Photosensitive resin, negative photosensitive resin composition, method for producing patterned cured film, and carboxyl group-containing resin

Abstract

To provide a photosensitive resin for use in a negative photosensitive resin composition capable of forming a cured film having a high refractive index and high transparency, a negative photosensitive resin composition containing the photosensitive resin, a method for producing a patterned cured film using the negative photosensitive resin composition, and a carboxy group-containing resin that can be an intermediate of the photosensitive resin.SOLUTION: A photosensitive resin is a carboxy group-containing resin having a constitutional unit of a specific structure. In the carboxy group-containing resin, at least some of the carboxy groups have (meth)acrylate compounds with carboxylic acid reactive groups added or fused thereto.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin, a negative-type photosensitive resin composition containing the photosensitive resin, a method for producing a patterned cured film using the negative-type photosensitive resin composition, and a carboxy group-containing resin that can be an intermediate for the photosensitive resin. [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 Application Laid-Open No. 62-135824 [Patent Document 4] Special Publication No. 2018-531311 Summary of the Invention [Problem to be solved by the invention]

[0009] However, it is difficult to achieve both a high refractive index and high transparency when a cured film (cured product) is formed using the negative photosensitive resin composition described in Patent Document 4. For this reason, there is a problem that the cured product formed using the negative photosensitive resin composition described in Patent Document 4 is difficult to use in applications requiring a high refractive index and high transparency, such as optical components such as microlenses and optical waveguides mounted on image sensors.

[0010] The present invention has been made in consideration of the above problems, and an object of the present invention is to provide a photosensitive resin that can be used in a negative photosensitive resin composition capable of forming a cured film having a high refractive index and high transparency, a negative photosensitive resin composition containing the photosensitive resin, a method for producing a patterned cured film using the negative photosensitive resin composition, and a carboxy group-containing resin that can be an intermediate of the photosensitive resin. [Means for solving the problem]

[0011] As a result of intensive research to achieve the above object, the present inventors have found that the above problems can be solved by a photosensitive resin in which a (meth)acrylate compound having a carboxylic acid reactive group is added or condensed to at least a part of the carboxyl groups of a carboxyl group-containing resin having a structural unit represented by the following formula (a1), and have completed the present invention. Specifically, the present invention provides the following:

[0012] A first aspect of the present invention is a photosensitive resin, which comprises a carboxyl group-containing resin having a structural unit represented by the following formula (a1), and a (meth)acrylate compound having a carboxylic acid reactive group is added to or condensed with at least a portion of the carboxyl groups of the carboxyl group-containing resin: [ka] (In formula (a1), R 1a and R 2a are each independently -R 4a S.R. 5a , -R 6a C(=O)R 7a represents an alkyl group having from 1 to 20 carbon atoms which may contain a heteroatom, or an aryl group having from 6 to 20 carbon atoms which may contain a heteroatom, 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, R 5arepresents 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 from 1 to 10 carbon atoms, an alkenyl group having from 1 to 10 carbon atoms, or an aryl group having from 6 to 15 carbon atoms, R 3a represents a tetravalent organic group containing an aromatic hydrocarbon group, R 3a The four carbonyl groups bonded to R 3a and is bonded to an aromatic hydrocarbon ring in the organic group as defined above; 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. [ka] (In formula (a2), Ring Z 1 and ring Z 2 each independently represents an aromatic hydrocarbon ring; 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.

[0013] A second aspect of the present invention is a negative type photosensitive resin composition comprising the photosensitive resin according to the first aspect and a photopolymerization initiator.

[0014] A third aspect of the present invention is a method for producing a photosensitive resin composition according to the second aspect, comprising the steps of: applying the negative type photosensitive resin composition according to the second aspect onto a substrate to form a coating film; A step of position-selectively exposing the coating film; developing the coating film after exposure; The present invention relates to a method for producing a patterned cured film, comprising the steps of:

[0015] A fourth aspect of the present invention is a carboxy group-containing resin having a structural unit represented by the following formula (a1-1). [ka] (In formula (a1-1), R 1a and R 2a are each independently -R 4a S.R. 5a , -R 6a C(=O)R 7a represents an alkyl group having from 1 to 20 carbon atoms which may contain a heteroatom, or an aryl group having from 6 to 20 carbon atoms which may contain a heteroatom, 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, 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 from 1 to 10 carbon atoms, an alkenyl group having from 1 to 10 carbon atoms, or an aryl group having from 6 to 15 carbon atoms, R 31a is expressed by the following formula (a1a): >Ar 1a -X 1 -Ar 2a <···(a1a) represents a tetravalent group represented by Ar 1a and Ar 2aeach independently represents an aromatic hydrocarbon group which may be substituted with an electron-donating group, X 1 Ar 1a and Ar 2a represents a divalent linking group which does not form a π-conjugated system together with 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. [ka] (In formula (a2), Ring Z 1 and ring Z 2 each independently represents an aromatic hydrocarbon ring; 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. Effect of the Invention

[0016] According to the present invention, it is possible to provide a photosensitive resin that can be used in a negative photosensitive resin composition capable of forming a cured film having a high refractive index and high transparency, a negative photosensitive resin composition containing the photosensitive resin, a method for producing a patterned cured film using the negative photosensitive resin composition, and a carboxy group-containing resin that can be an intermediate for the photosensitive resin. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The present invention will be described in detail below. ≪Photosensitive resin≫ The photosensitive resin of the present invention (hereinafter also referred to as "photosensitive resin (A)") is a carboxy group-containing resin having a constituent unit represented by the following formula (a1), in which a (meth)acrylate compound having a carboxylic acid reactive group is added to or condensed with at least a portion of the carboxy groups of the carboxy group-containing resin: [ka] (In formula (a1), R 1a and R 2a are each independently -R 4a S.R. 5a , -R 6a C(=O)R 7a represents an alkyl group having from 1 to 20 carbon atoms which may contain a heteroatom, or an aryl group having from 6 to 20 carbon atoms which may contain a heteroatom, 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, 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 from 1 to 10 carbon atoms, an alkenyl group having from 1 to 10 carbon atoms, or an aryl group having from 6 to 15 carbon atoms, R 3a represents a tetravalent organic group containing an aromatic hydrocarbon group, R 3a The four carbonyl groups bonded to R 3a and is bonded to an aromatic hydrocarbon ring in the organic group as defined above; 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. [ka] (In formula (a2), Ring Z 1 and ring Z 2 each independently represents an aromatic hydrocarbon ring; 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.

[0018] First, a carboxy group-containing resin having a structural unit represented by formula (a1) (hereinafter also referred to as "carboxy group-containing resin") will be described. As can be seen from the structure of formula (a1) above, the carboxyl group-containing resin having a constituent unit represented by formula (a1) has a carboxyl group in the constituent unit. Furthermore, as can be seen from the structure of formula (a2) above, the carboxyl group-containing resin having the structural unit represented by formula (a1) has a bisphenylfluorene structure as a basic structure in the structural unit.

[0019] 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.

[0020] In formula (a1), R 1a and R 2aThe 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.

[0021] 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. 5a In this case, it is particularly effective in terms of heat resistance, high transmittance and high refractive index.

[0022] 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.

[0023] R 3a represents a tetravalent organic group containing an aromatic hydrocarbon group, R 3a The four carbonyl groups bonded to R 3a It bonds to an aromatic hydrocarbon ring in a tetravalent organic group as a R 3a Examples of the aromatic hydrocarbon group included in the formula (1) include a group consisting of one benzene ring, a group formed by multiple benzene rings bonded via single bonds, a group formed by multiple benzene rings bonded via carbonyl groups, and a group formed by condensing multiple benzene rings. Also, R 3a The aromatic hydrocarbon group contained in may be one or more.

[0024] R 3a Examples of the tetravalent organic group containing an aromatic hydrocarbon group as the aromatic hydrocarbon group include a group consisting of only aromatic hydrocarbon groups and a group in which a plurality of aromatic hydrocarbon groups are linked via a linking group such as -O-, -S- or an alkylene group. A tetravalent organic group represented by the following formula (a1a) is preferred. >Ar 1a -X 1 -Ar 2a <···(a1a) (In formula (a1a), Ar 1a and Ar 2a each independently represents an aromatic hydrocarbon group which may be substituted with an electron-donating group, X 1 Ar 1a and Ar 2a represents a divalent linking group that does not form a π-conjugated system together with

[0025] In formula (a1a), Ar 1a and Ar 2a The aromatic hydrocarbon group as Ar is not particularly limited as long as the desired effect is not impaired. 1a and Ar 2a The aromatic hydrocarbon group as R 3a The aromatic hydrocarbon group is the same as that in the above. The electron-donating group is not particularly limited as long as it is a group generally recognized as an electron-donating group by those skilled in the art of chemistry. Examples of the electron-donating group include an alkoxy group, an amino group, and an alkyl group.

