WO2016043203A1

WO2016043203A1 - Positive photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic electroluminescent display device and touch panel

Info

Publication number: WO2016043203A1
Application number: PCT/JP2015/076219
Authority: WO
Inventors: 健太吉田; 一郎小山; 山田　悟
Original assignee: 富士フイルム株式会社
Priority date: 2014-09-17
Filing date: 2015-09-16
Publication date: 2016-03-24
Also published as: TW201612646A; JP6259109B2; JPWO2016043203A1; TWI667543B

Abstract

Provided are: a positive photosensitive resin composition which has excellent sensitivity and curability; a method for producing a cured film; a cured film; a liquid crystal display device; an organic electroluminescent display device; and a touch panel. This positive photosensitive resin composition contains: a resin which contains an acid group and/or an acid group protected by an acid-decomposable group, and which is cyclized and cured by means of a base; a thermal base generator represented by general formula (1); a photoacid generator; and a solvent. In formula (1), R¹ represents a hydrogen atom or an n-valent organic group; each of R²-R⁵ independently represents a hydrogen atom or an alkyl group; and n represents an integer of 1 or more.

Description

Positive photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic electroluminescence display device, and touch panel

The present invention relates to a positive photosensitive resin composition. More specifically, a positive photosensitive resin suitable for forming a planarizing film, a protective film, an interlayer insulating film, and the like of electronic components such as a liquid crystal display device, an organic electroluminescence display device, a touch panel, an integrated circuit element, and a solid-state imaging element Relates to the composition. The present invention also relates to a method for producing a cured film, a cured film obtained by curing a positive photosensitive resin composition, a liquid crystal display device using the cured film, an image display device such as an organic electroluminescence display device, and an input device such as a touch panel. .

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

In recent years, attempts have been made to perform heat treatment and film formation at a higher temperature (for example, about 300 ° C.) than before in order to increase the efficiency of production and the performance of image display devices.
Resin that cures by cyclization such as polyimide precursor and polybenzoxazole precursor can form a cured film with excellent heat resistance. Attempts have been made to form various fine patterns.
Patent Document 1 discloses a negative photosensitive resin composition containing an N-aromatic glycine derivative and a polymer precursor.
Patent Document 2 discloses a positive photosensitive resin composition containing an alkali-soluble resin, a photosensitive agent, and a thermal base generator. As the thermal base generator, a secondary amine having a carbamate protecting group and a heterocyclic structure containing a nitrogen atom is used.

JP 2006-282880 A JP 2013-152381 A

Patent Document 1, as described in paragraph 0014, can obtain a large solubility contrast regardless of the type of polyimide precursor resin, and as a result, a pattern having a good shape while maintaining a sufficient process margin. The invention aims to provide a photosensitive resin composition that can be obtained. In order to achieve this object, an N-aromatic glycine derivative is used as a photobase generator. That is, in Patent Document 1, an exposed portion is cured by imidizing a polyimide precursor resin using an amine generated by irradiating light to an N-aromatic glycine derivative as a catalyst to cure an exposed portion and an unexposed portion. A negative pattern is formed with a difference in solubility between the two.
Resins that are cured by cyclization with a base, such as polyimide precursors and polybenzoxazole precursors, can form cured films with excellent heat resistance. Heat treatment was required. For this reason, when a cured film is formed using such a resin, there is a risk that heat during the cyclization reaction of the resin may cause thermal damage to electronic components, and further reduction of the cyclization temperature is required. Therefore, further improvement in curability is desired.
However, Patent Document 1 does not discuss the reduction of the cyclization temperature, and in the examples, imidization is performed by heating at 300 ° C. for 1 hour.
Furthermore, Patent Document 1 is an invention relating to a negative photosensitive resin composition, and there is no description or suggestion about application to a positive photosensitive resin composition.

Patent Document 2 is an invention relating to a positive photosensitive resin composition, but the present inventor has examined the positive photosensitive resin composition disclosed in Patent Document 2 and found that an acid generated in an exposed area. Thus, it was found that the deprotection reaction of the thermal base generator is likely to occur and the sensitivity is likely to be lowered.

Therefore, an object of the present invention is to provide a positive photosensitive resin composition excellent in sensitivity and curability. Moreover, it aims at providing the manufacturing method of a cured film, a cured film, a liquid crystal display device, an organic electroluminescent display device, and a touch panel.

As a result of investigations by the inventors, a thermal base generator represented by the following general formula (1) and an acid group and / or a group in which an acid group is protected by an acid-decomposable group are contained, The present inventors have found that a positive photosensitive resin composition excellent in sensitivity and curability can be provided by using a resin that is cured and cured and a photoacid generator in combination, and the present invention has been completed. The present invention provides the following.
<1> a resin containing an acid group and / or a group in which the acid group is protected with an acid-decomposable group, cyclized and cured by a base, a thermal base generator represented by the following general formula (1), A positive photosensitive resin composition comprising a photoacid generator and a solvent;

In the formula, R ¹ represents a hydrogen atom or an n-valent organic group,
R ² to R ⁵ each independently represents a hydrogen atom or an alkyl group,
n represents an integer of 1 or more.
<2> The resin is at least one selected from a polybenzoxazole precursor containing a repeating unit represented by the general formula (2) and a polyimide precursor containing a repeating unit represented by the general formula (3). The positive photosensitive resin composition according to <1>,

In the formula, X ¹ and X ² each independently represent a tetravalent organic group,
Y ¹ and Y ² each independently represent a divalent organic group,
R ⁶ and R ⁸ each independently represents an acid-decomposable group,
R ⁷ and R ⁹ each independently represent a hydrogen atom, a crosslinkable group, an alkyl group, an acid-decomposable group, or a group represented by —CORc,
Rc represents an alkyl group or an aryl group.
<3> The resin is at least one selected from a polybenzoxazole precursor containing a repeating unit represented by the general formula (4) and a polyimide precursor containing a repeating unit represented by the general formula (5). The positive photosensitive resin composition according to <1>,

In the formula, X ³ and X ⁴ each independently represent a tetravalent organic group,
Y ³ and Y ⁴ each independently represent a divalent organic group,
R ¹⁰ and R ¹² represent a hydrogen atom,
R ¹¹ and R ¹³ each independently represent a hydrogen atom, a crosslinkable group, an alkyl group, or a group represented by —CORc,
Rc represents an alkyl group or an aryl group.
<4> The positive photosensitive resin composition according to <3>, further comprising a compound having a group in which at least a part of the acid group is protected with an acid-decomposable group.
<5> The positive photosensitive resin composition according to <4>, wherein the compound having a group in which at least a part of the acid group is protected with an acid-decomposable group is a compound represented by the following general formula (E1): object;

In the formula, R ²¹ represents a monovalent to hexavalent organic group,
R ²² and R ²³ each independently represents a hydrogen atom, an alkyl group or an aryl group,
Any one of R ²² and R ²³ is an alkyl group or an aryl group;
R ²⁴ represents an alkyl group or an aryl group, R ²⁴ may be bonded to R ²² or R ²³ to form a cyclic ether structure;
n1 represents an integer of 1 to 6.
<6> The positive photosensitive resin composition according to any one of <1> to <5>, wherein in general formula (1), n is 1 and R ¹ is an aryl group.
<7> The positive photosensitive resin composition according to any one of <1> to <6>, wherein the resin is a polybenzoxazole precursor.
<8> Applying the positive photosensitive resin composition according to any one of <1> to <7> to a substrate;
Removing the solvent from the applied positive photosensitive resin composition;
Exposing the positive photosensitive resin composition from which the solvent has been removed with actinic radiation;
Developing the exposed positive photosensitive resin composition with a developer;
And a step of thermally curing the developed positive photosensitive resin composition.
<9> The method for producing a cured film according to <8>, including a step of exposing the developed positive photosensitive resin composition after the step of developing and before the step of thermosetting.
<10> A cured film obtained by curing the positive photosensitive resin composition according to any one of <1> to <7>.
<11> The cured film according to <10>, which is an interlayer insulating film.
<12> A liquid crystal display device having the cured film according to <10> or <11>.
<13> An organic electroluminescence display device having the cured film according to <10> or <11>.
<14> A touch panel having the cured film according to <10> or <11>.

ADVANTAGE OF THE INVENTION According to this invention, it became possible to provide the positive photosensitive resin composition excellent in the sensitivity and sclerosis | hardenability, the manufacturing method of a cured film, a cured film, a liquid crystal display device, an organic electroluminescent display device, and a touch panel. .

1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. It is a composition conceptual diagram of other examples of a liquid crystal display. 1 shows a conceptual diagram of a configuration of an example of an organic EL display device. It is sectional drawing which shows the structural example of a capacitive touch panel. It is explanatory drawing which shows an example of a front plate. It is explanatory drawing which shows an example of a 1st transparent electrode pattern and a 2nd transparent electrode pattern.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
In this specification, 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 chromatograph) measurement. The weight average molecular weight and number average molecular weight of the polymer are, for example, HLC-8120 (manufactured by Tosoh Corporation), and TSK gel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mm ID × 30.0 cm) as a column. , By using THF (tetrahydrofuran) as an eluent.

The positive photosensitive resin composition of the present invention (hereinafter also referred to as photosensitive resin composition) contains (A) an acid group and / or a group in which an acid group is protected by an acid-decomposable group, and is cyclized by a base. And (B) a thermal base generator represented by the following general formula (1), (C) a photoacid generator, and (D) a solvent.
By setting it as the said structure, it can be set as the photosensitive resin composition excellent in the sensitivity and sclerosis | hardenability. An example of the mechanism of manifestation of the effect of the invention is estimated as follows, but is not particularly limited as long as the same effect can be obtained. That is, the thermal base generator represented by the general formula (1) is a compound having a carboxyl group, and has an acidic property in a normal state. For this reason, in the state before a heating, especially in an exposure stage, a composition can be made into an acidic state, generation | occurrence | production of the carboxyl group and phenolic hydroxyl group by exposure advances favorably, and the outstanding sensitivity is achieved. In this thermal base generator, the carboxyl group is decarboxylated or dehydrated and lost by heating and the amine site that has been neutralized and inactivated becomes active and becomes basic. That is, in the heating for curing after exposure, when the thermal base generator is heated, the reaction of the following formula proceeds to generate a base. And since the cyclization reaction of resin is accelerated | stimulated with the base generate | occur | produced from the thermal base generator, it is thought that curability improved.
Furthermore, since the acid liberated in the cured film can be neutralized, metal discoloration in the electrode part due to the influence of the acid can be suppressed, and display unevenness when an image display device or an input device is used. Can be improved.
Moreover, since the thermal base generator represented by the general formula (1) is acidic at room temperature (before heating), it does not promote the cyclization reaction of the resin. For this reason, even if it preserve | saves for a long time in the state which mixed the thermal base generator represented by General formula (1), and the resin which cyclizes with a base and a hardening is accelerated | stimulated, reaction will not advance if it does not heat. Therefore, it is excellent in storage stability.

The photosensitive resin composition of the present invention can be preferably used as a positive photosensitive resin composition, and can be particularly preferably used as a chemically amplified positive photosensitive resin composition.
Hereinafter, each component of the photosensitive resin composition of the present invention will be described.

<(A) Resin>
The photosensitive resin composition of the present invention contains a resin that contains an acid group and / or a group in which the acid group is protected by an acid-decomposable group, and is cyclized and cured by a base. The resin preferably has a group in which an acid group is protected with an acid-decomposable group. According to this aspect, a photosensitive resin composition excellent in sensitivity is easily obtained.
The resin is preferably a heterocyclic-containing polymer precursor capable of forming a heterocyclic-containing polymer by causing a cyclization reaction by heating. As the heterocyclic-containing polymer precursor, a polybenzoxazole precursor and / or a polyimide precursor are preferable, and a polybenzoxazole precursor is more preferable because a cured film excellent in permeability can be easily obtained. These resins have a high cyclization temperature, and conventionally cyclized by heating to 300 ° C. or higher. However, according to the present invention, even these resins are 300 ° C. or lower (preferably 200 ° C. or lower). Further, the cyclization reaction can be sufficiently advanced by heating at 180 ° C. or less, and the effects of the present invention can be obtained more remarkably.
The resin content in the photosensitive resin composition of the present invention is preferably 30 to 95% by mass with respect to the total solid content of the photosensitive resin composition. The lower limit is more preferably 40% by mass or more, and further preferably 50% by mass or more. The upper limit is more preferably 90% by mass or less.
Hereinafter, the polybenzoxazole precursor and the polyimide precursor will be described.

<< Polybenzoxazole precursor >>
(First aspect)
In the present invention, the polybenzoxazole precursor of the first aspect preferably has a group in which an acid group is protected by an acid-decomposable group, and includes a repeating unit represented by the following general formula (2). More preferred. The repeating unit represented by the following general formula (2) is preferably contained in a proportion of 50 to 100 mol%, more preferably 70 to 100 mol% of the total repeating units of the polybenzoxazole precursor.
The photosensitive resin composition using the polybenzoxazole precursor according to the first aspect is, for example, a photosensitive resin having excellent sensitivity and curability when used in combination with a photoacid generator that generates an acid having a pKa of 3 or less. The resin composition is easily obtained.

In the formula, X ¹ represents a tetravalent organic group, Y ¹ each independently represents a divalent organic group, R ⁶ independently represents an acid-decomposable group, and R ⁷ represents Each independently represents a hydrogen atom, a crosslinkable group, an alkyl group, an acid-decomposable group, or a group represented by —CORc, and Rc represents an alkyl group or an aryl group.

