CN112904674A - Negative photosensitive resin composition and method for producing cured film - Google Patents

Abstract

The present invention relates to a negative photosensitive resin composition and a method for producing a cured film. The present invention addresses the problem of providing a negative photosensitive resin composition capable of forming a cured film having high solvent resistance, a cured film formed from a cured product of the negative photosensitive resin composition, and a method for producing a cured film using the negative photosensitive resin composition. The solution is a negative photosensitive resin composition comprising a resin (A) having a specific structure and a photopolymerization initiator (B) having a specific structure, a cured film formed from a cured product of the negative photosensitive resin composition, and a method for producing a cured film using the negative photosensitive resin composition.

Description

Negative photosensitive resin composition and method for producing cured film

Technical Field

The present invention relates to a negative photosensitive resin composition and a method for producing a cured film using the negative photosensitive resin composition.

Background

Photosensitive resin compositions for displays, which are suitable for use in thin film transistor-type liquid crystal displays (TFT-LCDs), Organic Light Emitting Devices (OLEDs), Touch Screen Panels (TSPs), and the like, are classified into positive photosensitive materials and negative photosensitive materials according to a method of forming a pattern by a curing reaction or a photodecomposition reaction by UV (ultraviolet) irradiation. In the case of a positive photosensitive material, a region irradiated with UV undergoes a photolytic reaction and dissolves in a developer, thereby forming a pattern. In the case of a negative-type photosensitive material, a region irradiated with UV undergoes a photocuring reaction and is not dissolved in a developer, and a region not irradiated with UV is dissolved in a developer, thereby forming a pattern.

In particular, recently, in order to increase the light efficiency of a display, high transmittance and high refraction characteristics have been considered to be important. In order to ensure high heat resistance, chemical resistance (etching resistance), high transmittance, and high refractive index of the photosensitive resin composition, first, the structure and properties of the binder are very important in the composition constituting the photosensitive material. For these reasons, studies have been actively conducted on imparting photosensitivity to acrylic photosensitive resins used as typical binder resins for photosensitive resin compositions, and binder resins such as Novolac resin systems and polyimides. However, a photosensitive resin composition using an acrylic photosensitive resin, a Novolac resin, or the like, which has been conventionally used, has poor heat resistance in a high-temperature heat treatment process at 300 ℃ or higher, and thus generates impurities due to outgassing (outgassing), resulting in serious contamination of a display. The following problems are present: the transmittance is reduced due to the high temperature heat treatment, so that the light efficiency characteristics of the display are deteriorated.

For example, patent document 1 discloses a photosensitive resin composition produced by using a copolymer of an acrylic compound and an acrylate compound as a binder resin and an acrylate compound as a polyfunctional monomer. However, there are the following problems: since the difference in solubility between the exposed portion and the unexposed portion is insufficient, the developing property is not good, and a part of the binder resin which should remain in the developing process is dissolved in the developing solution, and it is difficult to obtain a fine pattern of 10 μm or less.

Patent documents 2 and 3 disclose photosensitive resist compositions containing polyamic acid as a polyimide precursor and a naphthoquinone diazide compound as a dissolution inhibitor to improve thermal stability, but have the following problems: when a high-resolution pattern is formed, the difference in dissolution rate between the exposed portion and the non-exposed portion is insufficient.

Further, the photosensitive resin composition is required to have a wide process margin which is excellent in adhesion to the lower layer and the upper layer and which enables formation of a fine pattern with high resolution under various process conditions according to the purpose of use, and high sensitivity characteristics are required as a photosensitive material, and therefore, studies for improving such characteristics are also actively conducted.

As a technique for solving the above problems, patent document 4 discloses a negative photosensitive resin composition and a positive photosensitive resin composition each using a polymer having a specific structure, which has excellent heat resistance, high transmittance, and high refractive property, as a binder resin.

Documents of the prior art

Patent document

Patent document 1: U.S. Pat. No. 4139391

Patent document 2: japanese laid-open patent publication No. 52-13315

Patent document 3: japanese laid-open patent publication No. 62-135824

Patent document 4: japanese Kokai publication 2018-531311

Disclosure of Invention

Problems to be solved by the invention

However, in the case of manufacturing a display, after a photosensitive resin layer is formed using a photosensitive resin composition, different layers may be laminated. For example, a light extraction film having improved light extraction efficiency may be produced by laminating a low refractive index layer on a high refractive index layer formed using a photosensitive resin composition. Such a lamination process is performed using a composition in which a component such as a resin is dissolved in a solvent, but when the high refractive index layer in which the low refractive index layer is laminated does not have resistance against the solvent, there is a possibility that the film thickness of the high refractive index layer cannot be secured by the lamination process, and there is a possibility that the properties such as the refractive index of the high refractive index layer are lowered.

However, when the negative photosensitive resin composition described in patent document 4 is used, the solvent resistance of the photosensitive resin layer (cured film) formed is poor, and therefore, there is a problem that a desired photosensitive resin layer cannot be realized if the above-mentioned lamination process is applied.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a negative photosensitive resin composition capable of forming a cured film having high solvent resistance, a cured film formed from a cured product of the negative photosensitive resin composition, and a method for producing a cured film using the negative photosensitive resin composition.

Means for solving the problems

The present inventors have conducted extensive studies in order to achieve the above object, and as a result, have found that the above object can be achieved by a negative photosensitive resin composition comprising a resin (a) having a specific structure and a photopolymerization initiator (B) having a specific structure, and have completed the present invention. Specifically, the present invention provides the following.

The 1 st aspect of the present invention is a negative photosensitive resin composition comprising a resin (a) having a structural unit represented by the following formula (a1), and a photopolymerization initiator (B) represented by the following formula (B1).

(in the formula (a1), R^1aAnd R^2aEach independently represents an alkyl group having 1 to 20 carbon atoms and may contain a hetero atom, an aryl group having 6 to 20 carbon atoms and may contain a hetero atom, -R^4aSR^5aor-R^6aC(＝O)R^7a，

R^3aRepresents a tetravalent aromatic hydrocarbon having 1 to 20 carbon atoms and optionally containing a hetero atomAn aromatic hydrocarbon group or an alicyclic hydrocarbon group,

a represents a divalent group represented by the following formula (a2),

j1 and j2 each independently represent an integer of 1 to 6,

R^4arepresents a single bond, an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 15 carbon atoms,

s represents a sulfur atom, and S represents a sulfur atom,

R^5arepresents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms,

R^6arepresents a single bond, an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms,

R^7arepresents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms (alkenyl group), or an aryl group having 6 to 15 carbon atoms. )

(in the formula (a2),

R^8aand R^9aEach independently represents a hydrogen atom, a hydroxyl group, a mercapto group, an amino group, a nitro group, a halogen atom, a cyano group or an alkyl group,

R^10aand R^11aEach independently represents a hydrogen atom, an alkyl group or an aryl group,

k1 and k2 each independently represent an integer of 0 to 4,

m1 and m2 each independently represent an integer of 0 to 3. )

(in the formula (b1),

R^1brepresents a hydrogen atom, a nitro group or a monovalent organic group,

R^2band R^3bEach independently represents a group which may have a substituentChain alkyl group, cyclic organic group which may have substituent, or hydrogen atom, R^2bAnd R^3bMay be bonded to each other to form a ring,

R^4brepresents a monovalent organic group, and represents a monovalent organic group,

R^5brepresents a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent,

p is an integer of 0 to 4 inclusive,

q is 0 or 1. )

The 2 nd aspect of the present invention is a cured film formed from a cured product of the negative photosensitive resin composition according to the 1 st aspect.

The 3 rd aspect of the present invention is a method for producing a cured film, including the steps of:

a step of coating the negative photosensitive resin composition according to claim 1 on a substrate to form a coating film; and

and exposing the coating film.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a negative photosensitive resin composition capable of forming a cured film having high solvent resistance, a cured film formed from a cured product of the negative photosensitive resin composition, and a method for producing a cured film using the negative photosensitive resin composition can be provided.

Detailed Description

The present invention will be described in detail below.

Negative photosensitive resin composition

The negative photosensitive resin composition includes a resin (a) having a structural unit represented by formula (a1) and a photopolymerization initiator (B) represented by formula (B1).

The negative photosensitive resin composition may contain an adhesion enhancer (C), a photopolymerizable compound (D), a solvent (S), and other components, as necessary.

Hereinafter, essential or optional components contained in the negative photosensitive resin composition and a method for producing the negative photosensitive resin composition will be described.

< resin (A) (Binder resin) >

The resin (a) has a structural unit represented by the following formula (a 1).

