Radiation-sensitive composition, cured product, lens, planarized film, method for producing cured product, and compound

Abstract

To provide a radiation-sensitive composition that allows for patterning, exhibits excellent chemical resistance and high temperature / high humidity resistance, and can produce a cured product with a high refractive index. [Solution] A radiation-sensitive composition containing a fluorene compound (A) having a specific heterocyclic structure selected from the group consisting of an azole ring structure and a fused ring structure of an azole ring and an aromatic ring, a photopolymerization initiator, and a compound (C) having a polymerizable carbon-carbon unsaturated bond.

Description

[Technical Field]

[0001] The present invention relates to radiation-sensitive compositions, cured products, lenses, planarized films, methods for producing cured products, and compounds. [Background technology]

[0002] Various image sensors, such as CCD (Charge-Coupled Device) image sensors and CMOS (Complementary Metal-Oxide-Semiconductor) image sensors, are used as solid-state image elements in imaging devices such as cameras. Solid-state image elements have tiny focusing lenses (hereinafter also called "microlenses") arranged in a regular pattern to concentrate light onto the photodiode, thereby improving sensor sensitivity.

[0003] Furthermore, in various display elements such as organic electroluminescent (OLED) elements and liquid crystal display elements, a structure has been adopted in which microlenses are provided on the light-emitting side of each pixel for the purpose of improving light extraction efficiency and adjusting the viewing angle. In self-emissive displays such as OLED display devices, attempts have been made to improve brightness and adjust the viewing angle by forming microlenses with high refractive index materials.

[0004] One known method for forming microlenses is the thermal flow method (see, for example, Patent Document 1). The thermal flow method is a method for forming a hemispherical microlens array by using a radiation-sensitive composition to form a pattern corresponding to the arrangement of microlenses on the top of a photodetector or light-emitting element, and then heating the pattern.

[0005] Conventionally, in the process of forming a cured film (e.g., a planarization film) for organic EL elements and liquid crystal display elements, a method has been employed in which a radiation-sensitive composition is applied to a substrate to form a coating film, the coating film is exposed through a photomask having a predetermined aperture pattern, and then the unexposed areas are dissolved and removed by contact with a developer to obtain a patterned cured film (see, for example, Patent Document 2). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2020-101659 [Patent Document 2] Japanese Patent Publication No. 2017-107024 [Overview of the project] [Problems that the invention aims to solve]

[0007] When obtaining a patterned and high refractive index cured product, the radiation-sensitive composition used to obtain the cured product must have sufficient solubility in the alkaline solution used as a developer, while also ensuring a high refractive index in the resulting cured product, thereby exhibiting good patterning properties. Furthermore, cured products used in optical applications such as microlenses and planarization films must have excellent chemical resistance and resistance to high temperatures and humidity.

[0008] The present invention has been made in view of the above problems, and one of its objectives is to provide a radiation-sensitive composition that allows for patterning, has excellent chemical resistance and high temperature and humidity resistance, and can produce a cured product with a high refractive index. [Means for solving the problem]

[0009] According to the present invention, the following radiation-sensitive compositions, cured products, lenses, planarized films, methods for producing cured products, and compounds are provided.

[0010] [1] A radiation-sensitive composition containing a fluorene compound (A) having at least one specific heterocyclic structure selected from the group consisting of an azole ring structure and a condensed ring structure of an azole ring and an aromatic ring, a photoinitiator, and a compound (C) having a polymerizable carbon-carbon unsaturated bond. [2] The radiation-sensitive composition according to [1] above, wherein the fluorene compound (A) is represented by the following formula (1). [Chemical formula] (In formula (1), Ar 1 is a group obtained by removing (m1 + n1 + 1) hydrogen atoms from an aromatic ring. Ar 2 is a group obtained by removing (m2 + n2 + 1) hydrogen atoms from an aromatic ring. R 1 and R 2 are each independently a monovalent substituent, or R 1 and R 2 are combined with each other to form a single bond, -O-, -S-, -NR 8 -, a methylene group or an ethylene group that connects the aromatic ring to which R 2 is bonded and the aromatic ring to which R 1 is bonded. R 8 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R 3 and R 4 are each independently a monovalent substituent. X 1 and X 2 are each independently a monovalent group having the specific heterocyclic structure. m1 and m2 are each independently an integer of 0 to 6. k1 and k2 are each independently an integer of 0 to 4. n1 is an integer of 1 to 6. n2 is an integer of 0 to 6. When there are a plurality of R 1 to R 4 , X 1 , X 2 , the plurality of R 1 to R 4 , X 1 , X 2 are the same or different.) [3] The radiation-sensitive composition according to [2] above, wherein X 1 and X 2 in the above formula (1) are represented by the following formula (2). *-W 1 -V 1 …(2) (In formula (2), W 1 V is a divalent organic group. 1 This group is either a group obtained by removing one hydrogen atom from the ring portion of a substituted or unsubstituted azole ring, or a group obtained by removing one hydrogen atom from the ring portion of a fused ring of an azole ring and an aromatic ring, or a substituted fused ring. (* represents a bond.) [4] A radiation-sensitive composition according to any of the above [1] to [3], wherein the specified heterocyclic structure is a monocyclic or fused ring structure having a triazole ring, a tetrazole ring, or an imidazole ring. [5] A radiation-sensitive composition according to any of [1] to [4] above, wherein compound (C) comprises a fluorene compound (CA) that does not have the specified heterocyclic structure. [6] The radiation-sensitive composition according to [5], wherein the content of the fluorene compound (A) is 5 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the fluorene compound (CA). [7] A radiation-sensitive composition according to any of [1] to [6] above, wherein compound (C) comprises a compound (CB) having a molecular weight of less than 600 and not having a fluorene structure. [8] The radiation-sensitive composition according to [7], wherein the compound (CB) comprises a compound (C1) having one or two polymerizable carbon-carbon unsaturated bonds in one molecule and a compound (C2) having three or more polymerizable carbon-carbon unsaturated bonds in one molecule. [9] A cured product obtained by curing any of the radiation-sensitive compositions described in [1] to [8] above, wherein the refractive index of light at a wavelength of 550 nm is 1.59 or higher.

[10] A lens formed from any of the radiation-sensitive compositions described in [1] to [8] above.

[11] A planarized film formed from any of the radiation-sensitive compositions described in [1] to [8] above.

[12] A method for producing a cured product, comprising the steps of: applying a radiation-sensitive composition from any of the above [1] to [8] onto a substrate to form a coating film; irradiating a part of the coating film with radiation; developing the radiation-irradiated coating film to form a pattern on the substrate; and heating the pattern.

[13] A method for producing the cured product according to

[12] , wherein the temperature at which the pattern is heated is 100°C or less.

[14] A compound represented by the following formula (1). [ka] (In formula (1), Ar 1 Ar is a group obtained by removing (m1+n1+1) hydrogen atoms from an aromatic ring. 2 R is a group obtained by removing (m2+n2+1) hydrogen atoms from an aromatic ring. 1 and R 2 These are either monovalent substituents independently of each other, or R 1 and R 2 and are combined with each other R 1 The aromatic ring to which R is bonded 2 The single bonds connecting the aromatic ring to which it is bonded, -O-, -S-, -NR 8 - represents a methylene group or an ethylene group. 8 R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 3 and R 4 These are monovalent substituents, independently of each other. 1 and X 2 R is a monovalent base that is independent of each other and is represented by the following equation (2). m1 and m2 are independent integers from 0 to 6. k1 and k2 are independent integers from 0 to 4. n1 is an integer from 1 to 6. n2 is an integer from 0 to 6. 1 ~R 4 , X 1 , X 2 If multiple R 1 ~R 4 , X 1 , X 2 They are either the same or different. *-W 1 -V 1 …(2) (In formula (2), W 1 V is a divalent organic group. 1 This group is either a group obtained by removing one hydrogen atom from the ring portion of a substituted or unsubstituted azole ring, or a group obtained by removing one hydrogen atom from the ring portion of a fused ring of an azole ring and an aromatic ring, or a substituted fused ring. (* represents a bond.) [Effects of the Invention]

[0011] The radiation-sensitive composition of the present invention allows for patterning while exhibiting excellent chemical resistance and high temperature and humidity resistance, and also yields a cured product with a high refractive index. Such a radiation-sensitive composition of the present invention is suitable for optical applications, and is particularly suitable for lens manufacturing or planarization film formation. [Brief explanation of the drawing]

[0012] [Figure 1] Magnified view of the lens pattern. (a) shows the state before post-baking, and (b) shows the state after post-baking. [Modes for carrying out the invention]

[0013] The following describes in detail matters related to the embodiments. In this specification, numerical ranges indicated using "~" include the numbers indicated before and after "~" as the lower and upper limits, respectively. Unless otherwise specified, each component may be used alone or in combination of two or more types.

[0014] Herein, in this specification, "hydrocarbon group" means a group that includes linear hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. "Linear hydrocarbon group" means a linear hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure and consists only of a linear structure. However, it may be saturated or unsaturated. "Alicyclic hydrocarbon group" means a hydrocarbon group that contains only the structure of an alicyclic hydrocarbon as its ring structure and does not contain an aromatic ring structure. However, it is not necessary to consist only of the structure of an alicyclic hydrocarbon, and it may also include a group that has a linear structure as part of it. "Aromatic hydrocarbon group" means a hydrocarbon group that contains an aromatic ring structure as its ring structure. However, it is not necessary to consist only of an aromatic ring structure, and it may also contain a linear structure or an alicyclic hydrocarbon structure as part of it. Furthermore, the aromatic ring structure of an aromatic hydrocarbon group may be monocyclic or fused. The ring structure of alicyclic hydrocarbon groups and aromatic hydrocarbon groups may have substituents consisting of hydrocarbon structures.

[0015] "(Meth)acrylic" encompasses both "acrylic" and "methacrylic." "(Meth)acryloyl group" encompasses both "acryloyl group" and "methacryloyl group." "Alkali soluble" means that it can dissolve or swell in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25°C.

[0016] ≪Radiation-sensitive composition≫ The radiation-sensitive composition of this disclosure (hereinafter also simply referred to as "this composition") contains the following components (A), (B), and (C). (A) Component: A fluorene compound having a specific heterocyclic structure selected from the group consisting of an azole ring structure and a fused ring structure of an azole ring and an aromatic ring (hereinafter also simply referred to as "compound (A)"). (B) Component: Photopolymerization initiator (C) Component: A compound having polymerizable carbon-carbon unsaturated bonds (hereinafter also referred to as "compound (C)") The following describes the details of each component contained in this composition and any components that may be added as needed.