X ¹ represents a tetravalent organic group. The tetravalent organic group is not particularly limited, but preferably has at least one cyclic structure, more preferably 1 to 10 cyclic structures, and still more preferably 1 to 5 cyclic structures.

The cyclic structure may be an aromatic ring, a heterocyclic ring, or an aliphatic ring, and preferably includes an aromatic ring or a heterocyclic ring, and more preferably includes an aromatic ring. When the tetravalent organic group has a cyclic structure, it is easy to form a cured film having excellent light resistance and chemical resistance.
Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring. As the heterocyclic ring, furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, pyrazoline ring, Examples include pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring. It is done. Examples of the aliphatic ring include a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring.

When the tetravalent organic group has a plurality of cyclic structures, the ring may be condensed, or a plurality of rings may be linked via a single bond or a linking group. The linking group, _{_{e.g., -O -, - S -,}} - C (CF 3) 2 -, - CH 2 -, - SO 2 -, - NHCO- and preferably a group comprising a combination thereof, -SO ₂ —, —CH ₂ —, —C (CF ₃ ) ₂ — and a group formed by a combination thereof are more preferable, and —C (CF ₃ ) ₂ — is more preferable.
The tetravalent organic group is preferably a group having a plurality of cyclic structures, and more preferably two or more aromatic rings are linked via a single bond or a linking group.

Specific examples of X ¹ include the following. In the following formula, either * 1 or * 2 represents a bond to —OR ⁷ , the other represents a bond to the polymer main chain, and either * 3 or * 4 represents represents a linking position to -OR ^8, the other represents a linking position to the polymer backbone.
X ¹ is preferably (X-1) to (X-4), more preferably (X-1), (x-3), or (X-4), and particularly preferably (X-1). When X ¹ is (X-1), a photosensitive resin composition excellent in solvent solubility and sensitivity is easily obtained.

R ⁶ represents an acid-decomposable group. Any acid-decomposable group is preferably used as long as it decomposes by the action of an acid to generate an alkali-soluble group such as a hydroxyl group or a carboxyl group. For example, an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group and the like can be mentioned, and an acetal group is preferable from the viewpoint of sensitivity.
Specific examples of the acid-decomposable group include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl. Group, trimethylsilyl ether group and the like. From the viewpoint of sensitivity, an ethoxyethyl group and a tetrahydrofuranyl group are preferred.

R ⁷ represents a hydrogen atom, a hydrogen atom, a crosslinkable group, an alkyl group, an acid-decomposable group, or a group represented by —CORc, and Rc represents an alkyl group or an aryl group.
The alkyl group represented by R ⁷ may be linear, branched or cyclic. In the case of a straight chain alkyl group, the carbon number is preferably 1-20, more preferably 1-15, still more preferably 1-10. In the case of a branched alkyl group, the carbon number is preferably 3 to 20, more preferably 3 to 15, and still more preferably 3 to 10. In the case of a cyclic alkyl group, the carbon number is preferably 3 to 15, more preferably 5 to 15, and more preferably 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.
The crosslinkable group represented by R ⁷ is not limited as long as a crosslinking reaction is caused by heat. Examples thereof include an epoxy group, an oxetanyl group, a group having an ethylenically unsaturated bond, a blocked isocyanate group, an alkoxymethyl group, a methylol group, and an amino group.
As the acid-decomposable group represented by R ⁷ , those described for R ⁶ can be mentioned, and the preferred range is also the same.
The alkyl group represented by Rc has the same meaning as the alkyl group described for R ⁷ , 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 polybenzoxazole precursor according to the first aspect, 5 to 80% of the acid groups of all the repeating units of the polybenzoxazole precursor are preferably protected with acid-decomposable groups, and 10 to 60% More preferably, it is protected with an acid-decomposable group. The lower limit is more preferably 15% or more. The upper limit is more preferably 50% or less, and still more preferably 45% or less. When the content of the acid-decomposable group is in the above range, the sensitivity is further improved. In addition, the acid group which all the repeating units of a polybenzoxazole precursor here mean the acid group which all the repeating units of the polybenzoxazole precursor of the state before performing protection by an acid-decomposable group have. The acid group is preferably a hydroxyl group directly bonded to an aromatic ring, and more preferably a phenolic hydroxyl group.

Y ¹ represents a divalent organic group. Examples of the divalent organic group include a cyclic aliphatic group, a linear aliphatic group, a branched aliphatic group, an aromatic ring group, and these, —CH ₂ —, —O—, —S—, Examples include groups consisting of a combination of at least one of —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ —.

Examples of the cyclic aliphatic group include a cyclic alkylene group, a cyclic alkenylene group, and a cyclic alkynylene group. The number of carbon atoms in the cyclic aliphatic group is preferably 3 to 15, and more preferably 6 to 12. When the carbon number is in the above range, a cured film excellent in light resistance and chemical resistance is easily obtained. The cyclic aliphatic group is preferably a 6-membered ring. The cyclic aliphatic group represented by Y ¹ 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 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 include an alkylene group, an alkenylene group, an alkynylene group, and a polyoxyalkylene group, and an alkylene group, an alkenylene group, and an alkynylene group are preferable, and an alkylene group is more preferable.
The carbon number of the linear or branched aliphatic group is preferably 4 to 20, more preferably 4 to 15, and still more preferably 4 to 12. When the carbon number is in the above range, the solvent solubility is good.
Specific examples of the linear or branched aliphatic group include a linear aliphatic dicarboxylic acid or a residue (aliphatic group) remaining after removal of the carboxyl group of the branched aliphatic dicarboxylic acid.
Examples of linear aliphatic dicarboxylic acids include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, and hexadecanedioic acid. , Heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, docosanedioic acid and the like.
Examples of branched aliphatic dicarboxylic acids include 3-methylglutaric acid, 3,3-dimethylglutaric acid, 2-methyladipic acid, 2-ethyladipic acid, 2-propyladipic acid, 2-butyladipic acid, 3 -Methyladipic acid, 3-tert-butyladipic acid, 2,3-dimethyladipic acid, 2,4-dimethyladipic acid, 3,3-dimethyladipic acid, 3,4-dimethyladipic acid, 2,4,4 -Trimethyladipic acid, 2,2,5,5-tetramethyladipic acid, 2-methylpimelic acid, 3-methylpimelic acid, 3-methylsuberic acid, 2-methylsebacic acid, nonane-2,5-dicarboxylic acid, etc. Can be mentioned.

The aromatic 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.

The first polybenzoxazole precursor is a repeating unit in which Y ¹ is a cyclic aliphatic group and a repeating unit in which Y ¹ is a linear or branched aliphatic group in total. It is preferable to contain 70 mol% or more of the unit, preferably 70 to 100 mol%, more preferably 80 to 100 mol%. The ratio of the repeating unit in which Y ¹ is a cyclic aliphatic group to the repeating unit in which Y ¹ is a linear or branched aliphatic group is 9: 1 to 3: 7 in molar ratio. It is preferably 8.5: 1.5 to 3.5: 6.5, more preferably 8: 2 to 4: 6.

<<< other repeating units >>>
The polybenzoxazole precursor may contain a repeating unit represented by the following general formula (4).
Moreover, the repeating unit represented by General formula (2) and repeating units other than the repeating unit represented by General formula (4) mentioned later (it is also mentioned another repeating unit) may be included.
Examples of the other repeating unit include a repeating unit represented by the general formula (a1) and a repeating unit represented by the general formula (a2).

In the general formula (a1), Y ¹¹ represents an aromatic ring group, a cyclic aliphatic group, a linear aliphatic group, a branched aliphatic group, or these, —CH ₂ —, —O—, — Represents a group consisting of a combination of at least one of S—, —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ —, and X ¹¹ represents an aromatic ring group, a cyclic aliphatic group A group consisting of a group group or a combination thereof with —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ —. To express.
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 the general formula (a2), 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 a group consisting of a combination with at least one of -C (CF ₃ ) _2- are represented, 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.

The divalent organic group represented by R ²⁰ and R ²¹ is not particularly limited, but specifically, a linear or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a carbon number Examples thereof include 3 to 20 divalent cycloaliphatic groups, or groups formed by combining these groups.
The carbon number of the linear or branched alkylene group is preferably 1-20, more preferably 1-10, and even more preferably 1-6. Specific examples include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, and a t-butylene group.
The carbon number of the arylene group is preferably 6 to 20, more preferably 6 to 14, and further preferably 6 to 10. 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.
The carbon number of the divalent cycloaliphatic group is preferably 3 to 20, more preferably 3 to 10, and further preferably 5 to 6. 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 straight chain 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. A group formed by combining groups formed by combining divalent cycloaliphatic groups having 3 to 20 carbon atoms is preferable. 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 are as follows: 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.
The carbon number of the linear or branched alkyl group is preferably 1-20, more preferably 1-10, still more preferably 1-6. 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.
The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 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 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.

(Second aspect)
In the present invention, it is more preferable that the polybenzoxazole precursor of the second aspect includes a repeating unit represented by the following general formula (4). The repeating unit represented by the following general formula (4) is preferably contained in a proportion of 50 to 100 mol%, more preferably 70 to 100 mol% of the total repeating units of the polybenzoxazole precursor.

In the formula, X ³ represents a tetravalent organic group, Y ³ represents a divalent organic group, R ¹⁰ represents a hydrogen atom, R ¹¹ represents a hydrogen atom, a crosslinkable group, an alkyl group, Alternatively, it represents a group represented by —CORc, and Rc represents an alkyl group or an aryl group.

X ³ and Y ³ in the general formula (4) have the same meanings as X ¹ and Y ¹ in the general formula (2), and preferred ranges thereof are also the same.
The crosslinkable group, alkyl group, and group represented by —CORc represented by R ^{11 in the} general formula (4) are represented by the crosslinkable group, alkyl group, and —CORc described in R ⁷ of the general formula (2). And the preferred range is also the same.

In the polybenzoxazole precursor of the second aspect, 5 to 100% of R ¹⁰ and R ¹¹ contained in all repeating units are preferably hydrogen atoms, and more preferably 60 to 95% are hydrogen atoms. . The lower limit is more preferably 70% or more. The upper limit is more preferably 90% or less. In particular, when the hydrogen atom content is in the above range, the sensitivity is further improved.
The polybenzoxazole precursor of the second aspect may further contain other repeating units described above. Examples of the other repeating unit include the repeating unit represented by the general formula (a1) and the repeating unit represented by the general formula (a2).
In the photosensitive resin composition using the polybenzoxazole precursor according to the second aspect, a quinonediazide compound is used as a photoacid generator, or at least a part of an acid group described later is protected with an acid-decomposable group. By further blending a compound having a group ((E) compound), a photosensitive resin composition excellent in sensitivity can be easily obtained.

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

In the polybenzoxazole precursor, one end or both ends are preferably groups represented by the general formula (b1), and both ends are more preferably groups represented by the general formula (b1). .
Formula (b1)

In the general formula (b1), Z represents a single bond, a carbon atom or a sulfur atom, R ³⁰ represents a monovalent organic group, n represents 0 or 1, and when Z is a single bond, a is 0. Yes, when Z is a carbon atom, a is 1, when Z is a sulfur atom, a is 2, and when n is 0, two R ³⁰ may be bonded to each other to form a ring. Good.

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

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

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

The polybenzoxazole precursor used in the present invention can be synthesized in consideration of the description in JP-A-2008-224970. Moreover, in this invention, it is preferable to seal | block a terminal with a monofunctional acid chloride. The end-capping with a monofunctional acid chloride can be synthesized at once, for example, by mixing the monofunctional acid chloride during the polymerization reaction.

<< Polyimide precursor >>
(First aspect)
In the present invention, the polyimide precursor of the first aspect preferably has a group in which an acid group is protected by an acid-decomposable group, and more preferably includes a repeating unit represented by the following general formula (3). . The repeating unit represented by the following general formula (3) is preferably contained in a proportion of 50 to 100 mol%, more preferably 70 to 100 mol% of the total repeating units of the polyimide precursor.
The photosensitive resin composition using the polyimide precursor of the first aspect is, for example, a photosensitive resin excellent in sensitivity and curability when used in combination with a photoacid generator that generates an acid having a pKa of 3 or less. A composition is easily obtained.

In the formula, X ² represents a tetravalent organic group, Y ² represents a divalent organic group, R ⁸ represents an acid-decomposable group, and R ⁹ represents a hydrogen atom, a crosslinkable group, an alkyl group. Represents a group, an acid-decomposable group, or a group represented by —CORc, and Rc represents an alkyl group or an aryl group.
Examples of X ² and Y ² in the general formula (3) include the same as X ¹ and Y ¹ described in the general formula (2), and preferred ranges are also the same.
The acid-decomposable group represented by R ^{8 in the} general formula (3), the crosslinkable group, the alkyl group, the acid-decomposable group, and the group represented by —CORc represented by R ⁹ are represented by R ^{6 in the} general formula (2). , R ⁷ , the same groups as the crosslinkable group, alkyl group, acid-decomposable group, and group represented by —CORc are mentioned, and the preferred range is also the same.

In the polyimide precursor of the first aspect, 5 to 80% of the acid groups of all the repeating units of the polyimide precursor are preferably protected with acid-decomposable groups, and 10 to 60% are preferably acid-decomposable groups. More preferably, it is protected by. The lower limit is more preferably 15% or more. The upper limit is more preferably 50% or less, and still more preferably 45% or less. According to this aspect, a highly sensitive photosensitive resin composition can be obtained. In particular, when the content of the acid-decomposable group is within the above range, the sensitivity is further improved. In addition, the acid group which all the repeating units of a polyimide precursor here have means the acid group which all the repeating units of the polyimide precursor of the state before performing protection by an acid-decomposable group have. The acid group is preferably a hydroxyl group directly bonded to an aromatic ring, and more preferably a phenolic hydroxyl group.

