to 3.0.

Specific examples of compound S include, for example, the structures shown below and the structures shown in the examples described later. Hereinafter, R represents a hydrogen atom or a methyl group, n100 represents an integer of 1 to 20, and Rf ^b represents a linear or branched perfluoroalkyl group having 3 to 8 carbon atoms. n100 is preferably an integer of 2 to 20. Rf ^b is preferably a linear perfluoroalkyl group having 4 to 6 carbon atoms.

<Alkoxysilane compound>
The photosensitive composition of the present invention may further contain an alkoxysilane compound as a component other than the polysiloxane component A. The alkoxysilane compound is preferably a compound having an alkoxysilane structure and at least one selected from the group consisting of an epoxy group, an ethylenically unsaturated group, an alkyl group substituted with a chloro group, and a mercapto group. By mix | blending such a compound, while being able to improve a sensitivity more, adhesiveness with the board | substrate at the time of hardening of a photosensitive composition can further be improved. In the present invention, the alkoxysilane compound is a compound different from the polysiloxane component A.
The alkoxysilane compound may contain only 1 type and may contain 2 or more types.
The molecular weight of the alkoxysilane compound is not particularly defined, but is preferably less than 1000, more preferably 500 or less. The lower limit of the molecular weight of the alkoxysilane compound is not particularly defined, but is preferably 100 or more and more preferably 200 or more. The number of silicon atoms in one molecule is preferably 1 or 2, and more preferably 1.

Specific examples of the alkoxysilane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropyl dialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Can be mentioned.
Examples of commercially available products include KBM-403, KBM-5103, KBM-303, and KBM-803 manufactured by Shin-Etsu Silicone Co., Ltd.

  When the photosensitive composition of the present invention contains an alkoxysilane compound, the content of the alkoxysilane compound is preferably 0.05 to 10% by mass in the total solid content of the photosensitive composition. The lower limit is more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more. The upper limit is more preferably 8% by mass or less, and particularly preferably 6% by mass or less.

<Compound having a crosslinkable group>
The photosensitive composition of the present invention may contain a compound having a crosslinkable group (hereinafter also referred to as “crosslinking agent”). By containing a crosslinking agent, a harder cured film can be obtained. In the present invention, the molecular weight of the crosslinking agent is preferably 200 to 1,000.

  The crosslinking agent is not limited as long as a crosslinking reaction is caused by heat. Examples thereof include compounds having two or more epoxy groups or oxetanyl groups in the molecule, blocked isocyanate compounds, alkoxymethyl group-containing compounds, and compounds having an ethylenically unsaturated group. Compounds having two or more epoxy groups or oxetanyl groups in the molecule, blocked isocyanate compounds and alkoxymethyl group-containing compounds are preferred, and compounds having two or more epoxy groups or oxetanyl groups in the molecule and alkoxymethyl group-containing compounds are More preferred is a compound having two or more epoxy groups and / or oxetanyl groups in the molecule. When a compound having two or more epoxy groups and / or oxetanyl groups in the molecule is blended, a cured film particularly excellent in heat resistance is easily obtained. Details of the crosslinking agent are described in paragraphs 0138 to 0147 of JP2014-238438, paragraphs 0082 to 0104 of WO2015 / 087831, and paragraphs 0120 to 0144 of WO2015 / 087829. Reference may be made to the description, the contents of which are incorporated herein.

  Examples of compounds having two or more epoxy groups or oxetanyl 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 the like. Can do. These are available as commercial products. For example, compounds having two or more epoxy groups in the molecule include JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Corporation), paragraph number 0189 of JP2011-221494A. The commercial item of description etc. are mentioned.

Although there is no restriction | limiting in particular in a block isocyanate compound, It is preferable that it is a compound which has a 2 or more block isocyanate group in 1 molecule from a sclerosing | hardenable viewpoint.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably. Moreover, it is preferable that the said blocked isocyanate group is a group which can produce | generate an isocyanate group with the heat | fever of 90 to 250 degreeC.

  The skeleton of the blocked isocyanate compound is not particularly limited, and any skeleton may be used as long as it has two isocyanate groups in one molecule, and is an aliphatic, alicyclic or aromatic polyisocyanate. It may be. Regarding specific examples of the skeleton, the description in paragraph 0144 of JP2014-238438A can be referred to, and the contents thereof are incorporated in the present specification.

Examples of the matrix structure of the blocked isocyanate compound include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable. As a specific example of the blocking agent, description in paragraph 0146 of JP2014-238438A can be referred to, and the contents thereof are incorporated in the present specification.

  As the alkoxymethyl group-containing compound, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylolated urea to an alkoxymethyl group, respectively. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of outgas generation amount, A methyl group is particularly preferred. Among these compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are preferable compounds, and alkoxymethylated glycoluril is particularly preferable from the viewpoint of transparency.

  As the compound having an ethylenically unsaturated group, a compound containing a (meth) acryloyl group is preferable. Examples of the compound containing a (meth) acryloyl group include compounds selected from the group consisting of acrylic acid esters and methacrylic acid esters. The compound having an ethylenically unsaturated group is preferably a compound having 2 or more (meth) acryloyl groups in one molecule (bifunctional (meth) acrylate), and a compound having 3 or more (trifunctional or more (meth) acrylate) ) Is more preferable. 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.

  When the photosensitive composition of this invention contains a crosslinking agent, it is preferable that content of a crosslinking agent is 0.01-50 mass parts with respect to 100 mass parts of polysiloxane component A, 0.1-0.1 mass parts. The amount is more preferably 30 parts by mass, and further preferably 0.5 to 25 parts by mass. By adding in this range, a cured film having excellent mechanical strength and solvent resistance can be obtained. Only one type of crosslinking agent may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.

