JP5550693B2 - Positive photosensitive resin composition for electronic member, cured film, and display device - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition for electronic members, a cured film using the positive photosensitive resin composition for electronic members, a liquid crystal display device or an organic EL device having the cured film. Moreover, it is related with the manufacturing method of the cured film using the positive photosensitive resin composition for electronic members.

  Organic EL display devices, liquid crystal display devices, and the like are provided with a patterned interlayer insulating film. In forming the interlayer insulating film, photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.

  In addition to transparency, interlayer insulating films and planarization films patterned using the photosensitive resin composition as described above are resistant to the etching solution and resist stripping solution used for electrode pattern formation (solvent resistance) Property) and liquid crystal contamination (electrical properties) are required to be a highly reliable cured film. In recent years, in order to make organic EL display devices and liquid crystal display devices have high-definition display characteristics, it is required that the photosensitive resin composition can be uniformly applied to a substrate and has high resolution.

  As a photosensitive resin composition that can ensure high reliability (transparency, solvent resistance) of the formed cured film, for example, a (meth) acrylate compound having an acetal structure or a ketal structure, radical polymerization having an epoxy group A radiation-sensitive resin composition containing a reactive compound, a resin that is a copolymer of other radical polymerizable compounds, and a compound that generates an acid having a pKa of 4.0 or less upon irradiation with radiation is known. (For example, refer to Patent Document 1).

  Patent Document 2 discloses (A1) a resin containing a structural unit having an acid-dissociable group, and (A2) a polymer or copolymer having a structural unit derived from an epoxy group-containing radical polymerizable monomer. (B) a positive photosensitive resin composition comprising a compound having two or more epoxy groups in the molecule and (C) a compound capable of generating an acid upon irradiation with an actinic ray having a wavelength of 300 nm or more. Proposed.

  Moreover, although not for electronic members, such as an interlayer insulation film, the resist underlayer film material which is disclosed by patent document 3 is disclosed.

JP 2004-264623 A JP 2009-258722 A JP 2007-17949 A

  Although the photosensitive resin composition as described above is known, it has high sensitivity and secures high reliability (solvent resistance) of the formed cured film, while also ensuring applicability and liquid crystal contamination (electrical characteristics). The present condition is that the photosensitive resin composition which can be compatible) is not yet found.

  The problem to be solved by the present invention is to provide a photosensitive resin composition excellent in sensitivity, coating property, and liquid crystal contamination (electrical property). Another object is to provide an organic EL display device and a liquid crystal display device that have a cured film formed of the photosensitive resin composition as an interlayer insulating film and have high reliability and high productivity.

  Based on the above problems, the inventors of the present invention have made extensive studies and found that the addition of a chain aliphatic epoxy compound can improve the unevenness of the muscles without deteriorating the electrical characteristics. I found out. Specifically, the above problem has been solved by the following means <1>, preferably <2> to <13>.

<1> (A) a polymer that satisfies the following (1) or (2),
(1) (a1) a polymer obtained by copolymerizing at least a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a crosslinkable group,
(2) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group (B) a photoacid generator, and
(C) A positive photosensitive resin composition for electronic members, comprising a chain aliphatic epoxy compound.
<2> The positive photosensitive resin composition for electronic members according to <1>, wherein the molecular weight of the (C) chain aliphatic epoxy compound is 2000 or less.
<3> The positive photosensitive resin composition for electronic members according to <1> or <2>, wherein the viscosity of the chain aliphatic epoxy compound at 25 ° C. is 3000 mPa · s or less.
<4> (C) The positive photosensitive resin for electronic members according to any one of <1> to <3>, wherein the chain aliphatic epoxy compound is a resin represented by the following general formula (X-1): Composition.
Formula (X-1)
(In General Formula (X-1), A is a linear or branched hydrocarbon group, which may have a hydroxyl group as a substituent, and n is an integer of 1 to 4.)
<5> Any one of <1> to <4>, wherein the structural unit (a1) is a structural unit having a residue whose carboxyl group is protected with an acetal, or a residue whose carboxyl group is protected with a ketal The positive photosensitive resin composition for electronic members as described in 2.
<6> The positive photosensitive resin composition for an electronic member according to any one of <1> to <5>, wherein the structural unit (a1) is a structural unit represented by the formula (A2 ′).
Formula (A2 ′)
(In Formula (A2 ′), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 6 carbon atoms, and R ³ represents an alkyl group having 1 to 6 carbon atoms or 4 to 7 carbon atoms. And R ² and R ³ may be linked to form a ring.)
<7> (C) The positive photosensitive resin for electronic members according to any one of <1> to <6>, wherein the chain aliphatic epoxy compound is a resin represented by the following general formula (X-2) Composition.
Formula (X-2)
(In General Formula (X-2), B is a linear or branched hydrocarbon group, which may have a hydroxyl group as a substituent, and n is an integer of 1 to 4.)
<8> The structural unit (a2) is a structural unit having a 3-membered or 4-membered cyclic ether group, and —NH—CH ₂ —O—R (R is an alkyl group having 1 to 20 carbon atoms). The positive photosensitive resin composition for electronic members according to any one of <1> to <7>, comprising at least one selected from the group consisting of structural units having a group represented by formula (1).
<9> (1) A step of applying the positive photosensitive resin composition for an electronic member according to any one of <1> to <8> on a substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) a post-baking step of thermosetting the developed photosensitive resin composition;
A method for forming a cured film comprising:
<10> The method for forming a cured film according to <9>, including a step of exposing the entire surface of the developed photosensitive resin composition after the developing step and before the post-baking step.
<11> A cured film formed by the method for forming a cured film according to <9> or <10>.
<12> The cured film according to <11>, which is an interlayer insulating film.
<13> An organic EL display device or a liquid crystal display device comprising the cured film according to <11> or <12>.

  According to the present invention, a photosensitive resin composition excellent in sensitivity, coating property and liquid crystal contamination (electrical property) has been provided.

1 shows a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.

  Hereinafter, the contents of the present invention will be described in detail. 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. The organic EL element in the present invention refers to an organic electroluminescence element.

  The positive photosensitive resin composition for electronic members of the present invention (hereinafter, also simply referred to as “photosensitive resin composition”) is (A) one or two that satisfy (1) and / or (2) below. The above polymer (hereinafter also referred to simply as “component A”), (1) (a1) a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a structure having a crosslinkable group A polymer obtained by copolymerizing at least units, (2) (a1) a polymer having a structural unit having a residue in which an acid group is protected by an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group And (B) a photoacid generator and (C) a chain aliphatic epoxy compound. The photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).

In addition, in the description of group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The method for introducing the structural unit contained in the polymer used in the present invention may be a polymerization method or a polymer reaction method. In the polymerization method, monomers containing a predetermined functional group are synthesized in advance, and then these monomers are copolymerized. In the polymer reaction method, after a polymerization reaction is performed, a necessary functional group is introduced into the structural unit using a reactive group contained in the structural unit of the obtained polymer. Here, as the functional group, a protective group for protecting an acid group such as a carboxyl group or a phenolic hydroxyl group and simultaneously decomposing and releasing them in the presence of a strong acid, a crosslinkable group such as an epoxy group or an oxetanyl group, Examples thereof include alkali-soluble groups (acid groups) such as phenolic hydroxyl groups and carboxyl groups.

(Component A)
The positive photosensitive resin composition of the present invention contains (Component A). The polymer of (Component A) may contain only 1 type, and may contain 2 or more types. By using (Component A), it is excellent in resistance to resist stripping solution and NMP, and is excellent in sensitivity and adhesion to the substrate when used as a cured film.
The structural unit (a1) and the structural unit (a2) may be the same structural unit, but are preferably different structural units.
Component A is preferably a resin that is insoluble in alkali and becomes alkali-soluble when the acid-decomposable group is decomposed. Here, the “acid-decomposable group” means a functional group that can be decomposed in the presence of an acid. “Alkali-soluble” means that a coating (thickness: 3 μm) formed by applying a solution of a compound (resin) on a substrate (usually coating) and heating at 90 ° C. for 2 minutes at 23 ° C. It means that the dissolution rate in a 0.4 wt% tetramethylammonium hydroxide aqueous solution is 0.01 μm / second or more. On the other hand, “alkali insoluble” means that the dissolution rate is less than 0.01 μm / second. The alkali dissolution rate of component A is more preferably less than 0.005 μm / second.

Component A is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. In addition, the component A may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, a structural unit derived from styrene or a vinyl compound.
Component A preferably contains 50 mol% or more, more preferably 80 mol% or more of monomer units derived from (meth) acrylic acid and / or its ester, based on all monomer units, more preferably 90 mol%. % Or more is more preferable, and 100 mol% is particularly preferable.

The method for introducing the structural unit contained in component A may be a polymerization method, a polymer reaction method, or a combination of these two methods.
In the polymerization method, for example, an ethylenically unsaturated compound having a residue in which an acid group is protected with an acid-decomposable group, an ethylenically unsaturated compound having a crosslinkable group, a carboxyl group and / or a phenolic hydroxyl group. An ethylenically unsaturated compound and the like can be mixed and subjected to addition polymerization to obtain a target polymer.
In the polymer reaction method, an epoxy group can be introduced by reacting epichlorohydrin with a polymer copolymerized with 2-hydroxyethyl methacrylate. In this way, after copolymerizing an ethylenically unsaturated compound having a reactive group, the reactive group remaining in the side chain is utilized to protect the phenolic hydroxyl group or carboxyl group with an acid-decomposable group by a polymer reaction. Functional groups such as cross-linked groups and / or crosslinkable groups can be introduced into the side chain.

<Structural unit (a1)>
Component A has (a1) at least a structural unit having a residue in which an acid group is protected with an acid-decomposable group. When Component A has the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained.
In the present invention, “residue in which an acid group is protected with an acid-decomposable group” means a residue in which a carboxyl group is protected with an acetal, a residue in which an acid group is protected with a ketal, and an acid group is a tertiary alkyl group Or a residue in which the acid group is protected with a tertiary alkyl carbonate group.
Preferred examples of the acid group include a carboxyl group and a phenolic hydroxyl group.
Specific examples of the residue in which the acid group is protected with an acid-decomposable group include, for example, an ester structure of a group represented by the formula (A1) described later, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group. And a tertiary alkyl functional group such as a t-butyl ester group and a t-butyl carbonate group.

(A1-1) Structural unit having a residue in which a carboxyl group is protected with an acid-decomposable group The structural unit having a residue in which a carboxyl group is protected with an acid-decomposable group is preferably the above (a1-1- 1) A structural unit having a residue in which a carboxyl group contained in the structural unit described in (a1-1-2) is protected by an acid-decomposable group.
The acid-decomposable group is not particularly limited, and any known acid-decomposable group in the positive resist for KrF and the positive resist for ArF can be used. Examples of acid-decomposable groups include groups that are relatively easily decomposed by acid (for example, acetal functional groups such as tetrahydropyranyl group and ethoxyethyl group), and groups that are relatively difficult to decompose by acid (for example, t-butyl ester). Groups, t-butyl functional groups such as t-butyl carbonate groups) are known. As the structural unit (a1-1), a structural unit having a residue in which a carboxyl group is protected with an acetal or a residue in which a carboxyl group is protected with a ketal has sensitivity, pattern shape, and contact hole formability. It is preferable from the viewpoint.