The polyimide precursor of the first aspect may contain a repeating unit represented by the general formula (5) described later. Moreover, the other repeating unit demonstrated with the polybenzoxazole precursor mentioned above may be included. Examples of the other repeating unit include the repeating unit represented by the general formula (a1) and the repeating unit represented by the general formula (a2).

(Second aspect)
In this invention, it is preferable that the polyimide precursor of a 2nd aspect contains the repeating unit represented by following General formula (5). The repeating unit represented by the following general formula (5) is preferably contained in a proportion of 50 to 100 mol%, more preferably 70 to 100 mol% of the total repeating units of the polyimide precursor.

In the formula, X ⁴ represents a tetravalent organic group, Y ⁴ represents a divalent organic group, R ¹² represents a hydrogen atom, R ¹³ represents a hydrogen atom, a crosslinkable group, an alkyl group, Alternatively, it represents a group represented by —CORc, and Rc represents an alkyl group or an aryl group.
Examples of X ⁴ and Y ⁴ in the general formula (5) include the same as X ¹ and Y ¹ described in the general formula (2), and preferred ranges are also the same.
The crosslinkable group, alkyl group, and group represented by —CORc represented by R ^{13 in the} general formula (5) are represented by the crosslinkable group, alkyl group, and —CORc described in R ⁷ of the general formula (2). Examples thereof are the same as those described above, and preferred ranges are also the same.

In the polyimide precursor of the second aspect, 5 to 100% of R ¹² and R ¹³ contained in all repeating units are preferably hydrogen atoms, and more preferably 60 to 95% are hydrogen atoms. The lower limit is more preferably 70% or more. The upper limit is more preferably 90% or less. In particular, when the hydrogen atom content is in the above range, the sensitivity is further improved.
The photosensitive resin composition using the polyimide precursor of the second aspect further uses a quinonediazide compound as a photoacid generator, or a compound in which at least a part of the acid group is protected with an acid-decomposable group. By doing so, it is easy to obtain a photosensitive resin composition excellent in sensitivity.

The polyimide precursor of the second aspect may contain other repeating units described for the polybenzoxazole precursor described above. Examples of the other repeating unit include the repeating unit represented by the general formula (a1) and the repeating unit represented by the general formula (a2).

The polyimide precursor preferably has a weight average molecular weight (Mw) of 3,000 to 200,000. The lower limit is more preferably 4,000 or more, and still more preferably 5,000 or more. The upper limit is more preferably 100,000 or less, and even more preferably 50,000 or less. The number average molecular weight (Mn) is preferably 1,000 to 50,000. The lower limit is more preferably 2,000 or more, and still more preferably 3,000 or more. The upper limit is more preferably 40,000 or less, and still more preferably 30,000 or less. By setting it as this range, the lithography performance and the cured film physical properties can be made excellent.
The polyimide precursor used in the present invention can be synthesized by reacting tetracarboxylic dianhydride and diamine. For example, it can be synthesized in consideration of the description in JP-A-2014-66764.

<(B) Thermal base generator>
The photosensitive resin composition of the present invention contains a thermal base generator represented by the following general formula (1). Hereinafter, the thermal base generator represented by the general formula (1) is also referred to as (B) thermal base generator.

In the formula, R ¹ represents a hydrogen atom or an n-valent organic group,
R ² to R ⁵ each independently represents a hydrogen atom or an alkyl group, and n represents an integer of 1 or more.

In general formula (1), R ¹ represents a hydrogen atom or an n-valent organic group. Examples of the organic group include an aliphatic group, an aromatic ring group, and a group formed by combining an aliphatic group or an aromatic ring group with a linking group described later. Examples of the linking group include —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, or a linking group in which a plurality of these are linked. . -COO- and -OCO- are preferred. Specific examples of the group formed by combining an aliphatic group or an aromatic ring group and a linking group include an alkoxycarbonyl group and an acyloxy group.
R ¹ is preferably an aromatic ring group. By making R ^{1 an} aromatic ring group, a base having a high boiling point can be easily generated at a lower temperature. By increasing the boiling point of the generated base, it is difficult to volatilize or decompose by heating during post-baking, and the cyclization of the resin can proceed more effectively. Examples of when R ¹ is a monovalent aromatic ring group include an aryl group and a heteroaryl group, and an aryl group is preferred.
Examples of when R ¹ is a monovalent aliphatic group include an alkyl group and an alkenyl group.
The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched or cyclic. The alkyl group may have a substituent or may be unsubstituted. Specific examples of the alkyl group include a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group.
The alkenyl group has preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 10 carbon atoms. The alkenyl group may be linear, branched or cyclic. The alkenyl group may have a substituent or may be unsubstituted. Examples of the alkenyl group include a vinyl group and a (meth) allyl group.
Examples of when R ¹ is a divalent aliphatic group include groups in which one or more hydrogen atoms have been removed from the above monovalent aliphatic group.
The aromatic ring group may be monocyclic or polycyclic. The aromatic ring group may be a heteroaromatic ring group containing a hetero atom. The aromatic ring group may have a substituent or may be unsubstituted. Specific examples of the aromatic ring group 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, Antoren ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and include phenazine ring, a benzene ring is most preferred.
In the aromatic ring group, a plurality of aromatic rings may be linked via a single bond or a linking group described later. Examples of the linking group include —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group (preferably a straight chain having 1 to 10 carbon atoms or A branched alkylene group), a cycloalkylene group (preferably a cycloalkylene group having 3 to 10 carbon atoms), or a linking group in which a plurality of these are linked. A group consisting of an alkylene group, —O— and a combination thereof is preferred, and a combination of an alkylene group and —O— is more preferred. The alkylene group and cycloalkylene group may be unsubstituted or may have a substituent. Examples of the substituent include those described later.
Specific examples of the aromatic ring group in which a plurality of aromatic rings are linked through a single bond or a linking group include biphenyl, diphenylmethane, diphenylpropane, diphenylisopropane, triphenylmethane, tetraphenylmethane, diphenoxymethane, di Examples include phenoxyethane.
The alkoxycarbonyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms. The alkoxycarbonyl group may be linear or branched. The alkoxycarbonyl group may have a substituent or may be unsubstituted.
The acyloxy group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms. The acyloxy group may be linear or branched. The acyloxy group may have a substituent or may be unsubstituted.

Examples of the substituent that the organic group represented by R ¹ may have include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy such as a methoxy group, an ethoxy group and a tert-butoxy group Groups; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, tert-butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; Groups, benzoyl groups, isobutyryl groups, acryloyl groups, methacryloyl groups and methoxalyl groups, etc .; alkylsulfanyl groups such as methylsulfanyl groups and tert-butylsulfanyl groups; phenylsulfanyl groups and p-tolylsulfanyl groups Arylsulfanyl group; alkyl group such as methyl group, ethyl group, tert-butyl group and dodecyl group; cycloalkyl group such as cyclopentyl group, cyclohexyl group, cycloheptyl group, adamantyl group; phenyl group, p-tolyl group, xylyl group , Cumenyl group, naphthyl group, anthryl group and phenanthryl group; hydroxyl group; carboxyl group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; Monoalkylamino group; dialkylamino group; arylamino group; diarylamino group thioxy group; carbamoyl group or a combination thereof.

R ² to R ⁵ each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom. A compound in which R ² to R ⁵ are represented by a hydrogen atom tends to generate a base by heating at a lower temperature.
The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 5, and particularly preferably a methyl group. The alkyl group may be linear or branched, and is preferably linear. The alkyl group may have a substituent and may be unsubstituted, but is preferably unsubstituted.

n represents an integer of 1 or more, preferably 1 to 5, more preferably 1 to 4, and still more preferably 1 or 2. The upper limit of n is the maximum number of substituents that an organic group can take when R ¹ represents an organic group. In the case where R ¹ represents a hydrogen atom, n is 1.

(B) The molecular weight of the thermal base generator is preferably from 100 to 1,000. The lower limit is more preferably 130 or more. The upper limit is more preferably 500 or less. The molecular weight value is a theoretical value obtained from the structural formula.
(B) The thermal base generator is preferably a compound that generates a base when heated to 120 to 250 ° C., and more preferably a compound that generates a base at 120 to 200 ° C. The base generation temperature is measured, for example, by using differential scanning calorimetry, heating the compound to 250 ° C. at 5 ° C./min in a pressure capsule, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.
(B) The base generated by the thermal base generator is preferably a cyclic amine.
(B) The boiling point of the base generated by the thermal base generator is preferably 80 ° C. or higher, preferably 100 ° C. or higher, and more preferably 140 ° C. or higher. The molecular weight of the generated base is preferably 80 to 500. The upper limit is more preferably 400 or less. The molecular weight value is a theoretical value obtained from the structural formula.

(B) Specific examples of the thermal base generator include the following compounds. Needless to say, the present invention is not limited to these examples.

In the photosensitive resin composition of the present invention, the content of the (B) thermal base generator is preferably 0.1 to 25 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 0.5 parts by mass or more, and further preferably 1 part by mass or more. For example, the upper limit is more preferably 20 parts by mass or less, and further preferably 15 parts by mass or less. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively.
In the photosensitive resin composition of the present invention, the content of the (B) thermal base generator is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the above-mentioned (A) resin. For example, the lower limit is more preferably 0.5 parts by mass or more, and further preferably 1 part by mass or more. For example, the upper limit is more preferably 20 parts by mass or less, and further preferably 15 parts by mass or less. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively.

<(C) Photoacid generator>
The photosensitive resin composition of the present invention contains a photoacid generator. The photoacid generator is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is not limited to its chemical structure. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with the sensitizer It can be preferably used in combination.
Preferred examples of the photoacid generator include a photoacid generator that generates an acid having a pKa of 3 or less, and a quinonediazide compound.
The photoacid generator that generates an acid having a pKa of 3 or less includes a resin containing a group in which an acid group is protected by an acid-decomposable group, preferably a repeating unit represented by the above general formula (2) Combined use with a polybenzoxazole precursor (polybenzoxazole precursor of the first aspect) and / or a polyimide precursor containing the repeating unit represented by the general formula (3) (polyimide precursor of the first aspect) By doing so, it is easy to obtain a photosensitive resin composition excellent in sensitivity.
Moreover, the polybenzoxazole precursor (polybenzoxazole precursor of 2nd aspect) containing the repeating unit represented by General formula (4) mentioned above, and / or the repeating unit represented by General formula (5) Sensitive photosensitivity can be obtained by using together a polyimide precursor containing polyimide (polyimide precursor of the second embodiment) and a compound having a group in which at least a part of the acid group described later is protected by an acid-decomposable group. The resin composition is easily obtained.
The quinonediazide compound is a resin containing an acid group, preferably a polybenzoxazole precursor (polybenzoxazole precursor of the second embodiment) containing the repeating unit represented by the general formula (4) described above, and / Or By using together with the polyimide precursor containing the repeating unit represented by General formula (5) (polyimide precursor of a 2nd aspect), the photosensitive resin composition excellent in the sensitivity is easy to be obtained.

<< Photoacid generator that generates an acid having a pKa of 3 or less >>
In the present invention, the photoacid generator that generates an acid having a pKa of 3 or less is preferably one that generates an acid having a pKa of 2 or less. In the present invention, pKa basically refers to pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured after changing to a solvent suitable for measurement. Specifically, the pKa described in the chemical handbook can be referred to. The acid having a pKa of 3 or less is preferably sulfonic acid or phosphonic acid, and more preferably sulfonic acid.

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

Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane compounds include compounds described in paragraph numbers 0083 to 0088 of JP2011-212494A; Examples of the compounds described in JP-A-2011-105645, paragraphs 0013 to 0049, and the contents thereof are incorporated in the present specification.
Specific examples of the imidosulfonate compound include compounds described in paragraph numbers 0065 to 0075 of WO2011 / 087011, and the contents thereof are incorporated in the present specification.

Examples of the onium salt compounds include diphenyl iodonium salts, triarylsulfonium salts, sulfonium salts, benzothiazonium salts, tetrahydrothiophenium salts, and the like.

Examples of the diphenyliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium Butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarsenate Bis (4-tert-butylphenyl) iodonium trifluoro Tansulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium camphorsulfonic acid, etc. Can be mentioned.

Examples of the triarylsulfonium salt include triphenylsulfonium tosylate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p- Toluene sulfonate, triphenylsulfonium butyl tris (2,6-difluorophenyl) borate and the like can be mentioned. It is also preferable to use triarylsulfonium salts having the following structure.

Examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts, and the like.

Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate, and the like.

Examples of the benzylsulfonium salt include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenyl Methylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenyl Examples include methylsulfonium hexafluorophosphate.

Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium. Hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl- 4-hydroxyphenylsulfonium hexafluorophosphate and the like.

Examples of substituted benzylsulfonium salts include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4-hydroxyphenylmethyl. Sulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3- And chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

Examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxybenzyl) ) Benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like.

Examples of the tetrahydrothiophenium salt include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethane. Sulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1,1 , 2,2-Tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyloxybicyclo) [2.2.1] heptan-2-yl) -1,1 2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptane-2- Yl) -1,1,2,2-tetrafluoroethanesulfonate.

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.
The alkyl group for R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group represented by R ²¹ has 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). It may be substituted with a bridged alicyclic group, preferably a bicycloalkyl group or the like.
The aryl group for R ²¹ is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.

The above compound containing an oxime sulfonate structure represented by the above general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-2).