<Basic compound>
The photosensitive composition of the present invention may contain a basic compound. Examples of the basic compound 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 paragraph numbers 0204 to 0207 of JP2011-221494A, the contents of which are incorporated herein. Specifically, for example, triethylamine, triethanolamine, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, triphenylimidazole, 1,5-diazabicyclo [4.3.0] -5-nonene, 1, 8-diazabicyclo [5.3.0] -7-undecene, and the like. A basic compound may be used individually by 1 type, or may use 2 or more types together.

  When the photosensitive composition of this invention contains a basic compound, content of a basic compound may be 0.001-3 mass parts with respect to 100 mass parts of all the solid components in a photosensitive composition. Preferably, it is 0.005-1 mass part. A basic compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types, it is preferable that the total amount becomes the said range.

<Antioxidant>
The photosensitive 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. Incorporated herein.
Preferred commercial products include 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 (manufactured by ADEKA, Inc.), IRGA Nox 1035, Irganox 1098, Tinuvin 144 (manufactured by BASF) can be mentioned.
It is preferable that content of antioxidant is 0.1-10 mass% with respect to the total solid of a photosensitive composition, It is more preferable that it is 0.2-5 mass%, 0.5 It is especially preferable that it is -4 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.

<Other ingredients>
The photosensitive composition of the present invention contains a sensitizer (such as 9,10-dibutoxyanthracene), a thermal radical generator, a thermal acid generator, an acid multiplier, a development accelerator, and an ultraviolet absorber as necessary. Well-known additives such as thickeners, organic or inorganic suspending agents, and the like can be added individually or in combination of two or more. Moreover, trimellitic acid can also be used as an additive. Further, it may further contain a surfactant other than the compound S.
As these compounds, for example, compounds described in paragraph numbers 0201 to 0224 of JP2012-88459A and compounds described in JP2014-238438A can be used, and the contents thereof are described in the present specification. Incorporated into.
In addition, the thermal radical generator described in paragraph Nos. 0120 to 0121 of JP2012-8223A, the nitrogen-containing compound and the thermal acid generator described in WO2011 / 136604A1 can be used, and the contents thereof are described in this specification. Incorporated into.

<Method for preparing photosensitive composition>
The photosensitive composition of the present invention can be prepared by mixing the respective components in a predetermined ratio and by an arbitrary method, and stirring and dissolving. The prepared photosensitive composition can be used after being filtered using, for example, a filter having a pore diameter of 0.2 μm. The pore diameter of the filter can be appropriately adjusted according to the target purity and the like, and examples include 0.05 μm, 0.1 μm, 0.3 μm, and 0.5 μm in addition to 0.2 μm.

The photosensitive composition of this invention can adjust solid content concentration, a viscosity, and surface tension according to the objective.
In the case of slit coating, the solid content concentration of the photosensitive composition is preferably 2 to 40% by mass, more preferably 3 to 30% by mass, and still more preferably 4 to 20% by mass. The viscosity when slit coating is preferably 1 to 40 mPa · s, more preferably 2 to 25 mPa · s, and most preferably 3 to 20 mPa · s.
The surface tension of the photosensitive composition is preferably 10 to 100 mN / m, more preferably 15 to 80 mN / m, and most preferably 20 to 50 mN / m from the viewpoint of applicability. In the present invention, the viscosity is a value at 25 ° C.

<Storage method of photosensitive composition>
The photosensitive 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 composition of this invention on a board | substrate,
(2) a step of removing the solvent from the applied photosensitive composition;
(3) A step of exposing the photosensitive composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive composition with a developer;
(5) A step of thermosetting (post-baking) the developed photosensitive composition.
Each step will be described below in order.

  In the step (1), it is preferable to apply the photosensitive composition of the present invention on a substrate to form a wet film (photosensitive composition layer) containing a solvent.

In the step (1), before the photosensitive 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 an inorganic substrate, a resin substrate, and a resin composite material substrate.
Examples of the inorganic substrate include a glass substrate, a quartz substrate, a silicon substrate, a silicon nitride substrate, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
As the resin substrate, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, Fluorine resin such as polybenzazole, 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, Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound Plate, and the like. When a resin substrate is used, a so-called roll-to-roll process can be used.
These substrates are rarely used in the above-described form, and a multilayer laminated structure such as a thin film transistor (TFT) element may be formed depending on the form of the final product.

The size of the substrate is not particularly limited. Productivity, the area of the substrate from the viewpoint of coating property is preferably 10000 mm ² or more 10000000Mm ² or less. For example, a size of 300 mm × 400 mm square and a size of 1000 mm × 1100 mm can be exemplified.

The method for applying the photosensitive composition to the substrate is not particularly limited. For example, methods such as a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, and a slit and spin method can be used. .
In the case of the slit coating method, the relative moving speed between the substrate and the slit die is preferably 50 to 120 mm / sec. Slit coating is preferred because it can be efficiently applied to a large substrate and has excellent productivity. And large substrate refers to a substrate area of 300000Mm ² more 10000000Mm ² or less.
The wet film thickness when the photosensitive composition is applied is not particularly limited, and can be applied with a film thickness according to the application. For example, 0.5-10 micrometers is preferable.
Before applying the photosensitive 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 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. The film thickness of the dry film can be selected according to the application and is not particularly limited. From the viewpoint of ease of solvent removal, 0.01 to 20 μm is preferable, 0.1 to 10 μm is more preferable, and 0.1 to 5.0 μm is most preferable.

