JP6400540B2 - Photosensitive composition, method for producing cured film, method for producing liquid crystal display device, method for producing organic electroluminescence display device, and method for producing touch panel - Google Patents

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 device (see Patent Documents 1 to 5).

  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. Polybenzoxazole and polyimide are known as materials having high heat resistance. Attempts have been made to form various fine patterns using a photosensitive composition containing a polybenzoxazole precursor or a polyimide precursor (Patent Document 6).

JP 2011-215596 A JP 2013-57836 A Japanese Patent Laying-Open No. 2015-72455 JP 2008-275949 A JP 2008-274070 A International Publication No. 2015/088781

  The photosensitive composition often uses a surfactant in order to improve the coating property. Also in patent document 1, in order to improve applicability | paintability, the fluorine-type surfactant is used. 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 2-5, it turned out that the applicability | paintability of a photosensitive composition and adhesiveness with the upper layer of a cured film cannot be made compatible. It was.

  Accordingly, an object of the present invention is to provide a photosensitive composition that can produce a cured film having good coating properties and excellent adhesion to an upper layer. 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.

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 properties and excellent adhesion to the upper layer can be produced without going through a process such as ashing, and the present invention has been completed. That is, the present invention provides the following.
<1> A polymer A having a structural unit represented by the following formula A, a photoacid generator that generates an acid having a pKa of 3 or less, a solvent, a structure represented by the following formula S1, and a formula represented by the following formula S2. A photosensitive composition comprising Compound S having the structure:
Formula A
In formula A, X ¹ and Y ¹ each independently represents a divalent or tetravalent organic group having 2 to 60 carbon atoms;
R ^A1 and R ^A2 each independently represent a hydrogen atom, an alkyl group or an acid-decomposable group;
m represents 0 or 2, n represents 0 or 2, m + n represents 2;
when m is 2, two R ^A2 may be the same or different and at least one represents an acid-decomposable group;
when n is 2, two R ^A1 may be the same or different and at least one represents an acid-decomposable group;
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 polymer 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 polymer A according to any one of <1> to <7>, wherein the polymer A is a polymer having a structural unit represented by the following formula A1;
Formula A1
In the formula, X ² represents a divalent organic group having 2 to 60 carbon atoms,
Y ² represents a tetravalent organic group having 2 to 60 carbon atoms,
R ^A1 independently represents a hydrogen atom, an alkyl group, or an acid-decomposable group, and represents at least one acid-decomposable group.
<9> The polymer A according to any one of <1> to <7>, wherein the polymer A is a polymer having a structural unit represented by the following formula A2;
Formula A2
In the formula, X ³ represents a tetravalent organic group having 2 to 60 carbon atoms,
Y ³ represents a divalent organic group having 2 to 60 carbon atoms,
R ^A2 independently represents a hydrogen atom, an alkyl group, or an acid-decomposable group, and represents at least one acid-decomposable group.
<10> The process of apply | coating the photosensitive composition in any one of <1>-<9> on a base material,
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.
<11> A method for manufacturing a liquid crystal display device, including the method for manufacturing a cured film according to <10>.
<12> A method for producing an organic electroluminescence display device, comprising the method for producing a cured film according to <10>.
<13> A method for manufacturing a touch panel, including the method for manufacturing a cured film according to <10>.

  It has become possible to provide a photosensitive composition that can produce a cured film having good coating properties and excellent adhesion to an upper layer without undergoing 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 comprises a polymer A described later, a photoacid generator that generates an acid having a pKa of 3 or less, a solvent, a structure represented by formula S1, and a structure represented by formula S2. And having a compound S.

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 passing 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 is excellent in hydrophobicity, and the structure represented by the formula S2 is excellent in hydrophilicity because it has a hydrophilic group. 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 the 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 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.

<Polymer A>
The photosensitive composition of this invention contains the polymer A which has a structural unit represented by the following formula A.
Formula A
In formula A, X ¹ and Y ¹ each independently represents a divalent or tetravalent organic group having 2 to 60 carbon atoms.
R ^A1 and R ^A2 each independently represent a hydrogen atom, an alkyl group, or an acid-decomposable group.
m represents 0 or 2, n represents 0 or 2, and m + n represents 2.
When m is 2, two R ^A2 may be the same or different, and at least one represents an acid-decomposable group.
When n is 2, two R ^A1 may be the same or different, and at least one represents an acid-decomposable group.

Examples of the divalent and tetravalent organic groups represented by X ¹ and Y ¹ include groups having 2 to 60 carbon atoms. Examples of the divalent and tetravalent organic groups represented by X ¹ include residues remaining after removal of the amino group of diamine. Examples of the divalent organic group represented by Y ¹ include residues remaining after removal of the carboxyl group of the dicarboxylic acid. Examples of the tetravalent organic group represented by Y ¹ include residues remaining after removal of the anhydride group from tetracarboxylic dianhydride.

Examples of the divalent and tetravalent organic groups include a chain aliphatic group, a cyclic aliphatic group, an aromatic ring group, a heterocyclic group, and a group formed by combining two or more of these via a single bond or a linking group. Is mentioned. Examples of the linking group include groups consisting of —O—, —S—, —C (CF ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —NHCO—, and combinations thereof. In the present invention, the chain aliphatic group means a linear or branched hydrocarbon group. The cycloaliphatic group means a cyclic hydrocarbon group.