Furthermore, among the acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the carboxyl group is a residue protected with an acetal or ketal represented by the formula (A1). In addition, when the carboxyl group is an acetal or ketal-protected residue represented by the formula (A1), the entire residue is —C (═O) —O—CR ¹ R ² (OR ³ ). It has a structure.

(In Formula (A1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or an aryl group, and at least ^one of R ¹ and R ² is an alkyl group or an aryl group. R ³ represents an alkyl group or an aryl group, and R ¹ or R ² and R ³ may be linked to form a cyclic ether, and the wavy line in formula (A1) (Represents the bonding position with the structure.)

In formula (A1), the alkyl group in R ¹ , R ² and R ³ may be linear, branched or cyclic.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group. Of these, a methyl group and an ethyl group are preferable.
The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group. Of these, monocyclic ones are preferable, and cyclohexyl groups are more preferable.
The alkyl group may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, aryl group having 6 to 20 carbon atoms, and 1 to 6 carbon atoms. The alkoxy group of can be illustrated. When it has a halogen atom as a substituent, R ¹ , R ² and R ³ become a haloalkyl group, and when it has an aryl group as a substituent, R ¹ , R ² and R ³ become an aralkyl group. As the aralkyl group, a benzyl group is preferable.

In formula (A1), the aryl group in R ¹ , R ² and R ³ preferably has 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group, and a phenyl group is preferable.

In the formula (A1), R ¹ , R ² and R ³ can be bonded to each other to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ¹ and R ² , R ¹ and R ³ or R ² and R ³ are bonded include, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.

In formula (A1), it is preferable that either R ¹ or R ² is a hydrogen atom or a methyl group.
As the radical polymerizable monomer used for forming the structural unit having the residue represented by the formula (A1), a commercially available one may be used, for example, paragraph 0025 of JP-A-2009-098616. Those synthesized by a known method such as the method described in ˜0026 may be used.

  As the structural unit (a1-1) having a residue in which a carboxyl group is protected with an acid-decomposable group, a structural unit represented by the formula (A2) is more preferable.

(In formula (A2), each R ¹ independently represents a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group. Alternatively, it represents an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group. )

In the formula, R ¹ is preferably a methyl group.
In formula (a1-1), R ² is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
In the formula, R ³ is preferably an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms, and more preferably an ethyl group or a cyclohexyl group.
In the formula, when R ² and R ³ are connected to form a ring, the group in which R ² and R ³ are connected is preferably an alkylene group having 3 to 6 carbon atoms, A propylene group or a 1,4-butylene group is more preferable.

  Among these, the structural unit (a1) is preferably a structural unit represented by the following formula (A2 ′) from the viewpoint of sensitivity.

(In Formula (A2 ′), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 6 carbon atoms, and R ³ represents an alkyl group having 1 to 6 carbon atoms or 4 to 7 carbon atoms. And R ² and R ³ may be linked to form a ring.)

  Preferable specific examples of the structural unit (a1-1) include the following structural units. R represents a hydrogen atom or a methyl group.

The structural unit (a1-1) may be a structural unit having a residue in which a carboxyl group is protected with a tertiary alkyl group represented by the formula (A3). The sensitivity is inferior to that of a residue protected with acetal or ketal, but it is preferable in terms of excellent storage stability. When the carboxyl group is a residue protected with a tertiary alkyl group represented by the formula (A3), the residue as a whole is —C (═O) —O—CR ¹ R ² R ^3. This is the structure.

In formula (A3), R ¹ , R ² and R ³ each independently represents an alkyl group or an aryl group, and any ^{two of} R ¹ , R ² and R ³ are bonded to each other to form a ring. Also good. The wavy line part in Formula (A3) represents the coupling position with another structure. Specific examples of the alkyl group and aryl group in R ^{1 to} R ³ of formula (A3) are the same as the specific examples of the alkyl group and aryl group in formula (A1).
In the formula (A3), preferred examples include a combination of R ¹ = R ² = R ³ = methyl group, and a combination of R ¹ = R ² = methyl group and R ³ = benzyl group.

(A1-2) Structural unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group (a1-2) As a structural unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group, a1-2-1) A structural unit having a residue in which the phenolic hydroxyl group of the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group is preferred.

(A1-2-1) Structural Unit Having Phenolic Hydroxyl Group Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene structural unit and a structural unit in a novolac resin. Among these, α-methylhydroxy A structural unit derived from styrene is preferred from the viewpoint of transparency. Among the structural units having a phenolic hydroxyl group, the structural unit represented by the formula (A4) is preferable from the viewpoints of transparency and sensitivity.

(In the formula (A4), R ²⁰ represents a hydrogen atom or a methyl group, R ²¹ represents a single bond or a divalent linking group, R ²² each independently represents a halogen atom or an alkyl group, 5 represents an integer of 5, b represents an integer of 0 to 4, and a + b is 5 or less.)

R ²⁰ is preferably a methyl group.
Examples of the divalent linking group for R ²¹ include an ester bond (—COO—) in which a carbon atom is bonded to the main chain, and an alkylene group. The alkylene group is preferably a linear or branched alkylene group having 1 to 6 carbon atoms. In the case of -COO-, the sensitivity can be improved and the transparency of the cured film can be further improved. Among these, R ²¹ is preferably a single bond or an ester bond. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.

Moreover, although a represents the integer of 1-5, it is preferable that a is 1 or 2 from the point that manufacture is easy, and it is more preferable that a is 1.
Further, the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R ²¹ is the reference (first position).
R ²² is a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, or a linear or branched alkyl group having 1 to 5 carbon atoms. Among these, a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferable because of easy production.

(A1-2) Structural unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group A structural unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group is (a1-2-1) A structural unit having a residue in which a phenolic hydroxyl group of a structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group.
As the acid-decomposable group, a known group can be used as described above, and is not particularly limited.
The basic physical properties of the resist, especially the sensitivity, pattern shape, and photosensitivity, should be a structural unit having a residue in which the phenolic hydroxyl group is protected with an acid-decomposable group, and the residue in which the phenolic hydroxyl group is protected with an acetal or ketal. It is preferable from the viewpoint of storage stability of the resin composition and formability of contact holes. Furthermore, among the residues in which the phenolic hydroxyl group is protected with an acid-decomposable group, it is more preferable from the viewpoint of sensitivity that the phenolic hydroxyl group is a residue protected with an acetal or ketal represented by the formula (A1). . In this case, the residue as a whole has a structure of —Ar—O—CR ¹ R ² (OR ³ ). Ar represents an arylene group.
Preferable examples of the acetal ester structure of the phenolic hydroxyl group include a combination of R ¹ = R ² = R ³ = methyl group, R ¹ = R ² = methyl group and R ³ = benzyl group.

  Examples of the radical polymerizable monomer used to form a monomer unit having a residue in which a phenolic hydroxyl group is protected with an acetal or ketal include, for example, a 1-alkoxyalkyl protector of hydroxystyrene, a hydroxystyrene Tetrahydropyranyl protector, 1-alkoxyalkyl protector of α-methylhydroxystyrene, tetrahydropyranyl protector of α-methyl-hydroxystyrene, tetrahydrofuranyl protector of α-methylhydroxystyrene, 1 of 4-hydroxyphenyl methacrylate -An alkoxyalkyl protector, a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate, a tetrahydrofuranyl protector of 4-hydroxyphenyl methacrylate, and the like. Among these, a 1-alkoxyalkyl protector of α-methylhydroxystyrene or a tetrahydrofuranyl protector of α-methylhydroxystyrene is preferable.

  Specific examples of the acetal protecting group and the ketal protecting group for the phenolic hydroxyl group include 1-alkoxyalkyl groups, such as 1-ethoxyethyl group, 1-methoxyethyl group, 1-n-butoxyethyl group, 1- Isobutoxyethyl group, 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) Examples thereof include an ethyl group, a 1-benzyloxyethyl group, a tetrahydropyranyl group, and a tetrahydrofuranyl group. Among them, a 1-ethoxyethyl group or a tetrahydrofuranyl group is preferable. These can be used alone or in combination of two or more.

  A commercially available thing may be used for the radically polymerizable monomer used in order to form a structural unit (a1-2), and what was synthesize | combined by the well-known method can also be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.

  Preferable specific examples of the structural unit (a1-2) include the following structural units, but the present invention is not limited thereto. R represents a hydrogen atom or a methyl group.

  In the monomer unit constituting the component (A), the content of the monomer unit (a1) is preferably from 3 to 70 mol%, and preferably from 5 to 60 mol, based on the copolymer of the component (A), from the viewpoint of sensitivity. % Is more preferable, and 10 to 50 mol% is more preferable.

  A structural unit having a residue in which a carboxyl group is protected with an acid-decomposable group develops faster than a structural unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group. Therefore, when it is desired to develop quickly, a structural unit having a residue in which a carboxyl group is protected with an acid-decomposable group is preferable. Conversely, when it is desired to delay development, it is preferable to use a structural unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group.

<Structural unit (a2)>
The component (A) has a monomer unit (a2) having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment. Preferred embodiments of the monomer unit having a crosslinkable group include a structural unit having a 3-membered or 4-membered cyclic ether residue, —NH—CH ₂ —O—R (R is an alkyl group having 1 to 20 carbon atoms) And a monomer unit containing at least one member selected from the group consisting of a structural unit having an ethylenically unsaturated group and a 3-membered or 4-membered cyclic ether residue. A structural unit having a group and a structural unit having a group represented by —NH—CH ₂ —O—R (wherein R is an alkyl group having 1 to 20 carbon atoms) is more preferable, and a 3-membered or 4-membered cyclic ether A structural unit having a residue is more preferred.

(A2-1) Structural unit having a 3-membered ring and / or 4-membered cyclic ether residue The (A) copolymer is a structural unit having a 3-membered ring and / or 4-membered cyclic ether residue. It is preferable to contain (monomer unit (a2-1)). The 3-membered cyclic ether residue is also called an epoxy group, and the 4-membered cyclic ether residue is also called an oxetanyl group. The structural unit (a2-1) having an epoxy group and / or oxetanyl group is preferably a monomer unit having an alicyclic epoxy group and / or oxetanyl group, more preferably a structural unit having an oxetanyl group. preferable. The component A is preferably contained as a structural unit having an epoxy group or an oxetanyl group. Further, the structural unit (a2-1) may include both an epoxy group and an oxetanyl group.

The alicyclic epoxy group is a group in which an aliphatic ring and an epoxy ring form a condensed ring. Specifically, for example, 3,4-epoxycyclohexyl group, 2,3-epoxycyclohexyl group, 2,3 -An epoxy cyclopentyl group etc. are mentioned preferably.
The group having an oxetanyl group is not particularly limited as long as it has an oxetane ring, but a (3-ethyloxetane-3-yl) methyl group can be preferably exemplified.
The structural unit having an epoxy group or oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, and may include one or more epoxy groups and one or more oxetanyl groups. Well, it may have two or more epoxy groups, or two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and oxetanyl groups, It is more preferable to have one or two oxetanyl groups in total, and it is even more preferable to have one epoxy group and one oxetanyl group.

  Specific examples of the radical polymerizable monomer used to form the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, acrylate-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, cycloaliphatic described in paragraphs 0031 to 0035 of Japanese Patent No. 4168443 Examples include compounds containing an epoxy skeleton That.

  Examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include, for example, (meth) acrylic acid having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Examples include esters.

  Examples of the radical polymerizable monomer used for forming the structural unit having an epoxy group or an oxetanyl group are preferably a monomer containing a methacrylic ester structure and a monomer containing an acrylic ester structure.

  Among these radically polymerizable monomers, more preferred are compounds containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and paragraphs of JP 2001-330953 A. (Meth) acrylic acid ester having an oxetanyl group described in 0011 to 0016, and particularly preferable is a (meth) acrylic acid ester having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. is there. Among these, preferred are 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyloxetane-3-yl) methyl acrylate, and methacrylic acid (3-ethyloxetane). -3-yl) methyl, most preferred are (3-ethyloxetane-3-yl) methyl acrylate and (3-ethyloxetane-3-yl) methyl methacrylate. These structural units can be used individually by 1 type or in combination of 2 or more types.

  Preferable specific examples of the structural unit (a2-1) include the following structural units.

(A2-2) Structural unit having a group represented by —NH—CH ₂ —O—R (R is an alkyl group having 1 to 20 carbon atoms) The copolymer used in the present invention is —NH—CH ₂ —. The structural unit (a2-2) having a group represented by O—R (R is an alkyl group having 1 to 20 carbon atoms) is also preferable. By having the structural unit (a2-2), a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group. The structural unit (a2) is more preferably a structural unit having a group represented by the following general formula (a2-20).
(In General Formula (a2-20), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms.)
R ² is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
Specific examples of R ² include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl, n-butyl and methyl are preferred.

(A2-3) Structural unit having an ethylenically unsaturated group As one of the structural units (a2) having a crosslinkable group, there may be mentioned a structural unit (a2-3) having an ethylenically unsaturated group (hereinafter, “ Monomer unit (a2-3) "). The structural unit (a2-3) having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in the side chain, having an ethylenically unsaturated group at the terminal, and having 3 to 16 carbon atoms. A structural unit having a side chain is more preferable, and a structural unit having a side chain represented by the formula (a2-3-1) is more preferable.

(In formula (a2-3-1), R ¹ represents a divalent linking group having 1 to 13 carbon atoms, and R ³ represents a hydrogen atom or a methyl group.)

R ¹ is a divalent linking group having 1 to 13 carbon atoms, and includes an alkenyl group, an arylene group, or a combination thereof, and includes bonds such as an ester bond, an ether bond, an amide bond, and a urethane bond. May be. The alkenyl group may be a cyclic alkenyl group. The divalent linking group may have a substituent such as a hydroxy group or a carboxyl group at an arbitrary position. Specific examples of R ¹ include divalent linking groups represented by formula (A-1) to formula (A-10).

  Among the side chains represented by the formula (a2-3-1), an aliphatic side chain is preferable. Among the side chains having a linking group represented by the formula (a2-3-1), a side chain whose terminal is an acryloyl group or a methacryloyl group is more preferable.

  Moreover, it is preferable that 1 mol of ethylenically unsaturated groups contained in the side chain represented by the formula (a2-3-1) are included with respect to 150 to 2,000 g of the polymer (A). It is more preferable that 1 mol is contained with respect to ˜1,300 g.

The method for obtaining the monomer unit (a2-3) having a side chain represented by the formula (a2-3-1) is not particularly limited, but for example, a polymer having a specific functional group may be obtained in advance by a polymerization method such as radical polymerization. Copolymer having a monomer unit (a2-3) by reacting with a group that reacts with the specific functional group and a compound having an ethylenically unsaturated group at the terminal (hereinafter referred to as a specific compound). Can be combined.
Here, examples of the specific functional group include a carboxyl group, an epoxy group, a hydroxy group, an amino group having active hydrogen, a phenolic hydroxyl group, and an isocyanate group. A monomer having a specific functional group for synthesizing a polymer having a specific functional group will be described later.

  As a combination of the specific functional group and a group that reacts with the specific functional group of the specific compound, a combination of a carboxyl group and an epoxy group, a combination of a carboxyl group and an oxetanyl group, a combination of a hydroxy group and an isocyanate group, Examples include a combination of a phenolic hydroxyl group and an epoxy group, a combination of a carboxyl group and an isocyanate group, a combination of an amino group and an isocyanate group, and a combination of a hydroxy group and an acid chloride.

  Examples of the specific compound include glycidyl methacrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, isocyanate ethyl methacrylate, isocyanate ethyl acrylate, methacrylic acid chloride, acrylic acid chloride, Examples include methacrylic acid and acrylic acid.

  Preferred combinations of the specific functional group and the specific compound include a combination of a carboxyl group that is a specific functional group and a glycidyl methacrylate that is a specific compound, and a combination of a hydroxy group that is a specific functional group and an isocyanate ethyl methacrylate that is a specific compound. Is mentioned.

  In the present invention, the monomer unit (a2-3) is preferably a monomer unit represented by the formula (a2-3-2).

(In the formula (a2-3-2), R ¹ has the formula (a preferred range has the same meaning as R ¹ is also similar .R ^2, R ³ are each independently of A2-3-1), hydrogen atom or Represents a methyl group.)

  Specific examples of the monomer having a specific functional group necessary for obtaining a polymer having a specific functional group are listed below, but the invention is not limited thereto.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono (2- (acryloyloxy) ethyl) phthalate, mono (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl) maleimide. , N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.
Examples of the monomer having an epoxy group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene, 1,7. -Octadiene monoepoxide, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate and the like.
Examples of the monomer having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3- Dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly (Ethylene glycol) ethyl ether methacrylate, 5-acryloyl Shi-6-hydroxy-norbornene-2-carboxylic-6-lactone, 5-methacryloyloxy-6-hydroxy-norbornene-2-carboxylic-6-lactone and the like.

Examples of the monomer having an amino group having active hydrogen include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.
Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide and the like.
Furthermore, as a monomer which has an isocyanate group, acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, m-tetramethyl xylene isocyanate, etc. are mentioned, for example.

  In the present invention, when obtaining a polymer having a specific functional group, the monomer having the specific functional group and (a1) a structural unit having a residue in which a carboxyl group is protected with an acid-decomposable group, or And a structural unit having a residue in which a phenolic hydroxyl group is protected with an acid-decomposable group. Furthermore, the monomer used as other monomer units (a3) other than (a1) and (a2) mentioned later can be used together.

  The method for obtaining the polymer having a specific functional group used in the present invention is not particularly limited. For example, in a solvent in which a monomer having a specific functional group, other monomers, and a polymerization initiator or the like coexist if desired, 50 to It can be obtained by a polymerization reaction at a temperature of 110 ° C. In that case, the solvent used will not be specifically limited if it dissolves the monomer which comprises the polymer which has a specific functional group, and the polymer which has a specific functional group. As a specific example, the solvent described in the (D) solvent mentioned later is mentioned. The polymer having the specific functional group thus obtained is usually in a solution state dissolved in a solvent.

  Next, the obtained polymer having the specific functional group is reacted with the specific compound to obtain a monomer unit (a2-3) having an ethylenically unsaturated group at the end of the side chain. At that time, a polymer solution having a specific functional group is usually subjected to the reaction. For example, a monomer unit (a2-3) can be obtained by reacting a solution of an acrylic polymer having a carboxyl group with glycidyl methacrylate at a temperature of 80 ° C. to 150 ° C. in the presence of a catalyst such as benzyltriethylammonium chloride. it can.

  Moreover, in order to form a monomer unit (a2-3), in addition to using the polymer reaction as described above, allyl methacrylate, allyl acrylate, or the like may be used as a radical polymerizable monomer. These monomer units can be used alone or in combination of two or more.

  In this invention, it is preferable that a monomer unit (a2-1) is included as a monomer unit (a2).

When the polymer containing the structural unit (a2) does not substantially contain the structural unit (a1), the structural unit (a2) is 5 to 90 in the polymer containing the structural unit (a2). Mol% is preferable and 20-80 mol% is more preferable.
When the polymer containing the structural unit (a2) contains the structural unit (a1), the single structural unit (a2) is contained in the polymer containing the structural unit (a1) and the structural unit (a2). From the viewpoint of chemical resistance, 3-70 mol% is preferable, and 10-60 mol% is more preferable.
In this invention, it is preferable to contain 3-70 mol% of structural units (a2) in all the structural units of (A) component irrespective of any aspect, and it is more preferable to contain 10-60 mol%. preferable.
Within the above numerical range, the transparency and chemical resistance of the cured film obtained from the photosensitive resin composition will be good.

<Other structural units (a3)>
Component A may further have another structural unit (a3) as long as the effects of the present invention are not hindered.
Examples of the radical polymerizable monomer used to form the structural unit (a3) include compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 (however, the above-described configuration). Units (a1) and (a2) are excluded.)
Moreover, it is preferable that the component A further has a structural unit which has an acid group as a structural unit (a3) from a viewpoint of a sensitivity.
The acid group is more preferably a structural unit having a carboxyl group and / or a phenolic hydroxyl group, and still more preferably a structural unit having a carboxyl group.
The structural unit (a3) is preferably a structural unit derived from at least one selected from the group consisting of acrylic acid, methacrylic acid, p-hydroxystyrene, and α-methyl-p-hydroxystyrene. Alternatively, a structural unit derived from methacrylic acid is more preferable, and a structural unit derived from methacrylic acid is particularly preferable.

The structural unit (a3) is preferably derived from at least one selected from the group consisting of a hydroxyl group-containing unsaturated carboxylic acid ester, an alicyclic structure-containing unsaturated carboxylic acid ester, styrene, and an N-substituted maleimide. Also included are structural units.
Among these, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, (meth) acrylic acid tricyclo [5.2.1.0 ² ] from the viewpoint of improving electrical characteristics. ^{, 6} ] decan-8-yloxyethyl, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid esters containing an alicyclic structure such as 2-methylcyclohexyl (meth) acrylate, Alternatively, a hydrophobic monomer such as styrene is preferable. From the viewpoint of sensitivity, 2-hydroxyethyl (meth) acrylate and N-substituted maleimide are preferable. Among these, (meth) acrylic acid esters having an alicyclic structure are more preferable. From the viewpoint of etching resistance, styrenes such as styrene and α-methylstyrene are preferable.
These structural units (a3) can be used individually by 1 type or in combination of 2 or more types.

  The lower limit of the content ratio of the monomer unit forming the structural unit (a3) in the case where the structural unit (a3) is contained in all the monomer units constituting the component A is preferably 1 mol% or more, and more preferably 5 mol% or more. More preferably, 20 mol% or more is still more preferable. The upper limit is preferably 70 mol% or less, more preferably 60 mol% or less, more preferably 50 mol% or less, more preferably 40 mol% or less, and particularly preferably 30 mol% or less.

The component A in this invention may be used individually by 1 type, and may be used in combination of 2 or more type. That is, the component A may be any embodiment that satisfies the following (1) and / or (2).
(1) Embodiment in which (a1) at least one kind of polymer obtained by copolymerizing at least a structural unit having a residue in which an acid group is protected with an acid-decomposable group and (a2) a crosslinkable group ( 2) A mode in which (a1) a polymer having a structural unit having a residue in which an acid group is protected by an acid-decomposable group and (a2) a polymer having a structural unit having a crosslinkable group are used in combination.