[0026] In formula (a1a), X 1 As a 1a and Ar 2a Examples of the divalent linking group that does not form a π-conjugated system with Ar include -O-, -S-, an alkylene group, and a combination of two or more selected from these. 1a and Ar 2a As long as a π-conjugated system containing X is not formed, 1 may contain an aromatic hydrocarbon ring such as a benzene ring or a naphthalene ring. In addition, a carbonyl group (-C(=O)-) or a vinylene group (-CH=CH-) may be included in Ar 1a and Ar 2a Since it forms a π-conjugated system with X 1 Does not apply. X 1 Even if is a single bond, Ar 1a and Ar 2aSince it forms a π-conjugated system with

[0027] An example of the group represented by formula (a1a) is a group represented by the following formula (a1b). >Ar 3a -(X 2 -Ar 5a ) n -X 3 -Ar 4a <···(a1b) (in (a1b), Ar 3a , Ar 4a and Ar 5a each independently represents an aromatic hydrocarbon group which may be substituted with an electron-donating group, X 2 and X 3 each independently represents an oxygen atom, a sulfur atom, or an alkylene group having 1 to 10 carbon atoms, n represents an integer between 0 and 2.

[0028] In formula (a1b), Ar 3a , Ar 4a and Ar 5a The aromatic hydrocarbon group and the electron donating group in 1a and Ar 2a The aromatic hydrocarbon group and the electron donating group in Ar 3a , and Ar 4a The aromatic hydrocarbon group as Ar is preferably a benzene-1,2,4-triyl group. 5a As the aromatic hydrocarbon group for , a p-phenylene group and an m-phenylene group are preferred, and a p-phenylene group is more preferred.

[0029] R 3a Specific examples of the above include the following tetravalent groups and the following tetravalent groups in which a hydrogen atom on the benzene ring is substituted with one or more electron-donating groups such as a methyl group, an ethyl group, a methoxy group, or an ethoxy group. [ka]

[0030] 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.

[0031] In formula (a2), ring Z 1 and ring Z 2 are each independently an aromatic hydrocarbon ring. Examples of the aromatic hydrocarbon ring include a naphthalene ring and a benzene ring, with the naphthalene ring being preferred in terms of increasing the refractive index.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] An example of the divalent group represented by formula (a2) is a divalent group represented by the following formula (a2-1). [ka] (In formula (a2-1), 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.

[0036] In formula (a2-1), R 8a ~R 11a , k1, k2, m1, and m2 are R in formula (a2). 8a ~R 11a , k1, k2, m1 and m2.

[0037] In addition, among the carboxyl group-containing resins having a structural unit represented by formula (a1), R 3a In other words, a carboxyl group-containing resin having a structural unit represented by the following formula (a1-1) is a novel resin. In addition, a carboxyl group-containing resin having a structural unit represented by the following formula (a1-1) has a high refractive index and high transmittance. [ka] (In formula (a1-1), R 1a and R 2a are each independently -R 4a S.R. 5a , -R 6a C(=O)R 7a represents an alkyl group having from 1 to 20 carbon atoms which may contain a heteroatom, or an aryl group having from 6 to 20 carbon atoms which may contain a heteroatom, 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, 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 from 1 to 10 carbon atoms, an alkenyl group having from 1 to 10 carbon atoms, or an aryl group having from 6 to 15 carbon atoms, R 31a is expressed by the following formula (a1a): >Ar 1a -X 1 -Ar 2a <···(a1a) represents a tetravalent group represented by Ar 1a and Ar 2a each independently represents an aromatic hydrocarbon group which may be substituted with an electron-donating group, X 1 Ar 1a and Ar 2a represents a divalent linking group which does not form a π-conjugated system together with 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. [ka] (In formula (a2), Ring Z1 and ring Z 2 each independently represents an aromatic hydrocarbon ring; 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.

[0038] The number of structural units represented by formula (a1) in the carboxyl group-containing resin having the structural unit represented by formula (a1) is not particularly limited. The number of structural units represented by formula (a1) in the carboxyl group-containing resin having the structural unit represented by formula (a1) is, for example, an integer of 1 to 30, preferably an integer of 1 to 10. Within this range, the heat resistance, high transmittance and high refraction properties are particularly excellent.

[0039] The mass average molecular weight of the carboxyl group-containing resin having a structural unit represented by formula (a1) may be, for example, preferably 1,000 g / mol or more and 100,000 g / mol or less, more preferably 1,500 g / mol or more and 50,000 g / mol or less, and even more preferably 2,000 g / mol or more and 10,000 g / mol or less.

[0040] The dispersity (mass average molecular weight Mw / number average molecular weight Mn) of the carboxyl group-containing resin having a structural unit represented by formula (a1) may be, for example, in the range of 1.0 or more and 5.0 or less, and preferably in the range of 1.5 or more and 4.0 or less.

[0041] In this specification, the mass average molecular weight, number average molecular weight, and dispersity can be measured by gel permeation chromatography (GPC).

[0042] The carboxyl group-containing resin having the constitutional unit represented by formula (a1) can be produced by the method described in Patent Document 4, for example. Specifically, the carboxyl group-containing resin having a constitutional unit represented by formula (a1) can be synthesized by synthesizing a compound (monomer) containing a hydroxyl group represented by formula (2) below from a compound represented by formula (1) below, and then polymerizing the resulting compound with a tetracarboxylic dianhydride represented by formula (3) below. [ka] (In formula (1), ring Z 1 and ring Z 2 , R 8a ~R 11a , k1, k2, m1 and m2 each represent the ring Z in formula (a2). 1 and ring Z 2 , R 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), ring Z 1 and ring Z 2 , R 8a ~R 11a , k1, k2, m1 and m2 each represent the ring Z in formula (a2). 1 and ring Z 2 , R 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.)

[0043] [ka] (In formula (3), R 3a is R in formula (a1). 3a is equivalent to

[0044] 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.

[0045] R 12a and R 13a 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.

[0046] 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.

[0047] The tetracarboxylic dianhydride represented by formula (3) may be used in an amount of, for example, 5 parts by mass or more and 40 parts by mass or less, 10 parts by mass or more and 30 parts by mass or less, or 10 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the compound containing a hydroxy group represented by formula (2) above.

[0048] In the production of the carboxyl group-containing resin having the structural unit represented by formula (a1), for example, after the start 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 carboxyl group-containing resin having the structural unit represented by formula (a1). However, since the terminal blocking agent tends to lower the refractive index, it is preferable not to use a terminal blocking agent. 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.

[0049] The terminal blocking agent may be added in an amount of, for example, 2 parts by mass or more and 10 parts by mass or less, 2 parts by mass or more and 5 parts by mass or less, or 3 parts by mass or more and 5 parts by mass or less, based on 100 parts by mass of the compound containing a hydroxy group represented by formula (2) above.

[0050] 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 acid anhydride, and a specific example thereof is phthalic anhydride.

