Radiation-sensitive composition, cured product, display device, imaging device, and method for producing cured product

Abstract

To provide a radiation-sensitive composition capable of forming a high-refractive-index cured product in a desired shape through fluidization by low-temperature heating.SOLUTION: A radiation-sensitive composition includes component (A): a compound represented by the formula (1) (excluding those having a (meth)acryloyloxy group), component (B): a photopolymerization initiator, component (C): a polymerizable compound (excluding component (D)), and component (D): a compound having a fluorene structure, an acidic group, and a (meth)acryloyloxy group within the molecule. (In the formula (1), each symbol is as defined in the specifications).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a radiation-sensitive composition, a cured product, a display device, an imaging device, and a method for producing the cured product. [Background technology]

[0002] 2. Description of the Related Art Various image sensors, such as a charge-coupled device (CCD) image sensor and a complementary metal-oxide-semiconductor (CMOS) image sensor, are used as solid-state imaging elements in imaging devices such as cameras.

[0003] In solid-state imaging devices, tiny light-collecting lenses (hereinafter also referred to as "microlenses") are usually arranged regularly to collect light on a light-receiving element (photodiode) and improve the sensor sensitivity. In addition, various display elements such as organic electroluminescence (organic EL) elements and liquid crystal display elements also adopt a display element structure in which a microlens is provided on the light-emitting side of each pixel for the purpose of improving light extraction efficiency and adjusting the viewing angle. Furthermore, in self-luminous displays such as organic EL display devices, attempts are being made to improve brightness and adjust the viewing angle by forming microlenses using high refractive index materials.

[0004] A thermal flow method is known as one method for forming a microlens (see, for example, Patent Document 1). The thermal flow method is a method in which a radiation-sensitive composition is used to form a pattern corresponding to a microlens on a light-receiving element or a light-emitting element, and then the formed pattern is subjected to a heat treatment to cause the pattern to flow, thereby forming a hemispherical microlens array.

[0005] Conventionally, in the field of organic EL elements and liquid crystal display elements, a radiation-sensitive composition has been applied onto a substrate, and a pattern has been formed by exposure and development processes, followed by a heat treatment to form a planarizing film. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2020-101659 A Summary of the Invention [Problem to be solved by the invention]

[0007] As a method for forming a high refractive index microlens or planarizing film as the microlens or planarizing film, a method using a high refractive index filler such as a metal oxide is known. However, the method using a metal oxide may have disadvantages such as complicated cleaning of the production line and easy contamination of the equipment. In addition, in the case of a material containing a large amount of high refractive index filler, the pattern after exposure and development is unlikely to flow due to heat, and it is often difficult to form a microlens or planarizing film by heat treatment (thermal flow).

[0008] A method of forming microlenses, planarization films, etc. by heat treatment (thermal flow) without using high refractive index fillers such as metal oxides is also known, but this conventional method often requires a high-temperature process of 150°C or more during the heat treatment, and there is concern that the conventional method is not suitable for processes that require low-temperature processing. In particular, when a microlens is provided on the light output side of each pixel for the purpose of improving the light extraction efficiency or adjusting the viewing angle in an organic EL element, or when a planarization film is provided in an organic EL element, etc., it is sometimes required that the microlens or planarization film can be formed at a low temperature (for example, 100°C or lower) in the manufacturing process of the organic EL element, considering that the organic light-emitting material is easily deteriorated by heat.

[0009] It was also found that when a conventional radiation-sensitive composition is used to form a microlens by a thermal flow method, the portion of the microlens that contacts the substrate (adherend) (hereinafter also referred to as the "hem") is wetted and spread by thermal flow, resulting in a microlens shape that is significantly different from the desired shape. Also, when a planarization film is formed by heat treatment, if the portion of the planarization film that contacts the substrate (adherend) (hem) is wetted and spread by thermal flow, the planarization film that is formed is thought to have a shape that is significantly different from the desired film shape, such as an excessively small taper angle or a filled contact hole.

[0010] The present invention has been made in consideration of the above-mentioned problems, and one object of the present invention is to provide a radiation-sensitive composition that can be fluidized by heating at a low temperature to form a cured product having a high refractive index in a desired shape. [Means for solving the problem]

[0011] The present inventors have found that the above-mentioned problems can be solved by the following configuration examples. That is, according to the present invention, the following radiation-sensitive composition, cured product, display device, imaging device, and method for producing the cured product are provided. A configuration example of the present disclosure is shown below.

[0012] [1] Component (A): A compound represented by the following formula (1) (however, having no (meth)acryloyloxy group), (B) component: a photopolymerization initiator, Component (C): a polymerizable compound (excluding component (D)), Component (D): a compound having a fluorene structure, an acidic group, and a (meth)acryloyloxy group in the molecule. A radiation-sensitive composition comprising:

[0013] [ka] (In formula (1), Ar 1 and Ar 2 are each independently an aromatic ring group. R 1 and R 2 are each independently a monovalent substituent, or R 1 and R 2 and are bonded to each other to form Ar 1 and Ar 2 The fused ring structure is a fused ring structure in which two aromatic rings are bonded together with a single bond, -O-, -S-, -NR 5 -, a carbonyl group, a methylene group, or an ethylene group. 5 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. m1 and m2 each independently represent an integer of 0 to 7. k1 and k2 each independently represent an integer of 0 to 4. When k1 is an integer of 2 or more, multiple R 3 are each independently a monovalent substituent, or are bonded together to form R 3 forms a condensed ring together with the benzene ring to which k2 is bonded. When k2 is an integer of 2 or more, multiple R 4 are each independently a monovalent substituent, or are bonded together to form R 4 forms a condensed ring together with the benzene ring to which it is attached. In formula (1), R 1 ~R 4 If there are multiple R 1 ~R 4 are the same or different.)

[0014] [2] The radiation-sensitive composition according to [1] above, wherein the component (D) is a compound represented by the following formula (2):

[0015] [ka] (In formula (2), Ar 1 and Ar 2 are each independently an aromatic ring group. R 1 and R 2are each independently a monovalent substituent, or R 1 and R 2 and are bonded to each other to form Ar 1 and Ar 2 The fused ring structure is a fused ring structure in which two aromatic rings are bonded together with a single bond, -O-, -S-, -NR 5 -, a carbonyl group, a methylene group, or an ethylene group. 5 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 group represented by the following formula (2X): n1 and n2 each independently represent an integer of 1 to 7. m1 and m2 each independently represent an integer of 0 to 6. k1 and k2 each independently represent an integer of 0 to 4. When k1 is an integer of 2 or more, multiple R 3 are each independently a monovalent substituent, or are bonded together to form R 3 forms a condensed ring together with the benzene ring to which k2 is bonded. When k2 is an integer of 2 or more, multiple R 4 are each independently a monovalent substituent, or are bonded together to form R 4 forms a condensed ring together with the benzene ring to which it is attached. However, R 1 ~R 4 , X 1 and X 2 At least one of these has an acidic group, and the compound represented by formula (2) has at least one acidic group. In formula (2), R 1 ~R 4 , X 1 and X 2 If there are multiple R 1 ~R 4 , X 1 and X 2 are the same or different.)

[0016] [ka] (In formula (2X), R 8 is an alkanediyl group having 2 to 4 carbon atoms. R 6 is a hydrogen atom or a methyl group. X is 0 or 1. R 9 is a hydrogen atom or -OY 1 It is. Y 1 is a hydrogen atom or "-C(=O)-R 7 R is a group represented by "-COOH". 7 is a divalent organic group having one or more carbon atoms. p is an integer of 0 to 4. When p is 2 or more, multiple R 8 are the same or different. "*" represents a bond.)

[0017] [3] The radiation-sensitive composition according to [1] or [2] above, which is for use in producing a microlens by a thermal flow method.

[0018] [4] A cured product obtained by curing the radiation-sensitive composition according to any one of [1] to [3] above. [5] The cured product according to [4] above, having a refractive index of 1.640 or more at a wavelength of 550 nm.

[0019] [6] The cured product according to [4] or [5] above, which is for use as an optical component. [7] A display device comprising the cured product according to any one of [4] to [6] above. [8] An imaging device comprising the cured product according to any one of [4] to [6].

[0020] [9] A step of applying the radiation-sensitive composition according to any one of the above [1] to [3] onto a substrate; a step of exposing the radiation-sensitive composition applied onto the substrate to radiation; developing the radiation-sensitive composition after irradiation; heating the developed radiation-sensitive composition; A method for producing a cured product comprising the steps of:

[0021]

[10] The method for producing a cured product according to [9] above, wherein the heating temperature in the step of heating the radiation-sensitive composition after development is 100° C. or lower.

[0022]

[11] The method for producing a cured product according to [9] or

[10] above, further comprising the step of heating the developed radiation-sensitive composition to melt the pattern and form a microlens. Effect of the Invention

[0023] According to the radiation-sensitive composition of the present disclosure, it is possible to easily form a cured product (e.g., a microlens and a planarizing film) having a desired shape and a high refractive index, particularly a microlens, by fluidizing the composition by heating at a low temperature. Such a radiation-sensitive composition of the present disclosure is suitable for manufacturing a microlens or forming a planarizing film. [Brief description of the drawings]

[0024] [Figure 1] 13 are enlarged photographs of the microlens pattern viewed from the front. (a) shows the state before post-baking, and (b) shows the state after post-baking. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] Matters related to the embodiments will be described in detail below. In this specification, a numerical range described using "to" means that the numerical range includes the numerical ranges before and after "to" as the lower and upper limits.