[0017] <(A) Component: Compound (A)> Compound (A) may be any compound having a fluorene skeleton and one or both of the following: an azole ring structure and a fused ring structure of an azole ring and an aromatic ring. In this specification, the fused ring structure of an azole ring and an aromatic ring is also referred to as the "azole fused ring structure." Furthermore, the term "specific heterocyclic structure" encompasses both the azole ring structure and the azole fused ring structure.

[0018] Compound (A) exhibits a high refractive index due to its fluorene skeleton. Furthermore, the specific heterocyclic structure introduced into compound (A) is thought to function as an alkali-soluble group and react with the polymerizable carbon-carbon unsaturated bond of compound (C) (specifically, through a Michael addition reaction). By using such compound (A) as a component of a radiation-sensitive composition for forming high refractive index materials, it is possible to obtain a cured product with a high refractive index while forming a negative pattern. In addition, during the formation of a cured product using this composition, it is thought that reactions between compounds (C) (specifically, polymerization reactions) proceed, as well as reactions between compound (A) and compound (C) via the specific heterocyclic structure. As a result, this composition containing compound (A), compound (C), and a photopolymerization initiator can produce a cured product with excellent chemical resistance and resistance to high temperature and humidity. Furthermore, this composition has the advantage of good storage stability, as the reaction between compound (A) and compound (C) via the specific heterocyclic structure is less likely to proceed during storage.

[0019] The azole ring structure is a five-membered heterocyclic structure containing one or more nitrogen atoms, and may have substituents on the ring portion. In the azole ring structure, the number of nitrogen atoms contained in the ring is preferably 2 to 4, in that it is possible to maintain a good balance between the reactivity with the polymerizable carbon-carbon unsaturated bond of compound (C) and the storage stability of the composition. Of these, the number of nitrogen atoms in the azole ring is more preferably 3 or 4 in that it is possible to form a cured film with excellent resistance to high temperature and high humidity and chemical resistance, and more preferably 3 in that a microlens with a better lens shape can be obtained.

[0020] When the azole ring structure has substituents, examples of substituents include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.), C1-C10 alkyl groups, C3-C12 cycloalkyl groups, C6-C12 aryl groups, C6-C12 aralkyl groups, amino groups, dialkylamino groups, and the like.

[0021] Specific examples of azole ring structures include pyrrole ring structures, pyrazole ring structures, imidazole ring structures, 1,2,3-triazole ring structures, 1,2,4-triazole ring structures, tetrazole ring structures, and pentazole ring structures, as well as ring structures having substituents on these ring portions. It is preferable that the azole ring structure of compound (A) has a pyrazole ring, imidazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, or tetrazole ring, as this allows for higher reactivity with the polymerizable carbon-carbon unsaturated bond of compound (C).

[0022] The azole condensed ring structure is a heterocyclic structure containing a fused ring of an azole ring and an aromatic ring (hereinafter also referred to as the "azole condensed ring"), and may have substituents on the ring portion. Examples of azole rings constituting the fused ring in the azole condensed ring structure include pyrrole rings, pyrazole rings, imidazole rings, and 1,2,3-triazole rings. Of these, the imidazole ring or the 1,2,3-triazole ring is preferred as the azole ring constituting the fused ring. Examples of aromatic rings constituting the fused ring together with the azole ring include benzene rings, pyridine rings, pyrimidine rings, and pyridazine rings. Examples of substituents are the same groups as those exemplified in the description of the azole ring structure.

[0023] The azole condensed ring structure of compound (A) is preferably a condensed ring structure of an imidazole ring or a 1,2,3-triazole ring and an aromatic ring. Preferred specific examples include the ring structures represented by the following formulas (az-1) to (az-3). [ka]

[0024] Compound (A) preferably has an azole ring structure as its specific heterocyclic structure, as this allows for easy acquisition of a cured product with high reactivity with compound (C) and excellent chemical resistance and high temperature / high humidity resistance. Furthermore, in order to obtain a radiation-sensitive composition with a good balance of alkali solubility, reactivity with compound (C), and storage stability while enhancing the chemical resistance and high temperature / high humidity resistance of the cured product, the specific heterocyclic structure of compound (A) is preferably a monocyclic or fused ring structure having a triazole ring, a tetrazole ring, or an imidazole ring. More specifically, this includes a triazole ring structure, a tetrazole ring structure, an imidazole ring structure, and a fused ring structure of a triazole ring, a tetrazole ring, or an imidazole ring with an aromatic ring.

[0025] Compound (A) may have only one specific heterocyclic structure in a single molecule, or it may have two or more. It is preferable for compound (A) to have multiple specific heterocyclic structures in a single molecule, as this allows for the production of cured products with superior chemical resistance and high temperature / high humidity resistance. Specifically, from the viewpoint of enhancing the improvement effect on the chemical resistance and high temperature / high humidity resistance of the cured product, and from the viewpoint of the ease of synthesis of compound (A), the number of specific heterocyclic structures in compound (A) is preferably 2 to 6, and more preferably 2 to 4.

[0026] Compound (A) may be a nonpolymer or a polymer. When compound (A) is a nonpolymer, it is preferable because a negative-type pattern can be formed by contact with an alkaline developer, and the pattern after exposure and development can be melted by heating at a low temperature (e.g., 100°C or below), allowing for the acquisition of microlenses with good shape and sufficient surface smoothing of the film.

[0027] The molecular weight of compound (A) is preferably 600 or more. A molecular weight of 600 or more is preferable because it allows for the formation of an organic film exhibiting good alkali developability, and because it allows for the production of a cured product with excellent heat resistance and chemical resistance. The molecular weight of compound (A) is more preferably 700 or more, and even more preferably 750 or more. Furthermore, from the viewpoint of causing melting by low-temperature heating and suppressing the viscosity of the composition from becoming too high, the molecular weight of compound (A) is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,200 or less. When compound (A) is a polymer (including oligomers), the molecular weight of compound (A) as described above is the weight-average molecular weight (Mw) in polystyrene terms, calculated by gel permeation chromatography (GPC).

[0028] A preferred specific example of compound (A) is the compound represented by the following formula (1). [ka] (In formula (1), Ar 1 Ar is a group obtained by removing (m1+n1+1) hydrogen atoms from an aromatic ring. 2 R is a group obtained by removing (m2+n2+1) hydrogen atoms from an aromatic ring. 1 and R 2 These are either monovalent substituents independently of each other, or R 1 and R 2 and are combined with each other R 1 The aromatic ring to which R is bonded 2 The single bonds connecting the aromatic ring to which it is bonded, -O-, -S-, -NR 8 - represents a methylene group or an ethylene group. 8 R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 3 and R 4 These are monovalent substituents, independently of each other. 1 and X 2These are monovalent groups having the specified heterocyclic structure, independently of each other. m1 and m2 are integers from 0 to 6, independently of each other. k1 and k2 are integers from 0 to 4, independently of each other. n1 is an integer from 1 to 6. n2 is an integer from 0 to 6. In the formula, R 1 ~R 4 , X 1 , X 2 If multiple R 1 ~R 4 , X 1 , X 2 They are either the same or different.

[0029] In the above equation (1), Ar 1 Or Ar 2 The aromatic ring possessed by Ar may be a monoring or a fused ring. 1 and Ar 2 The aromatic ring possessed is preferably an aromatic hydrocarbon ring, such as a benzene ring, naphthalene ring, indene ring, anthracene ring, phenanthrene ring, etc. Of these, Ar 1 Or Ar 2 The aromatic ring present is preferably a benzene ring or a naphthalene ring. 1 The aromatic rings that make up the compound may be one or multiple. 1 When there are multiple aromatic rings constituting the structure, it is preferable that these multiple aromatic rings are linked to each other by single bonds, for example, a biphenyl structure. 1 When there are multiple aromatic rings that make up Ar 1 In this case, (m1+n1+1) hydrogen atoms may be removed from the same aromatic ring or from different aromatic rings. 2 The same applies to this matter as well.

[0030] Preferred specific examples of groups obtained by removing (m1+n1+1) hydrogen atoms from an aromatic ring and groups obtained by removing (m2+n2+1) hydrogen atoms from an aromatic ring include groups obtained by removing (m1+n1+1) or (m2+n2+1) hydrogen atoms from a benzene ring, groups obtained by removing (m1+n1+1) or (m2+n2+1) hydrogen atoms from a naphthalene ring, and groups obtained by removing (m1+n1+1) or (m2+n2+1) hydrogen atoms from a biphenyl ring.

[0031] R 1 or R 2 When it is a monovalent substituent, examples of the monovalent substituent include a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkoxy group having 3 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an aralkyloxy group having 6 to 12 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a cycloalkylthio group having 3 to 12 carbon atoms, an arylthio group having 6 to 12 carbon atoms, an aralkylthio group having 6 to 12 carbon atoms, a cyano group, a nitro group, a dialkylamino group, a glycidyl group, and a glycidyl poly(alkylene oxide) group. A group selected from the group consisting of (let this be V 2 .) and the like can be mentioned. R 1 or R 2 When it is a substituted monovalent hydrocarbon group, examples of the substituent include each group included in V 2 . Further, the monovalent substituent represented by R 1 or R 2 may be a monovalent group having 2 to 20 carbon atoms in which some methylene groups of the substituted or unsubstituted hydrocarbon group are replaced by -O-, -CO-, -COO-, -S-, -NR 15 -, -CO-NR 15 - and the like (let this be V 3 ). R 15 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. When the group V 3 has a substituent, examples of the substituent include a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, a carboxy group, an acyl group, a nitro group, a cyano group, and the like.

[0032] Among these, R 1 or R 2The monovalent substituent represented by is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a glycidyl group, a glycidyl poly(alkylene oxide) group, or group V 3 It is preferable that the group be an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, a glycidyl group, or a glycidyl poly(alkylene oxide) group.

