Negative-type photosensitive resin composition and method for producing cured film

Abstract

To provide a negative type photosensitive resin composition capable of forming a cured film having high solvent resistance, a cured film formed of a cured product of the negative type photosensitive resin composition, and a method for producing a cured film using the negative type photosensitive resin composition.SOLUTION: A negative type photosensitive resin composition contains a resin (A) having a structure represented by the following formula (a1), and an oxime ester photopolymerization initiator (B) having a specific structure.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a negative-type photosensitive resin composition and a method for producing a cured film using the negative-type photosensitive resin composition. [Background technology]

[0002] Photosensitive resin compositions for displays, which are applied to thin film transistor liquid crystal displays (TFT-LCDs), organic light emitting devices (OLEDs), touch screen panels (TSPs), etc., are divided into positive-type photosensitive materials and negative-type photosensitive materials, depending on the method of forming a pattern by causing a curing reaction or a photodecomposition reaction by irradiation with UV (ultraviolet rays). In positive-type photosensitive materials, a pattern is formed when a photodecomposition reaction occurs in the UV-irradiated area and the material dissolves in the developer. In negative-type photosensitive materials, a photocuring reaction occurs in the UV-irradiated area and the material does not dissolve in the developer, while the area not exposed to UV dissolves in the developer, forming a pattern.

[0003] It is very important for the photosensitive resin composition to have resistance to heat treatment applied in the process and resistance to chemical etching and gas etching processes. In particular, in recent years, high transmittance and high refraction properties have been emphasized in order to increase the light efficiency of displays. In order to ensure the high heat resistance, chemical resistance (etching resistance), high transmittance and high refraction properties of the photosensitive resin composition, the structure and properties of the binder among the compositions constituting the photosensitive material are very important. For this reason, active research has been conducted on imparting photosensitivity to binder resins such as acrylic photosensitive resins, novolac resins, polyimides, etc., which are used as representative binder resins of photosensitive resin compositions. However, photosensitive resin compositions using acrylic photosensitive resins and novolac resins, which have been used conventionally, have poor heat resistance in high-temperature heat treatment processes of 300°C or more, and impurities are generated due to outgassing, causing serious display contamination. In addition, there is a problem that the transmittance decreases due to high-temperature heat treatment, deteriorating the light efficiency properties of the display.

[0004] For example, Patent Document 1 discloses a photosensitive resin composition prepared 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, the composition has poor development characteristics due to an insufficient difference in solubility between exposed and unexposed areas, and the binder resin that should remain during the development process is partially dissolved in the developer solution, making it difficult to obtain fine patterns of 10 μm or less.

[0005] In addition, Patent Documents 2 and 3 disclose photosensitive photoresist compositions that contain a polyamic acid as a polyimide precursor and a naphthoquinone diazide compound as a dissolution inhibitor to enhance thermal stability. However, when forming a high-resolution pattern, there is a problem that the difference in dissolution rate between exposed and unexposed areas is insufficient.

[0006] Furthermore, photosensitive resin compositions must have good adhesion to lower and upper layers, and a wide process margin that enables the formation of high-resolution fine patterns under various process conditions according to the intended use. Since photosensitive materials are required to have high sensitivity characteristics, research into improving such characteristics is being actively conducted.

[0007] As a technique for solving the above-mentioned problems, Patent Document 4 discloses a negative-type photosensitive resin composition and a positive-type photosensitive resin composition using, as a binder resin, a polymer with a specific structure having excellent heat resistance and high transmittance and high refractive index. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] U.S. Patent No. 4,139,391 [Patent Document 2] Japanese Patent Application Publication No. 52-13315 [Patent Document 3] Japanese Patent Publication No. 135824 / 1983 [Patent Document 4] JP 2018-531311 A Summary of the Invention [Problem to be solved by the invention]

[0009] Incidentally, when producing a display, a photosensitive resin layer may be formed using a photosensitive resin composition, and then a different layer may be laminated. For example, a light extraction film that improves 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 carried out using a composition in which a component such as a resin is dissolved in a solvent. However, if the high refractive index layer on which the low refractive index layer is laminated does not have resistance to the solvent, there is a concern that the film thickness of the high refractive index layer cannot be guaranteed by the lamination process, or that the properties such as the refractive index of the high refractive index layer may be reduced.

[0010] However, when the negative photosensitive resin composition described in Patent Document 4 is used, the formed photosensitive resin layer (cured film) has poor solvent resistance, and therefore, when the above-mentioned lamination process is applied, there is a problem that the desired photosensitive resin layer cannot be realized.

[0011] The present invention has been made in consideration of the above problems, and an object of the present invention is to provide a negative type photosensitive resin composition capable of forming a cured film having high solvent resistance, a cured film consisting of a cured product of the negative type photosensitive resin composition, and a method for producing a cured film using the negative type photosensitive resin composition. [Means for solving the problem]

[0012] As a result of intensive research into achieving the above object, the present inventors have found that the above problems can be solved by a negative photosensitive resin composition containing a resin (A) having a specific structure and a photopolymerization initiator (B) having a specific structure, and have thus completed the present invention. Specifically, the present invention provides the following.

[0013] A first 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). [ka] (In formula (a1), R 1a and R 2a each independently represents an alkyl group having 1 to 20 carbon atoms which may contain a heteroatom, an aryl group having 6 to 20 carbon atoms which may contain a heteroatom, -R 4a S.R. 5a or -R 6a C(=O)R 7a represents R 3a represents a tetravalent aromatic or alicyclic hydrocarbon group having from 1 to 20 carbon atoms and optionally containing a heteroatom, 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 4a represents a single bond, an alkylene group having from 1 to 10 carbon atoms, or an arylene group having from 6 to 15 carbon atoms, S represents a sulfur atom, R 5a represents an alkyl group having from 1 to 10 carbon atoms, or an aryl group having from 6 to 15 carbon atoms, R 6a represents a single bond, an alkylene group having from 1 to 10 carbon atoms, or an arylene group having from 6 to 10 carbon atoms, R 7a represents 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. [ka] (In formula (a2), R 8a and R 9aeach independently represents a hydrogen atom, a hydroxy group, a mercapto group, an amino group, a nitro group, a halogen atom, a cyano group, or an alkyl group, R 10a and R 11a each 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. [ka] (In formula (b1), R 1b represents a hydrogen atom, a nitro group, or a monovalent organic group, R 2b and R 3b each 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 2b and R 3b may be bonded to each other to form a ring, R 4b represents a monovalent organic group, R 5b represents a hydrogen atom, an alkyl group having from 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, p is an integer between 0 and 4, q is 0 or 1.

[0014] A second aspect of the present invention is a cured film comprising a cured product of the negative photosensitive resin composition according to the first aspect.

[0015] A third aspect of the present invention is a method for producing a photosensitive resin composition according to the first aspect, comprising the steps of: applying the negative type photosensitive resin composition according to the first aspect onto a substrate to form a coating film; and exposing the coating film to light. Effect of the Invention

[0016] According to the present invention, it is possible to provide a negative type photosensitive resin composition capable of forming a cured film having high solvent resistance, a cured film made of a cured product of the negative type photosensitive resin composition, and a method for producing a cured film using the negative type photosensitive resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The present invention will be described in detail below. <Negative photosensitive resin composition> The negative photosensitive resin composition contains a resin (A) having a structural unit represented by the following formula (a1), and a photopolymerization initiator (B) represented by the following 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.

[0018] Hereinafter, essential and optional components contained in the negative photosensitive resin composition and a method for producing the negative photosensitive resin composition will be described.