(in the formula (a1), R^1aAnd R^2aEach independently represents an alkyl group having 1 to 20 carbon atoms and may contain a hetero atom, an aryl group having 6 to 20 carbon atoms and may contain a hetero atom, -R^4aSR^5aor-R^6aC(＝O)R^7a，

R^3aRepresents a tetravalent aromatic hydrocarbon group or alicyclic hydrocarbon group having 1 to 20 carbon atoms and optionally containing a hetero atom,

a represents a divalent group represented by the following formula (a2),

j1 and j2 each independently represent an integer of 1 to 6,

R^4arepresents a single bond, an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 15 carbon atoms,

s represents a sulfur atom, and S represents a sulfur atom,

R^5arepresents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms,

R^6arepresents a single bond, an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms,

R^7arepresents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. )

(in the formula (a2),

R^8aand R^9aEach independently represents a hydrogen atom, a hydroxyl group, a mercapto group, an amino group, a nitro group, a halogen atom, a cyano group or an alkyl group,

R^10aand R^11aEach independently represents a hydrogen atom, an alkyl group or an aryl group,

k1 and k2 each independently represent an integer of 0 to 4,

m1 and m2 each independently represent an integer of 0 to 3. )

From the structure of the above formula (a2), it was confirmed that the resin (a) has a biphenyl fluorene structure as a basic structure in its structural unit.

In the formula (a1), the hetero atom means an element other than a carbon atom and a hydrogen atom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, and a silicon atom. These hetero atoms may be contained in plural. The heteroatom is preferably a sulfur atom, and in this case, the effect of particularly excellent heat resistance, chemical resistance, high permeability, high refraction, and optical properties is obtained.

In the formula (a1), R is^1aAnd R^2aThe alkyl group which may contain a hetero atom of (2) has 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, and more preferably 2 to 10 carbon atoms. Specific examples of the alkyl group which may contain a hetero atom include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, an n-decyl group and the like.

As R^1aAnd R^2aThe number of carbon atoms of the aryl group which may contain a hetero atom of (2) is 6 to 20, preferably 6 to 15, and more preferably 6 to 10. Specific examples of the aryl group which may contain a hetero atom include a phenyl group, a naphthyl group, a furyl group, a thienyl group and the like.

With respect to as R^4aSpecific examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an isopropylene group and the like.

With respect to as R^4aSpecific examples of the arylene group having 6 to 15 carbon atoms include phenylene and naphthylene.

With respect to as R^5aSpecific examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, ethyl, isopropyl, and the like,N-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl and the like.

With respect to as R^5aSpecific examples of the aryl group having 6 to 15 carbon atoms include phenyl and naphthyl groups.

R^1aAnd R^2ais-R^4aSR^5aIn the case, the film has particularly excellent heat resistance, high transmittance and high refraction.

With respect to as R^6aSpecific examples of the alkylene group having 1 to 10 carbon atoms of (A) include^4aExemplary alkylene groups are the same groups.

With respect to as R^6aSpecific examples of the arylene group having 6 to 10 carbon atoms include^4aExemplary arylene groups are the same groups.

With respect to as R^7aSpecific examples of the alkyl group having 1 to 10 carbon atoms include^5aExemplary alkyl groups are the same.

With respect to as R^7aSpecific examples of the aryl group having 6 to 15 carbon atoms include^5aExemplary aryl groups are the same.

With respect to as R^7aSpecific examples of the alkenyl group having 1 to 10 carbon atoms include vinyl group and allyl group.

As R^3aThe tetravalent alicyclic hydrocarbon group which may contain a hetero atom of (2) has 1 to 20 carbon atoms, preferably 4 to 10 carbon atoms, more preferably 4 to 6 carbon atoms.

As R^3aThe number of carbon atoms of the tetravalent aromatic hydrocarbon group which may contain a hetero atom of (b) is 1 to 20, preferably 6 to 15, more preferably 6 to 12.

To have such R^3aThe structure of (3) has excellent heat resistance, high transmittance and high refraction characteristics.

As R^3aSpecific examples thereof include tetravalent groups derived from tetracarboxylic dianhydrides described later.

j1 and j2 are each independently an integer of 1 to 6, preferably 1 to 3, more preferably 1 to 2.

In the formula (a2), R^8aAnd R^9aEach independently is hydrogen atom, hydroxyl (-OH), sulfhydryl (-SH), amino (-NH)₂) Nitro (-NO)₂) A halogen atom, a cyano group or an alkyl group.

With respect to as R^8aAnd R^9aSpecific examples of the halogen atom of (2) include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom.

As R^8aAnd R^9aThe alkyl group of (b) is, for example, an alkyl group having 1 to 10 carbon atoms. Specific examples thereof include those related to R^5aExemplary alkyl groups are the same.

R^8aAnd R^9aPreferably a hydrogen atom.

As R^10aAnd R^11aThe alkyl group of (b) is, for example, an alkyl group having 1 to 10 carbon atoms. Specific examples thereof include those related to R^5aExemplary alkyl groups are the same.

As R^10aAnd R^11aThe aryl group in (b) is, for example, an aryl group having 6 to 15 carbon atoms. Specific examples thereof include those related to R^5aExemplary aryl groups are the same.

k1 and k2 are each independently an integer of 0 to 4, preferably 0 to 2.

m1 and m2 are each independently an integer of 0 to 3, preferably 1 to 2.

The number of the structural units represented by the formula (a1) contained in the resin (a) is not particularly limited. The number of structural units represented by formula (a1) in resin (a) is, for example, an integer of 1 to 30, preferably an integer of 1 to 10. When the refractive index is within this range, the effects of heat resistance, high transmittance, and high refractive index are particularly excellent.

The mass average molecular weight of the resin (A) may be, for example, 1,000 to 100,000g/mol, preferably 2,000 to 50,000g/mol, and more preferably 3,000 to 10,000 g/mol. When the amount is within this range, the photosensitive material is excellent in heat resistance, and the development speed of the photosensitive material and the development with a developer are easy, whereby the pattern formation is easy, and a high residual film ratio is exhibited.

The degree of dispersion (mass average molecular weight Mw/number average molecular weight Mn) of the resin (A) may be, for example, in the range of 1.0 to 5.0, preferably in the range of 1.5 to 4.0. When the amount is within this range, the photosensitive material is excellent in heat resistance, and the development speed of the photosensitive material and the development with a developer are easy, whereby the pattern formation is easy, and a high residual film ratio is exhibited.

The mass average molecular weight, number average molecular weight, and degree of dispersion in the present specification can be measured by a Gel Permeation Chromatography (GPC) method.

By forming such a negative photosensitive resin composition containing both the specific resin (a) and the specific photopolymerization initiator (B) (details will be described later), a cured film having high solvent resistance can be formed as shown in examples described later. In addition, a negative photosensitive resin composition having excellent resolution can be obtained. In addition, since the resin (a) can be selected from a resin having a high refractive index and a resin having high functionality such as heat resistance, chemical resistance, and high permeability, a negative photosensitive resin composition containing the resin (a) can form a cured film having a high refractive index and a cured film having high functionality such as heat resistance, chemical resistance, and high permeability.

The resin (a) can be produced by the method described in patent document 4, for example.

Specifically, the resin (a) can be synthesized by: a hydroxyl group-containing compound (monomer) represented by the following formula (2) is synthesized from a compound represented by the following formula (1), and then subjected to a polymerization reaction with a tetracarboxylic dianhydride.

(in the formula (1), R^8a～R^11aK1, k2, m1 and m2 are respectively related to R in formula (a2)^8a～R^11aK1, k2, m1 and m2, R is the same as^12aAnd R^13aEach independently represents a hydroxyl group, a thiol group, or ammoniaA nitro group, a cyano group, an aliphatic or alicyclic alkyl group having 1 to 20 carbon atoms and containing a heteroatom, or an aryl group having 6 to 20 carbon atoms and containing a heteroatom. )

(in the formula (2), R^8a～R^11aK1, k2, m1 and m2 are respectively related to R in formula (a2)^8a～R^11aK1, k2, m1 and m2, R is the same as^1a、R^2aJ1 and j2 are respectively related to R in formula (a1)^1a、R^2aJ1 and j2 are the same. )

In the formula (1), the hetero atom means an element other than a carbon atom and a hydrogen atom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, and a silicon atom. These heteroatoms may be contained in plural. For example, R^12aAnd R^13aThe hetero atom may be contained in the form of a hydroxyl group, a thiol group, an amino group, a nitro group, or a cyano group.

As R^12aAnd R^13aThe aliphatic alkyl group or alicyclic alkyl group containing a hetero atom of (2) has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and particularly preferably 3 to 5 carbon atoms. Specific examples of the aliphatic alkyl group or alicyclic alkyl group containing a hetero atom include hydroxyalkyl groups or thioalkyl groups having 1 to 5 carbon atoms.

As R^12aAnd R^13aThe heteroatom-containing aryl group of (2) has 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably 7 to 10 carbon atoms.

R^12aAnd R^13aHydroxyl groups are preferred.

Examples of the tetracarboxylic dianhydride include tetracarboxylic dianhydrides represented by the following formula (3).