  The molecular weight of component A in the present invention is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, still more preferably 4,000 to 30,000, It is especially preferable that it is 10,000-16,000. In addition, it is preferable that the molecular weight of the component A in this invention is a polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC) when tetrahydrofuran (THF) is used as a solvent.

  The content of Component A in the photosensitive resin composition of the present invention is preferably 20 to 99% by weight, and preferably 30 to 95% by weight, based on the total solid content of the photosensitive resin composition. More preferably, it is 30 to 70% by weight. When the content is within this range, the pattern formability upon development is good. In addition, the solid content amount of the photosensitive resin composition represents an amount excluding volatile components such as a solvent.

(Component B) Photoacid Generator The photosensitive resin composition of the present invention contains (Component B) a photoacid generator.
Component B 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.
Component B is preferably a photoacid generator that generates an acid having a pKa of 4 or less, and more preferably a photoacid generator that generates an acid having a pKa of 3 or less.
Examples of the photoacid generator include sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, trichloromethyl-s-triazines, imide sulfonate compounds, and oxime sulfonate compounds.

Specific examples of these include the following.
As trichloromethyl-s-triazines, 2- (3-chlorophenyl) bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) bis (4,6-trichloromethyl) -s- Triazine, 2- (4-methylthiophenyl) bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) bis (4,6-trichloromethyl) -s-triazine, 2 -Piperonylbis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] bis (4,6-trichloromethyl) -s-triazine, 2- [2- (5 -Methylfuran-2-yl) ethenyl] bis (4,6-trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) Thenyl] bis (4,6-trichloromethyl) -s-triazine, or 2- (4-methoxynaphthyl) bis (4,6-trichloromethyl) -s-triazine and the like;

  Examples of 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'-tetradecaoxy) phenyliodonium hexafluoroantimonate, or phenyl-4- (2'-hydroxy-1'-) Tetradecaoxy) phenyliodonium p-toluenesulfonate, etc .;

  Triarylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, etc .;

  As quaternary ammonium salts, tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) borate, benzyl Dimethylphenylammonium butyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexyltris (p-chlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate and the like;

Examples of the diazomethane derivative include bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and the like;
Examples of imide sulfonate derivatives include trifluoromethylsulfonyloxybicyclo [2.2.1] hept-5-enedicarboximide, succinimide trifluoromethyl sulfonate, phthalimide trifluoromethyl sulfonate, N-hydroxynaphthalimide methanesulfonate, N-hydroxy- 5-norbornene-2,3-dicarboximidopropane sulfonate and the like;

  In addition to the above, the compounds described in JP-A 2010-282228, paragraphs 0031 to 0052 can also be employed.

  In the present invention, it is particularly preferable to use an oxime sulfonate compound from the viewpoint of high sensitivity. These photoacid generators can be used singly or in combination of two or more. Specific examples thereof include photoacid generators described in paragraphs 0029 to 0032 of JP-A No. 2004-264623, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethane. Sulfonate and the like are preferably used.

  The photosensitive resin composition of the present invention preferably further contains an oxime sulfonate compound having at least one oxime sulfonate residue represented by the following formula (b0) as (Component B) a photoacid generator. Note that the wavy line represents the bonding position with another chemical structure.

Formula (b0)
The oxime sulfonate compound having at least one oxime sulfonate residue represented by the formula (b0) is preferably a compound represented by the following formula (b1).

(In formula (b1), R ⁵ and R ⁶ each independently represent a monovalent organic group, R ⁵ and R ⁶ may be linked to form a ring, R ⁷ is an alkyl group, Represents an alkyl group or an aryl group.)

In the formula (b1), R ⁵ is an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, a biphenyl group, a naphthyl group, a 2-furyl group, or a 2-thienyl group. Represents an alkoxy group having 1 to 4 carbon atoms or a cyano group. When R ⁵ is a phenyl group, a biphenyl group, a naphthyl group or an anthranyl group, these groups include a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a nitro group. It may be substituted with a substituent selected from the group consisting of groups.
In the formula (b1), R ⁶ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogen having 1 to 5 carbon atoms. Represents a substituted alkoxy group, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W, an anthranyl group optionally substituted with W, a dialkylamino group, a morpholino group, or a cyano group. R ⁶ and R ⁵ may be bonded to each other to form a 5-membered ring or a 6-membered ring, and the 5-membered ring or 6-membered ring may have one or two arbitrary substituents. It may be bonded to a benzene ring.
In formula (b1), R ⁷ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogen having 1 to 5 carbon atoms. Represents an alkoxy group, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W, or an anthranyl group optionally substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents a halogenated alkoxy group.

As the alkyl group having 1 to 6 carbon atoms represented by R ⁵ , the description in paragraph number 0139 of JP2011-227449A can be referred to.
As the halogenated alkyl group having 1 to 4 carbon atoms represented by R ⁵ , the description in paragraph number 0140 of JP2011-227449A can be referred to.
Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ⁵ include a methoxy group and an ethoxy group.
When R ⁵ represents a phenyl group, a biphenyl group, a naphthyl group, or an anthranyl group, these groups can be referred to the description in paragraph number 0142 of JP2011-227449A.
As specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁶ , the description in paragraph number 0142 of JP2011-227449A can be referred to.
As specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ⁶ , the description of paragraph number 0143 in JP2011-227449A can be referred to.
As specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ⁶ , the description in paragraph No. 0144 of JP2011-227449A can be referred to.
As specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ⁶ , the description in paragraph No. 0144 of JP2011-227449A can be referred to.
As a specific example of the phenyl group which may be substituted with W represented by R ⁶ , the description of paragraph number 0145 of JP2011-227449A can be referred to.
As a specific example of the naphthyl group optionally substituted by W represented by R ⁶ , the description of paragraph number 0146 of JP2011-227449A can be referred to.
As a specific example of the anthranyl group which may be substituted with W represented by R ⁶ , description of paragraph number 0147 of JP2011-227449A can be referred to.
Examples of the dialkylamino group represented by R ⁶ include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, and a diphenylamino group.
As specific examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁷ , the description of paragraph number 0148 of JP2011-227449A can be referred to.
As specific examples of the alkoxy group having 1 to 10 carbon atoms represented by R ⁷ , the description of paragraph number 0148 of JP2011-227449A can be referred to.
As specific examples of the halogenated alkyl group having 1 to 5 carbon atoms represented by R ⁷ , the description in paragraph No. 0149 of JP2011-227449A can be referred to.
As specific examples of the halogenated alkoxy group having 1 to 5 carbon atoms represented by R ⁷ , the description in paragraph No. 0149 of JP2011-227449A can be referred to.
As a specific example of the phenyl group which may be substituted with W represented by R ⁷ , description of paragraph number 0150 of JP2011-227449A can be referred to.
As a specific example of the naphthyl group optionally substituted by W represented by R ⁷ , the description of paragraph number 0151 of JP2011-227449A can be referred to.
As a specific example of the anthranyl group which may be substituted with W represented by R ⁷ , the description of paragraph number 0152 of JP2011-227449A can be referred to.

An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and a halogenated alkoxy having 1 to 5 carbon atoms represented by W Specific examples include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and the number of carbon atoms represented by R ⁶ or R ^7. The thing similar to what was mentioned as a specific example of the halogenated alkoxy group of 1-5 is mentioned.

R ⁶ and R ⁵ may be bonded to each other to form a 5-membered ring or a 6-membered ring.
When R ⁶ and R ⁵ are bonded to each other to form a 5-membered ring or 6-membered ring, examples of the 5-membered ring or 6-membered ring include carbocyclic groups and heterocyclic ring groups. It may be a cyclopentane, cyclohexane, cycloheptane, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyran, pyridine, pyrazine, morpholine, piperidine or piperazine ring. The 5-membered ring or 6-membered ring may be bonded to an optionally substituted benzene ring, and examples thereof include tetrahydronaphthalene, dihydroanthracene, indene, chroman, fluorene, xanthene or thiol. Xanthene ring system. The 5-membered or 6-membered ring may contain a carbonyl group, examples of which include cyclohexadienone, naphthalenone and anthrone ring systems.

One of the suitable embodiments of the compound represented by the formula (b1) is a compound represented by the following formula (b1-1). The compound represented by the formula (b1-1) is a compound in which R ⁶ and R ⁵ in the formula (b1) are bonded to form a 5-membered ring.

(In formula (b1-1), R ⁷ has the same meaning as R ⁷ in formula (b1), X represents an alkyl group, an alkoxy group, or a halogen atom, t represents an integer of 0 to 3, When t is 2 or 3, the plurality of X may be the same or different.)

The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
As the halogen atom represented by X, a chlorine atom or a fluorine atom is preferable.
t is preferably 0 or 1.
In formula (b1-1), t is 1, X is a methyl group, the substitution position of X is the ortho position, R ⁷ is a linear alkyl group having 1 to 10 carbon atoms, 7,7 A compound having a -dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.

Specific examples of the oxime sulfonate compound represented by the formula (b1-1) include the following compound (i), compound (ii), compound (iii), compound (iv) and the like. One species may be used alone, or two or more species may be used in combination. Compounds (i) to (iv) can be obtained as commercial products.
It can also be used in combination with other types of photoacid generators.

As one of the preferable embodiments of the compound represented by the formula (b1),
R ⁵ represents an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a phenyl group, a chlorophenyl group, a dichlorophenyl group, a methoxyphenyl group, a 4-biphenyl group, a naphthyl group or an anthranyl group;
R ⁶ represents a cyano group;
R ⁷ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, or W An optionally substituted phenyl group, a naphthyl group optionally substituted with W, or an anthranyl group optionally substituted with W is represented, and W is a halogen atom, a cyano group, a nitro group, or a carbon atom number of 1 Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

  The compound represented by the formula (b1) is also preferably a compound represented by the following formula (b1-2).

In formula (b1-2), R ⁸ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a nitro group, and L represents an integer of 0 to 5. Represent. R ⁷ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, or W A phenyl group which may be substituted, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W; 10 represents an alkyl group, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

R ⁷ in the formula (b1-2) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group. Perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and may be methyl group, ethyl group, n-propyl group, n-butyl group or p-tolyl group. Particularly preferred.
The halogen atom represented by R ⁸ is preferably a fluorine atom, a chlorine atom or a bromine atom.
The alkyl group having 1 to 4 carbon atoms represented by R ⁸ is preferably a methyl group or an ethyl group.
The alkoxy group having 1 to 4 carbon atoms represented by R ⁸ is preferably a methoxy group or an ethoxy group.
As L, 0-2 are preferable, and 0-1 are particularly preferable.

Among the compounds represented by the formula (b1), as a preferable embodiment of the compound included in the compound represented by the formula (b1-2), R ⁵ is a phenyl group or 4-methoxy in the formula (b1). This is an embodiment in which a phenyl group is represented, R ⁶ represents a cyano group, and R ⁷ represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a 4-tolyl group.

  Hereinafter, among the compounds represented by the formula (b1), particularly preferred examples of the compounds included in the compound represented by the formula (b1-2) are shown, but the present invention is not limited thereto.