[0019] <Resin (A) (binder resin)> The resin (A) has a structural unit represented by the following formula (a1). [ka] (In formula (a1), R 1a and R 2a each independently represents an alkyl group having 1 to 20 carbon atoms which may contain a heteroatom, an aryl group having 6 to 20 carbon atoms which may contain a heteroatom, -R 4a S.R. 5a or -R 6a C(=O)R 7a represents R 3a represents a tetravalent aromatic or alicyclic hydrocarbon group having from 1 to 20 carbon atoms and optionally containing a heteroatom, 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 4a represents a single bond, an alkylene group having from 1 to 10 carbon atoms, or an arylene group having from 6 to 15 carbon atoms, S represents a sulfur atom, R 5a represents an alkyl group having from 1 to 10 carbon atoms, or an aryl group having from 6 to 15 carbon atoms, R 6a represents a single bond, an alkylene group having from 1 to 10 carbon atoms, or an arylene group having from 6 to 10 carbon atoms, R 7a represents 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. [ka] (In formula (a2), R 8a and R 9a each independently represents a hydrogen atom, a hydroxy group, a mercapto group, an amino group, a nitro group, a halogen atom, a cyano group, or an alkyl group, R 10a and R 11a each 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.

[0020] As can be seen from the structure of the above formula (a2), the resin (A) has a bisphenylfluorene structure as a basic structure in its constituent units.

[0021] In formula (a1), heteroatom means an element other than carbon atom and hydrogen atom. Examples of heteroatom include oxygen atom, nitrogen atom, sulfur atom, halogen atom, and silicon atom. These heteroatoms may be contained in a plurality of numbers. The heteroatom is preferably a sulfur atom, and in this case, it has particularly excellent effects on heat resistance, chemical resistance, high transmittance, high refraction, and optical properties.

[0022] In formula (a1), R 1a and R 2a The number of carbon atoms in the alkyl group which may contain a heteroatom as the heteroatom is from 1 to 20, preferably from 2 to 15, and more preferably from 2 to 10. Specific examples of the alkyl group which may contain a heteroatom 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, and an n-decyl group. R 1a and R 2a The number of carbon atoms in the aryl group which may contain a heteroatom as the heteroatom is 6 or more and 20 or less, preferably 6 or more and 15 or less, and more preferably 6 or more and 10 or less. Specific examples of the aryl group which may contain a heteroatom include a phenyl group, a naphthyl group, a furyl group, and a thienyl group.

[0023] R 4a Specific examples of the alkylene group having 1 to 10 carbon atoms as the alkylene group include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group. R 4a Specific examples of the arylene group having 6 to 15 carbon atoms as the aryl group include a phenylene group and a naphthylene group. R 5a Specific examples of the alkyl group having 1 to 10 carbon atoms as the alkyl group 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, and an n-decyl group. R 5a Specific examples of the aryl group having 6 to 15 carbon atoms as the aryl group include a phenyl group and a naphthyl group. R 1a and R 2a But -R 4a S.R. 5aIn this case, it is particularly effective in terms of heat resistance, high transmittance and high refractive index.

[0024] R 6a Specific examples of the alkylene group having 1 to 10 carbon atoms as R 4a Examples of the alkylene groups include the same alkylene groups as those exemplified for the above. R 6a Specific examples of the arylene group having 6 to 10 carbon atoms as R 4a The arylene groups mentioned above as examples of the arylene groups are also included. R 7a Specific examples of the alkyl group having 1 to 10 carbon atoms as R 5a Examples of the alkyl group include the same alkyl groups as those exemplified for the alkyl group. R 7a Specific examples of the aryl group having 6 to 15 carbon atoms as R 5a The aryl groups include the same groups as those exemplified for the aryl groups. R 7a Specific examples of the alkenyl group having 1 to 10 carbon atoms as the alkyl group include a vinyl group and an allyl group.

[0025] R 3a The number of carbon atoms in the tetravalent alicyclic hydrocarbon group which may contain a heteroatom as the substituent is 1 or more and 20 or less, preferably 4 or more and 10 or less, and more preferably 4 or more and 6 or less. R 3a The tetravalent aromatic hydrocarbon group which may contain a heteroatom as the aromatic ring has 1 or more and 20 or less carbon atoms, preferably 6 or more and 15 or less, and more preferably 6 or more and 12 or less carbon atoms. Such an R 3a The structure having the above structure has excellent effects on heat resistance, high transmittance and high refractive index. R 3a Specific examples of the group include tetravalent groups derived from tetracarboxylic dianhydrides described below.

[0026] j1 and j2 each independently represent an integer of 1 or more and 6 or less, preferably an integer of 1 or more and 3 or less, and more preferably an integer of 1 or more and 2 or less.

[0027] In formula (a2), R 8a and R 9a are each independently a hydrogen atom, a hydroxyl group (-OH), a mercapto group (-SH), an amino group (-NH2), a nitro group (-NO2), a halogen atom, a cyano group, or an alkyl group. R 8a and R 9a Specific examples of the halogen atom as include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. R 8a and R 9a The alkyl group as R is, for example, an alkyl group having 1 to 10 carbon atoms. 5a Examples of the alkyl group include the same alkyl groups as those exemplified for the alkyl group. R 8a and R 9a is preferably a hydrogen atom.

[0028] R 10a and R 11a The alkyl group represented by R is, for example, an alkyl group having 1 to 10 carbon atoms. 5a Examples of the alkyl group include the same alkyl groups as those exemplified for the alkyl group. R 10a and R 11a The aryl group as R is, for example, an aryl group having 6 to 15 carbon atoms. 5a The aryl groups include the same groups as those exemplified for the aryl groups.

[0029] k1 and k2 each independently represent an integer of 0 or more and 4 or less, and preferably an integer of 0 or more and 2 or less. m1 and m2 each independently represent an integer of 0 or more and 3 or less, and preferably an integer of 1 or more and 2 or less.

[0030] The number of structural units represented by formula (a1) contained in resin (A) is not particularly limited. The number of structural units represented by formula (a1) contained in resin (A) is, for example, an integer of 1 to 30, preferably an integer of 1 to 10. Within this range, the properties of heat resistance, high transmittance, and high refraction are particularly excellent.

[0031] The mass average molecular weight of the resin (A) may be, for example, 1,000 to 100,000 g / mol, preferably 2,000 to 50,000 g / mol, and more preferably 3,000 to 10,000 g / mol. Within this range, the resin has excellent heat resistance, and the developing speed of the photosensitive material and the developing solution are easy, which makes it easy to form a pattern and shows a high residual film rate.

[0032] The dispersity of the resin (A) (mass average molecular weight Mw / number average molecular weight Mn) may be, for example, in the range of 1.0 to 5.0, preferably in the range of 1.5 to 4.0. Within this range, the resin has excellent heat resistance, and the developing speed of the photosensitive material and the development with a developer are easy, which makes it easy to form a pattern and shows a high residual film rate.

[0033] In this specification, the mass average molecular weight, number average molecular weight, and dispersity can be measured by gel permeation chromatography (GPC).

[0034] By preparing a negative photosensitive resin composition containing such a specific resin (A) together with a specific photopolymerization initiator (B) described later in detail, a cured film having high solvent resistance can be formed as shown in the examples described later. In addition, a negative photosensitive resin composition having excellent resolution can be obtained. In addition, since a resin having a high refractive index or a resin having high functionality such as heat resistance, chemical resistance, and high transmittance can be selected as the resin (A), the negative photosensitive resin composition containing the resin (A) can form a cured film having a high refractive index or a cured film having high functionality such as heat resistance, chemical resistance, and high transmittance.

[0035] The resin (A) can be produced, for example, by the method described in Patent Document 4. Specifically, the resin (A) can be synthesized by synthesizing a compound (monomer) containing a hydroxy group represented by the following formula (2) from a compound represented by the following formula (1), and then polymerizing the resulting compound with a tetracarboxylic dianhydride. [ka] (In formula (1), R 8a ~R 11a , k1, k2, m1, and m2 are R in formula (a2), 8a ~R 11a , k1, k2, m1 and m2, and R 12a and R 13a each independently represents a hydroxyl group, a thiol group, an amino group, a nitro group, a cyano group, an aliphatic alkyl group or an alicyclic alkyl group containing a heteroatom and having from 1 to 20 carbon atoms, or an aryl group containing a heteroatom and having from 6 to 20 carbon atoms. [ka] (In formula (2), R 8a ~R 11a , k1, k2, m1, and m2 are R in formula (a2), 8a ~R 11a , k1, k2, m1 and m2, and R 1a , R 2a , j1 and j2 are R in formula (a1), 1a , R 2a , j1 and j2 are the same.)