In the step (3), the substrate provided with the dry film is irradiated with actinic rays having a predetermined pattern. In this step, an acid group such as a carboxy group or a phenolic hydroxyl group or a silanol group is generated in the exposed area, and the solubility in the developer in the exposed area is improved. That is, upon irradiation with actinic rays, the photoacid generator is decomposed to generate an acid. And the acid-decomposable group contained in a coating-film component is hydrolyzed by the catalytic action of the generated acid, and an acid group is generated.
As a light source of actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generator, etc. can be used, i-line (365 nm), h-line (405 nm), Actinic rays having a wavelength of 300 nm or more and 450 nm or less such as g-line (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. In addition, exposure using a so-called super-resolution technique can 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, and an annular illumination method. By using these super-resolution techniques, it is possible to form a higher definition pattern, which is preferable.
In the region where the acid catalyst is generated, post-exposure heat treatment (PEB) can be performed in order to accelerate the hydrolysis reaction. PEB can promote the formation of a carboxy group and a phenolic hydroxyl group from an acid-decomposable group. 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 polymer having an acid group such as a free carboxy group or a phenolic hydroxyl group is developed using a developer. A positive image is formed by removing the exposed area, which is easily dissolved in the developer.
The developer used in the development step preferably contains an aqueous solution of a basic compound. Examples of the basic compound include compounds described in paragraph 0171 of International Publication No. 2015/0887829, such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetra Butylammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferred. 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 and a phenolic hydroxyl group, and crosslinked with a crosslinking group, a crosslinking agent, etc. A cured film can be formed. Also, a cured film can be formed by condensation reaction of silanol groups.
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 (post-exposure) with actinic rays and post-baked to generate acid from the photoacid generator present in the unexposed areas, thereby promoting crosslinking. It can function as a catalyst that promotes the film curing reaction. As a preferable exposure amount when the post-exposure step is included, 100 to 3,000 mJ / cm ² is preferable, and 100 to 500 mJ / cm ² is particularly preferable.

  The cured film obtained from the photosensitive composition of the present invention can be used as a permanent film, but can also be used as a dry etching resist.

<Curing film>
The cured film of the present invention is a cured film obtained by curing the above-described photosensitive composition of the present invention. The cured film of the present invention can be suitably used as an interlayer insulating film.
The cured film of the present invention is excellent in the adhesion of the upper layer. For this reason, after forming the cured film of a predetermined pattern on the substrate by the above-described methods (1) to (5), the photosensitive composition of the present invention is further applied on the cured film, and the above-mentioned ( It is suitable for forming a cured film having a predetermined pattern by being overlapped by the methods 1) to (5). Thus, a more complicated pattern (for example, pattern with an unevenness | corrugation) can be formed by laminating | stacking the photosensitive composition of this invention and forming a pattern. In addition, the process of (1)-(5) can be repeated 3 times or more, and a more complicated pattern can also be formed.
By forming the interlayer insulating film with such a laminated structure, it is possible to achieve an improvement in aperture ratio, various functions and the like.

<Liquid crystal display device and manufacturing method thereof>
The liquid crystal display device of the present invention has the cured film of the present invention. Moreover, the manufacturing method of the liquid crystal display device of this invention includes the manufacturing method of the cured film of this invention.
The liquid crystal 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 composition of the present invention, and known liquid crystal display devices having various structures are used. Can be mentioned.
For example, specific examples of TFT (thin film transistor) included in the liquid crystal display device of the present invention include amorphous silicon, low-temperature polysilicon, and oxide semiconductor. As the oxide semiconductor, so-called IGZO (a semiconductor composed of indium, gallium, zinc, and oxygen) can be exemplified. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs. Regarding the liquid crystal display device, the description in paragraph 00196 of International Publication No. 2015/0887829 can be referred to, and the contents thereof are incorporated in the present specification.

Moreover, the liquid crystal display device shown in FIG. FIG. 1 shows a liquid crystal display device described in FIG. 1 of JP-A-2007-328210.
In FIG. 1, reference numeral SUB1 is a glass substrate, and has a plurality of scanning signal lines and a plurality of video signal lines intersecting with the plurality of scanning signal lines. In the vicinity of each intersection, a TFT (thin film transistor) is provided.
On the glass substrate SUB1, a base film UC, a semiconductor film PS, 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 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.
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 composition of the present invention.
The details of the liquid crystal display device shown in FIG. 1 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 and manufacturing method thereof>
The organic electroluminescence (organic EL) display device of the present invention has the cured film of the present invention. The method for producing an organic EL display device of the present invention includes the method for producing a 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 composition of the present invention, and known organic EL displays having various structures. An apparatus can be mentioned. Regarding the organic EL display device, the description in paragraph 00197 of International Publication No. 2015/0887829 can be referred to, and the contents thereof are incorporated in this specification.
As another aspect of the organic EL display device, the pixel separation film (19) and the planarization film (17) described in FIG. 1 of JP2012-203121A are formed using the photosensitive composition of the present invention. Can do. In addition, the high resistance layer (18), the inter-pixel insulating film (16), the interlayer insulating film (14), and the interlayer insulating film (12c) described in FIG. It can be formed using an object.

  The photosensitive composition of the present invention can also be used for forming barrier ribs of MEMS (Micro Electro Mechanical Systems) devices. Examples of the MEMS device include parts such as a SAW (Surface Acoustic Wave) filter, a BAW (Bulk Acoustic Wave) filter, a gyro sensor, a micro shutter for display, an image sensor, an electronic paper, an inkjet head, a biochip, and a sealant. It is done. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