2-60 are preferable, as for carbon number of a chain aliphatic group, 2-40 are more preferable, 2-30 are still more preferable, and 2-20 are especially preferable. The chain aliphatic group may have a substituent or may be unsubstituted. Examples of the substituent include a halogen atom, a hydroxy group, an alkoxy group, and an aryloxy group.
3-60 are preferable, as for carbon number of a cyclic aliphatic group, 3-40 are more preferable, 3-30 are still more preferable, and 3-20 are especially preferable. The cyclic aliphatic group may have a substituent or may be unsubstituted. Examples of the substituent include a halogen atom, a hydroxy group, an alkoxy group, and an aryloxy group.
6-60 are preferable, as for carbon number of an aromatic ring group, 6-40 are more preferable, 6-30 are still more preferable, and 6-20 are especially preferable. In the present invention, the aromatic ring group means an aromatic hydrocarbon group. The aromatic ring group may have a substituent or may be unsubstituted. Examples of the substituent include a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, and an aryloxy group.
Examples of the heterocyclic group include groups having a 5-membered, 6-membered or 7-membered heterocyclic ring. The heterocyclic group is preferably a group having a 5-membered or 6-membered heterocyclic ring. As the hetero atom constituting the heterocyclic ring, a nitrogen atom, an oxygen atom and a sulfur atom are preferable. The heterocycle is preferably an aromatic heterocycle. The heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, and an aryloxy group.

In the present invention, at least ^one of X ¹ and Y ¹ preferably has at least one cyclic structure (more preferably 1 to 10, more preferably 1 to 5). According to this aspect, a cured film excellent in heat resistance is easily obtained.

  The cyclic structure may be any of an aromatic ring, a heterocyclic ring, and an aliphatic ring, preferably an aromatic ring or a heterocyclic ring, and more preferably an aromatic ring. The aromatic ring, heterocyclic ring and aliphatic ring may be a single ring or a condensed ring. The aliphatic ring may have a crosslinked structure.

Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and the like.
Specific examples of the heterocyclic ring include furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, Pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring Etc.
Specific examples of the aliphatic ring include the structures shown below.

Specific examples of the tetravalent organic group include the following. In the following formula, either * 1 or * 2 represents a bond with -COOR ^A1 (or -OR ^A2 ), and the other represents a bond with the polymer main chain, * 3 or * 4 One of these represents a bond with -COOR ^A1 (or -OR ^A2 ), and the other represents a bond with the polymer main chain.

Specific examples of the divalent organic group include the following. In the following formulas, * represents a linkage with the polymer main chain.

R ^A1 and R ^A2 each independently represent a hydrogen atom, an alkyl group, or an acid-decomposable group.
When m is 2, two R ^A2 may be the same or different, and at least one represents an acid-decomposable group. When n is 2, two R ^A1 may be the same or different, and at least one represents an acid-decomposable group.

The alkyl group represented by R ^A1 and R ^A2 may be linear, branched or cyclic. In the case of a linear alkyl group, 1-20 are preferable, 1-15 are more preferable, and 1-10 are more preferable. In the case of a branched alkyl group, the carbon number is preferably 3-20, more preferably 3-15, and still more preferably 3-10. In the case of a cyclic alkyl group, the carbon number is preferably from 3 to 15, more preferably from 5 to 15, and more preferably from 5 to 10. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. The alkyl group may have a substituent or may be unsubstituted.
Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, cyano group, amide group and sulfonylamide group.

Any acid-decomposable group represented by R ^A1 and R ^A2 is preferably used as long as it decomposes by the action of an acid to generate an alkali-soluble group such as a hydroxy group or a carboxyl group. For example, an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group and the like can be mentioned, and an acetal group is preferable from the viewpoint of sensitivity.
Specific examples of the acid-decomposable group include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl. Group, trimethylsilyl ether group and the like. From the viewpoint of sensitivity, an ethoxyethyl group and a tetrahydrofuranyl group are preferred.

  In the present invention, the polymer A is preferably such that 5 to 80% of the acid groups of all the structural units of the polymer A are protected with acid-decomposable groups, and 10 to 60% are acid-decomposable groups. More preferably it is protected. According to this aspect, it can be set as the photosensitive composition excellent in the sensitivity. In addition, the acid group which all the structural units of the polymer A here mean the acid group which all the structural units of the polymer A of the state before performing protection by an acid-decomposable group have.

  In the present invention, the polymer A is represented by a polymer A1 having a structural unit represented by the following formula A1, a polymer A2 having a structural unit represented by the following formula A2, or the following formula A1 and the following formula A2. It may be a polymer A3 having a structural unit. The polymer A1 is a polyimide precursor. In addition, the polymer A2 is a polybenzoxazole precursor. Polymer A3 is a polyamideimide precursor. Among these, a polyimide precursor or a polybenzoxazole precursor is preferable.

Formula A1
In the formula, X ² represents a divalent organic group having 2 to 60 carbon atoms, Y ² represents a tetravalent organic group having 2 to 60 carbon atoms, and R ^A1 represents Independently represents a hydrogen atom, an alkyl group, or an acid-decomposable group, and represents at least one acid-decomposable group.

X ² in Formula A1 includes a residue remaining after removal of the amino group of the diamine. A preferable range of X ² is the same as the range described for X ¹ in Formula A.
Y ² in Formula A1 is a residue remaining after removal of the anhydride group from tetracarboxylic dianhydride. A preferable range of Y ² is the same as the range described for Y ¹ in Formula A.
At least one of X ² and Y ² is preferably a group containing a cyclic structure, more preferably a group containing an aromatic ring, an aromatic ring group, or two or more aromatic ring groups via a single bond or a linking group. Are particularly preferred.
R ^A1 independently represents a hydrogen atom, an alkyl group, or an acid-decomposable group, and represents at least one acid-decomposable group. The alkyl group and the acid-decomposable group are the same as those described for the alkyl group and the acid-decomposable group in Formula A, and the preferred ranges are also the same.
In the polymer A1, 5 to 80% of the acid groups of all the structural units of the polymer A1 are preferably protected with an acid-decomposable group, and 10 to 60% are protected with an acid-decomposable group. It is more preferable.