[0033] R 1 and R 2 However, when combined with each other, Ar 1 and Ar 2 When representing a fused ring structure composed of Ar, the fused ring structure is Ar 1 The aromatic ring and Ar 2 The aromatic ring inside is bonded by single bonds, -O-, -S-, and -NR. 8 - It has a structure linked by methylene groups or ethylene groups. 1 and R 2 Examples of fused ring structures formed by combining these rings include fluorene rings, tetrahydroanthracene rings, xanthene rings, and thioxanthene rings. Of these, xanthene rings are preferred.

[0034] From the perspective of increasing the refractive index of the cured product, compound (A) is Ar in formula (1) above. 1 and Ar 2 has a condensed polycyclic aromatic hydrocarbon ring, or R 1 and R 2 and are combined with each other Ar 1 and Ar 2 Compounds having a fused ring structure composed of the above formula (1) can preferably be used. From the viewpoint of increasing the refractive index of the cured product and the availability of the material, compound (A) is Ar 1 and Ar 2 A compound having a condensed polycyclic aromatic hydrocarbon ring can be more preferably used. Also, in terms of the availability of materials, as compound (A), Ar in formula (1) above is preferred. 1 and Ar 2Compounds having a monocyclic aromatic hydrocarbon ring (benzene ring) can preferably be used.

[0035] m1 and m2 are Ar 1 and Ar 2 It can be selected according to the type. m1 and m2 are preferably 0 to 3, and more preferably 0 or 1.

[0036] R 3 or R 4 Examples of monovalent substituents represented by include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.), C1-C10 alkyl groups, C3-C12 cycloalkyl groups, C6-C12 aryl groups, C6-C12 aralkyl groups, C1-C10 alkoxy groups, C3-C12 cycloalkoxy groups, C6-C12 aryloxy groups, C6-C12 aralkyloxy groups, C1-C10 alkylthio groups, C3-C12 cycloalkylthio groups, C6-C12 arylthio groups, C6-C12 aralkylthio groups, cyano groups, acyl groups, etc. 3 or R 4 The monovalent substituent represented by is preferably a halogen atom, a C1-C10 alkyl group, a C3-C12 cycloalkyl group, a C6-C12 aryl group, or a C6-C12 aralkyl group, and more preferably an iodine atom, a C1-C5 alkyl group, or a C6-C12 aryl group.

[0037] k1 and k2 are preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0038] X 1 and X 2 X is a monovalent group having an azole ring structure or an azole fused ring structure. 1 and X 2 The group is preferably represented by the following formula (2). *-W 1 -V 1 …(2) (In formula (2), W 1 V is a divalent organic group. 1This is a group obtained by removing one hydrogen atom from the ring portion of a substituted or unsubstituted azole ring or azole condensed ring. (* represents a bond.)

[0039] In the above equation (2), W 1 The divalent organic groups represented by include divalent substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, and some of the methylene groups of the substituted or unsubstituted hydrocarbon groups being -O-, -CO-, -COO-, -S-, -NR 9 -,-CO-NR 9 -A divalent group with 2 to 20 carbon atoms (R 9 Examples include hydrogen atoms or monovalent hydrocarbon groups having 1 to 6 carbon atoms.

[0040] W 1 When is a divalent hydrocarbon group having 1 to 20 carbon atoms, specific examples of such hydrocarbon groups include divalent chain hydrocarbon groups having 1 to 20 carbon atoms, divalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms. Also, W 1 If the compound has substituents, specific examples of such substituents include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.), hydroxyl groups, carboxyl groups, acyl groups, nitro groups, cyano groups, and the like.

[0041] From the standpoint of the availability of raw materials used in the synthesis of compound (A), W 1 This is a substituted or unsubstituted divalent chain hydrocarbon group having 1 to 20 carbon atoms, or a portion of the methylene groups of a substituted or unsubstituted chain hydrocarbon group is -O-, -CO-, -COO-, -S-, -NR 9 -or-CO-NR 9 It is more preferable that the group is a divalent chain group having 2 to 20 carbon atoms, which is replaced by -. From the viewpoint of the availability of raw materials and the ease of synthesis of compound (A), W 1 The substituents it has are preferably hydroxyl groups.

[0042] n1 is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. n2 is preferably 0 to 3, more preferably 0 to 2, even more preferably 0 or 1, and even more preferably 1.

[0043] Further specific examples of compound (A) include the compounds represented by formulas (a1-1) to (a1-20) below. In formulas (a1-5) and (a1-6) below, t is an integer between 1 and 6. [ka] [ka] [ka]

[0044] • Manufacturing of compound (A) The method of synthesizing compound (A) is not particularly limited and can be synthesized by appropriately combining standard organic chemistry methods. Compound (A) is, for example, X in formula (1) above. 1 and X 2 Alternatively, it can be obtained by reacting a compound having a monovalent group containing a first reactive group (hereinafter also referred to as a "fluorene precursor") with a functional group that can react with the first reactive group (hereinafter also referred to as a "second reactive group") and a reactive compound having a specific heterocyclic structure. Examples of the first reactive group include epoxy groups, hydroxyl groups, alkenyl groups, halogeno groups (fluoro groups, chloro groups, bromo groups, iodo groups, etc.), and tosyl groups. Examples of the second reactive group include thiol groups, halogeno groups, isocyanate groups, amino groups, and carboxyl groups. When the first reactive group is an epoxy group or an alkenyl group and the second reactive group is a thiol group, it is preferable in that the storage stability of the composition can be improved and the refractive index of the cured product obtained using compound (A) can be increased.

[0045] A specific example of a fluorene precursor having a primary reactive group is the compound represented by the following formula (7). [ka] (In formula (7), Ar 21 Ar is a group obtained by removing (m5+n5+1) hydrogen atoms from an aromatic ring. 22 This is a group obtained by removing (m6+n6+1) hydrogen atoms from an aromatic ring. 21 and R 22 These are either monovalent substituents independently of each other, or R 21 and R 22 and are combined with each other R 21 The aromatic ring to which R is bonded 22 The single bonds connecting the aromatic ring to which it is bonded, -O-, -S-, -NR 8 - represents a methylene group or an ethylene group. 1 and B 2 These are monovalent groups having a primary reactive group, independently of each other. m5 and m6 are integers from 0 to 6, independently of each other. n5 and n6 are integers from 1 to 6, independently of each other. R is present in the formula. 21 , R 22 B 1 B 2 If multiple R 21 , R 22 B 1 B 2 They are the same or different. 8 , R 3 , R 4 k1 and k2 are equivalent to those in equation (1) above, respectively.

[0046] In the above equation (7), Ar 21 and Ar 22 For specific and preferred examples, see Ar in formula (1) above. 1 and Ar 2 The explanation can be used as a reference. 21 or R 22 A specific example of a case where is a monovalent substituent is R in formula (1) above. 1 and R 2 V shown in the explanation 2 Similar bases can be cited. n5 and n6 are preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. m5 and m6 are preferably 0 to 3, more preferably 0 or 1, and even more preferably 0.

[0047] Specific examples of fluorene precursors having a primary reactive group include compounds represented by the following formula, where r is an integer from 0 to 5, and s is an integer from 0 to 6. 1 These are halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.). [ka]

[0048] Specific examples of reactive compounds having a second reactive group and a specific heterocyclic structure include compounds in which a thiol group, halogeno group, isocyanate group, amino group, or carboxyl group is bonded to a specific heterocyclic structure via a single bond or a divalent linking group (e.g., an alkanediyl group). When the second reactive group is a thiol group or a halogeno group, specific examples of thiol compounds and compounds having a halogeno group as reactive compounds include compounds represented by the following formulas. [ka]

[0049] The reaction between a fluorene precursor having a first reactive group and a reactive compound having a second reactive group and a specific heterocyclic structure (hereinafter also referred to as the "specific reactive compound") can preferably be carried out in a solvent. The amount of the specific reactive compound used is, for example, 0.2 to 2.0 moles, preferably 0.5 to 1.0 mole, per mole of the first reactive group of the fluorene precursor. Examples of solvents include esters, ethers, amides, ketones, hydrocarbons, and halogens. The reaction temperature is, for example, -20 to 100°C, preferably 0 to 60°C. The reaction time is, for example, 0.2 to 36 hours.

[0050] In the reaction between the fluorene precursor and the specific reactive compound, a compound having a second reactive group and not having a specific heterocyclic structure (hereinafter also referred to as "other reactive compounds") may be used in combination. Examples of other reactive compounds include compounds having a monovalent hydrocarbon group and a second reactive group; compounds having a monovalent sulfur-containing heterocyclic group and a second reactive group; and so on. The amount of other reactive compounds used is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, relative to the total amount of the specific reactive compound and other reactive compounds used in the reaction.

[0051] The above reaction yields compound (A), a reaction product of a fluorene precursor and a specific reactive compound. Compound (A) exhibits good alkali solubility due to its specific heterocyclic structure and good reactivity with compound (C). Furthermore, compound (A) is useful as a component for forming high-refractive index materials applied to various display elements such as organic EL elements and liquid crystal display elements, as well as solid-state image sensors, because it does not easily generate decomposition products.

[0052] In this composition, the content of compound (A) is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, per 100 parts by mass of solids contained in this composition (i.e., components other than the solvent in the radiation-sensitive composition). Furthermore, the content of compound (A) is preferably 70 parts by mass or less, and more preferably 60 parts by mass or less, per 100 parts by mass of solids contained in this composition. When the content of compound (A) is within the above range, a cured product with a good pattern shape and high refractive index can be obtained, and the cured product can be melted at a relatively low temperature (e.g., 100°C or below) during lens manufacturing, and a microlens with a good shape can be obtained.

[0053] In this specification, "solids" refers to components other than solvents that are optionally added to the radiation-sensitive composition. That is, "solids contained in this composition" refers to the components of compound (A), the photopolymerization initiator, and compound (C), plus components other than (A) to (C) and other than solvents. Therefore, even liquid additive components (e.g., surfactants) are included in the solids.

[0054] <(B) Component: Photopolymerization initiator> Preferably, a photoradical polymerization initiator can be used as the photopolymerization initiator, which generates radicals in response to radiation and initiates polymerization. The photopolymerization initiator used is not particularly limited. Examples of photopolymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, and acylphosphine oxide compounds.