[0026] In this specification, the term "hydrocarbon group" includes linear hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The term "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and / or a branched hydrocarbon group that does not contain a cyclic structure in the main chain and is composed only of a chain structure, and may be saturated or unsaturated. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. However, it is not necessary for the group to be composed only of an alicyclic hydrocarbon structure, and it also includes a group that has a chain structure as a part of it. In addition, the alicyclic hydrocarbon structure may be a single ring or a condensed ring. The term "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary for the ring structure to be composed of only an aromatic ring structure, and it may contain a chain structure or an alicyclic hydrocarbon structure as a part of the ring structure. The aromatic ring structure may be a single ring or a condensed ring. The ring structures of the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have a hydrocarbon group as a substituent.

[0027] In this specification, "(meth)acrylic" includes "acrylic" and "methacrylic". "(meth)acryloyl group" includes "acryloyl group" and "methacryloyl group". "Alkali-soluble" means that it is soluble or swellable in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 25°C.

[0028] ≪Radiation-sensitive composition≫ The radiation-sensitive composition of the present disclosure (hereinafter also referred to as "the composition") contains the following components (A), (B), (C), and (D). Unless otherwise specified, each component may be used alone or in combination of two or more. Component (A): A compound represented by the following formula (1) (however, the compound does not have a (meth)acryloyloxy group). Component (B): Photopolymerization initiator Component (C): A polymerizable compound (excluding component (D)). Component (D): a compound having a fluorene structure, an acidic group, and a (meth)acryloyloxy group in the molecule

[0029] [ka] (In formula (1), Ar 1 and Ar2 are each independently an aromatic ring group. R 1 and R 2 are each independently a monovalent substituent, or R 1 and R 2 and are bonded to each other to form Ar 1 and Ar 2 The fused ring structure is a fused ring structure in which two aromatic rings are bonded together with a single bond, -O-, -S-, -NR 5 -, a carbonyl group, a methylene group, or an ethylene group. 5 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. m1 and m2 each independently represent an integer of 0 to 7. k1 and k2 each independently represent an integer of 0 to 4. When k1 is an integer of 2 or more, multiple R 3 are each independently a monovalent substituent, or are bonded together to form R 3 forms a condensed ring together with the benzene ring to which k2 is bonded. When k2 is an integer of 2 or more, multiple R 4 are each independently a monovalent substituent, or are bonded together to form R 4 forms a condensed ring together with the benzene ring to which it is attached. In formula (1), R 1 ~R 4 If there are multiple R 1 ~R 4 are the same or different.)

[0030] [Component (A): Compound represented by formula (1)] The component (A) is a compound represented by formula (1), which is a compound having a fluorene structure without a (meth)acryloyloxy group. By using such a component (A), spreading of the base is suppressed even when fluidized by heating at a low temperature, and a cured product with a high refractive index can be easily formed in the desired shape.

[0031] In the formula (1), Ar 1 The aromatic ring group represented by the formula (1) is a group in which (m1+1) hydrogen atoms have been removed from an aromatic ring. 2 The aromatic ring group represented by the formula (I) is a group in which (m2+1) hydrogen atoms have been removed from an aromatic ring. 1 and Ar 2 The aromatic ring contained in may be a single ring or a condensed ring. Ar 1 and Ar 2 The aromatic ring contained in the aryl group is preferably an aromatic hydrocarbon ring, and examples of the aromatic ring include a benzene ring, a naphthalene ring, an indene ring, an anthracene ring, and a phenanthrene ring. 1 and Ar 2 The aromatic ring contained in is preferably a benzene ring or a naphthalene ring. R 1 and R 2 When is a monovalent substituent, it is preferable to use Ar 1 and Ar 2 Preferably, the alkyl group has a condensed polycyclic aromatic hydrocarbon ring, and more preferably has a naphthalene ring.

[0032] R 1 and R 2 are each independently a monovalent substituent, examples of the monovalent substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, an acidic group (a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a thiol group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfonamide group, etc.), an acyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a carbon an aryl group having 6 to 16 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyalkoxy 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, an amino group (-NR A RB [Applicable R A and R B are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.]), -NH-C(=O)-R [wherein R is the R 3 , R 4 and an alicyclic hydrocarbon group having 5 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have a substituent similar to that of the above.], -NH-SO2-R [wherein R is the same as R in the above-mentioned -NH-C(=O)-R.], -NH-C(=O)-NH-SO2-R [wherein R is the same as R in the above-mentioned -NH-C(=O)-R.], -OC(=O)-NH-SO2-R [wherein R is the same as R in the above-mentioned -NH-C(=O)-R.], and the like. Among these, R 1 and R 2 The monovalent substituent represented by the formula (I) is preferably a hydroxyl group, a carboxy group, 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 hydroxyalkoxy group having 1 to 10 carbon atoms, an amino group, -NH-C(=O)-R, or -NH-SO2-R, and more preferably a hydroxyl group, a carboxy group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyalkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an amino group, -NH-C(=O)-R, or -NH-SO2-R.

[0033] R 1 and R 2 are bonded together to form Ar 1 and Ar 2 When the fused ring structure is formed with Ar 1 Aromatic rings and Ar in 2 The aromatic ring in the middle is a single bond, -O-, -S-, -NR 5 -, a carbonyl group, a methylene group, or an ethylene group. 1 and R 2 Examples of the fused ring structure formed by bonding together include a fluorene ring, an anthrone ring, a xanthene ring, a thioxanthene ring, etc. Of these, a xanthene ring is preferred.

[0034] m1 and m2 are each independently an integer of 0 to 7; Ar 1 and Ar 2 It is preferable that either m1 or m2 is 1 or more, and more preferable that both are 1 or more. The upper limit of m1 and m2 is preferably 3, and more preferably 2. When either m1 or m2 is 1 or more, R 1 and R 2 It is preferable that at least one of the above groups contains an OR' group. The R' is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, or -(R"-O)nH [wherein the R" is an alkylene group having 1 to 4 carbon atoms, and n is an integer of 1 to 10.], and a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms is more preferable. The OR' group is Ar 1 and / or Ar 2 For example, it may be contained in R in the -NH-C(=O)-R.

[0035] R 3 and R 4 Examples of the monovalent substituent represented by the formula (I) include a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a hydroxyl group, an acidic group (such as a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, a thiol group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, or a sulfonamide group), an acyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms. a cycloalkoxy group having 3 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyalkoxy 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, an amino group (-NR A R B [Applicable RA and R B are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.]), -NH-C(=O)-R [wherein R is R 1 and R 2 The meaning of R in -NH-C(=O)-R is the same as that of R 1 and R 2 The meaning of R in -NH-C(=O)-R is the same as that of R 1 and R 2 R has the same meaning as R in -NH-C(=O)-R. ], -OC(=O)-NH-SO2-R [R is R 1 and R 2 R has the same meaning as R in -NH-C(=O)-R. 3 and R 4 The monovalent substituent represented by the formula (I) is preferably a hydroxyl group, a carboxy group, 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, or an aralkyl group having 6 to 12 carbon atoms, and more preferably a hydroxyl group, a carboxy group, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0036] When k1 is an integer equal to or greater than 2, multiple R 3 are each independently a monovalent substituent, or are bonded together to form R 3 forms a condensed ring together with the benzene ring to which k2 is bonded. When k2 is an integer of 2 or more, multiple R 4 are each independently a monovalent substituent, or are bonded together to form R 4 forms a condensed ring together with the benzene ring to which it is bonded. Examples of the condensed ring include a naphthalene ring, an indene ring, an anthracene ring, and a phenanthrene ring, and among these, a naphthalene ring is preferable. Note that k1 is an integer of 2, and two R 3 are combined together to form R 3 forms a naphthalene ring together with the benzene ring to which it is bonded, and when k2 is 0, the component (A) can be said to be a compound having a benzofluorene skeleton.

[0037] k1 and k2 each represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0038] Preferred specific examples of the compound (A) include the compounds represented by the following formulas (A-1) to (A-12).

[0039] [ka]

[0040] [ka]

[0041] The molecular weight of the component (A) is preferably 1000 or less, more preferably 800 or less, and although there is no particular lower limit, it is preferably 200 or more, more preferably 350 or more. When the molecular weight of component (A) is within the above range, spreading of the base is suppressed even when fluidized by heating at low temperatures, making it easy to form a cured product with a high refractive index in the desired shape.

[0042] The content of the (A) component in the present composition, relative to 100 parts by mass of the (D) component described below, is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 20 parts by mass or more, and is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, and even more preferably 30 parts by mass or less. When the content of component (A) is within the above range, a cured product with a high refractive index can be easily obtained, and the cured product can be fluidized at a relatively low temperature (for example, 100°C or less). Even when fluidized by heating at a low temperature, spreading of the base is suppressed, and a cured product with the desired shape can be easily obtained.

[0043] [Component (B): Photopolymerization initiator] Although there is no particular limitation on the component (B), a photoradical polymerization initiator that generates radicals in response to radiation and can initiate polymerization is preferable. Examples of the component (B) include an O-acyloxime compound, an acetophenone compound, a biimidazole compound, and an acylphosphine oxide compound.

[0044] Examples of O-acyloxime compounds include 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 1-(9-ethyl-6-benzoyl-9H-carbazol-3-yl)-octan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, and ethanone. -1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime).

[0045] Examples of the acetophenone compound include an α-aminoketone compound and an α-hydroxyketone compound. Specific examples of α-aminoketone compounds include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one. Specific examples of α-hydroxyketone compounds include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and 1-hydroxycyclohexylphenyl ketone.

[0046] Examples of the biimidazole compound 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.

