Negative photosensitive resin composition, cured product, and method for producing patterned cured product

Abstract

To provide a negative photosensitive resin composition capable of forming a patterned cured film that has a high refractive index and also has a convex lens shape, a cured product of the negative photosensitive resin composition, and a method for producing a cured product using the negative photosensitive resin composition.SOLUTION: A negative photosensitive resin composition comprises a resin (A) of a specific structure, a photopolymerization initiator (C), and a compound (D) of a specific structure. There are also provided a cured product of the negative photosensitive resin composition, and a method for producing a patterned cured film using the negative photosensitive resin composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a negative photosensitive resin composition, a cured product of the negative photosensitive resin composition, and a method for producing a patterned cured product using the negative photosensitive resin composition. [Background technology]

[0002] BACKGROUND ART Patterned cured products obtained by exposing and developing photosensitive resin compositions are used in electronic devices such as organic electroluminescence (EL) displays, liquid crystal displays, touch panels, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs).

[0003] Organic electroluminescent displays suffer from low light extraction efficiency, i.e., the efficiency with which generated light escapes the device. One light extraction method that solves this problem is to use a high refractive index pattern to reduce the difference in refractive index between layers (components), which is one of the causes of light loss before it leaves the interior. BACKGROUND ART As photosensitive resin compositions capable of forming high refractive index patterns (patterned cured products having a high refractive index), various negative photosensitive resin compositions have been proposed.

[0004] For light extraction applications, it is desirable for the material to have a convex lens shape in addition to a high refractive index. A convex lens shape is a shape in which the surface is a convex curved surface, and is a shape that can be used as a convex lens, for example. FIG. 1 is a schematic cross-sectional view illustrating the shape of a patterned cured product. As shown in FIG. 1, a patterned cured product 10 formed on a substrate 1 has a shape in which the surface is a convex curved surface (convex lens shape).

[0005] However, when a negative-type photosensitive resin composition is applied to photolithography, the portions of the coating film made of the negative-type photosensitive resin composition that have been cured by exposure to light remain undissolved in the developer during development, resulting in the formation of a patterned cured product. Therefore, when a conventional negative-type photosensitive resin composition is used, the cross-sectional shape of the patterned cured product generally tends to be inverted tapered or rectangular, and undercuts are likely to occur in the cross-section of the patterned cured product. When a conventional negative-type photosensitive resin composition is used, a patterned cured product having a cross-section with an inverted tapered shape is particularly likely to be formed. Figure 2 is a schematic cross-sectional view illustrating the shape of a patterned cured product. Figure 2(a) shows an inverted tapered shape, Figure 2(b) shows a shape with undercuts 20 (undercut shape), and Figure 2(c) shows a rectangular shape. As described above, it is difficult to form a patterned cured product in the shape of a convex lens using a negative photosensitive resin composition.

[0006] As a technique for solving the above-mentioned problems, Patent Document 1 discloses that a negative-type photosensitive resin composition for pattern formation, which contains a specific triazine ring-containing polymer, a crosslinking agent, and an organic solvent, can be used to form a convex lens-shaped pattern having a high refractive index. are. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2021 / 117692 Summary of the Invention [Problem to be solved by the invention]

[0008] However, the composition of Patent Document 1 essentially contains a specific triazine ring-containing polymer, and therefore it is desirable to be able to form a patterned cured product having a high refractive index and a convex lens shape using other negative-type photosensitive resin compositions.

[0009] The present invention has been made in consideration of the above-mentioned problems, and an object of the present invention is to provide a negative photosensitive resin composition that has a high refractive index and is capable of forming a patterned cured product having a convex lens shape, a cured product of the negative photosensitive resin composition, and a method for producing a cured product using the negative photosensitive resin composition. [Means for solving the problem]

[0010] As a result of extensive research to achieve the above object, the present inventors have discovered that the above problems can be solved by a negative-type photosensitive resin composition containing a resin (A) having a structural unit represented by the following formula (a1), a photopolymerization initiator (C), and a compound (D) represented by the following formula (d1), and have thus completed the present invention. Specifically, the present invention provides the following:

[0011] [1] A negative photosensitive resin composition comprising a resin (A) having a structural unit represented by the following formula (a1), a photopolymerization initiator (C), and a compound (D) represented by the following formula (d1): [ka] (In formula (a1), R 1a and R 2a each independently represents an alkyl group having 1 to 20 carbon atoms and optionally containing a heteroatom, an aryl group having 6 to 20 carbon atoms and optionally containing a heteroatom, -R 4a SR 5a or -R 6a C(=O)R 7a represents R 3a represents a tetravalent organic group, A represents a divalent group represented by the following formula (a2): j1 and j2 each independently represent an integer of 1 or more and 6 or less, R 4a represents a single bond, an alkylene group having from 1 to 10 carbon atoms, or an arylene group having from 6 to 15 carbon atoms, S represents a sulfur atom, R 5a represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, R 6a represents a single bond, an alkylene group having from 1 to 10 carbon atoms, or an arylene group having from 6 to 10 carbon atoms, R 7a represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. [ka] (In formula (a2), R 8a and R 9a each independently represents a hydrogen atom, a hydroxy group, a mercapto group, an amino group, a nitro group, a halogen atom, a cyano group, or an alkyl group, R 10a and R 11a each independently represents a hydrogen atom, an alkyl group, or an aryl group, k1 and k2 each independently represent an integer of 0 to 4, m1 and m2 each independently represent an integer of 0 or more and 3 or less. [ka] (In formula (d1), Ring Z 1 and ring Z 2 each independently represents an aromatic hydrocarbon ring, X 1d and X 2d each independently represents a single bond or a linking group, W 1d and W 2d each independently represents an acidic group, R 1d and R 2d each independently represents a hydrogen atom, a hydroxy group, a mercapto group, an amino group, a nitro group, a halogen atom, or an organic group; R 3d and R 4deach independently represents a hydrogen atom, an alkyl group, or an aryl group, n1 and n2 each independently represent an integer of 0 to 4, n3 and n4 each independently represent an integer of 0 to 3, When n1 is an integer between 2 and 4, multiple R 1d two of which may be bonded to each other to form a ring; When n2 is an integer between 2 and 4, multiple R 2d Two of the may be bonded to each other to form a ring.

[0012] [2] Ring Z in the formula (d1) 1 and ring Z 2 and each independently represent a naphthalene ring or a benzene ring.

[0013] [3] The aforementioned W 1d and W 2d and each independently represent a phenolic hydroxyl group or a carboxyl group.

[0014] [4] The negative photosensitive resin composition according to any one of the above [1] to [3], further comprising a photopolymerizable monomer (B).

[0015] [5] A cured product of the negative photosensitive resin composition according to any one of the above [1] to [4].

[0016] [6] A step of applying the negative photosensitive resin composition according to any one of the above [1] to [4] onto a substrate to form a coating film; a step of position-selectively exposing the coating film; developing the exposed coating film; and heating the developed coating film. [Effects of the Invention]

[0017] According to the present invention, it is possible to provide a negative photosensitive resin composition capable of forming a patterned cured product having a high refractive index and a convex lens shape, a cured product of the negative photosensitive resin composition, and a method for producing a cured product using the negative photosensitive resin composition. [Brief explanation of the drawings]

[0018] [Figure 1] FIG. 2 is a schematic cross-sectional view illustrating the shape of a patterned cured product. [Figure 2] FIG. 2 is a schematic cross-sectional view illustrating the shape of a patterned cured product. DETAILED DESCRIPTION OF THE INVENTION

[0019] The present invention will be described in detail below. <Negative-type photosensitive resin composition> The negative photosensitive resin composition contains a resin (A) having a structural unit represented by formula (a1), a photopolymerization initiator (C), and a compound (D) represented by formula (d1). The negative photosensitive resin composition may contain a photopolymerizable monomer (B), a solvent (S), and other components, as needed.

[0020] Hereinafter, essential and optional components contained in the negative photosensitive resin composition and a method for producing the negative photosensitive resin composition will be described.

[0021] <Resin (A) (binder resin)> The resin (A) has a structural unit represented by the following formula (a1). [ka] (In formula (a1), R 1a and R 2a each independently represents an alkyl group having 1 to 20 carbon atoms and optionally containing a heteroatom, an aryl group having 6 to 20 carbon atoms and optionally containing a heteroatom, -R 4a SR 5a or -R 6aC(=O)R 7a represents R 3a represents a tetravalent organic group, A represents a divalent group represented by the following formula (a2): j1 and j2 each independently represent an integer of 1 or more and 6 or less, R 4a represents a single bond, an alkylene group having from 1 to 10 carbon atoms, or an arylene group having from 6 to 15 carbon atoms, S represents a sulfur atom, R 5a represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, R 6a represents a single bond, an alkylene group having from 1 to 10 carbon atoms, or an arylene group having from 6 to 10 carbon atoms, R 7a represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. [ka] (In formula (a2), R 8a and R 9a each independently represents a hydrogen atom, a hydroxy group, a mercapto group, an amino group, a nitro group, a halogen atom, a cyano group, or an alkyl group, R 10a and R 11a each independently represents a hydrogen atom, an alkyl group, or an aryl group, k1 and k2 each independently represent an integer of 0 to 4, m1 and m2 each independently represent an integer of 0 or more and 3 or less.

[0022] As can be seen from the structure of the above formula (a2), the resin (A) has a bisphenylfluorene structure as a basic structure in its constituent units.

[0023] In formula (a1), heteroatoms refer to elements other than carbon and hydrogen atoms. Examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms, and silicon atoms. A plurality of these heteroatoms may be contained. The heteroatom is preferably a sulfur atom, which provides particularly excellent effects on heat resistance, chemical resistance, high transmittance, high refractive index, and optical properties.

[0024] In formula (a1), R 1a and R 2a The number of carbon atoms in the alkyl group which may contain a heteroatom as the heteroatom is from 1 to 20, preferably from 2 to 15, and more preferably from 2 to 10. Specific examples of the alkyl group which may contain a heteroatom include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, and an n-decyl group. R 1a and R 2a The number of carbon atoms in the aryl group which may contain a heteroatom as the heteroatom is 6 or more and 20 or less, preferably 6 or more and 15 or less, and more preferably 6 or more and 10 or less. Specific examples of the aryl group which may contain a heteroatom include a phenyl group, a naphthyl group, a furyl group, and a thienyl group.

[0025] 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 include a phenylene group and a naphthylene group. R 5aSpecific 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 SR 5a This provides particularly excellent effects in terms of heat resistance, high transmittance and high refractive index.

[0026] R 6a Specific examples of alkylene groups 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 are also exemplified. R 7a Specific examples of alkyl groups having 1 to 10 carbon atoms as R 5a Examples of the alkyl group include the same alkyl groups as those exemplified for the above. R 7a Specific examples of the aryl group having 6 to 15 carbon atoms as R 5a The aryl groups mentioned above are also examples of 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.

[0027] R 3a Examples of the tetravalent organic group as R include a tetravalent organic group containing an alicyclic hydrocarbon group and a tetravalent organic group containing an aromatic hydrocarbon group. 3ais typically a tetravalent residue obtained by removing two carboxylic acid anhydride groups from a tetracarboxylic acid dianhydride.