[0055] Examples of O-acyloxime compounds include 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], ethane-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime), 1-(9-ethyl-6-benzoyl-9H-carbazole-3-yl)-octan-1-oneoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-oneoxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H-carbazole-3-yl]-ethane-1-one oxime-O-benzoate, etanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime), etanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyloxime), etanone-1-[9-ethyl-6-(2-methyl-5-tetrahydro [Furanylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), etanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime), methanone,[8-[[(acetyloxy)imino][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl]-11-(2-ethylhexyl)-11H-benzo[a]carbazol-5-yl]-,(2,4,6-trimethylphenyl] Examples include phenyl), etanone, 1-[9-ethyl-6-(1,3-dioxolane,4-(2-methoxyphenoxy))-9H-carbazole-3-yl]-,1-(O-acetyloxime), methanone, (9-ethyl-6-nitro-9H-carbazole-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]-,O-acetyloxime, 1-propanone,3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime), etc.As the O-acyloxime compound, a compound having an O-benzoyloxime group is preferred from the viewpoint of improving the storage stability of this composition. Furthermore, a compound having an O-acetyloxime group is preferred because it allows for the acquisition of a cured product with a better lens shape.

[0056] Examples of acetophenone compounds include α-aminoketone compounds and α-hydroxyketone compounds. Specific examples of these include α-aminoketone compounds such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one. Examples of α-hydroxyketone compounds include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and 1-hydroxycyclohexylphenyl ketone.

[0057] Examples of biimidazole compounds include 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, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

[0058] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0059] The content of the photopolymerization initiator in this composition is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, based on 100 parts by mass of the total amount of polymerizable compounds (compound (A) and compound (C)) contained in this composition. Furthermore, the content of the photopolymerization initiator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 12 parts by mass or less, based on 100 parts by mass of the total amount of polymerizable compounds contained in this composition. By setting the content of the photopolymerization initiator within the above range, a radiation-sensitive composition exhibiting good curability and transparency can be obtained.

[0060] <(C) Component: Compound having polymerizable carbon-carbon unsaturated bonds> Compound (C) is a compound having a polymerizable carbon-carbon unsaturated bond. Compound (C) is a polymerizable compound that can produce a polymer upon irradiation with radiation. As compound (C), at least one selected from the group consisting of compounds (CA) and (CB) shown below can preferably be used. Compound (CA): Fluorene compounds that do not have a specific heterocyclic structure Compound (CB): A compound with a molecular weight of less than 600 that does not have a fluorene structure.

[0061] ·Compound (CA) Compound (CA) is a fluorene compound that differs from compound (A) in that it does not have a specific heterocyclic structure and has polymerizable carbon-carbon unsaturated bonds. Compound (CA) may be a nonpolymer or a polymer. If compound (CA) is a nonpolymer, its molecular weight is preferably 1,500 or less, and more preferably 1,000 or less. If compound (CA) is a polymer, examples of compound (CA) include the fluorene compounds described in International Publication No. 2009 / 119622, Japanese Patent Publication No. 2013-227534, and Japanese Patent No. 5782281 (Example 1).

[0062] In order to obtain lenses with a good shape, nonpolymers can preferably be used as the compound (CA). Specific examples of the compound (CA) when it is a nonpolymer include the compound represented by the following formula (3). [ka] (In formula (3), Ar 11 Ar is a group obtained by removing (m3+n3+1) hydrogen atoms from an aromatic ring. 12 R is a group obtained by removing (m4+n4+1) hydrogen atoms from an aromatic ring. 11 and R 12 These are either monovalent substituents independently of each other, or R 11 and R 12 and are combined with each other Ar 11 and Ar 12 This represents a fused ring structure formed together with R. 11 and R 12 and are combined with each other Ar 11 and Ar 12 The fused ring structure formed together consists of two aromatic rings bonded by single bonds, -O-, -S-, and -NR. 18 - It has a structure linked by methylene groups or ethylene groups. 18 X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 11 and X 12 These are monovalent groups that independently possess polymerizable carbon-carbon unsaturated bonds. 13 and R 14 These are independent monovalent substituents. m3 and m4 are independent integers from 0 to 6. k3 and k4 are independent integers from 0 to 4. n3 is an integer from 1 to 6. n4 is an integer from 0 to 6. R is present in the formula. 11 ~R 14 If multiple R 11 ~R 14 They are either the same or different.

[0063] In the above equation (3), Ar 11 Or Ar 12 The group represented by is Ar in formula (1) above. 1Or Ar 2 Groups similar to those exemplified above can be cited as examples of groups represented by [the symbol]. R 11 or R 12 As a monovalent substituent represented by , R 1 or R 2 In addition to the groups exemplified as monovalent substituents represented by , other examples include alkali-soluble groups (excluding groups having a specific heterocyclic structure), primary amino groups, secondary amino groups, alkoxyalkyl groups, alkoxyalkoxyalkyl groups, alkoxyalkoxy groups, cycloalkyloxyalkyl groups, hydroxyalkyl groups, hydroxyalkoxy groups, dihydroalkyl groups, dihydroalkoxy groups, hydroxycycloalkyl groups, and hydroxycycloalkoxy groups. Here, "alkali-soluble group" refers to a functional group that increases solubility in alkaline solutions by interacting with or reacting with alkali. Acidic groups can be cited as alkali-soluble groups, and specific examples include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, phosphate groups, and groups containing a sulfonamide structure (-S(=O)2-NH-). R 13 or R 14 As a monovalent substituent represented by , R 3 or R 4 Examples of monovalent substituents represented by the formula include groups similar to those exemplified above.

[0064] X 11 or X 12 Examples of monovalent groups represented by include groups having a (meth)acryloyl group, an alkenyl group, a vinylphenyl group, a vinyl ether group, or a maleimide group. 11 and X 12 A specific example of this is the group represented by the following formula (4). *-W 11 -Z 1 …(4) (In formula (4), W 11 Z is a divalent organic group. 1 This group is a (meth)acryloyl group, an alkenyl group, a vinylphenyl group, a vinyl ether group, or a maleimide group. (* indicates a bond.)

[0065] In the above equation (4), W 11 The divalent organic groups represented by include divalent substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, and some of the methylene groups of the substituted or unsubstituted hydrocarbon groups being -O-, -CO-, -COO-, -S-, -NR 10 -,-CO-NR 10 -A divalent group with 2 to 20 carbon atoms (R 10 Examples include hydrogen atoms or monovalent hydrocarbon groups having 1 to 6 carbon atoms. 11 A specific example of a hydrocarbon group when is a divalent hydrocarbon group having 1 to 20 carbon atoms is W in formula (2) above. 1 The same groups as those exemplified in the explanation can be cited. Also, W 11 If it has substituents, specific examples of such substituents include R 11 or R 12 Examples of monovalent substituents represented by the formula include groups similar to those exemplified above.

[0066] In terms of being able to increase the reactivity with a specific heterocyclic structure of compound (A), X 11 or X 12 The monovalent group represented by is preferably a (meth)acryloyl group. From the viewpoint of the availability of raw materials and the ease of synthesis of compound (CA), X 11 or X 12 A preferred example of a monovalent group represented by the formula (6) below is the group represented by the formula (6) below. [ka] (In formula (6), R 5 R is an alkanediyl group with 2 to 4 carbon atoms. 6 This is a hydrogen atom or a methyl group. 1 This is a hydrogen atom, "-C(=O)-R 7 -COOH or -C(=O)-NH-S(=O)2-R 8 " is R 7 R is a divalent organic group having 1 or more carbon atoms. 8is a monovalent organic group with 1 or more carbon atoms. p is an integer from 0 to 4. r is 0 or 1. If p is 2 or greater, there are multiple R's. 5 They are either the same or different. (* represents a combination.)

[0067] In equation (6) above, R 7 The divalent organic group represented by may have a chain-like structure, a cyclic structure, or may have both a chain-like and a cyclic structure. 7 Specific examples include divalent hydrocarbon groups, divalent groups containing -O-, -S-, -NR- (where R is a monovalent hydrocarbon group) between the carbon-carbon bonds of a hydrocarbon group, divalent groups formed by substituting any hydrogen atom of a hydrocarbon group with a monovalent heteroatom-containing group (e.g., alkoxy group, cycloalkoxy group, aryloxy group, aralkyloxy group, alkylthio group, cycloalkylthio group, arylthio group, aralkylthio group, etc.), and groups formed by removing two hydrogen atoms bonded to the same carbon in a hydrocarbon group, resulting in "=P(R) 10 )3" is a group (3 R 10 Examples of hydrocarbon groups include divalent groups formed by the substitution of each other with monovalent hydrocarbon groups, and divalent groups having a heterocyclic structure. Examples of hydrocarbon groups include alkanediyl groups having 1 to 10 carbon atoms, alkenediyl groups having 2 to 10 carbon atoms, divalent saturated or unsaturated alicyclic hydrocarbon groups having 3 to 20 carbon atoms, and divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms.

[0068] R 8 The monovalent organic group represented by may also have a chain-like structure, a cyclic structure, or both a chain-like and a cyclic structure. 8 A concrete example is R 7 An example of a divalent organic group represented by this formula is a group in which a hydrogen atom is bonded to one of the bonds of the example group.

[0069] m3 and m4 are preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. k3 and k4 are preferably 0 to 2, and more preferably 0 or 1. n3 and n4 are preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. r is preferably 1.

[0070] The compound represented by formula (3) above preferably has an alkali-soluble group together with a fluorene skeleton, in that it can improve the alkali developability of the composition while maintaining good reliability of the cured product. The alkali-soluble group of the compound represented by formula (3) above is preferably a carboxyl group, a sulfonamide structure-containing group, or a phenolic hydroxyl group, in that it has high solubility in alkaline developer.

[0071] Specific examples of compounds (CA) include those represented by formulas (d1-1) to (d1-5) below. [ka] (In formulas (d1-1) to (d1-5), R 30 R is a hydrogen atom or a methyl group. 30 They are either the same or different.

[0072] When compound (CA) is incorporated into this composition, the content of compound (CA) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 30 parts by mass or more, based on 100 parts by mass of the total amount of fluorene compounds (compound (A) and compound (CA)) contained in this composition. Furthermore, the content of compound (CA) is preferably 95 parts by mass or less, and more preferably 90 parts by mass or less, based on 100 parts by mass of the total amount of fluorene compounds contained in this composition. By setting the content of compound (CA) within the above range, a cured product with a good pattern shape can be obtained.