[0047] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0048] The content of the (B) component in the present composition is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and preferably 10 parts by mass or less, more preferably 7.5 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of the combined total of the (C) and (D) components described below. When the content of the component (B) is within the above range, a radiation-sensitive composition exhibiting good curability and transparency can be easily obtained.

[0049] [Component (C): Polymerizable compound] The polymerizable compound, which is the component (C), is preferably a compound having a polymerizable carbon-carbon unsaturated bond. The compound having a polymerizable carbon-carbon unsaturated bond is a component that can be copolymerized with the component (D) described below, and is a compound that can generate a polymer together with the component (D) upon irradiation with radiation. However, the component (C) is a compound different from the component (D).

[0050] When only the following component (D) is used as the polymerizable compound, a cured product with a high refractive index can be easily formed, but when a pattern is to be formed into a desired shape (particularly a microlens shape) by heat treatment, a high-temperature process of, for example, 120°C or higher is often required. In addition, when only the compound (D) is used as the polymerizable compound, a high exposure dose is often required to sufficiently cure the composition. In contrast, by using the component (D) and the component (C) in combination, for example, melting and fluidization of the pattern can be realized by a low-temperature process at 100°C or less, and a cured product with a desired shape (particularly a microlens shape) can be easily obtained. In addition, by using the component (C), the curing speed is improved and curing is possible with a relatively low exposure dose.

[0051] From the viewpoint of being able to keep the temperature of the heat treatment for forming a cured product of the desired shape as low as possible, the molecular weight of component (C) is preferably 1200 or less, more preferably 800 or less, and even more preferably 600 or less. In addition, from the viewpoint of being able to easily form a cured product that has a high refractive index, excellent solvent resistance, and excellent reliability such as low volatility, the molecular weight of component (C) is preferably 100 or more. The molecular weight of component (C) can be measured by mass spectrometry.

[0052] Examples of the component (C) include a (meth)acryloyl group-containing compound, a chain vinyl compound, an aromatic vinyl compound, and a maleimide compound. These compounds are preferred in that they have good copolymerizability with the component (D) and relatively high plasticity.

[0053] The component (C) may be either a monofunctional compound having one polymerizable group or a polyfunctional compound having two or more polymerizable groups. In addition, the component (C) may be a combination of a monofunctional compound and a polyfunctional compound.

[0054] Specific examples of the (C) component 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, and maleimide compounds. Among these, (meth)acryloyl group-containing compounds are preferred, and (meth)acryloyl group-containing compounds that are at least one 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 are more preferred.

[0055] Specific examples of the compound include (meth)acrylic acid esters having a chain structure, such as (meth)acrylic acid alkyl esters, (meth)acrylic acid hydroxyalkyl esters, (meth)acrylic acid alkoxyalkyl esters, and (meth)acrylic acid polyoxyalkylene esters.

[0056] Examples of the (meth)acrylic acid alkyl ester 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.

[0057] Examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

[0058] Examples of the alkoxyalkyl (meth)acrylate include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and propoxyethyl (meth)acrylate.

[0059] Examples of (meth)acrylic acid 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.

[0060] 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, tricyclo[5.2.1.0](meth)acrylate, and the like. 2,6 ]decan-8-yl, (meth)acrylic acid tricyclo[5.2.1.0 2,5 ]Decan-8-yloxyethyl, isobornyl (meth)acrylate, and the like.

[0061] Examples of the (meth)acrylic acid ester having an aromatic ring structure include phenyl (meth)acrylate, benzyl (meth)acrylate, 3-phenoxybenzyl (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.

[0062] Examples of the (meth)acrylamide compound include (meth)acryloylmorpholine, N-(2-hydroxyethyl)(meth)acrylamide, N-vinyl-2-pyrrolidone, and N-vinyl-ε-caprolactam.

[0063] Examples of the chain vinyl compound include propene, butene, pentene, and hexene.

[0064] Examples of the aromatic vinyl compound include styrene, methylstyrene, α-methylstyrene, t-butoxystyrene, and vinylnaphthalene.

[0065] Examples of the maleimide compound include N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N-(p-methylphenyl)maleimide.

[0066] Specific examples of when the component (C) is a polyfunctional compound include polyfunctional (meth)acrylic acid esters, polyfunctional aromatic vinyl compounds, and polyfunctional chain vinyl compounds. Examples of the polyfunctional (meth)acrylic acid ester include bifunctional (meth)acrylic acid esters, trifunctional or higher (meth)acrylic acid esters, etc. Specific examples of these include bifunctional (meth)acrylic acid esters such as ethylene glycol di(meth)acrylate, polyethylene 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, bisphenol A ethoxylate di(meth)acrylate, bisphenol F ethoxylate di(meth)acrylate, cresol novolac ethoxylate di(meth)acrylate, and biphenyl ethoxylate di(meth)acrylate.

[0067] Examples of the trifunctional or higher (meth)acrylic acid ester include trimethylolpropane tri(meth)acrylate, trimethylolpropane polypropylene glycol 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, ethylene oxide oligomer modified dipentaerythritol hexa(meth)acrylate (e.g., diethylene glycol modified dipentaerythritol hexa(meth)acrylate). tris(2-(meth)acryloyloxyethyl)phosphate, succinic acid modified pentaerythritol tri(meth)acrylate, succinic acid modified dipentaerythritol penta(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, a carboxy group-containing polybasic acid modified (meth)acrylic oligomer, and a polyfunctional urethane acrylate compound obtained using a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and a compound having one or more hydroxy groups in the molecule and having three, four or five (meth)acryloyloxy groups.

[0068] Examples of the polyfunctional aromatic vinyl compound include 1,3-divinylbenzene and 1,4-divinylbenzene.

[0069] Examples of the polyfunctional chain vinyl compound include 1,5-hexadiene, 1,6-heptadiene, and 1,7-octadiene.

[0070] Preferred specific examples of the component (C) include the compounds represented by the following formulas (C1-1) to (C1-50).

[0071] [ka]

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] [ka]

[0076] In formulas (C1-1) to (C1-50), R 20 is a hydrogen atom or a methyl group. m and n are each independently an integer of 0 to 10. x, y and z are each independently an integer of 0 to 10. In addition, R in formula (C1-48) is R in formula (C1-48). a , R b or R c Of the six R's, a R's are R a Of the six R's, b R's are R b Of the six R's, c R's are R c Here, a+b+c=6, and a is an integer of 1 or greater.

[0077] The content of the (C) component is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, per 100 parts by mass of the (D) component described below, from the viewpoints that a cured product having a desired shape can be easily formed by heat treatment at a low temperature, and a cured product having high heat resistance can be easily obtained, etc. Furthermore, the content of the (C) component is preferably 50 parts by mass or less, more preferably 20 parts by mass or less, per 100 parts by mass of the (D) component, from the viewpoints that a decrease in the refractive index of the obtained cured product can be suppressed, etc.

[0078] The component (C) preferably contains a compound having one or two polymerizable carbon-carbon unsaturated bonds in one molecule (hereinafter also referred to as "compound (C1)"). The content of compound (C1) is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, based on 100% by mass of component (C), because the pattern can be fluidized at low temperatures (for example, a temperature of 100° C. or less), and a cured product having a desired shape can be easily formed. The content of compound (C1) is preferably 50% by mass or less, more preferably 40% by mass or less, based on 100% by mass of component (C), because a cured product having excellent heat resistance and chemical resistance and high reliability can be easily formed.

[0079] In particular, when the component (C) is contained in the above-mentioned amount per 100 parts by mass of the component (D) and the compound (C1) is contained in the above-mentioned amount per 100 parts by mass of the component (C), it is preferable in that a cured product having a desired shape can be easily formed by heat treatment at a low temperature and that a cured product having high heat resistance can be easily formed.

[0080] [Component (D): a compound having a fluorene structure, an acidic group, and a (meth)acryloyloxy group in the molecule] The component (D) is a compound having a fluorene structure, an acidic group, and a (meth)acryloyloxy group in the molecule, and has a high refractive index and good alkali solubility and photopolymerizability (particularly photoradical polymerizability).

[0081] The fluorene structure includes a fluorene structure, a benzofluorene structure, a dibenzofluorene structure, and the like.

[0082] Examples of the acidic group include a carboxy group, a carboxyalkoxy group, a sulfonic acid group, a phenolic hydroxyl group, a thiol group, an imidazole group, a triazole group, a tetrazole group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfonamide group, a maleimide group, a silanol group, and a hydroxyalkyl group in which a hydrogen atom bonded to a carbon atom is substituted with an electron-withdrawing group.

[0083] The compound having a (meth)acryloyloxy group is not particularly limited, but is preferably a compound having a group represented by the following formula (2X).

[0084] The component (D) is preferably a compound represented by the following formula (2) (hereinafter also referred to as “compound (D1)”).

[0085] [ka] (In formula (2), Ar 1 and Ar 2 are each independently an aromatic ring group. R 1 and R 2 are each independently a monovalent substituent, or R 1 and R 2 and are bonded to each other to form Ar 1 and Ar 2 The fused ring structure is a fused ring structure in which two aromatic rings are bonded together with a single bond, -O-, -S-, -NR 5 -, a carbonyl group, a methylene group, or an ethylene group. 5 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 group represented by the following formula (2X): n1 and n2 each independently represent an integer of 1 to 7. m1 and m2 each independently represent an integer of 0 to 6. k1 and k2 each independently represent an integer of 0 to 4. When k1 is an integer of 2 or more, multiple R 3 are each independently a monovalent substituent, or are bonded together to form R 3 forms a condensed ring together with the benzene ring to which k2 is bonded. When k2 is an integer of 2 or more, multiple R 4are each independently a monovalent substituent, or are bonded together to form R 4 forms a condensed ring together with the benzene ring to which it is attached. However, R 1 ~R 4 , X 1 and X 2 At least one of these has an acidic group, and the compound represented by formula (2) has at least one acidic group. In formula (2), R 1 ~R 4 , X 1 and X 2 If there are multiple R 1 ~R 4 , X 1 and X 2 are the same or different.)

