JP2016212380A - Photosensitive resin composition, production method of cured film, cured film, liquid crystal display device, organic electroluminescence display device and touch panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in heat-resistant transparency and patterning property, and a production method of a cured film and a cured film, a liquid crystal display device, an organic electroluminescence display device and a touch panel each using the above composition.SOLUTION: The photosensitive resin composition comprises a polybenzoxazole precursor, a photoacid generator that generates an acid having a pKa of 3 or less, a heat base generator, and a solvent. The polybenzoxazole precursor has a phenolic hydroxyl group at least partially protected by an acid decomposable group. The heat base generator is a compound represented by formula (X) below. In formula (X), m represents an integer of 1 to 4; R, Rand Reach independently represent an alkyl group having 1 to 5 carbon atoms; Rrepresents an m-valent organic group which may have a hetero atom; and when m is 2 to 4, a plurality of R, R, and Reach may be the same or different.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition, a method for producing a cured film, a cured film, a liquid crystal display device, an organic electroluminescence display device, and a touch panel.

Image display devices such as liquid crystal display devices and organic electroluminescence display devices, and input devices such as touch panels are generally provided with a patterned interlayer insulating film.
For the formation of this 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.

  For example, Patent Document 1 describes “a positive photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitive agent (B), and a thermal base generator (C)”. ([Claim 1]).

JP 2013-152381 A

In recent years, attempts have been made to perform heat treatment and film formation at a higher temperature (for example, about 300 ° C.) than before in order to increase the efficiency of production and the performance of image display devices.
Therefore, the present inventors formed a film at a high temperature using the photosensitive resin composition described in Patent Document 1, and depending on the type of thermal base generator, transparency (hereinafter referred to as “heat-resistant transparency”). )) And patterning properties may be inferior.

  Therefore, the present invention provides a photosensitive resin composition excellent in heat-resistant transparency and patterning property, and a method for producing a cured film, a cured film, a liquid crystal display device, an organic electroluminescence display device, and a touch panel using the same. This is the issue.

As a result of intensive studies to achieve the above-mentioned problems, the present inventor has obtained a predetermined polybenzoxazole precursor, a photoacid generator that generates an acid having a pKa of 3 or less, and a thermal base generator having a specific structure. It was found that the use of a photosensitive resin composition having a good heat-resistant transparency and patterning property of the resulting cured film resulted in the completion of the present invention.
That is, it has been found that the above object can be achieved by the following configuration.

[1] A polybenzoxazole precursor, a photoacid generator that generates an acid having a pKa of 3 or less, a thermal base generator, and a solvent,
The polybenzoxazole precursor is a polybenzoxazole precursor in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group,
The photosensitive resin composition whose thermal base generator is a compound represented by a following formula (X).
Here, in the formula (X), m represents an integer of 1 to 4, R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 5 carbon atoms, and R ⁴ has a hetero atom. M-valent organic group which may be present. When m is 2 to 4, the plurality of R ¹ , R ² and R ³ may be the same or different.
[2] The photosensitive resin composition according to [1], wherein the polybenzoxazole precursor has a repeating unit represented by the following formula (1).
Here, in formula (1), X represents a tetravalent organic group containing an aromatic ring, Y represents a divalent organic group, R is independently a hydrogen atom, an alkyl group, and the following formula (2) Or a group represented by —CORc, and at least one R represents a structure represented by the following formula (2). Rc represents an alkyl group or an aryl group.
Here, in formula (2), * represents a bonding position with an oxygen atom, R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, and R ¹⁰³ represents an alkyl group. However, except for the case where both R ¹⁰¹ and R ¹⁰² are hydrogen atoms, R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether.
[3] The photosensitive resin composition according to [1] or [2], wherein the content of the thermal base generator is 0.1 to 30 parts by mass with respect to 100 parts by mass of the polybenzoxazole precursor.
[4] Any one of [1] to [3], wherein R ^{4 in the} formula (X) includes at least one selected from the group consisting of a hydroxy group, a carboxyl group, an alkyleneoxy group, and an alkoxysilyl group. Photosensitive resin composition.
[5] Any of [1] to [4], wherein m in formula (X) is 2, and R ^{4 in} formula (X) is a divalent aliphatic hydrocarbon group which may have a hetero atom. A photosensitive resin composition according to claim 1.
[6] The photosensitive resin composition according to [4], wherein m in formula (X) is 1.
[7] The polybenzoxazole precursor includes a repeating unit A in which Y in the formula (1) is a cyclic aliphatic group having 3 to 15 carbon atoms, and Y in the formula (1) has 4 to 4 carbon atoms. The photosensitive resin composition according to any one of [2] to [6], containing 20 repeating units B represented by a linear or branched aliphatic group.
[8] The photosensitive resin composition according to any one of [2] to [6], wherein the polybenzoxazole precursor contains at least an aromatic group having 6 to 20 carbon atoms in Y in the formula (1). .
[9] The polybenzoxazole precursor contains the repeating unit A and the repeating unit B in a ratio of 70 mol% or more of the total repeating units in the polybenzoxazole precursor. The photosensitive resin composition as described in [7] whose ratio of content is 9: 1-3: 7 by molar ratio.
[10] Any of [1] to [9], wherein the polybenzoxazole precursor is protected by an acid-decomposable group in 10 to 60% of the phenolic hydroxyl group of all repeating units of the polybenzoxazole precursor. A photosensitive resin composition according to claim 1.

[11] A step of applying the photosensitive resin composition according to any one of [1] to [10] to a substrate;
Removing the solvent from the applied photosensitive resin composition;
Exposing the photosensitive resin composition from which the solvent has been removed with actinic radiation;
Developing the exposed photosensitive resin composition with a developer;
A method for producing a cured film, comprising: thermally curing the developed photosensitive resin composition to obtain a cured film.
[12] The method for producing a cured film according to [11], including a step of exposing the developed photosensitive resin composition after the step of developing and before the step of thermosetting.
[13] A cured film obtained by curing the photosensitive resin composition according to any one of [1] to [10].
[14] The cured film according to [13], which is an interlayer insulating film.
[15] A liquid crystal display device having the cured film according to [13] or [14].
[16] An organic electroluminescence display device having the cured film according to [13] or [14].
[17] A touch panel having the cured film according to [13] or [14].

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition excellent in heat-resistant transparency and patterning property, the manufacturing method of a cured film using the same, a cured film, a liquid crystal display device, an organic electroluminescent display device, and a touch panel are provided. be able to.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, solid content is solid content in 25 degreeC.
In this specification, the weight average molecular weight and number average molecular weight of a polymer are defined as polystyrene conversion values by GPC (gel permeation chromatography) measurement. The weight average molecular weight and number average molecular weight of the polymer are, for example, HLC-8120 (manufactured by Tosoh Corporation), TSK gel Multipore HXL-M (Tosoh Corporation, 7.8 mm ID × 30.0 cm) as a column, and THF (tetrahydrofuran as eluent). ) Can be used.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention contains a polybenzoxazole precursor, a photoacid generator that generates an acid having a pKa of 3 or less, a thermal base generator, and a solvent.
The polybenzoxazole precursor is a polybenzoxazole precursor in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group.
The thermal base generator is a compound represented by the following formula (X).
Here, in the formula (X), m represents an integer of 1 to 4, R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 5 carbon atoms, and R ⁴ has a hetero atom. M-valent organic group which may be present. When m is 2 to 4, the plurality of R ¹ , R ² and R ³ may be the same or different.

The photosensitive resin composition of the present invention contains a thermal base generator represented by the above formula (X) together with the polybenzoxazole precursor and the photoacid generator that generates an acid having a pKa of 3 or less. Thereby, the heat-resistant transparency and patterning property of the cured film obtained become favorable.
Although this is not clear in detail, the inventor presumes as follows.
First, the polybenzoxazole precursor is cyclized (forms a benzoxazole ring) by firing at a high temperature to become a polybenzoxazole exhibiting excellent heat resistance and insulation.
Further, in this firing process (post-bake process), if an acid (for example, an acid generated by thermal decomposition of the photoacid generator) is present, the deprotected phenolic hydroxyl group is oxidized, Side reactions other than the ring closure reaction of the benzoxazole precursor proceed, and as a result, the transparency of the resulting cured film is reduced.
On the other hand, it is effective to add a base compound to suppress side reactions during heat curing by acid. However, when an unprotected base compound is added, the acid generated from the photoacid generator is neutralized. As a result, the patterning property is lowered.
And in this invention, by using the compound represented by the said Formula (X) which protected the primary amine as a thermal base generator, the side reaction in a baking process is suppressed, without reducing patterning property, It is considered that the ring-closing reaction of the benzoxazole precursor was allowed to proceed, so that the transparency and patterning properties were improved.
The photosensitive resin composition of Patent Document 1 also contains a thermal base generator, but has a heterocyclic structure containing a nitrogen atom as shown in Comparative Examples (particularly Comparative Examples 1 and 6) described later. When secondary amine is used, it is considered that the side reaction in the firing process could not be suppressed because transparency or patterning property is inferior.

The photosensitive resin composition of the present invention can be preferably used as a positive photosensitive resin composition, and can be particularly preferably used as a chemically amplified positive photosensitive resin composition.
Hereinafter, a polybenzoxazole precursor contained in the photosensitive resin composition of the present invention, a photoacid generator that generates an acid having a pKa of 3 or less, a thermal base generator and a solvent, and an optional additive Detailed description.

[Polybenzoxazole precursor]
The polybenzoxazole precursor contained in the photosensitive resin composition of the present invention is a polybenzoxazole precursor in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group.
Here, the “phenolic hydroxyl group” is a group formed by substituting a hydrogen atom of an aromatic ring with a hydroxy group. The “aromatic ring” may be either a monocyclic ring or a polycyclic ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and the like.
The “acid-decomposable group” means a group that decomposes by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group. Examples thereof include an alkyl ester group, and among them, an acetal group is preferable from the viewpoint of sensitivity. In addition, an acetal group means the group containing the oxygen atom couple | bonded with R in formula (1) mentioned later.

In the present invention, it is preferable that the polybenzoxazole precursor has a repeating unit represented by the following formula (1) from the viewpoints of heat resistance, insulation, film strength and the like.
Here, in formula (1), X represents a tetravalent organic group containing an aromatic ring, Y represents a divalent organic group, R is independently a hydrogen atom, an alkyl group, and the following formula (2) Or a group represented by —CORc, and at least one R represents a structure represented by the following formula (2). Rc represents an alkyl group or an aryl group.
Here, in formula (2), * represents a bonding position with an oxygen atom, R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, and R ¹⁰³ represents an alkyl group. However, except when R ¹⁰¹ and R ¹⁰² are both hydrogen atoms, R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether.

Specific examples of the tetravalent organic group containing an aromatic ring represented by X in the above formula (1) include the following organic groups.
In the tetravalent organic group shown below, either “* 1” or “* 2” represents a connecting portion with —OR in the above formula (1), and the other in the above formula (1). Represents a linking moiety to —NH—. Similarly, either “* 3” or “* 4” represents a connecting portion with —OR in the above formula (1), and the other represents a connecting portion with —NH— in the above formula (1). .

  In the formula (1), examples of the divalent organic group represented by Y include a divalent aliphatic hydrocarbon group and a divalent aromatic group. 15 cyclic aliphatic groups, linear or branched aliphatic groups having 4 to 20 carbon atoms, aromatic groups having 5 to 100 carbon atoms, and the like.

