JP6453186B2 - Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic electroluminescence display device, and touch panel - Google Patents

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 discloses a predetermined polybenzoxazole precursor having an acid-decomposable group, a photoacid generator having a pKa of 4 or less, a solvent, and a benzene ring and / or a phenolic hydroxyl group. A photosensitive resin composition containing a crosslinking agent having two or more reactive crosslinking groups is described ([Claim 1]).

International Publication No. 2015/088781

In recent years, attempts have been made to perform heat treatment or film formation at a higher temperature than conventional (for example, a temperature higher than 300 ° C.) in order to improve the performance of the image display device.
Therefore, the inventors of the present invention formed a film at a high temperature using the photosensitive resin composition described in Patent Document 1, and the patterning property and chemical resistance were good. It has been clarified that when a group constituting acetal, which is a group capable of leaving by the action of, is employed, transparency (hereinafter referred to as “heat-resistant transparency”) may be inferior.

  Accordingly, the present invention provides a photosensitive resin composition excellent in all of heat-resistant transparency, patterning property and chemical resistance, and a method for producing a cured film, a cured film, a liquid crystal display device, and organic electroluminescence using the same. It is an object to provide a display device and a touch panel.

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 solvent (alcohol) having a specific structure. It was found that the use of a photosensitive resin composition having a good heat-resistant transparency, patterning property and chemical resistance 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, and a solvent,
The polybenzoxazole precursor is a polybenzoxazole precursor in which at least a part of the phenolic hydroxyl group is protected in the form of an acetal,
The photosensitive resin composition in which a solvent contains the alcohol represented by the following formula (I) which consists of a hydrocarbon group and a hydroxyl group.
R ¹ (—OH) _m (I)
Here, in formula (I), R ¹ represents a hydrocarbon group having 6 to 15 carbon atoms, and m represents an integer of 1 to 3. When m is 2 or 3, the plurality of hydroxyl groups may be bonded to the same carbon atom in the hydrocarbon group constituting R ¹ or may be bonded to different carbon atoms.
[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 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.
[3] The photosensitive resin composition according to [1] or [2], wherein the alcohol content is 0.1 to 1000 parts by mass with respect to 100 parts by mass of the polybenzoxazole precursor.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the alcohol is an alcohol in which R ¹ in formula (I) is an alicyclic hydrocarbon group.
[5] The photosensitive resin composition according to any one of [1] to [4], further comprising an alkoxysilane compound having an epoxy group.
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the polybenzoxazole precursor includes a polybenzoxazole precursor having a partial structure represented by the following formula (3).

Here, in formula (3), * represents a bonding position, 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 Z represents In the case of a single bond, a is 0, 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 are It may be bonded to form a ring.
[7] The photosensitive resin composition according to any one of [1] to [6], wherein the solvent contains propylene glycol monoalkyl ether acetates or diethylene glycol dialkyl ethers.
[8] The photosensitive resin composition according to any one of [1] to [7], wherein the alcohol is at least one selected from the group consisting of cyclohexanol, cyclohexanediol, terpineol, and dihydroterpineol.
[9] Any of [1] to [8], wherein the polybenzoxazole precursor has 10 to 60% of the phenolic hydroxyl group of all the repeating units of the polybenzoxazole precursor protected in the form of an acetal. The photosensitive resin composition as described in 2.

[10] A step of applying the photosensitive resin composition according to any one of [1] to [9] to a substrate;
Removing a part of the solvent from the applied photosensitive resin composition;
Exposing the photosensitive resin composition from which the solvent has been partially 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.
[11] The method for producing a cured film according to [10], including a step of exposing the developed photosensitive resin composition after the step of developing and before the step of thermosetting.
[12] A cured film obtained by curing the photosensitive resin composition according to any one of [1] to [9].
[13] The cured film according to [12], which is an interlayer insulating film.
[14] A liquid crystal display device having the cured film according to [12] or [13].
[15] An organic electroluminescence display device having the cured film according to [12] or [13].
[16] A touch panel having the cured film according to [12] or [13].