General formula (B1-2)

In the formula (B1-2), R ⁴² represents an optionally substituted alkyl group or aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, and m4 represents an integer of 0 to 3 And when m4 is 2 or 3, the plurality of X may be the same or different.

Preferred ranges of R ^42, the same as the preferable range of the ^{R 21.}
The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. Further, the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom as X is preferably a chlorine atom or a fluorine atom.
m4 is preferably 0 or 1. In the above general formula (B2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R ⁴² is a linear alkyl group having 1 to 10 carbon atoms, 7,7- A compound that is a dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.

The compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-3).

General formula (B1-3)

In formula (B1-3), R ⁴³ has the same meaning as R ⁴² in formula (B1-2), and X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Represents a group, a cyano group or a nitro group, and n4 represents an integer of 0 to 5.

R ⁴³ in the above general formula (B1-3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n- A propyl group, a perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.
X ¹ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
n4 is preferably from 0 to 2, particularly preferably from 0 to 1.
As specific examples of the compound represented by the general formula (B1-3) and preferable examples of the oxime sulfonate compound, the description in paragraphs 0080 to 0082 of JP2012-163937A can be referred to, and the contents thereof are described in this application. Incorporated in the description.

The compound containing an oxime sulfonate structure represented by the above general formula (B1-1) is also preferably a compound represented by the following general formula (OS-1).

In the general formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group. R ¹⁰² represents an alkyl group or an aryl group.

X ¹⁰¹ represents —O—, —S—, —NH—, —NR ¹⁰⁵ —, —CH ² —, —CR ¹⁰⁶ H—, or —CR ¹⁰⁵ R ¹⁰⁷ —, wherein R ¹⁰⁵ to R ¹⁰⁷ are alkyl groups. Or an aryl group.
R ¹²¹ to R ¹²⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring.
R ¹²¹ to R ¹²⁴ are preferably a hydrogen atom, a halogen atom, and an alkyl group, and an embodiment in which at least two of R ¹²¹ to R ¹²⁴ are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which all of R ¹²¹ to R ¹²⁴ are hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.
The compound represented by the general formula (OS-1) is, for example, a compound represented by the general formula (OS-2) described in paragraph numbers 0087 to 0089 of JP2012-163937A Which is incorporated herein by reference.

Specific examples of the compound represented by the general formula (OS-1) include the compounds described in paragraph numbers 0128 to 0132 of JP2011-221494A (exemplary compounds b-1 to b-34). However, the present invention is not limited to this.
The compound having an oxime sulfonate structure represented by the general formula (B1-1) is represented by the following general formula (OS-3), the following general formula (OS-4) or the following general formula (OS-5). An oxime sulfonate compound is preferred.

In the general formulas (OS-3) to (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represents an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ are Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X ¹ to X ³ each independently represents an oxygen atom or a sulfur atom, n ¹ to n ³ each independently represents 1 or 2, and m ¹ to m ³ each independently represents an integer of 0 to 6 To express.

Regarding the above general formulas (OS-3) to (OS-5), for example, the description of paragraph numbers 0098 to 0115 of JP2012-163937A can be referred to, and the contents thereof are incorporated in the present specification.

In addition, the compound containing an oxime sulfonate structure represented by the above general formula (B1-1) is, for example, a compound represented by the general formula (OS-6) described in paragraph 0117 of JP2012-163937A. Particularly preferred is a compound represented by any of (OS-11), the contents of which are incorporated herein.
Preferred ranges in the above general formulas (OS-6) to (OS-11) are preferred ranges of (OS-6) to (OS-11) described in paragraph numbers 0110 to 0112 of JP2011-221494A. The contents of which are incorporated herein by reference.
Specific examples of the oxime sulfonate compound represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. The contents of which are incorporated herein by reference. The present invention is not limited to these.

The compound containing an oxime sulfonate structure represented by the above general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-4).

General formula (B1-4)

In General Formula (B1-4), R ¹ represents an alkyl group or an aryl group, and R ² represents an alkyl group, an aryl group, or a heteroaryl group. R ³ to R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. However, R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may be bonded to form an alicyclic ring or an aromatic ring. X represents —O— or S—.

R ¹ represents an alkyl group or an aryl group. The alkyl group is preferably a branched alkyl group or a cyclic alkyl group.
The alkyl group preferably has 3 to 10 carbon atoms. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferable. When the alkyl group has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferable.
Examples of the alkyl group include propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, hexyl group. 2-ethylhexyl group, cyclohexyl group, octyl group and the like, preferably isopropyl group, tert-butyl group, neopentyl group, and cyclohexyl group.
The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and still more preferably 6 to 7 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
The alkyl group and aryl group represented by R ¹ may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, an iodine atom), a linear, branched or cyclic alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), an alkenyl group, an alkynyl group, Aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, A nitro group, a hydrazino group, a heterocyclic group, etc. are mentioned. Further, these groups may be further substituted. Preferably, they are a halogen atom and a methyl group.

From the viewpoint of transparency, R ¹ is preferably an alkyl group, and from the viewpoint of achieving both storage stability and sensitivity, R ¹ is an alkyl group having a branched structure having 3 to 6 carbon atoms and a cyclic group having 5 to 7 carbon atoms. An alkyl group having a structure or a phenyl group is preferable, and an alkyl group having a branched structure having 3 to 6 carbon atoms or an alkyl group having a cyclic structure having 5 to 7 carbon atoms is more preferable. By adopting such a bulky group (particularly a bulky alkyl group) as R ¹ , the transparency can be further improved.
Among the bulky substituents, an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.

R ² represents an alkyl group, an aryl group, or a heteroaryl group. The alkyl group represented by R ² is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. It is a group.
As the aryl group, an aryl group having 6 to 10 carbon atoms is preferable. Examples of the aryl group include a phenyl group, a naphthyl group, a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable.
Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
The alkyl group, aryl group, and heteroaryl group represented by R ² may have a substituent. Examples of the substituent include an alkyl group and an aryl group R ¹ represents is same as the substituents which may be possessed.
R ² is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group. As the substituent for the phenyl group, a methyl group is preferred.

R ³ to R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom). The alkyl group represented by R ³ to R ⁶ has the same meaning as the alkyl group represented by R ² , and the preferred range is also the same. The aryl group represented by R ³ to R ⁶ has the same meaning as the aryl group represented by R ¹ , and the preferred range is also the same.
Among R ³ to R ⁶ , R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may combine to form a ring, and the ring forms an alicyclic ring or an aromatic ring. It is preferable that a benzene ring is more preferable.
R ³ to R ⁶ are a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chloro atom, bromine atom), or R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ It preferably constitutes a benzene ring, and a hydrogen atom, a methyl group, a fluorine atom, a chloro atom, a bromine atom, or R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ are bonded to form a benzene ring Is more preferable.
Preferred embodiments of R ³ to R ⁶ are as follows.
(Aspect 1) At least two are hydrogen atoms.
(Aspect 2) The number of alkyl groups, aryl groups, or halogen atoms is one or less.
(Aspect 3) R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ are combined to form a benzene ring.
(Aspect 4) An aspect satisfying the above aspects 1 and 2 and / or an aspect satisfying the

above aspects

1 and 3.

Specific examples of the general formula (B1-4) include the following compounds, but the present invention is not particularly limited thereto. In the exemplified compounds, Ts represents a tosyl group (p-toluenesulfonyl group), Me represents a methyl group, Bu represents an n-butyl group, and Ph represents a phenyl group.

As the imide sulfonate compound, an imide sulfonate compound having a structure represented by the following general formula (B2) can be preferably used.

(In the general formula (B2), R ²⁰⁰ represents a monovalent organic group having 16 or less carbon atoms. The wavy line represents a bond with another group.)

R ²⁰⁰ represents a monovalent organic group having 16 or less carbon atoms. R ²⁰⁰ preferably does not contain other than C, H, O, and F. Examples of R ²⁰⁰ include a methyl group, a trifluoromethyl group, a propyl group, a phenyl group, and a tosyl group.
A preferred embodiment of the compound containing the structure represented by the general formula (B2) is an imide sulfonate compound represented by the following general formula (I).

In the formula, R ¹ and R ² each represent a group represented by the following general formula (A) or a hydrogen atom. R ³ represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with any one or more of a halogen atom, an alkylthio group and an alicyclic hydrocarbon group, a halogen atom, an alkylthio group, an alkyl group and an acyl An aryl group having 6 to 20 carbon atoms which may be substituted with any one or more of the groups, an arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom and / or an alkylthio group, 10-camphoryl group Or represents the group represented by the following general formula (B).

In general formula (A), X ¹ represents an oxygen atom or a sulfur atom, Y ¹ represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrocarbon group having 1 to 12 carbon atoms. R ⁵ represents an alkylene group having 1 to 4 carbon atoms, R ⁶ represents a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms, or an alicyclic carbon atom having 3 to 10 carbon atoms. Represents a hydrogen group, a heterocyclic group, or a hydroxyl group. n represents an integer of 0 to 5. When n is 2 to 5, a plurality of R ⁵ may be the same or different.

In the formula, X ¹ represents an oxygen atom or a sulfur atom, Y ¹ represents a single bond or an alkanediyl group having 1 to 4 carbon atoms, R ¹¹ represents a hydrocarbon group having 1 to 12 carbon atoms, R ¹² represents an alkanediyl group having 1 to 4 carbon atoms, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a branch or an alicyclic hydrocarbon having 3 to 10 carbon atoms. Represents a group or a heterocyclic group, m represents 0 to 5, and when m is 2 to 5, a plurality of R ¹² may be the same or different.

In general formula (B), Y ² represents a single bond or an alkylene group having 1 to 4 carbon atoms, R ⁷ represents an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, carbon Represents an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms, and R ⁸ represents a single bond, an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, carbon Represents an arylene group having 6 to 20 carbon atoms or a halogenated arylene group having 6 to 20 carbon atoms, and R ⁹ represents an alkyl group having 1 to 18 carbon atoms which may be branched, or 1 to 1 carbon atoms which may be branched. 18 halogenated alkyl groups, aryl groups having 6 to 20 carbon atoms, halogenated aryl groups having 6 to 20 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, or halogenated arylalkyl groups having 7 to 20 carbon atoms. To express. a and b each independently represents 0 or 1, and at least one of a and b is 1.

Regarding the general formula (I), for example, the description of paragraph numbers 0019 to 0063 of International Publication No. WO11 / 087011 can be referred to, and the contents thereof are incorporated in the present specification. Examples of the compound represented by the general formula (I) include the following. In addition to the compounds exemplified below, the description of paragraphs 0065 to 0075 of International Publication No. WO11 / 087011 can be referred to, the contents of which are incorporated herein.

<Quinonediazide compound>
As the quinonediazide compound, a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with actinic rays can be preferably used. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used. As specific examples of these compounds, for example, description of paragraphs 0075 to 0078 of JP2012-088459A can be referred to, and the contents thereof are incorporated in the present specification.

In the condensation reaction of a phenolic compound or an alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazidesulfonic acid halide, preferably 30 to 85 moles relative to the number of OH groups in the phenolic compound or alcoholic compound. %, More preferably 1,2-naphthoquinonediazide sulfonic acid halide corresponding to 50 to 70 mol% can be used. The condensation reaction can be carried out by a known method.

Examples of the 1,2-quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, such as 2,3,4-triaminobenzophenone-1,2-naphtho Quinonediazide-4-sulfonic acid amide and the like are also preferably used. In addition, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfone Condensate with acid chloride (3.0 mol), 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) Mol)), 2,3,4,4′-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid ester (2.44 mol), etc. It may be used.

When the photosensitive resin composition of the present invention contains a photoacid generator that generates an acid having a pKa of 3 or less as a photoacid generator, the content of the photoacid generator that generates an acid having a pKa of 3 or less is The amount is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total solid components 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. The photoacid generator that generates an acid having a pKa of 3 or less may be used alone or in combination of two or more. When using 2 or more types of photo-acid generators, it is preferable that the total amount becomes the said range.
When the photosensitive resin composition of the present invention contains a quinonediazide compound as a photoacid generator, the content of the quinonediazide compound is 1 to 40 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. Is preferred. For example, the lower limit is more preferably 2 parts by mass or more, and still more preferably 10 parts by mass or more. For example, the upper limit is more preferably 35 parts by mass or less, and still more preferably 30 parts by mass or less. By setting the content of the quinonediazide compound within the above range, a sensitive photosensitive resin composition can be easily obtained.

<(D) Solvent>
The photosensitive resin composition of the present invention contains a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in a solvent. The solvent is preferably a solvent that dissolves essential components and optional components and does not react with each component.
In the present invention, a known solvent can be used as the solvent.
For example, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers (for example, Diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, etc.), diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides And lactones Kill. Further, the solvent described in paragraph Nos. 0174 to 0178 of JP2011-221494A and the solvent described in paragraph numbers 0167 to 0168 of JP2012-194290A are also included, and the contents thereof are incorporated in the present specification. .

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

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

The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass with respect to 100 parts by mass of all components in the photosensitive resin composition. The lower limit is more preferably 60 parts by mass or more. The upper limit is more preferably 90 parts by mass or less. Only one type of solvent may be used, or two or more types may be used. When using 2 or more types, it is preferable that the total amount becomes the said range.