(in the formula (3), R^3aAnd R in the formula (a1)^3aThe same is true. )

Specific examples of the tetracarboxylic acid dianhydride include pyromellitic dianhydride, 3,3 ', 4, 4' -biphenyltetracarboxylic acid dianhydride, 2,3,3 ', 4' -biphenyltetracarboxylic acid dianhydride, 2 ', 3, 3' -biphenyltetracarboxylic acid dianhydride, 3,3 ', 4, 4' -benzophenonetetracarboxylic acid dianhydride, 2 ', 3, 3' -benzophenonetetracarboxylic acid dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, Alicyclic tetracarboxylic dianhydrides such as bis (3, 4-dicarboxyphenyl) sulfone dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, 1,2,5, 6-naphthalene tetracarboxylic dianhydride, 9-bis (3, 4-dicarboxyphenyl) fluorenic dianhydride, 9-bis {4- (3, 4-dicarboxyphenoxy) phenyl } fluorenic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 2,3,5, 6-pyridine tetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, or 1,2,3, 4-cyclobutane tetracarboxylic dianhydride, 1,2,3, 4-cyclopentane tetracarboxylic dianhydride, 1,2,3, 4-cyclohexane tetracarboxylic dianhydride, and the like, alicyclic tetracarboxylic dianhydrides such as, Or 3,3 ', 4, 4' -diphenylsulfone tetracarboxylic dianhydride, and the like.

The polymerization reaction may be carried out at 100 to 130 ℃ or 110 to 120 ℃ for 2 to 24 hours or 4 to 12 hours, for example.

The tetracarboxylic dianhydride can be used, for example, in an amount of 5 to 40 parts by mass, 10 to 30 parts by mass, or 10 to 20 parts by mass, based on 100 parts by mass of the hydroxyl group-containing compound represented by the formula (2).

In the production of the resin (A), for example, the reaction may be carried out by adding an end-capping agent after the start of the polymerization reaction. The end-capping agent facilitates control of the mass average molecular weight of the resin (a).

The reaction of the blocking agent (blocking reaction) may be carried out at 100 to 130 ℃ or 110 to 120 ℃ for 30 minutes to 4 hours or 1 hour to 3 hours, for example.

The end-capping agent may be added in an amount of, for example, 2 to 10 parts by mass, 2 to 5 parts by mass, or 3 to 5 parts by mass, based on 100 parts by mass of the hydroxyl group-containing compound represented by the formula (2).

Examples of the end-capping agent include organic acids, organic acid anhydrides, and amic acids.

The end-capping agent is preferably an aromatic carboxylic acid anhydride, and specific examples thereof include phthalic anhydride. By using an aromatic carboxylic acid anhydride as the end-capping agent, the resin (a) has particularly excellent heat resistance, high transmittance and high refractive index characteristics.

In the case of using a blocking agent, the terminal structure of the resin (a) may be a structure derived from the blocking agent.

The terminal structure of the resin (a) may be derived from a raw material excessively added to the raw material such as the hydroxyl group-containing compound represented by the above formula (2) or tetracarboxylic dianhydride.

More specifically, the terminal structure of the resin (a) may be, for example, the following structures 1 to 4, and the mass average molecular weight of the resin (a) can be appropriately controlled. The structures of a plurality of terminals in the molecular chain of the resin constituting the resin (a) may be different from each other.

The following OX of structure 4 is a group formed by reacting the hydroxyl group in structure 3 with the above-mentioned capping agent. Among the following terminal structures, structure 4 is preferable from the viewpoint of development characteristics. The structure 4 is preferably a structure having OX derived from an organic acid anhydride such as a dicarboxylic anhydride such as phthalic anhydride or tetrahydrophthalic anhydride.

Structure 1: a structure in which a hydrogen atom is bonded to the left carbonyl oxygen group in the structure represented by formula (a1)

Structure 2: 2 of the plurality of carboxyl groups in the structure 1 have a structure of a carboxylic anhydride group

Structure 3: -CHR^2a-(CH₂)_j2-O-A-O-(CH₂)_j1-CH(OH)-R^1aStructure of the representation

Structure 4: -CHR^2a-(CH₂)_j2-O-A-O-(CH₂)_j1-CH(OX)-R^1aStructure of the representation

< photopolymerization initiator (B) >

The photopolymerization initiator (B) contained in the negative photosensitive resin composition is a photopolymerization initiator represented by the following formula (B1). The photopolymerization initiator is a component that generates an active species that can initiate polymerization of the resin (a) by visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray, or the like.

(in the formula (b1),

R^1brepresents a hydrogen atom, a nitro group or a monovalent organic group,

R^2band R^3bEach independently represents a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, R^2bAnd R^3bMay be bonded to each other to form a ring,

R^4brepresents a monovalent organic group, and represents a monovalent organic group,

R^5brepresents a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent,

p is an integer of 0 to 4 inclusive,

q is 0 or 1. )

In the formula (b1), R^1bIs a hydrogen atom, a nitro group or a monovalent organic group. R^1bTo the fluorene ring in formula (b1) to homo- (CO)_q6-membered aromatic rings different from the 6-membered aromatic ring to which the group represented by (A) is bonded. In the formula (b1), R^1bThe bonding position to the fluorene ring is not particularly limited. The compound represented by the formula (b1) has 1 or more R^1bIn this case, from the viewpoint of ease of synthesis of the compound represented by the formula (b1), it is preferable that R is 1 or more^1b1 of which is bonded to the 2-position in the fluorene ring. R^1bWhen there are plural, plural R^1bMay be the same or different.

R^1bWhen it is an organic group, R is in the range not impairing the object of the present invention^1bThe organic group is not particularly limited, and may be appropriately selected from various organic groups. As R^1bPreferable examples of the organic group includeAn alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenyl group which may have a substituent, a phenoxy group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, a phenylalkyl group which may have a substituent, a naphthyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthyloxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclic carbonyl group which may have a substituent, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, and the like.

R^1bIn the case of an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 6. In addition, R^1bWhen the alkyl group is used, it may be a straight chain or a branched chain. As R^1bSpecific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl groups. In addition, R^1bIn the case of an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propoxyethoxyethyl group, and a methoxypropyl group.

R^1bIn the case of an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 6. In addition, R^1bWhen the alkoxy group is used, it may be a straight chain or a branched chain. As R^1bSpecific examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, a n-hexyloxy group, a n-heptyloxy group, a n-octyloxy group, an isooctyloxy group, a sec-octyloxy group, a tert-octyloxy group, a n-nonyloxy groupIsononyl oxy, n-decyl oxy, isodecyl oxy and the like. In addition, R^1bIn the case of an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy, ethoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy, propoxyethoxyethoxy, and methoxypropoxy groups.

R^1bWhen the alkyl group is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms of the cycloalkyl group or the cycloalkoxy group is preferably 3 to 10, more preferably 3 to 6. As R^1bSpecific examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. As R^1bSpecific examples of the cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

R^1bIn the case of a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or the saturated aliphatic acyloxy group is preferably 2 to 21, more preferably 2 to 7. As R^1bSpecific examples of the saturated aliphatic acyl group include acetyl, propionyl, n-butyryl, 2-methylpropionyl, n-pentanoyl, 2-dimethylpropanoyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl, and n-hexadecanoyl. As R^1bSpecific examples of the saturated aliphatic acyloxy group include an acetyloxy group, a propionyloxy group, a n-butyryloxy group, a 2-methylpropionyloxy group, a n-pentanoyloxy group, a2, 2-dimethylpropionyloxy group, a n-hexanoyloxy group, a n-heptanoyloxy group, a n-octanoyloxy group, a n-nonanoyloxy group, a n-decanoyloxy group, a n-undecanoyloxy group, a n-dodecanoyloxy group, a n-tridecanoyloxy group, a n-tetradecanoyloxy group, a n-pentadecanoyloxy group, and a n-hexadecanoyloxy group.

R^1bWhen it is alkoxycarbonyl, the number of carbon atoms of alkoxycarbonyl is preferably 2 to 20, more preferably 2 to E7. As R^1bSpecific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, a n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, a n-hexyloxycarbonyl group, a n-heptyloxycarbonyl group, a n-octyloxycarbonyl group, an isooctyloxycarbonyl group, a sec-octyloxycarbonyl group, a tert-octyloxycarbonyl group, a n-nonyloxycarbonyl group, an isononyloxycarbonyl group, a n-decyloxycarbonyl group, and an isodecyloxyca.

R^1bIn the case of phenylalkyl, the number of carbon atoms in phenylalkyl is preferably 7 to 20, more preferably 7 to 10. In addition, R^1bIn the case of a naphthylalkyl group, the number of carbon atoms in the naphthylalkyl group is preferably 11 to 20, more preferably 11 to 14. As R^1bSpecific examples of phenylalkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl and 4-phenylbutyl. As R^1bSpecific examples of the naphthylalkyl group include an α -naphthylmethyl group, a β -naphthylmethyl group, a 2- (. alpha. -naphthyl) ethyl group, and a 2- (. beta. -naphthyl) ethyl group. R^1bWhen it is phenylalkyl or naphthylalkyl, R^1bMay further have a substituent on the phenyl group or the naphthyl group.