  The photosensitive composition of the present invention includes, for example, a bank layer (16) and a planarizing film (57) described in FIG. 2 of JP2011-107476A, and FIG. 4 (A) of JP2010-9793A. The partition wall (12) and the planarization film (102) described, the bank layer (221) and the third interlayer insulating film (216b) described in FIG. 10 of JP 2010-27591 A, and JP 2009-128577 A The second interlayer insulating film (125) and the third interlayer insulating film (126) shown in FIG. 4A, the planarizing film (12) and the pixel isolation insulating film shown in FIG. 3 of JP 2010-182638 A It can also be used to form (14) and the like. 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, touch panel display device and manufacturing method thereof>
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 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. Moreover, the manufacturing method of the touchscreen of this invention and a touchscreen display device contains the manufacturing method of the cured film of this invention.
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. In addition, the touch panel display device of the present invention may be a touch panel display device in which all or part of the insulating layer and / or protective layer of the touch panel or display device is made of a cured product of the photosensitive composition of the present invention.
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-T-2012-517051), a so-called on-cell type (for example, Japanese Patent Laid-Open No. 2013-168125) 19), OGS (One Glass Solution) type, TOL (Touch on Lens) type, and other configurations (for example, FIG. 6 of JP2013-164871A, FIG. 1 of WO2013 / 141066, and Patent No. 56737882) 2) and various out-cell types (so-called GG method, G1 method / G2 method, GFF method, GF2 method, GF1 method, G1F method, etc.).
As the touch panel, the description in paragraphs 0288 to 0296 of JP-A-2015-103102 and FIGS. 7 to 9 can be referred to, and the contents thereof are incorporated in the present specification.

  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.

FIG. 2 is a conceptual diagram illustrating an example of a liquid crystal display device having a touch panel function.
The cured film of the present invention is preferably applied to the protective film between the layers in FIG. 2, and is also preferably applied to an interlayer insulating film that separates the detection electrodes of the touch panel. As the detection electrode of the touch panel, transparent electrodes (ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), etc.) and metal electrodes (silver, copper, molybdenum, titanium, aluminum, etc., and their laminates and alloys Etc.) or a laminate of these.
2, 110 denotes a pixel substrate, 140 denotes a liquid crystal layer, 120 denotes a counter substrate, and 130 denotes a sensor unit. The pixel substrate 110 includes a polarizing plate 111, a transparent substrate 112, a common electrode 113, an insulating layer 114, a pixel electrode 115, and an alignment film 116 in order from the lower side of FIG. The counter substrate 120 includes an alignment film 121, a color filter 122, and a transparent substrate 123 in order from the lower side of FIG. The sensor unit 130 includes a retardation film 124, an adhesive layer 126, and a polarizing plate 127. In FIG. 2, reference numeral 125 denotes a sensor detection electrode. The cured film of the present invention includes an insulating layer (114) (also referred to as an interlayer insulating film) in the pixel substrate portion, various protective films (not shown), various protective films (not shown) in the pixel substrate portion, and a counter substrate portion. Can be used for various protective films (not shown), various protective films (not shown) for the sensor portion, and the like.

  In addition, a statically driven liquid crystal display device can display a pattern with high designability 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 No. 2001-125086.

  FIG. 3 is a conceptual diagram of the configuration of another example of a liquid crystal display device having a touch panel function. A lower display panel 200 corresponding to a thin film transistor panel provided with a thin film transistor (TFT) 440, and a color filter display panel provided with a plurality of color filters 330 on the surface facing the lower display panel 200 and facing the lower display panel 200. And the liquid crystal layer 400 formed between the lower display panel 200 and the upper display panel 300. The liquid crystal layer 400 includes liquid crystal molecules (not shown).

  The lower display panel 200 is disposed on the first insulating substrate 210, the thin film transistor (TFT) disposed on the first insulating substrate 210, the insulating film 280 formed on the upper surface of the thin film transistor (TFT), and the insulating film 280. A pixel electrode 290 is included. The thin film transistor (TFT) may include a gate electrode 220, a gate insulating film 240 covering the gate electrode 220, a semiconductor layer 250, ohmic contact layers 260 and 262, a source electrode 270, and a drain electrode 272. A contact hole 282 is formed in the insulating film 280 so that the drain electrode 272 of the thin film transistor (TFT) is exposed.

  The upper display panel 300 is disposed on one surface of the second insulating substrate 310, and the light shielding members 320 arranged in a matrix, the color filter 330 disposed on the second insulating substrate 310, the light shielding members 320, and An alignment film 350 disposed on the color filter 330 and a common electrode 370 disposed on the alignment film 350 and applying a voltage to the liquid crystal layer 400 corresponding to the pixel electrode 290 of the lower display panel 200 are included.

  In the liquid crystal display device illustrated in FIG. 3, the touch sensing electrode 410, the insulating film 420, the touch driving electrode 430, and the protective film 600 are disposed on the other surface of the second insulating substrate 310. In the liquid crystal display device, when the upper display panel 300 is formed, the sensing electrode 410, the insulating film 420, the touch drive electrode 430, and the like, which are components of the touch screen, can be formed together.

  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. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass. NMR is an abbreviation for nuclear magnetic resonance.

<Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn)>
Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions.
Column type: TSK gel Super (Tosoh)
Developing solvent: Tetrahydrofuran Column temperature: 40 ° C
Flow rate (sample injection volume): 10 μl
Device name: HLC-8220GPC (Tosoh)
Calibration curve base resin: polystyrene

<Synthesis example of polysiloxane>
(Synthesis of A1-1) Synthesis of polysiloxane having a carboxyl group protected by an acid-decomposable group and an epoxy group 3-Trichlorosilyl-1-cyclohexylcarboxylic acid methyl ester 12.4 g (0.045 mol), 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 obtained 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 protected with a tetrahydrofuranyl group, a carboxy group, an epoxy group, a methyl group, and a phenyl group in side chains.
Analysis by 1H-NMR revealed that 78 mol% of the carboxy group was tetrahydrofuranylated in A1-1.
The kind and molar ratio of the silane compound 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 4-hydroxybenzyltrimethoxysilane 114.2 g (0.5 mol), 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% by mass 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 prepared by dissolving 30 g of ethyl vinyl ether 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.
^{In the} analysis by ¹ H-NMR, it was confirmed that in A1-2, 70 mol% of the hydrogen atoms of the phenolic hydroxyl group were ethoxyethylated.
The kind and molar ratio of the silane compound 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 mol / L 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 normal temperature, 300 g of methyl isobutyl ketone and 250 mL of 0.01 mol / L 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 silanol groups were acetal protected.
^{In the} analysis by ¹ H-NMR, it was confirmed that in A1-4, 32.5 mol% of the silanol group was acetalized.