Here, examples of the cyclic aliphatic group having 3 to 15 carbon atoms include a cyclic alkylene group, a cyclic alkenylene group, and a cyclic alkynylene group, and a cyclic alkylene group is preferable. When it is a cyclic alkylene group, a cured film excellent in light resistance and chemical resistance can be obtained.
Carbon number of a cyclic aliphatic group is 3-15, and 6-12 are preferable. When the carbon number is in the above range, a cured film excellent in light resistance and chemical resistance can be obtained. The cyclic aliphatic group is preferably a 6-membered ring. The cyclic aliphatic group having 3 to 15 carbon atoms may have a substituent or may be unsubstituted. Unsubstituted is preferred.
Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogen atom.
When the cyclic aliphatic group has a substituent, the carbon number of the cyclic aliphatic group is the number excluding the carbon number of the substituent.
Specific examples of the cyclic aliphatic group having 3 to 15 carbon atoms include a residue (cyclic aliphatic group) remaining after removal of the carboxyl group of the cyclic aliphatic dicarboxylic acid. Specific examples include the following groups: a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a biscyclohexylene group, and an adamantylene group, and a cyclohexylene group or a biscyclohexylene group is preferable. More preferred. In the groups shown below, * represents the bonding position with the carbon atom (carbonyl carbon) constituting the carbonyl group adjacent to Y in the formula (1).

Examples of the linear or branched aliphatic group having 4 to 20 carbon atoms include an alkylene group, an alkenylene group, an alkynylene group, and a polyoxyalkylene group. An alkylene group, an alkenylene group, and an alkynylene group are preferable, and an alkylene group Is more preferable.
Carbon number of a linear or branched aliphatic group is 4-20, 4-15 are preferable and 4-12 are still more preferable. When the carbon number is in the above range, the solvent solubility is good.
Specific examples of the linear or branched aliphatic group having 4 to 20 carbon atoms include a linear aliphatic dicarboxylic acid or a residue (aliphatic group) remaining after removal of the carboxyl group of the branched aliphatic dicarboxylic acid. ).
Examples of linear aliphatic dicarboxylic acids include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, and hexadecanedioic acid. , Heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, docosanedioic acid and the like.
Examples of branched aliphatic dicarboxylic acids include 3-methylglutaric acid, 3,3-dimethylglutaric acid, 2-methyladipic acid, 2-ethyladipic acid, 2-propyladipic acid, 2-butyladipic acid, 3 -Methyladipic acid, 3-tert-butyladipic acid, 2,3-dimethyladipic acid, 2,4-dimethyladipic acid, 3,3-dimethyladipic acid, 3,4-dimethyladipic acid, 2,4,4 -Trimethyladipic acid, 2,2,5,5-tetramethyladipic acid, 2-methylpimelic acid, 3-methylpimelic acid, 3-methylsuberic acid, 2-methylsebacic acid, nonane-2,5-dicarboxylic acid, etc. Can be mentioned.

The aromatic group having 5 to 100 carbon atoms is preferably an aromatic group having 6 to 20 carbon atoms, and specific examples thereof include the following groups.
In addition, in the group shown below, * represents the bonding position with the carbonyl carbon in the above formula (1), and A represents —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, It represents a divalent group selected from the group consisting of —NHCO— and —C (CF ₃ ) ₂ —.

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

In the above formula (1), the structure represented by the above formula (2) represented by R is a structure corresponding to a protecting group for a phenolic hydroxyl group protected with an acid-decomposable group.
The alkyl group represented by R ¹⁰¹ , R ¹⁰² and R ^{103 in the} above formula (2) has the same meaning as the alkyl group described for R, and the preferred range is also the same. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include those described above.
Examples of the cyclic ether formed by linking R ¹⁰¹ or R ¹⁰² and R ¹⁰³ in the above formula (2) include the structures shown below. In the structure shown below, * represents a bonding position with an oxygen atom. The structure shown below is also called an acetal group when an oxygen atom bonded at the position of * is included.

Rc represents an alkyl group or an aryl group.
The alkyl group represented by Rc has the same meaning as the alkyl group described for R, and the preferred range is also the same. The alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include those described above.
The aryl group represented by Rc is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further preferably an aryl group having 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group, and a naphthyl group. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include those described above.

In the present invention, from the viewpoint of sensitivity, the polybenzoxazole precursor is an acid-decomposable group (especially the above formula (2)) in which 10 to 60% of the phenolic hydroxyl groups of all repeating units of the polybenzoxazole precursor are present. Are preferably protected by 15 to 50%.
Here, the phenolic hydroxyl group possessed by all repeating units of the polybenzoxazole precursor as used herein means the phenolic hydroxyl group possessed by all repeating units of the polybenzoxazole precursor in a state prior to protection with an acid-decomposable group. To do.

In the present invention, from the viewpoint of light resistance, the polybenzoxazole precursor comprises a repeating unit A in which Y in the above formula (1) is represented by a cyclic aliphatic group having 3 to 15 carbon atoms, and the above formula ( It is preferable that Y in 1) contains a repeating unit B represented by a linear or branched aliphatic group having 4 to 20 carbon atoms.
Here, a C3-C15 cyclic | annular aliphatic group and a C4-C20 linear or branched aliphatic group are synonymous with each aliphatic group demonstrated by Y in the said Formula (1). The preferred range is also the same.

In the present invention, from the viewpoint of light resistance, the polybenzoxazole precursor contains the repeating unit A and the repeating unit B in a total amount of 70 mol% or more of all repeating units in the polybenzoxazole precursor. It is preferable that it is contained in a proportion of 70 to 100 mol%, more preferably it is contained in a proportion of 80 to 100 mol%, and substantially only in the repeating unit A and the repeating unit B. It is particularly preferable that it is configured. According to this aspect, a cured film excellent in light resistance is easily obtained.
In the present invention, “substantially composed only of repeating unit A and repeating unit B” means that the content of repeating units other than repeating unit A and repeating unit B is, for example, 5 mol% or less. It is preferably 1 mol% or less, and more preferably not contained.

In the present invention, from the viewpoint of light resistance, the polybenzoxazole precursor preferably has a content ratio of the repeating unit A to the repeating unit B of 9: 1 to 3: 7 in terms of molar ratio, and 8.5. : 1.5 to 3.5: 6.5 is more preferable, and 8: 2 to 4: 6 is still more preferable.
For example, as repeating unit A, Y in the above formula (1) has a repeating unit represented by a cyclohexylene group or biscyclohexylene group, and as repeating unit B, Y in the above formula (1) is When it has a repeating unit represented by a linear or branched aliphatic group having 4 to 20 carbon atoms, the ratio of the content of the repeating unit A and the repeating unit B is 8.5: 1.5 to a molar ratio. 4: 6 is preferable, 7.5: 2.5 to 4: 6 is more preferable, 7.5: 2.5 to 5: 5 is still more preferable, and 7.5: 2.5 to 5.5: 4. 5 is more preferable, and 7.5: 2.5 to 6: 4 is particularly preferable.
Further, for example, as repeating unit A, Y in the above formula (1) has a repeating unit represented by an adamantylene group, and as repeating unit B, Y in the above formula (1) has 4 to 20 carbon atoms. When the repeating unit is represented by a linear or branched aliphatic group, the content ratio of the repeating unit A and the repeating unit B is preferably 6.5: 3.5 to 4: 6 in molar ratio. 6: 4 to 5: 5 are more preferable.

In the present invention, the polybenzoxazole precursor may contain a repeating unit other than the above-described repeating unit A and repeating unit B (hereinafter, also referred to as “other repeating unit”).
Examples of the other repeating unit include a repeating unit represented by the general formula (a1), a repeating unit represented by the general formula (a2), and a repeating unit represented by the general formula (a3).

In general formula (a1), X ¹⁰ represents a tetravalent organic group containing an aromatic ring, Y ¹⁰ represents an aromatic ring group, and R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an acid It represents a decomposable group or -CORc.
In the general formula (a1), X ¹⁰ is in the same range as X described in the above formula (1), and the preferred range is also the same. In the general formula (a1), R ¹¹ and R ¹² are in the same range as R described in the above formula (1), and the preferred range is also the same.
In general formula (a1), Y ¹⁰ represents an aromatic ring group. The aromatic ring group may be monocyclic or polycyclic. The aromatic ring group may be a heteroaromatic ring group containing a hetero atom. Specific examples of the aromatic ring include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acenaphthalene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene Ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring Benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, Ntoren ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and a phenazine ring.

In general formula (a2), Y ¹¹ represents an aromatic ring group, a cyclic aliphatic group, a linear aliphatic group, a branched aliphatic group, or these, —CH ₂ —, —O—, — _{S -, - SO 2 -,} - CO -, - NHCO-, and -C (CF _{3) 2} - of a group consisting of a combination of at least one, X ¹¹ is an aromatic ring group, cyclic aliphatic A group consisting of a group group or a combination thereof with —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ —. Represent.
Examples of the aromatic ring group, the cyclic aliphatic group, the linear aliphatic group, and the branched aliphatic group include those described above, and preferred ranges thereof are also the same.

In general formula (a3), Y ¹² represents an aromatic ring group, a cyclic aliphatic group, a linear aliphatic group, a branched aliphatic group, or these, —CH ₂ —, —O—, —S —, —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ — represent a group consisting of a combination of — and X ¹² represents a group containing a silicon atom.
Examples of the aromatic ring group, the cyclic aliphatic group, the linear aliphatic group, and the branched aliphatic group include those described above, and preferred ranges thereof are also the same.
The group containing a silicon atom represented by X ¹² is preferably a group represented by the following.
R ²⁰ and R ²¹ each independently represent a divalent organic group, and R ²² and R ²³ each independently represent a monovalent organic group.

No particular restriction on the divalent organic group represented by R ²⁰ and R ^21, but specifically a linear or branched alkylene group, an arylene group having 6 to 20 carbon atoms containing 1 to 20 carbon atoms, carbon atoms The group formed by combining 3-20 divalent cycloaliphatic groups or these is mentioned.
1-20 are preferable, as for carbon number of a linear or branched alkylene group, 1-10 are more preferable, and 1-6 are more preferable. Specific examples include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, and a t-butylene group.
6-20 are preferable, as for carbon number of an arylene group, 6-14 are more preferable, and 6-10 are more preferable. Specific examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a naphthylene group, and an anthracenylene group.
3-20 are preferable, as for carbon number of a bivalent cycloaliphatic group, 3-10 are more preferable, and 5-6 are more preferable. Examples of the divalent cycloaliphatic group include a 1,4-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,2-cyclohexylene group.
The linear or branched alkylene group having 1 to 20 carbon atoms, the arylene group having 6 to 20 carbon atoms, and the divalent cyclic aliphatic group having 3 to 20 carbon atoms may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, an amide group, and a sulfonylamide group.
The group formed by combining a linear or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent cyclic aliphatic group having 3 to 20 carbon atoms is not particularly limited. And a group formed by combining groups formed by combining divalent cycloaliphatic groups having 3 to 20 carbon atoms. Hereinafter, as specific examples of the group formed by combining a linear or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent cyclic aliphatic group having 3 to 20 carbon atoms, Although the following are mentioned, it is not limited to these.

Examples of the monovalent organic group represented by R ²² and R ²³ include a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.
1-20 are preferable, as for carbon number of a linear or branched alkyl group, 1-10 are more preferable, and 1-6 are still more preferable. Specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group.
6-20 are preferable, as for carbon number of an aryl group, C6-C14 is more preferable, and 6-10 are more preferable. Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group, and a naphthyl group.
The linear or branched alkyl group or aryl group having 1 to 20 carbon atoms may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, an amide group, and a sulfonylamide group.