R^1bIn the case of a heterocyclic group, the heterocyclic group is a five-or six-membered monocyclic ring containing N, S, O or 1 or more, or a heterocyclic group in which the monocyclic rings are condensed with each other or with a benzene ring. When the heterocyclic group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, tetrahydrofuran, and the like. R^1bWhen it is a heterocyclic group, the heterocyclic group may further have a substituentAnd (4) generation of base.

R^1bWhen it is a heterocyclylcarbonyl group, the heterocyclyl group and R contained in the heterocyclylcarbonyl group^1bThe same applies to heterocyclic groups.

R^1bIn the case of an amino group substituted with 1 or 2 organic groups, preferable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a saturated aliphatic acyl group having 2 to 21 carbon atoms, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclic group and the like. Specific examples of these preferred organic groups and R^1bThe same is true. Specific examples of the amino group substituted with 1 or 2 organic groups include methylamino, ethylamino, diethylamino, n-propylamino, di-n-propylamino, isopropylamino, n-butylamino, di-n-butylamino, n-pentylamino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino, phenylamino, naphthylamino, acetylamino, propionylamino, n-butyrylamino, n-valerylamino, n-hexanoylamino, n-heptanoylamino, n-octanoylamino, n-decanoylamino, benzoylamino, α -naphthoylamino, β -naphthoylamino and the like.

As R^1bThe substituents when the phenyl group, naphthyl group and heterocyclic group contained in (1) further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a saturated aliphatic acyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, morpholin-1-yl, piperazin-1-yl, halogen, nitro, cyano and the like. R^1bWhen the phenyl group, naphthyl group and heterocyclic group contained in (1) further have a substituent, the number of the substituent is not limited within the range not interfering with the object of the present invention, and is preferably 1 to 4. R^1bIn which comprisesWhen the phenyl group, naphthyl group and heterocyclic group have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, R is a group having a tendency to increase sensitivity^1bPreferably nitro, or R^6b-CO-represents a group. Within a range not impairing the object of the present invention, R^6bThe organic group is not particularly limited, and may be selected from various organic groups. With respect to as R^6bExamples of the suitable group include an alkyl group having 1 to 20 carbon atoms, an optionally substituted phenyl group, an optionally substituted naphthyl group, and an optionally substituted heterocyclic group. As R^6bAmong these groups, 2-methylphenyl, thiophen-2-yl and α -naphthyl are particularly preferable.

In addition, from the viewpoint of a tendency to improve transparency, R is defined as^1bPreferably a hydrogen atom. In addition, R is^1bIs a hydrogen atom and R^4bWhen the group is a group represented by the formula (R4-2) described later, the transparency tends to be further improved.

In the formula (b1), R^2bAnd R^3bEach is a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R^2bAnd R^3bMay be bonded to each other to form a ring. Of these groups, as R^2bAnd R^3bA chain alkyl group which may have a substituent is preferable. R^2bAnd R^3bWhen the alkyl group is a linear alkyl group which may have a substituent, the linear alkyl group may be a linear alkyl group or a branched alkyl group.

R^2bAnd R^3bIn the case of a chain alkyl group having no substituent, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. As R^2bAnd R^3bSpecific examples of the chain alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, n-decyl, and isodecyl groups. In addition, R^2bAnd R^3bIn the case of alkyl groups, the alkyl groups may contain ether linkages (-O-) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propoxyethoxyethyl group, and a methoxypropyl group.

R^2bAnd R^3bIn the case of a chain alkyl group having a substituent, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably straight.

The substituent which the alkyl group may have is not particularly limited within a range not interfering with the object of the present invention. Preferable examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, fluorine atom, chlorine atom and bromine atom are preferable. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclic group. As specific examples of cycloalkyl, with R^1bThe same applies to the preferred cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, and the like. As specific examples of heterocyclic groups, with R^1bThe same applies to the preferred examples of heterocyclic groups. R^1bIn the case of an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group contained in the alkoxycarbonyl group is preferably 1 to 10, more preferably 1 to 6.

When the chain alkyl group has a substituent, the number of the substituent is not particularly limited. The number of preferable substituents varies depending on the number of carbon atoms of the chain alkyl group. Typically, the number of substituents is 1 to 20, preferably 1 to 10, more preferably 1 to 6.

R^2bAnd R^3bIn the case of a cyclic organic group, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group. R^2bAnd R^3bWhen it is a cyclic organic group, the substituent which the cyclic organic group may have and R^2bAnd R^3bThe same applies to the case of a chain alkyl group.

R^2bAnd R^3bIn the case of an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably a phenyl group, a group in which a plurality of benzene rings are bonded via a carbon-carbon bond, or a group in which a plurality of benzene rings are condensed. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or fusing a plurality of benzene rings, the number of the benzene rings included in the aromatic hydrocarbon group is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. Preferable specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthryl group, and the like.

R^2bAnd R^3bIn the case of an alicyclic cyclic hydrocarbon group, the alicyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, but is preferably 3 to 20, and more preferably 3 to 10. Examples of the monocyclic cyclic hydrocarbon group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclododecyl (tetracyclodocecyl), adamantyl, and the like.

R^2bAnd R^3bIn the case of a heterocyclic group, the heterocyclic group is a five-or six-membered monocyclic ring containing N, S, O or 1 or more, or a heterocyclic group in which the monocyclic rings are condensed with each other or with a benzene ring. When the heterocyclic group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclic group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting the heterocyclic group include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydropyranFuran, and the like.

R^2bAnd R^3bMay be bonded to each other to form a ring. Comprising R^2bAnd R^3bThe radical of the ring formed is preferably cycloalkylene (cycloalkylidene group). R^2bAnd R^3bWhen the cycloalkylene group is formed by bonding, the ring constituting the cycloalkylene group is preferably a five-membered ring to a six-membered ring, and more preferably a five-membered ring.

R^2bAnd R^3bWhen the group to which the bond is formed is a cycloalkylene group, the cycloalkylene group may be fused with 1 or more other rings. Examples of the ring which may be fused with a cycloalkylene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, and the like.

R is defined as above^2bAnd R^3bAmong them, as a preferable example of the group, formula-A¹-A²The group shown. In the formula, A¹Is a linear alkylene radical, A²Is an alkoxy group, a cyano group, a halogen atom, a haloalkyl group, a cyclic organic group, or an alkoxycarbonyl group.

As A¹The number of carbon atoms of the linear alkylene group(s) is preferably 1 to 10, more preferably 1 to 6. A. the²In the case of an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. The number of carbon atoms of the alkoxy group is preferably 1 to 10, more preferably 1 to 6. A. the²In the case of a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a fluorine atom, a chlorine atom, and a bromine atom are more preferable. A. the²In the case of a haloalkyl group, the halogen atom contained in the haloalkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. The haloalkyl group may be linear or branched, and is preferably linear. A. the²Examples of cyclic organic radicals and R^2bAnd R^3bThe same applies to the cyclic organic group which is a substituent. A. the²Examples of alkoxycarbonyl radicals and R when alkoxycarbonyl radicals are present^2bAnd R^3bAs a substituent groupThe same applies to the alkoxycarbonyl group.

As R^2bAnd R^3bPreferable specific examples of the (C) include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-octyl group; alkoxyalkyl groups such as 2-methoxyethyl, 3-methoxy-n-propyl, 4-methoxy-n-butyl, 5-methoxy-n-pentyl, 6-methoxy-n-hexyl, 7-methoxy-n-heptyl, 8-methoxy-n-octyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, 5-ethoxy-n-pentyl, 6-ethoxy-n-hexyl, 7-ethoxy-n-heptyl, and 8-ethoxy-n-octyl; cyanoalkyl groups such as 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-cyano-n-pentyl, 6-cyano-n-hexyl, 7-cyano-n-heptyl, and 8-cyano-n-octyl; phenylalkyl groups such as 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, and 8-phenyl-n-octyl; cycloalkylalkyl groups such as 2-cyclohexylethyl, 3-cyclohexyl-n-propyl, 4-cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6-cyclohexyl-n-hexyl, 7-cyclohexyl-n-heptyl, 8-cyclohexyl-n-octyl, 2-cyclopentylethyl, 3-cyclopentyl-n-propyl, 4-cyclopentyl-n-butyl, 5-cyclopentyl-n-pentyl, 6-cyclopentyl-n-hexyl, 7-cyclopentyl-n-heptyl, and 8-cyclopentyl-n-octyl; an alkoxycarbonylalkyl group such as a 2-methoxycarbonylethyl group, a 3-methoxycarbonyl-n-propyl group, a 4-methoxycarbonyl-n-butyl group, a 5-methoxycarbonyl-n-pentyl group, a 6-methoxycarbonyl-n-hexyl group, a 7-methoxycarbonyl-n-heptyl group, an 8-methoxycarbonyl-n-octyl group, a 2-ethoxycarbonylethyl group, a 3-ethoxycarbonyl-n-propyl group, a 4-ethoxycarbonyl-n-butyl group, a 5-ethoxycarbonyl-n-pentyl group, a 6-ethoxycarbonyl-n-hexyl group, a 7-ethoxycarbonyl-n-heptyl group, and an 8-ethoxycarbonyl-; haloalkyl groups such as 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, 5-chloro-n-pentyl, 6-chloro-n-hexyl, 7-chloro-n-heptyl, 8-chloro-n-octyl, 2-bromoethyl, 3-bromo-n-propyl, 4-bromo-n-butyl, 5-bromo-n-pentyl, 6-bromo-n-hexyl, 7-bromo-n-heptyl, 8-bromo-n-octyl, 3,3, 3-trifluoropropyl, and 3,3,4,4,5,5, 5-heptafluoro-n-pentyl.