α- (methylsulfonyloxyimino) benzylcyanide (R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = methyl group)
α- (Ethylsulfonyloxyimino) benzyl cyanide (R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = ethyl group)
α- (n-propylsulfonyloxyimino) benzyl cyanide (R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = n-propyl group)
α- (n-butylsulfonyloxyimino) benzyl cyanide (R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = n-butyl group)
α- (4-Toluenesulfonyloxyimino) benzyl cyanide (R ⁵ = phenyl group, R ⁶ = cyano group, R ⁷ = 4-tolyl group)
α-[(Methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁵ = 4-methoxyphenyl group, R ⁶ = cyano group, R ⁷ = methyl group)
α-[(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁵ = 4-methoxyphenyl group, R ⁶ = cyano group, R ⁷ = ethyl group)
α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁵ = 4-methoxyphenyl group, R ⁶ = cyano group, R ⁷ = n-propyl group)
α-[(n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁵ = 4-methoxyphenyl group, R ⁶ = cyano group, R ⁷ = n-butyl group)
α-[(4-Toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ⁵ = 4-methoxyphenyl group, R ⁶ = cyano group, R ⁷ = 4-tolyl group)

  The compound having at least one oxime sulfonate residue represented by the formula (b0) is represented by the following formula (OS-3), formula (OS-4), or formula (OS-5). An oxime sulfonate compound is preferred.

(In the formulas (OS-3) to (OS-5), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R ² are each independently a hydrogen atom, an alkyl group, an aryl group, Or a plurality of R ^{6 s} each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group, X represents O or S, n Represents 1 or 2, m represents an integer of 0-6.)

In the formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group represented by R ¹ may have a substituent.
In the formulas (OS-3) to (OS-5), the alkyl group represented by R ¹ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
In the formulas (OS-3) to (OS-5), the aryl group represented by R ¹ is preferably an aryl group having 6 to 30 carbon atoms in total which may have a substituent.
In the formulas (OS-3) to (OS-5), the heteroaryl group represented by R ¹ is preferably a heteroaryl group having a total carbon number of 4 to 30 which may have a substituent. There may be at least one heteroaromatic ring. For example, the heteroaromatic ring and the benzene ring may be condensed.
Examples of the substituent that the alkyl group, aryl group or heteroaryl group represented by R ¹ may have include a halogen atom, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkyloxycarbonyl group, aryl Examples thereof include an oxycarbonyl group and an aminocarbonyl group.

In the formulas (OS-3) to (OS-5), R ² is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group.
In the formulas (OS-3) to (OS-5), it is preferable that one or two of R ² present in the compound is an alkyl group, an aryl group or a halogen atom, and one is an alkyl group. More preferably an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the rest is a hydrogen atom.
In the formulas (OS-3) to (OS-5), the alkyl group or aryl group represented by R ² may have a substituent.
Examples of the substituent that the alkyl group or aryl group represented by R ² may have include the same groups as the substituent that the alkyl group or aryl group in R ¹ may have.

In the formulas (OS-3) to (OS-5), the alkyl group represented by R ² is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent. It is more preferable that it is a C1-C6 alkyl group which may have a group.
As the alkyl group represented by R ² , a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group are preferable, and a methyl group is more preferable.

In the formulas (OS-3) to (OS-5), the aryl group represented by R ² is preferably an aryl group having 6 to 30 carbon atoms in total which may have a substituent.
The aryl group represented by R ² is preferably a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group.

In the formulas (OS-3) to (OS-5), X represents O or S, and is preferably O.
In the formulas (OS-3) to (OS-5), the ring containing X as a ring member is a 5-membered ring or a 6-membered ring.
In the formulas (OS-3) to (OS-5), n represents 1 or 2, and when X is O, n is preferably 1, and when X is S, n is 2 is preferable.

In the formulas (OS-3) to (OS-5), the alkyl group and alkyloxy group represented by R ⁶ may have a substituent.

In the formulas (OS-3) to (OS-5), the alkyl group represented by R ⁶ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
As the alkyloxy group represented by R ⁶ , a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group is preferable.
Examples of the aminosulfonyl group for R ⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and an aminosulfonyl group.
Examples of the alkoxysulfonyl group represented by R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.

Examples of the substituent that the alkyl group or alkyloxy group represented by R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, and an aryloxycarbonyl group. And aminocarbonyl group.

  In the formulas (OS-3) to (OS-5), m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. It is particularly preferred.

  The compound represented by the formula (OS-3) is particularly preferably a compound represented by the following formula (OS-6), formula (OS-10) or formula (OS-11), The compound represented by the formula (OS-4) is particularly preferably a compound represented by the following formula (OS-7), and the compound represented by the formula (OS-5) is represented by the following formula (OS −8) or a compound represented by the formula (OS-9) is particularly preferable.

In the formulas (OS-6) to (OS-11), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, R ⁷ represents a hydrogen atom or a bromine atom, R ⁸ represents a hydrogen atom, and a carbon number of 1 8 alkyl group, a halogen atom, chloromethyl group, bromomethyl group, bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, R ¹⁰ Represents a hydrogen atom or a methyl group.

R ¹ in the formulas (OS-6) to (OS-11) has the same meaning as R ¹ in the formulas (OS-3) to (OS-5), and preferred embodiments thereof are also the same.
R ⁷ in the formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
R ⁸ in the above formulas (OS-6) to (OS-11) is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or Represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. More preferred is a methyl group.
R ⁹ in Formula (OS-8) and Formula (OS-9) represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, and is preferably a hydrogen atom.
R ¹⁰ in the formulas (OS-8) to (OS-11) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
In the oxime sulfonate compound, the oxime steric structure (E, Z) may be either one or a mixture.

  Specific examples of the oxime sulfonate compounds represented by the formulas (OS-3) to (OS-5) include the following exemplary compounds, but the present invention is not limited thereto.

  Other suitable embodiments of the oxime sulfonate compound having at least one oxime sulfonate residue represented by the formula (b0) include those described in paragraphs 0117 to 0129 of JP2011-209719A. It is done.

  The content of the (Component B) photoacid generator in the photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by weight, and 0.5 to 10 parts by weight with respect to 100 parts by weight of the solid content. More preferably, it is a part.

(Component C) Chain aliphatic epoxy compound In this invention, (Component C) a chain aliphatic epoxy compound is included. By adding a chain aliphatic epoxy, it is possible to improve non-uniform stripes (especially radial stripes) when applying the composition (especially during spin coating) without deteriorating liquid crystal contamination (electrical properties). The reason for the improvement has not yet been clarified, but it is presumed that the fluidity of the composition coated on the substrate could be improved.
The chain aliphatic epoxy that can be used in the present invention has a molecular weight (in the case of a polymer, a weight average molecular weight) of preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less. . As a lower limit, it can be set as 100 or more, for example. In addition, when the weight average molecular weight of a chain aliphatic epoxy compound is not described in a catalog etc., it can estimate by calculation of (epoxy equivalent) x (number of functional groups). Further, the viscosity of the chain aliphatic epoxy at 25 ° C. is preferably 3000 mPa · s or less, more preferably 2000 mPa · s or less, and further preferably 1000 mPa · s or less. The lower limit is not particularly defined, but can be set to 5 mPa · s or more, for example.
The aliphatic epoxy compound used in the present invention is a resin having a linear and / or branched carbon chain and an epoxy group, and in addition to a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a chlorine atom, etc. May be combined. In the present invention, a resin comprising a linear and / or branched carbon chain, a hydrogen atom, and an epoxy group, or a group in which a hydroxyl group is substituted on the resin is particularly preferable. 1-4 are preferable and, as for the number of an epoxy group, 2 or 3 is more preferable.
In the present invention, it is also preferable that the cycloaliphatic epoxy compound is not substantially contained. By setting it as such a structure, it exists in the tendency for the effect of this invention to be exhibited more effectively. Here, “substantially not contained” means that it is not added at a level that affects the effects of the present invention, for example, 1% by weight or less of the total solid content.

The chain aliphatic epoxy compound used in the present invention is preferably a resin represented by the following general formula (X-1).
Formula (X-1)
(In General Formula (X-1), A is a linear or branched hydrocarbon group, which may have a hydroxyl group as a substituent, and n is an integer of 1 to 4.)
1-20 are preferable, as for carbon number of A, 1-15 are preferable, 2-10 are more preferable, and 2-6 are more preferable. n is an integer of 1 to 4, and 2 or 3 is preferable.

The chain aliphatic epoxy compound used in the present invention is more preferably a resin represented by the following general formula (X-2).
Formula (X-2)
(In General Formula (X-2), B is a linear or branched hydrocarbon group, which may have a hydroxyl group as a substituent, and n is an integer of 1 to 4.)
1-18 are preferable, as for carbon number of B, 1-13 are preferable and 2-8 are more preferable. n is an integer of 1 to 4, and 2 or 3 is preferable.

Examples of the chain aliphatic epoxy that can be preferably used in the present invention include Denacol EX-611 (11,800 mPa · s), EX-612 (11,900 mPa · s), EX-614 (21,200 mPa · s). , EX-614B (5,000 mPa · s), EX-622 (11,800 mPa · s), EX-512 (1,300 mPa · s), EX-521 (4,400 mPa · s), EX-411 (800 mPa S), EX-421 (650 mPa · s), EX-313 (150 mPa · s), EX-314 (170 mPa · s), EX-321 (130 mPa · s), EX- 211 (20 mPa · s), EX -212 (20 mPa · s), EX-810 (20 mPa · s), EX-811 (20 mPa · s), EX-850 (20 Pa · s), EX-851 (30 mPa · s), EX-821 (40 mPa · s), EX-830 (70 mPa · s), EX-832 (90 mPa · s), EX-841 (110 mPa · s), EX-911 (20 mPa · s), EX-941 (25 mPa · s), EX-920 (20 mPa · s), EX-931 (120 mPa · s), EX-212L (15 mPa · s), EX-214L (15 mPa · s)・ S), EX-321L (800 mPa · s), EX-850L (90 mPa · s), EX-211L (20 mPa · s), EX-946L (50 mPa · s), EX-946L (50 mPa · s), DLC -201 (10 mPa · s), DLC-203 (8 mPa · s), DLC-204 (1,700 mPa · s), DLC-205 15 mPa · s), DLC-206 (20 mPa · s), DLC-301 (60 mPa · s), DLC-402 (150 mPa · s) (manufactured by Nagase Chemtech, the viscosity in parentheses is 25 ° C), YH- 300 (140 to 160 mPa · s), YH-301 (160 to 220 mPa · s), YH-302 (700 to 1100 mPa · s), YH-315 (700 to 1100 mPa · s), YH-324 (3500 to 5500 mPa · s) s), YH-325 (4000 to 6000 mPa · s) (manufactured by Nippon Steel Chemical Co., Ltd.) and the like.
Among these, it is particularly preferable that it contains trimethylolpropane triglycidyl ether or neopentyl glycol diglycidyl ether shown in the following figure. Among these, EX-321, EX-321L, EX-211 and EX-211L (manufactured by Nagase Chemtech) correspond to it.

  The content of (Component C) the chain aliphatic epoxy compound in the photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the solid content, 0.5 to More preferably, it is 10 parts by weight.

(Component D) Solvent The photosensitive resin composition of the present invention preferably contains (Component D) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which essential components and optional components are dissolved.
As the solvent used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl. Ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether Examples include acetates, esters, ketones, amides, lactones and the like. Examples of the solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraph 0074 of JP-A-2009-258722.
Of the above solvents, diethylene glycol ethyl methyl ether and / or propylene glycol monomethyl ether acetate are particularly preferred.
These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is preferably a single type or a combination of two types, more preferably a combination of two types, and a combination of propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers. Is more preferable.