(Synthesis of A1-4) 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 type and amount of the protecting group are determined. Except for the adjustment, the following silane compounds were mixed and reacted in the same manner as A1-1, and a protective group was introduced by a polymer reaction to synthesize A1-4.
^{In the} analysis by ¹ H-NMR, it was 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 ratios, and the protective group is changed to an ethoxyethyl group. In the same manner as in A1-1 except that the amount was adjusted, the following silane compounds were mixed and reacted, a protective group was introduced by a polymer reaction, and A1-5 was synthesized.
^{In the} analysis by ¹ H-NMR, it was 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 by mixing and reacting the following silane compounds in the same manner as A1-1, introducing a protecting group by polymer reaction.
^The analysis by ¹ H-NMR confirmed that 82 mol% of the carboxy group was tetrahydrofuranylated in A1-5.

(Synthesis of A1-7) Synthesis of polysiloxane having a carboxyl group protected with an acid-decomposable group and an epoxy group 100 parts by mass of propylene glycol monomethyl ether was charged into a vessel equipped with a stirrer, 1.36 parts by mass of methoxysilane, 1.98 parts by mass of phenyltrimethoxysilane, 10.4 parts by mass of 3-trimethoxysilylpropyl succinic anhydride, and 9.9 parts of glycidoxypropyltrimethoxysilane. 44 parts by mass were charged and heated until the solution temperature reached 60 ° C.
After the solution temperature reached 60 ° C., 0.1 part by mass of phosphoric acid and 9 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 2 hours. After cooling to 45 ° C., 20 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, an A1-7 precursor was obtained. The A1-7 precursor had a weight average molecular weight (Mw) of 4000 and a dispersity (Mw / Mn (number average molecular weight)) of 2.0.
As a result of FT-IR (Fourier transform infrared spectroscopy) analysis of the A1-7 precursor, a broad absorption band due to OH groups derived from carboxyl groups in the vicinity of 2500 cm- ^{1 to} 3000 cm ⁻¹ was confirmed. -It confirmed that the succinic acid residue derived from trimethoxysilylpropyl succinic acid hydrolyzed and had a carboxyl group.

Next, 40 parts by mass of ethyl vinyl ether was added to the obtained A1-7 precursor solution, and the mixture was stirred at room temperature for 3 hours. A1-7 was obtained by reprecipitation, filtration, and drying. ^{In the} analysis by ¹ H-NMR, it was confirmed that about 60 mol% of the carboxy group was tetrahydrofuranylated in A1-7.

(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 in -1, the following silane compound was 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 to the A2-1 precursor by a polymer reaction. ^{In the} analysis by ¹ H-NMR, it was confirmed that 90 mol% of the carboxy group was tetrahydrofuranylated in A2-1. 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 kind and amount of the protective 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. ^{In the} analysis by ¹ H-NMR, it was confirmed that in A2-2, 85 mol% of the hydrogen atoms of the phenolic hydroxyl group were ethoxyethylated. 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 mol / L methanesulfonic 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 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 lower 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 0.01 mol / L 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.
^{In the} analysis by ¹ H-NMR, it was confirmed that 61.5 mol% of the silanol group was acetalized in A2-3.

(A2-4 synthesis) Synthesis of polysiloxane having a carboxy group protected with an acid-decomposable group Using a silane compound in the following compounds and molar ratio, the amount is adjusted by changing the protecting group to an ethoxyethyl group. A2-4 was synthesized in the same manner as A1-1 except that the following silane compounds were mixed and reacted and a protective group was introduced by a polymer reaction. ^{In the} 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 A1-1 was conducted except that a protective reaction with dihydrofuran was not performed. The following silane compounds were mixed, reacted, and deethylated 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 As in 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 Similar to A1-1 except that a silane compound is used in the following compounds and molar ratio and no protective group is introduced. 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.

<Synthesis Example of Compound S>
(Synthesis of S-1)
In a four-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet, methacrylic acid 56.0 g (0.65 mol), sulfuric acid 0.13 g, and toluene 111 g were placed. While maintaining the liquid temperature at 23 ° C. in a nitrogen atmosphere and stirring, 50.7 g (0.13 mol) of 2- (perfluorohexyl) ethyl vinyl ether (CHEMINOX FAVE-6, manufactured by Unimatec Co., Ltd., the following structure (A)) ) Was added over 2 hours, and after completion of the addition, the mixture was further stirred for 4.5 hours. The reaction solution was added to 345 g of a 10% by mass sodium carbonate aqueous solution and stirred. The organic layer was separated, washed 3 times with 110 g of 10% by weight aqueous sodium carbonate solution and twice with 112 g of pure water, and then concentrated under reduced pressure. The concentrated liquid was further purified by distillation under reduced pressure to obtain 2- (perfluorohexyl) ethyl methacrylate (the following structure (B)).
Next, 33 g of diethylene glycol ethyl methyl ether (MEDG) was introduced into a separable flask equipped with a stirrer, a thermometer, a dropping funnel and a nitrogen introducing tube, and the temperature was raised to 65 ° C.
Next, 2.0 g of 2- (perfluorohexyl) ethyl methacrylate (the following structure (B)), 8.0 g of hexabutylene glycol methacrylate (the following structure (C)), and 2,2′-azobis (2 , 4-dimethylvaleronitrile) (trade name “V-65”, manufactured by Wako Pure Chemical Industries, Ltd.) and a solution obtained by mixing 68 g of MEDG with a separable that was heated to 65 ° C. The solution was dropped into the flask over 6 hours. After dropping, the mixture was aged for 2 hours.
The obtained reaction solution was dropped into 700 g of heptane, and the precipitated polymer was recovered with Nutsche.
The obtained polymer was dried under reduced pressure to obtain the target S-1. The weight average molecular weight (Mw) of S-1 was 1900, and dispersity (Mw / Mn) was 1.74.