  According to the present invention, a photosensitive resin composition excellent in all of heat-resistant transparency, patterning property, and chemical resistance, and a method for producing a cured film, a cured film, a liquid crystal display device, and organic electroluminescence using the same. A display device and a touch panel can be provided.

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, and a solvent.
The polybenzoxazole precursor is a polybenzoxazole precursor in which at least a part of the phenolic hydroxyl group is protected in the form of an acetal.
Moreover, a solvent contains the alcohol represented by the following formula (I) which consists of a hydrocarbon group and a hydroxyl group.
R ¹ (—OH) _m (I)
Here, in formula (I), R ¹ represents a hydrocarbon group having 6 to 15 carbon atoms, and m represents an integer of 1 to 3. When m is 2 or 3, the plurality of hydroxyl groups may be bonded to the same carbon atom in the hydrocarbon group constituting R ¹ or may be bonded to different carbon atoms.

As described above, the photosensitive resin composition of the present invention comprises a predetermined polybenzoxazole precursor and a photoacid generator that generates an acid having a pKa of 3 or less, and an alcohol represented by the above formula (I) as a solvent. As a result, the resulting cured film has good heat-resistant transparency, patterning properties, and chemical resistance.
Although this is not clear in detail, the present inventors presume 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, if an acid is present in the film, side reaction of components derived from the protective group generated by deprotection proceeds, and as a result, the transparency of the resulting cured film is reduced. Become.
Therefore, in the present invention, by containing the alcohol represented by the above formula (I) as a solvent, the progress of side reactions in the firing process is suppressed without degrading the patterning property and chemical resistance, and benzoxazole It was considered that the heat-resistant transparency was improved because the ring-closing reaction of the precursor could be advanced. Specifically, since the alcohol represented by the above formula (I) is composed of a hydrocarbon group having 6 to 12 carbon atoms and a hydroxyl group, it is used in the examples of Patent Document 1 (International Publication No. 2015/088781). Unlike a solvent such as propylene glycol monomethyl ether acetate (PGMEA), which is partly left in the solvent removal step, it is considered that the effect of suppressing unwanted side reactions in the firing step is obtained. Since these alcohols have a hydroxyl group, they are hydrophilic, and even if part of them remain after the drying step, patterning properties are not deteriorated. On the other hand, the alcohol represented by the above formula (I) in the baking step eventually volatilizes out of the system, so that the alcohol does not remain in the film after baking, and the chemical resistance is reduced. It is not considered.

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.
Below, the polybenzoxazole precursor which the photosensitive resin composition of this invention contains, the photo-acid generator and solvent which generate | occur | produce the acid whose pKa is 3 or less, and the additive which contains arbitrarily are explained in full detail.

[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 in the form of an acetal.
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.
Further, “protected in the form of acetal” means an oxygen atom constituting a part of the phenolic hydroxyl group (for example, in the repeating unit represented by the formula (1) described later, in the formula (1) It means protecting so that a protecting group (acid-decomposable group) including an oxygen atom bonded to R becomes an acetal group.

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 above formula (1), examples of the divalent organic group represented by Y include a divalent aliphatic hydrocarbon group, specifically, a cyclic aliphatic group having 3 to 15 carbon atoms. And a linear or branched aliphatic group having 4 to 20 carbon atoms.

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 having excellent 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 having excellent light resistance and excellent 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.

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.

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 in the form of an acetal.
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 acetal in which 10 to 60% of the phenolic hydroxyl groups of all the repeating units of the polybenzoxazole precursor are represented by the above formula (2). The structure is preferably protected by 15 to 50%.
In addition, the phenolic hydroxyl group which all the repeating units of a polybenzoxazole precursor mentioned here mean the phenolic hydroxyl group which all the repeating units of the polybenzoxazole precursor of the state before protecting in the form of an acetal have. .

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 Group, or these, and —CH ₂ —, —O—, —S—,
A group consisting of a combination with —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ — is represented.
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 having 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 has a partial structure represented by the following formula (3) at one end or both ends because the heat-resistant transparency of the resulting cured film is better. Is preferred.