[0086] [ka] (In formula (2X), R 8 is an alkanediyl group having 2 to 4 carbon atoms. R 6 is a hydrogen atom or a methyl group. X is 0 or 1. R 9 is a hydrogen atom or -OY 1 It is. Y 1 is a hydrogen atom or "-C(=O)-R 7 R is a group represented by "-COOH". 7 is a divalent organic group having one or more carbon atoms. p is an integer of 0 to 4. When p is 2 or more, multiple R 8 are the same or different. "*" represents a bond.)

[0087] In the formula (2), Ar 1 The aromatic ring group represented by the formula (1) is a group in which (m1+n1+1) hydrogen atoms have been removed from an aromatic ring. 2 The aromatic ring group represented by the formula (1) is a group in which (m2+n2+1) hydrogen atoms have been removed from an aromatic ring. 1 and Ar 2The aromatic ring contained in may be a single ring or a condensed ring. Ar 1 and Ar 2 The aromatic ring contained in the aryl group is preferably an aromatic hydrocarbon ring, and examples of the aromatic ring include a benzene ring, a naphthalene ring, an indene ring, an anthracene ring, and a phenanthrene ring. 1 and Ar 2 The aromatic ring contained in is preferably a benzene ring or a naphthalene ring. Ar is a good choice because it has a high refractive index and is heat resistant. 1 and Ar 2 Preferably, the alkyl group has a condensed polycyclic aromatic hydrocarbon ring, and more preferably has a naphthalene ring.

[0088] R 1 and R 2 are each independently a monovalent substituent, examples of the monovalent substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group, the acidic group, an acyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 16 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyalkoxy 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, an amino group (-NR A R B [Applicable R A and R B are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.]), -NH-C(=O)-R [wherein R is the R 3 , R 4 and the like. Among these, R 1 and R 2The monovalent substituent represented by the following formula is preferably the above-mentioned acidic group, 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, or an alkoxy group having 1 to 10 carbon atoms, and more preferably the above-mentioned acidic group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0089] R 1 and R 2 are bonded together to form Ar 1 and Ar 2 When the fused ring structure is formed with Ar 1 Aromatic rings and Ar in 2 The aromatic ring in the middle is a single bond, -O-, -S-, -NR 5 -, a carbonyl group, a methylene group, or an ethylene group. 1 and R 2 Examples of the fused ring structure formed by bonding together include a fluorene ring, an anthrone ring, a xanthene ring, a thioxanthene ring, etc. Of these, a xanthene ring is preferred.

[0090] m1 and m2 are each independently an integer of 0 to 6; Ar 1 and Ar 2 Each of m1 and m2 is preferably 0 to 3, more preferably 0 or 1, and further preferably 0. n1 and n2 each independently represent an integer of 1 to 7, preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0091] R 3 and R 4Examples of the monovalent substituent represented by the formula (I) include a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a hydroxyl group, the acidic group, an acyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 16 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyalkoxy 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, an amino group (-NR A R B [Applicable R A and R B are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.]), -NH-C(=O)-R [wherein R is R 1 and R 2 R has the same meaning as R in -NH-C(=O)-R. 3 and R 4 The monovalent substituent represented by the following formula is preferably the above-mentioned acidic group, 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, or an aralkyl group having 6 to 12 carbon atoms, and more preferably the above-mentioned acidic group, an alkyl group having 1 to 5 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0092] When k1 is an integer equal to or greater than 2, multiple R 3 are each independently a monovalent substituent, or are bonded together to form R 3 forms a condensed ring together with the benzene ring to which k2 is bonded. When k2 is an integer of 2 or more, multiple R 4 are each independently a monovalent substituent, or are bonded together to form R 4 forms a condensed ring together with the benzene ring to which it is bonded. Examples of the condensed ring include a naphthalene ring, an indene ring, an anthracene ring, and a phenanthrene ring, and among these, a naphthalene ring is preferable. Note that k1 is an integer of 2, and two R3 are combined together to form R 3 forms a naphthalene ring together with the benzene ring to which it is bonded, and when k2 is 0, compound (D1) can be said to be a compound having a benzofluorene skeleton.

[0093] k1 and k2 each represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0094] X 1 and X 2 each independently represents a group represented by the formula (2X).

[0095] In formula (2X), R 8 The alkanediyl group having 2 to 4 carbon atoms represented by the formula (I) may be linear or branched. 8 Of these, a linear or branched alkanediyl group having 2 or 3 carbon atoms is preferred. p is preferably 0 to 2, and more preferably 0 or 1. R 6 is preferably a hydrogen atom.

[0096] "-C(=O)-R 7 -COOH" R 7 The divalent organic group represented by the formula (D1) may have a chain structure, a cyclic structure, or a combination of a chain structure and a cyclic structure. In addition, when compound (D1) is produced by reacting a (meth)acrylic acid adduct of an epoxy group-containing compound having a fluorene skeleton with a carboxylic acid anhydride, R 7 corresponds to a partial structure excluding the acid anhydride group of the carboxylic acid anhydride (more specifically, the group formed by dehydration condensation of two carboxy groups in one molecule).

[0097] R 7Specific examples of the above include a divalent hydrocarbon group, a divalent group containing -O-, -S-, -NR- (where R is a monovalent hydrocarbon group) or the like between the carbon-carbon bonds of the hydrocarbon group, a divalent group in which any hydrogen atom of the hydrocarbon group is replaced with a monovalent heteroatom-containing group (e.g., an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group), and two hydrogen atoms bonded to the same carbon in the hydrocarbon group are represented by "=P(R 9 A group represented by "(three R 9 are each independently a monovalent hydrocarbon group), and a divalent group having a heterocyclic structure. Examples of the divalent hydrocarbon group include an alkanediyl group having 1 to 10 carbon atoms, an alkenediyl group having 2 to 10 carbon atoms, a divalent saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0098] R 7 When is a divalent group having a heterocyclic structure, examples of the divalent group include groups having a nitrogen-containing heterocyclic structure, a sulfur-containing heterocyclic structure, or an oxygen-containing heterocyclic structure. Examples of the nitrogen-containing heterocyclic structure include a pyridine ring structure, a pyrimidine ring structure, a pyridazine ring structure, a pyrazine ring structure, and a triazine structure. Examples of the sulfur-containing heterocyclic structure include a thiophene ring structure and a 2,3-dihydro-1,4-dithiin ring structure. The oxygen-containing heterocyclic structure may, for example, be a furan ring structure.

[0099] From the viewpoint of achieving both a high refractive index of the obtained cured product and the ability to form the cured product into the desired shape by low-temperature heat treatment, R 7 is preferably a group having one or more heteroatoms selected from the group consisting of a sulfur atom, a nitrogen atom, and a phosphorus atom, or a group having a monocyclic aromatic hydrocarbon ring, a condensed polycyclic aromatic hydrocarbon ring, or an aliphatic hydrocarbon ring.

[0100] More specifically, from the viewpoint of being able to easily form a cured product with a high refractive index, R 7 is preferably a group having one or more heteroatoms selected from the group consisting of a sulfur atom, a nitrogen atom, and a phosphorus atom, or a group having a monocyclic aromatic hydrocarbon ring or a condensed polycyclic aromatic hydrocarbon ring. In addition, the generation of outgassing from the cured product can be suppressed. 7 is preferably a group having an aliphatic hydrocarbon ring.

[0101] R 7 Preferred specific examples of the group include groups represented by the following formulas (y-1) to (y-4).

[0102] [ka] (In formula (y-1), Ar 3 R is a (r+2)-valent monocyclic aromatic hydrocarbon ring group, a condensed polycyclic aromatic hydrocarbon ring group, a nitrogen-containing heterocyclic group, a sulfur-containing heterocyclic group, or an aliphatic hydrocarbon ring group. 10 is a monovalent substituent. r is an integer of 0 to 6. When r is 2 or more, multiple R 10 are the same or different. In formula (y-2), Ar 4 and Ar 5 are each independently a nitrogen-containing heterocyclic group or a sulfur-containing heterocyclic group. In formula (y-3), R 9 is a monovalent hydrocarbon group. 9 are the same or different. In formula (y-4), R 11 and R 12 are each independently an alkanediyl group. t is an integer of 1 to 3. When t is 2 or 3, multiple R 11 are the same or different. "*" represents a bond.)

[0103] Ar 3The monocyclic aromatic hydrocarbon ring group in the above formula (I) is a group obtained by removing (r+2) hydrogen atoms from a monocyclic aromatic hydrocarbon ring. The monocyclic aromatic hydrocarbon ring is preferably a benzene ring.

[0104] Ar 3 The fused polycyclic aromatic hydrocarbon ring group in the formula (I) is a group obtained by removing (r+2) hydrogen atoms from a fused polycyclic aromatic hydrocarbon ring. Examples of the fused polycyclic aromatic hydrocarbon ring include a naphthalene ring, an indene ring, an anthracene ring, and a phenanthrene ring, and a naphthalene ring is preferred.