(Synthesis of S-2 to S-33)
S-2 to S-33 were synthesized in the same manner as S-1 except that the raw materials were appropriately changed so that the polymers described in the following table were formed.

<Preparation of photosensitive composition>
The materials shown in the following table are mixed, stirred and dissolved to form a solution, filtered through a polyethylene filter having a pore size of 0.4 μm, and further filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm to obtain a photosensitive composition. Obtained. The numerical value which does not attach | subject the unit in particular in a table | surface is a mass part.
Polysiloxane was added so that the solid content would be the amount shown in the table. That is, when it was obtained as a solid, the solid content was added in the amount shown in the table, and when it was obtained as a solution, the solution was added so that the solid content was the amount shown in the table.

The details of the abbreviations indicating the compounds used in Examples and Comparative Examples are as follows.
(Polysiloxane)
The above A1-1 to A1-6, A2-1 to A2-4, and A3-1 to A3-3 were used.
(Compound S)
S-1 to S-33 shown above were used.

Ｂ−２：下記に示す構造（ＰＡＩ−１０１、みどり化学（株）製、ｐＫａ３以下の酸を発生する光酸発生剤）、Ｍｅはメチル基を表す。

Ｂ−３：下記に示す構造（ｐＫａ３以下の酸を発生する光酸発生剤）

Ｂ−４：下記に示す構造（Ｔｓはトシル基を表す、ｐＫａ３以下の酸を発生する光酸発生剤）

Ｂ−５：下記に示す構造（ｐＫａ３以下の酸を発生する光酸発生剤）

Ｂ−６：下記に示す構造（ＧＳＩＤ−２６−１、トリアリールスルホニウム塩（ＢＡＳＦ製）、ｐＫａ３以下の酸を発生する光酸発生剤）

(Photoacid generator)
B-1: Structure shown below (PAG-103, manufactured by BASF, photoacid generator that generates acid of pKa3 or less)

B-2: Structure shown below (PAI-101, manufactured by Midori Kagaku Co., Ltd., a photoacid generator that generates an acid of pKa3 or less), Me represents a methyl group.

B-3: Structure shown below (a photoacid generator that generates an acid having a pKa of 3 or less)

B-4: Structure shown below (Ts represents a tosyl group, a photoacid generator that generates an acid having a pKa of 3 or less)

B-5: Structure shown below (photoacid generator that generates an acid having a pKa of 3 or less)

B-6: Structure shown below (GSID-26-1, triarylsulfonium salt (manufactured by BASF), photoacid generator that generates an acid of pKa3 or less)

(solvent)
C-1: Diethylene glycol ethyl methyl ether C-2: Propylene glycol monomethyl ether acetate C-3: γ-butyrolactone C-4: 1, 3-butylene glycol diacrylate

(Basic compound)
DBU: 1,8-diazabicyclo [5.4.0] undec-7-ene TPI: triphenylimidazole

(Alkoxysilane compound)
KBM-403: KBM-403, Shin-Etsu Silicone Co., Ltd. KBM-303: KBM-303, Shin-Etsu Silicone Co., Ltd. KBE-403: KBE-403, Shin-Etsu Silicone Co., Ltd. KBM-5103: KBM-5103, Made by Shin-Etsu Silicone Co., Ltd.

Ｓ’−２：下記構造（構成単位Ｓ’−２−１：構成単位Ｓ’−２−２＝２０：８０（質量比）、Ｍｗ＝２６００）

(Other ingredients)
DPHA: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., cross-linking agent)
JER: JER157S60 (Mitsubishi Chemical Corporation, cross-linking agent)
AO-60: ADK STAB AO-60 (manufactured by ADEKA)
TA: trimellitic acid DBA: 9,10-dibutoxyanthracene S′-1: the following structure (structural unit S′-1-1: structural unit S′-1-2 = 20: 80 (mass ratio), Mw = 2600)

S′-2: The following structure (structural unit S′-2-1: structural unit S′-2-2 = 20: 80 (mass ratio), Mw = 2600)

<Evaluation>
(Applicability)
Each photosensitive composition was applied at a coating speed of 100 mm / sec on a 1,500 mm × 1,800 mm Cr vapor-deposited glass substrate (glass is EAGLE2000, Corning) treated with HMDS (hexamethyldisilazane) using a slit die. The coating was applied so as to have a dry film thickness of 2.0 μm while adjusting the coating flow rate under the condition of a gap of 100 μm, and vacuum-dried in a vacuum drying chamber so that the ultimate vacuum was 0.05 kPa (0.4 Torr). The dried substrate was dried on a hot plate at 95 ° C. for 120 seconds, and then observed in the dark using a Na lamp, white lamp and green lamp, and coating streaks and drying unevenness were evaluated according to the following criteria. .
1-4 is a practical range.
1: There are no coating stripes and coating unevenness.
2: There are no coating stripes, but there is slight coating unevenness.
3: There are a few coating stripes only at the periphery of the substrate, and there are slight coating unevenness.
4: There are a few coating stripes at the center of the substrate, and there are slight coating unevenness.
5: There are coating stripes and / or coating unevenness on the entire surface of the substrate.