In the above formula (3), * represents a bonding position, 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 Z represents a single bond. A is 0, 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 are bonded to each other. A ring may be formed.

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. Although there is no restriction | limiting in particular as a monovalent organic group, The thing of the formula weight per molecule 10-500 is illustrated. 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 formula (3) include, but are not limited to, the following. 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, patterning property will become more favorable and cured film physical property will also become favorable.

  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.

〔solvent〕
<Alcohol>
The solvent contained in the photosensitive resin composition of the present invention contains at least an alcohol represented by the following formula (I) composed of a hydrocarbon group and a hydroxyl group.
R ¹ (—OH) _m (I)
Here, in formula (I), R ¹ represents a hydrocarbon group having 6 to 15 carbon atoms, and m represents an integer of 1 to 3. When m is 2 or 3, the plurality of hydroxyl groups may be bonded to the same carbon atom in the hydrocarbon group constituting R ¹ or may be bonded to different carbon atoms.

Specific examples of the hydrocarbon group having 6 to 15 carbon atoms represented by R ¹ in the above formula (I) include linear chains such as hexane, heptane, octane, nonane, decane, dodecane, and 2-ethylhexane. Or branched aliphatic hydrocarbons; cycloaliphatic hydrocarbons such as cyclohexane, t-butylcyclohexane, dicyclopentadiene, tricyclodecane, isobornyl, adamantane, 2-methyl-2-adamantane; benzene, toluene, naphthalene, etc. And a hydrocarbon group obtained by removing m hydrogen atoms from the above.

In the present invention, because the heat transparency of the cured film obtained becomes better, alcohol represented by the formula (I), R ¹ in the formula (I) is an alicyclic hydrocarbon group The alcohol represented is preferred.
Specific examples of the alicyclic hydrocarbon group include monocyclic hydrocarbon groups such as a cyclohexane ring group, a cycloheptane ring group, and a cyclooctane ring group; a norbornane ring group, an adamantane ring group, and a bicyclooctane ring. Group, a bridged cyclic hydrocarbon ring group such as tricyclo [5.2.1.0 ^2,6 ] decane ring group; perhydronaphthalene (decalin) ring group, perhydroanthracene ring group, perhydrophenanthrene ring group, Condensed hydrogen group in which a plurality of 5- to 8-membered cycloalkane ring groups such as hydroacenaphthene ring group, perhydrofluorene ring group, perhydroindene ring group, perhydrophenalene ring group are condensed; And hydrocarbon groups except for.

In the present invention, the alcohol represented by the above formula (I) is selected from the group consisting of cyclohexanol, cyclohexanediol, terpineol and dihydroterpineol because the heat-resistant transparency of the cured film obtained is better. At least one is preferred.
Here, as terpineol, the compound represented by the following formula (4) (α-terpineol), the compound represented by the following formula (5) (β-terpineol), or the following formula (6) is represented. A compound (γ-terpineol) is exemplified, and examples of dihydroterpineol include a compound represented by the following formula (7) or a compound represented by the following formula (8).

  In the present invention, the content of the alcohol represented by the above formula (I) is 100 parts by mass of the polybenzoxazole precursor because the patterning property and heat-resistant transparency of the cured film obtained are both better. It is preferable that it is 0.1-1000 mass parts with respect to it, and it is more preferable that it is 50-500 mass parts.

<Other solvents>
The photosensitive resin composition of the present invention may contain other solvents in addition to the alcohol represented by the above formula (I).
Here, the other solvent is preferably a solvent that dissolves essential components and optional components and does not react with each component.
Specific examples of other solvents 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. Alkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, Examples include lactones. 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.
These other solvents can be used singly or in combination of two or more.

In the present invention, from the viewpoint of slit coatability, it is preferable to include propylene glycol monoalkyl ether acetates or diethylene glycol dialkyl ethers as other solvents.
Specific examples of the propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate.
Specific examples of diethylene glycol dialkyl ethers include diethylene glycol diethyl ether and diethylene glycol methyl ethyl ether.