[0036] In formula (1), the heteroatom refers to an element other than carbon and hydrogen atoms. Examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, and a silicon atom. A plurality of these heteroatoms may be included. For example, R 12a and R 13a may contain heteroatoms in the form of hydroxy, thiol, amino, nitro or cyano groups.

[0037] R 12a and R13a The number of carbon atoms in the aliphatic alkyl group or alicyclic alkyl group containing a hetero atom as the hetero atom is from 1 to 20, preferably from 1 to 10, more preferably from 3 to 8, and particularly preferably from 3 to 5. Specific examples of the aliphatic alkyl group or alicyclic alkyl group containing a hetero atom include a hydroxyalkyl group or a thioalkyl group having from 1 to 5 carbon atoms. R 12a and R 13a The number of carbon atoms in the aryl group containing a heteroatom as the hetero atom is 6 or more and 20 or less, preferably 6 or more and 15 or less, more preferably 6 or more and 10 or less, and particularly preferably 7 or more and 10 or less. R 12a and R 13a is preferably a hydroxy group.

[0038] The tetracarboxylic dianhydride may be one represented by the following formula (3).

[0039] [ka] (In formula (3), R 3a is R in formula (a1). 3a is equivalent to.)

[0040] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl) 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl) ) ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, or alicyclic tetracarboxylic dianhydrides such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and 1,2,3,4-cyclohexanetetracarboxylic dianhydride, or 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride.

[0041] The polymerization reaction can be carried out, for example, at 100 to 130° C., or 110 to 120° C. for 2 to 24 hours, or 4 to 12 hours.

[0042] The tetracarboxylic dianhydride may be used in an amount of, for example, 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 compound containing a hydroxy group represented by the above formula (2).

[0043] In the production of the resin (A), for example, after the initiation of the above-mentioned polymerization reaction, a terminal blocking agent may be added and reacted. The terminal blocking agent makes it easy to control the mass average molecular weight of the resin (A). This reaction with the end-capping agent (end-capping reaction) can be carried out, for example, at 100 to 130° C., or 110 to 120° C. for 30 minutes to 4 hours, or 1 to 3 hours.

[0044] The terminal blocking 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 compound containing a hydroxy group represented by the above formula (2).

[0045] The end-capping agent includes an organic acid, an organic acid anhydride, and an amide acid. The end-capping agent is preferably an aromatic carboxylic anhydride, and a specific example thereof is phthalic anhydride. By using an aromatic carboxylic anhydride as the end-capping agent, the resin (A) has particularly excellent effects in terms of heat resistance, high transmittance, and high refractive index.

[0046] When a terminal blocking agent is used, the terminal structure of the resin (A) may be a structure derived from the terminal blocking agent. Furthermore, the terminal structure of the resin (A) may be a structure derived from a raw material added in excess, such as the compound containing a hydroxy group represented by the above formula (2) or a tetracarboxylic dianhydride. More specifically, the terminal structure of the resin (A) may be, for example, the following Structure 1 to Structure 4, and the mass average molecular weight of the resin (A) can be appropriately controlled. The multiple terminal structures in the molecular chain of the resin constituting the resin (A) may be different from each other. The following OX in Structure 4 is a group generated by reacting the hydroxyl group in Structure 3 with the above-mentioned end-capping agent. Among the following end structures, Structure 4 is preferred in terms of development characteristics. As Structure 4, a structure having OX derived from an organic acid anhydride such as a dicarboxylic acid anhydride such as phthalic anhydride or tetrahydrophthalic anhydride is preferred. Structure 1: A structure in which a hydrogen atom is bonded to the carbonyloxy group at the left end of the structure represented by formula (a1). Structure 2: Structure 1 in which two of the carboxy groups have been replaced with carboxylic anhydride groups Structure 3:-CHR 2a -(CH2) j2 -OAO-(CH2) j1 -CH(OH)-R 1a The structure represented by Structure 4:-CHR 2a -(CH2) j2 -OAO-(CH2) j1 -CH(OX)-R 1a The structure represented by

[0047] <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 refers to a component that generates active species capable of initiating polymerization of the above-mentioned resin (A) by visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray, or the like. [ka] (In formula (b1), R 1b represents a hydrogen atom, a nitro group, or a monovalent organic group, R 2b and R 3b each 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 2b and R 3b may be bonded to each other to form a ring, R 4b represents a monovalent organic group, R 5brepresents a hydrogen atom, an alkyl group having from 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent, p is an integer between 0 and 4, q is 0 or 1.

[0048] In formula (b1), R 1b R is a hydrogen atom, a nitro group, or a monovalent organic group. 1b is -(CO) on the fluorene ring in formula (b1). q In formula (b1), R is bonded to a different 6-membered aromatic ring from the 6-membered aromatic ring bonded to the group represented by -. 1b The bonding position of the compound represented by formula (b1) to the fluorene ring is not particularly limited. 1b In the case where R is 1 or more, the compound represented by formula (b1) can be easily synthesized. 1b Preferably, one of R is bonded to the 2-position of the fluorene ring. 1b If there are multiple, there are multiple R 1b may be the same or different.

[0049] R 1b When R is an organic group, 1b R is not particularly limited as long as it does not impair the object of the present invention, and can be appropriately selected from various organic groups. 1bPreferred examples of the organic group include an 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 naphthoxy group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group substituted with one or two organic groups, a morpholin-1-yl group, and a piperazin-1-yl group.

[0050] R 1b When R is an alkyl group, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms. 1b When R is an alkyl group, it may be a straight chain or a branched chain. 1b Specific examples of when R is an alkyl group 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 isopentyl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, an n-decyl group, and an isodecyl group. 1b When is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of alkyl groups having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

[0051] R 1bWhen R is an alkoxy group, the alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms. 1b When R is an alkoxy group, it may be a straight chain or a branched chain. 1b Specific examples of when R is an alkoxy group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an isooctyloxy group, a sec-octyloxy group, a tert-octyloxy group, an n-nonyloxy group, an isononyloxy group, an n-decyloxy group, and an isodecyloxy group. 1b When is an alkoxy group, the alkoxy group may contain an ether bond (-O-) in the carbon chain. Examples of alkoxy groups having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

[0052] R 1b When R is a cycloalkyl group or a cycloalkoxy group, the cycloalkyl group or the cycloalkoxy group preferably has 3 to 10 carbon atoms, and more preferably has 3 to 6 carbon atoms. 1b Specific examples of R are cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. 1b Specific examples of when is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

[0053] R 1bWhen R is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the saturated aliphatic acyl group or the saturated aliphatic acyloxy group preferably has 2 to 21 carbon atoms, and more preferably has 2 to 7 carbon atoms. 1b Specific examples of R being a saturated aliphatic acyl group include an acetyl group, a propanoyl group, a n-butanoyl group, a 2-methylpropanoyl group, a n-pentanoyl group, a 2,2-dimethylpropanoyl group, a n-hexanoyl group, a n-heptanoyl group, a n-octanoyl group, a n-nonanoyl group, a n-decanoyl group, a n-undecanoyl group, a n-dodecanoyl group, a n-tridecanoyl group, a n-tetradecanoyl group, a n-pentadecanoyl group, and a n-hexadecanoyl group. 1b Specific examples of when is a saturated aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, a n-butanoyloxy group, a 2-methylpropanoyloxy group, a n-pentanoyloxy group, a 2,2-dimethylpropanoyloxy 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.

[0054] R 1b When R is an alkoxycarbonyl group, the alkoxycarbonyl group preferably has 2 to 20 carbon atoms, and more preferably has 2 to 7 carbon atoms. 1bSpecific examples of when is an alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, a sec-butyloxycarbonyl group, a tert-butyloxycarbonyl group, an n-pentyloxycarbonyl group, an isopentyloxycarbonyl group, a sec-pentyloxycarbonyl group, a tert-pentyloxycarbonyl group, an n-hexyloxycarbonyl group, an n-heptyloxycarbonyl group, an n-octyloxycarbonyl group, an isooctyloxycarbonyl group, a sec-octyloxycarbonyl group, a tert-octyloxycarbonyl group, an n-nonyloxycarbonyl group, an isononyloxycarbonyl group, an n-decyloxycarbonyl group, and an isodecyloxycarbonyl group.