The polybenzoxazole precursor in the present invention preferably has a structure in which the terminal is sealed with a monofunctional acid chloride. According to this aspect, a cured film with good transmittance is easily obtained. Examples of the monofunctional acid chloride include acetyl chloride, butyryl chloride, propionic acid chloride, 2-ethylhexanoic acid chloride, cyclohexanecarboxylic acid chloride, benzoyl chloride, naphthoyl chloride, acrylic acid chloride, heptanoic acid chloride, isobutyryl. Chloride, isononanoyl chloride, neodecanoyl chloride, octanoyl chloride, pivaloyl chloride, valeroyl chloride, methoxyacetyl chloride, acetoxyacetyl chloride, phenylacetyl chloride, cinnamoyl chloride, methacrylic acid chloride, 2-furoyl chloride , 3-chloropropionyl chloride, 4-chlorobutyryl chloride, 5-chlorovaleryl chloride, diethylcarbamoyl chloride, methyl chloroformate, ethyl chloroformate, Propyl chloroformate, n-butyl chloroformate, sec-butyl chloroformate, pentyl chloroformate, n-hexyl chloroformate, n-octyl chloroformate, 2-ethylhexyl chloroformate, cyclohexyl chloroformate, Examples include 4-tert-butylcyclohexyl chloroformate, cetyl chloroformate, benzyl chloroformate, and 2-chloroethyl chloroformate.
From the viewpoint of solvent solubility, an acid chloride having 3 or more carbon atoms is preferred. From the viewpoint of solvent resistance, an acid chloride having 12 or less carbon atoms is preferred. From the viewpoint of thermal stability, carboxylic acid chloride is preferred.

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

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

Specific examples of the group represented by the general formula (b1) include the following, but are not limited thereto. In the formula, Ph represents a phenyl group, and n-Pr represents an n-propylene group.

  The polybenzoxazole precursor preferably has a weight average molecular weight (Mw) of 3,000 to 200,000. The lower limit is more preferably 4,000 or more, and still more preferably 5,000 or more. The upper limit is more preferably 100,000 or less, and even more preferably 50,000 or less. The number average molecular weight (Mn) is preferably 1,000 to 50,000. The lower limit is more preferably 2,000 or more, and still more preferably 3,000 or more. The upper limit is more preferably 40,000 or less, and still more preferably 30,000 or less. By setting it as this range, the lithography performance and the cured film physical properties can be made excellent.

  In the present invention, the content of the polybenzoxazole precursor in the photosensitive resin composition is preferably 20 parts by mass or more and more preferably 30 parts by mass or more with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. Preferably, 40 parts by mass or more is particularly preferable. For example, the upper limit is preferably 99 parts by mass or less, more preferably 80 parts by mass or less, and particularly preferably 70 parts by mass or less. When using 2 or more types of polybenzoxazole precursor, it is preferable that the total amount becomes the said range.

  The polybenzoxazole precursor used in the present invention can be synthesized in consideration of the description in JP-A-2008-224970. Further, the end-capping with a monofunctional acid chloride can be synthesized at a time, for example, by mixing the monofunctional acid chloride during the polymerization reaction.

[Photoacid generator]
The photo-acid generator which the photosensitive resin composition of this invention has is a photo-acid generator which generate | occur | produces the acid whose pKa is 3 or less.
Here, pKa basically refers to pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured after changing to a solvent suitable for measurement. Specifically, the pKa described in the chemical handbook can be referred to.
The acid having a pKa of 3 or less is preferably sulfonic acid or phosphonic acid, and more preferably sulfonic acid.
The photoacid generator is preferably one that generates an acid having a pKa of 2 or less.

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

  Examples of photoacid generators include onium salt compounds, trichloromethyl-s-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. . Among these, onium salt compounds, imide sulfonate compounds, and oxime sulfonate compounds are preferable, and onium salt compounds and oxime sulfonate compounds are particularly preferable. A photo-acid generator can be used individually by 1 type or in combination of 2 or more types.

Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane compounds include the compounds described in paragraph numbers 0083 to 0088 of JP2011-221494A; And compounds described in paragraph numbers 0013 to 0049 of JP-A-2011-105645, and the contents thereof are incorporated in the present specification.
Specific examples of the imide sulfonate compound include the compounds described in paragraphs 0065 to 0075 of WO2011 / 087011, and the contents thereof are incorporated herein.

It is also preferable to use triarylsulfonium salts having the following structure.

  Preferred examples of the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B1-1).

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

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

  The compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound described in paragraph numbers 0108 to 0133 of JP 2014-238438 A.

  As an imide sulfonate type compound, a naphthalene imide type compound is preferable, the description of international publication WO11 / 087011 pamphlet can be referred to, These content is integrated in this-application specification.

In the present invention, the content of the photoacid generator is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. For example, the lower limit is more preferably 0.2 parts by mass or more, and further preferably 0.5 parts by mass or more. For example, the upper limit is more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.
Further, the content of the photoacid generator is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polybenzoxazole precursor. More preferably, it is 0.1-8 mass parts.
In addition, only 1 type may be used for a photo-acid generator, and it can also use 2 or more types together. When using 2 or more types of photo-acid generators, it is preferable that the total amount becomes the said range.

[Heat base generator]
The thermal base generator contained in the photosensitive resin composition of the present invention is a compound represented by the following formula (X).
Here, in the formula (X), m represents an integer of 1 to 4, R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 5 carbon atoms, and R ⁴ has a hetero atom. M-valent organic group which may be present. When m is 2 to 4, the plurality of R ¹ , R ² and R ³ may be the same or different.

In the formula (X), the carbon number of the alkyl group represented by R ^1, R ² and R ³ is 1-5, is preferably from 1 to 3, and more preferably 1 or 2. The total number of carbon atoms of the alkyl group represented by R ¹ , R ² and R ³ is preferably 3 or 4.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.

In the present invention, the thermal base generator is selected from the group consisting of a hydroxy group, a carboxyl group, an alkyleneoxy group, and an alkoxysilyl group, because R ⁴ in the above formula (X) is selected because the patterning property is better. Preferably, the compound contains at least one of the above.
Among these, R ⁴ in the above formula (X) is more preferably a compound containing a hydroxy group and / or a carboxyl group, and further preferably a compound containing a hydroxy group.

Specific examples of the compound in which R ⁴ in the above formula (X) contains a carboxyl group include compounds represented by the following formulas.

Specific examples of the compound in which R ⁴ in the above formula (X) contains a hydroxy group include compounds represented by the following formulas.

Specific examples of the compound in which R ⁴ in the above formula (X) contains both a hydroxy group and a carboxyl group include compounds represented by the following formulas.

Specific examples of the compound in which R ⁴ in the above formula (X) contains an alkoxysilyl group include compounds represented by the following formulas.

  As the compound containing such a functional group, m in the formula (X) is preferably 1 from the viewpoints of heat-resistant transparency and patterning properties.

In the present invention, from the viewpoint of heat-resistant transparency, in the thermal base generator, m in the above formula (X) may be 2, and R ⁴ in the above formula (X) may have a hetero atom. A compound that becomes a divalent aliphatic hydrocarbon group is preferred.
Specific examples of such a compound include compounds represented by the following formulas.

Examples of thermal base generators other than the compounds specifically exemplified above include compounds represented by the following formulas.

In the present invention, the content of the thermal base generator is preferably 0.1 to 10% by mass with respect to the total solid content from the viewpoint of heat-resistant transparency and patterning property, More preferably, it is 10 mass%, and it is still more preferable that it is 0.5-9 mass%.
The content of the thermal base generator is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polybenzoxazole precursor. More preferably, it is 0.1-15 mass parts.

〔solvent〕
The solvent which the photosensitive resin composition of this invention contains is not specifically limited, A well-known solvent can be used.
In addition, it is preferable that the photosensitive resin composition of this invention is prepared as a solution which melt | dissolved the essential component mentioned above and the arbitrary component mentioned later in the solvent. Moreover, as a solvent, the thing which melt | dissolves an essential component and an arbitrary component and does not react with each component is preferable.

  Specific examples of the solvent include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ethers. Acetates, diethylene glycol dialkyl ethers (eg, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether), diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates , Esters, ketones, a De, lactones and the like. In addition, the solvent described in paragraph Nos. 0174 to 0178 of JP2011-221494A and the solvent described in paragraph numbers 0167 to 0168 of JP2012-194290A are also included, the contents of which are incorporated herein. It is.

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

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

In this invention, it is preferable that content of a solvent is 50-95 mass parts with respect to 100 mass parts of all the components in the photosensitive resin composition. The lower limit is more preferably 60 parts by mass or more. The upper limit is more preferably 90 parts by mass or less.
Moreover, it is preferable that it is 500-2000 mass parts with respect to 100 mass parts of polybenzoxazole precursors, and, as for content of a solvent, it is more preferable that it is 700-1800 mass parts.
In addition, only one type of solvent may be used, or two or more types may be used. When using 2 or more types, it is preferable that the total amount becomes the said range.

[Adhesion improver]
The photosensitive resin composition of the present invention may contain an adhesion improving agent. Examples of the adhesion improving agent include alkoxysilane compounds.
The alkoxysilane compound is a compound that improves the adhesion between an insulating material and an inorganic material serving as a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum. It is preferable.
Specific examples of the adhesion improving agent include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and the like. Γ-methacryloxypropyltrialkoxysilane such as glycidoxypropyltrialkoxysilane, γ-glycidoxypropyl dialkoxysilane, 3-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyl Examples include trialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, and vinyltrialkoxysilane. Among these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, 3-methacryloxypropylmethyldimethoxysilane, 3-glycol. Sidoxypropyltrimethoxysilane is more preferred. These can be used alone or in combination of two or more.
The content of the adhesion improving agent is preferably 0.001 to 15 parts by mass, and more preferably 0.005 to 10 parts by mass with respect to 100 parts by mass of the total solid components of the photosensitive resin composition. Only one type of adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

[Sensitizer]
The photosensitive resin composition of the present invention may contain a sensitizer. The sensitizer absorbs actinic rays and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. For this reason, decomposition | disassembly of a photo-acid generator can be accelerated | stimulated by containing a sensitizer. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in the wavelength range of 350 to 450 nm.

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

  When the photosensitive resin composition of the present invention contains a sensitizer, the content of the sensitizer is 0.001 to 100 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. It is preferable. For example, the lower limit is more preferably 0.1 parts by mass or more, and still more preferably 0.5 parts by mass or more. For example, the lower limit is more preferably 50 parts by mass or less, and still more preferably 20 parts by mass or less. Two or more sensitizers can be used in combination. When two or more sensitizers are used in combination, the total amount is preferably within the above range.

[Crosslinking agent]
The photosensitive resin composition of the present invention may contain a crosslinking agent. By containing a crosslinking agent, a harder cured film can be obtained.
The crosslinking agent is not limited as long as a crosslinking reaction is caused by heat. Examples thereof include compounds having two or more epoxy groups or oxetanyl groups in the molecule, blocked isocyanate compounds, alkoxymethyl group-containing crosslinking agents, compounds having ethylenically unsaturated double bonds, and the like. Specifically, it is preferable to use the compounds described in paragraph numbers 0153 to 0163 of International Publication No. 2014/050730.

<Other cross-linking agents>
As other crosslinking agents, alkoxymethyl group-containing crosslinking agents described in paragraphs 0107 to 0108 of JP2012-8223A, compounds having an ethylenically unsaturated double bond, and the like can also be preferably used. The contents are incorporated herein. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.

  When the photosensitive resin composition of this invention has a crosslinking agent, it is preferable that content of a crosslinking agent is 0.01-50 mass parts with respect to 100 mass parts of polybenzoxazole precursors. For example, the lower limit is more preferably 0.1 parts by mass or more, and still more preferably 0.5 parts by mass or more. For example, the upper limit is more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less. If it is this range, the cured film excellent in mechanical strength and solvent resistance will be obtained. Only one type of crosslinking agent may be used, or two or more types may be used. When using 2 or more types, it is preferable that the total amount becomes the said range.