[0028] R 3a The tetravalent organic group containing an alicyclic hydrocarbon group as the aryl group has, for example, 1 or more and 20 or less carbon atoms, preferably 4 or more and 12 or less, and more preferably 4 or more and 6 or less carbon atoms. In formula (a1), R 3a The four carbonyl groups bonded to the tetravalent organic group containing the alicyclic hydrocarbon group as R 3a It is preferred that the alicyclic hydrocarbon group be bonded to the aliphatic hydrocarbon ring of the alicyclic hydrocarbon group. R 3a Examples of the alicyclic hydrocarbon group contained in the tetravalent organic group containing an alicyclic hydrocarbon group as above include groups in which one or more hydrogen atoms have been removed from a cycloalkyl group such as cyclobutane, cycloheptane, cyclohexane, etc. R 3a Examples of the tetravalent organic group containing an alicyclic hydrocarbon group as the above include a tetravalent alicyclic hydrocarbon group which may contain a heteroatom, and a tetravalent group in which two trivalent alicyclic hydrocarbon groups are linked by a heteroatom, a carbonyl group, or a single bond. Examples of the heteroatom include an oxygen atom and a sulfur atom. R 3a The number of alicyclic hydrocarbon groups contained in may be one or more. R 3a Specific examples of the tetravalent organic group containing an alicyclic hydrocarbon group as the tetravalent group include the following tetravalent groups, groups in which hydrogen atoms in the following tetravalent groups are substituted with alkyl groups such as methyl groups and ethyl groups, and tetravalent groups derived from tetracarboxylic dianhydrides described below. [ka]

[0029] R 3a The number of carbon atoms in the tetravalent organic group containing an aromatic hydrocarbon group as the aromatic hydrocarbon group is, for example, 6 or more and 20 or less, preferably 6 or more and 15 or less, and more preferably 6 or more and 12 or less. In formula (a1), R 3a The four carbonyl groups bonded to the tetravalent organic group containing the aromatic hydrocarbon group as R 3a It is preferred that the aromatic hydrocarbon ring is bonded to the aromatic hydrocarbon ring. R 3a Examples of the aromatic hydrocarbon group contained in the tetravalent organic group containing an aromatic hydrocarbon group as the aromatic hydrocarbon group 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 two or more.

[0030] R 3a Examples of the tetravalent organic group containing an aromatic hydrocarbon group as the tetravalent organic group include a tetravalent aromatic hydrocarbon group which may contain a heteroatom, and a group in which multiple aromatic hydrocarbon groups are linked by a linking group such as -O-, -S-, or an alkylene group. Examples of the group in which a plurality of aromatic hydrocarbon groups are linked by a linking group such as -O-, -S- or an alkylene group include tetravalent organic groups represented by the following formula (a1a). >Ar 1a -X 1 -Ar 2a <···(a1a) (In formula (a1a), Ar 1a and Ar 2a each independently represents an aromatic hydrocarbon group optionally 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

[0031] 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 3aThe aromatic hydrocarbon group is the same as the aromatic hydrocarbon group contained in the tetravalent organic group containing an aromatic hydrocarbon group as the aromatic hydrocarbon group. 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, and examples of the electron-donating group include an alkoxy group, an amino group, and an alkyl group.

[0032] In formula (a1a), X 1 As, Ar 1a and Ar 2a Examples of the divalent linking group that does not form a π-conjugated system together 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. A carbonyl group (-C(=O)-) or a vinylene (-CH=CH-) group 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 Ar is a single bond, 1a and Ar 2a Since it forms a π-conjugated system with

[0033] Examples of the group represented by formula (a1a) include groups 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 optionally substituted with an electron-donating group, X 2 and X 3each independently represents an oxygen atom, a sulfur atom, or an alkylene group having from 1 to 10 carbon atoms, n represents an integer between 0 and 2.

[0034] 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 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 as , a p-phenylene group and an m-phenylene group are preferred, and a p-phenylene group is more preferred.

[0035] R 3a Specific examples of the tetravalent organic group containing an aromatic hydrocarbon group as the tetravalent group include the following tetravalent groups, groups in which a hydrogen atom on the benzene ring in the following tetravalent groups is substituted with one or more electron-donating groups such as a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and tetravalent groups derived from tetracarboxylic dianhydrides described below. [ka]

[0036] 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.

[0037] In formula (a2), R 8a and R 9a are each independently a hydrogen atom, a hydroxy 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 9aSpecific 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 above. R 8a and R 9a is preferably a hydrogen atom.

[0038] R 10a and R 11a 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 above. 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 mentioned above are also examples of the aryl groups.

[0039] 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.

[0040] The number of structural units represented by formula (a1) contained in resin (A) is not particularly limited. The number of structural units represented by formula (a1) contained in resin (A) is, for example, an integer of 1 to 30, preferably an integer of 1 to 10. Within this range, particularly excellent effects are obtained in terms of heat resistance, high transmittance, and high refractive index.

[0041] The mass average molecular weight of the resin (A) can be, for example, 1,000 to 100,000 g / mol, preferably 2,000 to 50,000 g / mol, and more preferably 3,000 to 10,000 g / mol. Within this range, the resin exhibits excellent heat resistance, a high development rate for the photosensitive material, and ease of development with a developer, thereby facilitating pattern formation and exhibiting a high residual film rate.

[0042] The dispersity of the resin (A) (mass average molecular weight Mw / number average molecular weight Mn) can be, for example, in the range of 1.0 to 5.0, preferably in the range of 1.5 to 4.0. Within this range, the resin has excellent heat resistance, the development speed of the photosensitive material is high, and development with a developer is easy, which facilitates pattern formation and results in a high residual film rate.

[0043] The mass average molecular weight, number average molecular weight, and dispersity in this specification can be measured by gel permeation chromatography (GPC).

[0044] By preparing a negative-tone photosensitive resin composition containing such a specific resin (A) together with a specific compound (D) and a photopolymerization initiator (C), which will be described in detail later, it is possible to form a patterned cured product having a high refractive index and a convex lens shape, as shown in the examples described later. Furthermore, the negative-tone photosensitive resin composition can also form a patterned cured product having excellent transparency and solvent resistance.

[0045] Resin (A) can be produced, for example, by the method described in JP-A-2018-531311. Specifically, the resin (A) can be synthesized by synthesizing a compound (monomer) containing a hydroxy group represented by the following formula (2) from a compound represented by the following formula (1), and then polymerizing the resulting compound with a tetracarboxylic dianhydride. [ka] (In formula (1), R 8a ~R 11a, k1, k2, m1, and m2 are R in formula (a2), respectively. 8a ~R 11a , k1, k2, m1 and m2, and R 12a and R 13a each independently represents a hydroxy group, a thiol group, an amino group, a nitro group, a cyano group, an aliphatic alkyl group or an alicyclic alkyl group containing a heteroatom and having from 1 to 20 carbon atoms, or an aryl group containing a heteroatom and having from 6 to 20 carbon atoms. [ka] (In formula (2), R 8a ~R 11a , k1, k2, m1, and m2 are R in formula (a2), respectively. 8a ~R 11a , k1, k2, m1 and m2, and R 1a , R 2a , j1 and j2 are R in formula (a1), respectively. 1a , R 2a , j1 and j2.)

[0046] In formula (1), heteroatoms refer to elements other than carbon and hydrogen atoms. Examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms, and silicon atoms. A plurality of these heteroatoms may be contained. For example, R 12a and R 13a may contain heteroatoms in the form of hydroxy, thiol, amino, nitro or cyano groups.

[0047] 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 hydroxyalkyl groups or thioalkyl groups having from 1 to 5 carbon atoms. R 12a and R13a 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.

[0048] The tetracarboxylic dianhydride may be one represented by the following formula (3).

[0049] [ka] (In formula (3), R 3a is R in formula (a1). 3a is the same as

[0050] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, and 1,1-bis(3,4-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl) aromatic tetracarboxylic dianhydrides such as 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride; Examples of the tetracarboxylic acid dianhydride include hydrates, alicyclic tetracarboxylic acid dianhydrides such as 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, and 1,2,3,4-cyclohexanetetracarboxylic acid dianhydride, and tetracarboxylic acid dianhydrides, which are compounds in which two alicyclic hydrocarbon groups (e.g., cyclohexyl groups) are linked by a heteroatom (e.g., an oxygen atom), such as 1,1'-oxybiscyclohexane-3,3',4,4'-tetracarboxylic acid dianhydride.

[0051] The polymerization reaction can be carried out, for example, at 100° C. to 130° C., or 110° C. to 120° C. for 2 to 4 hours, or 4 to 12 hours.

[0052] The tetracarboxylic acid dianhydride 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 the above formula (2).

[0053] In the production of resin (A), for example, after the initiation of the above-mentioned polymerization reaction, a terminal blocking agent may be added to the reaction, which makes it easier to control the mass average molecular weight of resin (A). This reaction of the end-capping agent (end-capping reaction) can be carried out, for example, for 30 minutes to 4 hours, or for 1 hour to 3 hours, at 100°C to 130°C, or 110°C to 120°C.

[0054] The terminal blocking agent may be added in an amount of, for example, 2 to 10 parts by mass, 2 to 5 parts by mass, or 3 to 5 parts by mass, based on 100 parts by mass of the compound containing a hydroxy group represented by formula (2) above.

[0055] Examples of the end-capping agent include organic acids, organic acid anhydrides, and amide acids. The end-capping agent is preferably an aromatic carboxylic acid anhydride, a specific example of which is phthalic anhydride. By using an aromatic carboxylic acid anhydride as the end-capping agent, the resin (A) has particularly excellent effects in terms of heat resistance, high transmittance, and high refractive index.

[0056] When a terminal blocking agent is used, the terminal structure of the resin (A) may be a structure derived from the terminal blocking agent. Furthermore, the terminal structure of the resin (A) may be a structure derived from a raw material added in excess, such as a compound containing a hydroxy group represented by the above formula (2) or a tetracarboxylic dianhydride. More specifically, the terminal structure of the resin (A) may be, for example, the following structures 1 to 4, and the mass average molecular weight of the resin (A) can be appropriately controlled. The multiple terminal structures in the molecular chain of the resin constituting the resin (A) may be different from each other. The following OX in Structure 4 is a group generated by reaction of the hydroxyl group in Structure 3 with the above-mentioned end-capping agent. Among the following end structures, Structure 4 is preferred in terms of development characteristics. As Structure 4, a structure having OX derived from an organic acid anhydride such as a dicarboxylic acid anhydride such as phthalic anhydride or tetrahydrophthalic anhydride is preferred. Structure 1: A structure in which a hydrogen atom is bonded to the carbonyloxy group at the left end of the structure represented by formula (a1). Structure 2: Structure 1 in which two of the carboxyl groups have become carboxylic anhydride groups Structure 3:-CHR 2a -(CH2) j2 -OAO-(CH2) j1 -CH(OH)-R 1a The structure represented by Structure 4:-CHR 2a -(CH2) j2 -OAO-(CH2) j1 -CH(OX)-R 1a The structure represented by

[0057] The content of the resin (A) is preferably 25 to 90 parts by mass, more preferably 30 to 80 parts by mass, and even more preferably 40 to 70 parts by mass, relative to 100 parts by mass of the total solid content of the negative photosensitive resin composition. The solid content refers to components other than the solvent (S).