As R^2bAnd R^3bPreferred radicals in the above are ethyl and n-propylAlkyl, n-butyl, n-pentyl, 2-methoxyethyl, 2-cyanoethyl, 2-phenylethyl, 2-cyclohexylethyl, 2-methoxycarbonylethyl, 2-chloroethyl, 2-bromoethyl, 3,3, 3-trifluoropropyl, and 3,3,4,4,5,5, 5-heptafluoro-n-pentyl.

As R^4bExamples of preferred organic radicals of (1), with R^1bSimilarly, there may be mentioned alkyl, alkoxy, cycloalkyl, cycloalkoxy, saturated aliphatic acyl, alkoxycarbonyl, saturated aliphatic acyloxy, phenyl which may have a substituent, phenoxy which may have a substituent, benzoyl which may have a substituent, phenoxycarbonyl which may have a substituent, benzoyloxy which may have a substituent, phenylalkyl which may have a substituent, naphthyl which may have a substituent, naphthyloxy which may have a substituent, naphthoyl which may have a substituent, naphthyloxycarbonyl which may have a substituent, naphthoyloxy which may have a substituent, naphthylalkyl which may have a substituent, heterocyclic group which may have a substituent, heterocyclic carbonyl which may have a substituent, amino which is substituted by 1 or 2 organic groups, morpholin-1-yl, piperazin-1-yl and the like. Specific examples of these groups and for R^1bThe same applies to the specific examples described. In addition, as R^4bAlso preferred are cycloalkylalkyl groups, phenoxyalkyl groups which may have a substituent on the aromatic ring, and phenylthioalkyl groups which may have a substituent on the aromatic ring. Phenoxyalkyl group, and phenylthioalkyl group-optionally-substituted group and R^1bThe same applies to the substituents which the phenyl group may have.

In the organic radical, as R^4bPreferably, the alkyl group, the cycloalkyl group, the phenyl group which may have a substituent, or the cycloalkylalkyl group, the phenylthioalkyl group which may have a substituent on the aromatic ring are used. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is preferably1 to 8, more preferably 1 to 4, and particularly preferably 2. Among cycloalkylalkyl groups, cyclopentylethyl is preferred. The number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the phenylsulfanylalkyl groups which may have a substituent on the aromatic ring, 2- (4-chlorophenylthio) ethyl is preferred.

In addition, as R^4bAlso preferred is-A³-CO-O-A⁴The group shown. A. the³Is a divalent organic group, preferably a divalent hydrocarbon group, more preferably an alkylene group. A. the⁴Is a monovalent organic group, preferably a monovalent hydrocarbon group.

A³In the case of an alkylene group, the alkylene group may be linear or branched, and is preferably linear. A. the³In the case of an alkylene group, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

As A⁴Preferred examples of the alkyl group include an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. As A⁴Preferable specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, phenyl, naphthyl, benzyl, phenethyl, α -naphthylmethyl, and β -naphthylmethyl groups.

As a³-CO-O-A⁴Preferred specific examples of the group include 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-n-propoxycarbonylethyl, 2-n-butoxycarbonylethyl, 2-n-pentyloxycarbonylethyl, 2-n-hexyloxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-phenoxycarbonylethyl, 3-methoxycarbonyl-n-propyl, 3-ethoxycarbonyl-n-propyl, 3-n-propoxycarbonyl-n-propyl, 3-n-butoxycarbonyl-n-propyl, 3-n-pentyloxycarbonyl-n-propyl, 3-n-hexyloxycarbonyl-n-propyl, 3-benzyloxycarbonyl-n-propyl, and 3-phenoxycarbonyl-n-propyl.

Above pair R^4bHas been described as R^4bPreferred is a group represented by the following formula (R4-1) or (R4-2).

(in the formulae (R4-1) and (R4-2), R^7bAnd R^8bEach is an organic group, R is an integer of 0 to 4, R^7bAnd R^8bWhen present in adjacent positions on the phenyl ring, R^7bAnd R^8bCan be bonded to each other to form a ring, s is an integer of 1 to 8, t is an integer of 1 to 5, u is an integer of 0 to (t +3), R^9bIs an organic group. )

With respect to R in the formula (R4-1)^7bAnd R^8bExamples of organic radicals of (2) with R^1bThe same is true. As R^7bPreferably alkyl or phenyl. R^7bWhen the alkyl group is used, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. Namely, R^7bMost preferred is methyl. R^7bAnd R^8bWhen a ring is bonded to form a bond, the ring may be an aromatic ring or an aliphatic ring. As R in the group represented by the formula (R4-1)^7bAnd R^8bPreferred examples of the group having a ring formed thereon include naphthalen-1-yl group, 1,2,3, 4-tetrahydronaphthalen-5-yl group and the like. In the formula (R4-1), R is an integer of 0 to 4, preferably 0 or 1, more preferably 0.

In the above formula (R4-2), R^9bIs an organic group. Examples of the organic group include those related to R^1bAnd the organic groups illustrated are the same. Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. As R^9bExamples thereof include preferably methyl, ethyl, propyl, isopropyl and butyl, among which methyl is more preferred.

In the formula (R4-2), t is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1 or 2. In the formula (R4-2), u is an integer of 0 to (t +3), preferably 0 to 3, more preferably 0 to 2, and particularly preferably 0. In the formula (R4-2), s is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and particularly preferably 1 or 2.

In the formula (b1), R^5bIs a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As R^5bExamples of the substituent which may be contained in the alkyl group include a phenyl group and a naphthyl group. In addition, as R^5bExamples of the substituent which may be contained in the aryl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

In the formula (b1), R is^5bPreferable examples thereof include a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methylphenyl group, naphthyl group and the like, and among these, methyl group or phenyl group is more preferable.

The content of the photopolymerization initiator (B) is preferably 0.001 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and still more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the total solid components of the negative photosensitive resin composition.

The content of the photopolymerization initiator (B) is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and still more preferably 0.5 to 10% by mass, based on the total amount of the resin (a) and the photopolymerization initiator (B).

The photopolymerization initiator (B) represented by the formula (B1) may be used alone or in combination of two or more, and when two or more are used, the following (i) to (iii) are preferable.

(i)R^1bCompounds of the formula (I) and (II) R being hydrogen atoms^1bCombinations of compounds being nitro groups

(ii)R^4bA compound of the formula (R4-1) with R^4bCombinations of compounds of formula (R4-2)

(iii)R^4bIs a compound of formula (R4-1) or (R4-2) with R^4bA compound which is an alkyl group having 1 to 4 carbon atoms

Among them, from the viewpoint of improving the properties such as sensitivity and transmittance of a cured product, the combination of (i) is preferable, and the combination satisfying (ii) or (iii) and (i) is more preferable.

The mixing ratio (mass ratio) of each compound based on the combination of the above (i) to (iii) may be appropriately adjusted according to the characteristics such as the target sensitivity. For example, it is preferably 1: 99-99: 1, more preferably 10: 90-90: 10, more preferably 30: 70-70: 30.

preferable specific examples of the compound represented by the formula (b1) include the following compounds 1 to 41.

The negative photosensitive resin composition may contain a polymerization initiator other than the photopolymerization initiator (B).

Examples of the polymerization initiator other than the photopolymerization initiator (B) include oxime ester compounds, biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α -diketone compounds, polynuclear quinone compounds, phosphine compounds, triazine compounds, and the like other than the photopolymerization initiator (B).

Examples of oxime ester compounds other than the photopolymerization initiator (B) include 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), 1, 3-octanedione-1- [ (4-phenylthio) phenyl ] -2-benzoyloxime, and the like.