[Basic compounds]
The photosensitive resin composition of the present invention may contain a basic compound. The basic compound can be arbitrarily selected from those used in chemically amplified positive resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in JP-A-2011-221494, paragraphs 0204 to 0207, and the contents thereof are incorporated in the present specification.

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

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

[Surfactant]
The photosensitive resin composition of the present invention may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant. As the surfactant, for example, those described in paragraph Nos. 0201 to 0205 of JP2012-88459A and those described in paragraph Nos. 0185 to 0188 of JP2011-215580A can be used. Is incorporated herein by reference.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . The following trade names are KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by Mitsubishi Materials Kasei), MegaFac (manufactured by DIC), F-554 (manufactured by DIC), Florard Novec FC-4430 (manufactured by Sumitomo 3M), Surflon S-242 (AGC) Seimi Chemical), PolyFoxPF-6320 (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), and Ftergent FTX-218G (manufactured by Neos).
As the surfactant, compounds described in paragraph numbers 0151 to 0155 of JP-A No. 2014-238438 are also preferably used.

Surfactant can be used individually by 1 type or in mixture of 2 or more types.
When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is preferably 10 parts by mass or less with respect to 100 parts by mass of the total solid components of the photosensitive resin composition. 0.001-10 mass parts is more preferable, and 0.01-3 mass parts is still more preferable.

〔Antioxidant〕
The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, coloring of the cured film can be prevented. Furthermore, there is an advantage that a reduction in film thickness due to decomposition can be reduced and heat-resistant transparency is excellent.
Examples of antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites. Examples thereof include salts, thiosulfates, and hydroxylamine derivatives. Among these, phenolic antioxidants, hindered amine antioxidants, phosphorus antioxidants, amide antioxidants, hydrazide antioxidants, sulfur antioxidants from the viewpoint of coloring the cured film and reducing film thickness Agents are preferred, and phenolic antioxidants are most preferred. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include the compounds described in paragraph Nos. 0026 to 0031 of JP-A-2005-29515 and the compounds described in paragraph Nos. 0106 to 0116 of JP-A-2011-227106. It is incorporated herein.
Preferred commercially available products include ADK STAB AO-20, ADK STAB AO-60, ADK STAB AO-80, ADK STAB LA-52, ADK STAB LA-81, ADK STAB AO-412S, ADK STAB PEP-36, IRGANOX 1035, IRGANOX 1098, and Tinuvin 144. Can be mentioned.

  When the photosensitive resin composition of this invention has antioxidant, content of antioxidant is 0.1-10 mass parts with respect to 100 mass parts of all the solid components of the photosensitive resin composition. Preferably, it is 0.2-5 mass parts, and it is especially preferable that it is 0.5-4 mass parts. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good.

[Acid multiplication agent]
In the photosensitive resin composition of the present invention, an acid proliferating agent can be used for the purpose of improving sensitivity.
The acid proliferating agent is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid.
Specific examples of the acid proliferating agent include the acid proliferating agents described in paragraph numbers 0226 to 0228 of JP2011-221494A, the contents of which are incorporated herein.
When the photosensitive resin composition of the present invention contains an acid proliferation agent, the content of the acid proliferation agent is 10 to 1000 parts by mass with respect to 100 parts by mass of the photoacid generator. From the viewpoint of dissolution contrast with the exposed portion, it is preferably 20 to 500 parts by mass. The acid proliferating agent may be used alone or in combination of two or more. When two or more types of acid proliferating agents are used, the total amount is preferably within the above range.

[Development accelerator]
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, those described in paragraph Nos. 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
When the photosensitive resin composition of the present invention has a development accelerator, the addition amount of the development accelerator is 0 to 100 parts by mass of the total solid content of the photosensitive resin composition from the viewpoints of sensitivity and residual film ratio. 30 mass parts is preferable, 0.1-20 mass parts is more preferable, and it is most preferable that it is 0.5-10 mass parts.

[Other ingredients]
In the photosensitive resin composition of the present invention, known additives such as a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic suspending agent are independently added as necessary. 1 type, or 2 or more types can be added.
As these compounds, for example, compounds described in paragraph Nos. 0201 to 0224 of JP2012-8859A can be used, and the contents thereof are incorporated in the present specification.
Further, a thermal radical generator described in paragraphs 0120 to 0121 of JP2012-8223A, a nitrogen-containing compound and a thermal acid generator described in WO2011 / 136604A1, can be used, and the contents thereof are described in the present specification. Incorporated into.

<Impurity>
Since the photosensitive resin composition of the present invention may lead to deterioration of the storage stability of the composition and device contamination, it is preferable that the content of impurities is small.
Specific examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, or ions thereof, free halogen, halide ions, and the like. .
The content of these impurities is preferably 1000 ppb or less, more preferably 500 ppb or less, and even more preferably 100 ppb or less in the photosensitive resin composition of the present invention. Particularly for metal impurities, 20 ppb or less is particularly preferable. The lower limit is not particularly defined, but can be set to 10 ppt or more or 100 ppt or more from the viewpoint of practically reducing the limit or measurement limit.
As a method for reducing impurities in this way, use materials that do not contain these impurities in the raw materials of resins and additives, prevent contamination of these impurities when preparing the composition, and wash them when they are mixed. As a result, the amount of impurities can be within the above range. These impurities can be quantified by a known method such as ICP (Inductively Coupled Plasma) emission spectroscopy or atomic absorption spectroscopy.

In addition, the photosensitive resin composition of the present invention includes compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, hexane, and the like. It is preferably not included.
The content of these compounds is preferably 500 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less in the photosensitive resin composition of the present invention. The lower limit is not particularly defined, but can be set to 0.1 ppb or more or 1 ppb or more from the viewpoint of practically reducing the limit or measuring limit.
The content of these impurities can be suppressed by the same method as that for metal impurities, and can be quantified by a known measurement method.

[Method for preparing photosensitive resin composition]
The photosensitive resin composition of the present invention can be prepared by mixing each component at a predetermined ratio and by any method, stirring and dissolving. For example, the photosensitive resin composition of the present invention can also be prepared by mixing each component with a predetermined ratio after preparing each solution in advance in a solvent. The composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore size of 0.2 μm.
Here, the pore diameter of the filter can be appropriately adjusted according to the target purity and the like, and examples include 0.05 μm, 0.1 μm, 0.3 μm, and 0.5 μm in addition to 0.2 μm. The material of the filter can be appropriately selected according to the solvent used in the composition. Examples thereof include polypropylene, polyethylene, polyester, nylon, polytetrafluoroethylene, metal, activated carbon, and cellulose. Further, filtration can be repeated. For example, the aspect filtered twice, filtered five times, or filtered many times by circulation filtration can be mentioned.

The photosensitive resin composition of this invention can adjust solid content concentration, a viscosity, and surface tension according to the objective.
In the case of slit coating, the solid content concentration of the photosensitive resin composition is preferably 2 to 40% by mass, more preferably 3 to 30% by mass, and still more preferably 4 to 20% by mass.
Moreover, 1-40 mPa * s is preferable, as for the viscosity in slit coating, 2-25 mPa * s is more preferable, and 3-20 mPa * s is still more preferable. In the present invention, the viscosity is a value at 25 ° C.
Moreover, when spin-coating, 5-60 mass% is preferable, as for the solid content concentration of a composition, 7-50 mass% is more preferable, and 10-40 mass% is still more preferable.
On the other hand, the viscosity in the case of spin coating is preferably 5 to 100 mPa · s, more preferably 8 to 70 mPa · s, and still more preferably 10 to 50 mPa · s.
The surface tension is preferably 10 to 100 mN / m, more preferably 15 to 80 mN / m, and still more preferably 20 to 50 mN / m from the viewpoint of applicability.
Preferable specific examples include a composition for slit coating having a solid content concentration of 15% by mass, a viscosity of 5 mPa · s, and a surface tension of 27 mN / m.

[Storage method of photosensitive resin composition]
The photosensitive resin composition of this invention can be stored by a well-known method, for example, can be stored in a glass or metal sealed container.
At this time, the atmosphere can be air or nitrogen. From the viewpoint of preventing unexpected oxidation of the photosensitive resin composition, a nitrogen atmosphere is preferable.
The storage temperature can be a known temperature, and examples include room temperature (20 to 25 ° C.), refrigeration (0 to 5 ° C.), and freezing (−50 ° C. to −10 ° C.). From the viewpoint of preventing unexpected deterioration of the photosensitive resin composition, refrigeration or refrigeration is preferable, and refrigeration is more preferable. Specific examples include 5 ° C., −10 ° C., −20 ° C., and −30 ° C., and −20 ° C. is preferable.
Also, the storage period is not particularly limited. For example, after the composition is prepared, it is used after storage at −10 ° C. for 3 days, the embodiment is used after storage at −20 ° C. for 20 days, and after storage at −30 ° C. for 150 days. The aspect to be used can be mentioned.

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

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

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

  In the step (2), the solvent is removed from the wet film formed by applying the photosensitive resin composition by vacuum (vacuum) and / or heating to form a dry film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are within the above ranges, when performing the step (4) described later, the adhesion of the pattern tends to be better, and the residue tends to be further reduced.

In the step (3), the substrate provided with the dry film is irradiated with actinic rays having a predetermined pattern. In this step, a phenolic hydroxyl group is generated in the exposed area, and the solubility in the developer in the exposed area is improved. That is, in an embodiment comprising a polybenzoxazole precursor having a group in which a phenolic hydroxyl group is protected with an acid-decomposable group, and a photoacid generator, the photoacid generator is decomposed by irradiation with actinic rays, and the acid is Occur. Then, the acid-decomposable group is hydrolyzed by the catalytic action of the generated acid to produce a phenolic hydroxyl group.
As a light source of actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generator, etc. can be used, i-line (365 nm), h-line (405 nm), Actinic rays having a wavelength of 300 nm to 450 nm, such as g-line (436 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed. The exposure amount is preferably 1 to 500 mJ / cm ² .
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, and a laser exposure can be used. In addition, exposure using a so-called super-resolution technique can be performed. Examples of the super-resolution technique include multiple exposure in which exposure is performed a plurality of times, a method using a phase shift mask, and an annular illumination method. By using these super-resolution techniques, it is possible to form a higher definition pattern, which is preferable.

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

In the step (5), the obtained positive image is heated to thermally decompose the acid-decomposable group to generate a phenolic hydroxyl group and to cyclize (form a benzoxazole ring), thereby forming a cured film. Can be formed. Moreover, a cured film can also be formed by crosslinking a phenolic hydroxyl group with a crosslinking agent or the like. In the present invention, even in an embodiment that does not contain a crosslinkable group or a crosslinking agent, the polybenzoxazole precursor can be closed (cured) by heating to form a cured film.
This heating is preferably performed using a heating device such as a hot plate or an oven. The heating temperature is preferably 200 ° C to 350 ° C, more preferably 250 ° C to 350 ° C. The heating time is preferably 5 to 90 minutes on a hot plate and 30 to 120 minutes for an oven. By proceeding with a cyclization reaction or a crosslinking reaction by heating, a cured film excellent in heat resistance, hardness and the like can be formed. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
The lower the oxygen concentration in the heating atmosphere, the better. When heating in a nitrogen-substituted atmosphere, from the viewpoint of transparency of the cured film, the oxygen concentration (in terms of mol) of the heating atmosphere is preferably 1.0 ppt to 10%, more preferably 1.0 ppb to 5%, and 1.0 ppm. ~ 3% is most preferred.
As the post-bake process, for example, an oven in which the oxygen partial pressure is set to 100 ppm by nitrogen substitution is sequentially heated at 90 ° C. for 30 minutes, 120 ° C. for 30 minutes, 180 ° C. for 40 minutes, and 320 ° C. for 60 minutes. Can be mentioned.
Further, in the present invention, a middle bale performed at a relatively low temperature can be added before post-baking. When performing middle baking, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film. As a preferable exposure amount when the post-exposure step is included, 100 to 3,000 mJ / cm ² is preferable, and 100 to 500 mJ / cm ² is particularly preferable.
When performing the post-exposure process, the taper angle of the pattern when the pattern is formed can be increased. Conversely, when the post-exposure process is not performed, the taper angle of the pattern can be reduced. The presence / absence of the post-exposure step and the amount of exposure when performing post-exposure can be appropriately adjusted depending on the taper angle of the target pattern. Examples of the taper angle of the pattern include 15 °, 30 °, 45 °, 60 °, 75 °, and 90 °. Among these, when a cured film is used as the insulating film, the taper angles are preferably 30 °, 45 °, 60 °, and 75 °.