<(E) Compound having a group in which at least part of the acid group is protected with an acid-decomposable group>
The photosensitive resin composition of the present invention can contain a compound (also referred to as (E) compound) having a group in which at least a part of the acid group is protected with an acid-decomposable group.
A compound having a group in which at least a part of the acid group is protected by an acid-decomposable group means that at least a part of the acid group is protected by a protecting group, and the protecting group is eliminated by the action of an acid to be alkali-soluble. Is a compound that increases. The compound (D) plays a role of decreasing the alkali solubility in the non-exposed area and increasing the alkali solubility in the exposed area. As the acid group, a carboxy group or a phenolic hydroxyl group is preferable. In the present invention, the compound (E) is a compound different from the resin (A).
The acid-decomposable group is not particularly limited as long as it is a group that decomposes by the action of an acid, and examples thereof include an acetal group, a ketal group, a silyl group, a silyl ether group, and a tertiary alkyl ester group. In view of the above, an acetal group is preferable. Specific examples of the protecting group include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group, And trimethylsilyl ether group. From the viewpoint of sensitivity, an ethoxyethyl group and a tetrahydrofuranyl group are preferred.

The compound (E) may be a polymer (for example, Mw (weight average molecular weight) exceeding 5000 or even exceeding 10,000) or a low molecule (for example, 5000 or less). Molecules are preferable, and the molecular weight is preferably 3000 or less, and more preferably 1000 or less. As a lower limit of molecular weight, 150 or more are preferred and 300 or more are more preferred.

(E) It is preferable that a compound contains either an aromatic ring, a heterocyclic ring, or an alicyclic structure from a viewpoint of a dissolution inhibitory ability improvement. Moreover, it is preferable that (E) compound has 2 or more of acid groups protected in the molecule | numerator from a viewpoint of a sensitivity improvement.
The compound (E) is preferably a compound represented by the following general formula (E1).

In the general formula (E1), R ²¹ represents a monovalent to hexavalent organic group, R ²² and R ²³ each independently represents a hydrogen atom, an alkyl group or an aryl group, and R ²² and R Any one of ²³ is an alkyl group or an aryl group, R ²⁴ represents an alkyl group or an aryl group, R ²⁴ may be bonded to R ²² or R ²³ to form a cyclic ether, and n 1 Represents an integer of 1 to 6.

R ²² and R ²³ each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ²² and R ²³ is an alkyl group or an aryl group.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable. preferable. The alkyl group may have a substituent. The alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable. The aryl group may have a substituent.

R ²⁴ represents an alkyl group or an aryl group, and may combine with R ²² or R ²³ to form a cyclic ether. The alkyl group is preferably an alkyl group having 1 to 16 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and further an alkyl group having 1 to 4 carbon atoms. preferable. As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable.

R ²⁴ may be linked to R ²² or R ²³ to form a cyclic ether. The cyclic ether formed by linking with R ²² or R ²³ is preferably a 3- to 6-membered cyclic ether, more preferably a 5- to 6-membered cyclic ether.

R ²² and R ²³ are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ²⁴ is preferably bonded to an alkyl group having 1 to 4 carbon atoms, R ²² or R ²³ to form a tetrahydrofuranyl group.

R ²² to R ²⁴ may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), and these substituents may further have a substituent.

R ²¹ represents a monovalent to hexavalent organic group. R ²¹ is preferably a monovalent to hexavalent organic group having a molecular weight of 2000 or less, more preferably a 1 to 6 valent organic group having a molecular weight of 1500 or less, and further preferably a 1 to 6 valent organic group having a molecular weight of 1000 or less. .
The organic group represented by R ²¹ is preferably an organic group containing an aromatic ring or a heterocyclic ring and containing no atoms other than C, H, O and N atoms, and is an organic group containing a cyclic structure and / or a carbonyl group. More preferred is a group comprising a combination of an aromatic group, a cycloaliphatic group, a carbonyl group, an alkylene group, a phenylene group, and an oxygen atom.
Specifically, R ²¹ is preferably the following organic group when the acid group is a phenolic hydroxy group. In the formula, a wavy line represents a bonding site with an oxygen atom, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m and n each independently represents 0 to 4 Represents an integer.

Specifically, R ²¹ is preferably the following organic group when the acid group is a carboxy group. In the formula, a wavy line represents a bonding site with an oxygen atom, and R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 8 carbon atoms). , M and n each independently represents an integer of 0 to 4 (preferably 0).

Specific examples of the compound represented by the general formula (E1) include the following compounds, but the present invention is not particularly limited thereto.

The compound (E) is preferably a compound represented by the following general formula (E2).
General formula (E2)

(In General Formula (E2), R ¹ represents an n1-valent organic group. Ar represents an aryl group which may be substituted. A represents an integer of 0 or more. N1 represents an integer of 2 or more. Where n1-a is an integer of 1 or more.)

R ¹ represents an n1-valent organic group, preferably a divalent to octavalent organic group, more preferably a divalent to hexavalent organic group. R ¹ is preferably a hydrocarbon group having 2 to 15 carbon atoms, or a group mainly having a hydrocarbon group in which 1 to 2 oxygen atoms form an ether bond in the hydrocarbon group. Specifically, R ¹ represents an aliphatic hydrocarbon structure (for example, a linear alkylene structure, a branched alkylene structure, a cycloalkylene structure, a norbornane structure, a norbornene structure, a norbornane skeleton, or a structure in which a norbornene skeleton and a cycloalkylene skeleton are condensed). ), Aromatic hydrocarbon structures (such as benzene structures), aralkyl structures, structures in which these structures are combined, structures in which these structures are combined through ether bonds, and other tetrahydropyran structures The structure can be mentioned. As R ¹ , an alkylene structure, an alicyclic structure, an ether structure, an aralkyl structure, or a combination thereof is particularly preferable as a basic skeleton.

Ar represents an optionally substituted aryl group. As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable. Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group, and a naphthyl group.

a represents an integer of 0 or more, preferably an integer of 0 to 3, and more preferably 0. n represents an integer of 2 or more, preferably an integer of 2 to 8, more preferably an integer of 2 to 6, and more preferably 2.
In the step of synthesizing the compound represented by the general formula (E2), a may be obtained as a mixture having a distribution of 0 to n1, but the mixture can be preferably used as it is. N1-a is an integer of 1 or more, preferably 1-7. Ar represents an optionally substituted aryl group, and specific examples thereof include a phenyl group and a naphthyl group. Examples of the substituent include a halogen atom such as a chlorine atom; a methyl group, a tert-butyl group and the like. Preferred examples include alkyl groups; alkoxy groups such as methoxy groups.

Specific examples of the compound represented by the general formula (E2) include compounds described in paragraphs 0018 to 0025 of JP-A-2001-83709, the contents of which are incorporated herein.

The compound (E) is also preferably a compound having a repeating unit represented by the following general formula (E3).
General formula (E3)

(In General Formula (E3), R ²² and R ²³ each independently represent a hydrogen atom, an alkyl group, or an aryl group, and either one of R ²² and R ²³ is an alkyl group or an aryl group. ²⁴ represents an alkyl group or an aryl group, and may combine with R ²² or R ²³ to form a cyclic ether, R ²⁵ represents a hydrogen atom or a methyl group, and X represents a divalent organic group. Represents.)

R ²² to R ²⁴ have the same meanings as R ²² to R ²⁴ in formula (E1), and the preferred ranges are also the same.
X represents a divalent organic group. Examples of the divalent organic group represented by X include a phenylene group, a carbonyl group, and a p-phenylenecarbonyl group.
Preferable specific examples of the compound having a repeating unit represented by the general formula (E3) include a polymer having any one of the following structural units. R ²⁵ represents a hydrogen atom or a methyl group.

The weight average molecular weight of the compound having a repeating unit represented by the general formula (E3) is preferably 2000 to 50000, and more preferably 3000 to 20000.

When the compound having the repeating unit represented by the general formula (E3) is used as the (E) compound, it is preferable to copolymerize other components from the viewpoint of compatibility with (A) resin and developability. Other components are not particularly limited as long as they can be copolymerized with a compound having a repeating unit represented by formula (E3).

The other component is preferably a compound having a repeating unit represented by the following general formula (E4).
General formula (E4)

(In the general formula (E4), R ⁴¹ represents a hydrogen atom or a methyl group, X represents a single bond or a divalent organic group, R ⁴² represents an aryl group which may have a substituent, or Represents a hydroxyl group.)

X represents a single bond or a divalent organic group. Examples of the divalent organic group represented by X include a phenylene group, a carbonyl group, a carboxyl group, and a p-phenylenecarbonyl group.
R ⁴² is an optionally substituted aryl group, or a hydroxyl group, a aryl group which may have a substituent group, in the general formula (E1) with the same meaning as the aryl group R ²² is represented, The preferred range is also the same. The aryl group may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a hydroxyl group, and the like, and these substituents may further have a substituent. Good.

Preferable specific examples of the compound having a repeating unit represented by the general formula (E4) include a polymer having any one of the following structural units. R ⁴ represents a hydrogen atom or a methyl group.

The compound having a repeating unit represented by the general formula (E4) is preferably (1) to (3) from the viewpoint of compatibility with the resin (A), and (4) to (5) from the viewpoint of developability. Is preferred.

The ratio (% by mass) of the compound having a repeating unit represented by the general formula (E3) and the other components is preferably (E3) component / other components = 30/70 to 100/0, 40/60 to 80/20 is more preferable. A plurality of other components may be used in combination.

When the photosensitive resin composition of the present invention contains the compound (E), the content of the compound (E) is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the resin (A), and 10 to 40 parts by weight. Part is more preferred. By setting the content to 5 to 50 parts by mass, film physical properties and sensitivity can be improved. Moreover, 2 or more types of (E) compounds can be used, and when using 2 or more types, it is preferable that the total amount becomes the said range.

<Adhesion improver>
The photosensitive resin composition of the present invention may contain an adhesion improving agent. Examples of the adhesion improving agent include alkoxysilane compounds. The alkoxysilane compound is a compound that improves the adhesion between an insulating material and an inorganic material serving as a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum. It is preferable.
Specific examples of the adhesion improving agent include 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. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are preferred, γ-glycidoxypropyltrialkoxysilane is more preferred, 3-methacryloxypropylmethyldimethoxysilane, Sidoxypropyltrimethoxysilane is more preferred. These can be used alone or in combination of two or more.
The content of the adhesion improving agent is preferably 0.001 to 15 parts by mass and more preferably 0.005 to 10 parts by mass with respect to 100 parts by mass of the total solid component of the photosensitive resin composition. Only one type of adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

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

<< Compound having two or more epoxy groups or oxetanyl groups in the molecule >>
Examples of the compound having two or more epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like.
These are available as commercial products. Examples include JER152, JER157S70, JER157S65, JER175S70, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.) and other commercial products described in paragraph number 0189 of JP2011-212494. In addition, Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX -321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941 , EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC -301, DLC-402 (manufactured by Nagase Chemtech), YH-300, YH-301, YH-302, YH-315, YH 324, YH-325 (or Nippon Steel Chemical Co., Ltd.) and the like. These can be used alone or in combination of two or more.
Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.

As the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, PNOX (above, manufactured by Toagosei Co., Ltd.) can be used.
The compound containing an oxetanyl group may be used alone or in combination with a compound containing an epoxy group.

<< Block isocyanate compound >>
In the photosensitive resin composition of the present invention, a blocked isocyanate compound can also be preferably employed as a crosslinking agent. The blocked isocyanate compound is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably. The blocked isocyanate group is preferably a group capable of generating an isocyanate group by heating at 90 ° C. to 250 ° C.
The skeleton of the blocked isocyanate compound is not particularly limited, and any skeleton may be used as long as it has two isocyanate groups in one molecule. For example, aliphatic, alicyclic or aromatic polyisocyanate can be mentioned. Specific examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'- Diethyl ether diisocyanate, diphenylmethane-4,4′-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexane Isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methylene ditolylene-4,4'- Diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate and other isocyanate compounds and prepolymers derived from these compounds Type skeleton compounds. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.
Examples of the matrix structure of the blocked isocyanate compound include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, and an imide compound. Can do. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.

Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, alkyl lactate and the like.
Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of mercaptan compounds include alkyl mercaptans and aryl mercaptans.

The blocked isocyanate compound is available as a commercial product. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (above, manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate B -830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (manufactured by Mitsui Chemicals, Inc.), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, MFA-100, E402-B80B, SBN-70D, SBB-70P, K6000 (above, manufactured by Asahi Kasei Chemicals Corporation) ), Death Module BL1100, BL12 5 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumijour BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.) and the like are preferably used. Can do.

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

In the case where the photosensitive resin composition of the present invention has a crosslinking agent, the content of the crosslinking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass in total of the polymer component (A). 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 compound>
The photosensitive resin composition of the present invention may contain a basic compound. The basic compound can be arbitrarily selected from those used in the chemically amplified positive photosensitive resin composition. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in JP-A 2011-212494, 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, tetra-n-butylammonium benzoate and the like.

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 components in the photosensitive resin composition. Is more preferable, and 0.005 to 1 part by mass is more preferable. 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 numbers 0201 to 0205 of JP2012-88459A, and those described in paragraph numbers 0185 to 0188 of JP2011-215580A can be used. Is incorporated herein by reference.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . The following trade names are KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by Mitsubishi Materials Kasei Co., Ltd.), MegaFac (manufactured by DIC Corporation), F-554 (manufactured by DIC Corporation), Florard Novec FC-4430 (Sumitomo) 3M Co., Ltd.), Surflon S-242 (manufactured by AGC Seimi Chemical Co., Ltd.), PolyFox PF-6320 (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), Footgent FTX-218G (manufactured by Neos), etc. Can be mentioned.
Further, the surfactant is measured by gel permeation chromatography using the structural unit A and the structural unit B represented by the following general formula (I-1-1) and using tetrahydrofuran (THF) as a solvent. A preferred example is a copolymer having a polystyrene-equivalent weight average molecular weight (Mw) of 1,000 to 10,000. The weight average molecular weight (Mw) is more preferably 1,500 to 5,000.