Formula A2
In the formula, X ³ represents a tetravalent organic group having 2 to 60 carbon atoms, Y ³ represents a divalent organic group having 2 to 60 carbon atoms, and R ^A2 represents Independently represents a hydrogen atom, an alkyl group, or an acid-decomposable group, and represents at least one acid-decomposable group.

X ³ in formula A2 is a residue remaining after removal of the amino group of the diamine. A preferable range of X ³ is the same as the range described for X ¹ in Formula A. X ³ is preferably a group containing a cyclic structure, more preferably a group containing an aromatic ring, an aromatic ring group, or a group formed by combining two or more aromatic ring groups via a single bond or a linking group. Particularly preferred.
Y ³ in Formula A1 includes a residue remaining after removal of the carboxyl group from the dicarboxylic acid. A preferable range of Y ³ is the same as the range described for Y ¹ in Formula A.
R ^A2 independently represents a hydrogen atom, an alkyl group, or an acid-decomposable group, and represents at least one acid-decomposable group. The alkyl group and the acid-decomposable group are the same as those described for the alkyl group and the acid-decomposable group in Formula A, and the preferred ranges are also the same.
In the polymer A2, 5 to 80% of the acid groups of all the structural units of the polymer are preferably protected with an acid-decomposable group, and 10 to 60% are protected with an acid-decomposable group. Is more preferable.

  In the present invention, the polymer A may be one kind of polymer or may contain two kinds of polymers. Moreover, when two types of polymers are included, the polymer A1 and the polymer A2 may each contain one or more types. Moreover, the aspect which contains 2 or more types of polymers A1 and does not contain polymer A2 substantially may be sufficient. Moreover, the aspect which contains 2 or more types of polymer A2 and does not contain polymer A1 substantially may be sufficient. When two types of polymers are included, the polymer A1 is included in two or more types and the polymer A2 is not substantially included, or two or more types of polymers A2 are included and the polymer A1 is substantially included. The aspect which is not included is preferable. In addition, in this invention, it is preferable that content of polymer A1 in all the polymers A is 1 mass% or less with the aspect which does not contain polymer A1 substantially, and is 0.1 mass% or less. More preferably, the polymer A1 is not contained. Moreover, the aspect which does not contain polymer A2 substantially is that the content of polymer A2 in all polymers A is preferably 1% by mass or less, and more preferably 0.1% by mass or less. More preferably, the polymer A2 is not contained.

In the present invention, the polymer A preferably has a structure in which the terminal is sealed with a monofunctional acid chloride. According to this aspect, a cured film with good transmittance is easily obtained. Examples of monofunctional acid chlorides include acetyl chloride, butyryl chloride, propionic acid chloride, 2-ethylhexanoic acid chloride, cyclohexanecarboxylic acid chloride, benzoyl chloride, naphthoyl chloride, acrylic acid chloride, heptanoic acid chloride, isobutyryl. Chloride, isononanoyl chloride, neodecanoyl chloride, octanoyl chloride, pivaloyl chloride, valeroyl chloride, methoxyacetyl chloride, acetoxyacetyl chloride, phenylacetyl chloride, cinnamoyl chloride, methacrylic acid chloride, 2-furoyl chloride , 3-chloropropionyl chloride, 4-chlorobutyryl chloride, 5-chlorovaleryl chloride, diethylcarbamoyl chloride, methyl chloroformate, ethyl chloroformate , Propylchloroformate, n-butylchloroformate, sec-butylchloroformate, pentylchloroformate, n-hexylchloroformate, n-octylchloroformate, 2-ethylhexylchloroformate, cyclohexylchloroformate Mate, 4-tert-butylcyclohexyl chloroformate, cetyl chloroformate, benzyl chloroformate, 2-chloroethyl chloroformate, allyl chloroformate and the like.
From the viewpoint of solvent solubility, an acid chloride having 3 or more carbon atoms is preferred. From the viewpoint of solvent resistance, an acid chloride having 12 or less carbon atoms is preferred.

In the present invention, the polymer A is preferably a group represented by the general formula (b1) at one end or both ends, and both ends are groups represented by the general formula (b1). More preferred.
Formula (b1)
In general formula (b1), Z represents a single bond, a carbon atom or a sulfur atom, R ³⁰ represents a monovalent organic group, n represents 0 or 1, and when Z is a single bond, a is 0. Yes, when Z is a carbon atom, a is 1, when Z is a sulfur atom, a is 2, and when n is 0, two R ³⁰ may be bonded to each other to form a ring. Good.