[0051] When a terminal blocking agent is used, the terminal structure of the carboxyl group-containing resin having the constitutional unit represented by formula (a1) may be a structure derived from the terminal blocking agent. In addition, the terminal structure of the carboxyl group-containing resin having the constitutional unit represented by formula (a1) may be a structure derived from a raw material added in excess, among raw materials such as the compound containing a hydroxyl group represented by formula (2) above and tetracarboxylic dianhydride. More specifically, the terminal structure of the carboxyl group-containing resin having the structural unit represented by formula (a1) may be, for example, the following structures 1 to 3, and the mass average molecular weight of the carboxyl group-containing resin having the structural unit represented by formula (a1) can be appropriately controlled. The structures of the multiple terminals in the molecular chain of the resin constituting the carboxyl group-containing resin having the structural unit represented by formula (a1) may be different from each other. The following OX for Structure 3 is a group generated by the reaction of the hydroxyl group in Structure 2 with the above-mentioned terminal blocking agent. 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:-CHR 2a -(CH2) j2 -OAO-(CH2) j1 -CH(OH)-R 1a The structure represented by Structure 3:-CHR 2a -(CH2) j2 -OAO-(CH2) j1 -CH(OX)-R 1a The structure represented by

[0052] The photosensitive resin (A) is a resin in which a (meth)acrylate compound having a carboxylic acid reactive group is added or condensed to at least a portion of the carboxy groups of a carboxy group-containing resin having a structural unit represented by formula (a1). That is, the photosensitive resin (A) is a resin obtained by adding or condensing a (meth)acrylate compound having a carboxylic acid reactive group to at least a portion of the carboxy groups of a carboxy group-containing resin having a structural unit represented by formula (a1).

[0053] As can be seen from the structure of the above formula (a2), the photosensitive resin (A) has a bisphenylfluorene structure as a basic structure in its constituent units.

[0054] Furthermore, the photosensitive resin (A) has, in its constituent units, a (meth)acryloyloxy group derived from a (meth)acrylate compound having a carboxylic acid reactive group. In this specification, "(meth)acrylate" means both "acrylate" and "methacrylate", "(meth)acryl" means both "acryl" and "methacryl", and "(meth)acryloyloxy" means both "acryloyloxy" and "methacryloyloxy".

[0055] The carboxylic acid reactive group is a functional group that reacts with a carboxylic acid or a group derived from a carboxy group, such as a halocarbonyl group. That is, the carboxylic acid reactive group of a (meth)acrylate compound having a carboxylic acid reactive group undergoes an addition or condensation reaction with a carboxy group of a carboxy group-containing resin having a structural unit represented by formula (a1) or a group derived from a carboxy group.

[0056] Examples of the carboxylic acid reactive group include a group having an epoxy group, an amino group, a hydroxy group, an isocyanate group, etc. Examples of the group having an epoxy group include a glycidyl group, an epoxycyclopentyl group, an epoxycyclohexyl group, an epoxycyclopentylmethyl group, an epoxycyclohexylmethyl group, an epoxycyclopentylethyl group, and an epoxycyclohexylmethyl group, etc. Specific examples of the (meth)acrylate compound having a carboxylic acid reactive group include glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.

[0057] A negative type photosensitive resin composition containing such a photosensitive resin (A) together with a photopolymerization initiator (C) described later in detail can form a cured film having a high refractive index and high transparency, as shown in the examples described later. Therefore, the cured film formed by the negative type photosensitive resin composition containing the photosensitive resin (A) and the photopolymerization initiator (C) can be used as a member that requires a high refractive index and high transparency, for example, an optical member such as a microlens or optical waveguide mounted on an image sensor. Moreover, the negative photosensitive resin composition can form a patterned cured film by exposure and development. The negative photosensitive resin composition can also form a cured film having high solvent resistance.

[0058] Among the photosensitive resins (A), R 3a When R is a tetravalent organic group represented by formula (a1a), the refractive index and transparency of the cured product can be both at particularly high levels. 3a It is unclear why when is a tetravalent organic group represented by formula (a1a), the refractive index and transparency can be simultaneously achieved at particularly high levels. However, the tetravalent organic group represented by formula (a1a) has a structure in which both ends are aromatic hydrocarbon groups, and the π-conjugated system is interrupted between the aromatic hydrocarbon groups at both ends, which is presumably one of the reasons why the refractive index and transparency can be simultaneously achieved at particularly high levels.

[0059] The terminal structure of the photosensitive resin (A) is the same as the terminal structure of the carboxyl group-containing resin having the structural unit represented by the above formula (a1).

[0060] The weight average molecular weight of the photosensitive resin (A) may be, for example, preferably 1,100 g / mol or more and 100,500 g / mol or less, more preferably 1,600 g / mol or more and 50,500 g / mol or less, and even more preferably 2,100 g / mol or more and 10,500 g / mol or less.

[0061] The dispersity of the photosensitive resin (A) (mass average molecular weight Mw / number average molecular weight Mn) may be, for example, in the range of 1.0 or more and 5.0 or less, and preferably in the range of 1.5 or more and 4.0 or less.

[0062] The photosensitive resin (A) can be produced by an addition reaction or condensation reaction between a carboxyl group-containing resin having a structural unit represented by formula (a1) and a (meth)acrylate compound having a carboxylic acid reactive group. By this reaction, the (meth)acrylate compound having a carboxylic acid reactive group is added or condensed to at least a part of the carboxyl groups of the carboxyl group-containing resin having a structural unit represented by formula (a1).

[0063] The reaction can be carried out, for example, for 30 minutes to 5 hours, preferably 1 hour to 3 hours, at 80 to 120°C, preferably 90 to 110°C.

[0064] A (meth)acrylate compound having a carboxylic acid reactive group may be added to or condensed with all of the carboxy groups of the carboxy group-containing resin having a structural unit represented by formula (a1). However, from the viewpoint of the developability of a negative type photosensitive resin composition containing photosensitive resin (A), it is preferable that a (meth)acrylate compound having a carboxylic acid reactive group is added to or condensed with some of the carboxy groups of the carboxy group-containing resin having a structural unit represented by formula (a1) so that the carboxy groups remain in the photosensitive resin (A). For example, the molar ratio of the (meth)acrylate compound having a carboxylic acid reactive group to the carboxy group-containing resin having a structural unit represented by formula (a1) ((meth)acrylate compound having a carboxylic acid reactive group / carboxy group-containing resin having a structural unit represented by formula (a1)) is preferably 0.05 or more and 0.50 or less, more preferably 0.10 or more and 0.40 or less, and even more preferably 0.15 or more and 0.30 or less.

[0065] <Negative photosensitive resin composition> The negative photosensitive resin composition contains the above-mentioned photosensitive resin (A) and a photopolymerization initiator (C). The negative photosensitive resin composition may contain a photopolymerizable compound (B), an adhesion enhancer (D), a solvent (S), and other components, as necessary.

[0066] The negative type photosensitive resin composition containing the above-mentioned photosensitive resin (A) and the photopolymerization initiator (C) can form a cured film having a high refractive index and high transparency, as shown in the examples described below. Therefore, the cured film formed by the negative type photosensitive resin composition can be used as a member that requires a high refractive index and high transparency, for example, an optical member such as a microlens or optical waveguide mounted on an image sensor. Furthermore, the negative photosensitive resin composition can form a patterned cured film by exposure and development. Furthermore, the negative photosensitive resin composition can form a cured film having high solvent resistance. Hereinafter, essential or optional components other than the photosensitive resin (A) contained in the negative photosensitive resin composition and a method for producing the negative photosensitive resin composition will be described.

[0067] <Photopolymerizable compound (B)> The negative photosensitive resin composition may or may not contain a photopolymerizable compound (B). The photopolymerizable compound (B) 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 (B).

[0068] When a photopolymerizable compound (B) is included, the photopolymerizable compound (B) is preferably included in an amount of 0.1 part by mass or more and 200 parts by mass or less, more preferably 1 part by mass or more and 100 parts by mass or less, and even more preferably 10 parts by mass or more and 80 parts by mass or less, per 100 parts by mass of the photosensitive resin (A).

[0069] <Photopolymerization initiator (C)> The photopolymerization initiator (C) is not particularly limited, and any conventionally known photopolymerization initiator can be used. The photopolymerization initiator (C) may be an oxime ester compound. The oxime ester compound is preferably a compound having a partial structure represented by the following formula (c1).

[0070] [ka] (In formula (c1), n1 is 0 or 1, R c2 is a monovalent organic group, R c3 represents a hydrogen atom, an aliphatic hydrocarbon group having from 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, * is a bond.)

[0071] The compound having the partial structure represented by formula (c1) preferably has a carbazole skeleton, a fluorene skeleton, a diphenyl ether skeleton, or a phenyl sulfide skeleton. The compound having the partial structure represented by formula (c1) preferably has one or two partial structures represented by formula (c1).

[0072] An example of a compound having a partial structure represented by formula (c1) is a compound represented by the following formula (c2).

[0073] [ka] (In formula (c2), R c1 is a group represented by the following formula (c3), (c4), or (c5): n1 is 0 or 1, R c2 is a monovalent organic group, R c3 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.