[0073] Furthermore, when compound (CA) is incorporated into this composition, the content of compound (A) is preferably 5 parts by mass or more and 100 parts by mass or less per 100 parts by mass of compound (CA), from the viewpoint of obtaining a cured product with a good lens shape. The content of compound (A) is more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, per 100 parts by mass of compound (CA). Moreover, the content of compound (A) is more preferably 90 parts by mass or less, and even more preferably 80 parts by mass or less, per 100 parts by mass of compound (CA).

[0074] ·Compound (CB) Compound (CB) differs from compound (A) in that it does not have a specific heterocyclic structure and possesses polymerizable carbon-carbon unsaturated bonds, and differs from compound (CA) in that it does not have a fluorene structure. Here, while fluorene compounds exhibit a high refractive index, if a pattern is to be formed into an appropriate lens shape by melting it by heating using only a fluorene compound as the polymerizable compound, there is a concern that a high-temperature process of, for example, 120°C or higher will be required. Also, if only a fluorene compound is used as the polymerizable compound, a high exposure is required to obtain sufficient curability. In contrast, by using compounds (CA) and (CB) in combination as polymerizable compounds, the pattern can be suitably melted by a low-temperature process of, for example, 100°C or lower, and an appropriate lens shape can be obtained. In addition, the curing speed is improved, and curing becomes possible with a relatively low exposure.

[0075] From the viewpoint of keeping the melting temperature by heating as low as possible, the molecular weight of compound (CB) is preferably smaller than that of compound (A). Specifically, the molecular weight of compound (CB) is preferably less than 600, more preferably 550 or less, even more preferably 500 or less, and particularly preferably 450 or less. Furthermore, from the viewpoint of obtaining a cured product with a high refractive index and excellent reliability in terms of solvent resistance and low volatility, the molecular weight of compound (CB) is preferably 100 or more.

[0076] Examples of compound (CB) include (meth)acryloyl group-containing compounds, chain vinyl compounds, aromatic vinyl compounds, and maleimide compounds. These compounds are preferred because they have good reactivity with the reactive group (i.e., a group having a specific heterocyclic structure) of compound (A) and have relatively high plasticity.

[0077] Compound (CB) may be either a monofunctional compound or a polyfunctional compound. Furthermore, a combination of monofunctional and polyfunctional compounds may be used as compound (CB). Specific examples of compound (CB) being a monofunctional compound include (meth)acrylic acid esters having a chain structure, (meth)acrylic acid esters having an alicyclic structure, (meth)acrylic acid esters having an aromatic ring structure, (meth)acrylamide compounds, chain vinyl compounds, aromatic vinyl compounds, maleimide compounds, and the like. When compound (CB) is a monofunctional compound, a (meth)acryloyl group-containing compound is preferably used as compound (CB), and more preferably, at least one (meth)acrylic acid ester compound selected from the group consisting of (meth)acrylic acid esters having a chain structure, (meth)acrylic acid esters having an alicyclic structure, and (meth)acrylic acid esters having an aromatic ring structure can be used.

[0078] Specific examples of cases where compound (CB) is a monofunctional compound include (meth)acrylate esters with a chain structure, such as alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, and polyoxyalkylene (meth)acrylates. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, and n-stearyl (meth)acrylate. Examples of hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Examples of alkoxyalkyl (meth)acrylates include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and propoxyethyl (meth)acrylate. Examples of (meth)acrylate polyoxyalkylene esters include methoxydiethylene glycol (meth)acrylate, methoxytetraethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, ethoxydipropylene glycol (meth)acrylate, and 2-ethylhexyloxydiethylene glycol (meth)acrylate.

[0079] Examples of (meth)acrylic acid esters having an alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, 4-hydroxymethylcyclohexyl (meth)acrylate, and tricyclo(meth)acrylate [5.2.1.0 2,6 ] Decane-8-yl, (meth)acrylate tricyclo[5.2.1.0 2,5Examples include decane-8-yloxyethyl and isobornyl (meth)acrylate. Examples of (meth)acrylic acid esters having an aromatic ring structure include phenyl (meth)acrylate, benzyl (meth)acrylate, naphthylmethyl (meth)acrylate, naphthylethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenylthioethyl (meth)acrylate, m-phenoxyphenylmethyl (meth)acrylate, p-phenoxyphenylmethyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, polyethyleneoxynonylphenyl (meth)acrylate, (1-naphthyl)methyl (meth)acrylate, (2-naphthyl)methyl (meth)acrylate, and (1,1'-biphenyl-4-yl)methyl (meth)acrylate.

[0080] Examples of (meth)acrylamide compounds include (meth)acryloylmorpholine, N-(2-hydroxyethyl)(meth)acrylamide, N-vinyl-2-pyrrolidone, and N-vinyl-ε-caprolactam. Examples of chain vinyl compounds include propene, butene, pentene, and hexene. Examples of aromatic vinyl compounds include styrene, methylstyrene, α-methylstyrene, t-butoxystyrene, and vinylnaphthalene. Examples of maleimide compounds include N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N-(p-methylphenyl)maleimide.

[0081] Specific examples of compound (CB) being a polyfunctional compound include polyfunctional (meth)acrylic acid esters, aromatic vinyl compounds, and chain-like vinyl compounds. Examples of polyfunctional (meth)acrylic acid esters include difunctional (meth)acrylic acid esters and (meth)acrylic acid esters with three or more functions. Specific examples of these include, as difunctional (meth)acrylic acid esters, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate.

[0082] Examples of (meth)acrylic acid esters with three or more functions include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, tri(2-(meth)acryloyloxyethyl)phosphate, succinic acid-modified pentaerythritol tri Examples include (meth)acrylate, succinic acid-modified dipentaerythritol penta(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, carboxyl group-containing polybasic acid-modified (meth)acrylic oligomers, and polyfunctional urethane acrylate compounds obtained by reacting a compound having a linear alkylene group and an alicyclic structure and two or more isocyanate groups with a compound having one or more hydroxyl groups in the molecule and three, four or five (meth)acryloyloxy groups.

[0083] Examples of polyfunctional aromatic vinyl compounds include 1,3-divinylbenzene and 1,4-divinylbenzene. Examples of polyfunctional chain vinyl compounds include 1,5-hexadiene, 1,6-heptadiene, and 1,7-octadiene.

[0084] Preferred specific examples of compound (CB) include compounds represented by formulas (C1-1) to (C1-47) below. [ka] [ka]

[0085] [ka] (In formulas (C1-1) to (C1-47), R 20 R is a hydrogen atom or a methyl group. 20 If multiple R 20 m and n are either identical or different integers. m and n are independent integers between 0 and 6. x, y, and z are independent integers between 0 and 3, provided that 1 ≤ x + y + z ≤ 3.

[0086] From the viewpoint of obtaining a highly heat-resistant cured product while enabling the formation of an appropriate lens shape by heating at low temperatures, the content of compound (CB) is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the total amount of fluorene compounds (specifically, compound (A) and compound (CA)) contained in this composition. Furthermore, from the viewpoint of suppressing a decrease in the refractive index of the resulting cured product, the content of compound (CB) is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less, per 100 parts by mass of the total amount of fluorene compounds contained in this composition.

[0087] From the viewpoint of obtaining a radiation-sensitive composition with excellent patterning properties, compound (CB) preferably contains a compound having three or more polymerizable carbon-carbon unsaturated bonds in one molecule (hereinafter also referred to as "compound (C2)"). Specifically, compound (CB) is preferably compound (C2) or a mixture of compound (C1) and compound (C2) having one or two polymerizable carbon-carbon unsaturated bonds in one molecule (hereinafter also referred to as "compound (C1)"). Furthermore, compound (CB) is more preferably a mixture of compound (C1) and compound (C2) because it is easier to melt by heating at low temperatures and easier to obtain lenses with appropriate shapes.

[0088] The content of compound (C2) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, relative to the total amount of compound (CB) contained in the composition (100% by mass), in order to improve the patterning properties of the radiation-sensitive composition. Furthermore, from the viewpoint of obtaining a cured product with an appropriate lens shape by melting by heating at a low temperature, the content of compound (C2) is preferably 95% by mass or less, and more preferably 90% by mass or less, relative to the total amount of compound (CB) contained in the composition.

[0089] In this composition, the content of compound (C) is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and even more preferably 70 parts by mass or more, based on 100 parts by mass of the total amount of solids (components other than solvents) contained in this composition, from the viewpoint of improving sensitivity, improving lens shape, and providing excellent solvent resistance and high temperature and humidity resistance.

[0090] <Other ingredients> In addition to the above-mentioned compound (A), photopolymerization initiator, and compound (C), this composition may further contain other components (hereinafter also referred to as "other components"). Examples of other components include polymers with a molecular weight of 2,000 to 100,000 that do not have a fluorene structure (hereinafter also referred to as "polymer (P)"), solvents, and the like.

[0091] ·Polymer (P) This composition may further contain, as an additive component, a polymer (polymer (P)) different from compound (CA), having a molecular weight of 2,000 to 100,000. By incorporating polymer (P) into this composition, it is possible to improve the heat resistance of the resulting cured product.

[0092] Examples of polymers (P) include alkali-soluble polymers and carboxyl-containing photosensitive polymers. Examples of alkali-soluble polymers include (meth)acrylic acid / methyl (meth)acrylate copolymer, (meth)acrylic acid / benzyl (meth)acrylate copolymer, (meth)acrylic acid / 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate copolymer, (meth)acrylic acid / styrene / isoprene / tricyclodecanyl (meth)acrylate / 2-mono(hexahydroxyphthaloyloxy)ethyl (meth)acrylate copolymer, methacrylic-modified acrylic resin, and acid anhydride-modified acrylic resin.

[0093] Examples of carboxyl group-containing photosensitive polymers include acid-modified epoxy acrylates such as bisphenol A type epoxy acrylate, bisphenol F type epoxy acrylate, cresol novolac type epoxy acrylate, and biphenyl type epoxy acrylate. Specific examples of carboxyl group-containing photosensitive polymers include CCR-1235, CCR-1291H, ZAR-1035, ZAR-2000, ZFR-1401H, ZFR-1491H, ZCR-1569H, and ZCR-1798H (all manufactured by Nippon Kayaku Co., Ltd.).

[0094] When polymer (P) is incorporated into this composition, the polymer (P) content is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less, per 100 parts by mass of the fluorene compound contained in this composition. By setting the polymer (P) content within the above range, it is possible to obtain an appropriate lens shape by heating at low temperatures while also obtaining an improved heat resistance effect.