  In the present invention, the content in the case of containing another solvent is preferably 500 to 2000 parts by mass, more preferably 700 to 1800 parts by mass with respect to 100 parts by mass of the polybenzoxazole precursor. preferable.

[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.

  In this invention, it is preferable to contain the alkoxysilane compound which has an epoxy group among the said alkoxysilane compounds from the reason that the patternability and chemical resistance of the cured film obtained become more favorable.

  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 that belong to the following compounds and have 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 the compounds described in JP-A-2011-221494, paragraphs 0204 to 0207, the contents of which are incorporated herein.

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 Electronics Chemical Co., Ltd.), MegaFac (manufactured by DIC Corporation), F-554 (manufactured by DIC Corporation), Florard Novec FC- 4430 (manufactured by Sumitomo 3M), Surflon S-242 (manufactured by AGC Seimi Chemical Co., Ltd.), PolyFoxPF-6320 (manufactured by OMNOVA), SH-8400 (manufactured by Toray Dow Corning Silicone Co., Ltd.), and footent FTX-218G (manufactured by Neos Co., Ltd.).
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 A phenolic antioxidant is most preferred. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include the compounds described in paragraph 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 diameter of 0.2 μm.

[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 part of 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 application step (1), the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent.

Before performing the coating step (1), the substrate may be cleaned by alkali cleaning or plasma cleaning. Further, the substrate surface may be treated with hexamethyldisilazane or the like with respect to the cleaned substrate. The method of treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method of exposing the substrate to hexamethyldisilazane vapor.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
The resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound And the like.
These substrates may have a multi-layered 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 solvent removal step (2), a part of 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. Let it form. 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, the pattern adherence is better when the step (4) described later is performed, and the residue tends to be further reduced.
Here, in the solvent removal step (2), as described above, the alcohol represented by the formula (I) is considered to remain in the initial stage of the post-baking step. Or a step of removing a part of the alcohol represented by the above formula (I).

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

In the developing step (4), the polybenzoxazole precursor is developed using a developer. By removing the exposed area having a phenolic hydroxyl group that is easily dissolved in the developer, a positive image is formed.
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 post-baking step of (5), the obtained positive image is heated to thermally decompose the group protected in the form of acetal to form a phenolic hydroxyl group, and cyclize (form a benzoxazole ring). Thus, 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. 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.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process). When performing middle baking, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. 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.

  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.

[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, oxide semiconductor TFTs, 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.
In addition, as a liquid crystal driving method that can be adopted by the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Vertical Alignment) method, an IPS (In-Plane-Switching) method, an FFS (Fringe Field Switching) method, an OCB (OCB) (Optically 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, or JP-A-2005 -346054 can be used as the organic insulating film (212). Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.
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 TFTs included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
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.

[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 of 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 Co., Ltd.), 30.20 g (0.382 mol) of pyridine and 330 g of N-methylpyrrolidone (NMP) were added. This was stirred at room temperature and then cooled to −15 ° C. with a dry ice / methanol bath. 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.) was maintained while maintaining the reaction temperature at −5 ° C. to −15 ° C. 13.49 g (0.056 mol) of sebacoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.45 g (0.006 mol) of acetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 260.5 g of NMP The mixed solution 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 liquid 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 maintained at a reaction temperature of −0 ° C. or lower. Was dripped. 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 camphorsulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 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 polybenzoxazole (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]
In the synthesis of Resin A-1a, the same method as Resin A-1a was used except that 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of acetyl chloride. Resin A-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]
In the synthesis of Resin A-1a, the same method as Resin A-1a was used, except that 0.188 mol of sebacoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used without using 1,4-cyclohexyldicarbonyl chloride. Resin A-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) was used instead of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (Bis-AP-AF, manufactured by Central Glass Co., Ltd.). Resin A-5a was synthesized in the same manner as Resin A-1a except that 0.132 mmol of -4-hydroxyphenyl) sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.) 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, instead of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (Bis-AP-AF, manufactured by Central Glass Co., Ltd.), 9,9-bis Resin A-6a was synthesized in the same manner as Resin A-1a except that 0.132 mmol of (3-amino-4-hydroxyphenyl) fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.) 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, 3,3′- was used instead of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (Bis-AP-AF, manufactured by Central Glass Co., Ltd.). Resin A-7a was synthesized in the same manner as Resin A-1a except that 0.132 mol of dihydroxybenzidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.
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.) was used, and 0.094 mol of sebacoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used. Resin A-8a was synthesized by the same method as that for Resin A-1a except that.
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 converted value by 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 in the synthesis of Resin A-8a except that 0.094 mol of suberoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of sebacoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.). Resin A-9a was synthesized by the same method.
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 except that 0.056 mol of suberoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of sebacoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in the synthesis of resin A-1a. Resin A-10a was synthesized by the same method.
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]
Resin A-1a was synthesized except that 0.0560 mol of adipoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of sebacoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in the synthesis of resin A-1a. Resin A-11a was synthesized by the same method.
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 Co., Ltd.), 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 polybenzoxazole (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-1a (1H-NMR). The structure of PBO precursor A-13 is shown below.
<PBO precursor A-13>