  The content of Component D in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by weight, more preferably 100 to 2,000 parts by weight, with respect to 100 parts by weight of Component A. More preferably, it is 150 to 1,500 parts by weight.

  The content of the (component D) solvent in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by weight and 100 to 2,000 parts by weight per 100 parts by weight of the total solid content. Is more preferable, and it is still more preferable that it is 150-1,500 weight part.

<Other ingredients>
The photosensitive resin composition of the present invention can contain other components.
As other components, the photosensitive resin composition of the present invention preferably contains (L) a sensitizer from the viewpoint of sensitivity, and contains (H) a basic compound from the viewpoint of liquid storage stability. From the viewpoint of film physical properties, it is preferable to contain a crosslinking agent, from the viewpoint of substrate adhesion, it is preferable to contain (G) an adhesion improver, and from the viewpoint of coatability, (I) It is preferable to contain a surfactant.
Hereinafter, other components that can be contained in the photosensitive resin composition of the present invention will be described.

[Sensitizer]
The photosensitive resin composition of the present invention preferably contains a sensitizer (usually a photosensitizer).
By containing a photosensitizer, it is effective for improving exposure sensitivity, and is particularly effective when the exposure light source is a g-line or h-line mixed line.
As the photosensitizer, anthracene derivatives, acridone derivatives, thioxanthone derivatives, coumarin derivatives, base styryl derivatives, and distyrylbenzene derivatives are preferable.
Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 , 10-dibromoanthracene, 2-ethylanthracene and 9,10-dimethoxyanthracene are preferred.
As an acridone derivative, acridone, N-butyl-2-chloroacridone, N-methylacridone, 2-methoxyacridone and N-ethyl-2-methoxyacridone are preferable.
As the thioxanthone derivative, thioxanthone, diethylthioxanthone, 1-chloro-4-propoxythioxanthone, and 2-chlorothioxanthone are preferable.
As the coumarin derivative, coumarin-1, coumarin-6H, coumarin-110 and coumarin-102 are preferable.
Examples of the base styryl derivative include 2- (4-dimethylaminostyryl) benzoxazole, 2- (4-dimethylaminostyryl) benzothiazole, and 2- (4-dimethylaminostyryl) naphthothiazole.
Examples of the distyrylbenzene derivative include distyrylbenzene, di (4-methoxystyryl) benzene, and di (3,4,5-trimethoxystyryl) benzene.
Among these, an anthracene derivative is preferable, and 9,10-dialkoxyanthracene (an alkoxy group having 1 to 6 carbon atoms) is more preferable.
Specific examples of the photosensitizer include the following. In the following, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

  The content of the sensitizer in the photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by weight, and preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the total solid content. Is more preferable. When the content of the sensitizer is 0.1 parts by weight or more, desired sensitivity is easily obtained, and when it is 10 parts by weight or less, the transparency of the coating film is easily secured.

[Basic compounds]
The photosensitive resin composition of the present invention preferably contains a basic compound from the viewpoint of liquid storage stability.
The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.

Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0 ] -5-Nonene, 1,8-di And azabicyclo [5.3.0] -7-undecene.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

The basic compounds that can be used in the present invention may be used singly or in combination of two or more. However, it is preferable to use two or more in combination, and it is more preferable to use two in combination. Preferably, two kinds of heterocyclic amines are used in combination.
It is preferable that content of the basic compound in the photosensitive resin composition of this invention is 0.001-1 weight part with respect to 100 weight part of total solids, and is 0.002-0.2 weight part. More preferably.

[Adhesion improver]
The photosensitive resin composition of the present invention preferably contains an adhesion improver from the viewpoint of substrate adhesion.
Adhesion improvers that can be used in the photosensitive resin composition of the present invention are inorganic substances that serve as substrates, for example, silicon compounds such as silicon, silicon oxide, and silicon nitride, molybdenum, titanium, indium tin oxide, gold, copper, and aluminum. It is a compound that improves the adhesion between the metal and the insulating film. Specific examples include silane coupling agents and thiol compounds. The silane coupling agent as an adhesion improving agent used in the present invention is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
Among these, a silane coupling agent can be preferably exemplified. However, the silane coupling agent of the present invention refers to a compound having one hydrolyzable silyl group or silanol group in one molecule, and a silicon compound corresponding to Component X is not included in the silane coupling agent of the present invention. .
Preferred silane coupling agents include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ- Methacryloxypropyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltri An alkoxysilane is mentioned.
Among these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, and γ-glycidoxypropyltrialkoxysilane is more preferable.
These can be used alone or in combination of two or more. These are effective in improving the adhesion to the substrate and are also effective in adjusting the taper angle with the substrate.
0.1-20 weight part is preferable with respect to 100 weight part of total solids, and, as for content of the adhesion improving agent in the photosensitive resin composition of this invention, 0.5-10 weight part is more preferable.

[Surfactant]
The photosensitive resin composition of the present invention preferably contains a surfactant from the viewpoint of applicability.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, fluorine-based and silicone surfactants. .

The photosensitive resin composition of the present invention more preferably contains a fluorine-based surfactant and / or a silicone-based surfactant as the surfactant.
As these fluorosurfactants and silicone surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, Surfactants described in JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, and JP-A-2001-330953 are listed. Commercially available surfactants can also be used.
Examples of commercially available surfactants that can be used include EFTOP EF301, EF303 (above, Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (above, Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189, R08 (above, manufactured by DIC Corporation), Surflon S-382, SC101, 102, 103, 104, 105, 106 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox series (produced by OMNOVA), etc. Mention may be made of fluorine-based surfactants or silicone-based surfactants. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

  In addition, as a surfactant, the structural unit A and the structural unit B represented by the following formula (1) are included, and the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A preferred example is a copolymer having (Mw) of 1,000 or more and 10,000 or less.

(In the formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or carbon number. 1 represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are weight percentages representing a polymerization ratio, and p is a numerical value of 10% to 80% by weight. Q represents a numerical value of 20 wt% or more and 90 wt% or less, r represents an integer of 1 or more and 18 or less, and n represents an integer of 1 or more and 10 or less.)

The L is preferably a branched alkylene group represented by the following formula (2). R ⁵ in the formula (2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. More preferred is an alkyl group of 3.

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, more preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total solid content. More preferably, the content is 0.01 to 1 part by weight.

<Others>
If necessary, the photosensitive resin composition of the present invention may contain other components such as a plasticizer, a thermal radical generator, a thermal acid generator, an acid multiplier, a development accelerator, and an antioxidant. it can. As these components, for example, those described in JP2009-98616A, JP2009-244801A, and other known ones can be used. In addition, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators and the like may be added to the photosensitive resin composition of the present invention. .

(Method for forming cured film)
Next, the formation method of the cured film of this invention is demonstrated.
The method for forming a cured film of the present invention is not particularly limited except that the positive photosensitive resin composition of the present invention is used, but preferably includes the following steps (1) to (5).
(1) The step of applying (preferably coating) the positive photosensitive resin composition of the present invention onto a substrate (2) The step of removing the solvent from the applied photosensitive resin composition (3) The solvent was removed Step of exposing the photosensitive resin composition with actinic rays (4) Step of developing the exposed photosensitive resin composition with an aqueous developer (5) Post-baking step of thermosetting the developed photosensitive resin composition In the method for forming a cured film of the invention, after the exposure in the exposure step, the developing step (4) may be performed without performing a heat treatment.
Moreover, it may further include a step of exposing the entire surface of the developed photosensitive resin composition before the post-baking step.
Each step will be described below in order.

In the application step (1), it is preferable to apply the positive photosensitive resin composition of the present invention on a substrate to form a wet film containing a solvent.
In the solvent removal step (2), it is preferable to form a dry coating film on the substrate by removing the solvent from the applied film by vacuum (vacuum) and / or heating.

In the exposure step (3), it is preferable to irradiate the obtained coating film with an actinic ray having a wavelength of 300 nm to 450 nm. In this step, the specific acid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group in the structural unit (a1) contained in Component A is decomposed to generate an acid group.
In the region where the acid catalyst is generated, post exposure bake (hereinafter also referred to as “PEB”) may be performed as necessary in order to accelerate the decomposition reaction. PEB can promote the generation of acid groups from acid-decomposable groups.
The acid-decomposable group in the structural unit (a1) in the specific resin has a low activation energy for acid decomposition, and is easily decomposed by an acid derived from a photoacid generator by exposure to generate an acid group. There is no need. Therefore, it is preferable to perform the developing step after the exposure step without performing a heat treatment. More specifically, it is preferable to form a positive image by performing development in the development step (4) without performing PEB after the exposure step (3).
In addition, by performing PEB at a relatively low temperature, decomposition of the acid-decomposable group can be promoted without causing a crosslinking reaction. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 90 ° C. or lower.

In the development step (4), it is preferable to develop component A having a free acid group and component B having an acid group using an alkaline developer. A positive image can be formed by removing an exposed area containing a photosensitive resin composition having an acid group that is easily dissolved in an alkaline developer.
In the post-baking step (5), the obtained positive image is heated, for example, by thermally decomposing an acid group in the structural unit (b1) and an acid-decomposable group in the structural unit (a1). The cured acid film can be crosslinked with the crosslinkable group in the structural unit (a2) and the structural unit (b2) to form a cured film. This heating is preferably performed at a high temperature of 150 ° C. or more, more preferably 180 to 250 ° C., and particularly preferably 200 to 250 ° C. The heating time can be appropriately set depending on the heating temperature or the like, but is preferably in the range of 10 to 90 minutes.

Furthermore, it is preferable to include a step of exposing the entire surface of the developed photosensitive resin composition before the post-baking step, and the entire surface of the developed photosensitive resin composition is irradiated with actinic rays, preferably ultraviolet rays. If a process is added, a crosslinking reaction can be accelerated | stimulated with the acid which generate | occur | produces by irradiation of actinic light.
Next, the formation method of the cured film using the photosensitive resin composition of this invention is demonstrated concretely.

[Method for preparing photosensitive resin composition]
A solvent is mixed with the essential components of the specific resin and the acid generator in a predetermined ratio and in an arbitrary manner as required, and stirred to dissolve to prepare a photosensitive resin composition. For example, a photosensitive resin composition can be prepared by preparing a solution in which a specific resin or an acid generator is previously dissolved in a solvent and then mixing them in a predetermined ratio. The solution of the photosensitive resin composition prepared as described above can be used after being filtered using a filter having a pore size of 0.1 μm or the like.

<Application process and solvent removal process>
A desired dry coating film can be formed by applying the photosensitive resin composition to a predetermined substrate and removing the solvent by decompression and / or heating (pre-baking). Examples of the substrate include a polarizing plate, a glass plate provided with a black matrix layer and a color filter layer as necessary, and a transparent conductive circuit layer in manufacturing a liquid crystal display device. The application method to the substrate is not particularly limited, but application is preferable. For example, a slit coating method, a spray method, a roll coating method, a spin coating method, or the like can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Here, the large substrate means a substrate having a side of 1 m or more on each side.
In addition, (2) the heating conditions in the solvent removal step are such that the acid-decomposable group is decomposed in the structural unit (a1) in the component A in the unexposed area and the component A is not soluble in the alkaline developer. Yes, although it varies depending on the type and mixing ratio of each component, it is preferably about 70 to 120 ° C. for about 30 to 300 seconds.