[0095] ·solvent This composition is a liquid composition in which compound (A), a photopolymerization initiator, compound (C), and other components as needed are preferably dissolved or dispersed in a solvent. As the solvent, an organic solvent is preferred that dissolves each component of this composition and does not react with each component.

[0096] Specific examples of solvents include, for example, alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene diglycol monomethyl ether, ethylene diglycol ethyl methyl ether, dimethyl glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether; amides such as dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. Of these, it is preferable that the solvent includes at least one selected from the group consisting of ethers, esters, and ketones.

[0097] Other components, in addition to those mentioned above, include polymerization inhibitors, surfactants, antioxidants, sensitizers, softeners, plasticizers, adhesive aids, and UV absorbers. The proportions of these components are appropriately selected according to each component, within a range that does not impair the effects of this disclosure.

[0098] For example, surfactants can be used to improve the applicability of this composition (such as wetting spread and reduction of uneven application). Examples of surfactants include fluorinated surfactants, silicone surfactants, and nonionic surfactants.

[0099] Specific examples of surfactants include fluorine-based surfactants such as Megafac F-171, F-172, F-173, F-251, F-430, F-554, and F-563 (manufactured by DIC Corporation); Florard FC430 and FC431 (manufactured by Sumitomo 3M Corporation); Asahiguard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106, and S-611 (manufactured by AGC Seimi Chemical Co., Ltd.); Polyflow No. 75 and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.); FTX-218 (manufactured by Neos Co., Ltd.); and Ftop EF301, EF303, and EF352 (manufactured by Shin Akita Chemical Co., Ltd.).

[0100] Examples of silicone-based surfactants include the following product names: SH200-100cs, SH-28PA, SH-30PA, SH-89PA, SH-190, SH-8400, FLUID, SH-193, SZ-6032, SF-8428, DC-57, DC-190, PAINTAD19, FZ-2101, FZ-77, FZ-2118, L-7001, L-7002 (manufactured by Toray Dow Corning Silicone Co., Ltd.); Organosiloxane Polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); BYK-300, BYK-306, BYK-310, BYK-330, BYK-335, BYK-341, BYK-344, BYK-370, BYK-340, BYK-345 (manufactured by BIC Chemie Japan Co., Ltd.).

[0101] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate.

[0102] When a surfactant is incorporated into this composition, the surfactant content is preferably 0.01 to 1.5 parts by mass, more preferably 0.02 to 1.2 parts by mass, and even more preferably 0.05 to 1.0 parts by mass, based on 100 parts by mass of the total amount of compound (A) contained in this composition.

[0103] The adhesion aid is a component that improves the adhesion between the cured product formed using this composition and the substrate, and suppresses the peeling of the cured product during the developing process. A functional silane coupling agent having a reactive functional group can preferably be used as the adhesion aid. Examples of reactive functional groups in a functional silane coupling agent include carboxyl groups, (meth)acryloyl groups, epoxy groups, vinyl groups, and isocyanate groups.

[0104] Specific examples of functional silane coupling agents include, for example, trimethoxysilylbenzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane. Commercial functional silane coupling agents include, by trade name, KR-513, X-40-9296, X-12-1048, X-12-1050, and KBM-5803 (all manufactured by Shin-Etsu Silicone Co., Ltd.).

[0105] If the composition contains an adhesive aid, its content is preferably 0.01 parts by mass or more and 4 parts by mass or less, and more preferably 0.1 parts by mass or more and 2 parts by mass or less, per 100 parts by mass of compound (A) contained in the composition.

[0106] This composition can be obtained by mixing compound (A), a photopolymerization initiator, compound (C), and other optionally included components in predetermined proportions. The composition obtained by mixing each component may be filtered, for example, through a filter with a pore size of 0.5 μm or less.

[0107] The solid content concentration of this composition (i.e., the ratio of the total mass of components other than the solvent in the radiation-sensitive composition to the total mass of the radiation-sensitive composition) is appropriately selected considering viscosity, volatility, etc. The solid content concentration of this composition is preferably in the range of 1 to 60% by mass. A solid content concentration of 1% by mass or more is preferable because it ensures sufficient film thickness when this composition is applied to a substrate. Furthermore, a solid content concentration of 60% by mass or less is preferable because it prevents the film thickness from becoming excessively large, and allows for a moderately high viscosity of this composition, ensuring good coatability. The solid content concentration in this composition is more preferably 2 to 50% by mass, and even more preferably 5 to 40% by mass.

[0108] The total content of compound (A) and compound (C) in this composition is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, and even more preferably 85 parts by mass or more, based on 100 parts by mass of the total amount of solids (components other than solvent) contained in this composition, from the viewpoint of improving sensitivity and achieving a good lens shape by heating at low temperatures.

[0109] ≪Cured product and method for producing the same≫ The cured products of this disclosure can be manufactured using the radiation-sensitive composition of this disclosure described above. The cured products obtained with this composition have a high refractive index, excellent heat resistance and chemical resistance, and high transparency. Therefore, this composition can be preferably used as a radiation-sensitive composition for optical components. In particular, it is suitable as a radiation-sensitive composition for lens manufacturing to produce micro-focusing elements (hereinafter also referred to as "microlenses") provided in solid-state image sensors (e.g., CCD image sensors, CMOS image sensors) and display elements (e.g., organic EL elements, liquid crystal display elements).

[0110] The radiation-sensitive composition of the present disclosure described above is suitable as a negative-type pattern-forming material in which a pattern (i.e., a cured product formed by the radiation-sensitive composition) is formed by exposing a portion of an organic film formed by the radiation-sensitive composition, and then dissolving the unexposed portion of the organic film after exposure in an alkaline developer, and then melting the resulting pattern by heat treatment to form a lens shape. The method for producing the cured product of the present disclosure includes the following steps (I) to (IV). (I) A step of applying a radiation-sensitive composition onto a substrate to form a coating film. (II) A step of irradiating a portion of the coating with radiation. (III) A process of developing a radiation-irradiated coating to form a pattern on a substrate. (IV) Heating the pattern The following describes each step (steps (I) to (IV)).

[0111] <Process (I): Coating process> Step (I) is a step of forming a coating film on a substrate by applying the composition onto the substrate. Examples of substrates include glass substrates, silicon wafers, plastic substrates, plastic films, and substrates on which a colored resist, overcoat, anti-reflective film, various metal thin films, sealing films, etc., are formed on their surface. Examples of plastic substrates and plastic films include resin substrates and films made of plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethersulfone, polycarbonate, and polyimide. Various elements (for example, light-receiving elements such as photodiodes and light-emitting elements such as organic light-emitting diodes) may be pre-installed on these substrates.

[0112] As for the application method of this composition, suitable methods such as spraying, roll coating, rotary coating (spin coating), slit die coating, bar coating, and inkjet coating can be used. Of these, spin coating, bar coating, and slit die coating are preferred application methods.

[0113] After applying this composition to a substrate, a preheating process (pre-bake) may be performed to prevent dripping and other purposes. The pre-bake conditions can be appropriately set depending on the type and usage ratio of each component. For example, the pre-bake conditions can be 60 to 130°C for 30 seconds to 10 minutes. The film thickness of the formed coating after pre-bake is preferably 0.1 to 20 μm, and more preferably 0.2 to 15 μm.

[0114] <Process (II): Exposure process> Step (II) is a step in which a portion of the coating film formed in step (I) is irradiated with radiation. This radiation irradiation causes a curing reaction to proceed in the exposed area, and a cured product is obtained in which the exposed area has hardened. In step (II), the radiation irradiation of the coating film is carried out through a mask having a pattern (e.g., a dot pattern) for obtaining microlenses of the desired shape. The mask may be a multi-tone mask such as a halftone mask or a graytone mask.

[0115] Examples of radiation used to irradiate the coating include ultraviolet light, far ultraviolet light, X-rays, and charged particle beams. Examples of ultraviolet light include g-rays (wavelength 436 nm), i-rays (wavelength 365 nm), and KrF excimer laser light (wavelength 248 nm). Examples of X-rays include synchrotron radiation. Examples of charged particle beams include electron beams. Of these, ultraviolet light is preferred for irradiating the coating, and ultraviolet light with a wavelength of 200 nm to 380 nm is more preferred. Examples of light sources used include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers, and LED lamps. The radiation exposure dose is 500 J / m². 2 ~50,000 J / m 2 (50~500mJ / cm 2 ) is preferable.

[0116] <Step (III): Development step> Step (III) is a process of developing the coating film that has been irradiated with radiation in step (II) to form a pattern on the substrate. When manufacturing microlenses, this development step removes the unexposed parts of the coating film formed on the substrate, and a pattern with remaining exposed parts (more specifically, an uneven pattern formed by a large number of regularly arranged micro-cured particles) can be formed on the substrate. The micro-cured particles have, for example, a roughly rectangular cross-section.

[0117] Examples of alkaline aqueous solutions include aqueous solutions of alkali (basic compounds). Examples of alkaline aqueous solutions include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,5-diazabicyclo[4.3.0]-5-nonane. Alternatively, aqueous solutions obtained by adding an appropriate amount of water-soluble organic solvents such as methanol or ethanol or surfactants to an alkaline aqueous solution, or by adding a small amount of various organic solvents capable of dissolving this composition, may also be used as a developer.

[0118] As for the development method, any appropriate method such as the liquid-filling method, dipping method, agitation immersion method, or shower method can be used. The development time should be adjusted as appropriate depending on the composition of this composition. For example, the development time is 20 seconds to 120 seconds.

[0119] <Process (IV): Heating process> Step (IV) is a step of heating the developed pattern. When manufacturing microlenses, heating the developed pattern in step (IV) allows the micro-cured material on the substrate to be shaped into a lens. Furthermore, the heat treatment in step (IV) may further harden the composition while melting, for example, micro-cured material with a roughly rectangular cross-section. This makes it possible to obtain a microlens array in which hemispherical micro-cured material is regularly arranged on the substrate. The heat treatment can be carried out using a heating device such as an oven or a hot plate.