[0074] [ka] (In formula (c3), R c4 and R c5 are each independently a monovalent organic group, n2 is an integer between 0 and 3, When n2 is 2 or 3, multiple R c5 may be the same or different, and multiple R c5 may be bonded to each other to form a ring. * is a bond.)

[0075] [ka] (In formula (c4), R c6 and R c7each independently represents a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom, R c6 and R c7 may be bonded to each other to form a ring, R c7 and a benzene ring in the fluorene skeleton may be bonded to each other to form a ring, R c8 is a nitro group or a monovalent organic group, n3 is an integer between 0 and 4, * is a bond.)

[0076] [ka] (In formula (c5), R c9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group, A is S or O; n4 is an integer between 0 and 4, * is a bond.)

[0077] In formula (c3), R c4 R is a monovalent organic group. c4 can be selected from various organic groups as long as it does not impair the object of the present invention. As the organic group, a carbon atom-containing group is preferable, and a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms is more preferable. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 to 50, more preferably 1 to 20. R c4Preferred examples of the alkyl group include an alkyl group having from 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having from 3 to 20 carbon atoms which may have a substituent, a saturated aliphatic acyl group having from 2 to 20 carbon atoms which may have a substituent, an alkoxycarbonyl group having from 2 to 20 carbon atoms which may have a substituent, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having from 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having from 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent.

[0078] R c4 Among these, an alkyl group having 1 to 20 carbon atoms is preferred. The alkyl group may be linear or branched. In view of the good solubility of the compound represented by formula (c3) in the photosensitive resin composition, R c4 The number of carbon atoms in the alkyl group represented by R is preferably 2 or more, more preferably 5 or more, and particularly preferably 7 or more. In addition, in order to obtain a good compatibility between the compound represented by formula (c3) and other components in the photosensitive resin composition, c4 The number of carbon atoms in the alkyl group as the radical is preferably 15 or less, and more preferably 10 or less.

[0079] R c4 When has a substituent, suitable examples of the substituent include a hydroxyl group, an alkyl group having from 1 to 20 carbon atoms, an alkoxy group having from 1 to 20 carbon atoms, an aliphatic acyl group having from 2 to 20 carbon atoms, an aliphatic acyloxy group having from 2 to 20 carbon atoms, a phenoxy group, a benzoyl group, a benzoyloxy group, a group represented by -PO(OR)2 (R is an alkyl group having from 1 to 6 carbon atoms), a halogen atom, a cyano group, a heterocyclyl group, and the like.

[0080] R c4When R is a heterocyclyl group, the heterocyclyl group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. c4 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 together or such monocyclic ring is fused with a benzene ring. When the heterocyclyl group is a fused ring, the number of rings is up to 3. 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. R c4 When is a heterocyclyl group, examples of the substituent that the heterocyclyl group may have include a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, and the like.

[0081] The above-mentioned R c4 Preferred specific examples of the aryl 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 neopentyl group, a pentan-3-yl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and a 2-ethylhexyl group. Moreover, from the viewpoint of good solubility of the compound represented by formula (c3) in the photosensitive resin composition, an n-octyl group and a 2-ethylhexyl group are preferred, and a 2-ethylhexyl group is more preferred.

[0082] In formula (c3), R c5R is a monovalent organic group. c5 can be selected from various organic groups as long as it does not impair the object of the present invention. As the organic group, a carbon atom-containing group is preferable, and a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms is more preferable. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 to 50, more preferably 1 to 20. R c5 Examples of suitable monovalent organic groups include 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, naphthyloxy 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 1 or 2 organic groups, morpholin-1-yl groups, piperazin-1-yl groups, halogens, nitro groups, cyano groups, and substituents containing groups represented by HXC- or HXC- (wherein X is each independently a halogen atom).

[0083] R c5 When R is an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. c5 When R is an alkyl group, it may be a straight chain or a branched chain. c5Specific 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. c5 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.

[0084] R c5 When R is an alkoxy group, the number of carbon atoms in the alkoxy group is preferably 1 or more and 20 or less, and more preferably 1 or more and 6 or less. c5 When R is an alkoxy group, it may be a straight chain or a branched chain. c5 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. c5 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.

[0085] R c5 When R is a cycloalkyl group or a cycloalkoxy group, the cycloalkyl group or the cycloalkoxy group preferably has 3 or more and 10 or less carbon atoms, and more preferably has 3 or more and 6 or less carbon atoms. c5 Specific examples of R are cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. c5 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.

[0086] R c5 When 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 or more and 21 or less carbon atoms, and more preferably has 2 or more and 7 or less carbon atoms. c5 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. c5 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.

[0087] R c5 When R is an alkoxycarbonyl group, the alkoxycarbonyl group preferably has 2 or more and 20 or less carbon atoms, and more preferably has 2 or more and 7 or less carbon atoms. c5 Specific 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.

[0088] R c5 When R is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably 7 or more and 20 or less, and more preferably 7 or more and 10 or less. c5 When R is a naphthylalkyl group, the naphthylalkyl group preferably has 11 or more and 20 or less carbon atoms, and more preferably has 11 or more and 14 or less carbon atoms. c5 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. c5 Specific examples of R are naphthylalkyl groups include α-naphthylmethyl, β-naphthylmethyl, 2-(α-naphthyl)ethyl, and 2-(β-naphthyl)ethyl. c5 is a phenylalkyl group or a naphthylalkyl group, R c5 may further have a substituent on the phenyl group or naphthyl group.

[0089] R c5 When is a heterocyclyl group, the heterocyclyl group is R c4 is a heterocyclyl group, and the heterocyclyl group may further have a substituent. R c5 When is a heterocyclylcarbonyl group, the heterocyclyl group contained in the heterocyclylcarbonyl group is R c5 is a heterocyclyl group.

[0090] R c5 is an amino group substituted with one or two organic groups, suitable examples of the organic group include an alkyl group having from 1 to 20 carbon atoms, a cycloalkyl group having from 3 to 10 carbon atoms, a saturated aliphatic acyl group having from 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 from 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthylalkyl group having from 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl group. Specific examples of these suitable organic groups are c5 Specific 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.

[0091] R c5In the case where the phenyl group, naphthyl group, and heterocyclyl group contained in the formula (I) further have a substituent, examples of the substituent include a substituent containing a group represented by HX2C- or H2XC- (for example, a halogenated alkoxy group containing a group represented by HX2C- or H2XC-, a halogenated alkyl group containing a group represented by HX2C- or H2XC-), 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 piperazine-1-yl group, a benzoyl group, a halogen, a nitro group, and a cyano group. c5 When the phenyl group, naphthyl group, and heterocyclyl group contained in R further have a substituent, the number of the substituents is not limited as long as it does not impair the object of the present invention, and is preferably 1 to 4. c5 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.

[0092] R c5 When the benzoyl group contained in the above formula (1) further has a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazine-1-yl group, a 2-thenoyl group (thiophen-2-ylcarbonyl group), a furan-3-ylcarbonyl group, and a phenyl group.

[0093] Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom is preferable.

[0094] Examples of the substituent containing a group represented by HX2C- or H2XC- include a halogenated alkoxy group containing a group represented by HX2C- or H2XC-, a group having a halogenated alkoxy group containing a group represented by HX2C- or H2XC-, a halogenated alkyl group containing a group represented by HX2C- or H2XC-, a group having a halogenated alkyl group containing a group represented by HX2C- or H2XC-, and the like, and a halogenated alkoxy group containing a group represented by HX2C- or H2XC-, or a group having a halogenated alkoxy group containing a group represented by HX2C- or H2XC- is more preferred.

[0095] Examples of groups having a halogenated alkyl group containing a group represented by HX2C- or H2XC- include aromatic groups substituted with a halogenated alkyl group containing a group represented by HX2C- or H2XC- (e.g., phenyl group, naphthyl group, etc.) and cycloalkyl groups substituted with a halogenated alkyl group containing a group represented by HX2C- or H2XC- (e.g., cyclopentyl group, cyclohexyl group, etc.), and preferably aromatic groups substituted with a halogenated alkyl group containing a group represented by HX2C- or H2XC-.