Formula (I-1-1)

In formula (I-1-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom. Alternatively, it represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is 10 mass% to 80 mass%. Q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.

L is preferably a branched alkylene group represented by the following general formula (I-1-2).
R ⁴⁰⁵ in the general formula (I-1-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. And an alkyl group having 2 or 3 carbon atoms is more preferred. The sum of p and q is preferably 100.

Formula (I-1-2)

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 to 10 parts by mass is more preferable, and 0.01 to 3 parts by mass is even more preferable.

<Antioxidant>
The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, coloring of the cured film can be prevented. Furthermore, there is an advantage that a reduction in film thickness due to decomposition can be reduced and heat-resistant transparency is excellent.
Examples of antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites. Examples thereof include salts, thiosulfates, and hydroxylamine derivatives. Among these, phenolic antioxidants, hindered amine antioxidants, phosphorus antioxidants, amide antioxidants, hydrazide antioxidants, sulfur antioxidants from the viewpoint of coloring the cured film and reducing film thickness Agents are preferred, and phenolic antioxidants are most preferred. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include the compounds described in paragraph numbers 0026 to 0031 of JP-A-2005-29515, and the compounds described in paragraph numbers 0106 to 0116 of JP-A-2011-227106. It is incorporated herein.
Preferred commercially available products are 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 the present invention has an antioxidant, the content of the antioxidant is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid components of the photosensitive resin composition. The amount is preferably 0.2 to 5 parts by mass, and particularly preferably 0.5 to 4 parts by mass. 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 weight. 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 paragraphs 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 with respect to 100 parts by mass of the total solid content of the photosensitive resin composition from the viewpoint of sensitivity and residual film ratio. 30 parts by mass is preferable, 0.1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.

<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, the compounds described in JP-A-2012-88459, paragraph numbers 0201 to 0224 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 WO2011-133604A1, can be used, and the contents thereof are described in this specification. Incorporated into.

<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 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 (exposure step)
(5) Step of thermosetting the developed photosensitive resin composition (post-baking step)
Each step will be described below in order.

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

In the step (1), before the photosensitive resin composition is applied to the substrate, the substrate may be subjected to cleaning such as alkali cleaning or plasma cleaning. Further, the substrate surface may be treated with hexamethyldisilazane or the like with respect to the cleaned substrate. The method of treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method of exposing the substrate to hexamethyldisilazane vapor.
Examples of the substrate include 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 are rarely used in the above-described form, and a multilayer laminated structure such as a thin film transistor (TFT) element may be formed depending on the form of the final product.
The method for applying the photosensitive resin composition to the substrate is not particularly limited. 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 movement 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 to 10 μm is preferable.
Before applying the photosensitive resin composition of the present invention to the substrate, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.

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

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

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

In the step (5), by heating the obtained positive image, the acid-decomposable group is thermally decomposed to generate a carboxyl group or a phenolic hydroxyl group, and crosslinked with a crosslinkable group, a crosslinking agent, etc. A cured film can be formed. This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. It is preferable to By proceeding the crosslinking reaction in this way, a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like can be formed. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process). When middle baking is performed, 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 acid from the photoacid generator present in the unexposed areas and promote crosslinking. It can function as a catalyst that promotes the film curing reaction. The preferred exposure amount in the case of including a post-exposure step, preferably 100 ~ 3,000mJ / cm ^2, particularly preferably 100 ~ 500mJ / cm ^2.

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.
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 device>
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-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 liquid crystal driving methods that can be taken by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Virtual Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, OCB (Optical). Compensated Bend) method and the like.
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 Japanese Patent Application Laid-Open No. 2005-284291, or Japanese Patent Application Laid-Open No. 2005-346054. It can be used as an 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.
FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10. The liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel is disposed on all pixels disposed between two

glass substrates

14 and 15 having a polarizing film attached thereto. Corresponding TFT 16 elements are arranged. Each element formed on the glass substrate is wired with an ITO (Indium Tin Oxide) transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, a color filter 22 in which a layer of liquid crystal 20 and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, white LED, multicolor LED such as blue, red and green, fluorescent lamp (cold cathode tube), organic electroluminescence (organic EL) and the like can be mentioned.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, a flexible type can also be used. The second interlayer insulating film (48) described in JP2011-145686A, the interlayer insulating film (520) described in JP2009-258758A, JP It can be used as an organic insulating film (PAS) described in FIG. 1 of 2007-328210.
Further, even in a static drive type liquid crystal display device, a pattern with high designability can be displayed by applying the present invention. As an example, the present invention can be applied as an insulating film of a polymer network type liquid crystal as described in JP-A-2001-125086.

The liquid crystal display device shown in FIG. 1 of Japanese Patent Application Laid-Open No. 2007-328210 will be described with reference to FIG.
In FIG. 2, reference numeral SUB1 denotes a glass substrate, which has a plurality of scanning signal lines and a plurality of video signal lines intersecting with the plurality of scanning signal lines. A TFT is provided in the vicinity of each intersection.
On the glass substrate SUB1, a base film UC, a semiconductor film PS such as silicon, a gate insulating film GI, a TFT gate electrode GT, and a first interlayer insulating film IN1 are formed in this order from the bottom. A drain electrode SD1 of the TFT and a source electrode SD2 of the TFT are formed on the first interlayer insulating film IN1.
The drain electrode SD1 is connected to the drain region of the TFT through a contact hole formed in the gate insulating film GI and the first interlayer insulating film IN1. The source electrode SD2 is connected to the source region of the TFT through a contact hole formed in the gate insulating film GI and the first interlayer insulating film IN1.
A second interlayer insulating film IN2 is formed on the drain electrode SD1 and the source electrode SD2. An organic insulating film PAS is formed on the second interlayer insulating film IN2. The organic insulating film PAS can be formed using the photosensitive resin composition of the present invention.
On the organic insulating film PAS, a counter electrode CT and a reflective film RAL are formed.
A third interlayer insulating film IN3 is formed on the counter electrode CT and the reflective film RAL. A pixel electrode PX is formed on the third interlayer insulating film IN3. The pixel electrode PX is connected to the source electrode SD2 of the TFT through a contact hole formed in the second interlayer insulating film IN2 and the third interlayer insulating film IN3.
In the case where the organic insulating film PAS is formed using the photosensitive resin composition of the present invention, since the heat resistance of the organic insulating film PAS is excellent, the film forming temperature of the third interlayer insulating film IN3 is increased. And a denser film can be formed.
Note that the first interlayer insulating film IN1, the second interlayer insulating film IN2, and the third interlayer insulating film IN3 can also be formed using the photosensitive resin composition of the present invention.
The details of the liquid crystal display device shown in FIG. 2 can be referred to the description in Japanese Patent Application Laid-Open No. 2007-328210, and the contents thereof are incorporated in this specification.

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

Since the photosensitive resin composition of the present invention has good sensitivity and excellent pattern adhesion during development, it is formed using the photosensitive resin composition of the present invention as a structural member of a MEMS (Micro Electro Mechanical Systems) device. The resist pattern thus formed is used as a partition wall or incorporated as a part of a mechanical drive component. Examples of MEMS devices include parts such as SAW (Surface Acoustic Wave) filters, BAW (Bulk Acoustic Wave) filters, gyro sensors, micro shutters for displays, image sensors, electronic paper, inkjet heads, biochips, and sealants. It is done. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010- The partition wall (12) and the planarization film (102) described in FIG. 4 (a) of Japanese Patent No. 9793, the bank layer (221) and the third interlayer insulating film (216b) described in FIG. 10 of Japanese Patent Application Laid-Open No. 2010-27591. ), The second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4A of JP-A-2009-128577, and the flatness described in FIG. 3 of JP-A-2010-182638. It can also be used to form a chemical film (12) and a pixel isolation insulating film (14). In addition, spacers for maintaining the thickness of the liquid crystal layer in liquid crystal display devices, imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and micro lenses for optical fiber connectors are also used. It can be used suitably.

<Touch panel and touch panel display device>
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 resin composition of the present invention. Moreover, it is preferable that the touch panel of this invention has a transparent substrate, an electrode, an insulating layer, and / or a protective layer at least.
The touch panel display device of the present invention is preferably a touch panel display device having the touch panel of the present invention. As the touch panel of the present invention, any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, and an electromagnetic induction method may be used. Among these, the electrostatic capacity method is preferable.
Examples of the capacitive touch panel include those disclosed in JP 2010-28115 A and those disclosed in International Publication No. 2012/057165.
As a touch panel display device, a so-called in-cell type (for example, FIG. 5, FIG. 6, FIG. 7 and FIG. 8 in Japanese Patent Publication No. 2012-517051), a so-called on-cell type (for example, Japanese Patent Application Laid-Open No. 2012-43394). 14, International Publication No. 2012/141148, FIG. 2 (b)), OGS type, TOL type, and other configurations (for example, FIG. 6 of Japanese Patent Application Laid-Open No. 2013-164871). The 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 a cured film using the photosensitive resin composition of the present invention. It is preferable that
(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.

First, the configuration of the capacitive touch panel will be described. FIG. 4 is a cross-sectional view illustrating a configuration example of a capacitive touch panel. In FIG. 4, the capacitive touch panel 30 includes a front plate 31, a frame layer 32, a first transparent electrode pattern 33, a second transparent electrode pattern 34, an insulating layer 35, and a conductive element 36. And a transparent protective layer 37.

The front plate 31 is made of a transparent substrate such as a glass substrate, and tempered glass represented by gorilla glass manufactured by Corning Inc. can be used. In addition, as a transparent substrate, a glass substrate, a quartz substrate, a transparent resin substrate, etc. are mentioned preferably. Moreover, in FIG. 4, the side in which each element of the front plate 31 is provided is called a non-contact surface. In the capacitive touch panel 30, input is performed by bringing a finger or the like into contact with the contact surface of the front plate 31 (the surface opposite to the non-contact surface). Hereinafter, the front plate may be referred to as a “base material”.

A frame layer 32 is provided on the non-contact surface of the front plate 31. The frame layer 32 is a frame-like pattern around the display area formed on the non-contact side of the front panel of the touch panel, and is formed so as not to show the lead wiring and the like.
As shown in FIG. 5, the capacitive touch panel may be provided with a frame layer 32 so as to cover a part of the front plate 31 (a region other than the input surface in FIG. 5). Further, the front plate 31 can be provided with an opening 38 in part as shown in FIG. A mechanical switch by pressing can be installed in the opening 38.

As shown in FIG. 6, on the contact surface of the front plate 31, a plurality of first transparent electrode patterns 33 formed with a plurality of pad portions extending in the first direction via the connection portions, A plurality of second transparent electrode patterns 34 each including a plurality of pad portions that are electrically insulated from one transparent electrode pattern 33 and extend in a direction crossing the first direction; An insulating layer 35 that electrically insulates the electrode pattern 33 and the second transparent electrode pattern 34 is formed. The 1st transparent electrode pattern 33, the 2nd transparent electrode pattern 34, and the electroconductive element 36 mentioned later can be produced with a metal film, for example. As such a metal film, an ITO (Indium Tin Oxide) film; an IZO (Indium Zinc Oxide) film; a metal film such as Al, Cu, Ag, Ti, Mo, and alloys thereof; a metal oxide film such as SiO ₂ ; Is mentioned. At this time, the film thickness of each element can be 10 to 200 nm. Further, the amorphous ITO film can be crystallized into a polycrystalline ITO film by firing, and the electrical resistance can be reduced. Moreover, the 1st transparent electrode pattern 33, the 2nd transparent electrode pattern 34, and the electroconductive element 36 mentioned later are manufactured using the photosensitive transfer material which has the photosensitive resin composition using a conductive fiber. You can also In addition, when the first conductive pattern or the like is formed of ITO or the like, paragraphs 0014 to 0016 of Japanese Patent No. 4506785 can be referred to, and the contents thereof are incorporated in this specification.

Further, at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34 extends over both the non-contact surface of the front plate 31 and the region of the frame layer 32 opposite to the front plate 31. Can be installed. In FIG. 4, a diagram is shown in which the second transparent electrode pattern is installed across both areas of the non-contact surface of the front plate 31 and the surface opposite to the front plate 31 of the frame layer 32. Yes.

The first transparent electrode pattern 33 and the second transparent electrode pattern 34 will be described with reference to FIG. FIG. 6 is an explanatory diagram showing an example of the first transparent electrode pattern and the second transparent electrode pattern. As shown in FIG. 6, the first transparent electrode pattern 33 is formed such that the pad portion 33a extends in the first direction via the connection portion 33b. The second transparent electrode pattern 34 is electrically insulated by the first transparent electrode pattern 33 and the insulating layer 35, and extends in a direction intersecting the first direction (second direction in FIG. 6). It is constituted by a plurality of pad portions that are formed. Here, when the first transparent electrode pattern 33 is formed, the pad portion 33a and the connection portion 33b may be manufactured integrally, or only the connection portion 33b is manufactured, and the pad portion 33a and the second transparent electrode pattern 33 are formed. The electrode pattern 34 may be integrally formed (patterned). When the pad portion 33a and the second transparent electrode pattern 34 are integrally formed (patterned), as shown in FIG. 6, a part of the connection part 33b and a part of the pad part 33a are connected and an insulating layer is formed. Each layer is formed so that the first transparent electrode pattern 33 and the second transparent electrode pattern 34 are electrically insulated by 35.

In FIG. 4, a conductive element 36 is installed on the surface side of the frame layer 32 opposite to the front plate 31. The conductive element 36 is electrically connected to at least one of the first transparent electrode pattern 33 and the second transparent electrode pattern 34, and is different from the first transparent electrode pattern 33 and the second transparent electrode pattern 34. Is another element. In FIG. 4, a view in which the conductive element 36 is connected to the second transparent electrode pattern 34 is shown.