[0120] In step (IV), the heating temperature is preferably 100°C or less, more preferably 95°C or less, and even more preferably 90°C or less, from the viewpoint of applicability to high refractive index materials of organic EL elements. When manufacturing microlenses, the heating temperature in step (IV) is preferably 60°C or higher, and more preferably 70°C or higher, from the viewpoint of obtaining microlenses with high heat resistance and chemical resistance and good shape. The heating time can be set appropriately depending on the type of heating device, etc. For example, when heating is performed using a hot plate, the heating time is, for example, 5 to 60 minutes. When heating is performed using an oven, the heating time is, for example, 10 to 90 minutes. In step (IV), a step bake method in which multiple heat treatments are performed can also be used.

[0121] In particular, when microlenses are provided on the light-emitting side of each pixel in organic EL elements to improve light extraction efficiency and adjust the viewing angle, the manufacturing process of organic EL elements requires that the microlenses be formed at low temperatures (e.g., below 100°C), considering that organic light-emitting materials are susceptible to degradation by heat. Furthermore, in planarization films for organic EL elements, if the pattern after exposure and development can be melted by heating at low temperatures, it is possible to form a hardened film with a high degree of planarization while providing thermal protection for the organic light-emitting material. In this regard, with this composition, the pattern can be melted even when the heating temperature of the developed pattern is below 100°C, and a pattern of the desired shape can be obtained.

[0122] The manufacturing method of the present disclosure may further include, as an optional step, step (V): (V) A step of irradiating the cured product obtained by the above step (IV) with radiation (hereinafter also referred to as the "post-exposure step")

[0123] <Process (V): Post-exposure process> Step (V) is a step in which at least a portion of the developed coating film is further irradiated with radiation. By irradiating with radiation in step (V) (hereinafter also referred to as "post-exposure"), heat resistance, chemical resistance, etc. can be further improved, and a highly reliable cured product can be obtained. Specific examples of post-exposure include (1) a method of irradiating the coating film after the development step and before the heating step (i.e., the pattern before melting) with radiation, and (2) a method of irradiating the coating film after the heating step (i.e., the pattern after melting) with radiation. Of these, from the viewpoint of suitably achieving melting at low temperatures, method (2), that is, irradiating the cured product (e.g., microlenses) formed by heating the pattern with radiation, is preferred. The type of radiation and exposure conditions in post-exposure can be the same as those in step (II). The wavelength of the irradiation light, irradiation amount, light source, etc., during post-exposure may be the same as or different from those in step (II).

[0124] The microlenses obtained by the above manufacturing method have a good lens shape. The diameter of the microlenses is, for example, 1 μm to 100 μm. Furthermore, the microlenses obtained by this composition have excellent heat resistance and chemical resistance, as well as high transparency and refractive index. Therefore, the microlenses of this disclosure can be preferably used as microlenses for solid-state image sensors in imaging devices such as cameras, and as microlenses for various display elements such as organic EL elements and liquid crystal display elements. In particular, with this composition, a lens shape can be formed even when heating for melting is performed at a low temperature of 100°C or less. Therefore, it is particularly suitable for microlenses for the manufacture of organic EL elements where the application of a low-temperature process is required.

[0125] The method for manufacturing microlenses using this composition is not limited to the above. For example, microlenses may be manufactured by a method that includes the step of forming a pattern by inkjet coating a substrate with a radiation-sensitive composition. In this manufacturing method, a spherical lens-shaped pattern may be directly formed on the substrate by inkjet coating. Alternatively, a pattern may be formed on the substrate by inkjet coating, and then the pattern may be heated and melted to form a lens shape, similar to the manufacturing method described above. Specifically, the latter method includes a step of forming a pattern by inkjet coating instead of steps (I), (II), and (III) in the manufacturing method described above, and the pattern formed by this step is then made hemispherical by applying step (IV) in the manufacturing method described above to produce a lens.

[0126] <<Radiation-sensitive composition for forming a planar film and method for producing a planar film>> The cured product formed from the radiation-sensitive composition of this disclosure has a high refractive index and exhibits excellent chemical resistance. Furthermore, by heating the developed pattern at a low temperature, it melts sufficiently, and a cured film with excellent surface flatness can be obtained. Therefore, the radiation-sensitive composition of this disclosure is suitable as a material for forming planarization films provided on organic EL elements and liquid crystal display elements. The planarization film can be manufactured by a method including the above-described steps (I) to (IV). This method may further include the above-described step (V).

[0127] The radiation-sensitive composition described above is applied to a substrate and preheated at 85°C for 2 minutes to obtain a coating film with a thickness of 5.0 μm. This coating film is exposed to 200 mJ / cm² in i-ray equivalent. 2 A cured product with a refractive index of 1.59 or higher can be obtained by heating at 100°C for 40 minutes (post-bake) after irradiation with radiation. According to the radiation-sensitive composition of this disclosure, a cured film with a high refractive index of preferably 1.61 or higher, more preferably 1.64 or higher, can also be obtained under the above conditions. [Examples]

[0128] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. In the examples and comparative examples, "parts" and "%" are based on mass unless otherwise specified.

[0129] The abbreviations for the compounds used in the following examples are as follows: 1-1:9,9-Bis(4-glycidyloxyphenyl)fluorene 2-1:1,2,4-triazole-3-thiol 2-2:1H-tetrazole-5-thiol 2-3: Toluene thiol 2-4:2-Benzimidazole thiol BPFL: 9,9-Bis(4-hydroxyphenyl)fluorene (manufactured by JFE Chemical Corporation) [ka]

[0130] 1. Synthesis of Compounds (Synthesis Example 1) In a 300 mL three-necked flask equipped with a reflux condenser and thermometer, 30.0 g (64.9 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) of compound (1-1), 13.1 g (130 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), 209 mg (0.649 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) of tetrabutylammonium bromide, 30 mL of tetrahydrofuran, and 30 mL of ethanol were added and the mixture was heated and stirred at 60°C for 3 hours. After the reaction was complete, the reaction solution was allowed to cool to room temperature, 200 mL of methylene chloride was added, and the mixture was sequentially washed with 200 mL of saturated brine and 200 mL of ultrapure water. Subsequently, the organic layer was concentrated under reduced pressure, and the residue was vacuum-dried to obtain 40.9 g of a white powder of the compound represented by the following formula (A-1) (referred to as compound (A-1)). [ka]

[0131] (Synthesis Example 2) The same procedure as in Synthesis Example 1 was performed, except that compound (2-1) in Synthesis Example 1 was changed to compound (2-2), and the compound represented by the following formula (A-2) (referred to as compound (A-2)) was synthesized. [ka]

[0132] (Synthesis Example 3) The same procedure as in Synthesis Example 1 was performed, except that compound (2-1) in Synthesis Example 1 was replaced with a mixture of compound (2-1) and compound (2-3), to obtain the reaction product of compound (1-1) with compound (2-1) and compound (2-3) (referred to as mixture (A-3)). [ka]

[0133] (Synthesis Example 4) The same procedure as in Synthesis Example 1 was performed, except that compound (2-1) in Synthesis Example 1 was changed to compound (2-4), and the compound represented by the following formula (A-4) (referred to as compound (A-4)) was synthesized. [ka]

[0134] (Synthesis Example 5) The same procedure as in Synthesis Example 1 was followed, except that compound (2-1) in Synthesis Example 1 was replaced with a mixture of compound (2-1) and compound (2-4), to obtain compound (1-1) and the reaction product of compound (2-1) and compound (2-4) (referred to as mixture (A-5)). [ka]

[0135] (Comparative Synthesis Example 1) The same procedure as in Synthesis Example 1 was performed, except that compound (2-1) in Synthesis Example 1 was changed to compound (2-3), and the compound represented by the following formula (R-1) (referred to as compound (R-1)) was synthesized. [Chemical formula]

[0136] The types and amounts of raw materials used in Synthesis Examples 1 to 5 and Comparative Synthesis Example 1 are shown in Table 1. In Table 1, "equivalent" is in molar equivalent. [Table 1]

[0137] 2. Preparation of Radiation-Sensitive Composition Details of Compound (B), Compound (CB), Compound (CA) and Solvent (E) used for the preparation of radiation-sensitive compositions in Examples and Comparative Examples are shown below.

[0138] [Compound (B)] B-1: 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)] (Irgacure OXE01, manufactured by BASF) B-2: 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Irgacure 907, manufactured by BASF) B-3: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide B-4: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone B-5: TR-PBG-345 (O-acyl oxime compound, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) B-6: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxime) (Irgacure OXE-02, manufactured by BASF) B-7: Ethanone, 1-[9-ethyl-6-(1,3-dioxolane,4-(2-methoxyphenoxy))-9H-carbazol-3-yl]-, 1-(O-acetoxime) (Adeka Arcluz N-1919, manufactured by ADEKA) B-8: Methanon, (9-ethyl-6-nitro-9H-carbazol-3-yl)[4-(2-methoxy-1-methylethoxy)-2-methylphenyl]-, O-acetoxime (ADEKA ARKLES NCI-831, manufactured by ADEKA Corporation) B-9: 1-Propanone, 3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxime) (TR-PBG-304, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.) B-10: TR-PBG-3057 (O-acyl oxime compound, manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.)

[0139] <Compound (CB)> C-1: 2-Hydroxy-3-phenoxypropyl acrylate C-2: Polyethylene glycol diacrylate C-3: Dipentaerythritol hexaacrylate C-4: Pentaerythritol tetraacrylate C-5: Diethylene glycol modified dipentaerythritol hexaacrylate C-6: Trimethylolpropane polypropylene glycol triacrylate

[0140] <Compound (CA)> D-1: Norbornene dicarboxylic anhydride modified fluorene-containing acrylate (compound represented by the following formula (D-1)) D-2: Phthalic anhydride modified fluorene-containing acrylate (compound represented by the following formula (D-2)) D-3: Tosyl isocyanate modified fluorene-containing acrylate (compound represented by the following formula (D-3)) D-4: Fluorene-containing acrylate (compound represented by the following formula (D-4)) D-5: Acid anhydride modified fluorene-containing acrylic resin (polymer containing a structural unit represented by the following formula (D-5), Mw: 4000)

[0141]

Chemical formula

[0142] <Solvent (E)> E-1: Propylene glycol monomethyl ether acetate (PGMEA) E-2: Cyclopentanone (CPN)

[0143] (Example 1) 20 parts by mass of compound (A-1), 5 parts by mass of compound (B-1), 5 parts by mass of compound (C-1), 10 parts by mass of (C-3), 100 parts by mass of compound (D-1), 0.5 parts by mass of adhesive aid (3-glycidyloxypropyltrimethoxysilane), and 0.2 parts by mass of surfactant (FTX-218, manufactured by Neos Co., Ltd.) were mixed, and solvent (E-1) was added to achieve a solid content concentration of 35% by mass. The mixture was then stirred to dissolve each component. Next, the resulting mixture was filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[0144] (Examples 2-27 and Comparative Examples 1-3) A radiation-sensitive composition was prepared in the same manner as in Example 1, except that the types and amounts of each component (compound (A), compound (B), compound (CB), compound (CA), and solvent (E)) were changed as shown in Table 2.