<Exposure process>
(3) In the exposure step, the substrate provided with the dry coating film of the photosensitive resin composition is irradiated with an actinic ray having a predetermined pattern. Exposure may be performed through a mask, or a predetermined pattern may be drawn directly. Actinic rays having a wavelength of 300 nm to 450 nm can be preferably used. You may perform PEB as needed after an exposure process.
For exposure with actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a laser generator, an LED light source, or the like can be used.
When a mercury lamp is used, actinic rays having wavelengths such as g-line (436 nm), i-line (365 nm), and h-line (405 nm) can be preferably used. Mercury lamps are preferred in that they are suitable for large area exposure compared to lasers.

  In the case of using a laser, 343 nm and 355 nm are preferably used for a solid (YAG) laser, 351 nm (XeF) is preferably used for an excimer laser, and 375 nm and 405 nm are preferably used for a semiconductor laser. Among these, 355 nm and 405 nm are more preferable from the viewpoints of stability and cost. The coating can be irradiated with the laser once or a plurality of times. Specific examples and preferred ranges of the energy density, pulse width, laser frequency, exposure apparatus, and filter include those described in paragraphs 0098 to 0100 of JP2011-186398A.

<Development process>
(4) In the developing step, the exposed area is removed using a basic developer to form an image pattern. Examples of the basic compound used in the developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium bicarbonate, bicarbonate Alkali metal bicarbonates such as potassium; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. 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 not particularly limited as long as it can be developed, but it is preferably 10.0 to 14.0.
The development time is preferably 30 to 180 seconds, and the development method may be any of a liquid piling method, a dip method, a shower method, and the like. After the development, washing with running water is performed for 10 to 90 seconds to form a desired pattern.

<Post-bake process (crosslinking process)>
For a pattern corresponding to an unexposed area obtained by development, using a heating device such as a hot plate or oven, at a predetermined temperature, for example, 180 to 250 ° C., for a predetermined time, for example, 5-60 minutes on the hot plate, In the case of an oven, heat treatment is performed for 30 to 90 minutes to decompose an acid-decomposable group in the specific resin to generate a carboxyl group and / or a phenolic hydroxyl group, and an epoxy group and / or oxetanyl in the specific resin. By reacting with a crosslinkable group which is a group and crosslinking, a protective film and an interlayer insulating film excellent in heat resistance, hardness and the like can be formed. In addition, when heat treatment is performed, the transparency can be improved by performing the heat treatment in a nitrogen atmosphere.
Prior to the heat treatment, the substrate on which the pattern is formed is re-exposed with actinic rays and then post-baked (re-exposure / post-bake) to generate an acid from the acid generator (B) present in the unexposed portion. It is preferable to function as a catalyst for promoting crosslinking.
That is, the method for forming a cured film in the present invention preferably includes a step of re-exposing with actinic rays between the development step and the post-baking step.
The exposure in the re-exposure step may be performed by the same means as in the exposure step. In the re-exposure step, the entire surface of the substrate on which the film is formed by the photosensitive resin composition of the present invention is exposed. It is preferable. A preferable exposure amount in the re-exposure step is 100 to 1,000 mJ / cm ² .

The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention, and can be suitably used as an electronic member, particularly as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
By the photosensitive resin composition of the present invention, a cured film having a high sensitivity, generation of residues during development, and a surface having excellent smoothness is obtained, and the cured film is used as an interlayer insulating film. Useful. In addition, the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency, can form a good pattern shape, and has excellent surface smoothness. It is useful for applications of display devices and liquid crystal display devices.
As an organic EL display device or a liquid crystal display device to which the photosensitive resin composition of the present invention can be applied, a cured film formed using the photosensitive resin composition of the present invention is formed as a planarizing film, a protective film, or an interlayer insulating film. There is no particular limitation except for the use as a known organic EL display device and a liquid crystal display device having various structures.

[Organic EL display device, Liquid crystal display device]
The organic EL display device and the liquid crystal display device of the present invention are characterized by including the cured film of the present invention.
The organic EL display device or liquid crystal display device of the present invention is not particularly limited except that it has a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and has various structures. Various known organic EL display devices and liquid crystal display devices can be used.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device and the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
Further, liquid crystal display devices that can be taken by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Virtual Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field).
Examples thereof include a switching method and an OCB (Optical Compensated Bend) method.
Specific examples of the alignment method of the liquid crystal alignment film that can be taken by the liquid crystal display device of the present invention include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP2003-149647A or JP2011-257734A.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a color filter protective film, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.

FIG. 1 is a conceptual diagram showing an example of an organic EL display device using the photosensitive resin composition of the present invention. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, a planarizing film 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 1, a hole transport layer, an organic light-emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a first layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.

  FIG. 2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.

  The 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.

<Synthesis Example 1>
A flask equipped with a condenser and a stirrer was charged with 150 parts by weight of diethylene glycol ethyl methyl ether, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. In the solution, 41.3 parts by weight of 1-ethoxyethyl methacrylate, 23.9 parts by weight of glycidyl methacrylate, 5.6 parts by weight of methacrylic acid, 13.5 parts by weight of styrene, and a polymerization initiator 10.0 parts by weight of dimethyl-2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved and added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 2 hours. To the solution, 2.5 parts by weight of dimethyl-2,2′-azobis (2-methylpropionate) was further added and stirred for 2 hours to complete the reaction. Thereby, polymer A-1 was obtained. The weight average molecular weight was 13,000.

<Synthesis Examples 2 to 26>
Polymers A-2 to A-26 shown in the following table were synthesized in the same manner as in Synthesis Example 1 except that the monomers used and the amounts thereof were changed. The composition ratio (mol%) and weight average molecular weight (Mw) of each synthesized polymer are as shown in the following table.

Abbreviations in Table 1 are as follows.
MAEVE: 1-ethoxyethyl methacrylate (synthesis example will be described later)
MATHF: Tetrahydro-2H-furan-2-yl methacrylate (synthesis examples will be described later)
MACHOE: 1- (cyclohexyloxy) ethyl methacrylate (synthesis examples will be described later)
PHSEVE: 1-ethoxyethyl group protector of p-hydroxystyrene (synthesis example will be described later)
GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries)
OXE-30: Methacrylic acid (3-ethyloxetane-3-yl) methyl (3-ethyl-3-oxetanylmethyl methacrylate) (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
VBGE: p-vinylbenzylglycidyl ether M-100: cyclomer M-100 (3,4-epoxycyclohexylmethyl methacrylate, manufactured by Daicel Chemical Industries, Ltd.)
NBMA: n-butoxymethylacrylamide (manufactured by Tokyo Chemical Industry)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries)
HEMA: 2-ethylhexyl methacrylate (manufactured by Wako Pure Chemical Industries)
St: Styrene (manufactured by Wako Pure Chemical Industries)
DCPM: Methacrylic acid (Tricyclo [5.2.1.0 ^2,6 ] decan-8-yl) (manufactured by Hitachi Chemical, FA-513M)
MMA: Methyl methacrylate (Wako Pure Chemical Industries)

<Synthesis of MAEVE (1-ethoxyethyl methacrylate)>
To 144.2 parts (2 molar equivalents) of ethyl vinyl ether, 0.5 part of phenothiazine was added, and 86.1 parts (1 molar equivalent) of methacrylic acid was added dropwise while cooling the reaction system to 10 ° C. or lower. ) For 4 hours. After adding 5.0 parts of pyridinium p-toluenesulfonate, the mixture was stirred at room temperature for 2 hours and allowed to stand overnight at room temperature. To the reaction solution, 5 parts of sodium bicarbonate and 5 parts of sodium sulfate were added, and the mixture was stirred at room temperature for 1 hour. Insoluble matter was filtered and concentrated under reduced pressure at 40 ° C. or lower. .) 134.0 parts of 1-ethoxyethyl methacrylate in the 43-45 ° C./7 mmHg fraction were obtained as a colorless oil.

<Synthesis of MATHF (tetrahydrofuran-2-yl methacrylate)>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2,3-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated aqueous sodium hydrogen carbonate solution (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a yellow oily residue. Was distilled under reduced pressure to obtain 125 g of tetrahydrofuran-2-yl methacrylate (MATHF) as a colorless oily substance having a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg (yield 80%).

<Synthesis of MACHOE (1- (cyclohexyloxy) ethyl methacrylate)>
MACHOE was synthesized in the same manner as the MAEVE synthesis method.

<Synthesis of PHSEVE (1-ethoxyethyl protected form of α-methylhydroxystyrene)>
PHSEVE obtained PHSEVE as an ethyl acetal protector of a phenolic hydroxyl group by reacting α-methylhydroxystyrene with ethyl vinyl ether under an acid catalyst.

(Examples and Comparative Examples)
Each component was blended as shown in the following table, and dissolved in a mixed solvent of diethylene glycol methyl ethyl ether: propylene glycol monomethyl ether acetate = 1: 1 (weight ratio) so that the solid content concentration was 27% by weight. It filtered with the 0.2 micrometer membrane filter, and prepared the photosensitive resin composition of an Example and a comparative example, respectively.

The details of the abbreviations indicating the compounds used in Examples and Comparative Examples are as follows.
(B) Acid generator B-1: CGI-1397 (compound having the structure shown below, manufactured by Ciba Specialty Chemicals)
B-2: Triphenylsulfonium nonafluorobutanesulfonate B-3: Compound having the structure shown below (NAI-101, manufactured by Midori Chemical)

(L) Sensitizer L-1: DBA (9,10-dibutoxyanthracene, structure shown below, manufactured by Kawasaki Chemical Industry Co., Ltd.)
Bu in the above formula represents a butyl group.

(C) Chain aliphatic epoxy compound C-1: Denacol EX-612 (Chain aliphatic epoxy, manufactured by Nagase Chemtech Co., Ltd.), molecular weight: 664, viscosity at 25 ° C .: 11,900 mPa · s
C-2: Denacol EX-212L (chain aliphatic epoxy, manufactured by Nagase Chemtech Co., Ltd.), molecular weight: 270, viscosity at 25 ° C .: 15 mPa · s
C-3: Denacol EX-321 (chain aliphatic epoxy, manufactured by Nagase Chemtech Co., Ltd.), molecular weight: 280 to 420, viscosity at 25 ° C .: 130 mPa · s
C-4: Denacol EX-321L (chain aliphatic epoxy, manufactured by Nagase Chemtech Co., Ltd.), molecular weight: 320 to 480, viscosity at 25 ° C .: 800 mPa · s
C-5: Denacol EX-252 (cycloaliphatic epoxy, Nagase Chemtech Co., Ltd., molecular weight: 426, viscosity at 25 ° C .: 2200 mPa · s
C-6: JER-1004 (bisphenol A type epoxy, Mitsubishi Chemical Corporation, molecular weight: 1650 (value described in catalog)
C-7: Denacol EX-211L (chain aliphatic epoxy, manufactured by Nagase Chemtech Co., Ltd.), weight average molecular weight: 216, viscosity at 25 ° C .: 20 mPa · s

(G) Adhesion improver G-1: KBM-403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
G-2: KBE-403 (3-glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

(H) Basic compound H-1: 1,5-diazabicyclo [4.3.0] -5-nonene (manufactured by Tokyo Chemical Industry)
H-2: Tributylamine (manufactured by Tokyo Chemical Industry)

(I) Surfactant I-1: Fluorad FC-430 (saturated perfluoroalkyl group-containing acrylic resin, manufactured by 3M)
I-2: Polyether-modified silicone surfactant (KF-6012, manufactured by Shin-Etsu Chemical Co., Ltd.)
I-3: Emulgen 105 (manufactured by Kao Corporation) (polyoxyethylene lauryl ether)

  Each evaluation shown below was performed about the photosensitive resin composition of the Example and comparative example which were obtained by the above. The results are shown below.