[0055] R 1b When R is a phenylalkyl group, the phenylalkyl group preferably has 7 to 20 carbon atoms, more preferably 7 to 10 carbon atoms. 1b When R is a naphthylalkyl group, the naphthylalkyl group preferably has 11 to 20 carbon atoms, and more preferably has 11 to 14 carbon atoms. 1b Specific examples of R being a phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group. 1b Specific examples of R are naphthylalkyl groups include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl. 1b is a phenylalkyl group or a naphthylalkyl group, R 1b may further have a substituent on the phenyl group or naphthyl group.

[0056] R 1bis a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more N, S, or O, or a heterocyclyl group in which such monocyclic rings are fused to each other or to a benzene ring. When the heterocyclyl group is a fused ring, the number of fused rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of the heterocyclic ring constituting such a heterocyclyl 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 tetrahydrofuran. 1b When is a heterocyclyl group, the heterocyclyl group may further bear a substituent.

[0057] R 1b When is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is R 1b is a heterocyclyl group.

[0058] R 1b When R is an amino group substituted with one or two organic groups, suitable 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 naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl group. Specific examples of these suitable organic groups are 1bSpecific examples of the amino group substituted with the organic group 1 or 2 include a methylamino group, an ethylamino group, a diethylamino group, a n-propylamino group, a di-n-propylamino group, an isopropylamino group, a n-butylamino group, a di-n-butylamino group, a n-pentylamino group, a n-hexylamino group, a n-heptylamino group, a n-octylamino group, a n-nonylamino group, a n-decylamino group, a phenylamino group, a naphthylamino group, an acetylamino group, a propanoylamino group, a n-butanoylamino group, a n-pentanoylamino group, a n-hexanoylamino group, a n-heptanoylamino group, a n-octanoylamino group, a n-decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

[0059] R 1b In the case where the phenyl group, naphthyl group, and heterocyclyl group contained in R further have a substituent, examples of the 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, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group. 1b When the phenyl group, naphthyl group, and heterocyclyl group contained in R further have a substituent, the number of the substituents is not limited within a range that does not impair the object of the present invention, but is preferably 1 to 4. 1b When the phenyl group, naphthyl group, and heterocyclyl group contained in the formula (I) have multiple substituents, the multiple substituents may be the same or different.

[0060] Among the groups described above, R 1b As the group, a nitro group or R 6b A group represented by -CO- is preferred. 6b R is not particularly limited as long as it does not impair the object of the present invention, and can be selected from various organic groups.6b Examples of suitable groups for R include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclyl group which may have a substituent. 6b Among these groups, a 2-methylphenyl group, a thiophen-2-yl group, and an α-naphthyl group are particularly preferred. In addition, R tends to have good transparency. 1b is preferably a hydrogen atom. 1b is a hydrogen atom and R 4b When is a group represented by the formula (R4-2) described later, the transparency tends to be better.

[0061] In formula (b1), R 2b and R 3b R each represents a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. 2b and R 3b may be bonded to each other to form a ring. 2b and R 3b As R, a chain alkyl group which may have a substituent is preferable. 2b and R 3b When is a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

[0062] R 2b and R 3b When R is a chain alkyl group having no substituent, the chain alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms. 2b and R 3bSpecific examples of R being a 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. 2b and R 3b When is an alkyl group, the alkyl group may contain an ether bond (-O-) in the carbon chain. Examples of alkyl groups having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

[0063] R 2b and R 3b When is 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 in the substituent is not included in the number of carbon atoms in the chain alkyl group. The chain alkyl group having a substituent is preferably linear. The substituent that the alkyl group may have is not particularly limited as long as it does not impair the object of the present invention. Suitable 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 these, a fluorine atom, a chlorine atom, and a bromine atom are preferred. Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group. Specific examples of the cycloalkyl group include R 1b The preferred examples are the same as those when R is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group. Specific examples of the heterocyclyl group include R 1b The preferred examples are the same as those when R is a heterocyclyl group. 1bWhen is 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 in the alkoxy group contained in the alkoxycarbonyl group is preferably 1 to 10, and more preferably 1 to 6.

[0064] When the chain alkyl group has a substituent, the number of the substituent is not particularly limited. The number of the preferred substituent varies depending on the number of carbon atoms of the chain alkyl group. The number of the substituent is typically 1 to 20, preferably 1 to 10, and more preferably 1 to 6.

[0065] R 2b and R 3b When R is 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 heterocyclyl group. 2b and R 3b When R is a cyclic organic group, the substituent that the cyclic organic group may have is R 2b and R 3b is a chain alkyl group.

[0066] R 2b and R 3b is an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by bonding multiple benzene rings via carbon-carbon bonds, or a group formed by condensing multiple benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensing multiple benzene rings, the number of rings of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited, and is preferably 3 or less, more preferably 2 or less, and particularly preferably 1. Specific examples of preferred aromatic hydrocarbon groups include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

[0067] R 2b and R 3bWhen is an aliphatic cyclic hydrocarbon group, the aliphatic cyclic 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, a tetracyclododecyl group, and an adamantyl group.

[0068] R 2b and R 3b is a heterocyclyl group, the heterocyclyl group is a 5- or 6-membered monocyclic ring containing one or more N, S, or O, or a heterocyclyl group in which such monocyclic rings are fused to each other or to a benzene ring. When the heterocyclyl group is a fused ring, the number of fused rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. Examples of heterocycles constituting such heterocyclyl groups 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 tetrahydrofuran.

[0069] R 2b and R 3b may be bonded to each other to form a ring. 2b and R 3b The ring formed by R is preferably a cycloalkylidene group. 2b and R 3bWhen these are bonded to form a cycloalkylidene group, the ring that constitutes the cycloalkylidene group is preferably a 5-membered ring or a 6-membered ring, and more preferably a 5-membered ring.

[0070] R 2b and R 3b When the group formed by bonding with is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring that may be condensed with the cycloalkylidene 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, and a pyrimidine ring.

[0071] The above-mentioned R 2b and R 3b Among these, preferred examples of groups include those of formula -A 1 -A 2 In the formula, A 1 is a straight chain alkylene group, and A 2 is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

[0072] A 1 The linear alkylene group preferably has 1 to 10 carbon atoms, and more preferably has 1 to 6 carbon atoms. 2 When A is an alkoxy group, the alkoxy group may be linear or branched, and is preferably linear. The number of carbon atoms in the alkoxy group is preferably 1 to 10, and more preferably 1 to 6. 2 When A is a halogen atom, it 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. 2 When A is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl 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 halogenated alkyl group may be linear or branched, and is preferably linear. 2 When is a cyclic organic group, examples of the cyclic organic group include R2b and R 3b The same applies to the cyclic organic group that A has as a substituent. 2 When is an alkoxycarbonyl group, examples of the alkoxycarbonyl group include R 2b and R 3b The alkoxycarbonyl group represented by the formula (I) is the same as the alkoxycarbonyl group represented by the formula (I) as a substituent.