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

[Curing film]
The cured film of the present invention is a cured film obtained by curing the above-described photosensitive resin composition of the present invention. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention mentioned above.
The cured film of the present invention can be suitably used as an interlayer insulating film and a protective film.
The photosensitive resin composition of the present invention can provide an interlayer insulating film having high transparency even when baked at a high temperature. The interlayer insulation film formed using the photosensitive resin composition of the present invention has high transparency and is useful for applications such as a liquid crystal display device, an organic electroluminescence display device, and a touch panel.

The cured film of the present invention can have various physical properties depending on the application.
When used for an interlayer insulating film such as a semiconductor element, it is preferable that the relative dielectric constant is low from the viewpoint of reducing the parasitic capacitance generated in the element. In this case, the relative dielectric constant is preferably 1.5 to 4.0, and more preferably 2.2 to 3.2.
Moreover, when using the cured film of this invention for an insulating film, the one where a volume resistance is higher is preferable from a viewpoint of improving insulation. The volume resistance is preferably 1.0 × 10 ^{10 to} 1.0 × 10 ²⁰ Ω · cm, and more preferably 1.0 × 10 ^{13 to} 1.0 × 10 ¹⁸ Ω · cm.
Further, when the cured film of the present invention is used for an application requiring antistatic ability, the volume resistance is preferably 1.0 × 10 ^{4 to} 1.0 × 10 ¹³ Ω · cm, It is more preferable that it is × 10 ^{6 to} 1.0 × 10 ¹¹ Ω · cm.
Further, from the viewpoint of improving the fastness of the electronic device when forming the electronic device using the cured film, it is preferable that the cured film has a higher Young's modulus. A Young's modulus can mention 0.5-8.0GPa and 1.0-4.0GPa as a preferable example.
Further, from the viewpoint of improving the fastness of the electronic device when forming the electronic device using the cured film, it is preferable that the cured film has a higher elongation at break. Breaking elongation can give 20-200% and 50-150% as a preferable example.
Further, from the viewpoint of improving the robustness of the electronic device when forming the electronic device using the cured film, the glass transition temperature (Tg) of the cured film is preferably 100 to 500 ° C, more preferably 150 to 400 ° C. Preferably, 200-300 degreeC is the most preferable.
Further, from the viewpoint of preventing warpage of the substrate on which the cured film is formed, the linear expansion coefficient of the cured film is preferably close to the linear expansion coefficient of the substrate. For example, when using a metal substrate, a glass substrate, and a silicon substrate having a linear expansion coefficient in the range of 2 to 20 ppm / ° C., the linear expansion coefficient of the cured film is preferably 10 to 100 ppm / ° C., more preferably 15 to 65 ppm / ° C. preferable. Specific examples of the linear expansion coefficient of the cured film in that case include 15 ppm / ° C. and 25 ppm / ° C. Moreover, when using the resin substrate whose linear expansion coefficient is the range of 20-120 ppm / degreeC, 20-120 ppm / degreeC is preferable and, as for the linear expansion coefficient of a cured film, 40-80 ppm / degreeC is more preferable. Specific examples of the linear expansion coefficient of the cured film in that case include 48 ppm / ° C., 59 ppm / ° C., and 69 ppm / ° C. In addition, said linear expansion coefficient means the linear expansion coefficient in the temperature below Tg, when a cured film has Tg.
When the cured film of the present invention is used as a lens material, the refractive index is preferably high. In this case, for example, the refractive index at 400 nm is preferably 1.5 to 2.0, more preferably 1.6 to 1.8.
When the cured film of the present invention is used for an antireflection film, the refractive index is preferably low. In this case, for example, the refractive index at 400 nm is preferably 1.0 to 1.6, and more preferably 1.2 to 1.4.
When the cured film of the present invention is used for display applications, the minimum visible light transmittance of 400 nm to 700 nm per film thickness of 1.0 μm is preferably 80% or more, and more preferably 90% or more. The haze is preferably 3.0 or less, and more preferably 1.0 or less. When the chromaticity is expressed in the L * a * b * color system, the a * value is preferably −3.0 to 3.0, and the b * value is preferably −3.0 to 3.0. A particularly preferred specific example is a cured film having an a * value of 0.0 and a b * value of 0.0.
When the cured film of the present invention is used for display applications, the in-plane retardation of the cured film is preferably 10 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less.
The in-plane retardation is a value measured with a photoelastic constant measuring device with light at 25 ° C. and a wavelength of 550 nm. Specifically, the refractive index of the cured film is measured with a photoelastic constant measuring apparatus, and the direction in which the refractive index is maximum is taken as the X axis, and the direction perpendicular to the X axis is taken as the Y axis. When the refractive index in the X-axis direction is nx, the refractive index in the Y-axis direction is ny, and the thickness of the cured film is d, the value represented by (nx−ny) × d is the in-plane retardation. To do. A preferable specific example is a cured film having a thickness of 20 μm and an in-plane retardation of 0.5 nm.

[Liquid Crystal Display]
The liquid crystal display device of the present invention has the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a planarizing film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal display devices having various structures. Can be mentioned.
For example, specific examples of TFTs included in the liquid crystal display device of the present invention include amorphous silicon TFTs, low-temperature polysilicon TFTs, and oxide semiconductor TFTs. 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 driving methods that can be taken by the liquid crystal display device of the present invention include a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, an OCB (OCB) method. (Optical Compensated Bend) method.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) of JP-A-2005-284291, -346054 can be used as the organic insulating film (212). 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 JP-A Nos. 2003-149647 and 2011-257734.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.
For details of the liquid crystal display device, the descriptions in Japanese Patent Application Laid-Open Nos. 2007-328210 and 2014-238438 can be referred to, and the contents thereof are incorporated in the present specification.

[Organic electroluminescence display]
The organic electroluminescence (organic EL) display device of the present invention has the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known organic materials having various structures. An EL display device and a liquid crystal display device can be given.
For example, specific examples of the TFT included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
The details of the liquid crystal display device can be referred to the description in Japanese Patent Application Laid-Open No. 2014-238438, and the contents thereof are incorporated in this specification.
As another aspect of the organic EL display device, the pixel separation film (19) and the planarization film (17) described in FIG. 1 of JP2012-203121A are formed using the photosensitive resin composition of the present invention. be able to. In addition, the high resistance layer (18), the inter-pixel insulating film (16), the interlayer insulating film (14), and the interlayer insulating film (12c) described in FIG. 1 of JP 2013-196919 A are used as the photosensitive resin of the present invention. It can be formed using the composition.

[Touch panel and touch panel display]
The touch panel of the present invention is a touch panel in which all or part of the insulating layer and / or protective layer is made of a cured product of the photosensitive composition of the present invention. Moreover, it is preferable that the touch panel of this invention has a transparent substrate, an electrode, an insulating layer, and / or a protective layer at least.
The touch panel display device of the present invention is preferably a touch panel display device having the touch panel of the present invention. As the touch panel of the present invention, any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, and an electromagnetic induction method may be used. Among these, the electrostatic capacity method is preferable.
Examples of the capacitive touch panel include those disclosed in JP 2010-28115 A and those disclosed in International Publication No. 2012/057165.
As a touch panel display device, a so-called in-cell type (for example, FIG. 5, FIG. 6, FIG. 7 and FIG. 8 in Japanese Patent Publication No. 2012-517051), a so-called on-cell type (for example, Japanese Patent Application Laid-Open No. 2012-43394). 14, International Publication No. 2012/141148, FIG. 2 (b)), OGS type, TOL type, and other configurations (for example, FIG. 6 of JP2013-164871A).
The capacitive touch panel has at least the following elements (1) to (5) on the front plate and the non-contact side of the front plate, and the insulating layer (4) is the photosensitive resin composition of the present invention. It is preferable that it is a cured film using.
(1) Frame layer (2) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via connection portions (3) First transparent electrode pattern and electrical And a plurality of second transparent electrode patterns comprising a plurality of pad portions formed extending in a direction crossing the first direction. (4) First transparent electrode pattern and second transparent electrode pattern (5) The first transparent electrode pattern and the second transparent electrode pattern are electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern. Another conductive element In the capacitive input device of the present invention, it is preferable that a transparent protective layer is further provided so as to cover all or a part of the elements (1) to (5). The cured film of the present invention is more preferable. There.

  Hereinafter, the present invention will be described in more detail based on 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 should not be construed as being limited by the following examples. Unless otherwise specified, “part” and “%” are based on mass.

[Synthesis of Polybenzoxazole Precursor A-1]
A three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube was charged with 73.25 g (0.200 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (Bis-AP). -AF, Central Glass), 30.20 g (0.382 mol) pyridine and 330 g N-methylpyrrolidone (NMP) were added. This was stirred at room temperature and then cooled to −15 ° C. with a dry ice / methanol bath. 12. In this solution, 27.51 g (0.132 mol) of 1,4-cyclohexyldicarbonyl chloride (trade name 14-CHDC, manufactured by Nippon Light Metal Co., Ltd.), while maintaining the reaction temperature at −5 ° C. to −15 ° C. A mixed solution of 49 g (0.056 mol) of sebacoyl chloride (manufactured by Tokyo Chemical Industry), 0.45 g (0.006 mol) of acetyl chloride (manufactured by Tokyo Chemical Industry) and 260.5 g of NMP was added dropwise over 2 hours. . After the addition was complete, the resulting mixture was stirred at room temperature for 1 hour.
Next, this reaction solution was cooled to −5 ° C. or lower with an ice / methanol bath, and 1.80 g (0.023 mol) of acetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise while maintaining the reaction temperature at −0 ° C. or lower. . After completion of the dropwise addition, the mixture was further stirred for 1 hour.
The reaction was diluted with 550 g of NMP and poured into a vigorously stirred 4 L deionized / methanol (80/20 volume ratio) mixture, the precipitated white powder was collected by filtration and washed with deionized water. The polymer was dried at 50 ° C. for 2 days under vacuum to obtain Resin A-1a.
In a 500 mL eggplant flask, 25.00 g of resin A-1a, 125 g of NMP, 0.43 g (1.85 mmol) of camphor sulfonic acid (manufactured by Tokyo Chemical Industry) and 5.12 g (0.065 mol) of 2,3- Dihydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at room temperature for 1.5 hours. The resulting solution was diluted by adding 0.37 g of triethylamine and 150 g of NMP.
The resulting solution was poured into a vigorously stirred 2 L deionized water / methanol (80/20 volume ratio) mixture, the precipitated white powder was collected by filtration and washed with deionized water. The polymer was dried at 50 ° C. for 2 days under vacuum to obtain polybenzoxazole (PBO) precursor A-1. The weight average molecular weight of the obtained PBO precursor A-1 was 29,000 (polystyrene conversion value of gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-1 was 30% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-1a ( ¹ H-NMR). The structure of PBO precursor A-1 is shown below.
<PBO precursor A-1>