[0058] <Photopolymerizable Monomer (B)> The negative photosensitive resin composition may or may not contain the photopolymerizable monomer (B), but preferably contains the photopolymerizable monomer (B). The photopolymerizable monomer (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 monomer 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, multifunctional (meth)acrylic monomers and oligomers such as acrylate, 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 poly(poly) compounds thereof (polyethylene glycol diacrylate); polyester(meth)acrylate obtained by reacting (meth)acrylic acid with a polyester prepolymer obtained by condensing a polyhydric alcohol with a monobasic acid or a polybasic acid; polyurethane(meth)acrylate obtained by reacting a compound having a polyol group and two isocyanate groups with the resulting compound and then reacting with (meth)acrylic acid; Examples of suitable epoxy (meth)acrylate resins include those obtained by reacting epoxy resins such as bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, phenol or cresol novolac epoxy resins, resol epoxy resins, triphenolmethane epoxy resins, polycarboxylic acid polyglycidyl esters, polyol polyglycidyl esters, aliphatic or alicyclic epoxy resins, amine epoxy resins, and dihydroxybenzene epoxy resins with (meth)acrylic acid. Taking into consideration factors such as exposure sensitivity, it is preferable to use a polyfunctional (meth)acrylic monomer as the photopolymerizable monomer (B).

[0059] As the photopolymerizable monomer (B), a (meth)acrylate (B1) having an aromatic group is also preferred. In this specification, (meth)acrylate means both acrylate and methacrylate, (meth)acryloyl means both acryloyl and methacryloyl, and (meth)acrylic means both acrylic and methacrylic.

[0060] The aromatic group contained in the (meth)acrylate (B1) having an aromatic group is preferably a polycyclic aromatic group. The polycyclic aromatic group may be a group in which two or more rings including an aromatic ring are condensed, or a group in which two or more rings including an aromatic ring are bonded to each other via a single bond or a divalent linking group. The polycyclic aromatic group preferably has 7 or more and 12 or less ring-constituting carbon atoms. The polycyclic aromatic group may contain heteroatoms such as sulfur atoms, nitrogen atoms, and oxygen atoms as ring-constituting atoms. In the polycyclic aromatic group, one or more hydrogen atoms may be substituted with one or more groups selected from the group consisting of an alkyl group having from 1 to 5 carbon atoms, a cyano group, and a halogen atom. Examples of alkyl groups having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, sec-pentyl, and tert-pentyl groups. Of these groups, methyl and ethyl groups are preferred. Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Specific examples of polycyclic aromatic groups include groups in which one or more hydrogen atoms have been removed from aromatic hydrocarbons such as naphthalene and biphenyl, and groups in which one or more hydrogen atoms have been removed from aromatic heterocyclic compounds such as quinoline, isoquinoline, quinoxaline, cinnoline, quinazoline, phthalazine, naphthyridine, benzoxazole, benzothiazole, benzimidazole, indole, benzofuran, benzothiophene, isoindole, and isobenzofuran.

[0061] The (meth)acrylate (B1) having an aromatic group is preferably a compound represented by the following formula (b1). R b01 -(X b03 -X b02 ) mb2 -(X b01 ) mb1 -Ar b01 -((X b04 ) mb3 -(X b05 )) mb4 (b1) (In formula (b1), Ar b01 is a (mb4+1)-valent aromatic group having 7 to 12 carbon atoms and optionally substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a cyano group, and a halogen atom; R b01 is a (meth)acryloyl group-containing group, and X b01 is O and X b02 is an alkylene group optionally interrupted by one or more O; b03 is O and X b04 is O and X b05is an alkyl group which may be interrupted by one or more O, mb1 is 0 or 1, mb2 is 0 or 1, mb3 is 0 or 1, and mb4 is an integer of 0 or more. In the specification of the present application, the compound represented by formula (b1) is also referred to as "compound (b1)".

[0062] In formula (b1), Ar b01 is a (mb4+1)-valent aromatic group having from 7 to 12 carbon atoms and optionally substituted with one or more groups selected from the group consisting of an alkyl group having from 1 to 5 carbon atoms, a cyano group, and a halogen atom. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic group is preferably a polycyclic aromatic group. Examples of the aromatic group include groups obtained by removing (mb4+1) hydrogen atoms from aromatic hydrocarbons such as naphthalene and biphenyl, and groups obtained by removing (mb4+1) hydrogen atoms from aromatic heterocyclic compounds such as quinoline, isoquinoline, quinoxaline, cinnoline, quinazoline, phthalazine, naphthyridine, benzoxazole, benzothiazole, benzimidazole, indole, benzofuran, benzothiophene, isoindole, and isobenzofuran.

[0063] Ar b01 The aromatic group as may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a cyano group, and a halogen atom. Ar b01 There is no particular limitation on the number of substituents bonded to the aromatic group as the aromatic ring. Examples of alkyl groups having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, sec-pentyl, and tert-pentyl groups. Of these groups, methyl and ethyl groups are preferred. Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The above-described Ar b01 As the aromatic group for , groups in which (mb4+1) hydrogen atoms have been removed from naphthalene, biphenyl, quinoline, and benzothiazole are preferred. In addition, when it is desired to impart a higher refractive index to the cured product of a negative photosensitive resin composition, Ar b01 The aromatic group as is preferably substituted with a fluorine atom and / or a cyano group.

[0064] R b01 is a (meth)acryloyl group-containing group. b01 The (meth)acryloyl group-containing group as is preferably a (meth)acryloyl group.

[0065] X b02 is an alkylene group which may be interrupted by one or more O. b02 is preferably an alkylene group interrupted by one or more O. X b05 is an alkyl group which may be interrupted by one or more O. b05 is preferably an alkyl group interrupted by one or more O's. X b02 an alkylene group optionally interrupted by one or more O, and X b05 The number of carbon atoms in the alkyl group which may be interrupted by one or more O is not particularly limited as long as the desired effect is not impaired.

[0066] X b02 an alkylene group optionally interrupted by one or more O, and X b05 The alkyl group, which may be interrupted by one or more O's, as represented by (I), is preferably a group consisting of mb aliphatic chain saturated hydrocarbon groups selected from alkylene groups having from 1 to 4 carbon atoms, alkanetriyl groups having from 1 to 4 carbon atoms, and alkyl groups having from 1 to 4 carbon atoms, and (mb-1) O's connecting the mb aliphatic chain saturated hydrocarbon groups. Here, mb is an integer between 2 and 6 inclusive.

[0067] Suitable examples of alkylene groups having 1 to 4 carbon atoms include methylene, ethane-1,2-diyl (ethylene), propane-1,2-diyl, propane-1,3-diyl, butane-1,2-diyl, butane-1,3-diyl, and butane-1,4-diyl. Of these groups, ethane-1,2-diyl (ethylene), propane-1,2-diyl, and propane-1,3-diyl are preferred. Preferred examples of the alkanetriyl group having 1 to 4 carbon atoms include a propane-1,2,3-triyl group, a butane-1,2,3-triyl group, and a butane-1,2,4-triyl group. Of these groups, a propane-1,2,3-triyl group is preferred. Preferred examples of the alkyl group having 1 to 4 carbon atoms 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, and a tert-butyl group. Among these groups, a methyl group and an ethyl group are preferred.

[0068] X b02 The alkylene group, which may be interrupted by one or more O, as represented by the formula (I), is preferably a group consisting of mb alkylene groups having from 1 to 4 carbon atoms and (mb-1) Os connecting the mb alkylene groups. X b05 The alkyl group, which may be interrupted by one or more O's, as the alkyl group, is preferably a group consisting of (mb-1) alkylene groups having from 1 to 4 carbon atoms, one alkyl group having from 1 to 4 carbon atoms, and (mb-1) O's connecting the (mb-1) alkylene groups having from 1 to 4 carbon atoms and the one alkyl group having from 1 to 4 carbon atoms. Here, mb is an integer between 2 and 6 inclusive.

[0069] X b02 Specific preferred examples of the alkylene group which may be interrupted by one or more O include the following groups: -CH2CH2- -CH2CH2-O-CH2CH2- -(CH2CH2-O)2-CH2CH2- -(CH2CH2-O)3-CH2CH2- -(CH2CH2-O)4-CH2CH2- -(CH2CH2-O)5-CH2CH2- -(C(CH3)HCH2)2-OC(CH3)HCH2- -(C(CH3)HCH2)3-OC(CH3)HCH2- -(C(CH3)HCH2)4-OC(CH3)HCH2- -(C(CH3)HCH2)5-OC(CH3)HCH2- -(C(CH3)HCH2)2-OC(CH3)HCH2- -(C(CH3)HCH2)3-OC(CH3)HCH2- -(C(CH3)HCH2)4-OC(CH3)HCH2- -(C(CH3)HCH2)5-OC(CH3)HCH2- -(CH2CH2CH2)2-O-CH2CH2CH2- -(CH2CH2CH2)3-O-CH2CH2CH2- -(CH2CH2CH2)4-O-CH2CH2CH2- -(CH2CH2CH2)5-O-CH2CH2CH2- -CH2C(OCH2CH2CH2CH3)HCH2-

[0070] Among these groups, -CH2CH2-, -CH2CH2-O-CH2CH2-, -(CH2CH2-O)2-CH2CH2-, and -(CH2CH2-O)3-CH2CH2- is preferred.

[0071] X b05 Specific preferred examples of the alkylene group which may be interrupted by one or more O include the following groups: -CH2CH2-O-CH3 -CH2CH2-O-CH2CH3 -(CH2CH2)2-O-CH3 -(CH2CH2)2-O-CH2CH3 -(CH2CH2)3-O-CH3 -(CH2CH2)3-O-CH2CH3 -(CH2CH2)4-O-CH3 -(CH2CH2)4-O-CH2CH3 -(CH2CH2)5-O-CH3 -(CH2CH2)5-O-CH2CH3 -C(CH3)HCH2-O-CH3 -C(CH3)HCH2-O-CH2CH3 -(C(CH3)HCH2-O)2-CH3 -(C(CH3)HCH2-O)2-CH2CH3 -(C(CH3)HCH2-O)3-CH3 -(C(CH3)HCH2-O)3-CH2CH3 -(C(CH3)HCH2-O)4-CH3 -(C(CH3)HCH2-O)4-CH2CH3 -(C(CH3)HCH2-O)5-CH3 -(C(CH3)HCH2-O)5-CH2CH3 -CH2C(CH3)H-O-CH3 -CH2C(CH3)H-O-CH2CH3 -(CH2C(CH3)H-O)2-CH3 -(CH2C(CH3)H-O)2-CH2CH3 -(CH2C(CH3)H-O)3-CH3 -(CH2C(CH3)H-O)3-CH2CH3 -(CH2C(CH3)H-O)4-CH3 -(CH2C(CH3)H-O)4-CH2CH3 -(CH2C(CH3)H-O)5-CH3 -(CH2C(CH3)H-O)5-CH2CH3

[0072] In formula (b1), Xb03 is O and X b04 is O.