Examples of the acetophenone-based compound include an α -hydroxyketone-based compound, an α -aminoketone-based compound, and compounds other than these.

Specific examples of the α -hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, and 1-hydroxycyclohexylphenylketone, and specific examples of the α -aminoketone compound include 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, specific examples of compounds other than these include 2, 2-dimethoxyacetophenone, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone and the like.

These acetophenone compounds may be used alone or in combination of two or more. By using these acetophenone compounds, the strength of the film can be further improved.

Specific examples of the biimidazole compound include 2,2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetrakis (4-ethoxycarbonylphenyl) -1,2 ' -biimidazole, 2 ' -bis (2-bromophenyl) -4,4 ', 5,5 ' -tetrakis (4-ethoxycarbonylphenyl) -1,2 ' -biimidazole, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, 2 ' -bis (2, 4-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, 2 ' -bis (2,4, 6-trichlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, 2 ' -bis (2-bromophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, 2 ' -bis (2, 4-dibromophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, 2 ' -bis (2,4, 6-tribromophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2 ' -biimidazole, and the like.

Among the biimidazole compounds, 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2, 4-dichlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2,4, 6-trichlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -biimidazole and the like are preferable, and 2,2 '-bis (2, 4-dichlorophenyl) -4, 4', 5,5 '-tetraphenyl-1, 2' -biimidazole is particularly preferable.

< adhesion enhancer (C) >

The adhesion enhancer (C) is a component having an action of enhancing adhesion to the substrate, and is preferably a silane coupling agent having a reactive functional group such as a carboxyl group, (meth) acryloyl group, vinyl group, isocyanate group, epoxy group, or mercapto group. Specifically, the silane coupling agent is, for example, one or more selected from trimethoxysilylbenzoic acid, 3- ((meth) acryloyloxy) propyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, (3-isocyanatopropyl) triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane.

In the present specification, "(meth) acryloyl" means both "acryloyl" and "methacryloyl". The "(meth) acrylate" means both "acrylate" and "methacrylate", and the "(meth) acrylic group" means both "acrylic group" and "methacrylic group".

The adhesion enhancer (C) is partially overlapped with the silane coupling agent, and includes isocyanate compounds, epoxy compounds, (meth) acrylate compounds, vinyl compounds, and mercapto compounds, and more preferably epoxy compounds. Examples of the epoxy compound include an organic silane compound having an epoxy group, and more specifically, an alkoxysilane having an epoxy group and having 1 to 5 carbon atoms.

The content of the adhesion enhancer (C) is, for example, 0 to 10 parts by mass, preferably 0.01 to 10 parts by mass, 0.02 to 1 part by mass, or 0.05 to 0.1 part by mass based on 100 parts by mass of the resin (a), and when within this range, the adhesion to the substrate is excellent.

< photopolymerizable Compound (D) >

The negative photosensitive resin composition may or may not contain the photopolymerizable compound (D).

The photopolymerizable compound (D) is not particularly limited, and examples thereof include crosslinkable compounds having an ethylenically unsaturated bond.

The crosslinkable compound having an ethylenically unsaturated bond is usually a crosslinkable monomer having at least 2 or more ethylenically double bonds, and examples thereof include: ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butanediol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1, 6-hexanediol diacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, polyfunctional (meth) acrylic monomers and oligomers such as 1, 6-hexanediol dimethacrylate, Cardo epoxy diacrylate, and poly (poly-) compounds thereof (polyethylene glycol diacrylate);

polyester (meth) acrylate obtained by reacting (meth) acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid; urethane (meth) acrylate obtained by reacting a polyol with a compound having 2 isocyanate groups and then with (meth) acrylic acid;

epoxy (meth) acrylate resins obtained by reacting (meth) acrylic acid with epoxy resins such as bisphenol a type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol or cresol Novolac type epoxy resins, Resol type epoxy resins, triphenol methane type epoxy resins, polycarboxylic acid polyglycidyl esters, polyhydric alcohol polyglycidyl esters, aliphatic or alicyclic epoxy resins, amine epoxy resins, dihydroxybenzene type epoxy resins, and the like. In addition, in view of exposure sensitivity and the like, it is preferable to use a polyfunctional (meth) acrylic monomer as the photopolymerizable compound (D).

When the photopolymerizable compound (D) is contained, the photopolymerizable compound (D) is contained preferably in an amount of 0.1 to 200 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably 5 to 10 parts by mass, relative to 100 parts by mass of the resin (a).

< solvent (S) >

Examples of the solvent (S) include an organic solvent and water. The organic solvent is not particularly limited as long as it is an organic solvent of an acetate type, ether type, glycol type, ketone type, alcohol type, carbonate type, or the like, which is used in a general negative photosensitive resin composition and can dissolve the resin (a). Examples of the organic solvent include propylene glycol monomethyl ether acetate (PEGMEA), ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol, cyclohexanone, cyclopentanone, 3-ethoxypropionic acid, N-dimethylacetamide, N-methylpyrrolidone (NMP), N-methylcaprolactam, and the like.

The content of the solvent (S) is, for example, 20 to 95 parts by mass, preferably 30 to 90 parts by mass, and more preferably 50 to 80 parts by mass, relative to 100 parts by mass of the negative photosensitive resin composition. Within this range, a thin film can be easily formed by a conventional coating method, and a thin film having a desired thickness can be easily obtained after coating.

< other ingredients >

The negative photosensitive resin composition may contain an additive as needed. Examples of such additives include stabilizers, thermal crosslinking agents, photocuring accelerators, surfactants, alkali quenchers, antioxidants, adhesion promoters, defoaming agents, and the like, and they may be used alone or in a mixture as needed.

The surfactant is a component having an effect of improving coatability and coatability to a substrate, uniformity, and dirt removability. Examples of the surfactant include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surfactant, and a silicon-based surfactant is preferable. Examples of the silicon surfactant include polyether-modified polysiloxane, and more specific examples thereof include polyether-modified polydimethylsiloxane.

The content of the surfactant is, for example, 0.01 to 5 parts by mass, preferably 0.02 to 1 part by mass, or 0.05 to 0.1 part by mass, based on 100 parts by mass of the resin (A).

Examples of the stabilizer include a heat stabilizer and a light stabilizer.

The heat stabilizer is not particularly limited, and examples thereof include heat stabilizers which can be used in general negative photosensitive resin compositions, and can suppress a decrease in permeability of a formed cured product (organic film) in a post-heat treatment step and can increase the permeability of a remaining organic film. Examples of the heat stabilizer include phenol heat stabilizers, phosphite heat stabilizers, and lactone heat stabilizers. Preferable examples of the heat stabilizer include compounds represented by the following formulas (4) to (6).

The light stabilizer can be used as a light stabilizer that can be used in a general negative photosensitive resin composition, and examples thereof include a light stabilizer that can maximize the light resistance of a cured product (e.g., an organic insulating film) to be formed. Examples of the light stabilizer include benzotriazole light stabilizers, triazine light stabilizers, benzophenone light stabilizers, hindered amino ether light stabilizers, and hindered amine light stabilizers.

Method for producing negative photosensitive resin composition

The negative photosensitive resin composition can be produced by a usual method, and for example, can be produced by mixing the above components and filtering the mixture with a filter as necessary.

Cured film and method for producing cured film

By using the negative photosensitive resin composition, a cured film which can be used for displays such as TFT-LCD, OLED, and touch screen panel can be produced. The cured film produced can be patterned as desired.

A method for producing a cured film using the negative photosensitive resin composition will be described below.

First, the negative photosensitive resin composition is applied to a substrate to form a coating film.

The substrate on which the coating film is formed is not particularly limited, and conventionally known substrates can be used, and examples thereof include a silicon substrate, a glass substrate, and a substrate having a metal surface. As the metal species constituting the metal surface, copper, gold, and aluminum are preferable, and copper is more preferable.

In addition, since the heating temperature can be lowered when the cured film is formed, the negative photosensitive resin composition can be used for a substrate having low heat resistance. Examples of the substrate having low heat resistance include a substrate having flexibility (e.g., a substrate having flexibility). Examples of the flexible substrate include a plastic substrate, for example, a plastic substrate made of the following various plastic materials: polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); a polyimide; a polycarbonate; a polyamide; a polyacetal; polyphenylene ether; polyphenylene sulfide; polyether sulfone; polyether ether ketone; cyclic polyolefins such as homopolymers of norbornene monomers (addition polymers, ring-opening polymers, and the like), copolymers of norbornene monomers and olefin monomers (cyclic olefin copolymers such as addition polymers, ring-opening polymers, and the like), and derivatives thereof; vinyl polymers (e.g., (meth) acrylic resins such as polymethyl methacrylate (PMMA), polystyrene, polyvinyl chloride, acrylonitrile-styrene-butadiene resins (ABS resins), etc.); ethylene polymers (e.g., polyvinylidene chloride); cellulose resins such as cellulose Triacetate (TAC); an epoxy resin; a phenolic resin; a melamine resin; urea resin; a maleimide resin; an organosilicon; and so on.