Z represents a single bond, a carbon atom or a sulfur atom, and preferably a single bond or a carbon atom.
R ³⁰ represents a monovalent organic group. The monovalent organic group is not particularly limited, and examples thereof include those having a formula weight of 20 to 500 per molecule. Further, the atoms constituting the monovalent organic group are preferably selected from carbon atoms, oxygen atoms, nitrogen atoms, hydrogen atoms, and sulfur atoms, and are selected from carbon atoms, oxygen atoms, nitrogen atoms, and hydrogen atoms. It is more preferable.
Specifically, an alkyl group (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), an alkenyl group (preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), an alkynyl group ( Preferably it has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, an aryl group (preferably 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms), an alkoxy group (preferably 1 to 10 carbon atoms, More preferably 1 to 6 carbon atoms, carboxyl group, crosslinkable group, oxygen atom, carbonyl group, sulfonyl group, arylene group (preferably 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms), alkylene Group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), alkenylene group (preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), and alkynylene. (Preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms) and a combination of alkenyl group, alkynyl group, aryl group, carbonyl group, carboxyl group, oxygen atom, alkylene group, alkynylene group or arylene group It is more preferable that
These groups may have a substituent, and examples of the substituent include a hydroxy group, an alkyl group, a halogen atom, a cyano group, an amide group, and a sulfonylamide group.

  Specific examples of the group represented by the general formula (b1) include structures described in paragraph 0050 of International Publication No. 2015/087831. This content is incorporated herein.

(Other structural units)
The polymer A may further include a structural unit other than the formula A (hereinafter, also referred to as other structural unit).
Examples of other structural units include structural units represented by the following formulas a1 to a3. The other structural units are preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, and particularly preferably 30 mol% or less of all the structural units of the polymer A.

In formula a1, X ¹⁰ and Y ¹⁰ each independently represents a divalent or tetravalent organic group having 2 to 60 carbon atoms. R ^A10 and R ^A11 each independently represent a hydrogen atom or an alkyl group. m represents 0 or 2, n represents 0 or 2, and m + n represents 2. When m is 2, two R ^A11 may be the same or different. When n is 2, two R ^A10 may be the same or different.

Examples of the divalent or tetravalent organic group represented by X ¹⁰ and Y ^{10 in the} formula a1 include a chain aliphatic group, a cycloaliphatic group, an aromatic ring group, a heterocyclic group, and a single bond or a linkage thereof. A group formed by combining two or more groups through a group is exemplified. Examples of the linking group include groups consisting of —O—, —S—, —C (CF ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —NHCO—, and combinations thereof. These details include the groups described in X ^1, Y ¹ of the formula A.
Examples of the alkyl group represented by R ^A10 and R ^A11 of formula a1 include the alkyl groups described for R ^A1 and R ^A2 of formula A.

In formula a2, X ¹¹ and Y ¹¹ each independently represent a divalent organic group having 2 to 60 carbon atoms. Examples of the divalent organic group represented by X ¹¹ and Y ^{11 in} formula a2 include a chain aliphatic group, a cyclic aliphatic group, an aromatic ring group, a heterocyclic group, and a single bond or a linking group thereof. Examples include groups formed by combining two or more. Examples of the linking group include groups consisting of —O—, —S—, —C (CF ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —NHCO—, and combinations thereof. These details include the groups described in X ^1, Y ¹ of the formula A.

In formula a3, Y ¹² represents a divalent organic group having 2 to 60 carbon atoms, and X ¹² represents a group containing a silicon atom. Examples of the divalent organic group represented by Y ^{12 in the} formula a3 include a chain aliphatic group, a cyclic aliphatic group, an aromatic ring group, a heterocyclic group, and a combination of two or more thereof via a single bond or a linking group. The group which consists of. Examples of the linking group include groups consisting of —O—, —S—, —C (CF ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —NHCO—, and combinations thereof. These details include the groups described in X ^1, Y ¹ of the formula A.
The group containing a silicon atom represented by X ^{12 in the} formula a3 is preferably a group represented by the following.
R ²⁰ and R ²¹ each independently represent a divalent organic group, and R ²² and R ²³ each independently represent a monovalent organic group.

The divalent organic group represented by R ²⁰ and R ²¹ is not particularly limited. A group formed by combining two or more groups through a group is exemplified. Examples of the linking group include groups consisting of —O—, —S—, —C (CF ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —NHCO—, and combinations thereof. For these details, divalent organic group described for X ^1, Y ¹ of the formula A.

  In the present invention, the polymer A preferably has a weight average molecular weight (Mw) of 3,000 to 200,000. The lower limit is more preferably 4,000 or more, and still more preferably 5,000 or more. The upper limit is more preferably 100,000 or less, and even more preferably 50,000 or less. The number average molecular weight (Mn) is preferably 1,000 to 50,000. The lower limit is more preferably 2,000 or more, and still more preferably 3,000 or more. The upper limit is more preferably 40,000 or less, and still more preferably 30,000 or less. The dispersity (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1.5 to 3.5, and still more preferably 1.5 to 3.0. By setting it as this range, the lithography performance and the cured film physical properties can be made excellent.

  The content of the polymer 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 or more with respect to 100 parts by mass of the total solid components of the photosensitive composition. Is more preferable. The upper limit is more preferably 99 parts by mass or less, for example.

<Photo acid generator>
The photosensitive composition of the present invention contains a photoacid generator that generates an acid having a pKa of 3 or less. The photoacid generator is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is not limited to its chemical structure. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. 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).

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 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>
The photosensitive composition of the present invention contains a solvent. 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 is preferably a solvent 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. 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, and N-methylpyrrolidone.

  It is preferable that content of the solvent 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.

<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 the 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 the 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 polymer A. FIG. 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.

(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. 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.

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.

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 will be favorable and it will be easy to form the cured film excellent in adhesiveness with the upper layer laminated | stacked on the 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 will be favorable and it will be easy to form the cured film excellent in adhesiveness with an upper layer. 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.

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 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.

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. In the following, 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. 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.
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.