[Synthesis of Polybenzoxazole Precursor A-2]
Resin A-1a prepared in the synthesis of PBO precursor A-1 was used as PBO precursor A-2.
The weight average molecular weight of the used PBO precursor A-2 was 28,000 (polystyrene conversion value of gel permeation chromatography). Since the used PBO precursor A-2 does not protect the phenolic hydroxyl group, the protection rate is 0%. The structure of PBO precursor A-2 is shown below.
<PBO precursor A-2>

[Synthesis of Polybenzoxazole Precursor A-3]
Resin A-1a was synthesized in the same manner as Resin A-1a except that 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of acetyl chloride. -3a was synthesized.
Subsequently, the phenolic hydroxyl group was protected by the same method as PBO precursor A-1 except that resin A-3a was used in place of resin A-1a to obtain PBO precursor A-3.
The obtained PBO precursor A-3 had a weight average molecular weight of 28,000 (polystyrene converted value by gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-3 was 30% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-3a ( ¹ H-NMR). The structure of PBO precursor A-3 is shown below.
<PBO precursor A-3>

[Synthesis of Polybenzoxazole Precursor A-4]
Resin A-1a was synthesized in the same manner as Resin A-1a except that 0.188 mol of sebacoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used without using 1,4-cyclohexyldicarbonyl chloride. -4a was synthesized.
Subsequently, the phenolic hydroxyl group was protected by the same method as PBO precursor A-1 except that resin A-4a was used in place of resin A-1a to obtain PBO precursor A-4.
The obtained PBO precursor A-4 had a weight average molecular weight of 28,000 (polystyrene conversion value of gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-4 was 30% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-4a ( ¹ H-NMR). The structure of PBO precursor A-4 is shown below.
<PBO precursor A-4>

[Synthesis of Polybenzoxazole Precursor A-5]
In the synthesis of Resin A-1a, bis (3-amino-4-hydroxyphenyl) sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1,4-cyclohexyldicarbonyl chloride (trade name 14-CHDC, manufactured by Nippon Light Metal). Resin A-5a was synthesized by the same method as Resin A-1a except that 0.132 mmol was used.
Subsequently, the phenolic hydroxyl group was protected by the same method as PBO precursor A-1 except that resin A-5a was used in place of resin A-1a to obtain PBO precursor A-5.
The weight average molecular weight of the obtained PBO precursor A-5 was 25,000 (polystyrene conversion value of gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-5 was 28% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-5a ( ¹ H-NMR). The structure of PBO precursor A-5 is shown below.
<PBO precursor A-5>

[Synthesis of Polybenzoxazole Precursor A-6]
In the synthesis of resin A-1a, 9,9-bis (3-amino-4-hydroxyphenyl) fluorene (Tokyo Kasei) was used instead of 1,4-cyclohexyldicarbonyl chloride (trade name 14-CHDC, manufactured by Nippon Light Metal). Resin A-6a was synthesized by the same method as Resin A-1a, except that 0.132 mmol of (manufactured by Kogyo) was used.
Subsequently, the phenolic hydroxyl group was protected by the same method as PBO precursor A-1 except that resin A-6a was used in place of resin A-1a to obtain PBO precursor A-6.
The obtained PBO precursor A-6 had a weight average molecular weight of 24,000 (polystyrene conversion value of gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-6 was 26% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-6a ( ¹ H-NMR). The structure of PBO precursor A-6 is shown below.
<PBO precursor A-6>

[Synthesis of Polybenzoxazole Precursor A-7]
In the synthesis of Resin A-1a, 0.132 mol of 3,3′-dihydroxybenzidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 1,4-cyclohexyldicarbonyl chloride (trade name 14-CHDC, manufactured by Nippon Light Metal). Except that, Resin A-7a was synthesized by the same method as Resin A-1a.
Subsequently, the phenolic hydroxyl group was protected by the same method as PBO precursor A-1 except that resin A-7a was used in place of resin A-1a to obtain PBO precursor A-7.
The weight average molecular weight of the obtained PBO precursor A-7 was 23,000 (polystyrene conversion value of gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-7 was 27% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-7a ( ¹ H-NMR). The structure of PBO precursor A-7 is shown below.
<PBO precursor A-7>

[Synthesis of Polybenzoxazole Precursor A-8]
In the synthesis of Resin A-1a, 0.094 mol of 1,4-cyclohexyldicarbonyl chloride (trade name 14-CHDC, manufactured by Nippon Light Metal Co., Ltd.) and 0.094 mol of sebacoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were used. Resin A-8a was synthesized by the same method as Resin A-1a.
Subsequently, the phenolic hydroxyl group was protected by the same method as PBO precursor A-1 except that resin A-8a was used in place of resin A-1a to obtain PBO precursor A-8.
The obtained PBO precursor A-8 had a weight average molecular weight of 28,000 (polystyrene conversion value of gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-8 was 25% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-8a ( ¹ H-NMR). The structure of PBO precursor A-8 is shown below.
<PBO precursor A-8>

[Synthesis of Polybenzoxazole Precursor A-9]
Resin A-8a was synthesized in the same manner as Resin A-8a except that 0.094 mol of suberoyl chloride (manufactured by Tokyo Chemical Industry) was used instead of sebacoyl chloride (manufactured by Tokyo Chemical Industry). A-9a was synthesized.
Subsequently, the phenolic hydroxyl group was protected by the same method as PBO precursor A-1 except that resin A-9a was used in place of resin A-1a to obtain PBO precursor A-9.
The obtained PBO precursor A-9 had a weight average molecular weight of 28,000 (polystyrene conversion value of gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-9 was 31% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-9a ( ¹ H-NMR). The structure of PBO precursor A-9 is shown below.
<PBO precursor A-9>

[Synthesis of Polybenzoxazole Precursor A-10]
Resin A-1a was synthesized by the same method as Resin A-1a except that 0.056 mol of suberoyl chloride (manufactured by Tokyo Chemical Industry) was used instead of sebacoyl chloride (manufactured by Tokyo Chemical Industry). A-10a was synthesized.
Subsequently, the phenolic hydroxyl group was protected by the same method as PBO precursor A-1 except that resin A-10a was used in place of resin A-1a to obtain PBO precursor A-10.
The obtained PBO precursor A-10 had a weight average molecular weight of 28,000 (polystyrene conversion value of gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-10 was 29% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-10a ( ¹ H-NMR). The structure of PBO precursor A-10 is shown below.
<PBO precursor A-10>

[Synthesis of Polybenzoxazole Precursor A-11]
In the synthesis of Resin A-1a, the same method as Resin A-1a was used except that 0.0560 mol of adipoyl chloride (manufactured by Tokyo Chemical Industry) was used instead of sebacoyl chloride (manufactured by Tokyo Chemical Industry). Resin A-11a was synthesized.
Subsequently, except that resin A-11a was used in place of resin A-1a, the phenolic hydroxyl group was protected in the same manner as PBO precursor A-1, and PBO precursor A-11 was obtained.
The obtained PBO precursor A-11 had a weight average molecular weight of 28,000 (polystyrene conversion value of gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-11 was 30% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-11a ( ¹ H-NMR). The structure of PBO precursor A-11 is shown below.
<PBO precursor A-11>

[Synthesis of Polybenzoxazole Precursor A-12]
In the synthesis of Resin A-1a, the same as Resin A-1a except that Sebacoyl chloride is not used and 0.188 mol of 1,4-cyclohexyldicarbonyl chloride (trade name 14-CHDC, Nippon Light Metal Co., Ltd.) is used. Resin A-12a was synthesized by the method.
Subsequently, the phenolic hydroxyl group was protected by the same method as PBO precursor A-1 except that resin A-12a was used in place of resin A-1a to obtain PBO precursor A-12.
The weight average molecular weight of the obtained PBO precursor A-12 was 28,000 (polystyrene conversion value of gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-12 was 27% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-12a ( ¹ H-NMR). The structure of PBO precursor A-12 is shown below.
<PBO precursor A-12>

[Synthesis of Polybenzoxazole Precursor A-13]
124 g of resin A-9a obtained by synthesis of PBO precursor A-9, 125 g of NMP, 0.43 g (1.85 mmol) of camphor sulfonic acid (manufactured by Tokyo Chemical Industry), 5.47 g (0. 065 mol) of 3,4-dihydro-2H-pyran (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at room temperature for 1.5 hours. The resulting solution was diluted by adding 0.37 g of triethylamine and 150 g of NMP.
The resulting solution was poured into a vigorously stirred 2 L deionized water / methanol (80/20 volume ratio) mixture, the precipitated white powder was collected by filtration and washed with deionized water. The polymer was dried under vacuum at 50 ° C. for 2 days to obtain PBO precursor A-13.
The weight average molecular weight of the obtained PBO precursor A-13 was 28,000 (polystyrene conversion value of gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-13 was 27% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-9a (1H-NMR). The structure of PBO precursor A-13 is shown below.
<PBO precursor A-13>

[Synthesis of Polybenzoxazole Precursor A-14]
Resin A-1a was synthesized except that sebacoyl chloride and 1,4-cyclohexyldicarbonyl chloride were not used, but 0.188 mol of 4,4′-oxybis (benzoyl chloride) (manufactured by Tokyo Chemical Industry Co., Ltd.) was used. Resin A-14a was synthesized by the same method as A-1a.
Subsequently, the phenolic hydroxyl group was protected by the same method as PBO precursor A-1 except that resin A-14a was used in place of resin A-1a to obtain PBO precursor A-14.
The obtained PBO precursor A-14 had a weight average molecular weight of 28,000 (polystyrene conversion value by gel permeation chromatography) and a weight average molecular weight / number average molecular weight of 2.2.
The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-14 was 26% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-14a ( ¹ H-NMR). The structure of PBO precursor A-14 is shown below.
<PBO precursor A-14>

[Synthesis of Polybenzoxazole Precursor A-15]
Resin A-1a was synthesized in the same manner as Resin A-1a except that 0.188 mol of isophthaloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used without using sebacoyl chloride and 1,4-cyclohexyldicarbonyl chloride. Resin A-15a was synthesized by the method.
Subsequently, the phenolic hydroxyl group was protected by the same method as PBO precursor A-1 except that resin A-15a was used in place of resin A-1a to obtain PBO precursor A-15.
The obtained PBO precursor A-15 had a weight average molecular weight of 27,000 (polystyrene converted value by gel permeation chromatography) and a weight average molecular weight / number average molecular weight of 2.0.
The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-15 was 25% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-15a ( ¹ H-NMR). The structure of PBO precursor A-15 is shown below.
<PBO precursor A-15>

[Synthesis of Polybenzoxazole Precursor A-16]
In the synthesis of Resin A-1a, sebacyl chloride and 1,4-cyclohexyl dicarbonyl chloride were not used, 0.094 mmol of 4,4′-oxybis (benzoyl chloride) was used, and 0.094 mmol of isophthaloyl chloride was used. Except that, Resin A-16a was synthesized by the same method as Resin A-1a.
Subsequently, the phenolic hydroxyl group was protected by the same method as PBO precursor A-1 except that resin A-16a was used in place of resin A-1a to obtain PBO precursor A-16.
The obtained PBO precursor A-16 had a weight average molecular weight of 25,000 (polystyrene equivalent value in gel permeation chromatography) and a weight average molecular weight / number average molecular weight of 2.0.
The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-16 was 25% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-16a ( ¹ H-NMR). The structure of PBO precursor A-16 is shown below.
<PBO precursor A-16>