[0073] R 2b and R 3bPreferred specific examples of the aryl group include alkyl groups such as an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group; a 2-methoxyethyl group, a 3-methoxy-n-propyl group, a 4-methoxy-n-butyl group, a 5-methoxy-n-pentyl group, a 6-methoxy-n-hexyl group, a 7-methoxy-n-heptyl group, an 8-methoxy-n-octyl group, a 2-ethoxyethyl group, a 3-ethoxy-n-propyl group, alkoxyalkyl groups such as 2-cyanoethyl, 3-cyano-n-propyl, 4-cyano-n-butyl, 5-ethoxy-n-pentyl, 6-ethoxy-n-hexyl, 7-ethoxy-n-heptyl, and 8-ethoxy-n-octyl groups; 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 groups; 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 groups; phenylalkyl groups such as 2-cyclohexylethyl, 3-cyclohexyl-n-propyl, 4-cyclohexyl-n-butyl, 5-cyclohexyl-n-pentyl, 6- cycloalkylalkyl groups such as 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;2-Methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycarbonyl-n-heptyl group, and 8-ethoxycarbonyl-n-octyl group. alkoxycarbonylalkyl groups such as 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-heptafluoro-n-pentyl group; halogenated alkyl groups such as 2-chloroethyl group, 3-bromo-n-propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-heptafluoro-n-pentyl group;

[0074] R 2b and R 3b Among the above, preferred groups are an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, a 2-methoxyethyl group, a 2-cyanoethyl group, a 2-phenylethyl group, a 2-cyclohexylethyl group, a 2-methoxycarbonylethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 3,3,3-trifluoropropyl group, and a 3,3,4,4,5,5,5-heptafluoro-n-pentyl group.

[0075] R 4b Examples of suitable organic groups include R 1bSimilarly, alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, phenyl groups which may have a substituent, phenoxy groups which may have a substituent, benzoyl groups which may have a substituent, phenoxycarbonyl groups which may have a substituent, benzoyloxy groups which may have a substituent, phenylalkyl groups which may have a substituent, naphthyl groups which may have a substituent, naphthoxy groups which may have a substituent, naphthoyl groups which may have a substituent, naphthoxycarbonyl groups which may have a substituent, naphthoyloxy groups which may have a substituent, naphthylalkyl groups which may have a substituent, heterocyclyl groups which may have a substituent, heterocyclylcarbonyl groups which may have a substituent, amino groups substituted with one or two organic groups, morpholin-1-yl groups, and piperazin-1-yl groups. Specific examples of these groups include R 1b The same as that explained for R 4b As the substituent, a cycloalkylalkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring are also preferred. The substituent that the phenoxyalkyl group and the phenylthioalkyl group may have is R 1b The substituents are the same as those that the phenyl group contained in the above may have.

[0076] Among the organic groups, R 4bAs the alkyl group, an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, a cycloalkylalkyl group, or a phenylthioalkyl group which may have a substituent on the aromatic ring is preferred. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, an alkyl group having 1 to 4 carbon atoms is particularly preferred, and a methyl group is most preferred. Among the phenyl groups which may have a substituent, a methylphenyl group is preferred, and a 2-methylphenyl group is more preferred. The number of carbon atoms of the cycloalkylalkyl 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 preferably 1 to 8, more preferably 1 to 4, and particularly preferably 2. Among the cycloalkylalkyl groups, a cyclopentylethyl group 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 phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2-(4-chlorophenylthio)ethyl group is preferred.

[0077] Also, R 4b As for -A 3 -CO-OA 4 A group represented by the formula: 3 is a divalent organic group, preferably a divalent hydrocarbon group, and more preferably an alkylene group. 4 is a monovalent organic group, preferably a monovalent hydrocarbon group.

[0078] A 3 When A is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. 3 When is an alkylene group, the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

[0079] A 4Suitable examples of A 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. 4 Preferred specific examples of the alkyl group 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, a phenyl group, a naphthyl group, a benzyl group, a phenethyl group, an α-naphthylmethyl group, and a β-naphthylmethyl group.

[0080] -A 3 -CO-OA 4 Preferred specific examples of the group represented by the formula (I) include a 2-methoxycarbonylethyl group, a 2-ethoxycarbonylethyl group, a 2-n-propyloxycarbonylethyl group, a 2-n-butyloxycarbonylethyl group, a 2-n-pentyloxycarbonylethyl group, a 2-n-hexyloxycarbonylethyl group, a 2-benzyloxycarbonylethyl group, a 2-phenoxycarbonylethyl group, a 3-methoxycarbonyl-n-propyl group, a 3-ethoxycarbonyl-n-propyl group, a 3-n-propyloxycarbonyl-n-propyl group, a 3-n-butyloxycarbonyl-n-propyl group, a 3-n-pentyloxycarbonyl-n-propyl group, a 3-n-hexyloxycarbonyl-n-propyl group, a 3-benzyloxycarbonyl-n-propyl group, and a 3-phenoxycarbonyl-n-propyl group.

[0081] That's all, R 4b I explained about R 4b is preferably a group represented by the following formula (R4-1) or (R4-2). [ka] (In the formulas (R4-1) and (R4-2), R 7b and R 8b are each an organic group, r is an integer of 0 to 4, and R 7b and R 8b When R is located at adjacent positions on the benzene ring, 7b and R 8band may 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 9b is an organic group.)

[0082] R in formula (R4-1) 7b and R 8b Examples of organic groups for are R 1b Same as R 7b R is preferably an alkyl group or a phenyl group. 7b When R is an alkyl group, the number of carbon atoms therein is preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. That is, R 7b Most preferably, R is a methyl group. 7b and R 8b When R is bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. 7b and R 8b Suitable examples of the group in which and form a ring include a naphthalene-1-yl group, a 1,2,3,4-tetrahydronaphthalene-5-yl group, etc. In the above formula (R4-1), r is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

[0083] In the above formula (R4-2), R 9b is an organic group. The organic group is R 1b Examples of the organic group include the same groups as those described for the organic group. Among the organic groups, an alkyl group is preferable. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. R 9b Preferred examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, and among these, a methyl group is more preferred.

[0084] In the above 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 above formula (R4-2), u is 0 to (t+3), preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0. In the above 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.

[0085] In formula (b1), R 5b R is 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. 5b When R is an alkyl group, the substituent that it may have is preferably a phenyl group, a naphthyl group, etc. 5b When is an aryl group, preferred examples of the substituent that may be substituted include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

[0086] In formula (b1), R 5b Preferred examples of the alkyl group include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, and a naphthyl group, and among these, a methyl group or a phenyl group is more preferred.

[0087] 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 further preferably 0.5 to 10 parts by mass, per 100 parts by mass of the total solid content of the negative photosensitive resin composition. The content of the photopolymerization initiator (B) is preferably 0.1 to 50 mass%, more preferably 0.5 to 30 mass%, and even more preferably 0.5 to 10 mass%, based on the total of the resin (A) and the photopolymerization initiator (B).

[0088] The photopolymerization initiator (B) represented by formula (b1) may be used alone or in combination of two or more. When two or more types are used, the following (i) to (iii) are preferred. (i)R 1b Compounds where R is a hydrogen atom1b Combination with a compound in which is a nitro group (ii)R 4b A compound represented by the formula (R4-1) and R 4b A combination with a compound represented by formula (R4-2) (iii)R 4b is a compound represented by the formula (R4-1) or (R4-2) 4b is an alkyl group having 1 to 4 carbon atoms Among these, in terms of improving properties such as sensitivity and transmittance of the cured product, the combination of (i) above is preferred, and a combination that satisfies the above (i) and either (ii) or (iii) is more preferred.

[0089] The compounding ratio (mass ratio) of each compound in the combinations (i) to (iii) above may be appropriately adjusted according to the desired characteristics such as sensitivity, etc. For example, it is preferably 1:99 to 99:1, more preferably 10:90 to 90:10, and even more preferably 30:70 to 70:30.

[0090] Preferable specific examples of the compound represented by formula (b1) include the following compounds 1 to 41. [ka]

[0091] [ka]

[0092] 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 other than the photopolymerization initiator (B), biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, phosphine compounds, and triazine compounds.

[0093] Examples of oxime ester compounds other than the photopolymerization initiator (B) include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(0-acetyloxime) and 1,3-octanedione-1[(4-phenylthio)phenyl]2-benzoyl-oxime.

[0094] Examples of the acetophenone-based compounds include α-hydroxyketone-based compounds, α-aminoketone-based compounds, and other compounds.

[0095] Specific examples of α-hydroxyketone compounds include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and 1-hydroxycyclohexylphenyl ketone. Specific examples of α-aminoketone compounds include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1. Specific examples of compounds other than these include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, and 2,2-dimethoxy-2-phenylacetophenone. These acetophenone compounds can be used alone or in combination of two or more. By using these acetophenone compounds, the strength of the thin film can be further improved.