(Adhesion with upper layer)
The substrate produced in the same manner as in the applicability evaluation was covered with a 21% aqueous solution of FHD-5 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) and allowed to stand for 60 seconds. After standing still, pure water was sprayed in the form of a shower to wash away the developer and then air dried. Further, the dried substrate was heated at 230 ° C. for 60 minutes, and then cut into a size of 100 mm × 100 mm. Using the ITO (Indium Tin Oxide) sputtering apparatus SME-200E manufactured by ULVAC, Inc., the substrate having become a small piece was formed into an ITO film at a sputtering temperature of 23 ° C. and a film thickness of 50 nm, and 220 ° C. for 30 minutes. Heated. On the obtained substrate with ITO, a cross-cut test was carried out with a score of 2 mm in accordance with JIS K5600-5-6: 1999 to evaluate the adhesion of ITO. 1-4 is a practical range.
1: Total area of ITO film peeled off from cured film surface is less than 3% 2: Total area of ITO film peeled off from cured film surface is 3% or more and less than 8% 3: Total area of ITO film peeled off from cured film surface 8% or more and less than 15% 4: Total area of ITO film peeled off from cured film surface is 15% or more and less than 25% 5: Total area of ITO film peeled off from cured film surface is 25% or more

<Heat resistance>
The substrate produced in the same manner as in the applicability evaluation was covered with a 21% by weight aqueous solution (developer) of FHD-5 (manufactured by FUJIFILM Electronics Materials) and left still for 60 seconds. After standing still, pure water was sprayed in the form of a shower to wash away the developer and then air dried. Further, the substrate was heat-treated at 230 ° C. for 60 minutes in a nitrogen atmosphere, and the thickness (t0) of the cured film was measured. Further, as a heat resistance test, the obtained cured film was heated in an oven at 320 ° C. for 60 minutes in a nitrogen atmosphere. The thickness (t1) of the cured film after heating was measured. The film thickness change rate before and after the heat test was calculated from the following formula. A and B are practical ranges in the following evaluation criteria.
Film thickness change rate (%) = (| t0−t1 | / t0) × 100
A: Film thickness change rate of less than 5% B: Film thickness change rate of 5% or more and less than 10% C: Film thickness change rate of 10% or more

<Pattern formability>
About the photosensitive composition of each Example, the board | substrate produced similarly to applicability | paintability evaluation exposed 6 micrometer hole pattern using MPA-7800 + (made by Canon Inc.). Subsequently, it was covered with a 21% by mass aqueous solution (developer) of FHD-5 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) and allowed to stand at 23 ° C. for 60 seconds. After standing still, pure water was sprayed in the form of a shower to wash away the developer and let it air dry. The dried substrate was heated at 230 ° C. for 60 minutes, and the pattern shape was observed with an optical microscope (300 times magnification) and a scanning electron microscope (SEM) (5000 times magnification). It was confirmed that there was no residue and good resolution and a clean hole pattern shape. In addition, the exposure amount with respect to each photosensitive composition was calculated | required with the following method.
About each photosensitive composition, the board | substrate produced similarly to applicability | paintability evaluation was exposed through the mask which has a hole pattern of 6 micrometers using Canon Inc. MPA 5500CF (high pressure mercury lamp). The exposed photosensitive composition was developed with a 21% by weight aqueous solution (developer) of FHD-5 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) at 23 ° C. for 60 seconds, and then treated with ultrapure water. Rinse second. By these operations, the optimum i-line exposure amount (Eopt) when resolving a 6 μm hole was determined and used as the exposure amount.

As shown in the above table, the examples had good coating properties, and the obtained cured films were excellent in adhesion to the upper layer. Furthermore, the heat resistance and pattern formation were also excellent.
On the other hand, the comparative example was inferior in at least one of applicability | paintability and adhesiveness with an upper layer.

<Production of display device>
(Example 1001)
1 except that the pixel separation film (19) and the planarization film (17) were produced using the photosensitive composition of Example 1 in the display device shown in FIG. It produced according to 2012-203121 gazette. The display device was excellent in display characteristics.
(Examples 1002 to 1098)
In Example 1001, a display device was produced in the same manner as in Example 1001, except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Examples 2 to 98. The display device was excellent in display characteristics.

(Example 2001)
1 except that the interpixel insulating film (16) and the interlayer insulating film (14) were produced using the photosensitive composition of Example 1 in the display device shown in FIG. 1 of JP2013-196919A. It produced according to 2013-196919 gazette. The display device was excellent in display characteristics.
(Examples 2002 to 2098)
In Example 2001, a display device was produced in the same manner as in Example 2001 except that the photosensitive composition of Example 1 was replaced with the photosensitive composition of Examples 2 to 98. The display device was excellent in display characteristics.

(Example 3001)
The liquid crystal display device shown in FIG. 1 of JP-A-2007-328210 was prepared according to JP-A-2007-328210 except that the organic insulating film PAS was prepared using the photosensitive composition of Example 1. . The display device was excellent in display characteristics.
(Examples 3002 to 3098)
A display device was produced in the same manner as in Example 3001, except that in Example 3001, the photosensitive composition of Example 1 was replaced with the photosensitive composition of Examples 2 to 98. The display device was excellent in display characteristics.