[Synthesis of Polybenzoxazole Precursor A-17]
124 g of resin A-16a obtained by synthesis of PBO precursor A-16, 125 g of NMP, 0.43 g (1.85 mmol) of camphor sulfonic acid (manufactured by Tokyo Chemical Industry), 4.69 g (0. 065 mol) of ethyl vinyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at room temperature for 1.5 hours. The resulting solution was diluted by adding 0.37 g of triethylamine and 150 g of NMP.
The resulting solution was poured into a vigorously stirred 2 L deionized water / methanol (80/20 volume ratio) mixture, the precipitated white powder was collected by filtration and washed with deionized water. The polymer was dried under vacuum at 50 ° C. for 2 days to obtain PBO precursor A-17.
The obtained PBO precursor A-17 had a weight average molecular weight of 25,000 (polystyrene conversion value by gel permeation chromatography) and a weight average molecular weight / number average molecular weight of 2.0. The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-17 was 28% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-16a ( ¹ H-NMR). The structure of PBO precursor A-17 is shown below.
<PBO precursor A-17>

[Synthesis of Polybenzoxazole Precursor A-18]
Resin A-18a was synthesized in the same manner as Resin A-16a except that 5-norbornene-2,3-dicarboxylic anhydride was used in place of acetyl chloride in the synthesis of Resin A-16a.
Subsequently, the phenolic hydroxyl group was protected by the same method as PBO precursor A-17 except that resin A-18a was used in place of resin A-16a to obtain PBO precursor A-18.
The weight average molecular weight of the obtained PBO precursor A-18 was 26,000 (polystyrene conversion value of gel permeation chromatography), and the weight average molecular weight / number average molecular weight was 2.0.
The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-18 was 27% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-18a ( ¹ H-NMR). The structure of PBO precursor A-18 is shown below.
<PBO precursor A-18>

[Synthesis of Polybenzoxazole Precursor A-19]
PBO precursor A-19 was synthesized by the same method as PBO precursor A-17 except that resin A-1a was used instead of resin A-16a in the synthesis of PBO precursor A-17.
The obtained PBO precursor A-19 had a weight average molecular weight of 25,000 (polystyrene equivalent value in gel permeation chromatography), and the weight average molecular weight / number average molecular weight was 2.0.
The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-19 was 26% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-1a ( ¹ H-NMR). The structure of PBO precursor A-19 is shown below.
<PBO precursor A-19>

[Synthesis of Polybenzoxazole Precursor A-20]
Resin A-20a was synthesized in the same manner as Resin A-1a except that propionyl chloride (manufactured by Daicel) was used instead of acetyl chloride in the synthesis of Resin A-1a.
Subsequently, the phenolic hydroxyl group was protected by the same method as PBO precursor A-1 except that resin A-20a was used in place of resin A-1a to obtain PBO precursor A-20.
The weight average molecular weight of the obtained PBO precursor A-20 was 27,000 (polystyrene conversion value of gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-20 was 29% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-20a ( ¹ H-NMR). The structure of PBO precursor A-20 is shown below.
<PBO precursor A-20>

[Synthesis of Polybenzoxazole Precursor A-21]
PBO precursor A-21 was synthesized by the same method as PBO precursor A-17 except that resin A-20a was used in place of resin A-16a in the synthesis of PBO precursor A-17.
The weight average molecular weight of the obtained PBO precursor A-21 was 29,000 (polystyrene conversion value of gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-21 was 28% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-20a ( ¹ H-NMR). The structure of PBO precursor A-21 is shown below.
<PBO precursor A-21>

[Synthesis of Polybenzoxazole Precursor A-22]
Resin A-22a was synthesized by the same method as Resin A-16a except that propionyl chloride (manufactured by Daicel) was used instead of acetyl chloride in the synthesis of Resin A-16a.
Subsequently, the phenolic hydroxyl group was protected by the same method as PBO precursor A-1 except that resin A-22a was used in place of resin A-16a to obtain PBO precursor A-22.
The weight average molecular weight of the obtained PBO precursor A-22 was 27,000 (polystyrene conversion value of gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-22 was 29% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-22a ( ¹ H-NMR). The structure of PBO precursor A-22 is shown below.
<PBO precursor A-22>

[Synthesis of Polybenzoxazole Precursor A-23]
PBO precursor A-23 was synthesized by the same method as PBO precursor A-17 except that resin A-22a was used instead of resin A-16a in the synthesis of PBO precursor A-17.
The obtained PBO precursor A-23 had a weight average molecular weight of 27,000 (polystyrene conversion value of gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-23 was 30% with respect to the total phenolic hydroxyl group amount (molar amount) of the resin A-22a ( ¹ H-NMR). The structure of PBO precursor A-23 is shown below.
<PBO precursor A-23>

[Photoacid generator]
As the photoacid generator, the following compounds were used.

<B-1>
Structure shown below (PAG-103, manufactured by BASF, photoacid generator that generates an acid having a pKa of 3 or less)

<B-2>
The structure shown below (PAI-101, manufactured by Midori Kagaku, a photoacid generator that generates an acid with a pKa of 3 or less), Me represents a methyl group.

<B-3>
The structure shown below (a photoacid generator that generates an acid having a pKa of 3 or less, and a synthesis example will be described later).

<B-4>
The structure shown below (a photoacid generator that generates an acid having a pKa of 3 or less, a synthesis example will be described later), and Ts represents a tosyl group.

<B-5>
Structure shown below (a photoacid generator that generates an acid having a pKa of 3 or less, a synthesis example will be described later)

<B-6>
Structure shown below (GSID-26-1, triarylsulfonium salt (manufactured by BASF), photoacid generator that generates an acid having a pKa of 3 or less)

<B-7>
TAS-200 (naphthoquinone diazide, manufactured by Toyo Gosei Co., Ltd.)

〔solvent〕
As the solvent, the following solvents were used.
C-1: High Solve EDM (manufactured by Toho Chemical)
C-2: Propylene glycol monomethyl ether acetate (PGMEA, manufactured by Daicel)
C-3: γ-butyrolactone

[Heat base generator]
As the photoacid generator, the following compounds were used.

<S-1>
Structure shown below
(Synthesis of S-1)
200 g (1.74 mol) of trans-4-aminocyclohexanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 810 g of methanol are added to a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, and ice water is used. Cooled to 0 ° C. While stirring this solution, 379.0 g (1.74 mol) of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of the dropwise addition, the resulting mixture was stirred at 40 ° C. for 1 hour, and then concentrated under reduced pressure at 50 ° C. for 1 hour to obtain 360 g of the intended S-1.

<S-2>
Structure shown below
(Synthesis of S-2)
S-1 was synthesized in the same manner as S-1, except that 1.74 mol of 3-aminopropyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of trans-4-aminocyclohexanol. -2 was synthesized.

<S-3>
Structure shown below (1- (tert-butoxycarbonyl) -4-hydroxypiperidine, manufactured by Tokyo Chemical Industry Co., Ltd.)

<S-4>
Structure shown below (trans-4-aminocyclohexanol, manufactured by Tokyo Chemical Industry Co., Ltd.)

<S-5>
Structure shown below (3-amino-1- (tert-butoxycarbonyl) pyrrolidine, manufactured by Tokyo Chemical Industry Co., Ltd.)

<S-6>
Structure shown below
(Synthesis of S-6)
In the synthesis of S-1, S-1 was used except that 1.74 mol of 1,4-butanediol bis (3-aminopropyl) ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of trans-4-aminocyclohexanol. S-6 was synthesized by the same method as described above.

<S-7>
Structure shown below
(Synthesis of S-7)
In the synthesis of S-1, S-1 was used except that 1.74 mol of 4-hydroxy-D-(-)-2-phenylglycine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of trans-4-aminocyclohexanol. S-7 was synthesized by the same method as described above.

<S-8>
Structure shown below (N- (tert-butoxycarbonyl) glycine, manufactured by Tokyo Chemical Industry Co., Ltd.)

<S-9>
Structure shown below
(Synthesis of S-9)
In the synthesis of S-1, in place of di-tert-butyl dicarbonate, 1.74 mol of di-tert-amyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used. -9 was synthesized.

<S-10>
Structure shown below
(Synthesis of S-10)
In the synthesis of S-1, in the same manner as S-1, except that 1.74 mol of 2- (2-aminoethoxy) ethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of trans-4-aminocyclohexanol. , S-10 was synthesized.

<S-11>
Structure shown below (4- (tert-amyloxycarbonylamino) cyclohexanecarboxylic acid, manufactured by Tokyo Chemical Industry Co., Ltd.)

[Other ingredients]
<Alkoxysilane compound>
J-1: 3-Glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
J-2: 1,2-bis (triethoxysilyl) ethane (KBE-3026, Shin-Etsu Chemical Co., Ltd.)
<Sensitizer>
J-3: 9,10-dibutoxyanthracene (anthracure UVS-1331, manufactured by Kawasaki Chemical Industries)
<Surfactant>
W-1: Fluorosurfactant (FTX-218, manufactured by Neos)
W-2: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC)

<Synthesis Method of B-3>
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated, and the crystals were diluted with diisopropyl ether (10 mL). The slurry was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and a 50 mass% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, then reslurried with methanol (20 mL), filtered and dried to obtain the compound B-3 (the above structure) (2.3 g).
In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-3 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q, 1H) , 2.4 (s, 3H), 1.7 (d, 3H).

<Method for synthesizing B-4>
After 4.0 g of 1-amino-2-naphthol hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) is suspended in 16 g of N-methylpyrrolidone (Wako Pure Chemical Industries), 3.4 g of sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries) is added. , 4.9 g of methyl 4,4-dimethyl-3-oxovalerate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise and heated at 120 ° C. for 2 hours in a nitrogen atmosphere. After allowing to cool, water and ethyl acetate were added to the reaction mixture and the phases were separated, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-1-2A. Crude B-1-2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate C-1-2A.
C-1-2A (1.7 g) and p-xylene (6 mL) were mixed, 0.23 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated at 140 ° C. for 2 hours. . After allowing to cool, water and ethyl acetate were added to the reaction mixture and the phases were separated. The organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude C-1-2B.
Tetrahydrofuran (THF) (2 mL) and the whole amount of crude C-1-2B were mixed, and ice-cooled 2 M hydrochloric acid / THF solution 6.0 mL, and then isopentyl nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (0.84 g) were added dropwise. The mixture was warmed to room temperature and stirred for 2 hours. Water and ethyl acetate were added to the obtained reaction mixture for liquid separation, and the organic layer was washed with water, dried over magnesium sulfate, filtered and concentrated to obtain Intermediate Intermediate C-1-2C.
The total amount of crude intermediate C-1-2C was mixed with acetone (10 mL), and triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) (1.2 g), p-toluenesulfonyl chloride (manufactured by Tokyo Chemical Industry) (1.4 g) under ice cooling. Then, the mixture was warmed to room temperature and stirred for 1 hour. Water and ethyl acetate were added to the obtained reaction mixture for liquid separation, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude C-4. Crude C-4 was reslurried with cold methanol, filtered and dried to obtain B-4 (1.2 g).
The ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-4 is δ = 8.5-8.4 (m, 1H), 8.0-7.9 (m, 4H), 7.7-7. .6 (m, 2H), 7.6-7.5 (m, 1H), 7.4 (d, 2H), 2.4 (s, 3H), 1.4 (s, 9H) .

<Method for synthesizing B-5>
A separable flask equipped with a stirrer and a thermometer was charged with 33.6 g of N-hydroxynaphthalimide sodium salt, 0.72 g of 4-dimethylaminopyridine and 300 ml of tetrahydrofuran, and stirred and dissolved at room temperature of 25 ° C. Next, 42 g of (+) 10-camphorsulfonyl chloride was added and stirred for 3 hours, and then 15 g of triethylamine was added, followed by stirring at room temperature for 10 hours. Subsequently, the reaction solution was put into 300 ml of distilled water, and the deposited precipitate was separated by filtration. This precipitation was repeated several times using acetone and hexane to obtain 12 g of N-camphorsulfonyloxy-1,8-naphthalimide.