[0096] Specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole. Examples of such aryl-1,2'-biimidazole include 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

[0097] Among the above biimidazole compounds, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and the like are preferred, with 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole being particularly preferred.

[0098] <Adhesion enhancer (C)> The adhesion enhancer (C) is a component having the effect of improving the adhesive strength with the substrate, and is preferably a silane coupling agent having a reactive functional group such as a carboxyl group, a (meth)acryloyl group, a vinyl group, an isocyanate group, an epoxy group, a mercapto group, etc. Specifically, it is one or more selected from the group consisting of trimethoxysilylbenzoic acid, 3-((meth)acryloyloxy)propyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, (3-isocyanatopropyl)triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. In this specification, "(meth)acryloyl" means both "acryloyl" and "methacryloyl". Furthermore, "(meth)acrylate" means both "acrylate" and "methacrylate", and "(meth)acrylic" means both "acrylic" and "methacrylic".

[0099] The adhesion enhancer (C) includes, although it overlaps with the above-mentioned silane coupling agent, isocyanate-based compounds, epoxy-based compounds, (meth)acrylate-based compounds, vinyl compounds, and mercapto-based compounds, and is more preferably an epoxy-based compound. The epoxy-based compound includes, for example, an organic silane compound having an epoxy group, and a more specific example includes an alkoxysilane having an epoxy group and having 1 to 5 carbon atoms.

[0100] 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). Within this range, excellent adhesive strength to the substrate is obtained.

[0101] <Photopolymerizable compound (D)> The negative photosensitive resin composition may or may not contain a photopolymerizable compound (D). The photopolymerizable compound (D) is not particularly limited, but examples thereof include crosslinkable compounds having an ethylenically unsaturated bond. The crosslinkable compound having an ethylenically unsaturated bond is generally a crosslinkable unit having at least two or more ethylenic double bonds, such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, etc. multifunctional (meth)acrylic monomers and oligomers such as tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, cardo epoxy diacrylate and their poly(poly-)compounds (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; polyurethane(meth)acrylate obtained by reacting a compound having a polyol group and two isocyanate groups with the resulting mixture and then reacting with (meth)acrylic acid; Examples of epoxy (meth)acrylate resins include those obtained by reacting 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, polyol polyglycidyl esters, aliphatic or alicyclic epoxy resins, amine epoxy resins, and dihydroxybenzene type epoxy resins with (meth)acrylic acid. In consideration of exposure sensitivity and the like, it is preferable to use a polyfunctional (meth)acrylic monomer as the photopolymerizable compound (D).

[0102] When a photopolymerizable compound (D) is contained, the photopolymerizable compound (D) is contained in an amount of preferably 0.1 to 200 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 5 to 10 parts by mass, per 100 parts by mass of the resin (A).

[0103] <Solvent (S)> Examples of the solvent (S) include organic solvents and water. The organic solvent is not particularly limited as long as it is an organic solvent such as acetate, ether, glycol, ketone, alcohol, and carbonate used in general negative photosensitive resin compositions and dissolves 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,N-dimethylacetamide, N-methylpyrrolidone (NMP), and N-methylcaprolactam.

[0104] 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 using a conventional coating method, and a thin film of a desired thickness can be easily obtained after coating.

[0105] <Other ingredients> The negative photosensitive resin composition may contain additives as required. Examples of such additives include stabilizers, thermal crosslinking agents, photocuring accelerators, surfactants, base quenchers, antioxidants, adhesion aids, and defoamers, which may be used alone or in combination as required.

[0106] The surfactant is a component that has the effect of improving the coating property and application property, uniformity, and dirt removal on the substrate. Examples of the surfactant include fluorine-based surfactants, silicon-based surfactants, and nonionic surfactants, and preferably silicon-based surfactants. Examples of the silicon-based surfactant include polyether-modified polysiloxane, and a more specific example is polyether-modified polydimethylsiloxane.

[0107] 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).

[0108] Examples of the stabilizer include a heat stabilizer and a light stabilizer.

[0109] The heat stabilizer can be a heat stabilizer that can be generally used in negative photosensitive resin compositions, and is not particularly limited. For example, a heat stabilizer that can suppress the decrease in transmittance during the post-heat treatment process of the cured product (organic film) formed and increase the transmittance of the remaining organic film can be used. Examples of the heat stabilizer include phenol-based heat stabilizers, phosphite-based heat stabilizers, and lactone-based heat stabilizers. Examples of preferred heat stabilizers include compounds represented by the following formulas (4) to (6).

[0110] [ka]

[0111] [ka]

[0112] [ka]

[0113] The light stabilizer may be any light stabilizer that can be generally used in negative photosensitive resin compositions, and examples of the light stabilizer include those that can maximize the light resistance of the cured product (e.g., organic insulating film) that is formed. Examples of the light stabilizer include benzotriazole-based light stabilizers, triazine-based light stabilizers, benzophenone-based light stabilizers, hindered aminoether-based light stabilizers, and hindered amine-based light stabilizers.

[0114] <<Method for producing negative photosensitive resin composition>> The negative photosensitive resin composition can be produced by a general method, for example, by mixing the above-mentioned components and filtering the mixture using a filter as necessary.

[0115] <Cured film and method for producing the cured film> The negative photosensitive resin composition can be used to produce a cured film that can be used in displays such as TFT-LCD, OLED, touch screen panel, etc. The produced cured film may be patterned as necessary. A method for producing a cured film using the above negative photosensitive resin composition will be described below.

[0116] First, the negative photosensitive resin composition is applied onto a substrate to form a coating film. The substrate on which the coating film is formed is not particularly limited, and may be a conventionally known substrate, such as a silicon substrate, a glass substrate, or a substrate having a metal surface. The metal species constituting the metal surface is preferably copper, gold, or aluminum, and more preferably copper. In addition, the negative photosensitive resin composition can be used on a substrate having low heat resistance because the heating temperature can be lowered when forming a cured film. Examples of substrates having low heat resistance include substrates having flexibility (e.g., substrates having flexibility). Examples of flexible substrates include plastic substrates made of various plastic materials such as polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyimide; polycarbonate; polyamide; polyacetal; polyphenylene oxide; polyphenylene sulfide; polyether sulfone; polyether ether ketone; homopolymers of norbornene-based monomers (addition polymers, ring-opening polymers, etc.), copolymers of norbornene-based monomers and olefin-based monomers such as copolymers of norbornene and ethylene (cyclic olefin copolymers such as addition polymers and ring-opening polymers, etc.), and derivatives of these cyclic polyolefins; vinyl polymers (e.g., (meth)acrylic resins such as polymethyl methacrylate (PMMA), polystyrene, polyvinyl chloride, acrylonitrile-styrene-butadiene resin (ABS resin), etc.); vinylidene polymers (e.g., polyvinylidene chloride, etc.); cellulose resins such as triacetyl cellulose (TAC); epoxy resins; phenolic resins; melamine resins; urea resins; maleimide resins; and silicone.

[0117] The method for applying the negative photosensitive resin composition is not particularly limited, and any known method may be used, such as spin coating, dip coating, roll coating, screen coating, spray coating, flow coating, screen printing, inkjet, and drop casting.

[0118] The thickness of the coating film to be formed varies depending on the coating method, the solids concentration of the negative photosensitive resin composition, the viscosity, etc., and is not particularly limited, but it can usually be coated so that the film thickness after drying is 0.5 to 100 μm.

[0119] If necessary, the coating film may be dried by any method, including, but not limited to, a method of volatilizing the solvent by vacuum, infrared irradiation, or heating.

[0120] Next, the coating film is exposed to light. In the exposure step, the coating film is irradiated with energy rays such as excimer laser, far ultraviolet rays, ultraviolet rays, visible light rays, electron beams, X-rays, g-rays (wavelength 436 nm), i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), or a mixture of these rays. In the exposure, a contact type, proximity type, projection type, or other exposure method may be used. The amount of energy radiation to be irradiated varies depending on the composition of the negative photosensitive resin composition, but is, for example, 140 mJ / cm 2 or less, preferably 5 to 100 mJ / cm 2 , more preferably 10 to 60 mJ / cm 2 It is. By exposing the coating film to light, a curing reaction occurs and a cured product (cured film) is formed.