[0073] In formula (b1), mb1 is 0 or 1, mb2 is 0 or 1, mb3 is 0 or 1, and mb4 is an integer of 0 or greater. It is preferable that both mb1 and mb2 are 1. The upper limit of mb4 is not particularly limited. The value of mb4 is determined by the b01 The value of mb4 is preferably 0 or more and 2 or less, more preferably 0 or 1. In view of ease of availability and synthesis of compound (b1), mb4 is preferably 0.

[0074] In formula (b1), X b01 , X b03 , and X b04 The number of O and X as b02 and X b05 The total number of O's contained in is not particularly limited, and may be 0, 1 or more, or 4 or more. X b01 , X b03 , and X b04 The number of O and X as b02 and X b05 The upper limit of the total number of O contained in is not particularly limited as long as the desired effect is not impaired, but is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.

[0075] The compound (b1) explained above is preferably a compound represented by the following formula (b1-1). R b01 -X b03 -X b02 -X b01 -Ar b02 ···(b1-1) (In formula (b1-1), Ar b02 is a monovalent aromatic group having from 7 to 12 carbon atoms, which may be substituted with one or more groups selected from the group consisting of an alkyl group having from 1 to 5 carbon atoms, a cyano group, and a halogen atom; R b01is a (meth)acryloyl group-containing group, and X b01 is O and X b02 is an alkylene group optionally interrupted by one or more O; b03 is O.)

[0076] In formula (b1-1), Ar b02 is a monovalent aromatic group having from 7 to 12 carbon atoms and optionally substituted with one or more groups selected from the group consisting of an alkyl group having from 1 to 5 carbon atoms, a cyano group, and a halogen atom. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic group is preferably a polycyclic aromatic group. Examples of the aromatic group include aromatic hydrocarbon groups such as a naphthyl group and a biphenylyl group, and aromatic heterocyclic groups such as a quinolinyl group, an isoquinolinyl group, a quinoxalinyl group, a cinnolinyl group, a quinazolinyl group, a phthalazinyl group, a naphthyridinyl group, a benzoxazolyl group, a benzothiazolyl group, a benzimidazolyl group, an indolyl group, a benzofuranyl group, a benzothiophenyl group, an isoindolyl group, and an isobenzofuranyl group.

[0077] Ar b02 The aromatic group as may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a cyano group, and a halogen atom. Ar b02 There is no particular limitation on the number of substituents bonded to the aromatic group as the aromatic ring. Examples of alkyl groups having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, sec-pentyl, and tert-pentyl groups. Of these groups, methyl and ethyl groups are preferred. Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The above-described Ar b02The aromatic group as is preferably a naphthyl group, a biphenylyl group, a quinolinyl group, or a benzothiazolyl group. In addition, when it is desired to impart a high refractive index to the cured product of the photosensitive composition, Ar b02 Preferably, the aromatic group as is substituted with a cyano group.

[0078] In formula (b1-1), X b01 , X b02 , X b02 , and R b01 The same applies to those in formula (b1).

[0079] The method for producing the compound (b1), which is the compound represented by the formula (b1) explained above, is not particularly limited. A method for producing a compound represented by formula (b1-1), which is preferred among compounds (b1), will be described below. Compounds represented by formula (b1) but which do not fall under formula (b1-1) can also be produced by appropriately modifying the method for producing a compound represented by formula (b1-1).

[0080] The method for producing the compound represented by formula (b1-1) is not particularly limited. A preferred method for producing the compound represented by formula (b1-1) includes reacting a compound represented by formula (b1-1a) with a compound represented by formula (b1-1b) in the presence of a base to obtain a compound represented by formula (b1-1c): -X of the compound represented by the following formula (b1-1c): b03 The terminal hydrogen atom represented by -H is R b01 and substituting the group represented by the formula: HX b01 -Ar b02 ···(b1-1a) HX b03 -X b02 -Hal···(b1-1b) HX b03 -X b02 -X b01 -Ar b02 ···(b1-1c) (In formula (b1-1a), formula (b1-1b), and formula (b1-1c), Ar b02, X b01 ~X b03 are the same as those in formula (b1-1), and Hal is a halogen atom.

[0081] The reaction of the compound represented by formula (b1-1a) with the compound represented by formula (b1-1b) in the presence of a base is usually carried out in the presence of an organic solvent. The organic solvent used in the reaction of the compound represented by formula (b1-1a) with the compound represented by formula (b1-1b) is not particularly limited as long as it does not inhibit the progress of the reaction. Since the reaction is carried out in the presence of a base, the organic solvent is preferably an organic solvent that does not have an acidic group such as a carboxy group or a sulfonic acid group, or a hydroxyl group. The organic solvent is preferably an aprotic polar organic solvent, since it facilitates the reaction to proceed smoothly. Suitable examples of the aprotic polar organic solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetrahydrofuran, cyclopentyl methyl ether, acetonitrile, and hexamethylphosphoric triamide.

[0082] The amount of the organic solvent used is not particularly limited, and is preferably 0.5 to 50 times by mass, more preferably 0.7 to 20 times by mass, and even more preferably 1 to 10 times by mass, relative to the mass of the base, the mass of the compound represented by Formula (b1-1a), and the mass of the compound represented by Formula (b1-1b).

[0083] The base may be any basic compound used in the so-called Williamson ether synthesis, without any particular limitation. Suitable examples of the base include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydride, potassium hydride, metallic sodium, and metallic potassium.

[0084] The amount of base used in the reaction of the compound represented by formula (b1-1a) with the compound represented by formula (b1-1b) is not particularly limited, as long as it is possible to produce the desired amount of the compound represented by formula (b1-1c). The amount of base used is, for example, preferably 0.8 to 10 moles, more preferably 0.9 to 5 moles, and even more preferably 1 to 3 moles, per mole of the compound represented by formula (b1-1a).

[0085] The amount of the compound represented by formula (b1-1b) used is not particularly limited as long as it is possible to produce the desired amount of the compound represented by formula (b1-1c). The amount of the compound represented by the base formula (b1-1b) used is, for example, preferably 0.8 mol or more and 10 mol or less, more preferably 0.9 mol or more and 5 mol or less, and even more preferably 1 mol or more and 3 mol or less, per 1 mol of the compound represented by the base formula (b1-1a).

[0086] The temperature at which the compound represented by formula (b1-1a) and the compound represented by formula (b1-1b) are reacted is not particularly limited, as long as the desired amount of the compound represented by formula (b1-1c) can be produced. The reaction temperature is, for example, preferably 0°C or higher and 200°C or lower, more preferably 10°C or higher and 180°C or lower, and even more preferably 20°C or higher and 150°C or lower. When the reaction is carried out at a temperature higher than the boiling point of the organic solvent, the reaction may be carried out using a pressure-resistant vessel. The time for reacting the compound represented by formula (b1-1a) with the compound represented by formula (b1-1b) is not particularly limited as long as the desired amount of the compound represented by formula (b1-1c) can be produced. The reaction time is typically preferably from 1 hour to 2 days, more preferably from 2 hours to 1 day, and more preferably from 3 hours to 18 hours.

[0087] Next, the compound represented by formula (b1-1c) obtained by the above method is reacted with -X b03 The terminal hydrogen atom represented by -H is b01 The group is substituted with a group represented by the formula: -X b03 The terminal hydrogen atom represented by -H is b01 There is no particular limitation on the method for substituting the group represented by -X b03 The terminal hydrogen atom represented by -H is b01 The method of substituting the group represented by R b01 The (meth)acryloyl group-containing group represented by the formula (I) is appropriately selected depending on the type of the (meth)acryloyl group-containing group represented by the formula (I).

[0088] For example, R b01 is a (meth)acryloyl group, for example, a (meth)acrylic acid halide such as (meth)acryloyl chloride may be used as the -X b03 By reacting with a group represented by -H, -X b03 The terminal hydrogen atom represented by -H can be substituted with a (meth)acryloyl group. The reaction of the compound represented by formula (b1-1c) with the (meth)acrylic acid halide is preferably carried out in an organic solvent. The type of organic solvent is not particularly limited as long as it is a solvent that does not react with the compound represented by formula (b1-1c) and the (meth)acrylic acid halide. Alternatively, the compound represented by formula (b1-1) can be obtained by condensing (meth)acrylic acid with the compound represented by formula (b1-1c) according to a well-known ester synthesis method.

[0089] The compound represented by formula (b1-1) can also be produced by a method comprising reacting a compound represented by the following formula (b1-1a) with a compound represented by the following formula (b1-d) in the presence of a base to obtain a compound represented by formula (b1-1). HX b01 -Ar b02 ···(b1-1a) R b01 -X b03 -X b02 -Hal···(b1-1d) (In formula (b1-1a) and formula (b1-1d), Ar b02 , X b01 ~X b03are the same as those in formula (b1-1), and Hal is a halogen atom.

[0090] The reaction of the compound represented by formula (b1-1a) with the compound represented by formula (b1-d) in the presence of a base is carried out in the same manner as the reaction of the compound represented by formula (b1-1a) with the compound represented by formula (b1-b) in the presence of a base described above.

[0091] The compound represented by formula (b1-1) produced by the above method is purified as necessary and then blended into a photosensitive composition. Purification methods include well-known methods such as chromatography (e.g., column chromatography) and recrystallization.

[0092] Preferable specific examples of the compound (b1) include the following compounds: Compounds in which the linking group connecting the acryloyloxy group or methacryloyloxy group to the aryloxy group or heteroaryloxy group in the following compounds is changed to a group selected from the group consisting of -(CH2CH2-O)2-CH2CH2-, -(CH2CH2-O)3-CH2CH2-, -(CH2CH2-O)2-CH2CH2-, and -(CH2CH2-O)3-CH2CH2- are also preferred as compound (b1). [ka] [ka] [ka]

[0093] When the negative photosensitive resin composition contains the photopolymerizable monomer (B), the content of the photopolymerizable monomer (B) is preferably 0.1 parts by mass or more and 200 parts by mass or less, more preferably 1 part by mass or more and 70 parts by mass or less, and even more preferably 5 parts by mass or more and 40 parts by mass or less, relative to 100 parts by mass of the resin (A).

[0094] <Photopolymerization initiator (C)> The negative photosensitive resin composition contains a photopolymerization initiator (C). The photopolymerization initiator refers to a component that generates active species that can initiate polymerization of the resin (A) or polymerization of the photopolymerizable monomer (B), which is optionally contained, by irradiation with visible light, ultraviolet light, far ultraviolet light, charged particle beams, X-rays, or the like.

[0095] 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).

[0096] [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.)

[0097] 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).

[0098] Examples of compounds having a partial structure represented by formula (c1) include compounds represented by the following formula (c2).

[0099] [ka] (In formula (c2), R c1is 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.

[0100] [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.)

[0101] [ka] (In formula (c4), R c6 and R c7 each 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.)

[0102] [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.)