The coating method of the negative photosensitive resin composition is not particularly limited, and a known method can be used. Examples of the coating method include spin coating, dip coating, roll coating, screen coating, spray coating, flow coating, screen printing, ink jet, and drop-casting.

The film thickness of the coating film to be formed varies depending on the coating method, the concentration of the solid component of the negative photosensitive resin composition, the viscosity, and the like, and is not particularly limited, and the coating film may be generally applied so that the film thickness after drying becomes 0.5 to 100 μm.

The coating film may be dried as necessary. The drying method is not particularly limited, and examples thereof include a method of volatilizing the solvent by vacuum, infrared irradiation, and heating.

Next, the coating film is exposed. In the exposure step, energy rays such as excimer laser, far ultraviolet ray, visible light, electron beam, X-ray, g-ray (wavelength 436nm), i-ray (wavelength 365nm), h-ray (wavelength 405nm), or a mixture thereof are irradiated. For the exposure, exposure methods such as contact, proximity, and projection methods can be used.

The amount of the energy ray to be irradiated varies depending on the composition of the negative photosensitive resin composition, and is, for example, 140mJ/cm²Preferably 5 to 100mJ/cm²More preferably 10 to 60mJ/cm²。

The coating film is exposed to light to cause a curing reaction, thereby forming a cured product (cured film).

The exposure may be a position-selective exposure. The position-selective exposure is performed, for example, via a negative mask. By performing the position-selective exposure, a patterned cured film can be formed.

When the coating film is exposed in a position-selective manner, the exposed coating film is developed with a developer to obtain a cured film patterned into a desired shape.

The developing method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used.

The developer is appropriately selected according to the composition of the negative photosensitive resin composition. As the developer, an alkaline aqueous solution, which is more environmentally friendly and less expensive than an organic solvent, can be used. Examples of the alkaline developing solution include an aqueous solution of quaternary ammonium hydroxide such as tetramethylammonium hydroxide (TMAH) or tetraethylammonium hydroxide, and an aqueous amine solution such as ammonia, ethylamine, propylamine, diethylamine, or triethylamine.

The coating film after exposure may be heated (post exposure bake (PEB) or postbake). The heating temperature is not particularly limited, and is, for example, 80 ℃ to 250 ℃, preferably 80 ℃ to 200 ℃, more preferably 80 ℃ to 150 ℃, and still more preferably 85 ℃ to 100 ℃. When a substrate having low heat resistance is used, it is difficult to use a substrate having low heat resistance because heating at a high temperature may adversely affect the substrate.

When the coating film is exposed in a position-selective manner, the heating (PEB) is preferably performed after the step of exposing the coating film and before the step of developing the coating film.

When a substrate having high heat resistance is used, the substrate may be further heated at 80 ℃ to 250 ℃ after the development step after the PEB step or after the development step without the PEB step after exposure (post-baking).

The cured film (cured product) produced by the above production method is formed using the above negative photosensitive resin composition, and therefore has high solvent resistance. A cured film formed using the negative photosensitive resin composition has high resistance to an organic solvent such as propylene glycol monomethyl ether acetate (PEGMEA) or N-methylpyrrolidone (NMP). Therefore, it is suitable for the following uses: a use of a composition obtained by dissolving a component such as a resin in a solvent to form another layer on the cured film to produce a laminate; use of an adhesive comprising a solvent.

In addition, since the negative photosensitive resin composition has excellent resolution, a patterned cured film having a fine pattern can be produced. For example, a patterned cured film having a fine pattern with a line width of 20 μm or less, preferably 10 μm or less can be produced.

Further, by using the negative photosensitive resin composition containing the resin (a), a cured film having a high refractive index, a cured film having high functionality such as heat resistance, chemical resistance, and high permeability can be produced. For example, a cured film having a high refractive index is laminated with a low refractive index film, thereby providing a light extraction film having excellent light extraction efficiency. In addition, the cured film having excellent heat resistance can minimize taper angle and outgassing.

Such a cured film or a patterned cured film can be used for production or coating materials of elements such as semiconductor elements, LCD elements, OLED elements, solar cell elements, flexible display elements, touch panel manufacturing elements, and nanoimprint lithography elements.

Examples

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[ Synthesis example 1]

(monomer Synthesis)

The first stage is as follows: synthesis of 2, 2' - (((((9H-fluorene-9, 9-diyl) bis (4, 1-phenylene)) bis (oxy)) bis (methylene)) bis (ethylene oxide)

Step A: after a reflux condenser (reflux condenser) and a thermometer were placed in a three-necked flask, 42.5g of 9, 9-bisphenol fluorene was added, and 220mL of 2- (chloromethyl) oxirane was quantitatively determined and injected. 100mg of tetrabutylammonium bromide are added, stirring is then started and the temperature is raised to 90 ℃. After confirming that the content of unreacted materials is less than 0.3%, vacuum distillation was performed.

And B: the temperature was lowered to 30 ℃, dichloromethane was then injected, and NaOH was slowly added. After confirming that the product was 96% or more by High Performance Liquid Chromatography (HPLC), the reaction was terminated by dropwise addition of 5% HCl. The reaction was extracted to separate layers, and then the organic layer was washed with water and washed to neutrality. With MgSO₄The organic layer was dried and then concentrated by distillation under reduced pressure using a rotary evaporator. Methylene chloride was added to the concentrated product, and stirring was performed while raising the temperature to 40 ℃, and methanol was added, and then the temperature of the solution was lowered and stirred. The resulting solid was filtered and dried under vacuum at room temperature to obtain 52.7g (yield: 94%) of a white solid powder, which was passed through a filter to give a corresponding structure¹H NMR was confirmed.

CDCl₃In (1)¹H NMR: 7.75(2H), 7.36-7.25 (6H), 7.09(4H), 6.74(4H), 4.13(2H), 3.89(2H), 3.30(2H), 2.87(2H), 2.71 (2H).

And a second stage: synthesis of 3, 3' - (((9H-fluoren-9, 9-diyl) bis (4, 1-phenylene)) bis (oxy)) bis (1- (phenylthio) propan-2-yl) (BTCP monomer)

After a reflux condenser and a thermometer were placed in a three-necked flask, the first stage reaction mass (1000g), 524g of thiophenol, 617g of ethanol were added and stirred. 328g of triethylamine was slowly added dropwise to the reaction solution. After confirming the disappearance of the starting material by High Performance Liquid Chromatography (HPLC), the reaction was terminated. After completion of the reaction, ethanol was distilled off under reduced pressure. The organic was dissolved in dichloromethane, then washed with water, and then dichloromethane was removed by distillation under reduced pressure. The concentrated organic matter was dissolved in ethyl acetate, and then an ether solvent was added dropwise thereto and stirred for 30 minutes. The compound was distilled under reduced pressure to give 945g (64% yield) of a pale yellow oil, which was structured by¹H NMR was confirmed.

CDCl₃In (1)¹H NMR：7.82(2H)、7.38～6.72(20H)、6.51(4H)、4.00(2H)、3.97(2H)、3.89(2H)、3.20(2H)、3.01(2H)、2.64(2H)。

(production of resin (A) (Binder resin)) production of resin A1

After a reflux condenser and a thermometer were placed in a three-necked flask, 200g of the BTCP monomer synthesized in the second stage dissolved in 50% Propylene Glycol Methyl Ether Acetate (PGMEA) solvent was added, and the temperature was raised to 115 ℃. 31.1g of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride was added dropwise at 115 ℃ and then stirred for 6 hours while maintaining 115 ℃. 7.35g of phthalic anhydride was added, and the mixture was further stirred for 2 hours, followed by terminating the reaction. After cooling, a solution of resin A1 having a mass average molecular weight of 3,500g/mol and a dispersity of 2.2 was obtained.

[ Synthesis example 2]

(production of resin (A)) production of resin A2

After a reflux condenser and a thermometer were placed in a three-necked flask, 200g of the BTCP monomer synthesized in the second stage dissolved in 50% PGMEA solvent was added, and the temperature was raised to 115 ℃. 28.4g of 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride was added dropwise at 115 ℃ and then stirred for 6 hours while maintaining 115 ℃. 7.35g of phthalic anhydride was added, and the mixture was further stirred for 2 hours to terminate the reaction. After cooling, a solution of resin A2 having a mass average molecular weight of 5,000g/mol and a degree of dispersion of 2.4 was obtained.

As the photopolymerization initiator (B), compound 6 was used.