[0096] Examples of groups having a halogenated alkoxy group containing a group represented by HX2C- or H2XC- include aromatic groups substituted with a halogenated alkoxy group containing a group represented by HX2C- or H2XC- (e.g., phenyl group, naphthyl group, etc.), alkyl groups substituted with a halogenated alkoxy group containing a group represented by HX2C- or H2XC- (e.g., methyl group, ethyl group, n-propyl group, i-propyl group, etc.), and cycloalkyl groups substituted with a halogenated alkoxy group containing a group represented by HX2C- or H2XC- (e.g., cyclopentyl group, cyclohexyl group, etc.), and the like. An aromatic group substituted with a halogenated alkoxy group containing a group represented by HX2C- or H2XC- is preferred.

[0097] Also, R c5As 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 c5 The substituents are the same as those that the phenyl group contained in the above may have.

[0098] Among the monovalent organic groups, R c5 As the alkyl group, an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, a phenylthioalkyl group which may have a substituent on the aromatic ring are 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 cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. The number of carbon atoms of the alkylene group contained in the cycloalkylalkyl group is 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.

[0099] In the group represented by formula (c3), R c5 There are multiple R c5 When R are bonded to each other to form a ring, the ring formed may be a hydrocarbon ring or a heterocycle. Examples of heteroatoms contained in the heterocycle include N, O, and S. c5The ring formed by bonding with each other is particularly preferably an aromatic ring. Such an aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Such an aromatic ring is preferably an aromatic hydrocarbon ring. In formula (c3), a plurality of R c5 Specific examples of when they are bonded to each other to form a benzene ring are shown below.

[0100] [ka]

[0101] In the group represented by formula (c4), R c8 R is a nitro group or a monovalent organic group. c8 is -(CO) on the fused ring in formula (c4). n1 In formula (c4), R is bonded to a 6-membered aromatic ring different from the aromatic ring bonded to the group represented by -. c8 The bonding position of R is not particularly limited. c8 In the case where R is 1 or more, the compound represented by formula (c4) can be easily synthesized. c8 It is preferable that one of the groups represented by formula (c4) is bonded to the 7-position of the fluorene skeleton. c8 In the case where R has the formula (c4), the group represented by the formula (c4) is preferably represented by the following formula (c6): c8 If there are multiple, multiple R c8 may be the same or different.

[0102] [ka] (In formula (c6), R c6 , R c7 , R c8 , n3 is R in formula (c4), c6 , R c7 , R c8 , similar to n3.)

[0103] R c8 When R is a monovalent organic group, c8is not particularly limited as long as it does not impair the object of the present invention. As the organic group, a carbon atom-containing group is preferable, and a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms is more preferable. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 to 50, more preferably 1 to 20. R c8 In the case where R is a monovalent organic group, a preferable example is c5 Suitable examples of the monovalent organic group as the substituent include the same groups as those mentioned above.

[0104] In formula (c4), R c6 and R c7 R each represents a chain alkyl group which may have a substituent, a chain alkoxy group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. c6 and R c7 may be bonded to each other to form a ring. c6 and R c7 As R, a chain alkyl group which may have a substituent is preferable. c6 and R c7 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.

[0105] R c6 and R c7 When R is a chain alkyl group having no substituent, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 6 or less. c6 and R c7 Specific 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.c6 and R c7 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.

[0106] R c6 and R c7 When is a chain alkyl group having a substituent, the number of carbon atoms of the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. In this case, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the chain alkyl group. The chain alkyl group having a substituent is preferably linear.

[0107] 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 an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, 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 c8 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 c8 The preferred examples are the same as those when R is a heterocyclyl group. c8 When 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.

[0108] When the chain alkyl group has a substituent, the number of the substituent is not particularly limited. The number of the preferred substituent varies according to the number of carbon atoms of the chain alkyl group. The number of the substituent is typically 1 or more and 20 or less, preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.

[0109] R c6 and R c7 When R is a chain alkoxy group having no substituent, the chain alkoxy group preferably has 1 or more and 20 or less carbon atoms, more preferably has 1 or more and 10 or less carbon atoms, and particularly preferably has 1 or more and 6 or less carbon atoms. c6 and R c7 Specific examples of the chain alkoxy group include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, n-pentyloxy, isopentyloxy, sec-pentyloxy, tert-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, n-nonyloxy, isononyloxy, n-decyloxy, and isodecyloxy. c6 and R c7 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.

[0110] R c6 and R c7 When R is a chain alkoxy group having a substituent, the substituent that the alkoxy group may have is c6 and R c7 is a chain alkyl group.

[0111] R c6 and R c7When 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. c6 and R c7 When R is a cyclic organic group, the substituent that the cyclic organic group may have is R c6 and R c7 is a chain alkyl group.

[0112] R c6 and R c7 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.

[0113] R c6 and R c7 When 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, more preferably 3 to 10. Examples of monocyclic cyclic hydrocarbon groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, tetracyclododecyl group, and adamantyl group.

[0114] R c6 and R c7 When R in formula (c3) is a heterocyclyl group, c5 Examples of the heterocyclyl group include the heterocyclyl group represented by the above formula.

[0115] R c6 and R c7 may be bonded to each other to form a ring. c6 and R c7 The ring formed by R is preferably a cycloalkylidene group. c6 and R c7 When 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.

[0116] R c7 When a ring is formed with the benzene ring of the fluorene skeleton, the ring may be an aromatic ring or an aliphatic ring.

[0117] R c6 and R c7 When the group formed by bonding 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.

[0118] The above-mentioned R c6 and R c7 Among these, a suitable example of the group is a group represented by the formula -A1-A2, in which A1 is a linear alkylene group, and A2 is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.

[0119] The number of carbon atoms of the linear alkylene group of A1 is preferably 1 to 10, more preferably 1 to 6. When A2 is an alkoxy group, the alkoxy group may be linear or branched, and linear is preferred. The number of carbon atoms of the alkoxy group is preferably 1 to 10, and more preferably 1 to 6. When A2 is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is preferred, and a fluorine atom, a chlorine atom, or a bromine atom is more preferred. When A2 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 a fluorine atom, a chlorine atom, or a bromine atom is more preferred. The halogenated alkyl group may be linear or branched, and linear is preferred. When A2 is a cyclic organic group, examples of the cyclic organic group include R c6 and R c7 When A2 is an alkoxycarbonyl group, examples of the alkoxycarbonyl group include R c6 and R c7 The alkoxycarbonyl group represented by the formula (I) is the same as the alkoxycarbonyl group represented by the formula (I) as a substituent.

[0120] R c6 and R c7Preferred 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;

[0121] R c6 and R c7 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.

[0122] In the formula (c5), A is particularly preferably S, since a photopolymerization initiator having excellent sensitivity can be easily obtained.

[0123] In formula (c5), R c9 is a monovalent organic group, a halogen atom, a nitro group, or a cyano group. R in formula (c5) c9When is a monovalent organic group, it can be selected from various organic groups as long as it does not impair the object of the present invention. As the organic group, a carbon atom-containing group is preferable, and a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms is more preferable. The number of carbon atoms of the carbon atom-containing group is not particularly limited, and is preferably 1 to 50, more preferably 1 to 20. In formula (c5), R c9 In the case where R is an organic group, a preferable example is c5 Examples of the monovalent organic group include the same groups as those mentioned above.

[0124] R c9 Among these, a benzoyl group, a naphthoyl group, a benzoyl group substituted with a group selected from the group consisting of an alkyl group having from 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-1-yl group, and a phenyl group, a nitro group, and a benzofuranylcarbonyl group which may have a substituent are preferred, and a benzoyl group, a naphthoyl group, a 2-methylphenylcarbonyl group, a 4-(piperazin-1-yl)phenylcarbonyl group, and a 4-(phenyl)phenylcarbonyl group are more preferred.

[0125] In formula (c5), n4 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. When n4 is 1, R c9 The binding position of R c9 is preferably in the para position relative to the bond to the oxygen atom or sulfur atom.

[0126] In formulas (c1) and (c2), R c2 The monovalent organic group as is not particularly limited as long as it does not impair the object of the present invention. As the organic group, a carbon atom-containing group is preferable, and a group consisting of one or more carbon atoms and one or more atoms selected from the group consisting of H, O, S, Se, N, B, P, Si, and halogen atoms is more preferable. The number of carbon atoms in the carbon atom-containing group is not particularly limited, and is preferably 1 to 50, more preferably 1 to 20. R c2 Preferable examples of the monovalent organic group as R c5 Specific examples of these groups include the monovalent organic group R c5 The groups are the same as those described above. Also, R c2 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 in formula (c3). c5 The substituents are the same as those of the phenyl group, naphthyl group, and heterocyclyl group contained in the above formula (1) when they further have a substituent.