[0103] In formula (c3), R c4 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 preferred, 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 preferred. 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 c4 Suitable examples of 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.

[0104] 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 c4The number of carbon atoms in the alkyl group as R is preferably 2 or more, more preferably 5 or more, and particularly preferably 7 or more. In addition, in order to obtain good compatibility between the compound represented by formula (c3) and other components in the photosensitive resin composition, c4 The alkyl group as the alkyl group preferably has 15 or less carbon atoms, more preferably 10 or less carbon atoms.

[0105] 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, and a heterocyclyl group.

[0106] R c4 When 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 atoms, or a heterocyclyl group in which such monocyclic rings are fused together or such monocyclic rings are fused with a benzene ring. When the heterocyclyl group is a fused ring, the number of monocyclic rings constituting the fused ring is limited to three. Examples of heterocyclic rings constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. R c4When 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.

[0107] The above-described R c4 Specific preferred 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. Furthermore, in view of the 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.

[0108] In formula (c3), R c5 is a monovalent organic group or a nitro 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 preferred, 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 preferred. 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 c5Examples of suitable monovalent organic groups include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, an optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted benzoyl group, an optionally substituted phenoxycarbonyl group, an optionally substituted benzoyloxy group, an optionally substituted phenylalkyl group, an optionally substituted naphthyl group, an optionally substituted naphthoxy group, an optionally substituted naphthoyl group, an optionally substituted naphthoxycarbonyl group, an optionally substituted naphthyloxy group, an optionally substituted naphthylalkyl group, an optionally substituted heterocyclyl group, an optionally substituted heterocyclylcarbonyl group, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, a piperazin-1-yl group, a halogen atom, a nitro group, a cyano group, and a substituent containing a group represented by HXC- or HXC- (wherein each X is independently a halogen atom).

[0109] 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. c5 Specific examples of when R is an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, an n-decyl group, and an isodecyl group. c5When 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.

[0110] 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.

[0111] R c5 When R is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms in the cycloalkyl group or cycloalkoxy group is preferably 3 or more and 10 or less, and more preferably 3 or more and 6 or less. c5 Specific examples of R are cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.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.

[0112] 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, more preferably 2 or more and 7 or less carbon atoms. c5 Specific examples of R are saturated aliphatic acyl groups include acetyl, propanoyl, n-butanoyl, 2-methylpropanoyl, n-pentanoyl, 2,2-dimethylpropanoyl, n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl, n-decanoyl, n-undecanoyl, n-dodecanoyl, n-tridecanoyl, n-tetradecanoyl, n-pentadecanoyl, and n-hexadecanoyl groups. c5 Specific examples of when is a saturated aliphatic acyloxy group include an acetyloxy group, a propanoyloxy group, an n-butanoyloxy group, a 2-methylpropanoyloxy group, an n-pentanoyloxy group, a 2,2-dimethylpropanoyloxy group, an n-hexanoyloxy group, an n-heptanoyloxy group, an n-octanoyloxy group, an n-nonanoyloxy group, an n-decanoyloxy group, an n-undecanoyloxy group, an n-dodecanoyloxy group, an n-tridecanoyloxy group, an n-tetradecanoyloxy group, an n-pentadecanoyloxy group, and an n-hexadecanoyloxy group.

[0113] 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. c5Specific 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.

[0114] 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 are phenylalkyl groups include benzyl, 2-phenylethyl, 3-phenylpropyl, and 4-phenylbutyl groups. 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 phenyl alkyl group or a naphthyl alkyl group, R c5 may further have a substituent on the phenyl group or naphthyl group.

[0115] R c5 is a heterocyclyl group, the heterocyclyl group is 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.

[0116] 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 naphthoyl 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 include R c5 Specific examples of the amino group substituted with one or two organic groups include a methylamino group, an ethylamino group, a diethylamino group, an n-propylamino group, a di-n-propylamino group, an isopropylamino group, an n-butylamino group, a di-n-butylamino group, an n-pentylamino group, an n-hexylamino group, an n-heptylamino group, an n-octylamino group, an n-nonylamino group, an n-decylamino group, a phenylamino group, a naphthylamino group, an acetylamino group, a propanoylamino group, an n-butanoylamino group, an n-pentanoylamino group, an n-hexanoylamino group, an n-heptanoylamino group, an n-octanoylamino group, an n-decanoylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

[0117] R c5When 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 from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, a saturated aliphatic acyl group having from 2 to 7 carbon atoms, an alkoxycarbonyl group having from 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having from 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having from 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having from 1 to 6 carbon atoms, a morpholin-1-yl group, a piperazin-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 above formula (I) have multiple substituents, the multiple substituents may be the same or different.

[0118] R c5 When the benzoyl group included in the 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 piperazin-1-yl group, a 2-thenoyl group (thiophen-2-ylcarbonyl group), a furan-3-ylcarbonyl group, and a phenyl group.

[0119] Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom is preferred.

[0120] 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-, and a group having a halogenated alkyl group containing a group represented by HX2C- or H2XC-, and more preferably 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-.

[0121] 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 aromatic groups substituted with a halogenated alkyl group containing a group represented by HX2C- or H2XC- are preferred.

[0122] 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, naphthyl, etc.), alkyl groups substituted with a halogenated alkoxy group containing a group represented by HX2C- or H2XC- (e.g., methyl, ethyl, n-propyl, i-propyl, etc.), and cycloalkyl groups substituted with a halogenated alkoxy group containing a group represented by HX2C- or H2XC- (e.g., cyclopentyl, cyclohexyl, etc.), and preferably aromatic groups substituted with a halogenated alkoxy group containing a group represented by HX2C- or H2XC-.

[0123] 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 substituents which the phenoxyalkyl group and the phenylthioalkyl group may have are R c5 The substituents are the same as those that the phenyl group contained in

[0124] Among the monovalent organic groups, R c5 The alkyl group is preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, a cycloalkylalkyl group, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The alkyl group is preferably an alkyl group having from 1 to 20 carbon atoms, more preferably an alkyl group having from 1 to 8 carbon atoms, particularly preferably an alkyl group having from 1 to 4 carbon atoms, and most preferably a methyl group. 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 in the cycloalkylalkyl group contained in the cycloalkylalkyl group is preferably from 5 to 10, more preferably from 5 to 8, and particularly preferably 5 or 6. The number of carbon atoms in the alkylene group contained in the cycloalkylalkyl group is preferably from 1 to 8, more preferably from 1 to 4, and particularly preferably 2. Among the cycloalkylalkyl groups, a cyclopentylethyl group is preferred. The number of carbon atoms in the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring is preferably from 1 to 8, more preferably from 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.

[0125] 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 heterocyclic ring. Examples of heteroatoms contained in the heterocyclic ring include N, O, and S. c5The ring formed by bonding together 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), when a plurality of R c5 Specific examples of when these are bonded to each other to form a benzene ring are shown below.

[0126] [ka]

[0127] In the group represented by formula (c4), R c8 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 When the compound represented by formula (c4) has a structure in which one or more R c8 It is preferable that one of the groups represented by formula (c4) is bonded to the 7-position of the fluorene skeleton. c8 When 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.

[0128] [ka] (In formula (c6), R c6 , R c7 , R c8 , n3 are R in formula (c4), c6 , R c7 , R c8 , similar to n3.)

[0129] 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 preferred, 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 preferred. 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 is a monovalent organic group, R in formula (c3) c5 Suitable examples of the monovalent organic group as the aryl group include the same groups as those mentioned above.

[0130] In formula (c4), R c6 and R c7 R is 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 preferred. 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.

[0131] 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 when R is a chain 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.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.

[0132] R c6 and R c7 When is a chain alkyl group having a substituent, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. In this case, the number of carbon atoms in the substituent is not included in the number of carbon atoms in the chain alkyl group. The chain alkyl group having a substituent is preferably linear.

[0133] 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, preferably linear. The number of carbon atoms in the alkoxy group contained in the alkoxycarbonyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less.

[0134] When the chain alkyl group has a substituent, the number of the substituent is not particularly limited. The preferred number of the substituent varies depending on 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, and more preferably 1 or more and 6 or less.

[0135] 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 when R is a chain 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. 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.

[0136] 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.

[0137] 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.

[0138] R c6 and R c7 When is an aromatic hydrocarbon group, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by multiple benzene rings bonded 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 benzene rings 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 preferred examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.

[0139] R c6 and R c7 When is an alicyclic hydrocarbon group, the alicyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms in the alicyclic 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, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, isobornyl, tricyclononyl, tricyclodecyl, tetracyclododecyl, and adamantyl.

[0140] R c6 and R c7 is a heterocyclyl group, R in formula (c3) c5 Examples of the heterocyclyl groups include the same groups as the heterocyclyl groups mentioned above.

[0141] R c6 and R c7 may be bonded to each other to form a ring. c6 and R c7 The group consisting of 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 or 6-membered ring, and more preferably a 5-membered ring.

[0142] 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.

[0143] R c6 and R c7 When the group formed by bonding is a cycloalkylidene group, the cycloalkylidene group may be fused with one or more other rings. Examples of rings that may be fused 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.

[0144] The above-described R c6 and R c7 Among these, a preferred example of the group is a group represented by the formula -A1-A2, where 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.

[0145] The number of carbon atoms in the linear alkylene group of A1 is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When A2 is an alkoxy group, the alkoxy group may be linear or branched, with linear being preferred. The number of carbon atoms in the alkoxy group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less. When A2 is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is preferred, with fluorine atom, chlorine atom, or bromine atom being more preferred. When A2 is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, chlorine atom, bromine atom, or iodine atom, with fluorine atom, chlorine atom, or bromine atom being more preferred. The halogenated alkyl group may be linear or branched, with linear being 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 is the same as the alkoxycarbonyl group which the alkoxycarbonyl group has as a substituent.

[0146] R c6 and R c7Preferred specific examples of the alkyl 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-cyano-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; alkyl 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 a cyclohexyl-n-hexyl group, a 7-cyclohexyl-n-heptyl group, an 8-cyclohexyl-n-octyl group, a 2-cyclopentylethyl group, a 3-cyclopentyl-n-propyl group, a 4-cyclopentyl-n-butyl group, a 5-cyclopentyl-n-pentyl group, a 6-cyclopentyl-n-hexyl group, a 7-cyclopentyl-n-heptyl group, and an 8-cyclopentyl-n-octyl group;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;

[0147] 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.

[0148] In the formula (c5), A is particularly preferably S, since this makes it easier to obtain a photopolymerization initiator with excellent sensitivity.

[0149] 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 preferred, 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 preferred. 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. In formula (c5), R c9 is an organic group, R in formula (c3) c5 Examples of the monovalent organic group include the same groups as those mentioned above.

[0150] 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 an optionally substituted benzofuranylcarbonyl group 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.

[0151] 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.

[0152] In formulas (c1) and (c2), R c2 The monovalent organic group as the organic group 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 preferred, 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 preferred. 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. Rc2 Suitable examples of the monovalent organic group as R in formula (c3) include c5 Specific examples of these groups include the monovalent organic groups represented by 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 included in the above when they further have a substituent.