[0105] Ar 3 The nitrogen-containing heterocyclic group in the formula (I) is a group obtained by removing (r+2) hydrogen atoms from a nitrogen-containing heterocycle. Examples of the nitrogen-containing heterocycle include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, and a triazine ring.

[0106] Ar 3 The sulfur-containing heterocyclic group in the formula (I) is a group in which (r+2) hydrogen atoms have been removed from a sulfur-containing heterocycle. Examples of the sulfur-containing heterocycle include a thiophene ring and a 2,3-dihydro-1,4-dithiin ring.

[0107] Ar 3 The aliphatic hydrocarbon ring group in the above formula (I) is a group in which (r+2) hydrogen atoms have been removed from a saturated or unsaturated aliphatic hydrocarbon ring. The aliphatic hydrocarbon ring may be monocyclic or polycyclic, such as a condensed aliphatic ring or a bridged aliphatic ring. Specific examples of the aliphatic hydrocarbon ring include saturated monocyclic aliphatic rings such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring; unsaturated monocyclic aliphatic rings such as a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, and a cycloheptene ring; condensed aliphatic rings such as decahydronaphthalene and octahydronaphthalene; and bridged aliphatic rings such as a bicyclo[2.2.2]oct-5-ene ring and a norbornene ring (bicyclo[2.2.1]hept-5-ene ring).

[0108] From the viewpoint of being able to easily form a cured product with a high refractive index, Ar 3The aliphatic hydrocarbon ring group represented by the formula (I) is preferably a group in which (r+2) hydrogen atoms have been removed from an unsaturated aliphatic hydrocarbon ring, more preferably a group in which (r+2) hydrogen atoms have been removed from an unsaturated bridged aliphatic hydrocarbon ring, and further preferably a group having a bicyclo[2.2.2]oct-5-ene ring or a norbornene ring.

[0109] R 10 The monovalent substituent represented by the formula: R 1 and R 2 When R is a monovalent substituent, specific examples thereof include the same groups as those exemplified above. 10 The monovalent substituent represented by the following formula is preferably a halogen atom, a hydroxyl group, a carboxy group, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, or an arylthio group having 6 to 12 carbon atoms.

[0110] Ar 4 and Ar 5 The nitrogen-containing heterocyclic group and sulfur-containing heterocyclic group in the above formula include groups in which one hydrogen atom has been removed from a substituted or unsubstituted nitrogen-containing heterocyclic ring or sulfur-containing heterocyclic ring. Specific examples of the nitrogen-containing heterocyclic ring and sulfur-containing heterocyclic ring include Ar 3 Examples of the nitrogen-containing heterocycle and sulfur-containing heterocycle are the same as those exemplified as specific examples of the nitrogen-containing heterocycle. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms. 4 and Ar 5 Of these, a substituted or unsubstituted monovalent sulfur-containing aromatic heterocyclic group is preferred.

[0111] R 9 Examples of the monovalent hydrocarbon group in formula (y-3) include a linear or branched alkyl group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms. 9 may be the same or different. In view of the fact that a cured product having a high refractive index can be easily formed, the three R 9At least one of R is preferably a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and 9 It is more preferable that all of R are monovalent aromatic hydrocarbon groups having 6 to 12 carbon atoms. 9 is preferably a substituted or unsubstituted phenyl group.

[0112] R 11 and R 12 The alkanediyl group in R may be linear or branched. 11 and R 12 The alkanediyl group represented by the following formula (I) preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms.

[0113] In addition, n1 X in formula (2) 1 and n2 X's 2 Y can be included in 1 At least one of the following is "-C(=O)-R 7 In view of maintaining alkali solubility during development and excellent flowability upon heating at low temperatures, the compound (D1) is preferably a group represented by "-C(=O)-R 7 It is preferable that the alkyl group has 1 to 6 groups represented by "-COOH", and it is more preferable that the alkyl group has 1 to 2 groups represented by "-COOH".

[0114] R 9 At least one of is -OY 1 And Y 1 "-C(=O)-R 7 Preferred specific examples of the group represented by formula (2X) in the case where it is "--COOH" include groups represented by each of the following formulas (x1-1) to (x1-25).

[0115] [ka] (In the formula, "*" represents a bond.)

[0116] [ka] (In the formula, "*" represents a bond.)

[0117] [ka] (In the formula, "*" represents a bond.)

[0118] [ka] (In the formula, "*" represents a bond.)

[0119] Y is a polymer that has a high refractive index and can be easily formed into a desired shape by low-temperature heat treatment. 1 "-C(=O)-R 7 When the group represented by formula (2X) is —COOH, the group represented by formula (2X) is preferably a group represented by each of formulas (x1-1) to (x1-3), (x1-7) to (x1-13), (x1-16), (x1-17), and (x1-22) to (x1-25).

[0120] As the component (D), a polymer (for example, a dimer or trimer) of the compound represented by the formula (2) may be used.

[0121] Furthermore, the component (D) may be a compound other than the compound represented by formula (2) (hereinafter also referred to as "compound (D2)"). Examples of the compound (D2) include compounds described in Japanese Patent No. 6263631, compounds containing a polymer structure described in Japanese Patent No. 6059754, and polymers described in Japanese Patent No. 6175259.

[0122] Preferred specific examples of the compound (D2) include compounds represented by the following formula (D-4) or (D-5).

[0123] [ka]

[0124] The component (D) preferably has a lower molecular weight than the polymer component blended as a base resin in a conventional radiation-sensitive composition used to form a high refractive index material, for example. By using such a component (D) as a component of a radiation-sensitive composition for forming a high refractive index material, a negative pattern can be formed by contact with an alkaline developer, and the pattern after exposure and development can be fluidized by heating at a lower temperature. In addition, by including the component (D), a cured product with a high refractive index can be easily formed.

[0125] The weight average molecular weight (Mw) of component (D) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably at least 600, more preferably at least 700, and even more preferably at least 800. When Mw is within this range, an organic film that exhibits good alkaline developability can be easily formed, and a cured product that has excellent heat resistance and chemical resistance can be easily formed. Furthermore, the Mw is preferably 30,000 or less, more preferably 15,000 or less, and even more preferably 5,000 or less, from the viewpoints that a cured product of a desired shape can be easily formed by heat treatment at a low temperature and that the viscosity of the composition can be prevented from becoming too high.

[0126] The content of component (D) in the present composition is preferably 50% by mass or more, more preferably 60% by mass or more, relative to 100% by mass of the solid content of the present composition (i.e., all components other than the solvent in the present composition), and is preferably 95% by mass or less, more preferably 90% by mass or less. When the content of component (D) is within the above range, a cured product with a high refractive index can be easily formed, and the cured product can be fluidized at a relatively low temperature (for example, 100°C or lower), making it easy to form a cured product in the desired shape.

[0127] [Other ingredients] In addition to the above-mentioned components (A) to (D), the present composition may further contain other components (hereinafter also referred to as "other components") within the range in which the effects of the present invention are not impaired. Examples of other components include polymers, solvents, polymerization inhibitors, surfactants, antioxidants, sensitizers, softeners, plasticizers, adhesion aids, and ultraviolet absorbers. The blending ratio of these other components is appropriately selected depending on each component within a range that does not impair the effects of the present invention.

[0128] Polymer The composition may further contain a polymer (hereinafter also referred to as "polymer (E)") as an additive component. By blending the polymer (E) in the composition, the heat resistance of the resulting cured product is improved, and a cured product with a high refractive index and excellent reliability can be easily formed.

[0129] Examples of the polymer (E) include an alkali-soluble polymer, a radiation-sensitive polymer containing a fluorene skeleton, and a radiation-sensitive polymer containing a carboxy group. The molecular weight of the polymer (E) is preferably 2,000 or more and 100,000 or less.

[0130] Examples of the alkali-soluble polymer 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, (meth)acrylic acid-modified (meth)acrylic resin, and acid anhydride-modified (meth)acrylic resin.

[0131] Examples of the radiation-sensitive polymer containing a fluorene skeleton include the polymers described in WO 2009 / 119622.

[0132] Specific examples of the carboxy group-containing radiation-sensitive polymer that can be used include commercially available products such as CCR-1235, CCR-1291H, ZAR-1035, ZAR-2000, ZFR-1401H, ZFR-1491H, ZCR-1569H, and ZCR-1798H (all manufactured by Nippon Kayaku Co., Ltd.).

[0133] When the composition contains polymer (E), the amount of polymer (E) is preferably 50 parts by mass or less, more preferably 20 parts by mass or less, per 100 parts by mass of component (D). When the amount of polymer (E) is within the above range, a cured product having a desired shape and excellent heat resistance can be easily formed by low-temperature heat treatment.

[0134] ·solvent The present composition is preferably a liquid composition in which the components (A) to (D) and other components that are blended as necessary are dissolved or dispersed in a solvent (hereinafter also referred to as "solvent (F)"). As the solvent (F), an organic solvent that dissolves each component blended in the present composition and does not react with each component is preferable.

[0135] Specific examples of the solvent (F) include 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 glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, dimethylene 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, the solvent (F) preferably contains at least one selected from the group consisting of ethers, esters, and ketones.

[0136] Surfactants For example, the use of a surfactant can improve the coatability (wetting and spreading properties and reduction of coating unevenness) of the present composition. Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.

[0137] As the fluorine-based surfactant, commercially available products may be used, and examples of the commercially available products include Megafac F-171, F-172, F-173, F-251, F-430, F-554, and F-563 (manufactured by DIC Corporation); Fluorad FC430 and FC431 (manufactured by Sumitomo 3M Limited); 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.); F-top EF301, EF303, and EF352 (manufactured by Shin-Akita Chemical Co., Ltd.).