[0127] Among the organic groups, R c2 As the substituents containing the group represented by HX2C- or H2XC-, alkyl groups, cycloalkyl groups, phenyl groups which may have a substituent, cycloalkylalkyl groups, and phenylthioalkyl groups which may have a substituent on the aromatic ring are preferred. For alkyl groups, phenyl groups which may have a substituent, the number of carbon atoms in the cycloalkyl group contained in the cycloalkylalkyl group, the number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group, the cycloalkylalkyl group, the number of carbon atoms in the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring, or the phenylthioalkyl group which may have a substituent on the aromatic ring, R in formula (c3) c5 is the same as:

[0128] Also, R c2 A group represented by -A3-CO-O-A4 is also preferred. A3 is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A4 is a monovalent organic group, preferably a monovalent hydrocarbon group.

[0129] When A3 is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. When A3 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.

[0130] Preferable examples of A4 include an alkyl group having from 1 to 10 carbon atoms, an aralkyl group having from 7 to 20 carbon atoms, and an aromatic hydrocarbon group having from 6 to 20 carbon atoms. Specific preferable examples of A4 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.

[0131] Specific preferred examples of the group represented by -A3-CO-O-A4 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.

[0132] Also, R c2 Also preferred as the group are groups represented by the following formula (c7) or (c8). [ka] (In formulas (c7) and (c8), R c10 and R c11are each independently a monovalent organic group, n5 is an integer between 0 and 4, R c10 and R c11 When R is located at adjacent positions on the benzene ring, c10 and R c11 and may be bonded to each other to form a ring, R c12 is a monovalent organic group, n6 is an integer between 1 and 8, n7 is an integer between 1 and 5, n8 is an integer between 0 and (n7+3).

[0133] R in formula (c7) c10 and R c11 The organic group represented by R in formula (c4) is c8 Same as R c10 R is preferably a halogenated alkoxy group containing a group represented by HX2C- or H2XC-, a halogenated alkyl group containing a group represented by HX2C- or H2XC-, an alkyl group, or a phenyl group. c10 and R c11 When R is bonded to form a ring, the ring may be an aromatic ring or an aliphatic ring. c10 and R c11 Preferred examples of the group in which the ring is formed include a naphthalene-1-yl group and a 1,2,3,4-tetrahydronaphthalene-5-yl group. In the above formula (c7), n7 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.

[0134] In the above formula (c8), R c12 is an organic group. As the organic group, R in formula (c4) c8 Examples of the organic groups include the same groups as those described for the organic groups. Among the organic groups, an alkyl group is preferred. 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 c12Preferred 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.

[0135] In the above formula (c8), n7 is an integer of 1 or more and 5 or less, preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2. In the above formula (c8), n8 is an integer of 0 or more and (n7+3) or less, preferably an integer of 0 or more and 3 or less, more preferably an integer of 0 or more and 2 or less, and particularly preferably 0. In the above formula (c8), n8 is an integer of 1 or more and 8 or less, preferably an integer of 1 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, and particularly preferably 1 or 2.

[0136] In formula (c2), R c3 R is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent. c3 When is an aliphatic hydrocarbon group, preferred examples of the substituent that may be possessed by the group include a phenyl group, a naphthyl group, and the like.

[0137] In formulas (c1) and (c2), R c3 Preferred examples of such an alkyl group include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-cyclopentylethyl group, a 2-cyclobutylethyl group, a cyclohexylmethyl group, a phenyl group, a benzyl group, a methylphenyl group, and a naphthyl group. Of these, a methyl group or a phenyl group is more preferred.

[0138] Represented by formula (c2) and R c1 As specific preferred examples of the compound having a group represented by formula (c3), the following compounds can be mentioned. [ka]

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] Represented by formula (c2) and R c1 Preferable specific examples of the compound having a group represented by formula (c4) include the following compounds. [ka]

[0143] [ka]

[0144] [ka]

[0145] [ka]

[0146] [ka]

[0147] Represented by formula (c2) and R c1 Preferable specific examples of the compound having a group represented by formula (c5) include the following compounds. [ka]

[0148] Examples of the photopolymerization initiator (C) other than the oxime ester compound include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-dimethylaminophenyl)butan-1-one, 2-(4-methylbenzyl)-2-diethylamino-1-(4-morpholinophenyl)butan-1-one, and 2-methyl-1-phenyl-2-morpholinopropane. -1-one, 2-methyl-1-[4-(hexyl)phenyl]-2-morpholinopropan-1-one, 2-ethyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and other α-aminoketone compounds; 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl α-Hydroxyketone-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzyl methyl ketal; benzophenone-based photopolymerization initiators such as benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl, 4'-methyldiphenyl sulfide, and 4,4'-bisdiethylaminobenzophenone Photopolymerization initiators: thioxanthone-based photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-pipenyl-4.6-Bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxystyryl)-6 -Triazine, 2-[4-(4-methoxystyryl)phenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine and other triazine-based photopolymerization initiators; carbazole-based photopolymerization initiators; 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-ethoxycarbophenyl)-1,2'-biimidazole, 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, 2,2'-bis(2-bromophenyl)- Examples of such photopolymerization initiators include biimidazole-based photopolymerization initiators such as 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and benzimidazoline-based photopolymerization initiators as represented by the following formula. [ka]

[0149] The photopolymerization initiators may be used alone or in combination of two or more. By using two or more types in combination, it becomes easy to effectively utilize light rays having a wide range of wavelengths contained in the exposure light, and it is also easy to adjust the sensitivity of the negative photosensitive resin composition to an appropriate range.

[0150] The content of the photopolymerization initiator (C) in the total solid content of the negative photosensitive resin composition is preferably from 0.5% by mass to 15% by mass, and more preferably from 1% by mass to 10% by mass.

[0151] When a photopolymerization initiator other than the oxime ester compound is used in combination, the ratio of the mass of the oxime ester compound to the mass of the photopolymerization initiator (C) is preferably 50 mass% or more, more preferably 50 mass% or more and 99 mass% or less, particularly preferably 70 mass% or more and 97 mass% or less, and most preferably 80 mass% or more and 95 mass% or less.

[0152] The content of the photopolymerization initiator (C) is preferably 0.001 parts by mass or more and 30 parts by mass or less, more preferably 0.1 parts by mass or more and 20 parts by mass or less, and even more preferably 0.5 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the total solid content of the negative photosensitive resin composition. The solid content is the component other than the solvent (S). The content of the photopolymerization initiator (C) is preferably 0.1 mass% or more and 50 mass% or less, more preferably 0.5 mass% or more and 30 mass% or less, and even more preferably 0.5 mass% or more and 10 mass% or less, based on the total of the photosensitive resin (A) and the photopolymerization initiator (C).

[0153] <Adhesion enhancer (D)> The negative photosensitive resin composition may or may not contain an adhesion enhancer (D). The adhesion enhancer (D) 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.

[0154] The adhesion enhancer (D) 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 more preferably epoxy-based compounds. The epoxy-based compounds include, for example, organic silane compounds having an epoxy group, and more specifically, alkoxysilanes having 1 to 5 carbon atoms having an epoxy group.

[0155] The content of the adhesion enhancer (D) is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.5% by mass or more and 30% by mass or less, and even more preferably 0.5% by mass or more and 10% by mass or less, based on the total amount of the photosensitive resin (A) and the photopolymerizable compound (B). Within this range, excellent adhesive strength to the substrate is obtained.

[0156] <Solvent (S)> The negative photosensitive resin composition may or may not contain a 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 photosensitive 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.

[0157] The content of the solvent (S) is, for example, preferably 20 parts by mass or more and 95 parts by mass or less, more preferably 30 parts by mass or more and 90 parts by mass or less, and even more preferably 50 parts by mass or more and 80 parts by mass or less, 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.

[0158] <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.

[0159] 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.