[0153] Among the organic groups, R c2 As the substituent, a substituent containing the group represented by HX2C- or H2XC-, an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, a cycloalkylalkyl group, or a phenylthioalkyl group which may have a substituent on the aromatic ring is preferred. With regard to the alkyl group, the phenyl group 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:

[0154] 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.

[0155] 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.

[0156] Preferred 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 preferred 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.

[0157] 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.

[0158] Also, R c2 As the group, groups represented by the following formula (c7) or (c8) are also preferred. [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) inclusive.)

[0159] R in formula (c7) c10 and R c11 The organic group represented by R in formula (c4) c8 Similar to R c10 As R, 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 is preferred. 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 Suitable examples of the group in which and form a ring include a naphthalen-1-yl group and a 1,2,3,4-tetrahydronaphthalen-5-yl group. In the above formula (c7), n5 is an integer of 0 or more and 4 or less, preferably 0 or 1, and more preferably 0.

[0160] 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, alkyl groups are preferred. The alkyl groups 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.

[0161] 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 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), n6 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.

[0162] 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, the substituent that may be substituted therewith is preferably a phenyl group, a naphthyl group, or the like.

[0163] In formulas (c1) and (c2), R c3 Preferred examples of the alkyl group include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-cyclopentylethyl group, a 2-cyclobutylethyl group, a cyclohexylmethyl group, a phenyl group, a benzyl group, a methylphenyl group, and a naphthyl group, and among these, a methyl group or a phenyl group is more preferred.

[0164] Represented by formula (c2), and R c1 Specific preferred examples of the compound having a group represented by formula (c3) include the following compounds: [ka]

[0165] [ka]

[0166] [ka]

[0167] [ka]

[0168] Represented by formula (c2), and R c1 Specific preferred examples of the compound having a group represented by formula (c4) include the following compounds: [ka]

[0169] [ka]

[0170] [ka]

[0171] [ka]

[0172] [ka]

[0173] Represented by formula (c2), and R c1 Specific preferred examples of the compound having a group represented by formula (c5) include the following compounds: [ka]

[0174] 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. α-aminoketone compounds such as 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 ... α-hydroxyketone-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzil methyl ketal; benzophenone-based photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 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, etc.; 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-ethoxycarbonylphenyl)-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 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 2,2'-bis(2,4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; and benzimidazoline-based photopolymerization initiators such as those represented by the following formula: [ka]

[0175] The photopolymerization initiators can 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 in a wide range of wavelengths contained in the exposure light and to adjust the sensitivity of the negative photosensitive resin composition to an appropriate range.

[0176] 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% by mass or more, more preferably 50% by mass or more and 99% by mass or less, particularly preferably 70% by mass or more and 97% by mass or less, and most preferably 80% by mass or more and 95% by mass or less.

[0177] 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-type photosensitive resin composition. The content of the photopolymerization initiator (C) 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 of the resin (A) and the photopolymerization initiator (C).

[0178] <Compound (D)> The negative photosensitive resin composition contains a compound (D) represented by the following formula (d1). [ka] (In formula (d1), Ring Z 1 and ring Z 2 each independently represents an aromatic hydrocarbon ring, X 1d and X 2d each independently represents a single bond or a linking group, W 1d and W 2d each independently represents an acidic group, R 1d and R 2d each independently represents a hydrogen atom, a hydroxy group, a mercapto group, an amino group, a nitro group, a halogen atom, or an organic group; R 3d and R 4d each independently represents a hydrogen atom, an alkyl group, or an aryl group, n1 and n2 each independently represent an integer of 0 to 4, n3 and n4 each independently represent an integer of 0 to 3, When n1 is an integer between 2 and 4, multiple R 1d two of which may be bonded to each other to form a ring; When n2 is an integer between 2 and 4, multiple R 2d Two of the may be bonded to each other to form a ring.

[0179] Ring Z 1 and ring Z 2 Examples of the aromatic hydrocarbon ring include a benzene ring, a fused polycyclic aromatic hydrocarbon ring [for example, a fused bicyclic hydrocarbon ring (for example, a fused bicyclic hydrocarbon ring having from 8 to 20 carbon atoms such as a naphthalene ring, preferably a fused bicyclic hydrocarbon ring having from 10 to 18 carbon atoms), and a fused bicyclic to tetracyclic aromatic hydrocarbon ring such as a fused tricyclic aromatic hydrocarbon ring (for example, an anthracene ring, a phenanthrene ring, etc.)]. Ring Z 1 and ring Z 2 is preferably a benzene ring or a naphthalene ring, more preferably a naphthalene ring.

[0180] X 1d and X 2d Examples of the linking group as the alkyl group include an oxyalkylene group (-O-alkylene group-), a carbonyl group, a group in which two hydrogen atoms have been removed from dicyclohexyl ketone, and a group in which two hydrogen atoms have been removed from bicyclohexyl.

[0181] Also, W 1d and W 2d When the acidic group as the —X 1d -W 1d or a group represented by -X 2d -W 2d The group represented by -O-CO-X 3d A group represented by —COOH is also preferred. 3dare residues obtained by removing the dicarboxylic anhydride group from various dicarboxylic anhydrides or polycarboxylic monoanhydrides.

[0182] W 1d and W 2d Examples of acidic groups include phenolic hydroxyl groups, carboxyl groups, and sulfonic acid groups (-SO3H). A phenolic hydroxyl group refers to a hydroxyl group (OH) that is directly bonded to a carbon atom in an aromatic ring.

[0183] R 1d and R 2d Examples of the halogen atom as the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 1d and R 2d The organic group as the alkyl group may include an alkyl group or an aryl group which may contain a heteroatom. R 1d and R 2d The number of carbon atoms in the organic group as the alkyl group is preferably 1 or more and 40 or less, more preferably 1 or more and 30 or less, even more preferably 1 or more and 20 or less, and particularly preferably 1 or more and 10 or less. R 1d and R 2d Specific examples of organic groups as R 5a Examples of the alkyl and aryl groups include the same groups as those exemplified for the above. R 3d and R 4d As the alkyl group or aryl group, R 5a Examples of the alkyl and aryl groups include the same groups as those exemplified for the above.

[0184] Specific examples of compound (D) represented by formula (d1) include the following compounds, compounds obtained by reacting the hydroxyl group of the following compounds with a dicarboxylic acid anhydride or a polycarboxylic acid monoanhydride, such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, or trimellitic anhydride, and groups obtained by substituting the hydroxy group in the following compounds with a carboxy group or a sulfonic acid group. [ka]

[0185] By preparing a negative-type photosensitive resin composition containing such a compound (D) represented by formula (d1) together with the resin (A) and the photopolymerization initiator (C), it is possible to form a patterned cured product having a high refractive index and a convex lens shape, as shown in the examples described later. For example, the refractive index at 23° C. of a cured product formed using the above-mentioned negative photosensitive resin composition can be made to be 1.60 or higher, and even 1.64 or higher. As described above, the convex lens shape is a shape in which the surface is a convex curved surface, and is a shape that can be used as a convex lens, for example. As shown in Fig. 1, a patterned cured product 10 formed on a substrate 1 using the above-described negative photosensitive resin composition has a shape in which the surface is a convex curved surface (convex lens shape). As shown in Fig. 1, the patterned cured product 10 having a convex lens shape has a curved surface on the side opposite to the substrate 1 (top) rather than a flat surface.

[0186] The patterned cured product formed using the negative photosensitive resin composition has a high refractive index and a convex lens shape, making it suitable for use in light extraction from organic electroluminescent displays. Furthermore, the patterned cured product formed using the negative photosensitive resin composition can be used as a lens for various electronic devices (organic electroluminescent displays, liquid crystal displays, touch panels, optical semiconductor elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, organic thin-film transistors, etc.).

[0187] The mechanism by which a patterned cured product having a high refractive index and a convex lens shape can be formed is unknown, but is presumed to be as follows. The resin (A) and the photopolymerizable monomer (B) contained as needed are polymerized and cured in the exposed areas by site-selective exposure, and during subsequent development, they remain without dissolving in the developer, thereby forming a patterned cured product. On the other hand, it is believed that the compound (D) represented by formula (d1) does not contribute to curing by exposure, or contributes only to a very small extent. In addition, the compound (D) represented by the formula (d1) has high solubility in a developer. For this reason, when the above-mentioned negative photosensitive resin composition is used, the compound (D) represented by formula (d1) makes it difficult for the exposed area to cure and increases the solubility in a developer, which makes the exposed area more likely to have a rounded shape, resulting in a convex lens shape. Furthermore, the cured product (polymer) of the resin (A) and the compound (D) represented by formula (d1) have high refractive indices, and therefore, when the negative photosensitive resin composition is used, a patterned cured product having a high refractive index is formed.

[0188] On the other hand, if the compound (D) represented by formula (d1) is not contained, the effect of the compound (D) represented by formula (d1) cannot be obtained, and it is therefore difficult to form a patterned cured product having a high refractive index and a convex lens shape.

[0189] Furthermore, the negative photosensitive resin composition can form a cured product with excellent transparency. For example, the transmittance of a cured product formed using the negative photosensitive resin composition described above at a wavelength of 400 nm can be made to be 90% or more. Furthermore, the L of the cured product formed using the negative photosensitive resin composition described above * a * b * b in color space * The value can be 1.5 or less. Furthermore, the haze (turbidity) of a cured product formed using the negative photosensitive resin composition can be reduced to 0.10 or less.

[0190] Furthermore, the negative-type photosensitive resin composition described above can form a cured product with excellent solvent resistance. The cured product formed using the negative-type photosensitive resin composition has high resistance to organic solvents such as propylene glycol monomethyl ether acetate (PEGMEA). Therefore, the composition is suitable for applications in which a composition in which components such as a resin are dissolved in a solvent is used to form another layer on the cured product to produce a laminate material, or for applications in which a solvent-containing adhesive is used.

[0191] Furthermore, because the negative photosensitive resin composition has excellent resolution, it is possible to produce a patterned cured film having a fine pattern. For example, it is possible to produce a patterned cured product 10 having a width (x in FIG. 1) of 30 μm or less, preferably 20 μm or less. The lower limit of the width x is, for example, 5 μm or more. Furthermore, the height (y in FIG. 1) of the patterned cured product 10 is, for example, 0.1 μm or more and 10 μm or less.

[0192] The content of the compound (D) represented by formula (d1) is preferably 1 part by mass or more and 60 parts by mass or less, more preferably 3 parts by mass or more and 50 parts by mass or less, and even more preferably 5 parts by mass or more and 40 parts by mass or less, relative to 100 parts by mass of the solid content of the negative-type photosensitive resin composition. The degree of roundness (degree of convex lens shape) of the cured product can be adjusted by adjusting the content of the compound (D) represented by formula (d1). For example, increasing the content of the compound (D) represented by formula (d1) can make the cured product rounder.

[0193] <Solvent (S)> The negative photosensitive resin composition preferably contains a solvent (S). Examples of the solvent (S) include organic solvents and water. The organic solvent is not particularly limited as long as it can dissolve the resin (A), and may be an acetate-based, ether-based, glycol-based, ketone-based, alcohol-based, or carbonate-based organic solvent commonly used in negative photosensitive resin compositions. Examples of the organic solvent include propylene glycol monomethyl ether acetate (PEGMEA), propylene glycol monomethyl ether, 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.