[0121] The exposure may be a position-selective exposure. The position-selective exposure is performed, for example, through a negative mask. By performing the position-selective exposure, a patterned cured film can be formed.

[0122] When the coating film is exposed position-selectively, the exposed coating film can be developed with a developer to obtain a cured film patterned in a desired shape. The developing method is not particularly limited, and for example, a dipping method, a spray method, or the like can be used. The developer is appropriately selected depending on the composition of the negative photosensitive resin composition. An alkaline aqueous solution may be used as the developer, which is more environmentally friendly and economical than organic solvents. Examples of the alkaline developer include aqueous solutions of quaternary ammonium hydroxide such as tetramethylammonium hydroxide (TMAH) and tetraethylammonium hydroxide, and aqueous solutions of amines such as ammonia, ethylamine, propylamine, diethylamine, and triethylamine.

[0123] The coating film after exposure may be heated (post-exposure bake (PEB) or post-baking). The heating temperature is not particularly limited, but is, for example, 80° C. to 250° C., preferably 80° C. to 200° C., more preferably 80° C. to 150° C., and even more preferably 85° C. to 100° C. When a substrate with low heat resistance is used, it is difficult to use a substrate with low heat resistance because heating at a high temperature may adversely affect the substrate, but it is possible to use a substrate with low heat resistance by heating at a low temperature. When the coating film is exposed to light in a position-selective manner, the above-mentioned heating (PEB) is preferably carried out after the step of exposing the coating film and before the step of developing it. When a substrate with high heat resistance is used, heating (post-baking) may be further performed at 80°C or higher and 250°C or lower after the development step following the PEB step, or after the development step following exposure without performing the PEB step.

[0124] The cured film (cured product) produced by the above-mentioned production method has high solvent resistance because it is formed using the above-mentioned negative photosensitive resin composition. The cured film formed using the above-mentioned negative photosensitive resin composition has high resistance to organic solvents such as propylene glycol monomethyl ether acetate (PEGMEA) and N-methylpyrrolidone (NMP). Therefore, it is suitable for use in applications in which a laminate material is produced by forming another layer on the above-mentioned cured film using a composition in which a resin or other component is dissolved in a solvent, or in applications in which an adhesive containing a solvent is applied.

[0125] In addition, since the negative photosensitive resin composition has excellent resolution, it is possible to produce a patterned cured film having a fine pattern. For example, it is possible to produce a patterned cured film having a fine pattern with a line width of 20 μm or less, preferably 10 μm or less.

[0126] In addition, by using the negative photosensitive resin composition containing the resin (A), it is possible to produce a cured film having a high refractive index and a cured film having high functionality such as heat resistance, chemical resistance, and high transparency. For example, a cured film having a high refractive index can be laminated with a low refractive index film to become a light extraction film having excellent light extraction efficiency. In addition, a cured film having excellent heat resistance can minimize taper angle and gas emission.

[0127] Such cured films and patterned cured films are applicable to the production of elements such as semiconductor elements, elements for LCDs, elements for OLEDs, elements for solar cells, elements for flexible displays, elements for touch screen manufacturing, and elements for nanoimprint lithography, and to coating materials. EXAMPLES

[0128] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. [Synthesis Example 1] (Monomer synthesis) Step 1: 2,2'-((((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(methylene))bis(oxirane) synthesis [ka]

[0129] Step A: After setting a reflux condenser and a thermometer in a three-neck flask, add 42.5 g of 9,9-bisphenol fluorene and 2-(chloro) 220 mL of methyl)oxirane was measured and then poured in. 100 mg of tetrabutylammonium bromide was added, and stirring was started, and the temperature was raised to 90° C. After confirming that the content of unreacted matter was less than 0.3%, distillation was performed under reduced pressure.

[0130] Step B: After lowering the temperature to 30°C, dichloromethane was poured in and NaOH was gradually added. After confirming that the product was 96% or more by high performance liquid chromatography (HPLC), the reaction was terminated by adding 5% HCl dropwise. The reactants were extracted and separated into layers, and the organic layer was washed with water until it became neutral. The organic layer was dried over MgSO4 and then concentrated by distillation under reduced pressure using a rotary evaporator. Dichloromethane was added to the concentrated product and stirred while raising the temperature to 40°C, and methanol was added, and the solution temperature was lowered and stirred. The solid produced was filtered and dried in vacuum at room temperature to obtain 52.7g of a white solid powder (yield 94%), the structure of which is 1 Confirmed by 1 H NMR.

[0131] In CDCl 1 H NMR: 7.75(2H), 7.36 to 7.25(6H), 7.09(4H), 6.74(4H), 4.13(2H), 3.89(2H), 3.30(2H), 2.87(2H), 2.71(2H).

[0132] Step 2: Synthesis of 3,3'-(((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(1-(phenylthio)propan-2-ol) (BTCP monomer) [ka]

[0133] After setting a reflux condenser and a thermometer in a three-neck flask, the first-stage reactant (1000g), 524g of thiophenol, and 617g of ethanol were added and stirred. 328g of triethylamine was gradually dripped into the reaction solution. After confirming that the starting material had disappeared by high performance liquid chromatography (HPLC), the reaction was terminated. After the reaction was completed, the ethanol was removed by distillation under reduced pressure. The organic matter was dissolved in dichloromethane and washed with water, and the dichloromethane was removed by distillation under reduced pressure. The concentrated organic matter was dissolved in ethyl acetate, and the ether solvent was dripped and stirred for 30 minutes. The compound was distilled under reduced pressure to obtain 945g of pale yellow oil (yield 64%), and its structure was confirmed by 1H NMR.

[0134] In CDCl 1 H 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).

[0135] (Production of Resin (A) (Binder Resin)) Production of Resin A1 [ka]

[0136] After setting a reflux condenser and a thermometer in a three-neck flask, 200 g of BTCP monomer synthesized in two steps dissolved in 50% propylene glycol methyl ether acetate (PGMEA) solvent was added and heated to 115 ° C. 31.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride was added dropwise at 115 ° C. and stirred for 6 hours while maintaining the temperature at 115 ° C. 7.35 g of phthalic anhydride was added and stirred for another 2 hours, after which the reaction was terminated. After cooling, a solution of resin A1 with a mass average molecular weight of 3,500 g / mol and a dispersity of 2.2 was obtained.

[0137] [Synthesis Example 2] (Production of Resin (A)) Production of Resin A2 [ka]

[0138] After setting a reflux condenser and a thermometer in a three-neck flask, 200 g of BTCP monomer synthesized in two steps dissolved in 50% PGMEA solvent was added and heated to 115 ° C. 28.4 g of 3,3',4,4'-benzophenonetetracarboxylic dianhydride was added dropwise at 115 ° C. and stirred for 6 hours while maintaining the temperature at 115 ° C. 7.35 g of phthalic anhydride was added and stirred for another 2 hours, after which the reaction was terminated. After cooling, a solution of resin A2 with a mass average molecular weight of 5,000 g / mol and a polydispersity of 2.4 was obtained.

[0139] Compound 6 was used as the photopolymerization initiator (B). [ka]

[0140] [Example 1] A negative photosensitive resin composition was produced 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-based surfactant (polyester-modified polydimethylsiloxane, BYK-310, manufactured by BYK-Chemie) as a surfactant in propylene glycol monomethyl ether acetate (PEGMEA) as solvent (S) to a solids concentration of 20% by mass.

[0141] [Example 2] A negative photosensitive resin composition was produced in the same manner as in Example 1, except that the amount of the adhesion enhancer (C) was increased to three parts by mass.

[0142] [Example 3] A negative photosensitive resin composition was produced in the same manner as in Example 1, except that the amount of the adhesion enhancer (C) was changed to 5 parts by mass.