[0138] As the silicone surfactant, commercially available products may be used, and examples of the commercially available products include 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, and L-7002 (manufactured by Dow Toray Co., Ltd.); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); BYK-300, 306, 310, 330, 335, 341, 344, 370, 340, and 345 (manufactured by BYK Japan Co., Ltd.).

[0139] 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.

[0140] When a surfactant is added to the present composition, the amount of the surfactant added 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 part by mass, per 100 parts by mass of component (D).

[0141] Antioxidants For example, by using an antioxidant, degradation due to cleavage of the polymer molecules of the present composition can be suppressed, and durability and the like can be improved. Examples of the antioxidant include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxa-spiro[5.5]undecane, and thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate].

[0142] When an antioxidant is incorporated into the present composition, the amount of the antioxidant 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 part by mass, per 100 parts by mass of component (D).

[0143] Adhesion aid Use of the present composition containing an adhesion aid can improve the adhesion between the formed cured product and a substrate (adherend), thereby preventing the cured product from peeling off from the substrate during a development process or the like. As the adhesion aid, a functional silane coupling agent having a reactive functional group is preferred. Examples of the reactive functional group contained in the functional silane coupling agent include a carboxy group, a (meth)acryloyl group, an epoxy group, a vinyl group, and an isocyanate group.

[0144] Specific examples of functional silane coupling agents include trimethoxysilylbenzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

[0145] When an adhesion aid is incorporated into the present composition, the amount added is preferably 0.01 to 4 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the component (D).

[0146] [Method of preparing the composition] The present composition can be prepared by mixing the components (A) to (D) and any other components that may be added. After mixing the components, the resulting mixture may be filtered, if necessary, through a filter having a pore size of, for example, 0.5 μm or less.

[0147] The solid content concentration of the composition (i.e., the ratio of the total mass of the components other than the solvent in the composition to the total mass of the composition) is appropriately selected in consideration of viscosity, volatility, etc. The solid content concentration of the composition is preferably 1 to 60 mass%, more preferably 2 to 50 mass%, and even more preferably 5 to 40 mass%. If the solid content concentration is equal to or higher than the lower limit, it is preferable in that a sufficient thickness of the coating film can be ensured when the composition is applied to a substrate (adherend). On the other hand, if the solid content concentration is equal to or lower than the upper limit, it is preferable in that the viscosity of the composition can be appropriately increased and good coatability can be ensured.

[0148] The content of the polymerizable compound in the present composition (i.e., the total amount of the component (C) and the component (D)) is preferably 60 mass % or more, more preferably 70 mass % or more, and even more preferably 75 mass % or more, relative to 100 mass % of the solid content in the present composition, from the viewpoints of improving sensitivity and enabling a cured product of a desired shape to be easily formed by heat treatment.

[0149] The present composition is suitable for use in optical members used in at least a part of imaging devices such as cameras, various display elements such as organic EL elements and liquid crystal display elements, etc. In particular, when the present composition is used to form a cured product through heat treatment, a cured product having a desired microlens shape or planarizing film shape can be easily formed, and therefore the composition can be suitably used as a radiation-sensitive composition for producing microlenses or planarizing films, particularly as a radiation-sensitive composition for producing microlenses by a thermal flow method.

[0150] ≪Cured product≫ The cured product of the present disclosure (hereinafter also referred to as the "present cured product") is a cured product of the present composition, and specifically, is formed by irradiating the present composition with radiation. In this manner, the present cured product formed from the present composition has excellent heat resistance, transparency, and a high refractive index.

[0151] The shape of the cured product is not particularly limited, but in terms of better exerting the effects of the present invention, it is preferably a microlens or a planarizing film, and more preferably a microlens. The present cured product is preferably used as an optical member used in at least a part of an imaging device such as a camera, various display elements such as an organic electroluminescence (EL) element and a liquid crystal display element. That is, the present cured product is preferably used as a material for an optical member. Specifically, it can be preferably used as an optical member such as a microlens of a solid-state imaging element provided in an imaging device such as a camera, or a microlens of various display elements such as an organic electroluminescence (OLED) element, a liquid crystal display element (LCD), and μLED provided in a display device. It can also be preferably used as a planarizing film provided in an organic electroluminescence (EL) element, a liquid crystal display element, etc.

[0152] The refractive index of the cured product at a wavelength of 550 nm is preferably 1.640 or more, and more preferably 1.660 or more. A cured product having a refractive index within the above range can be said to have a high refractive index, and can be suitably used for optical components. Specifically, the refractive index can be measured by the method described in the examples below.

[0153] [Method of manufacturing the cured product] The method for producing the present cured product includes a step of irradiating the present composition with radiation. When irradiating with radiation, a mask having a predetermined pattern may be used as necessary, and development may be performed after irradiation with radiation using the mask, and heat treatment may be performed after irradiation with radiation.

[0154] The present composition is particularly suitable as a negative pattern-forming material in which a pattern (i.e., a cured product formed from the present composition) is formed by exposing a portion of an organic film formed from the present composition to light, and dissolving the unexposed portion of the exposed organic film in an alkaline developer, and then the pattern is fluidized by heat treatment to form a desired shape (e.g., a microlens shape, a planarized film shape).

[0155] Suitable examples of the method for producing a microlens, which is one embodiment of the present cured product, include the following first and second production methods.

[0156] <First manufacturing method> The first production method is a method including the following steps (I) to (IV) and may further include the following step (V).

[0157] (Process (I): Coating process) Step (I) is a step of forming a coating film (organic film) on a substrate by applying the present composition onto the substrate.

[0158] Examples of the substrate include glass substrates, silicon wafers, plastic substrates, and substrates having colored resists, overcoats, anti-reflection films, various metal thin films, sealing films, etc. formed on the surfaces thereof.

[0159] Examples of the plastic substrate include resin substrates (resin films) made of plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethersulfone, polycarbonate, and polyimide. The substrate may be provided in advance with various elements (for example, a light receiving element such as a photodiode, or a light emitting element such as an organic light emitting diode).

[0160] The composition can be applied by any suitable method, such as spraying, roll coating, rotary coating (spin coating), slit die coating, bar coating, inkjet coating, etc. Of these, spin coating, bar coating, and slit die coating are preferred.

[0161] After the composition is applied onto a substrate, the composition may be preheated (prebaked) for the purpose of preventing dripping, etc. The prebaking conditions can be appropriately set depending on the types and usage ratios of each component used in the composition, and can be, for example, at 60 to 130° C. for about 30 seconds to 10 minutes.

[0162] The thickness of the coating film formed after pre-baking is preferably 0.1 to 20 μm, and more preferably 0.2 to 15 μm.

[0163] (Step (II): Exposure step) Step (II) is a step of irradiating a part of the coating film formed in step (I) with radiation. This radiation exposure causes a curing reaction to proceed in the exposed part, and a cured product is obtained in which the exposed part is cured. In step (II), the coating film is usually irradiated with radiation through a mask having a pattern (e.g., a dot pattern) for obtaining a microlens having a desired shape. The mask may be a multi-tone mask such as a halftone mask or a graytone mask.

[0164] Examples of the radiation to be irradiated onto the coating film include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams. Examples of ultraviolet rays include g-rays (wavelength 436 nm), i-rays (wavelength 365 nm), and KrF excimer laser light (wavelength 248 nm). X-rays include, for example, synchrotron radiation. An example of the charged particle beam is an electron beam. Among these, ultraviolet light is preferred, and ultraviolet light having a wavelength of 200 nm or more and 380 nm or less is more preferred.

[0165] Examples of light sources used for irradiation include low pressure mercury lamps, high pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, and excimer lasers. The radiation exposure is 500 to 50,000 J / m 2 (50~5,000mJ / cm 2 ) is preferred.

[0166] (Process (III): Development process) Step (III) is a step of forming a pattern on the substrate by developing the coating film and the cured product obtained in step (II). This development step removes the coating film formed on the substrate in the unexposed areas, and a pattern (e.g., a concave-convex pattern formed by a large number of regularly arranged micro-cured products) in which the cured product (micro-cured product) in the exposed areas remains can be formed on the substrate.

[0167] The developer may be an aqueous solution of an alkali (basic compound). Examples of the alkali 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. The aqueous alkali solution may contain an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant, or may contain a small amount of any of various organic solvents capable of dissolving the present composition.

[0168] The concentration of the developer can be appropriately determined depending on the composition of the composition, but is usually from 0.01 to 10% by mass, preferably from 0.5 to 5% by mass.

[0169] As the developing method, for example, a puddle method, a dipping method, a swing immersion method, a shower method, or other suitable method can be used. The developing time may be appropriately adjusted depending on the composition of the present composition, and is, for example, 20 to 120 seconds.

[0170] After the development step, if necessary, a step of washing the developed patterned substrate with pure water or the like may be carried out. In addition, a step of drying the patterned substrate after development or after the cleaning may be performed. The drying conditions are not particularly limited, but may be, for example, the same conditions as those for the pre-baking.

[0171] (Step (IV): heating step) Step (IV) is a step in which the developed pattern is heated and melted to form the micro-cured material on the substrate into a lens shape by a thermal flow method. By the heat treatment in step (IV), the composition can be further cured while causing thermal flow of the micro-cured product pattern. By the step (IV), it is possible to obtain a microlens (array) in which minute hemispherical cured products are arranged (regularly) on a substrate.