[0160] The content of the surfactant is preferably in the range of 0.01 to 5 parts by mass, 0.02 to 1 part by mass, or 0.05 to 0.1 parts by mass, based on 100 parts by mass of the photosensitive resin (A).

[0161] Examples of the stabilizer include a heat stabilizer and a light stabilizer.

[0162] 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).

[0163] [ka]

[0164] [ka]

[0165] [ka]

[0166] 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.

[0167] <<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.

[0168] <Production method of cured film> The negative photosensitive resin composition can be used to produce a cured film (cured product) that can be used in displays such as TFT-LCD, OLED, and touch screen panels, and optical components such as microlenses and optical waveguides mounted on image sensors. The produced cured film may be patterned as necessary. A method for producing a patterned cured film using the above negative photosensitive resin composition will be described below.

[0169] 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.

[0170] 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.

[0171] 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. Generally, the coating can be performed so that the thickness after drying is 0.5 μm or more and 100 μm or less.

[0172] 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.

[0173] Next, the coating film is exposed to light in a selective manner. The selective exposure is performed, for example, through a negative mask. By performing the selective exposure, a patterned cured film can be formed. The exposure is performed by selectively irradiating the coating film with energy rays such as excimer laser, far ultraviolet rays, ultraviolet rays, visible light, 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. For the exposure, contact, proximity, projection, or other exposure methods 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 less than or equal to 5 mJ / cm 2 More than 100mJ / cm 2 or less, more preferably 10 mJ / cm 2 More than 60mJ / cm 2 The following is the result. By exposing the coating film to light, a curing reaction occurs.

[0174] Next, the exposed coating film is developed with a developer to obtain a cured film patterned into a desired shape. The developing method is not particularly limited, and for example, a dipping method, a 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.

[0175] 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 or higher and 250°C or lower, preferably 80°C or higher and 200°C or lower, more preferably 80°C or higher and 150°C or lower, and even more preferably 85°C or higher and 110°C or lower. It is preferable to carry out post-exposure bake (PEB), which is heating carried out after the step of exposing the coating film and before the step of developing.

[0176] The cured film (cured product) produced by the above-mentioned production method has a high refractive index and high transparency because it is formed using the above-mentioned negative photosensitive resin composition. Therefore, the cured film formed using the above-mentioned negative photosensitive resin composition can be used as a member that requires a high refractive index and high transparency.

[0177] In addition, the negative photosensitive resin composition has high solvent resistance, and therefore has high resistance to organic solvents such as propylene glycol monomethyl ether acetate (PEGMEA), etc. Therefore, the composition is preferably used in applications in which a composition in which a resin or other component is dissolved in a solvent is used to form another layer on the cured film to produce a laminate material, or in applications in which an adhesive containing a solvent is applied to the cured film.

[0178] Such a patterned cured film can be used for various applications, such as 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, as well as for coating materials and optical members such as microlenses and optical waveguides to be mounted on image sensors. EXAMPLES

[0179] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0180] <Synthesis of compound A (3,3'-(((9H-fluorene-9,9-diyl)bis(4,1-naphthyl))bis(oxy))bis(1-(phenylthio)propan-2-ol)> [ka] A reflux condenser and a thermometer were set in a three-neck flask, and then 2,2'-((((9H-fluorene-9,9-diyl)bis(4,1-naphthyl))bis(oxy))bis(methylene))bis(oxirane) (1000 g), thiophenol (524 g), and ethanol (617 g) were added and stirred. Triethylamine (328 g) was gradually added dropwise to 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 recrystallized with ethyl acetate to obtain compound A (945 g, 64% yield) as a pale yellow solid, and its structure was 1 Confirmed by HNMR. in CDCl 1 H NMR: 6.98~7.84 (30H), 4.19 (4H), 4.00 (2H), 2.92 (4H), 2.21 (2H).

[0181] <Production of Carboxy Group-Containing Resin> [Synthesis Example 1] Carboxy group-containing resin a-1 (R 3a is the following tetravalent group) [ka]

[0182] After setting a reflux tube and a thermometer in a three-neck flask, 10 g of compound A, 2.79 g of pyromellitic anhydride, and 30 g of propylene glycol methyl ether acetate were added, and the mixture was heated and stirred at 115°C for 10 hours to terminate the reaction. By cooling the mixture, a solution of carboxyl group-containing resin a-1 with a mass average molecular weight of 5,200 g / mol was obtained.

[0183] [Synthesis Example 2] Carboxy group-containing resin a-2 (R 3a is the following tetravalent group) [ka]

[0184] After setting a reflux condenser and a thermometer in a three-neck flask, 10 g of compound A, 3.76 g of 4,4'-biphthalic anhydride, and 30 g of propylene glycol methyl ether acetate were added, and the mixture was heated and stirred at 115°C for 10 hours to terminate the reaction. By cooling the mixture, a solution of carboxyl group-containing resin a-2 with a mass average molecular weight of 3,500 g / mol was obtained.

[0185] [Synthesis Example 3] Carboxy Group-Containing Resin a-3 (R 3a is the following tetravalent group) [ka]

[0186] After setting a reflux condenser and a thermometer in a three-neck flask, 10 g of compound A, 4.12 g of 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 30 g of propylene glycol methyl ether acetate were added, and the mixture was heated and stirred at 115°C for 10 hours to terminate the reaction. By cooling the mixture, a solution of carboxyl group-containing resin a-3 with a mass average molecular weight of 4,800 g / mol was obtained.

[0187] [Synthesis Example 4] Carboxy Group-Containing Resin a-4 (R 3a is the following tetravalent group) [ka]

[0188] After setting a reflux condenser and a thermometer in a three-neck flask, 10 g of compound A, 4.91 g of 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, and 30 g of propylene glycol methyl ether acetate were added, and the mixture was heated and stirred at 115°C for 10 hours to terminate the reaction. By cooling the mixture, a solution of carboxyl group-containing resin a-4 with a mass average molecular weight of 2,200 g / mol was obtained.

[0189] [Synthesis Example 5] Carboxy Group-Containing Resin a-5 (R 3a is the following tetravalent group) [ka]

[0190] After setting a reflux condenser and a thermometer in a three-neck flask, 10 g of compound A, 3.96 g of 4,4'-oxydiphthalic anhydride, and 30 g of propylene glycol methyl ether acetate were added, and the mixture was heated and stirred at 115°C for 10 hours to terminate the reaction. By cooling the mixture, a solution of carboxyl group-containing resin a-5 with a mass average molecular weight of 2,800 g / mol was obtained.

[0191] [Comparative Synthesis Example 1] According to Production Example 1 described in Patent Document 4 (JP Patent Publication No. 2018-531311), a carboxyl group-containing resin a-6 (R 3a is a tetravalent group, and Z in formula (a2) is a carboxyl group-containing resin having a structural unit represented by formula (a1): 1 and Z 2 is a benzene ring, and k1, k2, m1 and m2 are 0) was obtained. [ka]

[0192] <Production of photosensitive resin> [Synthesis Example 6] Production of Photosensitive Resin A-1 0.45 g of glycidyl methacrylate was added to the solution of carboxyl group-containing resin a-1 obtained in Synthesis Example 1 at room temperature, and the mixture was stirred at 95° C. for 2 hours. 0.25 moles of glycidyl methacrylate was added per mole of compound A used in Synthesis Example 1. The mixture was then cooled to room temperature, and propylene glycol monomethyl ether acetate was added to give a solid content (non-volatile content) concentration of 30% by mass, to obtain a solution of photosensitive resin A-1 having a mass average molecular weight of 5,600 g / mol. The addition of glycidyl methacrylate was confirmed by measuring the acid value of the solid content.

[0193] [Synthesis Example 7] Production of Photosensitive Resin A-2 0.45 g of glycidyl methacrylate was added to the solution of carboxyl group-containing resin a-2 obtained in Synthesis Example 2 at room temperature, and the mixture was stirred at 95° C. for 2 hours. 0.25 moles of glycidyl methacrylate was added per mole of compound A used in Synthesis Example 2. The mixture was then cooled to room temperature, and propylene glycol monomethyl ether acetate was added to give a solid content (non-volatile content) concentration of 30% by mass, to obtain a solution of photosensitive resin A-2 having a mass average molecular weight of 3,700 g / mol. The addition of glycidyl methacrylate was confirmed by measuring the acid value of the solid content.