[Synthesis of Polybenzoxazole Precursor A-14]
In the synthesis of Resin A-1a, except that 1,4-cyclohexyldicarbonyl chloride and sebacoyl chloride were not used, but 0.094 mol of isophthaloyl chloride and 4,4′-oxybis (benzoyl chloride) were used respectively. 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 weight average molecular weight of the obtained PBO precursor A-14 was 25,000 (polystyrene conversion value of gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-14 was 29% 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-3a was synthesized except that 1,4-cyclohexyl dicarbonyl chloride and sebacoyl chloride were not used, but 0.094 mol of isophthaloyl chloride and 4,4′-oxybis (benzoyl chloride) were used respectively. Resin A-15a was synthesized by the same method as A-3a.
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 21,000 (polystyrene conversion value of gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-15 was 30% 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>

[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〕
<Other solvents>
C-1: High Solve EDM (manufactured by Toho Chemical Industry Co., Ltd.)
C-2: Propylene glycol monomethyl ether acetate (PGMEA, manufactured by Daicel Corporation)
C-3: γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation)

<Alcohol>
D-1: Dihydroterpineol (manufactured by Nippon Terpene Chemical Co., Ltd.)
D-2: n-hexanol D-3: cyclohexanol D-4: 1,2-cyclohexanediol D-5: 1,2,6-hexanetriol D-6: 1-adamantanol D-7: 1- ( Bicyclo [2.2.1] heptan-1-yl) -2-pentanol D-8: Menthol (manufactured by Wako Pure Chemical Industries, Ltd.)
D-9: Mixture of α-terpineol, β-terpineol and γ-terpineol (Turpineol C, manufactured by Nippon Terpene Chemical Co., Ltd.)
D-10: α-Terpineol (manufactured by Nippon Terpene Chemical Co., Ltd.)
D-11: Tripropylene glycol D-12: Stearyl alcohol

[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.)
Made)
<Surfactant>
W-1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC Corporation)

W-2: Fluorosurfactant (FTX-218, manufactured by Neos Co., Ltd.)

<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>
4.0 g of 1-amino-2-naphthol hydrochloride is suspended in 16 g of N-methylpyrrolidone, 3.4 g of sodium bicarbonate is added, and then 4.9 g of methyl 4,4-dimethyl-3-oxovalerate is added dropwise. And heated at 120 ° C. for 2 hours under 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-2A. Crude B-2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate B-2A.
B-2A (1.7 g) and p-xylene (6 mL) were mixed, 0.23 g of p-toluenesulfonic acid monohydrate was added, and the mixture was 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 B-2B.
THF (2 mL) and the whole amount of crude B-2B were mixed, 2 mL hydrochloric acid / THF solution 6.0 mL was added dropwise under ice cooling, then isopentyl nitrite (0.84 g) was added dropwise, and the temperature was raised to room temperature (25 ° C.) for 2 hours. Stir. 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 B-2C.
The total amount of intermediate crude B-2C was mixed with acetone (10 mL), triethylamine (1.2 g) and p-toluenesulfonyl chloride (1.4 g) were added under ice cooling, and the mixture was warmed to room temperature and stirred for 1 hour. did. 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 B-2. Crude B-2 was reslurried with cold methanol, filtered and dried to obtain B-4 (1.2 g).
In addition, 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) there were.