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.
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 higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, and pentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

  In the present invention, the molecular weight of the crosslinking agent is preferably 200 to 1,000.

  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 the polymer A, 0.1-30 It is more preferable that it is a mass part, and it is still more preferable that it is 0.5-25 mass parts. 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 A phenolic antioxidant is most preferred. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include the compounds described in paragraph numbers 0026 to 0031 of JP-A-2005-29515, and the 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 adjusted as appropriate 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.

<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.
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. .
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 (alkali soluble group) such as a carboxyl group or a phenolic hydroxyl 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 ultra-high 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 step (4), a polymer having an acid group such as a liberated carboxyl group or 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), the obtained positive image is heated, and the polymer A is closed (cured) to form a cured film. The heating temperature for ring-closing (curing) the polymer A is preferably from 180 to 400 ° C, more preferably from 220 to 350 ° C. The heating time is preferably 15 to 120 minutes. This heating can be performed using a heating device such as a hot plate or an oven.
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 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages.

Prior to post-baking, the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure) and then post-baked to generate acid from the photoacid generator present in the unexposed areas and promote 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 has excellent upper layer adhesion. 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 planarizing 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 No. 00197 of International Publication No. 2015/0887829 can be referred to, and the contents thereof are incorporated in the present 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 of an example of a liquid crystal display device having a touch panel function.
For example, 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 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 Polymer A>
(Synthesis of Polymer A1-1) (Synthesis of Polyimide Precursor)
In a flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 123-1,42 g of trans-1,4-cyclohexanediamine (CHDA) was added, and an NMP (N-methyl-2-pyrrolidone) 2399.4 g flask was added. After CHDA was dissolved in NMP, 300.00 g of 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride (BPDA) was added to the flask. The mixture was stirred at 60 ° C. for 4 hours and then allowed to cool to room temperature (25 ° C.). Next, 30.27 g of phthalic anhydride was added to the flask and stirred at room temperature for 10 hours to obtain a colorless and transparent polyamic acid solution. Further, 15 g of acetyl chloride was added to the flask and reacted at 23 ° C. for 24 hours to seal the amine terminal. It was poured into a large amount of hexane and reprecipitated. 15 parts by mass of the resulting precipitate was dissolved in 85 parts by mass of NMP. Thereby, a solution of polyamic acid ester a1-1 was obtained.
Next, 185 mol parts of ethyl vinyl ether and 0.1 mol part of 10-camphorsulfonic acid are added to 1 mol part of the polyamic acid ester a1-1 in the obtained polyamic acid ester a1-1 solution. The mixture was further stirred at room temperature for 2 hours. Thereafter, the reaction solution was neutralized with triethylamine, extracted with distilled water and ethyl acetate, and then the organic layer was concentrated to obtain a polyamic acid ester (polymer A1-1) in which the carboxyl group was protected. When obtained polymer A1-1 was analyzed by GPC (polystyrene conversion value), the weight average molecular weight (Mw) was 19100, and dispersion degree (Mw / Mn) was 2.71. Moreover, the carboxyl group protection rate of polymer A1-1 was 60% with respect to the total amount (mol amount) of polymer A1-1 (< ¹ > H-NMR).

(Synthesis of Polymers A1-2 to A1-6)
In the synthesis of the polymer A1-1, each raw material was changed as described in the following table, and the synthesis was performed in the same manner as A1-1 except that the conditions were appropriately adjusted.

(Synthesis of Polymer A1-7)
After adding 80 g of propylene glycol monoethyl ether acetate (PGMEA) as a polymerization solvent to the reaction vessel, diamine and tetracarboxylic dianhydride are added to the polymerization solvent so that the solid content concentration becomes 20% by mass with respect to a total of 80 g of the polymerization solvent. Added inside. At this time, the tetracarboxylic dianhydride added 90 mol part with respect to 100 mol part of the whole quantity of diamine. In this synthesis example, 2,2′-bis (4-aminophenyl) hexafluoropropane was used as the diamine compound, and after dissolution, 2,3,5-tricarboxy was used as the tetracarboxylic dianhydride. Cyclopentyl acetate dianhydride was charged. The mixture was then reacted at 65 ° C. for 3 hours. Further, acetyl chloride was added and reacted at 23 ° C. for 24 hours to seal the amine terminal. As a result, about 100 g of a polyamic acid ester a1-7 solution having a solid content concentration of 20% by mass and a solution viscosity of 100 mPa · s was obtained.
Next, 185 mol parts of ethyl vinyl ether and 0.1 mol part of 10-camphorsulfonic acid are added to 1 mol part of the polyamic acid ester a1-7 in the solution of the obtained polyamic acid ester a1-7. The mixture was further stirred at room temperature for 2 hours. Thereafter, the reaction solution was neutralized with triethylamine, extracted with distilled water and ethyl acetate, and then the organic layer was concentrated to obtain a polyamic acid ester (polymer A1-7) in which the carboxyl group was protected. When the obtained polymer A1-7 was analyzed by GPC, the weight average molecular weight (Mw) was 8800, and dispersion degree (Mw / Mn) was 2.2. Moreover, the carboxyl group protection rate of the polymer A1-7 was 35% with respect to the total carboxyl group amount (molar amount) of the polymer A1-7 ( ¹ H-NMR).

(Synthesis of polymers A1-8 to A1-9)
In the synthesis of the polymer A1-7, each raw material was changed as described in the following table and synthesized in the same manner as A1-7 except that the conditions were appropriately adjusted.