[0145] 3. Evaluation of radiation-sensitive compositions The properties of the radiation-sensitive compositions prepared in Examples 1-27 and Comparative Examples 1-3 were evaluated as follows. The evaluation results are shown in Table 2.

[0146] [Evaluation of refractive index] Each radiation-sensitive composition was applied to an alkali-free glass substrate using a spin coater, and then pre-baked on a hot plate at 85°C for 2 minutes to form a coating with a thickness of 9 μm. Next, the resulting coating was subjected to a high-pressure mercury lamp at a concentration of 200 mJ / cm². 2Irradiation was performed with the specified exposure dose. After irradiation, development was carried out for 80 seconds at 25°C using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23°C as the developer, followed by a 60-second wash with pure water. After that, drying was performed to form a film on the glass substrate made of the radiation-sensitive composition. Next, a cured film was formed by post-baking in an oven at 85°C for 40 minutes. The refractive index of the obtained cured film at 550 nm was measured using a prism coupler (manufactured by Metricon) and evaluated according to the following evaluation criteria. Excellent (◎): Refractive index ≥ 1.63 Fairly good (○): 1.63 > Refractive index ≥ 1.61 Acceptable (△): 1.61 > Refractive index ≥ 1.59 Defective (×): 1.59 > Refractive Index

[0147] [Evaluation of lens shape] Each radiation-sensitive composition was applied to an alkali-free glass substrate using a spin coater, and then pre-baked on an 85°C hot plate for 2 minutes to form a coating with a thickness of 9.0 μm. Next, the resulting coating was exposed to a high-pressure mercury lamp at a dose of 200 mJ / cm² through a photomask having multiple circular retention patterns with a diameter of 25 μm. 2Irradiation was performed. Subsequently, development was carried out for 80 seconds at 25°C using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23°C as the developer, followed by a further 60-second wash with pure water. After drying, a pattern consisting of numerous micro-hardened particles formed by the radiation-sensitive composition was formed on the glass substrate (see Figure 1(a)). Furthermore, post-bake was performed in an oven at 85°C for 60 minutes, and a lens pattern in which numerous microlenses were regularly arranged was formed on the substrate by the thermal flow of each micro-hardened particle. The substrates before and after post-bake were observed using a scanning electron microscope (SEM). As shown in Figure 1(b), if a hemispherical lens could be formed by thermal flow due to post-bake, it was evaluated as "good (◎)". If a lens close to hemispherical could be formed, it was evaluated as "fairly good (○)". If there was some thermal flow but the lens shape was trapezoidal when viewed from the side, it was evaluated as "acceptable (△)". If the thermal flow was insufficient and the shape did not change (i.e., it remained rectangular when viewed from the side, as shown in Figure 1(a)), it was evaluated as "poor (×)".

[0148] [Evaluation of resistance to high temperature and high humidity] The substrates having the lens patterns obtained in the [Lens Shape Evaluation] above were stored in a constant temperature and humidity chamber at 85°C and 85% humidity for 120 hours. The transmittance of the lenses was measured before and after storage. If there was no change in transmittance before and after storage, it was evaluated as "Good (◎)", if the change in transmittance was greater than 0% and less than or equal to 5%, it was evaluated as "Fair (○)", if it was greater than 5% and less than 10%, it was evaluated as "Acceptable (△)", and if it was 10% or more, it was evaluated as "Poor (×)". The transmittance of the lenses was measured using a micro-ultraviolet-visible-near-infrared spectrophotometer (manufactured by JASCO Corporation).

[0149] [Evaluation of chemical resistance] The substrate having the lens pattern obtained in the above [Evaluation of lens shape] was immersed in PGMEA for 30 seconds. Then, the substrate was taken out, washed with ultrapure water, and air-dried. If there was no change in the lens film thickness before and after immersion in PGMEA, it was evaluated as "Good (◎)". If the change in the film thickness exceeded 0% and was 5% or less, it was evaluated as "Somewhat good (○)". If it exceeded 5% and was less than 10%, it was evaluated as "Passable (△)". If it was 10% or more, it was evaluated as "Poor (×)". The film thickness of the lens pattern was measured with a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation).

[0150]

Table 2

[0151] As shown in Table 2, the radiation-sensitive compositions of Examples 1 to 27 had evaluations of "◎", "○", or "△" for refractive index, lens shape, high temperature and high humidity resistance, and chemical resistance, and the balance of various properties was good. In contrast, the radiation-sensitive compositions of Comparative Examples 1 to 3 that did not contain Compound (A) had evaluations of "×" for high temperature and high humidity resistance and chemical resistance, and were inferior to those of Examples 1 to 27.

[0152] From the above results, it became clear that a radiation-sensitive composition containing a fluorene compound (A) having a specific heterocyclic structure, a photopolymerization initiator, and a compound (C) having a polymerizable carbon-carbon unsaturated bond can be patterned, and has excellent chemical resistance and high temperature and high humidity resistance, and moreover, a cured product with a high refractive index can be obtained.

Claims

1. A fluorene compound (A) having a specific heterocyclic structure selected from the group consisting of an azole ring structure and a fused ring structure of an azole ring and an aromatic ring, Photopolymerization initiator and A compound (C) having a polymerizable carbon-carbon unsaturated bond, A radiation-sensitive composition containing the following:

2. The radiation-sensitive composition according to claim 1, wherein the fluorene compound (A) is represented by the following formula (1). 【Chemistry 1】 (In formula (1), Ar １ is a group obtained by removing (m1 + n1 + 1) hydrogen atoms from an aromatic ring. Ar ２ is a group obtained by removing (m2 + n2 + 1) hydrogen atoms from an aromatic ring. R １ and R ２ are each independently a monovalent substituent, or R １ and R ２ are combined with each other to form a single bond, -O-, -S-, -NR ８ -, a methylene group or an ethylene group that connects the aromatic ring to which R １ is bonded and the aromatic ring to which R ２ is bonded. R ８ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ３ and R ４ are each independently a monovalent substituent. X １ and X ２ are each independently a monovalent group having the specific heterocyclic structure. m1 and m2 are each independently an integer of 0 to 6. k1 and k2 are each independently an integer of 0 to 4. n1 is an integer of 1 to 6. n2 is an integer of 0 to 6. When there are a plurality of R １ to R ４ , X １ , X ２ , the plurality of R １ to R ４ , X １ , X ２ are the same or different. )

3. In the above equation (1) X １ and X ２ The radiation-sensitive composition according to claim 2, wherein is represented by the following formula (2). *-W １ -V １ …(2) (In formula (2), W １ V is a divalent organic group. １ This group is either a group obtained by removing one hydrogen atom from the ring portion of a substituted or unsubstituted azole ring, or a group obtained by removing one hydrogen atom from the ring portion of a fused ring of an azole ring and an aromatic ring, or a substituted fused ring. (* indicates a bond.)

4. The radiation-sensitive composition according to claim 1, wherein the specified heterocyclic structure is a monocyclic or fused ring structure having a triazole ring, a tetrazole ring, or an imidazole ring.

5. The radiation-sensitive composition according to claim 1, wherein the compound (C) comprises a fluorene compound (CA) that does not have the specific heterocyclic structure.

6. The radiation-sensitive composition according to claim 5, wherein the content of the fluorene compound (A) is 5 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the fluorene compound (CA).

7. The radiation-sensitive composition according to claim 1, wherein the compound (C) comprises a compound (CB) having a molecular weight of less than 600 and not having a fluorene structure.

8. The radiation-sensitive composition according to claim 7, wherein the compound (CB) comprises a compound (C1) having one or two polymerizable carbon-carbon unsaturated bonds in one molecule, and a compound (C2) having three or more polymerizable carbon-carbon unsaturated bonds in one molecule.

9. A cured product obtained by curing a radiation-sensitive composition according to any one of claims 1 to 8, wherein the refractive index of light at a wavelength of 550 nm is 1.59 or more.

10. A lens formed from a radiation-sensitive composition according to any one of claims 1 to 8.

11. A planarized film formed by the radiation-sensitive composition according to any one of claims 1 to 8.

12. A step of applying a radiation-sensitive composition according to any one of claims 1 to 8 onto a substrate to form a coating film, A step of irradiating a part of the coating film with radiation, A step of developing a coating film irradiated with radiation to form a pattern on the substrate, A step of heating the aforementioned pattern, A method for producing a cured product, including the following:

13. The method for producing a cured product according to claim 12, wherein the temperature at which the pattern is heated is 100°C or lower.

14. A compound represented by the following formula (1). 【Chemistry 2】 (In formula (1), Ar １ Ar is a group obtained by removing (m1 + n1 + 1) hydrogen atoms from an aromatic ring. ２ R is a group obtained by removing (m² + n² + 1) hydrogen atoms from an aromatic ring. １ and R ２ These are either monovalent substituents independently of each other, or R １ and R ２ and are combined with each other R １ The aromatic ring to which R is bonded ２ The single bond connecting the aromatic ring to which it is attached, -O-, -S-, -NR ８ - represents a methylene group or an ethylene group. ８ R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ３ and R ４ These are monovalent substituents, independently of each other. １ and X ２ R is a monovalent base that is independent of each other and is represented by the following formula (2). m1 and m2 are independent integers from 0 to 6. k1 and k2 are independent integers from 0 to 4. n1 is an integer from 1 to 6. n2 is an integer from 0 to 6. １ ~R ４ , X １ , X ２ If multiple R １ ~R ４ , X １ , X ２ They are either the same or different. *-W １ -V １ …(2) (In formula (2), W １ V is a divalent organic group. １ This group is either a group obtained by removing one hydrogen atom from the ring portion of a substituted or unsubstituted azole ring, or a group obtained by removing one hydrogen atom from the ring portion of a fused ring of an azole ring and an aromatic ring, or a substituted fused ring. (* indicates a bond.)

Images