[Examples 1-48 and Comparative Examples 1-6]
Each component mentioned above was mixed with the kind and addition amount which are shown in the following table | surface, and it filtered with the filter made from polytetrafluoroethylene with a hole diameter of 0.2 micrometer, and obtained each photosensitive resin composition.
In addition, about Example 44, other than carrying out slit coating of each photosensitive resin composition with the slit nozzle coater made from Toray Engineering on a glass substrate (Corning 1737, 0.7 mm thickness (made by Corning)) Evaluation was performed in the same manner as in the examples.

[Evaluation]
About each prepared photosensitive resin composition, the heat resistant transparency, patterning property, and pattern shape were evaluated by the method and reference | standard shown below. These results are shown in the table below.

<Heat resistant transparency>
Each photosensitive resin composition was spin-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) and then pre-baked on a hot plate at 90 ° C. for 120 seconds to evaporate the solvent. A photosensitive resin composition layer having a thickness of 0.0 μm was formed.
Thereafter, this substrate was heated in an oven at 300 ° C./60 minutes under nitrogen to obtain a cured film.
The cured film was further heated in an oven at 300 ° C./60 minutes under nitrogen, and then the transmittance was measured at a wavelength of 400 nm using a transmittance meter (MCPD-3000 manufactured by Otsuka Electronics). evaluated. The greater the transmittance, the higher the heat-resistant transparency, and evaluations 1 and 2 are in the practical range.
1: 95% or more 2: 93% or more 3: 90% or more 4: 85% or more

<Patternability>
After each photosensitive resin composition was spin-coated on a glass substrate (EAGLE XG, 0.7 mm thick (Corning)) exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, 90 ° C./120 seconds. Pre-baking was performed on a hot plate to volatilize the solvent, and a film made of a photosensitive resin composition layer having a film thickness of 4.0 μm was formed.
Subsequently, the formed film was exposed using a Canon MPA 5500CF (high pressure mercury lamp) through a mask on which a 10 μm hole pattern was formed. The exposed film was developed with an alkali developer (2.38% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds. The exposure amount when the hole diameter equivalent to that of the mask was resolved by these operations was determined as the optimum i-line exposure amount (Eopt).
Further, the formed film was exposed at the optimum i-line exposure amount through a mask on which patterns having hole diameters of 4, 6, and 8 μm were formed. The exposed film was developed with an alkali developer (2.38% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
The formed pattern was observed with a scanning electron microscope, and the actual hole diameter was measured. The actual hole diameter was defined by the size of the bottom (bottom surface) of the film.
Next, the ratio of the size difference between the hole diameter of 4 μm and the actual hole pattern diameter corresponding thereto was calculated.
Similarly, the ratio of the size difference between the hole diameter of 6 μm and the corresponding actual hole pattern diameter was calculated.
Similarly, the ratio of the size difference between the hole diameter of 8 μm and the actual hole pattern diameter corresponding thereto was calculated.
The calculated ratio was evaluated according to the following criteria. The smaller the difference between the actual hole diameter and the mask diameter, the better the patterning property and the easier the panel design. Evaluations 1, 2 and 3 are practical ranges.
The average size difference ratio of each diameter of 1: 4, 6 and 8 μm is within 10%. 2: The average size difference ratio of each diameter of 4: 4, 6 and 8 μm is over 10% and within 20%. The average of the size difference ratio of each diameter of 3: 4, 6, 8 μm exceeds 20% and within 30% The average of the ratio of the size difference of each diameter of 4: 4, 6, 8 μm is 30 Exceeding 40% and within 40% 5: 4, 6, and 8 μm, the average ratio of the size difference of each diameter exceeds 40%

<Pattern shape>
A substrate having a hole pattern formed on the film was heated in an oven at 300 ° C. for 60 minutes under nitrogen using a mask having a hole diameter of 6 μm in the patterning evaluation.
The heated substrate was cleaved, and the cross-sectional shape of the hole pattern was observed from the horizontal direction with a scanning electron microscope. The angle (taper angle) between the bottom (bottom) and top (top) of the hole pattern was measured.
The measured angle was evaluated according to the following criteria. The higher the taper angle, the easier the high-definition panel design becomes, and evaluations 1 and 2 are in the practical range.
1: 70-80 °
2: 60-70 °
3: 50-60 °
4: 50 ° or less

As is clear from the results shown in the above table, when a thermal base generator that does not correspond to the compound represented by the above formula (X) is used, either the heat-resistant transparency or patterning property of the resulting cured film is It was found to be inferior (Comparative Examples 1, 3 and 6). Comparative Examples 1 and 3 are examples using the thermal base generator exemplified in Patent Document 1 (Japanese Patent Laid-Open No. 2013-152381).
Moreover, when the polybenzoxazole precursor A-2 which does not protect the phenolic hydroxyl group was used, it turned out that either the heat-resistant transparency and patterning property of the cured film obtained are inferior (Comparative Example 2 and 4). Moreover, it turned out that the comparative examples 2 and 4 are inferior in pattern shape.
Moreover, when the photo-acid generator which does not generate | occur | produce the acid whose pKa is 3 or less was used, it turned out that it is inferior to heat-resistant transparency and a pattern shape is also inferior (comparative example 5).

In contrast, a polybenzoxazole precursor in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group, a photoacid generator that generates an acid having a pKa of 3 or less, and the above formula (X) When a photosensitive resin composition containing a thermal base generator and a solvent is used, both the heat-resistant transparency and patterning property of the resulting cured film are good, and the pattern shape to be formed is also good. (Examples 1-48).
From the comparison of Examples 1 to 8, when R ⁴ in the above formula (X) is a compound containing a hydroxy group as a thermal base generator, both heat-resistant transparency and patterning tend to be better. I found out that
Further, from the comparison of Examples 1, 13, and 21, the polybenzoxazole precursor is a repeating unit A in which Y in the formula (1) is represented by a cyclic aliphatic group having 3 to 15 carbon atoms, and When Y in Formula (1) has a repeating unit B represented by a linear or branched aliphatic group having 4 to 20 carbon atoms, any of heat-resistant transparency, patternability, and pattern shape may be Was found to tend to be better.

Example 101
In the liquid crystal display device shown in FIG. 1 of JP-A-2007-328210, the organic insulating film PAS was formed by the following method to obtain a liquid crystal display device.
First, according to Japanese Patent Application Laid-Open No. 2007-328210, an array substrate formed until just before the organic insulating film PAS of the liquid crystal display device described in FIG.
Next, this substrate was exposed to HMDS vapor for 30 seconds, and then the photosensitive resin composition of Example 1 was slit-coated and then pre-baked on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent. A thick photosensitive resin composition layer was formed.
Next, the obtained photosensitive resin composition layer was exposed to an optimal exposure amount through a 6 μmφ hole pattern mask using MPA 7800CF manufactured by Canon Inc., and heated on a hot plate at 70 ° C. for 90 seconds. did.
The exposed resin composition layer was developed with an alkali developer (0.6% tetramethylammonium hydroxide aqueous solution), and then rinsed with ultrapure water. Subsequently, the entire surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 320 mJ / cm ² (energy intensity: 20 mW / cm ² , measured by i-line), and then the substrate was exposed to 320 in an oven in a nitrogen atmosphere. An organic insulating film PAS was obtained by heating at 60 ° C. for 60 minutes.
Thereafter, a liquid crystal display device was obtained according to Japanese Patent Application Laid-Open No. 2007-328210. In this embodiment, since a material having high heat resistance is used for PAS, the interlayer insulating film IN3 is formed at the same temperature as the interlayer insulating film IN2. Thereby, IN3 could be made into a dense film.
When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed very good display characteristics and had high reliability.

[Examples 102 to 150]
A liquid crystal display device was produced in the same manner as in Example 101 except that the composition of Example 1 was replaced with the composition of Examples 2 to 50 in Example 101, respectively. The liquid crystal display device had good display characteristics and high reliability.

Claims (17)

A polybenzoxazole precursor, a photoacid generator that generates an acid having a pKa of 3 or less, a thermal base generator, and a solvent,
The polybenzoxazole precursor is a polybenzoxazole precursor in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group,
A photosensitive resin composition, wherein the thermal base generator is a compound represented by the following formula (X).
Here, in the formula (X), m represents an integer of 1 to 4, R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 5 carbon atoms, and R ⁴ has a hetero atom. It represents an m-valent organic group that may be present. When m is 2 to 4, the plurality of R ¹ , R ² and R ³ may be the same or different. The photosensitive resin composition of Claim 1 in which the said polybenzoxazole precursor has a repeating unit represented by following formula (1).
Here, in the formula (1), X represents a tetravalent organic group containing an aromatic ring, Y represents a divalent organic group, R represents a hydrogen atom, an alkyl group, and the following formula (2) ) Or a group represented by —CORc, and at least one R represents a structure represented by the following formula (2). Rc represents an alkyl group or an aryl group.
In the formula (2), * represents a bonding position with an oxygen atom, R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, and R ¹⁰³ represents an alkyl group. However, except for the case where both R ¹⁰¹ and R ¹⁰² are hydrogen atoms, R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether.   The photosensitive resin composition of Claim 1 or 2 whose content of the said thermal base generator is 0.1-30 mass parts with respect to 100 mass parts of said polybenzoxazole precursors. The photosensitivity according to any one of claims 1 to 3, wherein R ^{4 in the} formula (X) includes at least one selected from the group consisting of a hydroxy group, a carboxyl group, an alkyleneoxy group, and an alkoxysilyl group. Resin composition. M is 2 in the formula (X), the formula R ⁴ a (X) is an aliphatic divalent hydrocarbon group which may have a hetero atom, any one of claims 1-4 The photosensitive resin composition as described in 2.   The photosensitive resin composition of Claim 4 whose m of said Formula (X) is 1.   The polybenzoxazole precursor includes a repeating unit A in which Y in the formula (1) is a cyclic aliphatic group having 3 to 15 carbon atoms, and Y in the formula (1) is 4 to 4 carbon atoms. The photosensitive resin composition of any one of Claims 2-6 containing the repeating unit B represented by 20 linear or branched aliphatic groups.   The photosensitive resin composition according to any one of claims 2 to 6, wherein the polybenzoxazole precursor contains at least an aromatic group in which Y in the formula (1) has 6 to 20 carbon atoms.   The polybenzoxazole precursor contains the repeating unit A and the repeating unit B in a proportion of 70 mol% or more of the total repeating units in the polybenzoxazole precursor, and the repeating unit A and the repeating unit The photosensitive resin composition of Claim 7 whose ratio of content with B is 9: 1-3: 7 by molar ratio.   The polybenzoxazole precursor is any one of claims 1 to 9, wherein 10 to 60% of the phenolic hydroxyl groups of all repeating units of the polybenzoxazole precursor are protected with the acid-decomposable groups. The photosensitive resin composition according to item. Applying the photosensitive resin composition according to any one of claims 1 to 10 to a substrate;
Removing the solvent from the applied photosensitive resin composition;
Exposing the photosensitive resin composition from which the solvent has been removed with actinic radiation;
Developing the exposed photosensitive resin composition with a developer;
A method for producing a cured film, comprising: thermally curing the developed photosensitive resin composition to obtain a cured film.   The manufacturing method of the cured film of Claim 11 including the process of exposing the developed photosensitive resin composition after the said image development process and before the said thermosetting process.   The cured film formed by hardening | curing the photosensitive resin composition of any one of Claims 1-10.   The cured film of Claim 13 which is an interlayer insulation film.   A liquid crystal display device comprising the cured film according to claim 13 or 14.   An organic electroluminescence display device comprising the cured film according to claim 13.   A touch panel having the cured film according to claim 13.