The tetracarboxylic dianhydride in the following table is a compound having the following structure.

The diamine in the following table is a compound having the following structure.

(Synthesis of polymer A2-1) (Synthesis of polybenzoxazole precursor)
In a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 82.41 g (0.225 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (Bis-AP) was added. -AF, Central Glass Co., Ltd.) and 330 g of NMP were added. This was stirred at 40 ° C. and then cooled to 3 ° C. with an ice bath. While maintaining the reaction temperature at 0 ° C. to 10 ° C., 29.64 g (0.142 mol) of 1,4-cyclohexanedicarboxylic acid dichloride, 14.53 g (0.0607 mol) of sebacoyl chloride (Tokyo Kasei) was added to this solution. Kogyo Co., Ltd.), 0.487 g (0.00620 mol) of acetyl chloride (Tokyo Chemical Industry Co., Ltd.) and 115.69 g of NMP, 32.53 g (0.411 mol) of pyridine ( Wako Pure Chemical Industries, Ltd.) and a mixed solution containing 84.70 g of NMP were simultaneously added dropwise over 4 hours. After completion of the dropwise addition, the reaction solution (0.05 g) was diluted with 5.00 g of tetrahydrofuran (THF). When the GPC measurement of the obtained solution was carried out, the weight average molecular weight (Mw) was 20000 (polystyrene conversion value).
Next, 1.65 g (0.00789 mol) of 1,4-cyclohexanedicarboxylic acid dichloride and 0.807 g (0.00338 mol) of sebacoyl chloride were added to this solution while maintaining the reaction temperature at 0 ° C. to 10 ° C. (Manufactured by Tokyo Chemical Industry Co., Ltd.), 0.0271 g (0.000345 mol) of acetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 6.43 g of NMP, and 1.81 g (0.0229 mol) of A mixed solution of pyridine (manufactured by Wako Pure Chemical Industries, Ltd.) and 4.71 g of NMP was added dropwise simultaneously over 10 minutes.
Next, 1.64 g (0.0208 mol) of acetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.65 g (0.0208 mol) of pyridine were added dropwise while maintaining the reaction solution at 0 ° C. to 10 ° C. . After completion of the dropwise addition, the mixture was further stirred for 1 hour to remove greed and warm to room temperature.
This reaction liquid was diluted with 300 g of isopropanol, and simultaneously with 2800 g of water, it was poured into a vigorously stirred 600 g of deionized water / isopropanol (80/20 volume ratio) mixture, and the precipitated white powder was recovered by filtration. And washed with deionized water / isopropanol. The polymer was dried at 50 ° C. for 2 days under vacuum to obtain a polymer a2-1.
To the eggplant flask, 25.00 g of polymer a2-1 and 225 g of THF were added, and placed in an 80 ° C. water bath under a nitrogen flow until the solution was 83 g. To this was added 167 g of THF, and the solution was concentrated to 83 g. 42 g of THF and 0.24 g (0.00103 mol) of (+)-10-camphorsulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and dissolved at room temperature, and then cooled to 15 ° C. did. To this, 2.35 g (0.0335 mol) of 2,3-dihydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at 15 ° C. for 1 hour. To this, 0.25 g of 2,3-dihydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at 15 ° C. for 1 hour. The obtained solution was quenched by adding 0.16 g of triethylamine and 0.80 g of THF.
The resulting solution was transferred to a three-necked flask, and 60 g of 2-butanone, 60 g of ethyl acetate, and 90 g of water were added. After stirring this liquid mixture at 60 degreeC for 10 minute (s), it moved to the separating funnel, after removing the lower layer, it moved to the three necked flask. To this was added 20 g of 2-butanone and 90 g of water. The mixture was stirred at 60 ° C. for 10 minutes, then transferred to a separatory funnel and allowed to stand overnight, and then the lower layer was removed. The remaining 80 g of the upper layer was transferred to an eggplant flask, 11 g of diethylene glycol ethyl methyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 32 g of ethyl acetate were added, and the mixture was concentrated under reduced pressure at 50 ° C. for 1 hour. To this was added 32 g of ethyl acetate, and the mixture was further concentrated under reduced pressure for 30 minutes. Then, it heated up to 70 degreeC, concentrated under reduced pressure for 2 hours, and cooled to room temperature. By adding 3.0 g of diethylene glycol ethyl methyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), a 30 mass% solution of PBO precursor (polymer A2-1) in diethylene glycol ethyl methyl ether was obtained. When obtained polymer A2-1 was analyzed by GPC (polystyrene conversion value), the weight average molecular weight (Mw) was 23000, and dispersion degree (Mw / Mn) was 2.1. Moreover, the hydroxy group protection rate of the polymer A2-1 was 27% with respect to the total hydroxy group amount (molar amount) of the polymer A2-1 ( ¹ H-NMR).

(Synthesis of polymers A2-2 to A2-25)
In the synthesis of polymer A2-1, each raw material was changed as described in the following table, and synthesized in the same manner as A2-1 except that the conditions were appropriately adjusted.