[ example 1]

A negative photosensitive resin composition was prepared by dissolving 93 parts by mass of resin a1 as resin (a), 5.6 parts by mass of compound 6 as photopolymerization initiator (B), 0.93 parts by mass of 3-glycidoxypropyltrimethoxysilane as adhesion enhancer (C), and 0.13 parts by mass of a siloxane surfactant (polyester-modified polydimethylsiloxane, BYK-310, BYK-Chemie co., Ltd) as a surfactant in propylene glycol monomethyl ether acetate (PEGMEA) as solvent (S) so that the solid concentration became 20 mass%.

[ example 2]

A negative photosensitive resin composition was produced in the same manner as in example 1, except that the loading of the adhesion enhancer (C) was changed to 3 times by mass.

[ example 3]

A negative photosensitive resin composition was produced in the same manner as in example 1, except that the loading of the adhesion enhancer (C) was changed to 5 times by mass.

[ example 4]

A negative photosensitive resin composition was produced in the same manner as in example 3, except that 3- (methacryloyloxy) propyltrimethoxysilane was used instead of 3-glycidoxypropyltrimethoxysilane as the adhesion enhancer (C).

[ example 5]

A negative photosensitive resin composition was prepared by dissolving 85 parts by mass of resin a1 as a resin (a), 5 parts by mass of compound 6 as a photopolymerization initiator (B), 3 parts by mass of 3-glycidoxypropyltrimethoxysilane as an adhesion enhancer (C), 0.2 parts by mass of a silicone surfactant (polyester-modified polydimethylsiloxane, BYK-310, BYK-Chemie co., Ltd), and 6.5 parts by mass of dipentaerythritol hexaacrylate as a photopolymerizable compound (D) in propylene glycol monomethyl ether acetate (PEGMEA) as a solvent (S) so that the solid content concentration became 20 mass%.

Comparative example 1

A negative photosensitive resin composition was produced in the same manner as in example 3, except that an oxime ester type photopolymerization initiator having the following formula, which does not belong to formula (B1), was used instead of compound 6 as the photopolymerization initiator (B).

Comparative example 2

A negative photosensitive resin composition was produced in the same manner as in example 3, except that an oxime ester type photopolymerization initiator (1- [4- (phenylthio) phenyl ] -1, 2-octanedione 2- (O-benzoyl oxime), Irgacure OXE01, BASF Japan ltd.) which does not belong to the formula (B1) was used instead of the compound 6 as the photopolymerization initiator (B).

Comparative example 3

A negative photosensitive resin composition was produced in the same manner as in comparative example 1, except that resin a2 was used instead of resin a1 as resin (a).

Comparative example 4

A negative photosensitive resin composition was produced in the same manner as in comparative example 2, except that resin a2 was used instead of resin a1 as resin (a).

[ evaluation of solvent resistance ]

The negative photosensitive resin compositions obtained in examples 1 to 5 and comparative examples 1 to 4 were each coated on a substrate made of polyethylene terephthalate (PET) by a spin coater at 800 to 900rpm for 15 seconds, and then dried at 85 ℃ for 180 seconds by a hot plate to form a coating film having a thickness of 5 μm.

The dried coating film was irradiated with ultraviolet light with an exposure gap of 25 μm using a proximity exposure machine (product name: TME-150RTO, TOPCON). The exposure amount was 30mJ/cm²。

The coating film after exposure was subjected to post-baking at 85 ℃ for 300 seconds, whereby a cured film was obtained.

The resulting cured film was immersed in propylene glycol monomethyl ether acetate (PEGMEA) at 26 ℃ for 300 seconds.

The cured films before and after immersion were observed with a Scanning Electron Microscope (SEM) at 5000 × magnification, and the solvent resistance was evaluated according to the following criteria.

Evaluation was also made with the immersion solvent being N-methylpyrrolidone (NMP).

Evaluation was also made under the post-baking condition of 100 ℃ for 300 seconds.

The results are shown in Table 1.

In addition, with respect to the negative photosensitive resin composition obtained in example 5, solvent resistance evaluation was also performed in the same manner as described above except that post-baking was not performed. The results are described as example 6.

(PEGMEA)

Good: before and after immersion, the cured film did not change

X: before and after immersion, the cured film has changed

(NMP)

Good: the change rate of the thickness of the cured film before and after the impregnation is less than 10%

X: the rate of change in the thickness of the cured film before and after immersion is 10% or more

[ evaluation of resolving power ]

The negative photosensitive resin compositions obtained in examples 1 to 5 and comparative examples 1 to 4 were each coated on a substrate made of polyethylene terephthalate (PET) by a spin coater at 800 to 900rpm for 15 seconds, and then dried at 85 ℃ for 180 seconds by a hot plate to form a coating film having a thickness of 5 μm.

The dried coating film was irradiated with ultraviolet light through a negative mask having a pattern with a width of 10 μm, with an exposure gap of 25 μm using a proximity exposure machine (product name: TME-150RTO, TOPCON). The exposure amount was 30mJ/cm²。

The coating film after exposure was baked at 85 ℃ for 300 seconds (PEB), and then developed in a 2.38 mass% TMAH aqueous solution at 26 ℃ for 30 seconds, thereby obtaining a cured film.

The cured film obtained was observed with a Scanning Electron Microscope (SEM) at a magnification of 5000, and the film having a pattern width of 10 μm was evaluated as good, while the film having no pattern width of 10 μm was evaluated as poor.

The results are shown in Table 1.

The negative photosensitive resin composition obtained in example 5 was also evaluated for resolution in the same manner as described above, except that PEB was not performed. The results are described as example 6.

[ Table 1]

From examples 1 to 6, it is understood that the negative photosensitive resin composition comprising the resin (a) having the structural unit represented by the formula (a1) and the photopolymerization initiator (B) represented by the formula (B1) is excellent in solvent resistance. Further, it is found that these negative photosensitive resin compositions are also excellent in resolution.

On the other hand, as is clear from comparative examples 1 to 4, when the negative photosensitive resin composition contains the resin (a) having the structural unit represented by formula (a1) but does not contain the photopolymerization initiator (B) represented by formula (B1), the solvent resistance is inferior to that in examples 1 to 6. Further, the resolution was inferior to that of examples 1 to 6.

Claims (9)

1. A negative photosensitive resin composition comprising a resin (A) having a structural unit represented by the following formula (a1) and a photopolymerization initiator (B) represented by the following formula (B1),

in the formula (a1), R^1aAnd R^2aEach independently represents an alkyl group which may contain a hetero atom and has 1 to 20 carbon atoms, an aryl group which may contain a hetero atom and has 6 to 20 carbon atoms, -R^4aSR^5aor-R^6aC(＝O)R^7a，

R^3aRepresents a tetravalent aromatic hydrocarbon group or alicyclic hydrocarbon group which has 1 to 20 carbon atoms and may contain a hetero atom,

a represents a divalent group represented by the following formula (a2),

j1 and j2 each independently represent an integer of 1 or more and 6 or less,

R^4arepresents a single bond, an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 15 carbon atoms,

s represents a sulfur atom, and S represents a sulfur atom,

R^5arepresents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms,

R^6arepresents a single bond, an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms,

R^7arepresents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms,

in the formula (a2), the first and second,

R^8aand R^9aEach independently represents a hydrogen atom, a hydroxyl group, a mercapto group, an amino group, a nitro group, a halogen atom, a cyano group or an alkyl group,

R^10aand R^11aEach independently represents a hydrogen atom, an alkyl group or an aryl group,

k1 and k2 each independently represent an integer of 0 or more and 4 or less,

m1 and m2 each independently represent an integer of 0 or more and 3 or less,

in the formula (b1),

R^1brepresents a hydrogen atom, a nitro group or a monovalent organic group,

R^2band R^3bEach independently represents a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, R^2bAnd R^3bMay be bonded to each other to form a ring,

R^4brepresents a monovalent organic group, and represents a monovalent organic group,

R^5brepresents a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent,

p is an integer of 0 to 4 inclusive,

q is 0 or 1.

2. The negative photosensitive resin composition according to claim 1, further comprising an adhesion enhancer (C).

3. A cured film formed from a cured product of the negative photosensitive resin composition according to claim 1 or 2.

4. A method for producing a cured film, comprising the steps of:

a step of forming a coating film by coating the negative photosensitive resin composition according to claim 1 or 2 on a substrate; and

and exposing the coating film.

5. The method for producing a cured film according to claim 4, comprising a step of heating the coating film after the exposure step, after the step of exposing the coating film.

6. The method for producing a cured film according to claim 4, wherein the step of exposing the coating film is a step of exposing the coating film in a position-selective manner,

the manufacturing method further includes a step of developing the coating film after exposure.

7. The method of producing a cured film according to claim 6, wherein a step of heating the coating film after the exposure is included after the step of exposing the coating film to light and before the step of developing the coating film.

8. The method for producing a cured film according to claim 5 or 7, wherein a heating temperature in the step of heating the coating film after the exposure is 85 ℃ or higher and 100 ℃ or lower.

9. The method of manufacturing a cured film according to claim 4, wherein the substrate is a substrate having flexibility.