  110: pixel substrate, 111: polarizing plate, 112: transparent substrate, 113: common electrode, 114: insulating layer, 115: pixel electrode, 116: alignment film, 120: counter substrate, 121: alignment film, 122: color filter, 123: Transparent substrate, 124: Retardation film, 126: Adhesive layer, 127: Polarizing plate, 130: Sensor part, 200: Lower display panel, 210: Insulating substrate, 220: Gate electrode, 240: Gate insulating film, 250: Semiconductor layer, 260: ohmic contact layer, 270: source electrode, 272: drain electrode, 280: insulating film, 282: contact hole, 290: pixel electrode, 300: upper display panel, 310: insulating substrate, 320: light shielding member, 330: Color filter, 350: Alignment film, 370: Common electrode, 400: Liquid crystal layer, 410: Sensing electrode, 420 Insulating film, 430: touch drive electrode, 600: protective film, 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 insulating film, PS: semiconductor film, PX: pixel electrode, RAL: reflective film, SD1: drain electrode, SD2: source electrode, SUB1: glass substrate, UC: base film

Claims (14)

Polysiloxane component A satisfying at least one of the following 1 and 2,
1: at least one 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 containing a polysiloxane having a structural unit a1 having a group and a structural unit a2 having a crosslinkable group;
2: At least one 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 a1 having a group and a polysiloxane having a structural unit a2 having a crosslinkable group;
a photoacid generator B that generates an acid having a pKa of 3 or less,
Solvent C, and
Compound S having a structure represented by the following formula S1 and a structure represented by the following formula S2,
A photosensitive composition comprising:

In the formula, the wavy line represents the bonding position with the atomic group constituting the compound S,
R ¹ represents an alkyl group,
R ² represents a hydrogen atom or an alkyl group,
L ¹ represents a single bond or a divalent linking group, and when L ¹ represents a divalent linking group, R ¹ may combine with L ¹ to form a ring,
Rf represents a fluoroalkyl group having 3 or more fluorine atoms,
L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group,
R ¹⁰⁰ represents a hydrogen atom, a hydroxy group or an alkyl group having 1 to 12 carbon atoms,
n represents an integer of 0 to 30,
when n is 0, R ¹⁰⁰ represents a hydroxy group;
When n is 1, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms or a carbonyl group, R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
When n is 2 to 30, L ¹⁰⁰ represents an alkylene group having 1 to 12 carbon atoms, R ¹⁰⁰ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and a plurality of L ¹⁰⁰ may be the same. Well, it can be different.   The photosensitive composition of Claim 1 which contains 0.001-20 mass parts of said compounds S with respect to 100 mass parts of the said polysiloxane component A. 3.   The compound S is a polymer having a structural unit S1-1 having a structure represented by the formula S1 in a side chain and a structural unit S2-1 having a structure represented by the formula S2 in a side chain. The photosensitive composition of Claim 1 or 2. 4. The compound S according to claim 1, wherein the compound S is a polymer having a structural unit represented by the following formula S1-2 and a structural unit represented by the following formula S2-2. A photosensitive composition;

In the formula, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R ¹² represents an alkyl group,
R ¹³ represents a hydrogen atom or an alkyl group,
L ¹⁰ represents a single bond or a divalent linking group, and when L ¹⁰ represents a divalent linking group, R ¹² may combine with L ¹⁰ to form a ring,
Rf represents a fluoroalkyl group having 3 or more fluorine atoms,
L ¹⁰¹ represents an alkylene group having 1 to 12 carbon atoms,
R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
n1 represents an integer of 0 to 30,
when n1 is 0 or 1, R ¹⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
When n1 is 2 to 30, the plurality of L ¹⁰¹ may be the same or different. 5. The compound S according to claim 1, wherein the compound S is a polymer having a structural unit represented by the following formula S1-3 and a structural unit represented by the following formula S2-3. A photosensitive composition;

In the formula, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R ²² represents an alkyl group having 1 to 3 carbon atoms,
R ²³ represents a hydrogen atom,
L ²⁰ represents an alkylene group having 1 to 12 carbon atoms,
Rf ¹ represents a C 3-6 perfluoroalkyl group,
R ²² may combine with L ²⁰ to form a ring,
L ²⁰¹ represents an alkylene group having 1 to 12 carbon atoms,
R ²⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
n2 represents an integer of 1 to 20, and when n2 is 2 to 20, the plurality of L ²⁰¹ may be the same or different.   The compound S is a polymer containing the structural unit S1-1 and the structural unit S2-1 in an amount of 70% by mass or more of the total structural units of the compound S, and the structural unit S1-1. 6. The photosensitive composition according to claim 3, wherein a mass ratio with the structural unit S2-1 is the structural unit S1-1: the structural unit S2-1 = 5: 95 to 95: 5. object.   The photosensitive composition of any one of Claims 1-6 whose weight average molecular weights of the said compound S are 100-100000. The structural unit a1 is at least one selected from structural units represented by the following general formula a1-1 and structural units represented by the following general formula a1-2. 2. The photosensitive composition according to item 1;

In general formula a1-1 and general formula a1-2, a represents 0 or 1,
R ^1A and R ^2A each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ^1A and R ^2A represents an alkyl group or an aryl group, and R ^3A represents an alkyl group or an aryl group. R ^1A or R ^2A and R ^3A may be linked to form a cyclic ether,
R ^4A represents an alkyl group, an aryl group, or an aralkyl group,
L ^1A represents a single bond or a divalent linking group,
L ^2A 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 composition of any one of Claims 1-8 whose crosslinkable group which the said polysiloxane component has is at least 1 sort (s) chosen from cyclic ether and the group which has an ethylenically unsaturated bond. .   The photosensitive composition according to claim 1, wherein the polysiloxane further includes a structural unit having at least one group selected from a carboxy group and a phenolic hydroxyl group. The process of apply | coating the photosensitive composition of any one of Claims 1-10 on a board | substrate,
Removing the solvent from the applied photosensitive composition;
Exposing the photosensitive composition from which the solvent has been removed with actinic rays,
Developing the exposed photosensitive composition with a developer; and
Heat-curing the developed photosensitive composition;
The manufacturing method of the cured film containing this.   A method for producing a liquid crystal display device, comprising the method for producing a cured film according to claim 11.   The manufacturing method of an organic electroluminescent display apparatus containing the manufacturing method of the cured film of Claim 11.   The manufacturing method of a touch panel including the manufacturing method of the cured film of Claim 11.

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