<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 dissolved by stirring 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 to 26, Reference Example 27, Examples 28 to 41, and Comparative Examples 1 to 4]
Each component mentioned above was mixed by 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 the following description, Reference Example 27 is referred to as Example 27.

[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 Table 1 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 heated on a hot plate at 90 ° C. for 120 seconds to remove the solvent, and the film thickness 4 A photosensitive resin composition layer having a thickness of 0.0 μm was formed.
Thereafter, this substrate was heated in an oven at 350 ° C./60 minutes under nitrogen to obtain a cured film.
After further heating this cured film in an oven at 350 ° C./60 minutes under nitrogen, the transmittance was measured at a wavelength of 400 nm using a transmittance meter (MCPD-3000 manufactured by Otsuka Electronics Co., Ltd.). evaluated. The greater the transmittance, the higher the heat-resistant transparency, and the evaluations 1 to 3 are in the practical range.
1: 90% or more 2: 87% or more and less than 90% 3: 85% or more and less than 87% 4: 80% or more and less than 85% 5: less than 80%

<Patternability>
After each photosensitive resin composition was spin-coated on a glass substrate (EAGLE XG, 0.7 mm thickness (Corning)) exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, 90 ° C./120 The mixture was heated on a second hot plate to remove the solvent, thereby forming a film made of a photosensitive resin composition layer having a thickness of 4.0 μm.
Next, the formed film was exposed using a MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. through a mask on which a 6 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 substrate on which the hole pattern was formed was heated in an oven at 350 ° C./60 minutes under nitrogen.
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 to 3 are in the practical range.
1: 75 degree or more and less than 85 degree 2: 65 degree or more and less than 75 degree 3: 55 degree or more and less than 65 degree 4: 45 degree or more and less than 55 degree 5: Less than 45 degree

<Chemical resistance>
Each photosensitive resin composition was spin-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to form a film. A film composed of a photosensitive resin composition layer having a thickness of 4.0 μm was formed.
Thereafter, this substrate was heated in an oven at 350 ° C./60 minutes under nitrogen to obtain a cured film.
After measuring the film thickness of the cured film, the film was immersed in NMP at 80 ° C. for 10 minutes, the film was pulled up to remove the surface liquid, and the film thickness was measured immediately. The film thickness before immersion was compared with the film thickness after immersion, and the increased ratio was expressed in percent. The smaller the numerical value, the better the NMP resistance of the cured film, and the evaluations 1 to 3 are in the practical range.
Swell ratio (%) = film thickness after immersion (μm) / film thickness before immersion (μm) × 100
1: 100% or more and less than 103% 2: 103% or more and less than 105% 3: 103% or more and less than 108% 4: 108% or more and less than 110% 5: 110% or more or film reduction by dissolution

As is clear from the results shown in Table 1 above, when the PBO precursor A-2 in which the acid group is not protected is used and a photoacid generator (B-7: naphthoquinonediazide) having a pKa greater than 3 is used. It was found that the heat-resistant transparency was inferior (Comparative Example 1).
Moreover, when alcohol was not used as a solvent, it turned out that heat-resistant transparency is inferior (comparative example 2).
Further, when tripropylene glycol is used as a solvent and a predetermined alcohol composed of a hydrocarbon group having 6 to 15 carbon atoms and a hydroxyl group is not used, the heat-resistant transparency is good, but the patterning property may be inferior. Okay (Comparative Example 3).
Further, when stearyl alcohol was used as a solvent and a predetermined alcohol consisting of a hydrocarbon group having 6 to 15 carbon atoms and a hydroxyl group was not used, the heat-resistant transparency was good, but the patterning property and chemical resistance were good. It was found to be inferior (Comparative Example 4).