(Synthesis of Polymer A2-26)
In a three-necked flask, 293 g (0.8 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (manufactured by Nippon Kayaku Co., Ltd.), 126.6 g (1.6 mol) Of pyridine and 1.2 kg of N-methyl-2-pyrrolidone (NMP) were added. This was stirred at room temperature and then cooled to −25 ° C. in a dry ice / acetone bath. While maintaining the reaction temperature at −20 ° C. to −30 ° C., 73.9 g (0.364 mol) of isophthaloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 107.4 g (0.364 mol) were added to this solution. Of 4,4′-oxybisbenzoyl chloride (obtained by converting 4,4′-oxybisbenzoic acid (manufactured by Aldrich) into acid chloride by a conventional method) and 700 g of NMP were added dropwise.
After the addition was complete, the resulting reaction was stirred at room temperature for 16 hours. The reaction solution is then diluted with 2 L of acetone, poured into 50 L of deionized water with vigorous stirring, the precipitated white powder is recovered by filtration, and a mixture of deionized water and water / methanol (50/50 mass ratio) Washed by. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain a polymer a2-26. The yield was almost quantitative, and when the polymer a2-26 was analyzed by GPC (polystyrene conversion value), the weight average molecular weight (Mw) was 6400, and the dispersity (Mw / Mn) was 2.1.
400 g of the polymer a2-26 was dissolved in PGMEA to obtain a solution having a solid content concentration of 15% by mass. To this, 21 g of allyl chloroformate (manufactured by Tokyo Chemical Industry) and 16 g of pyridine were added and stirred at room temperature for 3 hours. The obtained reaction solution was washed with water, 200 g of toluene was added, and the solvent was distilled off at 50 ° C. in order to remove water in the system by azeotropic dehydration to obtain a solution having a solid content concentration of 15% by mass. The water content in the system was 0.01%. 15 g of ethyl vinyl ether and 0.1 g of p-toluenesulfonic acid were added and stirred at room temperature for 3 hours. Furthermore, 15 g of ethyl vinyl ether and 0.1 g of p-toluenesulfonic acid were added and stirred at room temperature for 3 hours. 20 g of triethylamine was added to the resulting solution, the reaction solution was washed with water three times, diluted once by adding PGMEA 1 L, and then the solvent was distilled off at 50 ° C. to remove water in the system by azeotropic dehydration. A 45 mass% PGMEA solution of polymer A2-26 was prepared. When the polymer A2-26 was analyzed by GPC (polystyrene equivalent value), the weight average molecular weight (Mw) was 6600, and the dispersity (Mw / Mn) was 2.2. Further, from ¹ H-NMR, it was confirmed that the introduction rate of allyl chloroformate was quantitative. Further, the hydroxy group protection rate (ethyl acetal group protection rate) of the polymer A2-26 was 21% with respect to the total hydroxy group amount (molar amount) of the polymer A2-26.

(Synthesis of A2-27)
In the synthesis of the polymer A2-26, each raw material was changed as described in the following table, and the synthesis was performed in the same manner as the A2-26 except that the conditions were appropriately adjusted.

In the table, Bis-AP-AP, AHS, AHF, and HAB are compounds having the following structures.

<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 shown 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 especially the unit in a table | surface is a mass part.
In addition, the polymer A was added so that solid content might become the quantity of table | surface description. 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.
(Polymer A)
A1-1 to A1-9 and A2-1 to A2-27 shown in Tables 1 and 2 were used.
(Compound S)
S-1 to S-33 shown in Table 3 were used.

(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 Chemical Co., Ltd., a photoacid generator that generates an acid of pKa3 or lower), 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: N-methylpyrrolidone C-4: γ-butyrolactone

(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.

(Other ingredients)
DPHA: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., crosslinking 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 on a 1,500 mm × 1,800 mm Cr vapor-deposited glass substrate (glass is EAGLE 2000, Corning) treated with HMDS (hexamethyldisilazane) at a coating speed of 100 mm / sec. The coating was applied so as to have a dry film thickness of 3 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 prepared 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 320 ° C. for 60 minutes in a nitrogen atmosphere, 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., ITO was deposited on the substrate in the form of a small piece so that the sputtering temperature was 23 ° C. and the film thickness was 50 nm. Heated at 0 ° C. for 30 minutes. On the obtained substrate with ITO, a cross-cut test was performed with a cut at 1 mm intervals according to 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 1% 2: Total area of ITO film peeled off from cured film surface is 1% or more and less than 5% 3: Total area of ITO film peeled off from cured film surface 5% or more and less than 10% 4: The total area of the ITO film peeled off from the cured film surface is 10% or more and less than 15% 5: The total area of the ITO film peeled off from the cured film surface 15% or more

<Heat resistance>
The substrate prepared in the same manner as the applicability evaluation was covered with a 21% aqueous solution of FHD-5 (manufactured by FUJIFILM Electronics Materials) and left stationary 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 subjected to a heat treatment at 320 ° C. for 60 minutes in a nitrogen atmosphere, and the film thickness (t0) of the cured film was measured with a stylus type film thickness meter (DektakXT, manufactured by Bruker). 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 6 micrometer hole pattern was exposed using the board | substrate produced similarly to applicability | paintability evaluation using MPA-7800 + (made by Canon Inc.). Subsequently, it was covered with a 21% aqueous solution of FHD-5 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) and left still 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. Further, the dried substrate was heated in a nitrogen atmosphere at 150 ° C. for 30 minutes, and subsequently in a nitrogen atmosphere at 350 ° C. for 30 minutes, and then the pattern shape was changed to an optical microscope (magnification 300 times), scanning electron microscope (SEM) ( Observation was performed at a magnification of 5000 times. 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 photosensitive composition after exposure was developed with a 21% aqueous solution of FHD-5 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds. 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)
Except that the display device shown in FIG. 1 of JP 2012-203121 A was prepared using the photosensitive composition of Example 1-1 for the pixel separation film (19) and the planarization film (17). It produced according to Unexamined-Japanese-Patent No. 2012-203121. The display device was excellent in display characteristics.
(Examples 1002-1160)
Example 1001 is the same as Example 1001 except that the photosensitive composition of Example 1-1 was replaced with the photosensitive composition of Examples 1-2 to 1-80 and 2-1 to 2-80. A display device was produced in the same manner. The display device was excellent in display characteristics.