<Evaluation of sensitivity>
Each photosensitive resin composition is slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (Corning)), then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent, and the film thickness A photosensitive resin composition layer having a thickness of 3.0 μm was formed.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive resin composition layer was developed with an alkali developer (0.4 wt% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
By these operations, the optimum i-line exposure (Eopt) when resolving 10 μm line and space at 1: 1 was defined as sensitivity. The evaluation criteria are as follows. “1” and “2” are levels that have no practical problem. The results are shown in the table below.
1: Eopt is less than 40 mJ / cm ² 2: Eopt is 40 mJ / cm ² or more and less than 60 mJ / cm ² 3: Eopt is 60 mJ / cm ² or more and less than 80 mJ / cm ² 4: Eopt is 80 mJ / cm ² or more 5: Unable to pattern

<Evaluation of chemical resistance (stripping solution resistance)>
After each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to obtain a film thickness of 3 A photosensitive resin composition layer having a thickness of 0.0 μm was formed.
The obtained photosensitive resin composition layer is subjected to a cumulative irradiation amount of 300 mJ / cm ² (illuminance: 20 mW / cm ² , i-line) using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Then, this substrate was heated in an oven at 230 ° C. for 1 hour to obtain a cured film.
The cured film was immersed in monoethanolamine at 60 ° C. for 5 minutes, the film was pulled up and the liquid on the surface was wiped off, and the film thickness was measured immediately. The film thickness before immersion was compared with the film thickness after immersion, and the increased ratio was expressed in percent. The results are shown in the table below. The smaller the numerical value, the better the peel resistance of the cured film, and 1 or 2 is preferable.
Swell ratio (%) = film thickness after immersion (μm) / film thickness before immersion (μm) × 100
1: 100% or more and less than 102% 2: 102% or more and less than 105% 3: 105% or more and less than 110% 4: 110% or more and less than 115% 5: 115% or more

<Evaluation of coatability>
In each photosensitive resin composition preparation, a photosensitive resin composition was prepared in the same manner except that the amount of the solvent was adjusted to a viscosity of 18.0 mPa · s, and the coating property was evaluated. Using a SF-700G manufactured by Dainippon Screen Mfg. Co., Ltd., a glass substrate having a size of 550 mm × 650 mm was spin-coated so that the coating thickness after drying was 4.1 μm. Drying was performed on a hot plate at 90 ° C. for 120 seconds. The coated surface was visually observed to count the number of radial stripes and evaluated according to the following criteria. The results are shown in the table. 1, 2, 3 are acceptable.
No streak-like unevenness on the coated surface: 1
1-3 pieces: 2
4-5 pieces: 3
6 or more: 4

<Evaluation of liquid crystal contamination (electrical property evaluation)>
Each of the photosensitive resin compositions prepared in each Example and Comparative Example was spin-coated on a 100 mm × 100 mm glass substrate to a dry film thickness of 5 μm and dried at 90 ° C. for 120 seconds. After exposing the entire surface at 300 mJ / cm ² , post-baking was performed at 230 ° C. for 60 minutes in a convection oven. After peeling off and pulverizing the completed coating film, 9 mg was mixed with 2 g of liquid crystal (MLC-6608, manufactured by Merck), heated at 120 ° C. for 5 hours, and then an ultra-micro ammeter (Digital Ultra High, manufactured by ADC Corporation) Resistance / microammeter: 8340 A) was used to measure the liquid crystal specific resistance. Evaluation results were determined as follows.
1: The specific resistance is 1.0 × 10 ¹³ (Ω · cm) or more.
2: The specific resistance is 1.0 × 10 ¹² (Ω · cm) or more and less than 1.0 × 10 ¹³ (Ω · cm).
3: The specific resistance is 1.0 × 10 ¹¹ or more and less than 1.0 × 10 ¹² (Ω · cm).
4: The specific resistance is less than 1.0 × 10 ¹¹ (Ω · cm).
The higher the specific resistance of the liquid crystal, the lower the degree of contamination of the liquid crystal and the better the panel reliability.

  As is apparent from the above table, when the composition of the present invention was used, it was found that the composition was excellent in all of sensitivity, solvent resistance, coatability and electrical properties (however, only Example 67 ( It was found that the sensitivity was low because MAA was not included in A).

(Example 124)
Using the photosensitive resin composition of Example 1, using the UV-LED light source exposure machine instead of the PLA-501F exposure machine (super high pressure mercury lamp) manufactured by Canon Inc. Carried out. As a result, the same result as in Example 1 was obtained.

(Example 125)
Similar to the sensitivity evaluation performed on the photosensitive resin composition of Example 25, except that the photosensitive resin composition of Example 25 was used and the substrate was changed from a glass substrate to a silicon wafer, the sensitivity was changed. Evaluation was performed. As a result, the same result as in Example 25 was obtained.

(Example 126)
Using the photosensitive resin composition of Example 52, the exposure machine was changed from a Canon-made PLA-501F exposure machine (extra-high pressure mercury lamp) to a Nikon Corporation FX-803M (gh-Line stepper). Except for the change, the sensitivity was evaluated in the same manner as the sensitivity evaluation performed on the photosensitive resin composition of Example 52. As a result, the same result as in Example 52 was obtained.

(Example 127)
Except for using the photosensitive resin composition of Example 103 and changing the exposure machine from a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. to a 355 nm laser exposure machine and performing 355 nm laser exposure. Evaluated the sensitivity in the same manner as the sensitivity evaluation performed on the photosensitive resin composition of Example 103. As a result, the same result as in Example 103 was obtained.
As the 355 nm laser exposure machine, “EGIS” manufactured by Buoy Technology Co., Ltd. was used (wavelength 355 nm, pulse width 6 nsec), and the exposure amount was measured using “PE10B-V2” manufactured by OPHIR.

  As described above, it can be seen that the photosensitive resin compositions of the examples exhibit excellent sensitivity regardless of the substrate and the exposure machine.

(Example 128)
A liquid crystal display device using a thin film transistor (TFT) was manufactured by the following method (see FIG. 2). In the active matrix type liquid crystal display device described in FIG. 1 and FIG. 2 of Japanese Patent No. 3312003, a cured film 17 was formed as an interlayer insulating film as follows to obtain a liquid crystal display device. That is, the bottom gate type TFT 1 was formed on the glass substrate 6, and the insulating film 3 made of Si 3 N 4 was formed so as to cover the TFT 1. Next, after forming a contact hole in the insulating film 3, a wiring 2 (height of 1.0 μm) connected to the TFT 1 through the contact hole was formed on the insulating film 3.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 115 on the substrate, pre-baking (90 ° C. × 2 minutes) on a hot plate, and then applying high pressure from above the mask. After irradiating i-line (365 nm) with 25 mJ / cm ² (illuminance 20 mW / cm ² ) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C. for 60 minutes. The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average level difference of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2.000 nm.

  When a drive voltage was applied to the obtained liquid crystal display device and a gray test signal was input, the gray display was visually observed and evaluated for the occurrence of display unevenness. I couldn't.

(Example 129)
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 1).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is for connecting the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 107 on the substrate, pre-baking on a hot plate (90 ° C. × 2 minutes), and then applying high pressure from above the mask. After irradiating 45 mJ / cm ² (illuminance 20 mW / cm ² ) with i-line (365 nm) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C. for 60 minutes. The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.

  Next, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped using a resist stripping solution (mixed solution of monoethanolamine and dimethyl sulfoxide (DMSO)). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

  Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film, the photosensitive resin composition of Example 108 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process can be prevented.

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

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

  1: TFT (thin film transistor), 2: wiring, 3: insulating film, 4: flattening film, 5: first electrode, 6: glass substrate, 7: contact hole, 8: insulating film, 10: liquid crystal display device, 12 : Backlight unit, 14, 15: Glass substrate, 16: TFT, 17: Cured film, 18: Contact hole, 19: ITO transparent electrode, 20: Liquid crystal, 22: Color filter

Claims (13)

(A) a polymer that satisfies the following (1) or (2),
(1) (a1) a polymer obtained by copolymerizing at least a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a crosslinkable group,
(2) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group (B) a photoacid generator, and
(C) A positive-type photosensitive resin composition for electronic members , comprising a chain aliphatic epoxy compound having 2 to 4 epoxy groups . (C) The positive photosensitive resin composition for electronic members of Claim 1 whose molecular weight of a chain | strand-shaped aliphatic epoxy compound is 2000 or less. (C) The positive photosensitive resin composition for electronic members of Claim 1 or 2 whose viscosity at 25 degrees C of a chain | strand-shaped aliphatic epoxy compound is 3000 mPa * s or less. (C) The positive photosensitive resin composition for electronic members of any one of Claims 1-3 whose chain | strand-shaped aliphatic epoxy compound is resin represented by the following general formula (X-1).
Formula (X-1)
(In General Formula (X-1), A is a linear or branched hydrocarbon group, which may have a hydroxyl group as a substituent, and n is an integer of 2 to 4.) 5. The structural unit (a1) according to claim 1, wherein the structural unit (a1) is a structural unit having a residue in which a carboxyl group is protected with an acetal, or a residue in which a carboxyl group is protected with a ketal. Positive type photosensitive resin composition for electronic members. The positive photosensitive resin composition for electronic members according to claim 1, wherein the structural unit (a1) is a structural unit represented by the formula (A2 ′).
Formula (A2 ′)
(In Formula (A2 ′), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 6 carbon atoms, and R ³ represents an alkyl group having 1 to 6 carbon atoms or 4 to 7 carbon atoms. And R ² and R ³ may be linked to form a ring.) (C) The positive photosensitive resin composition for electronic members of any one of Claims 1-6 whose chain | strand-shaped aliphatic epoxy compound is resin represented by the following general formula (X-2).
Formula (X-2)
(In General Formula (X-2), B is a linear or branched hydrocarbon group, which may have a hydroxyl group as a substituent, and n is an integer of 2 to 4.) The structural unit (a2) is represented by a structural unit having a 3-membered or 4-membered cyclic ether group, and —NH—CH ₂ —O—R (R is an alkyl group having 1 to 20 carbon atoms). The positive photosensitive resin composition for electronic members of any one of Claims 1-7 containing at least 1 chosen from the group which consists of a structural unit which has a group. (1) A step of applying the positive photosensitive resin composition for an electronic member according to any one of claims 1 to 8 on a substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) a post-baking step of thermosetting the developed photosensitive resin composition;
A method for forming a cured film comprising: The formation method of the cured film of Claim 9 including the process of exposing the developed photosensitive resin composition to the whole surface after the said image development process and before the said post-baking process. The cured film formed by the formation method of the cured film of Claim 9 or 10. The cured film according to claim 11, which is an interlayer insulating film. An organic EL display device or a liquid crystal display device comprising the cured film according to claim 11.