[0194] The content of the solvent (S) is, for example, 20 to 95 parts by mass, preferably 30 to 90 parts by mass, and more preferably 50 to 80 parts by mass, relative to 100 parts by mass of the negative photosensitive resin composition. Within this range, thin films can be easily formed using conventional coating methods, and a thin film of the desired thickness can be easily obtained after coating.

[0195] <Other ingredients> The negative photosensitive resin composition may contain additives as needed. Examples of such additives include stabilizers, adhesion enhancers, thermal crosslinking agents, photocuring accelerators, surfactants, base quenchers, antioxidants, adhesion promoters, antifoaming agents, and polymerization inhibitors such as thermal polymerization inhibitors. These additives may be used alone or in combination as needed.

[0196] The surfactant is a component that has the effect of improving the coating properties and application properties of the substrate, uniformity, and dirt removal. Examples of the surfactant include fluorine-based surfactants, silicon-based surfactants, and nonionic surfactants, with silicon-based surfactants being preferred. Examples of the silicon-based surfactant include polyether-modified polysiloxane, and a more specific example is polyether-modified polydimethylsiloxane.

[0197] The content of the surfactant is, for example, 0.01 parts by mass or more and 5 parts by mass or less, preferably 0.02 parts by mass or more and 1 part by mass or less, and more preferably 0.05 parts by mass or more and 0.5 parts by mass or less, based on 100 parts by mass of the resin (A).

[0198] Examples of the polymerization inhibitor include phenol-based polymerization inhibitors, such as compounds represented by the following formula: The polymerization inhibitor is used to suppress the deterioration (gelation) of the photopolymerizable monomer (B) over time in the container.

[0199] [ka]

[0200] The content of the polymerization inhibitor is, for example, 0.01 parts by mass or more and 5 parts by mass or less, preferably 0.05 parts by mass or more and 3 parts by mass or less, and more preferably 0.1 parts by mass or more and 1 part by mass or less, based on 100 parts by mass of the resin (A).

[0201] The adhesion enhancer is a component that has the effect of improving 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. Specific examples include 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.

[0202] Examples of adhesion enhancers include isocyanate compounds, epoxy compounds, (meth)acrylate compounds, vinyl compounds, and mercapto compounds, although these overlap with the silane coupling agents described above. Epoxy compounds are preferably organic silane compounds having an epoxy group, and more specifically, alkoxysilanes having an epoxy group and 1 to 5 carbon atoms.

[0203] The content of the adhesion enhancer is, for example, from 0 to 10 parts by mass, preferably from 0.01 to 8 parts by mass, and more preferably from 1 to 5 parts by mass, based on 100 parts by mass of the resin (A). Within this range, excellent adhesive strength to the substrate is obtained.

[0204] <Method for producing negative-type photosensitive resin composition> The negative photosensitive resin composition can be produced by a general method, for example, by mixing the above components and filtering them using a filter as needed.

[0205] <Method for producing cured product and patterned cured product> The negative photosensitive resin composition can be used to produce a cured product that can be used in electronic devices such as organic electroluminescence (EL) displays, liquid crystal displays, touch panels, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs). A method for producing a patterned cured product using the above negative photosensitive resin composition will be described below.

[0206] 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 conventionally known substrates can be used, such as silicon substrates, glass substrates, and substrates having a metal surface. The metal species constituting the metal surface are preferably copper, gold, or aluminum, and more preferably copper. Furthermore, since the negative photosensitive resin composition can be used at a low heating temperature when forming a cured product, a substrate with low heat resistance can be used. Examples of substrates with low heat resistance include flexible substrates. Examples of flexible substrates include plastic substrates made of various plastic materials such as polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyimide; polycarbonate; polyamide; polyacetal; polyphenylene oxide; polyphenylene sulfide; polyether sulfone; polyether ether ketone; homopolymers of norbornene-based monomers (addition polymers, ring-opening polymers, etc.), copolymers of norbornene-based monomers and olefin-based monomers such as copolymers of norbornene and ethylene (cyclic olefin copolymers such as addition polymers and ring-opening polymers), and derivatives of these cyclic polyolefins; vinyl polymers (e.g., (meth)acrylic resins such as polymethyl methacrylate (PMMA), polystyrene, polyvinyl chloride, acrylonitrile-styrene-butadiene resin (ABS resin)); vinylidene polymers (e.g., polyvinylidene chloride); cellulose resins such as triacetyl cellulose (TAC); epoxy resins; phenolic resins; melamine resins; urea resins; maleimide resins; and silicone.

[0207] 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 printing, and drop casting.

[0208] The thickness of the coating film to be formed varies depending on the coating method, the solid content concentration of the negative photosensitive resin composition, the viscosity, etc., and is not particularly limited, but the coating can usually be carried out so that the film thickness after drying is 0.5 μm or more and 100 μm or less.

[0209] If necessary, the coating film may be dried. The drying method is not particularly limited, but examples include methods of volatilizing the solvent by vacuum, infrared irradiation, or heating. The heating conditions are not particularly limited, but for example, the heating temperature is 70°C or higher and 100°C or lower, and the heating time is 60 seconds or higher and 300 seconds or lower.

[0210] Next, the coated film is exposed to light in a selective manner. The position-selective exposure is carried out, for example, through a negative mask. By carrying out the position-selective exposure, a patterned cured film can be formed. For example, using a mask with a hole pattern allows for the formation of a cured product in the shape of a partially cut-out sphere, and using a mask with a line and space pattern allows for the formation of a partially cut-out cylinder (a semi-cylindrical shape) (e.g., a cylindrical lens).

[0211] In the exposure step, 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 are irradiated. In the exposure, exposure methods such as contact, proximity, and projection 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 5 mJ / cm 2 More than 100mJ / cm 2 Less than or equal to 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 and a cured product (cured film) is formed.

[0212] Next, the exposed coating film is developed with a developer. 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 alkaline developers include aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide (TMAH) and tetraethylammonium hydroxide, and aqueous solutions of amines such as ammonia, ethylamine, propylamine, diethylamine, and triethylamine.

[0213] By heating (post-baking) the developed coating film, a patterned cured film having the desired convex lens shape can be obtained. The temperature to which the coating film is heated after development is not particularly limited, but is preferably 70°C or higher and 400°C or lower, more preferably 80°C or higher and 200°C or lower, and even more preferably 85°C or higher and 150°C or lower.

[0214] The coating film after exposure but before development may be heated (post-exposure bake (PEB)). The temperature to which the coating film is heated after exposure but before development is not particularly limited, and is, for example, from 80° C. to 250° C., preferably from 80° C. to 200° C., more preferably from 80° C. to 150° C., and even more preferably from 85° C. to 100° C. When a substrate with low heat resistance is used, it is difficult to use a substrate with low heat resistance because heating at a high temperature may have an adverse effect on the substrate, but heating at a low temperature makes it possible to use a substrate with low heat resistance.

[0215] The patterned cured product (cured film) produced by the above-mentioned production method is formed using the negative-type photosensitive resin composition, and therefore has a high refractive index and a convex lens shape. Therefore, it is suitable for use in light extraction in organic electroluminescent displays. It can also be used as a lens for various electronic devices (such as organic electroluminescent displays, liquid crystal displays, touch panels, optical semiconductor elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors). [Example]

[0216] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. [Synthesis Example 1] (Monomer synthesis) One-step: 2,2'-((((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(methylene))bis(oxirane) synthesis [ka]

[0217] Step A: After setting up a reflux condenser and a thermometer in a three-neck flask, add 42.5 g of 9,9-bisphenol fluorene and 2-(chloro) After measuring 220 mL of methyl oxirane, it was poured in. After adding 100 mg of tetrabutylammonium bromide, stirring was started and the temperature was raised to 90°C. After confirming that the content of unreacted material was less than 0.3%, it was distilled under reduced pressure.

[0218] Step B: After lowering the temperature to 30°C, dichloromethane was poured in and NaOH was gradually added. After confirming that the product was 96% or more by high performance liquid chromatography (HPLC), the reaction was terminated by adding 5% HCl dropwise. The reactant was extracted and separated into layers, and the organic layer was washed with water until neutral. The organic layer was dried over MgSO4 and then concentrated by distillation under reduced pressure using a rotary evaporator. Dichloromethane was added to the concentrated product and stirred while the temperature was raised to 40°C, and methanol was added, and the solution temperature was lowered and stirred. The resulting solid was filtered and dried in vacuum at room temperature to obtain 52.7 g of a white solid powder (yield 94%), the structure of which is 1 Confirmed by 1 H NMR.

[0219] in CDCl 1H NMR: 7.75(2H), 7.36 to 7.25(6H), 7.09(4H), 6.74(4H), 4.13(2H), 3.89(2H), 3.30(2H), 2.87(2H), 2.71(2H).

[0220] Two-step synthesis of 3,3'-(((9H-fluorene-9,9-diyl)bis(4,1-phenylene))bis(oxy))bis(1-(phenylthio)propan-2-ol) (BTCP monomer) [ka]

[0221] A three-neck flask was equipped with a reflux condenser and a thermometer, and the reaction mixture from step 1 (1000 g), 524 g of thiophenol, and 617 g of ethanol were added and stirred. 328 g of triethylamine was slowly added dropwise to the reaction solution. The reaction was terminated after confirming the disappearance of the starting material by high-performance liquid chromatography (HPLC). After completion of the reaction, the ethanol was removed by vacuum distillation. The organic matter was dissolved in dichloromethane and washed with water, after which the dichloromethane was removed by vacuum distillation. The concentrated organic matter was dissolved in ethyl acetate, and then ether solvent was added dropwise and stirred for 30 minutes. The compound was distilled under reduced pressure to obtain 945 g of pale yellow oil (64% yield), the structure of which was confirmed by 1H NMR.

[0222] in CDCl 1 H NMR:7.82(2H), 7.38~6.72(20H), 6.51(4H), 4.00(2H), 3.97(2H), 3.89(2H), 3.20(2H), 3.01(2H), 2.64(2H).

[0223] (Production of Resin (A) (Binder Resin)) Production of Resin A1 [ka]

[0224] A three-neck flask was equipped with a reflux condenser and a thermometer. 200 g of the two-stage synthesized BTCP monomer dissolved in 50% propylene glycol methyl ether acetate (PGMEA) solvent was added and heated to 115°C. At 115°C, 31.1 g of the tetracarboxylic dianhydride (Cas 640737-51-5, 1,3-Isobenzofurandione, 5,5'-oxybis[hexahydro-(9CI, ACI))) was added dropwise and stirred for 6 hours while maintaining the temperature at 115°C. 7.35 g of the aromatic carboxylic anhydride (phthalic anhydride) was added and stirred for an additional 2 hours, after which the reaction was terminated. After cooling, a solution of Resin A1 was obtained with a mass-average molecular weight of 3,000 g / mol and a polydispersity of 2.5.