(Example 2001)
Except that the display device described in FIG. 1 of JP2013-196919A was formed using the photosensitive composition of Example 1-1, the inter-pixel insulating film (16) and the interlayer insulating film (14), It produced according to Unexamined-Japanese-Patent No. 2013-196919. The display device was excellent in display characteristics.
(Examples 2002 to 2160)
Example 2001 is the same as Example 2001 except that the photosensitive composition of Example 1-1 was replaced with the photosensitive composition of Examples 1-2 to 1-80 and 2-1 to 2-80. A display device was produced in the same manner. The display device was excellent in display characteristics.

(Example 3001)
According to Japanese Patent Laid-Open No. 2007-328210, the liquid crystal display device shown in FIG. 1 of Japanese Patent Laid-Open No. 2007-328210 is prepared except that the organic insulating film PAS is formed using the photosensitive composition of Example 1-1. Produced. The display device was excellent in display characteristics.
(Examples 3002 to 3160)
Example 3001 is the same as Example 3001 except that the photosensitive composition of Example 1-1 was replaced with the photosensitive composition of Examples 1-2 to 1-80 and 2-1 to 2-80. A display device was produced in the same manner. The display device was excellent in display characteristics.

(Example 4001)
The liquid crystal display device shown in FIG. 1 of Japanese Patent Application Laid-Open No. 2007-328210 is the same as that described in Japanese Patent Application Laid-Open No. 2007-2007 except that the organic insulating film PAS is formed using the photosensitive composition of Example 1-46 as follows. It was produced in accordance with Japanese Patent No. 328210. The display device was excellent in display characteristics.
According to JP 2007-328210 A, up to IN2 was produced. Thereafter, the composition of Example 1-46 was slit-coated, solvent removed, pattern exposure to a hole shape, and tetramethylammonium hydroxide (TMAH) 0. 0 so that the film thickness after heat curing was half of the predetermined film thickness. Paddle development was performed with a 5% by mass aqueous solution for 60 seconds, heating was performed at 180 ° C. for 30 minutes in a nitrogen atmosphere, and heating was performed at 320 ° C. for 60 minutes to form a cured film having a film thickness half the predetermined film thickness.
On the above cured film, a cured film having a film thickness half the predetermined film thickness was similarly formed using the composition of Example 1-46. By these, PAS which is a laminated body (laminated structure of the cured film of a half film thickness) of the cured film was formed. Thereafter, a liquid crystal display device was produced according to Japanese Patent Application Laid-Open No. 2007-328210.

(Examples 4002 to 4005)
Example 4001 is the same as Example 4001 except that the photosensitive composition of Example 1-46 was replaced with the photosensitive composition of Examples 1-78, 2-46, 2-70, and 2-78. A display device was produced in the same manner. 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 (13)

A polymer A having a structural unit represented by the following formula A;
a photoacid generator that generates an acid having a pKa of 3 or less;
Solvent,
Compound S having a structure represented by the following formula S1 and a structure represented by the following formula S2,
A photosensitive composition comprising:
Formula A
In formula A, X ¹ and Y ¹ each independently represents a divalent or tetravalent organic group having 2 to 60 carbon atoms;
R ^A1 and R ^A2 each independently represent a hydrogen atom, an alkyl group or an acid-decomposable group;
m represents 0 or 2, n represents 0 or 2, m + n represents 2;
when m is 2, two R ^A2 may be the same or different and at least one represents an acid-decomposable group;
when n is 2, two R ^A1 may be the same or different and at least one represents an acid-decomposable group;
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 said polymers A.   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. The compound S is a structural unit represented by the following formula S1-3, a polymer having a structural unit represented by the following formula S2-3, according to any one of claims 1 to 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. The photosensitive composition of Claim 3 whose mass ratio with the said structural unit S2-1 is structural unit S1-1: structural unit S2-1 = 5: 95-95: 5. The weight average molecular weight of compound S is 300 to 100,000, photosensitive composition according to any one of claims 1 to 6. The said polymer A is a photosensitive composition of any one of Claims 1-7 which is a polymer which has a structural unit represented by following formula A1;
Formula A1
In the formula, X ² represents a divalent organic group having 2 to 60 carbon atoms,
Y ² represents a tetravalent organic group having 2 to 60 carbon atoms,
R ^A1 independently represents a hydrogen atom, an alkyl group, or an acid-decomposable group, and represents at least one acid-decomposable group. The said polymer A is a photosensitive composition of any one of Claims 1-7 which is a polymer which has a structural unit represented by following formula A2.
Formula A2
In the formula, X ³ represents a tetravalent organic group having 2 to 60 carbon atoms,
Y ³ represents a divalent organic group having 2 to 60 carbon atoms,
R ^A2 independently represents a hydrogen atom, an alkyl group, or an acid-decomposable group, and represents at least one acid-decomposable group. Applying the photosensitive composition according to any one of claims 1 to 9 on a 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.   The manufacturing method of the liquid crystal display device containing the manufacturing method of the cured film of Claim 10.   The manufacturing method of an organic electroluminescent display apparatus containing the manufacturing method of the cured film of Claim 10.   The manufacturing method of a touch panel including the manufacturing method of the cured film of Claim 10.