[0172] The heat treatment can be carried out using a heating device such as an oven or a hot plate. The heating temperature in step (IV) may be appropriately selected depending on the substrate and the present composition used, but from the viewpoint of being applicable to high refractive index materials for organic electroluminescence elements, it is preferably 100° C. or less, more preferably 95° C. or less, and even more preferably 85° C. or less. In addition, from the viewpoints of high heat resistance and chemical resistance and ease of forming microlenses of a desired shape, the heating temperature in step (IV) is preferably 60° C. or more, more preferably 80° C. or more.

[0173] According to the present composition, microlenses of a desired shape can be formed even when the heat treatment is performed at a low temperature of 100° C. or less. In this way, by performing the heat treatment at a low temperature of 100° C. or less, organic EL elements and the like that require the application of low-temperature processes can be used as the substrate. The heating time can be appropriately set 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 the step (IV), a step bake method in which heat treatment is performed multiple times can also be used.

[0174] (Step (V): Post-exposure step) Step (V) is a step of further irradiating the cured product (microcured product) after development obtained in step (III) and / or the microlens obtained in step (IV) with radiation. Among these, the step of further irradiating the microlens obtained in step (IV) with radiation is preferred from the viewpoint that a microlens of a desired shape can be easily formed by low-temperature thermal flow.

[0175] By irradiating with radiation in step (V) (hereinafter also referred to as "post-exposure"), the heat resistance, chemical resistance, etc. can be further improved, and highly reliable microlenses can be easily formed. Among these, the type of radiation and the exposure conditions in the post-exposure can be the same as those in step (II). Note that the conditions such as the wavelength and dose of the irradiated light and the light source in the post-exposure may be the same as or different from those in step (II).

[0176] <Second manufacturing method> The second manufacturing method includes a step of forming a pattern by inkjet coating or nanoimprinting the present composition on a substrate. In the second lens manufacturing method, a pattern of a spherical lens shape may be directly formed on the substrate by inkjet coating or nanoimprinting. Alternatively, a pattern (e.g., a dot pattern) may be formed on the substrate by inkjet coating or nanoimprinting, and then the same step (IV) as in the first manufacturing method may be performed to form a desired microlens shape. The second production method may include a step similar to step (V) in the first production method.

[0177] The planarization film, which is one embodiment of the present cured product, can be produced by a method similar to that of the first production method, except that, for example, in step (II) in the first production method, no mask is used or, for example, a pattern other than a dot pattern is used.

[0178] ≪Display device≫ The display device of the present disclosure is not particularly limited as long as it contains the present cured product, and may have any conventionally known configuration other than the inclusion of the present cured product. Examples of the display device include liquid crystal displays (LCDs), organic electroluminescence (EL) displays using organic light emitting diodes (OLEDs), μLED displays, electrochromic displays (ECDs), electroluminescent displays (ELDs), and displays using quantum dot-organic electroluminescence (QD-OLEDs).

[0179] <Imaging device> The imaging device of the present disclosure is not particularly limited as long as it contains the present cured product, and may have any conventionally known configuration other than the inclusion of the present cured product. Examples of the imaging device include video cameras, digital cameras, mobile phones with a camera function, endoscopic cameras, capsule-type endoscopic cameras, microscopes, medical or healthcare cameras (e.g., cameras for taking images of blood vessels by receiving infrared light), vehicle-mounted cameras (e.g., cameras for taking images of the surroundings and interior of a vehicle, and cameras for detecting the distance between vehicles), surveillance cameras, cameras for person authentication, and industrial cameras. EXAMPLES

[0180] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0181] The weight average molecular weight (Mw) of the compound is a polystyrene-equivalent value measured by gel permeation chromatography (GPC) under the following conditions. Column: TSKgelGRCXLII, manufactured by Tosoh Corporation Solvent: Tetrahydrofuran Temperature: 40℃ Pressure: 68kgf / cm 2

[0182] [Preparation of Radiation-Sensitive Composition] In the examples and comparative examples, the compounds (A) to (D) and the solvent (F) used in the preparation of the radiation-sensitive compositions are shown in detail below.

[0183] <Compound (A)> A-1 to A-12: Compounds represented by the following formulas (A-1) to (A-12)

[0184] [ka]

[0185] [ka]

[0186] Compound (A-1): 6,6'-(9H-fluorene-9,9-diyl)bis(2-naphthol) (BNF, manufactured by JiangSu Ever Galaxy Chemical Co., Ltd.) Compound (A-2): 9,9'-bis(4-hydroxyphenyl)fluorene (BPFL, manufactured by JFE Chemical) Compound (A-3): 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene (BCF, manufactured by JFE Chemical Corporation) Compound (A-4): 2,2'-[9H-fluorene-9,9-diylbis(naphthalene-6,2-diyloxy)]diethanol (BNF-EO, manufactured by JiangSu Ever Galaxy Chemical Co., Ltd.)

[0187] Compound (A-5): 100g (0.22mol) of 6,6'-(9H-fluorene-9,9-diyl)bis(2-naphthol), 94.5g (0.67mol) of iodomethane, 92.0g (0.67mol) of potassium carbonate, and 1L of dimethylsulfoxide were charged into a 2L three-neck flask equipped with a thermometer and a nitrogen inlet tube, and stirred at 25°C for 6 hours. After the reaction was completed, the reaction solution was poured into 2L of distilled water, and the precipitated solid was filtered and washed with water. Next, the filtered solid was dried in a vacuum to obtain 103g of a white powder of compound (A-5) represented by the above formula (A-5).

[0188] Compound (A-6): 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (BAHF, manufactured by JFE Chemical Corporation)

[0189] Compound (A-7): 200g (0.53mol) of 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 156g (1.05mol) of phthalic anhydride, and 2L of N-methyl-2-pyrrolidone were charged into a 2L three-neck flask equipped with a thermometer and a nitrogen inlet tube, and stirred at 25°C for 12 hours. After the reaction was completed, the reaction solution was poured into 4L of distilled water, and the precipitated solid was filtered and washed with water. The filtered solid was then vacuum dried to obtain 310g of a white powder of compound (A-7) represented by the above formula (A-7).

[0190] Compound (A-8): 100g (0.29mol) of 4,4'-(9H-fluorene-9,9-diyl)dianiline, 79.3g (0.57mol) of salicylic acid, 92.5g (0.29mol) of tetrabutylammonium bromide, and 178g (0.57mol) of triphenyl phosphite were charged into a 2L three-neck flask equipped with a thermometer and a nitrogen inlet tube, and the mixture was stirred at 120°C for 2 hours. After the reaction was completed, 1L of dichloromethane was added to the reaction solution cooled to room temperature, and the mixture was separated and washed with a 2N aqueous hydrochloric acid solution and water. The organic layer was then concentrated under reduced pressure, and 1L of methanol was added to the crude product to recrystallize, thereby obtaining 160g of a white powder of compound (A-8) represented by the formula (A-8).

[0191] Compound (A-9): 250g (0.72mol) of 4,4'-(9H-fluorene-9,9-diyl)dianiline, 358g (1.58mol) of naphthalene-2-sulfonyl chloride, and 1L of pyridine were charged into a 2L three-neck flask equipped with a thermometer and a nitrogen inlet tube, and stirred at 25°C for 3 hours. After the reaction was completed, pyridine was distilled off by vacuum concentration, and the mixture was acidified with 2N hydrochloric acid water, and then separated and washed with dichloromethane and water. The organic layer was then concentrated under reduced pressure and dried in vacuum to obtain 472g of a white powder of compound (A-9) represented by the above formula (A-9).

[0192] Compound (A-10): 480 g of white powder of compound (A-10) represented by the above formula (A-10) was obtained in the same manner as in the synthesis example of compound (A-9), except that the naphthalene-2-sulfonyl chloride in the synthesis example of compound (A-9) was changed to 358 g (1.58 mol) of naphthalene-1-sulfonyl chloride.

[0193] Compound (A-11): 100g (0.29mol) of 4,4'-(9H-fluorene-9,9-diyl)dianiline and 200mL of tetrahydrofuran were charged into a 1L three-neck flask equipped with a thermometer and a nitrogen inlet tube, and cooled with ice. Then, 119g (0.57mol) of p-toluenesulfonyl isocyanate was slowly added dropwise so that the internal temperature did not exceed 20°C, and the mixture was stirred at 25°C for 1 hour. After the reaction was completed, the reaction solution was poured into 1L of ethanol, and the precipitated solid was filtered off. Next, the filtered solid was dried in a vacuum to obtain 182g of a white powder of the compound (A-11) represented by the above formula (A-11).

[0194] Compound (A-12): 147 g of white powder of compound (A-12) represented by the above formula (A-12) was obtained in the same manner as in the synthesis example of compound (A-11), except that 4,4'-(9H-fluorene-9,9-diyl)dianiline in the synthesis example of compound (A-11) was changed to 6,6'-(9H-fluorene-9,9-diyl)bis(2-naphthol).

[0195] <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 Strong Electronics New Materials Co., Ltd.)