[0194] [Synthesis Example 8] Production of Photosensitive Resin A-3 0.45 g of glycidyl methacrylate was added to the solution of carboxyl group-containing resin a-3 obtained in Synthesis Example 3 at room temperature, and the mixture was stirred at 95° C. for 2 hours. 0.25 moles of glycidyl methacrylate was added per mole of compound A used in Synthesis Example 3. The mixture was then cooled to room temperature, and propylene glycol monomethyl ether acetate was added to give a solid content (non-volatile content) concentration of 30% by mass, to obtain a solution of photosensitive resin A-3 having a mass average molecular weight of 5100 g / mol. The addition of glycidyl methacrylate was confirmed by measuring the acid value of the solid content.

[0195] [Synthesis Example 9] Production of Photosensitive Resin A-4 0.45g of glycidyl methacrylate was added to the solution of carboxyl group-containing resin a-4 obtained in Synthesis Example 4 at room temperature, and the mixture was stirred at 95°C for 2 hours. 0.25 moles of glycidyl methacrylate was added per mole of compound A used in Synthesis Example 4. The mixture was then cooled to room temperature, and propylene glycol monomethyl ether acetate was added to give a solid content (non-volatile content) concentration of 30% by mass, to obtain a solution of photosensitive resin A-4 having a mass average molecular weight of 2400g / mol. The addition of glycidyl methacrylate was confirmed by measuring the acid value of the solid content.

[0196] [Synthesis Example 10] Production of Photosensitive Resin A-5 0.45 g of glycidyl methacrylate was added to the solution of carboxyl group-containing resin a-5 obtained in Synthesis Example 5 at room temperature, and the mixture was stirred at 95°C for 2 hours. 0.25 moles of glycidyl methacrylate was added per mole of compound A used in Synthesis Example 5. The mixture was then cooled to room temperature, and propylene glycol monomethyl ether acetate was added to give a solid content (non-volatile content) concentration of 30% by mass to obtain a solution of photosensitive resin A-5 having a mass average molecular weight of 3,100 g / mol. The addition of glycidyl methacrylate was confirmed by measuring the acid value of the solid content.

[0197] <Preparation of negative-type photosensitive resin composition and patterned cured film> [Examples 1 to 5 and Comparative Example 1] 60 parts by mass of photosensitive resins A-1 to A-5 or carboxyl group-containing resin a-6 listed in Table 1 as a photosensitive resin, 30 parts by mass of the following B-1 as a photopolymerizable compound (B), 5 parts by mass of the following compound P-1 as a photopolymerization initiator (C), and 5 parts by mass of 3-acryloxypropyltrimethoxysilane as a silane coupling agent having a reactive functional group were dissolved in propylene glycol monomethyl ether acetate as a solvent (S) so that the solid content concentration was 30 mass%, to prepare negative photosensitive resin compositions of Examples 1 to 5 and Comparative Example 1. [ka]

[0198] The obtained negative photosensitive resin composition was applied to a glass substrate using a spin coater and heated (dried) at 100° C. for 2 minutes to form a coating film having a thickness of 3 μm. After drying, the coating film was exposed to a negative mask with a 10 μm wide pattern, and a high-pressure mercury lamp was used as the light source, with an integrated exposure of 50 mJ / cm 2 The exposure was carried out so that The coating film after exposure was heated at 100° C. for 2 minutes (PEB), and then the refractive index and transmittance were measured by the following method. Thereafter, the coating film was developed for 180 seconds with a 2.38 mass % tetramethylammonium hydroxide aqueous solution (water-soluble alkaline developer) at 25° C., and then washed with water to obtain a patterned cured film. The solvent resistance of the obtained patterned cured film was evaluated by the following method, and the results are shown in Table 1.

[0199] [Refractive index measurement] For the coating film (cured film) after PEB, the refractive index at a wavelength of 550 nm was determined using a prism coupler manufactured by Metricon.

[0200] [Transmittance measurement] For the coating film (cured film) after PEB, the transmittance value at a wavelength of 400 nm was determined using a multichannel spectrometer (MCPD-3000) manufactured by Otsuka Electronics Co., Ltd.

[0201] [Solvent resistance measurement] The obtained patterned cured film was immersed in propylene glycol monomethyl ether acetate for 1 minute, the film thickness was measured before and after immersion, and the remaining film ratio was calculated by the following formula. Remaining film rate (%) = (film thickness after immersion / film thickness before immersion) x 100

[0202] [Table 1]

[0203] As shown in Table 1, it can be seen that the cured film formed by the negative type photosensitive resin composition of the example containing a photosensitive resin in which a (meth)acrylate compound having a carboxylic acid reactive group is added or condensed to at least a part of the carboxyl group of the carboxyl group-containing resin having a structural unit represented by formula (a1) and a photopolymerization initiator has a high refractive index and high transparency. It can also be seen that these cured films have a high residual film rate and excellent solvent resistance. In addition, in both the examples and the comparative examples, a pattern with a width of 10 μm was formed.

[0204] On the other hand, according to Comparative Example 1, it is found that when the negative photosensitive resin composition does not contain a photosensitive resin in which a (meth)acrylate compound having a carboxylic acid reactive group is added or condensed to at least a part of the carboxyl groups of the carboxyl group-containing resin having a structural unit represented by formula (a1), it is not possible to achieve both a high refractive index and high transparency. Also, it is found that the solvent resistance of the cured film of Comparative Example 1 is extremely inferior to that of the Examples.

[0205] <Evaluation of carboxyl group-containing resin> [Reference examples 1~6] To a solution of carboxyl group-containing resins a-1 to a-5 or a-6 shown in Table 2 as a carboxyl group-containing resin, propylene glycol monomethyl ether acetate was added so that the solid concentration (non-volatile content) was 30 mass % to prepare a carboxyl group-containing resin solution. The solution of the carboxyl group-containing resin was applied to a glass substrate using a spin coater and heated (dried) at 100° C. for 2 minutes to form a coating film with a thickness of 3 μm. The refractive index and transmittance of the coating film thus obtained were measured as described below. The results are shown in Table 2.

[0206] [Refractive index measurement] The refractive index of the resulting coating film was determined at a wavelength of 550 nm using a prism coupler manufactured by Metricon.

[0207] [Transmittance measurement] The transmittance of the obtained coating film at a wavelength of 400 nm was determined using a multichannel spectrometer (MCPD-3000) manufactured by Otsuka Electronics Co., Ltd.

[0208] [Table 2]

[0209] As shown in Table 2, among the carboxyl group-containing resins having a structural unit represented by formula (a1), R 3a a-4 or a-5 is a tetravalent organic group represented by formula (a1a), 3a It can be seen that the refractive index and transmittance are both achieved at a higher level than in a-1 to a-3 and a-6, which are not tetravalent organic groups represented by formula (a1a).

Claims

1. A photosensitive resin comprising a carboxyl group-containing resin having a structural unit represented by the following formula (a1), in which a (meth)acrylate compound having a glycidyl group is added to or condensed with at least a portion of the carboxyl groups of the carboxyl group-containing resin: 【Chemistry 1】 (In formula (a1), R １ａ and R ２ａ Each independently represents -R ４ａ represents SR5a, R ４ａ represents an alkylene group having 1 to 10 carbon atoms, R ５ａ represents an aryl group having from 6 to 15 carbon atoms, R ３ａ below: 【Chemistry 2】 represents a tetravalent group A represents a divalent group represented by the following formula (a2-1): j1 and j2 each independently represent an integer of 1 or more and 2 or less. 【Chemistry 3】 (In formula (a2-1), R 8a and R 9a each independently represent 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 represent a hydrogen atom, an alkyl group, or an aryl group; k1 and k2 each represent 0; m1 and m2 represent 0.

2. The R ３ａ The photosensitive resin according to claim 1 , wherein: 【Chemistry 4】

3. A negative photosensitive resin composition comprising the photosensitive resin according to claim 1 or 2 and a photopolymerization initiator.

4. The negative type photosensitive resin composition according to claim 3 , further comprising a photopolymerizable compound.

5. A step of applying the negative type photosensitive resin composition according to claim 3 or 4 onto a substrate to form a coating film; A step of position-selectively exposing the coating film; developing the coating film after exposure; A method for producing a patterned cured film, comprising:

6. The method for producing a patterned cured film according to claim 5 , 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.

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