On the other hand, when a predetermined polybenzoxazole precursor, a photoacid generator that generates an acid having a pKa of 3 or less, and an alcohol having a specific structure are used, heat-resistant transparency and patterning of the resulting cured film It turned out that both property and chemical resistance become favorable (Examples 1-41).
Further, from the comparison between Example 1 and Example 2, when the polybenzoxazole precursor has a partial structure (acetyl group) represented by the above formula (3) at the terminal, the heat resistance of the resulting cured film It was found that the transparency was better.
Moreover, it turned out that the patternability and chemical resistance of the cured film obtained become more favorable when the alkoxysilane compound which has an epoxy group is used from contrast of Example 1, 25, and 26. FIG.
Further, from the comparison between Examples 1 and 27 to 29, when the alcohol content is 50 to 500 parts by mass with respect to 100 parts by mass of the polybenzoxazole precursor, the heat-resistant transparency of the cured film obtained is better. I found out that
Moreover, from the comparison of Example 1 and 30 to 37, when R ¹ in the above formula (I) is an alcohol represented by an alicyclic hydrocarbon group, the resulting cured film has better heat-resistant transparency. I found out that

Claims (15)

A polybenzoxazole precursor, a photoacid generator that generates an acid having a pKa of 3 or less, and a solvent,
The polybenzoxazole precursor is a polybenzoxazole precursor in which at least a part of the phenolic hydroxyl group is protected in the form of an acetal,
The solvent is seen containing an alcohol represented by the following formula consisting of a hydrocarbon group and a hydroxyl group (I),
The photosensitive resin composition whose content of the said alcohol is 50-500 mass parts with respect to 100 mass parts of said polybenzoxazole precursors .
R ¹ (—OH) _m (I)
Here, in said formula (I), R < ¹ > represents a C6-C15 hydrocarbon group, m represents the integer of 1-3. When m is 2 or 3, the plurality of hydroxyl groups may be bonded to the same carbon atom in the hydrocarbon group constituting R ¹ or may be bonded to different carbon atoms. 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 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. The photosensitive resin composition of Claim 1 or 2 whose said alcohol is alcohol by which R < ¹ > in the said formula (I) is represented by an alicyclic hydrocarbon group. Furthermore, the photosensitive resin composition of any one of Claims 1-3 containing the alkoxysilane compound which has an epoxy group. The photosensitive resin composition of any one of Claims 1-4 in which the said polybenzoxazole precursor contains the polybenzoxazole precursor which has a partial structure represented by following formula (3).

In the formula (3), * represents a bonding position, Z represents a single bond, a carbon atom or a sulfur atom, R ³⁰ represents a monovalent organic group, n represents 0 or 1, Z Is a single bond, a is 0, 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 are They may be bonded to each other to form a ring. The photosensitive resin composition of any one of Claims 1-5 in which the said solvent contains propylene glycol monoalkyl ether acetates or diethylene glycol dialkyl ethers. The alcohol, cyclohexanol, cyclohexanediol, is at least one selected from the group consisting of terpineol and dihydro terpineol, the photosensitive resin composition according to any one of claims 1-6. The polybenzoxazole precursor according to any one of claims 1 to 7 , wherein 10 to 60% of the phenolic hydroxyl groups contained in all repeating units of the polybenzoxazole precursor are protected in the form of acetals. The photosensitive resin composition as described. Applying the photosensitive resin composition according to any one of claims 1 to 8 to a substrate;
Removing a part of the solvent from the applied photosensitive resin composition;
Exposing the photosensitive resin composition from which the solvent has been partially 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 9 including the process of exposing the developed photosensitive resin composition after the process of developing and before the process of thermosetting. The cured film formed by hardening | curing the photosensitive resin composition of any one of Claims 1-8 . The cured film according to claim 11 , which is an interlayer insulating film. Having a cured film according to claim 11 or 12, the liquid crystal display device. Having a cured film according to claim 11 or 12, an organic electroluminescent display device. Having a cured film according to claim 11 or 12, a touch panel.