[0143] [Example 4] A negative photosensitive resin composition was produced in the same manner as in Example 3, except that 3-(methacryloyloxy)propyltrimethoxysilane was used as the adhesion enhancer (C) instead of 3-glycidoxypropyltrimethoxysilane.

[0144] [Example 5] A negative photosensitive resin composition was produced by dissolving 85 parts by mass of resin A1 as resin (A), 5 parts by mass of compound 6 as photopolymerization initiator (B), 3 parts by mass of 3-glycidoxypropyltrimethoxysilane as adhesion enhancer (C), 0.2 parts by mass of a siloxane-based surfactant (polyester modified polydimethylsiloxane, BYK-310, manufactured by BYK-Chemie) as a surfactant, and 6.5 parts by mass of dipentaerythritol hexaacrylate as a photopolymerizable compound (D) in propylene glycol monomethyl ether acetate (PEGMEA) as solvent (S) to a solids concentration of 20% by mass.

[0145] [Comparative Example 1] A negative type photosensitive resin composition was produced in the same manner as in Example 3, except that an oxime ester-based photopolymerization initiator having the structure of the following formula, which does not correspond to formula (b1), was used instead of compound 6 as the photopolymerization initiator (B). [ka]

[0146] [Comparative Example 2] A negative type photosensitive resin composition was produced in the same manner as in Example 3, except that an oxime ester photopolymerization initiator not corresponding to formula (b1) (1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(o-benzoyloxime), Irgacure OXE01, BASF Japan Ltd.) was used instead of compound 6 as the photopolymerization initiator (B).

[0147] [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 as Resin (A) instead of Resin A1.

[0148] [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 as Resin (A) instead of Resin A1.

[0149] [Evaluation of Solvent Resistance] Each of the negative photosensitive resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 4 was applied onto a substrate made of polyethylene terephthalate (PET) using a spin coater at 800 to 900 rpm for 15 seconds, and then dried on a hot plate at 85°C for 180 seconds to form a coating film with a thickness of 5 μm. The dried coating film was irradiated with ultraviolet light using a proximity exposure machine (product name: TME-150RTO, manufactured by Topcon Corporation) with an exposure gap of 25 μm. The exposure dose was 30 mJ / cm. 2 It was decided. The exposed coating film was post-baked at 85° C. for 300 seconds to obtain a cured film. The obtained cured film was immersed in propylene glycol monomethyl ether acetate (PEGMEA) at 26° C. for 300 seconds. The cured films before and after immersion were observed with a scanning electron microscope (SEM) at 5000 magnifications, and the solvent resistance was evaluated according to the following criteria. An evaluation was also performed using N-methylpyrrolidone (NMP) as the immersion solvent. An evaluation was also performed with post-baking conditions of 100° C. for 300 seconds. The results are shown in Table 1. The negative photosensitive resin composition obtained in Example 5 was also subjected to a solvent resistance evaluation in the same manner as above, except that post-baking was not performed. The results are shown in Example 6. (PEGMEA) ◯: No change in the cured film before and after immersion ×: There is a change in the cured film before and after immersion (NMP) ○: The change in thickness of the cured film before and after immersion is less than 10% ×: The change in thickness of the cured film before and after immersion is 10% or more.

[0150] [Resolution evaluation] Each of the negative photosensitive resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 4 was applied onto a substrate made of polyethylene terephthalate (PET) using a spin coater at 800 to 900 rpm for 15 seconds, and then dried on a hot plate at 85°C for 180 seconds to form a coating film with a thickness of 5 μm. The dried coating film was irradiated with ultraviolet light using a proximity exposure machine (product name: TME-150RTO, manufactured by Topcon Corporation) through a negative mask with a 10 μm-wide pattern, with an exposure gap of 25 μm. The exposure dose was 30 mJ / cm. 2 It was decided. The exposed coating film was baked (PEB) at 85° C. for 300 seconds and then developed in a 2.38 mass % TMAH aqueous solution at 26° C. for 30 seconds to obtain a cured film. The obtained cured film was observed with a scanning electron microscope (SEM) at 5000x magnification. If a 10 μm wide pattern was formed, it was rated as ◯, and if a 10 μm wide pattern was not formed, it was rated as ×. The results are shown in Table 1. In addition, the negative photosensitive resin composition obtained in Example 5 was evaluated for resolution in the same manner as above, except that PEB was not performed. The results are shown in Example 6.

[0151] [Table 1]

[0152] According to Examples 1 to 6, it is found that the negative type photosensitive resin composition containing the resin (A) having the structural unit represented by formula (a1) and the photopolymerization initiator (B) represented by formula (b1) has excellent solvent resistance. It is also found that these negative type photosensitive resin compositions have excellent resolution.

[0153] On the other hand, according to Comparative Examples 1 to 4, when the negative photosensitive resin composition contains a resin (A) having a structural unit represented by formula (a1) but does not contain a photopolymerization initiator (B) represented by formula (b1), the solvent resistance is inferior to that of Examples 1 to 6. In addition, the resolution is also inferior to that of Examples 1 to 6.

Claims

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): 【Chemistry 1】 (In formula (a1), R １ａ and R ２ａ each independently represents an alkyl group having 1 to 20 carbon atoms which may contain a heteroatom, an aryl group having 6 to 20 carbon atoms which may contain a heteroatom, -R ４ａ S.R. ５ａ Or -R ６ａ C(=O)R ７ａ represents R ３ａ represents a tetravalent aromatic hydrocarbon group or alicyclic hydrocarbon group having from 1 to 20 carbon atoms and optionally containing a heteroatom, A represents a divalent group represented by the following formula (a2): j1 and j2 each independently represent an integer of 1 to 6, R ４ａ represents a single bond, an alkylene group having from 1 to 10 carbon atoms, or an arylene group having from 6 to 15 carbon atoms, S represents a sulfur atom; R ５ａ represents an alkyl group having from 1 to 10 carbon atoms, or an aryl group having from 6 to 15 carbon atoms, R ６ａ represents a single bond, an alkylene group having from 1 to 10 carbon atoms, or an arylene group having from 6 to 10 carbon atoms, R ７ａ represents 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. 【Chemistry 2】 (In formula (a2), R ８ａ and R ９ａ each independently represents a hydrogen atom, a hydroxy group, a mercapto group, an amino group, a nitro group, a halogen atom, a cyano group, or an alkyl group, R １０ａ and R １１ａ each 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. 【Chemistry 3】 (In formula (b1), R １ｂ represents a hydrogen atom, a nitro group, or a monovalent organic group, R ２ｂ and R ３ｂ each 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 ２ｂ and R ３ｂ may be bonded to each other to form a ring, R ４ｂ represents a monovalent organic group, R ５ｂ represents a hydrogen atom, an alkyl group having from 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, q is 0 or 1.

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

3. The negative type photosensitive resin composition according to claim 2, wherein the content of the adhesion enhancer (C) is 0.01 to 10 parts by mass based on 100 parts by mass of the resin (A).

4. A negative type photosensitive resin composition described in any one of claims 1 to 3, further comprising a polyester-modified polydimethylsiloxane.

5. A cured film comprising a cured product of the negative photosensitive resin composition according to any one of claims 1 to 4.

6. A step of applying the negative type photosensitive resin composition according to any one of claims 1 to 4 onto a substrate to form a coating film; and exposing the coating film to light.

7. The method for producing a cured film according to claim 6 , further comprising, after the step of exposing the coating film, a step of heating the coating film after the exposure.

8. the step of exposing the coating film is a step of exposing the coating film in a position-selective manner, The method for producing a cured film according to claim 6 , further comprising a step of developing the coating film after exposure.

9. The method for producing a cured film according to claim 8 , further comprising, after the step of exposing the coating film and before the step of developing, a step of heating the coating film after the exposure.

10. The method for producing a cured film according to claim 7 or 9, wherein a heating temperature in the step of heating the coating film after the exposure is 85° C. or higher and 100° C. or lower.

11. The method for producing a cured film according to any one of claims 6 to 10, wherein the substrate is a flexible substrate.

Images