[0196] <Compound (C)> C-1: 2-hydroxy-3-phenoxypropyl acrylate C-2: Polyethylene glycol diacrylate C-3: Mixture of dipentaerythritol hexaacrylate (40% by mass) and dipentaerythritol pentaacrylate (60% by mass) C-4: Pentaerythritol tetraacrylate C-5: Diethylene glycol modified dipentaerythritol hexaacrylate C-6: Trimethylolpropane polypropylene glycol triacrylate C-7: N-(2-hydroxyethyl)acrylamide

[0197] <Compound (D)> 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: Benzofluorene-containing acrylate (compound represented by the following formula (D-3)) D-4: A copolymer of benzofluorene-containing acrylate, acrylic acid, and 3-(acryloyloxy)-2-hydroxypropyl methacrylate (a compound represented by the following formula (D-4), Mw: 4000). The mass ratio of the copolymer is 70 / 15 / 15 (mass ratio) of benzofluorene-containing acrylate, acrylic acid, and 3-(acryloyloxy)-2-hydroxypropyl methacrylate. D-5: Acid anhydride modified fluorene-containing acrylic resin (compound represented by the following formula (D-5), Mw: 4000)

[0198] [ka]

[0199] <Comparative compound (d)> d-1: A copolymer of butyl acrylate, acrylic acid, and 3-(acryloyloxy)-2-hydroxypropyl methacrylate (a compound represented by the following formula (d-1), Mw: 4000). The mass ratio of the copolymer is butyl acrylate, acrylic acid, and 3-(acryloyloxy)-2-hydroxypropyl methacrylate = 80 / 10 / 10 (mass ratio).

[0200] [ka]

[0201] <Solvent (F)> F-1: Propylene glycol monomethyl ether acetate (PGMEA) F-2: Cyclopentanone (CPN) F-3: N-methylpyrrolidone (NMP) F-4: Propylene glycol monomethyl ether (PEGME)

[0202] Example 1 30 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 adhesion aid (3-glycidyloxypropyltrimethoxysilane), and 0.2 parts by mass of surfactant (NEOS Co., Ltd. "FTX-218") were mixed, and then solvent (F-1) was added so that the solid content concentration was 35% by mass, and each component was dissolved by stirring. Next, the obtained mixture was filtered through a membrane filter with a pore size of 0.2 μm to prepare a radiation-sensitive composition.

[0203] (Examples 2 to 35 and Comparative Examples 1 to 3) Radiation-sensitive compositions were prepared in the same manner as in Example 1, except that the types and amounts of each component were changed as shown in Table 1.

[0204] [Evaluation of Radiation-Sensitive Composition] The properties of the radiation-sensitive compositions prepared in Examples 1 to 35 and Comparative Examples 1 to 3 were evaluated as follows. The evaluation results are shown in Table 1.

[0205] <Evaluation of refractive index> Each of the prepared radiation-sensitive compositions was applied onto a non-alkali glass substrate using a spinner, and then prebaked on a hot plate at 100°C for 3 minutes to form a coating film with a thickness of 9.0 μm. The coating film was then irradiated with a high-pressure mercury lamp (illuminance at 365 nm: approximately 500 mW / cm 2 ) at 300mJ / cm 2 The substrate was then exposed to radiation at an exposure dose of 1000 nm. Thereafter, development was performed at 25°C by puddle method using a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 23°C as a developer for 60 seconds, followed by washing with pure water for 60 seconds, and then drying the substrate. Thereafter, the substrate was post-baked for 40 minutes in an oven at 85°C to form a cured film. The refractive index of the obtained cured film at a wavelength of 550 nm was measured using a rotating compensator type spectroscopic ellipsometer SE-2000 (manufactured by emilab Semiconductor Physics Laboratory Co. Ltd.). Table 1 shows the evaluation results evaluated according to the following evaluation criteria and the measured refractive index values.

[0206] Evaluation criteria AA: Refractive index ≧ 1.660 BB:1.660>Refractive index≧1.640 CC:1.640>Refractive index

[0207] <Evaluation of pattern wetting and spreading> Each of the prepared radiation-sensitive compositions was applied onto a non-alkali glass substrate using a spinner, and then pre-baked on a hot plate at 100° C. for 3 minutes to form a coating film with a thickness of 9.0 μm. Next, the resulting coating film was exposed to light using a projection exposure device (high pressure mercury lamp; illuminance at 365 nm: approximately 500 mW / cm) through a photomask having a circular pattern with a diameter of 15 μm. 2 ) at 300mJ / cm 2 The radiation exposure was carried out at an exposure dose of 1000 x 1000 nm.

[0208] Thereafter, development was performed by the puddle method at 25°C using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23°C as the developer for 60 seconds, followed by washing with pure water for 60 seconds, and then drying the substrate to form a pattern consisting of multiple microscopic bodies formed by the radiation-sensitive composition on the substrate (an enlarged photograph of the pattern at this stage is shown in Figure 1(a)). The diameter (width) of the portion of the resulting pattern in contact with the substrate was measured using an optical microscope. The measured diameter (width) of the pattern was designated as Y μm.

[0209] Thereafter, the substrate was post-baked in an oven at 85°C for 40 minutes to form a lens pattern consisting of a plurality of minute bodies formed from the radiation-sensitive composition on the substrate (an enlarged photograph of the lens pattern at this stage is shown in Figure 1(b)). The diameter (width) of the portion of the resulting lens pattern in contact with the substrate was measured using an optical microscope. The measured diameter (width) of the lens pattern was designated Z µm.

[0210] The wet spread of the pattern was evaluated according to the following evaluation criteria. The evaluation results according to the following evaluation criteria and the calculated ZY value are shown in Table 1. The smaller the difference between the pattern diameter (width) Y μm before post-bake and the lens pattern diameter (width) Z μm after post-bake, the more suppressed the wet spread of the pattern is.

[0211] Evaluation criteria AA:(ZY)≦Y×0.2 BB:Y×0.2<(ZY)≦Y×0.4 CC:(ZY)>Y×0.4 -: No pattern was found

[0212] [Table 1]

Claims

1. Component (A): a compound represented by the following formula (1) (having no (meth)acryloyloxy group), Component (B): a photopolymerization initiator; Component (C): a polymerizable compound (excluding component (D)), Component (D): a compound having a fluorene structure, an acidic group, and a (meth)acryloyloxy group in the molecule. A radiation-sensitive composition comprising: 【Chemistry 1】 (In formula (1), Ar 1 and Ar 2 are each independently an aromatic ring group. R 1 and R 2 are each independently a monovalent substituent, or R 1 and R 2 and are bonded to each other to form Ar 1 and Ar 2 The fused ring structure is a fused ring structure in which two aromatic rings are bonded together with a single bond, —O—, —S—, —NR 5 -, a carbonyl group, a methylene group, or an ethylene group. 5 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. m1 and m2 each independently represent an integer of 0 to 7. k1 and k2 each independently represent an integer of 0 to 4. When k1 is an integer of 2 or more, multiple R 3 are each independently a monovalent substituent, or are bonded together to form R 3 forms a condensed ring together with the benzene ring to which it is attached. When k2 is an integer of 2 or more, a plurality of R 4 are each independently a monovalent substituent, or are bonded together to form R 4 forms a condensed ring together with the benzene ring to which it is attached. In formula (1), R 1 ~R 4 When there are multiple R 1 ~R 4 are the same or different.)

2. The radiation-sensitive composition according to claim 1 , wherein the component (D) is a compound represented by the following formula (2): 【Chemistry 2】 (In formula (2), Ar 1 and Ar 2 are each independently an aromatic ring group. R 1 and R 2 are each independently a monovalent substituent, or R 1 and R 2 and are bonded to each other to form Ar 1 and Ar 2 The fused ring structure is a fused ring structure in which two aromatic rings are bonded together with a single bond, —O—, —S—, —NR 5 -, a carbonyl group, a methylene group, or an ethylene group. 5 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 group represented by the following formula (2X): n1 and n2 each independently represent an integer from 1 to 7. m1 and m2 each independently represent an integer of 0 to 6. k1 and k2 each independently represent an integer of 0 to 4. When k1 is an integer of 2 or more, multiple R 3 are each independently a monovalent substituent, or are bonded together to form R 3 forms a condensed ring together with the benzene ring to which it is attached. When k2 is an integer of 2 or more, a plurality of R 4 are each independently a monovalent substituent, or are bonded together to form R 4 forms a condensed ring together with the benzene ring to which it is attached. However, R 1 ~R 4 , X 1 and X 2 At least one of these has an acidic group, and the compound represented by formula (2) has at least one acidic group. In formula (2), R 1 ~R 4 , X 1 and X 2 When there are multiple R 1 ~R 4 , X 1 and X 2 are the same or different.) 【Chemistry 3】 (In formula (2X), R 8 is an alkanediyl group having 2 to 4 carbon atoms. R 6 is a hydrogen atom or a methyl group. X is 0 or 1. R 9 is a hydrogen atom or -OY 1 It is. Y 1 is a hydrogen atom or "-C(=O)-R 7 -COOH" group. 7 is a divalent organic group having one or more carbon atoms. p is an integer of 0 to 4. When p is 2 or more, a plurality of R 8 are the same or different. "*" represents a bond.)

3. The radiation-sensitive composition according to claim 1, which is used for producing a microlens by a thermal flow method.

4. A cured product obtained by curing the radiation-sensitive composition according to any one of claims 1 to 3.

5. The cured product according to claim 4, which has a refractive index of 1.640 or more at a wavelength of 550 nm.

6. The cured product according to claim 4, which is for use as an optical member.

7. A display device comprising the cured product according to claim 4.

8. An imaging device comprising the cured product according to claim 4.

9. A step of applying the radiation-sensitive composition according to any one of claims 1 to 3 onto a substrate; a step of exposing the radiation-sensitive composition applied onto the substrate to radiation; developing the radiation-sensitive composition after irradiation; heating the developed radiation-sensitive composition; A method for producing a cured product comprising the steps of:

10. The method for producing a cured product according to claim 9 , wherein the heating temperature in the step of heating the radiation-sensitive composition after development is 100° C. or lower.

11. The method for producing a cured product according to claim 9 , wherein the pattern is melted to form a microlens by a step of heating the developed radiation-sensitive composition.

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