Moreover, in FIG. 4, the transparent protective layer 37 is installed so that all of each component may be covered. The transparent protective layer 37 may be configured to cover only a part of each component. The insulating layer 35 and the transparent protective layer 37 may be made of the same material or different materials.

The touch panel display device including the capacitive touch panel and the capacitive touch panel as a constituent element is “Latest Touch Panel Technology” (Techno Times, issued July 6, 2009), supervised by Yuji Mitani, “Touch Panel The configurations disclosed in “Technology and Development” CMC Publishing (2004, 12), “FPD International 2009 Forum T-11 Lecture Textbook”, “Cypress Semiconductor Corporation Application Note AN2292” and the like can be applied.

The touch panel of the present invention can be manufactured, for example, as follows.
That is, the photosensitive resin composition of the present invention is applied by various methods such as an inkjet coating method so as to be in contact with the ITO electrode, and an opening pattern having a predetermined shape is formed on the photosensitive resin composition applied to the ITO electrode. It can be manufactured through Step 2 in which a mask is placed and exposed by irradiation with active energy rays, Step 3 in which the exposed photosensitive resin composition is developed, and Step 4 in which the photosensitive resin composition after development is heated. .

In Step 1, when the photosensitive resin composition is applied so as to be in contact with the ITO electrode, it is sufficient that at least a part of the applied photosensitive resin composition of the present invention is in contact with the ITO electrode.
Step 2 can be performed in the same manner as the exposure step described above, and the preferred embodiment is also the same.
Step 3 can be performed in the same manner as the development step described above, and the preferred embodiment is also the same.
Step 4 can be performed in the same manner as the post-baking step described above, and the preferred embodiment is also the same.
Moreover, as an example of the ITO electrode pattern in the touch panel of this invention, the pattern shown in FIG. 6 mentioned above is mentioned preferably.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass. NMR is an abbreviation for nuclear magnetic resonance.

(Synthesis of Resin A-1) Synthesis of Polybenzoxazole Precursor In a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 293 g (0.8 mol) of hexafluoro-2,2-bis (3 -Amino-4-hydroxyphenyl) propane (Bis-AP-AF, manufactured by Central Glass Co., Ltd.), 158.2 g (2.0 mol) of pyridine and 1.2 kg of N-methyl-2-pyrrolidone (NMP) Added. This was stirred at room temperature and then cooled to −15 ° C. with a dry ice / methanol bath. To this solution, while maintaining the reaction temperature at −5 ° C. to −15 ° C., 73.9 g (0.364 mol) of isophthaloyl chloride (IC, manufactured by Tokyo Chemical Industry Co., Ltd.), 107.4 g (0.364 mol) ), 4,4′-oxybisbenzoyl chloride (ODC, manufactured by Tokyo Chemical Industry Co., Ltd.) and 700 g of NMP (1-methyl-2-pyrrolidone) were added dropwise. After the addition was complete, the resulting mixture was stirred at room temperature for 16 hours.
Next, the reaction solution was cooled to −5 ° C. or lower with an ice / methanol bath, and 17.0 g (0.217 mol) of acetyl chloride was added dropwise while maintaining the reaction temperature at −0 ° C. or lower. After completion of the dropwise addition, the mixture was further stirred for 16 hours.
This reaction solution is diluted with 2 L of NMP, poured into 20 L of deionized water with vigorous stirring, the precipitated white powder is recovered by filtration, and washed with deionized water and a water / methanol (50/50 mass ratio) mixture. did. The polymer was dried under vacuum at 50 ° C. for 2 days to obtain Resin A-1a.
25.0 g of Resin A-1a, 125 g of NMP and 125 g of methyl ethyl ketone were added to a 500 mL eggplant flask and concentrated under reduced pressure at 60 ° C. until the contents became 150 g. To this, 0.4 g of camphorsulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.0 g of 2,3-dihydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred at room temperature for 3 hours. . The resulting solution was diluted by adding 0.5 g of triethylamine and 150 g of NMP. The resulting solution was poured into 1 L of deionized water with vigorous stirring, the precipitated white powder was collected by filtration and washed with deionized water and a water / methanol (50/50 mass ratio) mixture. The polymer was dried under vacuum at 50 ° C. for 2 days to obtain Resin A-1. The weight average molecular weight of the obtained resin A-1 was 16000 (polystyrene conversion value of gel permeation chromatography). The hydroxyl group protection rate of the obtained resin A-1 was 30% with respect to the total hydroxyl amount (molar amount) of the resin A-1a ( ¹ H-NMR).

(Synthesis of resins A-2 to A-6)
Resin A-1 was synthesized by the same method except that the dicarboxylic acid dichloride used in the synthesis method was changed to the dicarboxylic acid dichloride shown in the following table. Resin A-5 was not protected by dihydrofuran.

(Synthesis of Resin A-7) Synthesis of Polyimide Precursor In a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 14.06 g (64.5 mmol) of pyromellitic dianhydride (Tokyo Chemical Industry Co., Ltd.) )), 11.08 g (58.7 mmol) of 4,4′-oxydianiline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 150 g of NMP were added and stirred at 80 ° C. for 12 hours. Further, 0.60 g (12.8 mmol) of ethanol was added, and the mixture was further stirred for 6 hours.
This reaction solution is diluted with 2 L of NMP, poured into 20 L of deionized water with vigorous stirring, the precipitated white powder is recovered by filtration, and washed with deionized water and a water / methanol (50/50 mass ratio) mixture. did. The polymer was dried under vacuum at 50 ° C. for 2 days to give Resin A-7a. Thereafter, Resin A-7 was synthesized by the same method as Resin A-1.

(Synthesis of Resins A-8 to 10)
Resin A-7 was synthesized by the same method except that tetracarboxylic dianhydride in the synthesis method was changed to tetracarboxylic dianhydride shown in the following table. Resin A-9 was not protected with dihydrofuran.

<Preparation of photosensitive resin composition>
Each component shown in the following table was mixed and filtered through a polytetrafluoroethylene filter having a pore size of 0.2 μm to obtain each photosensitive resin composition. The numerical value which does not attach | subject the unit in particular in a table | surface is a mass part.

<Liquid stability>
The container containing 10 g of the photosensitive resin composition was sealed and allowed to stand in an environment of 25 ° C. and humidity 65%. The time until the cyclization of the polybenzoxazole precursor or the polyimide precursor progressed and the solid was precipitated was evaluated. Solid precipitation was filtered through a mesh having a pore size of 0.8 μm, and the presence or absence of foreign matter on the mesh was visually observed. The longer the time until the solid precipitates, the higher the stability of the composition, which is a preferable result, and A, B, and C are in the practical range.
A: Solid precipitation was not observed even after 20 days B: Solid was precipitated within 20 days after 10 days C: Solid was precipitated within 10 days after 5 days D: Solid precipitated within 5 days

<Sensitivity>
Each photosensitive resin composition is SK-N1300G (Dainippon Screen) on a glass substrate (1100 × 1300 mm size, 0.7 mm thickness, manufactured by Corning) that has been surface-treated with hexamethyldisilazane (HMDS) vapor for 1 minute. After slit coating, the pressure was reduced to 0.26 kPa (2.0 Torr) and pre-baked on a hot plate at 100 ° C. for 90 seconds to volatilize the solvent to form a photosensitive resin composition layer having a thickness of 3.0 μm. . Next, the obtained photosensitive resin composition layer was exposed to a 5.0 μm hole pattern using an MPAsp-H760 exposure machine manufactured by Canon Inc. After heating on a hot plate at 80 ° C. for 90 seconds, development was performed with an alkali developer (0.6 mass% tetramethylammonium hydroxide aqueous solution) (25 ° C., 70 seconds), and rinsed with ultrapure water for 30 seconds. Thus, the exposure amount at which a hole pattern having a diameter of 5.0 μm at the bottom was formed was defined as sensitivity. The smaller the required exposure amount (the higher the sensitivity), the better, and A, B, and C are practical ranges.
A: 100mJ / cm ² less B: 100mJ / cm ² or more 150 mJ / cm ² less than C: 150mJ / cm ² or more 200 mJ / cm ² less than D: 200mJ / cm ² or more

<Transmissivity>
A glass substrate (OA-10 (manufactured by Nippon Electric Glass Co., Ltd.)) was exposed to HMDS vapor for 30 seconds, each photosensitive resin composition was slit-coated, and the solvent was volatilized by vacuum drying. Pre-baked on a second hot plate to form a photosensitive resin composition layer having a thickness of 2.0 μm. Then, it exposed so that an integrated irradiation amount might be set to 300 mJ / cm < ² > (energy intensity: 20 mW / cm < ² >) using the ultrahigh pressure mercury lamp, and this board | substrate was heated in nitrogen atmosphere at 300 degreeC / 60 minutes. The transmittance of the cured film was measured at a wavelength of 400 nm using a spectrophotometer (U-3000: manufactured by Hitachi, Ltd.). The unit is expressed in%. A, B and C are practical levels.
A: 90% or more B: 85% or more and less than 90% C: 80% or more and less than 85% D: Less than 80%

<Curing property>
A glass substrate (OA-10 (manufactured by Nippon Electric Glass Co., Ltd.)) was exposed to HMDS vapor for 30 seconds, each photosensitive resin composition was slit-coated, and the solvent was volatilized by vacuum drying. Pre-baked on a second hot plate to form a photosensitive resin composition layer having a thickness of 2.0 μm.
The photosensitive resin composition was scraped and subjected to thermogravimetric analysis (TGA measurement) in a state maintained at 250 ° C. in nitrogen to evaluate the cyclization time. As the cyclization reaction progresses, the precursor loses weight, and the time until the weight loss does not occur was evaluated according to the following criteria. The shorter the time, the faster the cyclization rate, and A, B, and C are practical ranges.
A: Over 10 minutes and under 30 minutes B: Over 30 minutes over 60 minutes C: Over 60 minutes over 90 minutes D: Over 90 minutes Or it did not cyclize.

<Evaluation of display unevenness (panel reliability)>
A liquid crystal display device using a thin film transistor (TFT) was produced by the following method. In the active matrix type liquid crystal display device shown in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows to obtain a liquid crystal display device.
That is, as a pretreatment for improving the wettability of the substrate and the interlayer insulating film 17 in paragraph 0058 of Japanese Patent No. 3321003, the substrate is exposed to hexamethyldisilazane vapor for 30 seconds, and then each photosensitive resin composition is spun. After coating application, the solvent was volatilized by prebaking on a hot plate at 120 ° C. for 2 minutes to form a photosensitive resin composition layer having a thickness of 2.0 μm. Next, the obtained photosensitive resin composition layer was irradiated with an integrated irradiation amount of 300 mJ / cm ² (illuminance 20 mW / cm ² ) using an ultrahigh pressure mercury lamp from above the mask, and then developed with an alkaline aqueous solution. A pattern was formed, and heat treatment was performed at 300 ° C. for 60 minutes in a nitrogen atmosphere. The applicability when applying the photosensitive resin composition of the example was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development, and baking.
The obtained liquid crystal display device was allowed to stand for 24 hours under forced conditions (temperature 85 ° C./relative humidity 80% RH, LH-113 constant temperature and humidity chamber manufactured by Espec), and the liquid crystal display device was taken out. When a drive voltage was applied to the liquid crystal display device and a gray test signal was input, the gray display was visually observed, and the presence or absence of display unevenness was evaluated according to the following evaluation criteria. A to C are preferred on the following criteria, and A or B is more preferred.
A: No unevenness at all (very good)
B: Slight unevenness is observed on the edge of the glass substrate, but there is no problem in the display (good)
C: Slight unevenness on the display, but practical level (normal)
D: Display is uneven (bad)

From the above results, the photosensitive resin compositions of the examples had good sensitivity and curability and both satisfied practical levels. Furthermore, it was excellent in storage stability, permeability, and display unevenness.
On the other hand, in the photosensitive resin composition of the comparative example, at least one of sensitivity and curability was less than a practical level.

The details of the abbreviations indicating the compounds used in Examples and Comparative Examples are as follows.
(A) Resins A-1 to A-10: Resins A-1 to A-10 described above
(B) Compound B-1: N-phenyliminodiacetic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
B-2: 1,2-bis (2-aminophenoxy) ethane-N, N, N ′, N′-4 acetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
B-3: N-methyliminodiacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
B-4: N-benzyliminodiacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
<The following are comparative compounds>
R-1: N-methylglycine (manufactured by Tokyo Chemical Industry Co., Ltd.)
R-2: N-phenylglycine (manufactured by Tokyo Chemical Industry Co., Ltd.)
R-3: N, N-dimethylglycine (manufactured by Tokyo Chemical Industry Co., Ltd.)
R-4: N, N-di (2-hydroxyethyl) glycine (manufactured by Tokyo Chemical Industry Co., Ltd.)
R-5: N- (tert-butoxycarbonyl) -L-prolinol (manufactured by Tokyo Chemical Industry Co., Ltd.)
R-6: N, N-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd. (C) Photoacid generator C-1: structure shown below (PAG-103, manufactured by BASF Corp., photoacid that generates an acid having a pKa of 3 or less) Generator)

C-2: Structure shown below (PAI-101, manufactured by Midori Chemical Co., a photoacid generator that generates an acid having a pKa of 3 or less), Me represents a methyl group.

C-3: 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)

C-4: Structure shown below (a photoacid generator that generates an acid having a pKa of 3 or less, synthesis examples will be described later), and Ts represents a tosyl group.