[0225] [Synthesis Example 2] Synthesis of Compound B2 ((meth)acrylate having an aromatic group) A 300 mL reactor was charged with 2-phenylphenol (20.0 g, 0.118 mol), potassium carbonate (32.5 g, 0.235 mol), 2-[2-(2-chloroethoxy)ethoxy]ethanol (23.8 g, 0.141 mol), and 200 mL of dimethylformamide. After the atmosphere in the reactor was replaced with nitrogen, the reaction solution in the reactor was stirred at an internal temperature of 90°C for 10 hours to react 2-phenylphenol with 2-[2-(2-chloroethoxy)ethoxy]ethanol. The reaction mixture was then cooled to room temperature. Water was added to the cooled mixture, and toluene was then added to extract the product into the toluene. The solvent was removed from the separated toluene layer, and the residue was purified by silica gel chromatography to obtain 26.8 g of compound IM1 (yield 75%). Next, in a 300 mL reactor, compound IM1 (26.8 g, 0.089 mol), triethylamine (10.8 g, 0.106 mol), and 270 mL of tetrahydrofuran were mixed. The resulting solution was cooled in an ice bath. Acryloyl chloride (9.60 g, 0.106 mol) was added dropwise to the cooled solution while maintaining the internal temperature at 5°C or less. The reaction solution to which acrylic chloride had been added was stirred at room temperature for 2 hours, and then the precipitated salt was filtered. The solvent was removed from the resulting filtrate using an evaporator to obtain a viscous liquid. The resulting viscous liquid was purified by silica gel chromatography to obtain 15.7 g (yield 50%) of compound B2 as a colorless liquid. 1 The results of H-NMR measurements are as follows: 1 H-NMR (DMSO): 3.52(s, 4H), 3.63(t, 2H), 3.72(t, 2H), 4.12(t, 2H), 4.20(t, 2H), 5.90(dd, 1H), 6.12(dd, 1H), 6.35(dd, 1H), 7.05-7.60(m, 9H) [ka]

[0226] As the photopolymerizable monomer (B), dipentaerythritol hexaacrylate (B1) and the above compound B2 were used.

[0227] As the photopolymerization initiator (C), the following C1 was used. [ka]

[0228] As the compound (D) represented by formula (d1), the following D1 was used. [ka]

[0229] Other additives used were E1 below as a thermal polymerization inhibitor, E2 below as an adhesion promoter, and E3, a siloxane surfactant (polyester-modified polydimethylsiloxane, BYK-310, manufactured by BYK-Chemie) as a surfactant. [ka]

[0230] [Examples 1 and 2 and Comparative Example 1] Resin A1 as resin (A), photopolymerizable monomer (B), photopolymerization initiator (C), compound (D), and other additives (thermal polymerization inhibitor, adhesion promoter, surfactant) of the types and parts by mass shown in Table 1 were dissolved in solvent (S) to a solids concentration of 40 mass% to produce negative photosensitive resin compositions of Examples 1 and 2 and Comparative Example 1. The solvent (S) was a mixed solvent of 50 mass% propylene glycol monomethyl ether (PE) and 50 mass% propylene glycol monomethyl ether acetate (PEGMEA).

[0231] <Refractive index> The negative photosensitive resin compositions obtained in the examples and comparative examples were applied to a silicon wafer having a diameter of 6 inches using a spin coater, and then heated (prebaked) at 100°C for 120 seconds to form a coating film having a thickness of 1.0 μm. The formed coating film was irradiated with a mixed light of g, h, and i rays at 100 mJ / cm using an ultraviolet irradiation device (HMW-532D, manufactured by ORC). 2 The entire surface was exposed to an exposure dose of 1000 ppm. A 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was dropped onto the exposed coating film, and then puddle development was performed by leaving the film to stand for 60 seconds. The film was then heated (post-baked) at 100°C for 20 minutes to obtain a cured product (cured film) of the negative photosensitive resin composition. The refractive index of the resulting cured film was measured at a wavelength of 550 nm at a temperature of 23° C. using a spectroscopic ellipsometer (product name: M-2000, manufactured by J.A. Woollam Japan Co., Ltd.) The results are shown in Table 2.

[0232] <Transmittance> A cured film was obtained in the same manner as in the above <Refractive Index>, except that a glass substrate (EAGLEXG, Corning, 100 mm x 100 mm x 0.7 mm) was used instead of a silicon wafer and a coating film with a thickness of 10 μm was formed. The transmittance value at a wavelength of 400 nm was measured at a temperature of 23°C using a multichannel spectrometer (MCPD-3000) manufactured by Otsuka Electronics Co., Ltd. The results are shown in Table 2.

[0233] <Solvent resistance> The negative photosensitive resin compositions obtained in the examples and comparative examples were applied to a glass substrate (Corning EAGLEXG, 100 mm x 100 mm x 0.7 mm) using a spin coater, and then heated at 80°C for 120 seconds to form a coating film with a thickness of 8.0 μm. The formed coating film was irradiated with a UV irradiation device (HMW-532D, ORC) using a mixed light of g, h, and i rays at 100 mJ / cm. 2 The entire surface was exposed to an exposure dose of 1000 ppm. A 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was added dropwise to the exposed coating film, followed by puddle development in which the film was left to stand for 60 seconds. The developed coating film was heated at 100°C for 20 minutes to obtain a cured film of the negative photosensitive resin composition. The resulting cured film was immersed in propylene glycol monomethyl ether acetate (PEGMEA) at 23°C for 300 seconds. The thickness of the cured film was measured before and after immersion, and the remaining film ratio, which is the ratio of the film thickness after immersion to the film thickness before immersion, was calculated. A residual film rate of more than 97% but not more than 99% was evaluated as ◯, and a residual film rate of 97% or less was evaluated as ×. The results are shown in Table 2.

[0234] <Pattern shape> The negative photosensitive resin compositions obtained in the Examples and Comparative Examples were applied to a silicon wafer using a spin coater, and then heated at 80°C for 120 seconds to form a coating film with a thickness of 8.0 μm. The formed coating film was irradiated (exposed) with a mixed light of g, h, and i rays using an exposure device (MPA600FA, manufactured by Canon Inc.) through a negative mask for forming a line and space pattern with a line width of 20 μm and a space width of 20 μm. The exposure dose was 20 mJ / cm. 2The exposed coating film was subjected to puddle development in which a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was dropped onto the film and then allowed to stand for 60 seconds. The developed coating film was heated at 100°C for 20 minutes to obtain a patterned cured film (resist pattern) of the negative photosensitive resin composition. The cross-sectional shape of the resulting patterned cured film (resist pattern) was observed using an SEM photograph and evaluated according to the following criteria. The results are shown in Table 2. 〇: Lens shape ×: Rectangular shape

[0235] <Haze> The haze of the cured film obtained in the same manner as in <Refractive Index> was measured using a desktop spectrophotometer manufactured by Hunter Associates Laboratory, Inc. As a result, the haze (turbidity) values ​​of Examples 1 and 2 and Comparative Example 1 were all low.

[0236] * (Coloring of the cured product) The cured film obtained in the same manner as in <Refractive Index> was measured for L using a haze meter NDH-5000 (manufactured by Hondenshoku Industries Co., Ltd.). * a * b * b in color space * The values ​​were measured. As a result, in Examples 1 and 2 and Comparative Example 1, * All of these values ​​were low, and it can be said that the cured product was not colored.

[0237] [Table 1]

[0238] [Table 2]

[0239] ​According to Examples 1 and 2, a patterned cured product formed using a negative photosensitive resin composition containing a resin (A) having a structural unit represented by formula (a1), a photopolymerization initiator (C), and a compound (D) represented by formula (d1) has a high refractive index and a convex lens shape, and is also excellent in solvent resistance and transparency.

[0240] On the other hand, according to Comparative Example 1, when the negative photosensitive resin composition contains a resin (A) having a structural unit represented by formula (a1) but does not contain a compound (D) represented by formula (d1), the formed patterned cured product has a refractive index inferior to that of Examples 1 and 2 and does not have a convex lens shape. [Explanation of symbols]

[0241] 1 board 10 Patterned cured product

Claims

1. A negative photosensitive resin composition comprising a resin (A) having a structural unit represented by the following formula (a1), a photopolymerization initiator (C), and a compound (D) represented by the following formula (d1): 【Chemistry 1】 (In formula (a1), R １ａ and R ２ａ each independently represents an alkyl group having 1 to 20 carbon atoms and optionally containing a heteroatom, an aryl group having 6 to 20 carbon atoms and optionally containing a heteroatom, -R ４ａ SR ５ａ or -R ６ａ C(=O)R ７ａ represents R ３ａ represents a tetravalent organic group, A represents a divalent group represented by the following formula (a2): j1 and j2 each independently represent an integer of 1 or more and 6 or less, R ４ａ represents a single bond, an alkylene group having from 1 to 10 carbon atoms, or an arylene group having from 6 to 15 carbon atoms, S represents a sulfur atom; R ５ａ represents an alkyl group having from 1 to 10 carbon atoms, or an aryl group having from 6 to 15 carbon atoms, R ６ａ represents a single bond, an alkylene group having from 1 to 10 carbon atoms, or an arylene group having from 6 to 10 carbon atoms, R ７ａ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. 【Chemistry 2】 (In formula (a2), R ８ａ and R ９ａ each independently represents a hydrogen atom, a hydroxy group, a mercapto group, an amino group, a nitro group, a halogen atom, a cyano group, or an alkyl group, R １０ａ and R １１ａ each independently represents a hydrogen atom, an alkyl group, or an aryl group, k1 and k2 each independently represent an integer of 0 to 4, m1 and m2 each independently represent an integer of 0 to 3. 【Transformation 3】 (In formula (d1), Ring Z １ and Ring Z ２ each independently represents an aromatic hydrocarbon ring, X １ｄ and X ２ｄ each independently represents a single bond or a linking group, W １ｄ and W ２ｄ each independently represents an acidic group, R １ｄ and R ２ｄ each independently represents a hydrogen atom, a hydroxy group, a mercapto group, an amino group, a nitro group, a halogen atom, or an organic group; R ３ｄ and R ４ｄ each independently represents a hydrogen atom, an alkyl group, or an aryl group, n1 and n2 each independently represent an integer of 0 to 4, n3 and n4 each independently represent an integer of 0 to 3, When n1 is an integer of 2 or more and 4 or less, a plurality of R １ｄ two of which may be bonded to each other to form a ring; When n2 is an integer of 2 or more and 4 or less, a plurality of R ２ｄ Two of these may be bonded to each other to form a ring.)

2. Ring Z in formula (d1) １ and Ring Z ２ and each independently represent a naphthalene ring or a benzene ring.

3. The W １ｄ and W ２ｄ and each independently represent a phenolic hydroxyl group or a carboxyl group.

4. The negative photosensitive resin composition according to claim 1 , further comprising a photopolymerizable monomer (B).

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

6. A step of applying the negative photosensitive resin composition according to any one of claims 1 to 4 onto a substrate to form a coating film; a step of position-selectively exposing the coating film; developing the exposed coating film; and heating the developed coating film.

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