C-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)

C-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)

C-7: TAS-200 (naphthoquinone diazide, manufactured by Toyo Gosei Co., Ltd.)
DBA: 9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei Co., Ltd., sensitizer)
(D) Solvent NMP: N-methyl-2-pyrrolidone (E) compound (compound having a group in which at least a part of the acid group is protected with an acid-decomposable group)
E-1: The following compound, molecular weight 494 (protecting the phenolic hydroxyl group of 9,9-bis (4-hydroxyphenyl) fluorene (manufactured by JFE Chemical) with ethyl vinyl ether according to a conventional method)

(F) Crosslinking agent F-1: JER157S65 (Epoxy crosslinking agent: manufactured by Japan Epoxy Resin Co., Ltd.)
F-2: JER157S70 (Epoxy crosslinking agent: manufactured by Japan Epoxy Resin Co., Ltd.)
F-3: JER1007K (Epoxy crosslinking agent: manufactured by Japan Epoxy Resin Co., Ltd.)
(G) Adhesion promoter G-1: γ-glycidoxypropyltrialkoxysilane (KBM-403: manufactured by Shin-Etsu Chemical Co., Ltd.)
(H) Surfactant H-1: Perfluoroalkyl group-containing nonionic surfactant (F-554: manufactured by DIC)

<< Synthesis of C-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, reslurried with methanol (20 mL), filtered and dried to obtain a compound of C-3 (the above structure) (2.3 g).
Note that 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).

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

<< Synthesis of C-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 reprecipitated several times with acetone and hexane to obtain 12 g of N-camphorsulfonyloxy-1,8-naphthalimide.

<Production of organic EL display device>
(Example 100)
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 3).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 1 on a substrate, pre-baking (90 ° C./120 seconds) on a hot plate, and then applying high pressure from above the mask. After irradiating i-line (365 nm) with 45 mJ / cm ² (energy intensity 20 mW / cm ² ) using a mercury lamp, heat treatment was performed on a 90 ° C. hot plate at 90 ° C. for 120 seconds, and then an alkaline aqueous solution (0. 4% TMAH aqueous solution) to form a pattern, and using an ultra-high pressure mercury lamp, the whole surface is exposed so that the integrated irradiation amount is 300 mJ / cm ² (energy intensity: 20 mW / cm ² , i-line), Heat treatment at 300 ° C./60 minutes was performed.
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.

Next, a bottom emission type organic EL element was formed on the obtained flattening film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, a resist was applied, pre-baked, exposed through a mask having a desired pattern, heat-treated, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film 8, the photosensitive resin composition of Example 3 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.

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

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

(Example 101)
In the liquid crystal display device described in FIG. 1 of JP-A-2007-328210, the organic insulating film PAS was formed by the following method to obtain a liquid crystal display device.
First, according to Japanese Patent Application Laid-Open No. 2007-328210, an array substrate formed until just before the organic insulating film PAS of the liquid crystal display device described in FIG.
Next, this substrate was exposed to HMDS vapor for 30 seconds, and then the photosensitive resin composition of Example 1 was slit-coated and then pre-baked on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent. A thick photosensitive resin composition layer was formed.
Next, the obtained photosensitive resin composition layer was subjected to an optimum exposure dose mJ / cm ² (energy intensity: 20 mW / cm ²⁾ through a hole pattern mask having a diameter of 5 μm using MPA 7800CF manufactured by Canon Inc. , I-line) Exposed and heated on a hot plate at 80 ° C. for 90 seconds. The exposed resin composition layer was developed with an alkali developer (0.6% tetramethylammonium hydroxide aqueous solution), and then rinsed with ultrapure water. Subsequently, the entire surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm ² (energy intensity: 20 mW / cm ² , measured with i-line), and then the substrate was heated at 300 ° C. in an oven at 60 ° C. The organic insulating film PAS was obtained by heating for a few minutes.
Thereafter, a liquid crystal display device was obtained according to Japanese Patent Application Laid-Open No. 2007-328210. In this embodiment, since a material having high heat resistance is used for PAS, the interlayer insulating film IN3 is formed at the same temperature as the interlayer insulating film IN2. Thereby, IN3 could be made into a dense film.
When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed very good display characteristics and had high reliability.

<Production of touch panel>
(Example 102)
A touch panel display device was produced by the method described below.
<Formation of first transparent electrode pattern>
<< Formation of transparent electrode layer >>
A front plate of tempered glass (300 mm × 400 mm × 0.7 mm) with a frame layer formed in advance is introduced into a vacuum chamber, and an ITO target (indium: tin = 95: 5) with a SnO ₂ content of 10% by mass. (Molar ratio)) was used to form an ITO thin film having a thickness of 40 nm by DC magnetron sputtering (conditions: substrate temperature 250 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa), and a transparent electrode layer was formed. A formed front plate was obtained. The surface resistance of the ITO thin film was 80Ω / □.

Next, a commercially available etching resist was applied onto ITO and dried to form an etching resist layer. The distance between the exposure mask (quartz exposure mask having a transparent electrode pattern) surface and the etching resist layer is set to 100 μm, pattern exposure is performed at an exposure amount of 50 mJ / cm ² (i-line), and development is performed with a developer. Then, a post-baking treatment at 130 ° C. for 30 minutes was performed to obtain a front plate on which a transparent electrode layer and a photosensitive resin layer pattern for etching were formed.

The front plate on which the transparent electrode layer and the photo-sensitive resin layer pattern for etching are formed is immersed in an etching tank containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.), treated for 100 seconds, and etched resist. The exposed transparent electrode layer not covered with the layer was dissolved and removed to obtain a front plate with a transparent electrode layer pattern with an etching resist layer pattern.
Next, the transparent electrode layer-patterned front plate with the etching resist layer pattern is immersed in a dedicated resist stripping solution, the etching photosensitive resin layer is removed, and the frame layer and the first transparent electrode pattern A front plate formed was obtained.

<< Formation of insulating layer >>
On the front plate on which the frame layer and the first transparent electrode pattern were formed, the photosensitive resin composition of Example 1 was applied and dried (film thickness: 1 μm, 90 ° C., 120 seconds) to form a photosensitive resin composition layer. Got. The distance between the surface of the exposure mask (quartz exposure mask having a pattern for insulating layer) and the photosensitive resin composition layer was set to 30 μm, and pattern exposure was performed with the optimum exposure amount obtained by sensitivity evaluation.
Next, after heat treatment at 90 ° C. for 2 minutes on a hot plate, development was performed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 15 seconds, and further with ultrapure water for 10 seconds. Rinse. Subsequently, post baking was performed at 300 ° C. for 60 minutes to obtain a front plate on which a frame layer, a first transparent electrode pattern, and an insulating layer pattern were formed.

<Formation of second transparent electrode pattern>
<< Formation of transparent electrode layer >>
In the same manner as the formation of the first transparent electrode pattern, the front plate formed up to the insulating layer pattern was subjected to DC magnetron sputtering treatment (conditions: substrate temperature 50 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa). An ITO thin film having a thickness of 80 nm was formed to obtain a front plate on which a transparent electrode layer was formed. The surface resistance of the ITO thin film was 110Ω / □.
Furthermore, in the same manner as the formation of the first transparent electrode pattern, etching was performed and the etching resist layer was removed to form the frame layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1. A front plate on which an insulating layer pattern and a second transparent electrode pattern were formed was obtained.

<Formation of Conductive Element Different from First and Second Transparent Electrode Pattern>
Similar to the formation of the first and second transparent electrode patterns, the first transparent electrode pattern, the insulating layer pattern formed using the photosensitive resin composition of Example 1, and the second transparent electrode pattern The front plate on which was formed was subjected to DC magnetron sputtering to obtain a front plate on which an aluminum (Al) thin film having a thickness of 200 nm was formed.
Further, etching is performed in the same manner as the formation of the first transparent electrode pattern, and the etching resist layer is removed to form the frame layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1. A front plate on which conductive elements different from the insulating layer pattern, the second transparent electrode pattern, and the first and second transparent electrode patterns were formed was obtained.

<Formation of transparent protective layer>
In the same manner as the formation of the insulating layer, the photosensitive resin composition of Example 1 was applied and dried (film thickness: 1 μm) on the front plate formed up to the conductive element different from the first and second transparent electrode patterns. , 90 ° C. for 120 seconds) to obtain a photosensitive resin composition film. Further, exposure, heat treatment, development, post-exposure (1,000 mJ / cm ² ), and post-bake treatment are performed to form the frame layer, the first transparent electrode pattern, and the photosensitive resin composition of Example 1. Insulating layer pattern, second transparent electrode pattern, insulating layer formed using the photosensitive resin composition of Example 1 so as to cover all the conductive elements different from the first and second transparent electrode patterns A front plate laminated with a (transparent protective layer) was obtained.

<Production of touch panel display device>
A liquid crystal display device manufactured by the method described in Japanese Patent Laid-Open No. 2009-47936 is bonded to the previously manufactured front plate, and a touch panel display device including a capacitive touch panel as a constituent element is manufactured by a known method. did.

<Evaluation of front plate and touch panel display>
There is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and other conductive elements, while the first transparent electrode pattern and the second transparent electrode pattern Between the electrode patterns, there was insulation, and good display characteristics as a touch panel were obtained.

1: TFT, 2: wiring, 3: insulating film, 4: planarization film, 5: first electrode, 6: glass substrate, 7: contact hole, 8: insulating film, 10: liquid crystal display device, 12: backlight Units 14, 15: glass substrate, 16: TFT, 17: cured film, 18: contact hole, 19: ITO transparent electrode, 20: liquid crystal, 22: color filter, 30: capacitive touch panel, 31: front Face plate, 32: Frame layer, 33: First transparent electrode pattern, 33a: Pad portion, 33b: Connection portion, 34: Second transparent electrode pattern, 35: Insulating layer, 36: Conductive element, 37: Transparent protection Layer, 38: opening, CT: counter electrode, GI: gate insulating film, GT: gate electrode, IN1: first interlayer insulating film, IN2: second interlayer insulating film, IN3: third interlayer insulating film, PAS: Organic Film, PS: semiconductor film, PX: pixel electrode, RAL: reflective film, SD1: drain electrode, SD2: source electrode, SUB1: glass substrate, UC: base film

Claims

A resin containing at least one group selected from an acid group and a group in which the acid group is protected by an acid-decomposable group, and curable by cyclization with a base;
A thermal base generator represented by the following general formula (1);
A photoacid generator;
Solvent,
A positive photosensitive resin composition comprising:

In the formula, R 1 represents a hydrogen atom or an n-valent organic group,
R 2 to R 5 each independently represents a hydrogen atom or an alkyl group,
n represents an integer of 1 or more.
The resin is at least one selected from a polybenzoxazole precursor containing a repeating unit represented by the general formula (2) and a polyimide precursor containing a repeating unit represented by the general formula (3). The positive photosensitive resin composition according to claim 1;

In the formula, X 1 and X 2 each independently represent a tetravalent organic group,
Y 1 and Y 2 each independently represent a divalent organic group,
R 6 and R 8 each independently represents an acid-decomposable group,
R 7 and R 9 each independently represent a hydrogen atom, a crosslinkable group, an alkyl group, an acid-decomposable group, or a group represented by —CORc,
Rc represents an alkyl group or an aryl group.
The resin is at least one selected from a polybenzoxazole precursor containing a repeating unit represented by the general formula (4) and a polyimide precursor containing a repeating unit represented by the general formula (5). The positive photosensitive resin composition according to claim 1;

In the formula, X 3 and X 4 each independently represent a tetravalent organic group,
Y 3 and Y 4 each independently represent a divalent organic group,
R 10 and R 12 represent a hydrogen atom,
R 11 and R 13 each independently represent a hydrogen atom, a crosslinkable group, an alkyl group, or a group represented by —CORc,
Rc represents an alkyl group or an aryl group.
Furthermore, the positive photosensitive resin composition of Claim 3 containing the compound which has a group in which at least one part of the acid group was protected by the acid-decomposable group.
The positive photosensitive resin composition according to claim 4, wherein the compound having a group in which at least a part of the acid group is protected with an acid-decomposable group is a compound represented by the following general formula (E1);

In the formula, R 21 represents a monovalent to hexavalent organic group,
R 22 and R 23 each independently represents a hydrogen atom, an alkyl group or an aryl group,
Any one of R 22 and R 23 is an alkyl group or an aryl group;
R 24 represents an alkyl group or an aryl group, R 24 may be bonded to R 22 or R 23 to form a cyclic ether structure;
n1 represents an integer of 1 to 6.
6. The positive photosensitive resin composition according to claim 1, wherein in the general formula (1), n is 1 and R 1 is an aryl group.
The positive photosensitive resin composition according to any one of claims 1 to 6, wherein the resin is a polybenzoxazole precursor.
Applying the positive photosensitive resin composition according to any one of claims 1 to 7 to a substrate;
Removing the solvent from the applied positive photosensitive resin composition;
Exposing the positive photosensitive resin composition from which the solvent has been removed with actinic radiation;
Developing the exposed positive photosensitive resin composition with a developer;
And a step of thermally curing the developed positive photosensitive resin composition.
The method for producing a cured film according to claim 8, comprising a step of exposing the developed positive photosensitive resin composition after the developing step and before the thermosetting step.
A cured film obtained by curing the positive photosensitive resin composition according to any one of claims 1 to 7.
The cured film according to claim 10, which is an interlayer insulating film.
A liquid crystal display device having the cured film according to claim 10 or 11.
An organic electroluminescence display device comprising the cured film according to claim 10 or 11.
A touch panel having the cured film according to claim 10 or 11.